TW202441289A - Compound, composition, method for expressing sensitivity-enhancing effect, and preparation method - Google Patents

Abstract

The present invention provides a compound represented by following formula (1): (in formula (1), RG is a group comprising at least one cyclic structure, I is an iodine atom, R ¹may be the same or different, and is a monovalent functional group having 0 to 30 carbon atoms, and does not comprise a polymerizable unsaturated bond, n is an integer of 1 to 5, and m is an integer of 1 to 5).

Description

Compound, composition, method for showing sensitization effect and manufacturing method

The present invention relates to a compound, a composition, a method for exhibiting a sensitizing effect and a manufacturing method.

In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, due to the progress of lithography technology, the miniaturization of semiconductors (patterns) and pixels has been rapidly advanced. Therefore, materials corresponding to miniaturization are expected. For example, Patent Document 1 discloses an anti-etching agent composition, which contains a compound having a structure with multiple aromatic rings cross-linked and having iodine atoms. The anti-etching agent composition has excellent etching resistance. In addition, Patent Document 2 discloses a compound having a polymerizable group and an iodine atom. The anti-etching agent composition containing the compound can form an anti-etching pattern with excellent CD uniformity. [Prior technical document] [Patent document]

[Patent document 1] International Publication No. 2020/040161 [Patent document 2] Japanese Patent Publication No. 2021-188040

[The problem that the invention wants to solve]

It is desired to develop a lithography composition that can correspond to miniaturization, preferably a compound useful for an anti-etching agent composition. In view of the above situation, the subject of the present invention is to provide a compound useful as a lithography composition, a composition containing the compound, a method of using the compound to exhibit a sensitization effect, and a method for producing the compound. [Means for solving the problem]

The inventors discovered that compounds with specific structures can solve the above-mentioned problems.

That is, the present invention includes the following aspects. [1] A compound represented by the following formula (1): (In the formula, RG is a group containing at least one cyclic structure, I is an iodine atom, ^R1 is a monovalent functional group which may be the same or different and has 0 to 30 carbon atoms and does not contain a polymerizable unsaturated bond, n is an integer from 1 to 5, and m is an integer from 1 to 5.) [2] As in the above compound, wherein the above RG is a group derived from benzene, naphthalene, anthracene, pyrene, a heteroaromatic ring or a polycyclic aliphatic ring which may have a substituent, and the above R1 is ^one selected from: ^Rf selected from the group consisting of a hydroxyl group and an ether group having a protective group, and ^Rg , a alkyl group having 0 to 30 carbon atoms which may have a substituent. [3] As in the above compound, wherein the above ^Rf is ^Rf' selected from the group consisting of one or more hydroxyl groups and an ether group having a protective group which can be removed by acid, alkali or heat. [4] The above compound, wherein RG is a group derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene or adamantane which may have a substituent. [5] The above compound, wherein RG is a group derived from benzene, naphthalene or adamantane which may have a substituent. [6] The above compound, wherein R ¹ is selected from -OR ² , -COOR ³ , -CH ₂ -OR ⁴ or -CHO, wherein R ² is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, or an aryl group having 1 to 30 carbon atoms, R ³ is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms which may have a substituent, or an aryl group having 1 to 29 carbon atoms, and R ⁴ is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms which may have a substituent, or an aryl group having 1 to 29 carbon atoms. [7] The above compound, wherein R ¹ has a protecting group. [8] The above compound is represented by any one of the following formulae: (wherein, Z is I, ^R1 or a linking group for forming a dimer, I and ^R1 have the same definitions as in formula (1), A is a group having a protecting group, R is an organic group that is not a functional group, ^R1 , A, and R are bonded at positions where they can be bonded, r1 to r4 are integers of 0 to 5, and the total of r1 to r4 in one benzene is less than the valence of benzene); (wherein, I, A, and ^R1 are defined as above, R" is a hydrogen atom or an organic group other than ^R1 , s1 is 1 to 7, s2 to s3 are 0 to 7, and s4 is an integer of 1 to 7; however, the total of s1 to s4 is less than the valence of naphthalene, and at least one of s2 and s3 is selected so as to be 1 or more); (wherein, I, ^R1 , and R" are as defined above, t1 is an integer from 1 to 10, t2 is an integer from 1 to 9, and t3 is an integer from 1 to 14; however, the total of t1 to t3 is less than the valence of adamantane.) [9] The above compound is represented by any one of the following formulae: (wherein, I, Z, R, ^R1 and A have the same meanings as in formula (Bz)); (wherein, I, R ¹ , A, and R" are the same as those defined in formula (N); x and y are 0 or 1, but at least one of them is 1; s4' represents the number of R" that can be combined with the 1, 7, and 8 positions of naphthalene, which is an integer of 1 to 3); (wherein, I, R ¹ , and R” have the same meanings as in formula (Ad), one of D is I, and the other of D is R ¹ ). [10] The above compound is represented by any one of the following formulae: (wherein, I, Z, R, R ¹ , and A have the same definitions as in formula (Bz)); (wherein, I, R ¹ , R ″, A, x, y, s4 ′ have the same meanings as in formula (n)); (wherein, I, ^R1 , and R" have the same definitions as in formula (Ad)). [11] The above-mentioned compound, wherein the aforementioned ^R1 is a hydroxyl group, a carboxylic acid group, an ester group, or a hydroxyalkyl group, when the aforementioned A is A' represented by ^-ORa - ^ORb ( ^Ra is a linear or branched alkyl group having 1 to 3 carbon atoms; ^Rb is a monovalent linear or branched alkyl group having 1 to 3 carbon atoms, or a cyclic alkyl group, or a divalent cyclic alkyl group that forms a ring together with an adjacent oxygen atom), the A' is contained in 1 or more groups. [12] The above-mentioned compound, wherein RG is a group derived from benzene that may have a substituent. [13] The above-mentioned compound, wherein when RG is a benzene-containing group, and there are multiple ^R1s , the R ¹ does not include a combination of an alkoxy group (except when having a protecting group) and an aldehyde group, a combination of the alkoxy group and a hydroxyl group, and a combination of a hydroxyl group and an aldehyde group. When RG is a naphthalene-containing group and there are multiple R ^1s , the R ¹ does not include a combination of a hydroxyl group and a carboxylic acid group. [14] The above compound is represented by the following formula (Bz4): (wherein, I, R, A and Z have the same definitions as in formula (Bz); R1 ^' is a monovalent functional group other than a hydroxyl group which may be the same or different and has 0 to 30 carbon atoms and does not contain a polymerizable unsaturated bond; r1', r2', r4' are integers from 0 to 5, and the total of r1', r2', r4' is less than the valence of benzene). [15] The above compound is represented by the following formula (Bz4-1): (wherein, I, R, Z and R ^1' have the same definitions as in formula (Bz4); r1', r2', r4' are integers ranging from 0 to 5, and the sum of r1', r2', r4' is less than the valence of benzene.) [16] The above compound is represented by the following formula (Bz4-2): (wherein, I has the same definition as in formula (Bz4), r4' is an integer from 0 to 4, and r5' is an integer from 0 to 4). [17] The compound as described above is represented by any one of the following formulae; [18] The compound as described above, which is represented by any one of the following formulae: (wherein, I, R, Z, A and ^R1 are the same as defined in formula (Bz); A' is a group having a protecting group, represented by ^-ORa - ^ORb , -O-CO- ^ORb or -ORa ^- CO- ^ORb ; ^Ra is a linear or branched alkyl group having 1 to 3 carbon atoms; ^Rb is a monovalent linear or branched alkyl group having 1 to 3 carbon atoms, or a cyclic alkyl group, or a divalent cyclic alkyl group that forms a ring together with an adjacent oxygen atom). [19] The compound as described above is represented by any of the following formulae: (wherein, I, ^R1 , and A are the same as defined in formula (Bz); A' is a group having a protecting group, represented by ^-ORa - ^ORb , -O-CO- ^ORb, or -ORa ^- CO- ^ORb ; ^Ra is a linear or branched alkyl group having 1 to 3 carbon atoms; ^Rb is a monovalent linear or branched alkyl group having 1 to 3 carbon atoms, or a cyclic alkyl group, or a divalent cyclic alkyl group that forms a ring together with an adjacent oxygen atom; Z' is I, ^R1, or a hydrogen atom). [20] The above compound, wherein RG is a group derived from naphthalene that may have a substituent. [21] The above compound, which is represented by any of the following formulae: (wherein, I, R ¹ , R ″, A, x, y, s4′ have the same meanings as in formula (n)). [22] The above compound is represented by any one of the following formulae: (wherein, I, ^R1 , and R" have the same definitions as in formula (n); A' is a group having a protecting group, represented by ^-ORa - ^ORb , -O-CO- ^ORb , or -ORa ^- CO- ^ORb ; ^Ra is a linear or branched alkyl group having 1 to 3 carbon atoms; ^Rb is a monovalent linear or branched alkyl group having 1 to 3 carbon atoms, or a cyclic alkyl group, or a divalent cyclic alkyl group that forms a ring together with an adjacent oxygen atom). [23] The compound as described above, wherein the aforementioned ^R1 is a hydroxyl group, a carboxylic acid group, an ester group, or a hydroxyalkyl group. [24] The compound as described above, which is represented by any one of the following formulae: (wherein, I, R ¹ , A, A′, x, and y have the same meanings as in formula (n)). [25] The compound as described above, wherein RG is a group derived from adamantane which may have a substituent. [26] The compound as described above, which is represented by any one of the following formulae: (wherein, I, ^R1 , and R" have the same definitions as in formula (Ad)). [27] The compound as described above, wherein the aforementioned ^R1 is a hydroxyl group, a carboxylic acid group, an ester group, or a hydroxyalkyl group. [28] The compound as described above, which is represented by any one of the following formulae: (wherein, I and ^R1 have the same definitions as in formula (Ad)). [29] A composition comprising the compound as described above. [30] The composition as described above, which is used for lithography. [31] The composition as described above, which comprises two or more compounds represented by the aforementioned formula (1). [32] The composition as described above, which further comprises a compound represented by the following formula (DMO-1) or the following formula (BP0-1) or a combination thereof: (wherein, RG, I, ^R1 have the same definitions as in formula (1), Q is a radical or a single bond caused by a radical that binds molecules, n' is an integer from 0 to 5 and less than n, m' is an integer from 1 to 5 and less than m, and b is an integer from 1 to 4). [33] The above composition, wherein the compound represented by the aforementioned formula (DM0-1) is a compound represented by the following formula (DM1a), (Dn1) or (Da1), and the compound represented by the aforementioned formula (BP0-1) is a compound represented by the following formula (BP1a), (Bn1) or (Ba1): (wherein, Z is I, ^R1 or a linking group for forming a dimer, I and ^R1 have the same definitions as in formula (1), A is a group having a protecting group, R is an organic group that is not a functional group, ^R1 , A, and R are bonded at positions where they can be bonded, r1 to r4 are integers of 0 to 5, and the total of r1 to r4 in one benzene is less than the valence of benzene); (wherein, I, ^R1 , and A are the same as defined in formula (DM1a), R" is a hydrogen atom or an organic group other than ^R1 , I, ^R1 , A, and R" are bonded at a bondable position, Q is the same as defined in formula (DM0-1), s1 is 1 to 7, s2 to s3 are 0 to 7, and s4 is an integer of 1 to 7; however, the total of s1 to s4 is less than the valence of naphthalene, and is selected so that any one of s2 and s3 is 1 or more; nd is an integer of 1 to 4); (wherein, I and ^R1 have the same definitions as in formula (Dn1), R" is a hydrogen atom or an organic group other than ^R1 , ^Rd is a single bond or -O- (ether bond), t1 is an integer of 1 to 10, t2 is an integer of 1 to 9, and t3 is an integer of 1 to 13; however, the total of t1 to t3 is less than the valence of diamond); (wherein, I, Z, R, ^R1 , A have the same definitions as in formula (DM1a), r1, r2, r3 are integers ranging from 0 to 5, a1 and r4a are integers ranging from 0 to 4, a1 and r4a satisfy a1+r4a≤r4; wherein, r4 has the same definition as in formula (DM1a)); (wherein, I, ^R1 , R", and A have the same definitions as in formula (Dn1) and (Da1), s2-s4 have the same definitions as in formula (Dn1), s1b is an integer from 0 to 6 and is an integer satisfying s1b≤(s1-1); wherein s1 has the same definition as in formula (Dn1)); (wherein, I, ^R1 , and R" have the same definitions as in formula (Dn1) and (Da1), t2 and t3 have the same definitions as in formula (Da1), t1b is an integer from 0 to 9 and satisfies t1b≤(t1-1); wherein t1 has the same definition as in formula (Da1)). [34] The above composition comprises a compound represented by the above formula (DM0-1). [35] The above composition, wherein the compounds represented by formula (1) and formula (DM0-1) satisfy the following relationship: 0.1≧[the amount of the compound of formula (DM0-1) (mol)]÷[the amount of the compound of formula (1) (mol)]≧0.000001. [36] The above composition, wherein it comprises a compound represented by formula (BP0-1). [37] In the above composition, the compound represented by formula (BP0-1) is: a compound represented by formula (BP1a) wherein Z is not 1, a compound represented by formula (Bn1), or a compound represented by formula (Ba1). [38] In the above composition, the compounds represented by formula (1), formula (DM0-1), and formula (BP0-1) satisfy the following relationship: 0.1≧([the total amount of the compound of formula (DM0-1) and the compound of formula (BP0-1) (mol)])÷[the amount of the compound of formula (1) (mol)]≧0.000001. [39] As described above, the compound represented by the aforementioned formula (DM0-1) is a compound represented by the following formula (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x) or (Ba1-eb), and the compound represented by the aforementioned formula (BP0-1) is a compound represented by the following formula (BP1a-Dt), (Bn1-Dt) or (Ba1-Dt): (wherein, Z, R, R ¹ , A, r1, r2, r3, and r4a have the same meanings as in Formula (BP1a)); (wherein, Z, I, R ¹ , A, R, r1 to r4 have the same definitions as in formula (DM1a)); (wherein, Z, R ¹ , A, R, r1 to r4 have the same definitions as in formula (DM1a)); (wherein, R ¹ , R ”, A, s2 to s4 have the same definitions as in formula (Bn1)); (wherein, I, R ¹ , A, R”, Q, s1 to s4 have the same definitions as in formula (Dn1)); (wherein, R ¹ , A, R”, Q, s2 to s4 have the same definitions as in formula (Dn1)); (wherein, R ¹ , R ″, t2, t3 have the same definitions as in formula (Ba1)); (wherein, I, R ¹ , R ″, R ^d , t1-t3 have the same definitions as in formula (Da1)); (wherein, R ¹ , R ″, R ^d , t2-t3 have the same definitions as in formula (Da1)); (wherein, I, R ¹ , R ″, R ^d , t1-t3 have the same definitions as in formula (Da1)); (wherein, I, R ¹ , R ″, R ^d , t1-t3 have the same definitions as in formula (Da1)); (wherein, I, ^R1 , R", ^Rd , t1-t3 are the same as defined in formula (Da1)). [40] A composition as described above, wherein RG of the formula (1) is a group derived from benzene which may have a substituent. [41] A composition as described above, wherein RG of the formula (1) is a group derived from naphthalene which may have a substituent. [42] A composition as described above, wherein RG of the formula (1) is a group derived from adamantane which may have a substituent. [43] A composition as described above, which exhibits a sensitizing effect when irradiated with radiation. [44] A composition as described above, wherein the content of metal impurities is less than 1 ppm. [45] A method for exhibiting a sensitizing effect, which is a method for exhibiting a sensitizing effect when a composition for lithography is irradiated with radiation using the compound as described above. [46] A method as described in [45], wherein two or more of the compounds as described above are used. [47] A method for producing the above-mentioned compound comprises the step of introducing an iodine atom or an ^R1 group into the compound containing the above-mentioned RG group. [48] A method for producing the above-mentioned compound is a method for producing a compound represented by the above-mentioned formula (1), wherein the compound represented by the above-mentioned formula (1) is represented by the formula (Bz), (wherein, I, Z, R ¹ , A, R, r1-r4 are the same as those defined in formula (DM1a)); the preparation method comprises: 1) preparing a compound represented by formula (MB); (wherein, I, ^R1 , R, r1, r2 are the same as defined in formula (Bz), and ^R1 , R, OH are bonded at any position where they can be bonded); 2) an iodination step of iodizing the compound; 3) a protecting group introduction step of introducing a protecting group into the compound; and 4) a reduction step of reducing the compound. [49] A method for producing a compound as described in [48], wherein the protecting group introduction step comprises the step of introducing a protecting group into the hydroxyl group of formula (MB) using an inorganic base. [50] A method for producing the above-mentioned compound, which is a method for producing a compound represented by formula (1), wherein the compound represented by formula (1) is represented by formula (Bz), (wherein, I, Z, R ¹ , A, R, r1 to r4 have the same definitions as in formula (DM1a)); the preparation method comprises: 1) preparing a compound represented by formula (Bz4), (wherein, I, R, A, and Z have the same definitions as in formula (Bz), R1 ^' is a monovalent functional group other than a hydroxyl group which may be the same or different and has 0 to 30 carbon atoms and does not contain a polymerizable unsaturated bond, r1', r2', and r4' are integers from 0 to 5, and the total of r1', r2', and r4' is less than the valence of benzene); 2) the iodination step of iodizing the compound is performed once or twice or more. [51] A method for producing the above-mentioned compound, which is a method for producing a compound represented by the aforementioned formula (1), wherein the compound represented by the aforementioned formula (1) is represented by formula (Bz), (wherein, I, Z, R ¹ , A, R, r1 to r4 have the same definitions as in formula (DM1a)); the preparation method comprises: 1) preparing a compound represented by formula (Bz5); (wherein, I, Z, ^R1 , A, R, r1 to r4 have the same definitions as in formula (DM1a)); 2) a step of esterifying the carboxylic acid of the compound represented by formula (Bz5); 3) a step of reducing the obtained ester group to convert it into a hydroxymethyl group. [52] A method for producing the above-mentioned compound, which is a method for producing the compound represented by the aforementioned formula (1), wherein the compound represented by the aforementioned formula (1) is represented by formula (N), (wherein, I, R ¹ , A, and R" are the same as those defined in formula (Dn1) and (Bn1), however, I, R ¹ , R" and A are bonded at any bondable position, s1 is 1 to 7, s2 to s3 are 0 to 7, and s4 is an integer of 1 to 7; however, the total of s1 to s4 is less than the valence of naphthalene, and is selected in such a way that any one of s2 and s3 is 1 or more); the production method comprises: 1) preparing a compound represented by formula (MN); (wherein, ^R1 , R", s3, s4 have the same definitions as in formula (N)); 2) an iodination step of iodizing the compound; 3) a protecting group introduction step of introducing a protecting group into the compound; and 4) a reduction step of reducing the compound. [53] A method for producing the compound described above, which is a method for producing a compound represented by the aforementioned formula (1), wherein the compound represented by the aforementioned formula (1) is represented by formula (Ad), (wherein, I, R ¹ , and R” are the same as those defined in formula (Da1); I, R ¹ , and R” are bonded at any position where they can be bonded; t1 is an integer of 1 to 10, t2 is an integer of 1 to 9, and t3 is an integer of 1 to 14; however, the total of t1 to t3 is less than the valence of adamantane); the preparation method comprises: 1) preparing a compound represented by formula (MA); (wherein ^R1 , R", t2 and t3 have the same definitions as in formula (Ad)); 2) an iodination step of iodinating the compound. [54] A method for producing a compound as described in any one of [48] to [53], wherein the iodination step comprises: an iodination step of a system consisting of a multiphase system comprising an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent. [55] A method for producing a compound as described in any one of [48] to [53], wherein the iodination step comprises a step of concentrating the reaction solution while distilling off water during the reaction. [56] A method for producing a compound as described in any one of [48] to [53], wherein the iodination step comprises feeding the substrate and the iodination agent and then standing for 1 to 48 hours. [57] A method for producing the above compound, comprising any one or more steps selected from: 1) the step of preparing a compound represented by formula (Ad-A-3-0); 2) the step of preparing a compound represented by formula (Ad-A-3-1); and 3) the step of preparing a compound represented by formula (Ad-A-3-2), [58] A method for producing the compound of [57], comprising: 1) preparing a compound represented by formula (Ad-A-3-0); 2) an oxidation step of oxidizing the compound represented by formula (Ad-A-3-0); 3) a step of esterifying the carboxylic acid of the obtained compound; 4) a step of hydrolyzing the ester group of the obtained compound to convert it into a carboxylic acid; 5) an iodination step of iodination. [59] The production method of any one of [47] to [58] further comprises a step of treating with an adsorbent. [60] The compound as described above is represented by the following formula (Ad-A-3): [61] The compound as described above is represented by the following formula (Ad-A-4): [Effect of invention]

A compound useful as a lithography composition, a composition containing the compound, a method of using the compound to exhibit a sensitization effect, and a method of producing the compound can be provided. Furthermore, by using the compound and composition of the present invention in a lithography process, a sensitization effect can be obtained.

Hereinafter, the present invention will be described in detail. In the present invention, "~" in "X~Y" etc. includes its end values X and Y.

1. Compounds The compounds of this embodiment are represented by the following formula (1).

[RG] In the formula, RG is a group containing at least one cyclic structure. The valence of RG can be appropriately adjusted by the number of I, R ¹ , substituents other than R ¹ described below, etc. The group containing a cyclic structure may contain an aromatic ring, an aliphatic ring, or a heterocyclic ring, but is preferably a group having 6 to 60 carbon atoms, and more preferably a group derived from an aromatic ring, a heteroaromatic ring, cyclohexane, cyclododecane, dicyclopentane, tricyclodecane, or a polycyclic aliphatic ring such as adamantane, etc., which may have a substituent. In addition, RG may not contain a ring assembly in which a single ring is bonded by a single bond (for example, biphenyl, binaphthyl, dicyclopropyl, etc.). In this case, RG is preferably a group having at least one cyclic structure selected from a monocyclic aromatic ring structure, a condensed-ring aromatic structure, and a polycyclic aliphatic ring structure.

Among them, from the viewpoint of availability, RG is preferably a group derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene or a polycyclic alicyclic ring which may have a substituent, more preferably a group derived from benzene, naphthalene, anthracene, pyrene, a heteroaromatic ring or a polycyclic alicyclic ring which may have a substituent, further preferably a group derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene or adamantane which may have a substituent, and particularly preferably a group derived from benzene, naphthalene or adamantane.

[I] In the formula, I is an iodine atom. n represents the number of I, which is an integer of 1 to 5. From the perspective of sensitization effect, solubility in solvents, and chemical stability, n is preferably an integer of 1 to 3, and more preferably 1 or 2. By making n greater than 1, a sensitization effect can be obtained, and by making n less than 5, the solubility of the compound in solvent components widely used in semiconductors and the stability of the compound itself can be ensured.

[R ¹ ] R ¹ is a monovalent functional group having 0 to 30 carbon atoms and containing no polymerizable unsaturated bond, which may be the same or different. R ¹ may be replaced with other groups or combined with other groups to produce a derivative of the compound of formula (1). The so-called polymerizable unsaturated bond refers to an ethylenic double bond or triple bond. When R ¹ is as described above, its stability and solubility are excellent.

^R1 is a functional group other than an alkyl group. ^R1 is, for example, an alkoxy group having 1 to 30 carbon atoms, a carboxylic acid group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 1 to 30 carbon atoms, an aldehyde group, a halogen atom other than an iodine atom, a nitro group, an amine group, a thiol group, a cyano group, or a hydroxyl group. Among them, from the viewpoint of the sensitization effect, etc., ^R1 is preferably a hydroxyl group, a carboxylic acid group, an ester group, a hydroxyalkyl group, a halogen atom other than an iodine atom, a nitro group, an amine group, or a cyano group. Among these groups, the group that may have a substituent may have a substituent. Unless otherwise defined, the so-called "substitution" means that one or more hydrogen atoms in the functional group are replaced by a substituent. The "substituent" is not particularly limited, but examples thereof include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a thiol group, a heterocyclic group, a linear aliphatic alkyl group having 1 to 20 carbon atoms, a branched aliphatic alkyl group having 3 to 20 carbon atoms, a cyclic aliphatic alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group having 0 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an acyl group having 1 to 30 carbon atoms (preferably an alkacyloxy group having 1 to 20 carbon atoms, an aryloxy group having 7 to 30 carbon atoms), an alkoxycarbonyl group having 2 to 20 carbon atoms, or an alkylsilanyl group having 1 to 20 carbon atoms. These groups may form a ring structure in a substituent or in a group having a substituent, or with other R ^1. Preferred examples of groups that can form a ring structure include a glycidyl group, a cyclic acetal group, and a group having an acetal protecting group structure with two adjacent hydroxyl groups.

Among them, ^R1 is preferably selected from a hydroxyl group, a carboxylic acid group, an ester group or a hydroxyalkyl group, and more preferably a group represented by ^-OR2 , an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxylic acid group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms or an aldehyde group. In the present invention, ^R2 is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 1 to 30 carbon atoms or a cyclic alkyl ether group having 1 to 5 carbon atoms. The aforementioned carboxylic acid group or carboxylic acid ester group is more preferably represented by ^-COOR3 . In the present invention, ^R3 is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms or an aryl group having 1 to 29 carbon atoms. The alkoxyalkyl group or hydroxyalkyl group is more preferably represented by -CH ₂ -OR ^4. In the present invention, R ⁴ is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms, or an aryl group having 1 to 29 carbon atoms. The alkyl group or aryl group may have a substituent. Examples of the substituent include alkoxy groups. Therefore, in one embodiment, R ² of the -OR ² may be -CH ₂ -OC ₂ H ₅ .

The alkyl group in the aforementioned R ² to R ⁴ is preferably methyl, ethyl or propyl (including isomers; the same below). The aforementioned aryl group is preferably phenyl or naphthyl.

^R1 may have a protecting group. A protecting group is a group that dissociates under specific conditions, also known as a dissociating group. The protecting group is preferably an acid-dissociating group that dissociates in the presence of an acid. Preferred examples of the protecting group include: 1-substituted ethyl, 1-substituted n-propyl, 1-branched alkyl, silyl, acyl, 1-substituted alkoxymethyl, cyclic ether, alkoxycarbonyl or alkoxycarbonylalkyl. In one embodiment, ^R1 may be a hydroxyl or carboxylic acid group protected by a protecting group. For example, ^R1 is -O- _CH2 -O-R'. R' is, for example, an alkyl group having 1 to 5 carbon atoms. This embodiment is equivalent to the case where ^R1 is ^-OR2 (however, ^R2 is _CH3 ) and ^R2 has an alkoxy group (-O-R') as a substituent. When R ¹ is a group having a protecting group, as described below, R ¹ may be represented by A or A'.

In the formula, m represents the number of ^R1 , which is an integer of 1 to 5. From the viewpoint of solubility in solvents, m is preferably 4, 3, 2 or 1. When m is 2 or 3, the plural ^R1s may be different or the same. m is more preferably 2 or 3, and further preferably 2. The total number of m and n is appropriately adjusted according to the valence of RG.

If necessary, the aforementioned compound may have an organic group other than R ¹ as a substituent. Examples of the organic group include an alkyl group having 1 to 30 carbon atoms. The group may be present in plural numbers. However, it is preferred that the aforementioned compound does not contain an organic group other than R ¹ and an iodine atom.

When RG is a benzene-containing group and there are multiple ^R1s , the ^R1 does not include a combination of an alkoxy group and an aldehyde group, a combination of an alkoxy group and a hydroxyl group, and a combination of an aldehyde group and a hydroxyl group. The alkoxy group here is excluded if it has a protecting group. The alkoxy group is, for example, a methoxy group or an ethoxy group. When RG is a naphthalene-containing group and there are multiple ^R1s , the ^R1 does not include a combination of a hydroxyl group and a carboxylic acid group.

When RG is benzene, naphthalene, anthracene, pyrene, a heteroaromatic ring, or a group derived from a polycyclic aliphatic ring, ^R1 is preferably one selected from one or more ^Rf and zero or more ^Rg . In addition, ^R1 is one selected from one or more ^Rf' and zero or more ^Rg . ^Rf is selected from the group consisting of a hydroxyl group and an ether group having a protective group. ^Rf' is selected from the group consisting of a hydroxyl group and an ether group having a protective group that can be removed by acid, alkali or heat. ^Rg is a alkyl group having 0 to 30 carbon atoms that may have a substituent. In particular, when RG is a benzene or naphthalene structure, ^R1 is preferably selected from the group consisting of ^Rf consisting of one or more hydroxyl groups and ether groups having a protective group, and zero or more alkyl groups ^Rg having a carbon number of 0 to 30 which may have a substituent. ^Rf is more preferably selected from the group consisting of ^Rf' consisting of one or more hydroxyl groups and ether groups having a protective group that can be removed by acid, alkali or heat. When the compound of formula (1) has these groups as ^R1 , the linking reaction of the compound with other compounds can proceed smoothly.

As mentioned above, the compound of formula (1) can be linked to other compounds. For example, the compound of formula (1) can also be a dimer to a pentamer. The polymer will be described later.

1-2. Preferred embodiment (1) Embodiment 1 In the embodiment 1, RG is benzene. In this embodiment, from the viewpoint of sensitization effect and ease of use, the compound represented by formula (1) (hereinafter referred to as "the compound of formula (1)", etc.) is preferably a compound represented by formula (Bz).

A is a group having a protecting group. Since A becomes a functional group by removing the protecting group, it is a kind of R ^1. As described above, the protecting group is preferably an acid-dissociable group. Therefore, the group having a protecting group is preferably a hydroxyl group or a carboxylic acid group protected by an acid-dissociable group. A may be A' represented by -OR ^a -OR ^b ; in this case, the compound of formula (Bz) preferably contains more than 1 of this A'. ^Ra and R ^b will be described later.

R is an organic group which is not a functional group. Examples of the organic group include an alkyl group having 1 to 30 carbon atoms.

Z is I, ^R1 or a linker for forming a dimer. When Z is a linker for forming a dimer, two molecules are bonded by a single bond to form a dimer. The dimer is included in the compound represented by the formula (DM1a) described below. Z may not contain a linker for forming a dimer. When Z does not contain a linker for forming a dimer, Z is specifically indicated as Z'.

In the formula, I and ^R1 are as defined above. From the viewpoint of the sensitizing effect, ^R1 is preferably a hydroxyl group, a carboxylic acid group, an ester group, a hydroxyalkyl group, a halogen atom other than an iodine atom, a nitro group, an amine group or a cyano group.

^R1 , R and A are bonded at any bondable position. r1 to r4 are integers of 0 to 5, and the sum of r1 to r4 is less than the valence of benzene. In addition, r1 to r4 are preferably integers of 1 to 4, more preferably integers of 1 to 3, and particularly preferably integers of 1 or 2. However, it is preferred that at least one of r2 and r3 is 1 or more. The preferred embodiment of the compound is described below from the viewpoints of sensitization effect and ease of use.

[Bz1 system] The compound of formula (Bz) is preferably represented by formula (Bz1). The compound of formula (Bz1) has one R ¹ that is not derived from Z. In the present specification, unless otherwise specified, each substituent of a compound has the same definition as in the compound group to which the compound belongs.

(Bz1-1 system) The compound of formula (Bz1) is preferably represented by formula (Bz1-1). The compound of formula (Bz1-1) has one R ¹ which is not derived from Z at the meta-position of I.

The compound of formula (Bz1-1) is preferably represented by formula (1b), and more preferably represented by formula (1b-3). Z' may be I, ^R1 or a hydrogen atom, and A and Z, or A and Z' may form a ring structure together with a protecting group.

Furthermore, the compound of formula (Bz1-1) is preferably represented by formula (1b-1), and more preferably represented by formula (1b-4).

(Bz1-2 system) The compound of formula (Bz1) is preferably represented by formula (Bz1-2). The compound of formula (Bz1-2) has one R ¹ not derived from Z at the para position of I. A and Z may form a ring structure together with a protecting group. In addition, Z and R ¹ may form a ring structure together with a protecting group.

The compound of formula (Bz1-2) is preferably represented by formula (Bz1-2-1), and more preferably represented by formula (Bz1-2-2). A and Z, or A and Z', may form a ring structure together with a protecting group.

(Bz1-3 system) Furthermore, the compound of formula (Bz1) is preferably represented by formula (Bz1-3). This compound has one R ¹ which is not derived from Z at the adjacent position of I. A and Z may form a ring structure together with a protecting group.

The compound of formula (Bz1-3) is preferably represented by formula (Bz1-3-1), and more preferably represented by formula (Bz1-3-2).

A' is a group having a protecting group, and is represented by ^-ORa - ^ORb , -O-CO- ^ORb , ^-ORa -CO- ^ORb , or ^-ORa -O-CO- ^Rb . ^Ra is a linear or branched alkyl group having 1 to 3 carbon atoms. ^Rb is a monovalent linear or branched alkyl group or a cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group that forms a ring together with an adjacent oxygen atom. A cyclic structure including ^Ra and ^Rb may be formed. However, A' may be present in 1 or more.

[Bz2 system] The compound of formula (Bz) is preferably represented by formula (Bz2): This compound has two R ¹ groups not derived from Z at positions that are not adjacent to each other.

The compound (Bz2) is preferably represented by the formula (Bz2-1).

[Bz3 system] The compound of formula (Bz) is preferably represented by formula (Bz3). The compound has two R ^1s not derived from Z at adjacent positions. A' is as defined above, and there are 1 or more of them.

[Particularly Preferred Aspects] Among the above, from the viewpoint of the sensitizing effect, the compound represented by formula (1b-1) is particularly preferred as the compound represented by formula (Bz1). This compound has R ¹ , two iodine atoms, and one or more A's. The compound represented by formula (1b-1) is described below.

R ¹ is preferably a hydroxyalkyl group or an aldehyde group, and is particularly preferably a hydroxyalkyl group. The method of introducing a hydroxyalkyl group into benzene is not limited, and examples thereof include: a method of introducing a carboxylic acid group as R ¹ and then reducing the carboxylic acid group. The reduction method can be carried out by a known method.

In formula (1b-1), A' is a group having a protecting group, represented by ^-ORa - ^ORb , -O-CO- ^ORb , ^-ORa- CO- ^ORb or ^-ORa -O-CO- ^Rb . ^Ra is a linear or branched alkyl group having 1 to 3 carbon atoms. ^Rb is a monovalent linear or branched alkyl group or a cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group that forms a ring together with an adjacent oxygen atom. A cyclic structure including ^Ra and ^Rb can be formed. However, A' is present at least 1.

In another embodiment, ^Rb is a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, an aliphatic group containing a linear, branched or cyclic heteroatom having 1 to 30 carbon atoms, or an aromatic group containing a linear, branched or cyclic heteroatom having 1 to 30 carbon atoms. The aliphatic group, aromatic group, aliphatic group containing a heteroatom, or aromatic group containing a heteroatom may further have a substituent. As the substituent here, the above-mentioned ones can be listed, but preferably, a linear, branched or cyclic aliphatic group having 1 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms. Among these, ^Rb is preferably an aliphatic group. The aliphatic group in R ^b is preferably a branched or cyclic aliphatic group. The carbon number of the aliphatic group is preferably 1 to 20, more preferably 3 to 10, and further preferably 4 to 8. The aliphatic group is not particularly limited, but examples thereof include methyl, isopropyl, sec-butyl, t-butyl, isobutyl, cyclohexyl, methylcyclohexyl, and adamantyl. Among these, t-butyl, cyclohexyl, or adamantyl is preferred.

As other R ^b , groups having the following structures can be used.

In another embodiment, A' is represented by -CO-OR ^b or -C-CyE. CyE is a cyclic ester group which may have a substituent. A' is preferably a group represented by the following formula, for example.

When a plurality of R ^1s exist in the compound belonging to formula (Bz), R ¹ does not include a combination of an alkoxy group (except for the case of having a protecting group) and an aldehyde group, a combination of an alkoxy group (except for the case of having a protecting group) and a hydroxy group, and a combination of an aldehyde group and a hydroxy group.

In the above formula (1b-1), R ¹ is preferably a hydroxyl group, a carboxylic acid group, an ester group, an aldehyde group or a hydroxyalkyl group. A' is preferably represented by -OR ^a -OR ^b .

Specific examples of the compound represented by formula (1b-1) or (1b-4) are shown below, but are not limited thereto.

Specific examples of the compound represented by formula (1b) or (1b-3) are shown below, but are not limited thereto.

Specific examples of the compound represented by formula (Bz1-3-2) are shown below, but are not limited thereto.

Specific compounds belonging to the compound of formula (Bz) are shown below.

[Bz4 system] From the viewpoint of suppressing defects in the anti-corrosion agent pattern, the compound of formula (Bz) is preferably represented by formula (Bz4).

Wherein, I, R, A and Z have the same meanings as above.

R ^1' is a functional group other than a monovalent hydroxyl group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, which may be the same or different, and is preferably not an alkyl group. R ^1' is, for example, an alkoxy group having 1 to 30 carbon atoms, a carboxylic acid group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 2 to 30 carbon atoms, an aldehyde group, a halogen atom other than an iodine atom, a nitro group, an amino group, a cyano group, or a thiol group. Among them, from the viewpoint of the sensitization effect, etc., R ^1' is preferably a carboxylic acid group, an ester group, or a hydroxyalkyl group. Among these groups, the group that may have a substituent may have a substituent other than a hydroxyl group. R1', R2', and R4' are preferably integers of 0 to 5, more preferably integers of 0 to 3, and particularly preferably integers of 0 to 2. r4' is preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 3. The total of r1', r2', and r4' is less than the valence of benzene.

[Particularly Preferred Aspects] Among the above, from the viewpoint of further suppressing defects in the resist pattern, the compound represented by formula (Bz4) is more preferably a compound represented by formula (Bz4-1). Furthermore, from the viewpoint of suppressing defects in the resist pattern, it is preferred that the iodine atom in formula (Bz4-1) is not bonded to two adjacent positions with respect to one -CH ₂ OH group.

In the formula, I, R, Z and R ^1' are the same as those defined in formula (Bz4). r1', r2', r4' are integers of 0 to 5, and the sum of r1', r2', r4' is less than the valence of benzene. The compound of formula (Bz4-1) is particularly preferably represented by formula (Bz4-2). The compound has a hydroxymethyl group and an iodine atom.

In the formula, I has the same definition as in formula (Bz4), r4' is an integer of 0 to 4, and r5' is an integer of 0 to 4. From the perspective of improving the sensitivity of the anti-corrosion agent, r4' is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3. r5' is preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.

Specific compounds belonging to the compounds of formula (Bz4), formula (Bz4-1) and formula (Bz4-2) are shown below.

(2) The second aspect In the second aspect, RG is naphthalene. In the second aspect, from the viewpoints of sensitization effect and ease of use, the compound is preferably represented by formula (N).

In the formula, ^R1 is a monovalent functional group having 0 to 30 carbon atoms and containing no polymerizable unsaturated bonds, which may be the same or different. ^R1 has the same definition as in the first aspect, but from the viewpoint of sensitization effect, etc., ^R1 is preferably a hydroxyl group, a carboxylic acid group, an ester group or a hydroxyalkyl group. As described in the first aspect, A is a group having a protecting group. A may be A' represented by -OR ^a -OR ^b ; in this case, the compound of formula (N) preferably contains 1 or more A'. R" is a hydrogen atom or an organic group other than ^R1 . I, ^R1 , R" and A are bonded to any bondable position. s1 is preferably an integer of 1 to 7, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3. s2~s3 are preferably integers of 0 to 7, more preferably integers of 0 to 5, and particularly preferably 1 to 3. s4 is preferably an integer of 1 to 7, more preferably an integer of 1 to 6. However, s4 is a number that satisfies s4≤8-s1-s2-s3. In addition, the total of s1 to s4 is less than the valence of naphthalene. However, at least one of s2 and s3 is 1 or more. In the following, preferred compounds are described from the viewpoints of sensitization effect and ease of use.

In another embodiment, the compound in which RG is naphthalene may have a linking group Z for forming a dimer. The compound is represented by formula (N'). In the formula, the definitions of each substituent are as described above, and the binding position is also arbitrary. s1 is preferably an integer of 1 to 7, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3. s2 to s3 are preferably integers of 0 to 7, more preferably integers of 0 to 5, and particularly preferably 1 to 3. s4 is preferably an integer of 1 to 7, more preferably an integer of 1 to 6. s5 is preferably an integer of 1 to 2. However, the total of s1 to s5 is less than the valence of naphthalene, and at least one of s2 and s3 is 1 or more.

The compound of formula (N) is preferably represented by formula (n), formula (2n) or formula (3n). I, R ¹ , A, and R" are the same as defined in formula (N). x and y are 0 or 1, but at least one of them is 1. s4' represents the number of R" that can be bonded to the 1st, 7th, and 8th positions of naphthalene (wherein the carbon at the top of the right ring is regarded as the 1st position, and the same applies hereinafter), which is an integer of 1 to 3.

[(n) System] The compound of formula (n) is preferably represented by formula (1n), and more preferably represented by formula (1n-1). As described above, when there are a plurality of R ^1s , the R ^1s do not include a combination of a hydroxyl group and a carboxylic acid group.

In addition, the compound of formula (n) is preferably represented by formula (1n'), and more preferably represented by formula (1n'-1). As described above, when there are a plurality of R ^1s , the R ^1s do not include a combination of a hydroxyl group and a carboxylic acid group.

[(2n) system] The compound of formula (2n) is preferably represented by formula (2n-1), and more preferably represented by formula (2n-1-1). As described above, when there are a plurality of R ^1s , the R ^1s do not include a combination of a hydroxyl group and a carboxylic acid group.

[(3n) system] The compound of formula (3n) is preferably represented by formula (3n-1), and more preferably represented by formula (3n-1-1). As described above, when there are a plurality of R ^1s , the R ^1s do not include a combination of a hydroxyl group and a carboxylic acid group.

The compound of formula (3n) is preferably represented by formula (3n-2), and more preferably represented by formula (3n-2-1). As described above, when there are a plurality of R ^1s , the R ^1s do not include a combination of a hydroxyl group and a carboxylic acid group.

Specific examples of the compound of formula (N) are shown below. In the compounds shown below, R ^c is a monovalent group having 0 to 29 carbon atoms and having no polymerizable unsaturated bond.

Non-limiting specific examples of compounds belonging to formula (N) are disclosed below.

In the above formula, A is a group having a protective group. Examples of A are shown below, but are not limited thereto.

(3) The third aspect In the third aspect, RG is an alicyclic ring having a polycyclic structure with 3 to 30 carbon atoms. Substituents such as I and ^R1 in the alicyclic ring may be present at any position. Specific examples of the alicyclic ring include the following structures. The alicyclic rings may have more alicyclic structures.

From the viewpoint of sensitization effect and availability, RG is preferably diamond. Therefore, in this embodiment, the compound of formula (1) is preferably represented by formula (Ad).

In the formula, I, ^R1 and R" are defined as above, however, I, ^R1 and R" are bonded to any position of the adamantane. When ^R1 is a group having a protecting group, the protecting group is preferably an acid-dissociable group as described above. Therefore, the group having a protecting group is preferably a hydroxyl group or a carboxylic acid group protected by an acid-dissociable group. Among them, from the viewpoint of sensitization effect, etc., ^R1 is preferably a hydroxyl group, a carboxylic acid group, an ester group or a hydroxyalkyl group. In this case, the other ^R1 may be A or A' represented by -OR ^a -OR ^b . The compound of formula (Ad) preferably contains more than 1 A. t1 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3. t2 is preferably an integer of 1 to 9, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3. t3 is preferably an integer of 1 to 14, more preferably an integer of 5 to 14, and particularly preferably an integer of 8 to 14. However, t3 is a number that satisfies t3≤16-t1-t2. In addition, the total of t1 to t3 is less than the valence of diamond. In the following, the preferred compounds are described from the viewpoints of sensitization effect and ease of use. Moreover, the compound in which RG is diamond may have a linking group Z for forming a dimer at any position.

The compound of formula (Ad) is preferably represented by formula (Ad1). In one embodiment, one of D is I, and the other of D is R ¹ . In another embodiment, two Ds are R ¹ .

The compound of formula (Ad) is preferably represented by formula (1a), (2a) or (3a).

The compounds of formula (1a), (2a) and (3a) are preferably represented by the following formula.

Furthermore, the compound of formula (Ad1) is preferably represented by the following formula.

In the formula, I and R ¹ are as defined above. The organic group is as described in the first aspect or the second aspect. The compound preferably has 1 to 2 iodine atoms.

In formulae (1a) to (3a), R ¹ is preferably a hydroxyl group, a carboxylic acid group, an ester group (which may have a substituent such as a halogen other than an iodine atom) or a hydroxyalkyl group.

Non-limiting specific examples of the compound represented by formula (Ad1) are shown below.

1-3. Polymer As described above, the compound of formula (1) may be a polymer. In this case, RG preferably does not include a ring group that combines a single ring with a single bond (for example, biphenyl, binaphthyl, dicyclopropyl, etc.). RG is preferably a cyclic structure group selected from at least one of a monocyclic aromatic ring structure, a condensed ring aromatic structure, and a polycyclic aliphatic ring structure. In this case, at least a part of R ¹ is preferably the following group, which connects two or more molecules. An alcohol group; an acetal group; a carbonate group; a glycidyl group; a carboxylic acid group; a carboxylic acid halogenated group; an aldehyde group; or an alkyl group having 1 to 30 carbon atoms or an aryl group having 1 to 30 carbon atoms which may have a substituent, wherein the substituent is any one of an alcohol group, an acetal group, a carbonate group, a glycidyl group, a carboxylic acid group, and a carboxylic acid halogenated group. The carbonate group may be an alkoxycarbonyloxy group or an aryloxycarbonyloxy group which may have a substituent.

When the compound of formula (1) is a polymer, the compound is preferably represented by the following formula.

In the formula, RG, I, and ^R1 have the same definitions as in formula (1). n' is an integer from 0 to 5 and less than n, preferably an integer from 1 to 3. m' is an integer from 1 to 5 and less than m, preferably an integer from 1 to 4. b is an integer from 1 to 4, preferably an integer from 1 to 3, and more preferably an integer from 1 or 2. Q is a single bond or a group caused by ^R1 that binds molecules. When Q is caused by Z, Q is a single bond, which means that the repeating units are bound by a single bond. When Q is caused by ^R1 that binds molecules, Q is, for example, an ester group.

[Bz system] In a preferred embodiment, the compound of the above formula (DM0-1) is represented by formula (DM1a).

In the formula, R, R ¹ , A, Z, and r1 to r4 have the same meanings as in the compound of formula (Bz). In the compound, Z is preferably R ¹ .

The compound of formula (DM1a) is preferably a compound represented by formula (DM1b).

In the formula, I, R, R ¹ , A, and Z have the same meanings as in formula (DM1a).

The compound represented by formula (DM1b) is preferably a compound represented by formula (DM1c1).

In the formula, I, R, R ¹ , A, and Z have the same meanings as in formula (DM1a).

The compound represented by formula (DM1c1) is preferably a compound represented by formula (DM1d11).

In the formula, I, R, R ¹ , A, and Z have the same meanings as in formula (DM1a).

The compound represented by formula (DM1c1) is preferably a compound represented by formula (DM1d12).

In the formula, I, R, ^R1 , and Z have the same definitions as in formula (DM1a). A' is a group having a protecting group, which is represented by -ORa ^{- ORb} , -O-CO- ^ORb , ^-ORa -CO- ^ORb , or ^-ORa- O-CO- ^Rb . ^Ra is a linear or branched alkyl group having 1 to 3 carbon atoms. ^Rb is a monovalent linear, branched, or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group, which forms a ring together with an adjacent oxygen atom. A cyclic structure including ^Ra and ^Rb may be formed. However, A' may be present at least 1.

The compound represented by formula (DM1b) is preferably a compound represented by formula (DM1c2).

In the formula, I, R, R ¹ , A, and Z have the same meanings as in formula (DM1a).

The compound represented by formula (DM1c2) is preferably a compound represented by the following formula (DM1d21).

In the formula, I, R, R ¹ , A, and Z have the same meanings as in formula (DM1a).

The compound represented by formula (DM1c1) is preferably a compound represented by formula (DM1d22).

In the formula, I, R, R ¹ , and Z have the same meanings as in formula (DM1a). A' has the same meanings as in formula (DM1d12).

The compound represented by formula (DM1b) is preferably a compound represented by formula (DM1c3).

In the formula, I, R, R ¹ , A, and Z have the same meanings as in formula (DM1a).

The compound represented by formula (DM1c3) is preferably a compound represented by formula (DM1d31).

In the formula, I, R, R ¹ , A, and Z have the same meanings as in formula (DM1a).

The compound represented by formula (DM1b) is preferably a compound represented by formula (DM1c4).

In the formula, I, R, R ¹ , A, and Z have the same meanings as in formula (DM1a).

The compound represented by formula (DM1c4) is preferably a compound represented by formula (DM1d41).

In the formula, I, R, R ¹ , A, and Z have the same meanings as in formula (DM1a). A' has the same meanings as in formula (DM1d12).

The compound of formula (DM1a) is preferably a compound represented by formula (DM1e).

wherein I, R, A, and Z have the same definitions as in formula (DM1a); and R ^1' , r1' , r2' , and r4' have the same definitions as in formula (Bz4).

The compound of formula (DM1e) is preferably a compound represented by formula (DM1e1).

The compound of formula (DM1e1) is preferably a compound represented by formula (DM1e2).

An example of a dimer compound is shown below. In the formula, I, R, R ¹ , and A have the same definitions as in formula (Bz). This compound is equivalent to the compound of formula (1b), wherein Z is a compound for forming a linking group of the dimer.

The specific dimer compound is shown below.

[N system] In another preferred embodiment, the compound of the above formula (DM0-1) is represented by the formula (Dn1).

Each substituent has the same meaning as in formula (N). nd is an integer of 1 to 4, preferably an integer of 1 to 2. Preferably, Q is a single bond and nd is 1.

The compound represented by formula (Dn1) is preferably a compound represented by formula (Dn1a).

In formula (Dn1a), I, R ¹ , R", A, and nd are as defined in formula (Dn1). x and y are each 0 or 1, and at least one of x and y is 1. s4' represents the number of R" bonded to the 1st, 7th, and 8th positions of naphthalene.

The compound represented by formula (Dn1a) is preferably a compound represented by formula (Dn1b1).

In formula (Dn1b1), I, R ¹ , R″, A, and nd are the same as defined in formula (Dn1), x and y are each 0 or 1, and at least one of x and y is 1. s4′ is the same as defined in formula (Dn1a).

The compound represented by formula (Dn1b1) is preferably a compound represented by formula (Dn1c11).

In formula (Dn1c11), I, R ¹ , R″, A, and nd are the same as defined in formula (Dn1); x and y are each 0 or 1, and at least one of x and y is 1. nd is preferably 2.

The compound represented by formula (Dn1b1) is preferably a compound represented by formula (Dn1c12).

In formula (Dn1c12), I, R ¹ , R″ and nd have the same meanings as in formula (Dn1). A′ is a group having a protecting group and is represented by -OR ^a -OR ^b , -O-CO-OR ^b or -OR ^a -CO-OR ^b . nd is preferably 2.

The compound represented by formula (Dn1a) is preferably a compound represented by formula (Dn1b2).

In formula (Dn1b2), I, R ¹ , R″, A, and nd are the same as defined in formula (Dn1), x is 0 or 1, and at least one x is 1. s4′ is the same as defined in formula (Dn1a).

The compound represented by formula (Dn1b2) is preferably a compound represented by formula (Dn1c21).

In formula (Dn1c21), I, R ¹ , R ″, A, and nd have the same definitions as in formula (Dn1), and Z has the same definition as in formula (DM1a). A' is a group having a protecting group, represented by -OR ^a -OR ^b , -O-CO-OR ^b or -OR ^a -CO-OR ^b . Wherein, ^Ra is a linear or branched alkyl group having 1 to 3 carbon atoms. R ^b is a monovalent linear or branched alkyl group having 1 to 3 carbon atoms, or a cyclic alkyl group, or a divalent cyclic alkyl group, which forms a ring together with the adjacent oxygen atom. nd is preferably 2.

The compound represented by formula (Dn1a) is preferably a compound represented by formula (Dn1b3).

In formula (Dn1b3), I, R ¹ , R″, A, and nd are the same as defined in formula (Dn1), y is each 0 or 1, and at least one of x and y is 1. nd is preferably 2.

The compound represented by formula (Dn1b3) is preferably a compound represented by formula (Dn1c31).

In formula (Dn1c31), I, R ¹ , R ″, and nd have the same definitions as in formula (Dn1), and Z has the same definition as in formula (DM1a). A′ is a group having a protecting group, represented by -OR ^a -OR ^b , -O-CO-OR ^b or -OR ^a -CO-OR ^b . Wherein, ^Ra is a linear or branched alkyl group having 1 to 3 carbon atoms. R ^b is a monovalent linear or branched alkyl group having 1 to 3 carbon atoms, or a cyclic alkyl group, or a divalent cyclic alkyl group, which forms a ring together with the adjacent oxygen atom. nd is preferably 2.

The compound represented by formula (Dn1b3) is preferably a compound represented by formula (Dn1c32).

In formula (Dn1c32), I, R ¹ , R ″, and nd have the same definitions as in formula (Dn1), and Z has the same definition as in formula (DM1a). A' is a group having a protecting group, represented by -OR ^a -OR ^b , -O-CO-OR ^b or -OR ^a -CO-OR ^b . Wherein, ^Ra is a linear or branched alkyl group having 1 to 3 carbon atoms. R ^b is a monovalent linear or branched alkyl group having 1 to 3 carbon atoms, or a cyclic alkyl group, or a divalent cyclic alkyl group, which forms a ring together with the adjacent oxygen atom. nd is preferably 2. The following shows non-limiting specific examples of formula (Dn1).

[Ad system] In another preferred embodiment, the compound of the aforementioned formula (DM0-1) is represented by formula (Da1). The compound of formula (Da1) is more preferably represented by formula (Da2).

Each substituent etc. has the same meaning as in formula (Ad).

The compound represented by formula (Da1) is preferably a compound represented by formula (Da1a).

In formula (Da1a), I, R, R ¹ , R″, and Rd have the same meanings as in formula (Da1).

The compound represented by formula (Da1a) is preferably a compound represented by formula (Da1b).

In formula (Da1b), I, R, R ¹ , R″, and Rd have the same meanings as in formula (Da1a).

In another preferred embodiment, the compound of formula (DM0-1) is represented by formula (Da1c11).

In formula (Da1c11), I, R'' and ^R1 have the same definitions as in formula (Da1a), and ba is an integer ranging from 2 to 5.

The compound represented by formula (Da1b) is preferably a compound represented by formula (Da1c12).

In formula (Da1c12), I, R, R″, and R ¹ have the same meanings as in formula (Da1a).

1-4. Production method The aforementioned compound can be produced by any method within the scope of not damaging its effect. However, a production method comprising the step of introducing an iodine atom or an ^R1 group into a compound containing the aforementioned RG group is preferred. For example, the step of introducing an iodine atom into a compound having an aromatic ring can be implemented by reacting the compound having the aromatic ring with iodine _I2 under acid or alkaline conditions. By this reaction, compounds and dimers having different numbers of iodine atoms can be produced. These production ratios are adjusted according to the reaction conditions. In particular, when the reaction temperature is lowered or the reaction time is shortened, there tend to be more compounds with fewer iodine atoms and fewer dimers. When the reaction temperature is high or the reaction time is long, there tends to be fewer compounds with fewer iodine atoms and more dimers. In addition, the step of introducing iodine atoms into a compound having an alicyclic ring can be implemented by reacting the compound having the alicyclic ring with HI (hydrogen iodide). A preferred method for preparing the aforementioned compound may include: an iodine atom is introduced as an iodination step of a substitution reaction in a raw material comprising RG, a functional group that can replace iodine atoms by a substitution reaction, and further R ¹ as required. In addition, another method for preparing the aforementioned compound may include: an iodination step of introducing iodine as a free radical, a cation or anion in a raw material comprising RG and R ¹ as required.

[Iodination step] As the iodination step, the following methods can be appropriately selected: a method of introducing halogen from an amine group by Sandmeier reaction or the like, a method of reacting iodine chloride in an organic solvent (e.g., Japanese Patent Publication No. 2012-180326, Japanese Patent Publication No. 2000-256231, Japanese Patent Publication No. 2010-159233, J. Chem. Soc. 636, 1943), a method of dropping iodine into an alkaline aqueous solution of phenol in the presence of β-cyclodextrin under alkaline conditions (Japanese Patent Publication No. 63-101342, Japanese Patent Publication No. 2003-64012), etc.

The iodination agent is not particularly limited, and examples thereof include iodine chloride, iodine, N-iodosuccinimide, iodic acid, hydrogen iodide (including hydroiodic acid and aqueous hydrogen iodide solution), etc. In the iodination step, the ratio of the iodination agent to the substrate is preferably 1.2 molar times or more, more preferably 1.5 molar times or more, and further preferably 2.0 molar times or more.

The iodination introduction reaction can be carried out by reacting at least an iodizing agent with a substrate, for example, by using the methods described in non-patent literature such as Adv. Synth. Catal. 2007, 349, 1159-1172, Organic Letters; Vol. 6; (2004); p.2785-2788, "Organic Synthesis Reagents and Synthesis Methods of Bromine and Iodine Compounds" (supervised by Hitomi Suzuki, written by Manak Research Institute, published by Maruzen); US5300506, US5434154, US2009/281114, EP1439164, WO2006/101318, etc., and the target compound can be obtained under known iodine introduction reaction conditions. Examples of usable iodizing agents include iodine compounds, iodine monochloride, N-iodosuccinimide, benzyltrimethylammonium dichloroiodate, tetraethylammonium iodide, tetrabutylammonium iodide, lithium iodide, sodium iodide, potassium iodide, 1-chloro-2-iodoethane, silver iodide fluoride, tert-butyl hypoiodide, 1,3-diiodo-5,5-dimethylhydantoin, iodine-morpholine complex, trifluoroacetyl hypoiodide, iodine-acid iodine, iodine-periodic acid, iodine-hydrogen peroxide, 1-iodoheptafluoropropane, triphenylphosphonic acid-methyl iodide, iodine-copper(I) acetate, 1-chloro-2-iodoethane, iodine-copper(II) acetate, and the like, but are not limited thereto.

One or more additives may be added to the iodination reaction for the purpose of promoting the reaction and inhibiting the production of byproducts. Examples of additives include: acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, p-toluenesulfonic acid, ferric chloride, aluminum chloride, copper chloride, antimony pentachloride, silver sulfate, silver nitrate, and silver trifluoroacetate; bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, and potassium bicarbonate; oxidants such as ammonium barium nitrate (IV) and sodium peroxodisulfate; inorganic compounds such as sodium chloride, potassium chloride, mercuric (II) oxide, and barium oxide; organic compounds such as anhydrous acetic acid; and porous substances such as zeolite. In the iodination step, the ratio of the additive to the iodizing agent is preferably 1.0 molar times, more preferably 1.2 molar times or more, more preferably 1.5 molar times or more, and even more preferably 2.0 molar times or more.

In the iodination step, it is preferred to introduce iodine into the mother nucleus using at least an iodine source and an oxidizing agent. It is preferred to use an iodine source and an oxidizing agent from the viewpoint of improving reaction efficiency and purity. As an iodination source, for example, the above-mentioned iodizing agents can be listed. As an oxidizing agent, for example, iodic acid, periodic acid, hydrogen peroxide, and other additives (hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, silver trifluoroacetate, ammonium nitrate (IV) (CAN), etc.) can be listed. In addition, for phenols having a carboxylic acid group or a nitro group, an iodine cation species formed by combining an iodine source such as iodine with a silver salt or fuming sulfuric acid can be used to carry out the iodination reaction. In addition, for other relatively inert aromatic compounds, iodination reaction can be carried out by combining an iodine source and an inorganic salt to form hypoiodous acid and iodine cation species. As an example of an inorganic salt, potassium peroxydisulfate and the like can be appropriately used. A method of introducing iodine into an aliphatic alcohol group by substitution reaction can be appropriately used. As an iodizing agent, hydrogen halides, phosphorus halides, sulfonyl halides (NaI/acetone combination), sulfinyl halides, halogenated trimethylsilanes, Weiersmeier reagents, and Appel reactions (combinations of triphenylphosphine and iodine sources) can be appropriately used.

The reaction in the iodination step can be carried out in a pure state without a solvent. Examples of usable reaction solvents include: halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; alkane solvents such as hexane, cyclohexane, heptane, pentane, and octane; aromatic hydrocarbon solvents such as benzene and toluene; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol; ether solvents such as diethyl ether, diisopropyl ether, and tetrahydrofuran; acetic acid, dimethylformamide, dimethyl sulfoxide, water, and the like.

The reaction temperature of the iodination step is not particularly limited, and can be any temperature between the freezing point and the boiling point of the solvent used in the reaction, but is preferably 0°C to 150°C, more preferably 20°C to 150°C, and further preferably 50°C to 120°C. In addition, the reaction time of the iodination step is not particularly limited, but is preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and further preferably 1 to 12 hours. For the purpose of more efficient iodination, the reaction system can be refluxed. In addition, for the purpose of controlling the concentration of the iodizing agent in the reaction system, a reflux tube equipped with a Dean-Stark apparatus or the like can be used to control the concentration of the iodizing agent in the reaction solution.

The iodine substitution reaction in the iodination step can be carried out by reacting at least an iodizing agent with a substrate, for example, by using the Sandmeier reaction described in Chemistry-A European Journal, 24(55), 14622-14626; 2018, Synthesis (2007)(1), 81-84, etc., to obtain the target compound by known iodine substitution reaction conditions.

[Protective group introduction step] In the preferred method for producing the aforementioned compound, the protective group represented by A' can be introduced into RG by a known method. For example, the method described in Green's Protective Groups in Organic Synthesis (written by Peter G.M. Wuts, WILEY) p17~p553 can be appropriately selected.

In the step of introducing the protecting group, the ratio of the protecting group introducing agent to the substrate is not particularly limited, but is preferably 0.5 molar times or more, more preferably 1.0 molar times or more, and further preferably 1.5 molar times or more. The reaction temperature in the step of introducing the protecting group is not particularly limited, but generally a temperature of 0°C to 200°C is more suitable. From the perspective of yield, a temperature of 10°C to 190°C is preferred, a temperature of 25°C to 150°C is more preferred, and a temperature of 50°C to 100°C is further preferred. In the reaction of this aspect, the preferred temperature range is 0°C to 100°C. In addition, the reaction time of the protecting group introduction step is not particularly limited, but is preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and further preferably 1 to 12 hours.

[Reduction step] In the compound of the aforementioned formula (1), when R ¹ is a hydroxyalkyl group or an aldehyde group, it can be obtained by, for example, introducing a carboxylic acid group, an ester group or an aldehyde group as R ¹ and then subjecting it to reduction.

As a reduction method, a known method can be used, for example, a method using metal hydrogenated compounds such as sodium borohydride, lithium aluminum hydroxide, sodium bis(2-methoxyethoxy)aluminum hydroxide (SBMEA), diisobutylaluminum hydroxide (DIBAL); a method using metal hydrides such as aluminum hydroxide; a method using these reducing agents together with a reducing auxiliary such as aluminum chloride, ethanedithiol, etc. The reducing agent can be used by modifying a part of the structure with an alkoxy group or a alkyl group, and combining it with a Lewis acid to adjust the reducing ability. As a solvent for the reduction reaction, a known solvent such as methanol, ethanol, 2-propanol, DMF, DMSO, etc. can be used. The reaction temperature can be carried out at room temperature or under heating conditions, but it can also be carried out under cooling to adjust the reactivity, and there is no particular restriction, but it is preferably -20°C to 150°C, more preferably 0°C to 150°C, and further preferably 20°C to 120°C. In the reduction step, the ratio of the reducing agent to the substrate is not particularly limited, but it is preferably 0.5 molar times or more, more preferably 1.0 molar times or more, and further preferably 1.5 molar times or more. In addition, the reaction time of the reduction step is not particularly limited, but it is preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and further preferably 1 to 12 hours.

The compound in this embodiment is preferably obtained as a crude product by the above reaction and then further purified to remove residual metal impurities. That is, from the perspective of preventing the resin from deteriorating over time and storage stability, and further from the perspective of the manufacturing yield caused by process suitability, defects, etc. when the resin is applied to the semiconductor manufacturing process, it is preferred to avoid the residual metal impurities. The metal impurities may originate from the reaction aids in the manufacturing steps of the compound or the reaction tanks and other manufacturing equipment used for the manufacturing.

The residual amount of the above-mentioned metal impurities is preferably less than 1 ppm, more preferably less than 100 ppb, further preferably less than 50 ppb, further more preferably less than 10 ppb, and most preferably less than 1 ppb relative to the compound. In particular, for metal species such as Fe, Ni, Sn, Zn, Cu, Sb, W, and Al, which are classified as transition metals, when the metal residual amount is more than 1 ppm, there is a concern that it may become a factor causing the material to be modified and deteriorated over time due to the interaction with other compounds. In addition, for alkaline metals and alkaline metals such as Na, K, Ca, and Mg, when the above-mentioned metal residues are contained in the resin and the metal residues are more than 1 ppm, when the resin is used in the semiconductor manufacturing step using the compound, the metal residues cannot be sufficiently reduced, which becomes a factor of reducing the yield due to defects and performance degradation caused by the residual metal in the semiconductor manufacturing step, and there is a concern about the reduction of characteristics due to the doping effect of the metal element on the substrate.

The purification method is not particularly limited, and the method described in International Publication No. 2015/080240, the method described in International Publication No. 2018/159707, etc. can be used. Specifically, the purification method comprises dissolving the aforementioned compound in an arbitrary organic solvent that is immiscible with water to obtain an organic phase, contacting the organic phase with an acidic aqueous solution for extraction treatment, thereby transferring the metal components contained in the organic phase containing the aforementioned compound and the organic solvent to the aqueous phase, and then separating the organic phase and the aqueous phase. The so-called arbitrary organic solvent that is immiscible with water refers to an organic solvent generally classified as a non-water-soluble solvent. The organic solvent is not particularly limited, but is preferably an organic solvent that can be safely used in semiconductor manufacturing processes. The amount of the organic solvent used is usually 10% by mass relative to the compound used.

Specific examples of the organic solvent used include those described in International Publication No. 2015/080240. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, etc. are preferred, and cyclohexanone and propylene glycol monomethyl ether acetate are particularly preferred.

As the aforementioned acidic aqueous solution, it is appropriately selected from aqueous solutions in which widely known organic and inorganic compounds are dissolved in water. For example, it can be listed: those described in International Publication 2015/080240. Each of these acidic aqueous solutions can be used alone, or two or more can be used in combination. As acidic aqueous solutions, for example, it can be listed: inorganic acid aqueous solutions and organic acid aqueous solutions. As inorganic acid aqueous solutions, for example, it can be listed: aqueous solutions containing one or more selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. As organic acid aqueous solutions, for example, it can be listed: aqueous solutions containing one or more selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid. The pH range of the acidic aqueous solution is about 0 to 5, and more preferably about pH 0 to 3.

As other production methods, a method using a filter as described below, a method using an adsorptive ion exchange resin, passing the liquid through a column, dispersing and suspending the ion exchange resin in a container, or a method by distillation can be appropriately used.

In the method for producing the compound represented by formula (1), the order and number of the iodination step, the protecting group introduction step and the reduction step are not particularly limited and can be appropriately selected according to the structure of the target compound.

1-5. Purification method [Filter purification step (liquid passing step)] In the filter passing step, the filter used to remove the metal component from the solution containing the aforementioned compound and the solvent can generally use a commercially available filter for liquid filtration. There is no particular restriction on the filtering accuracy of the filter, but the nominal pore size of the filter is preferably 0.2 μm or less, more preferably less than 0.2 μm, further preferably less than 0.1 μm, further more preferably less than 0.1 μm, and even more preferably less than 0.05 μm. In addition, the lower limit value of the nominal pore size of the filter is not particularly limited, but is generally 0.005 μm. The nominal pore size in the present invention refers to the nominal pore size that shows the separation performance of the filter, for example, the pore size determined by the test method determined by the filter manufacturer such as the bubble point test, mercury intrusion test, and standard particle supplementation test. When a commercial product is used, it is the value stated in the manufacturer's catalog data. By setting the nominal pore size to less than 0.2μm, the metal component content of the solution after passing through the filter (liquid flow) once can be effectively reduced. In the second embodiment, in order to further reduce the content of each metal component in the solution, the filter liquid flow step can be performed more than twice.

As the form of the filter, a hollow membrane filter, a thin film filter, a pleated membrane filter, and a filter filled with a filter material such as non-woven fabric, cellulose, and diatomaceous earth can be used. Among the aforementioned filters, the filter is preferably one or more selected from the group consisting of a hollow membrane filter, a thin film filter, and a pleated membrane filter. In addition, from the perspective of having particularly high-precision filtering accuracy and a relatively high filtering area compared to other forms, it is particularly preferred to use a hollow membrane filter.

The materials of the aforementioned filter can be listed as follows: polyolefins such as polyethylene and polypropylene; polyethylene resins having functional groups capable of ion exchange by graft polymerization; resins containing polar groups such as polyamide, polyester, and polyacrylonitrile; and fluorinated resins such as fluorinated polyethylene (PTFE). Among the aforementioned, the filter material of the filter is preferably one or more selected from the group consisting of polyamide, polyolefin resin, and fluorinated resin. In addition, from the perspective of reducing the effect of heavy metals such as chromium, polyamide is particularly preferred. Moreover, from the perspective of avoiding the dissolution of metal from the filter material, it is preferred to use a filter other than a sintered metal material.

Examples of polyamide filters (hereinafter referred to as trademarks) include, but are not limited to, Polyfix nylon series manufactured by KITZ Micro Filter Co., Ltd., Ultipleated P-Nylon 66 and UlchiporeN66 manufactured by Nippon Pole Co., Ltd., Life AsurePSN series and Life AsureEF series manufactured by 3M Co., Ltd. Examples of polyolefin filters include, but are not limited to, Uruchi Pleated PE Clean and Ion Clean manufactured by Nippon Pole Co., Ltd., Protego series, Microguard PlusHC10 and Optimizer D manufactured by Nippon Entegris Co., Ltd. As polyester filters, for example, although not limited to the following, there can be listed: GeraflowDFE manufactured by Central Filter Industry Co., Ltd., Breeze typePMC manufactured by Nippon Filter Co., Ltd., etc. As polyacrylonitrile filters, for example, although not limited to the following, there can be listed: Super Filters AIP-0013D, ACP-0013D, ACP-0053D manufactured by Advantech Toyo Co., Ltd., etc. As fluororesin filters, for example, although not limited to the following, there can be listed: EnflonHTPFR manufactured by Nippon Pole Co., Ltd., LifesureFA series manufactured by 3M Co., Ltd., etc. These filters can be used individually or in combination of two or more types.

In addition, the filter may also contain an ion exchanger such as a cation exchange resin, a cation charge regulator that generates a zeta potential in a filtered organic solvent solution, etc. Filters containing ion exchangers are not limited to the following, but examples thereof include: Protego series manufactured by Nippon Entegris Co., Ltd., Clan graft manufactured by Fiber Optics Co., Ltd., etc. In addition, filters containing substances having a positive Zeta potential such as polyamide polyamine epichlorohydrin cationic resins are not limited to the following, but examples thereof include: Zeta Plus 40QSH (registered trademark), Zeta Plus 020GN (registered trademark) manufactured by 3M Co., Ltd., or Life Asure EF (registered trademark) series, etc.

[Ion exchange resin treatment step] As another purification method, there can be cited a method of treating a solution containing the aforementioned compound with an ion exchange resin. As the ion exchange resin, a known ion exchange resin having a function corresponding to the target metal element can be appropriately used. Purification using an ion exchange resin is a step of ion exchange of the purified substance containing the aforementioned compound or ion adsorption by a chelating group. The components removed by the ion exchange resin treatment step are not limited, but for example, the acid component and the metal ions contained in the metal component can be cited.

There are no particular limitations on the method for implementing the ion exchange method, and a known method can be used. Generally, there can be cited a method in which a solution containing the aforementioned compound is passed through (liquid flow) a filling portion filled with an ion exchange resin. In addition, there can also be cited a method in which an ion exchange resin is added to a treatment container for a solution containing the aforementioned compound and dispersed or suspended, and then the ion exchange resin is separated and removed by a method such as filtration separation to obtain a solution that has been subjected to a purification treatment. The treatment step of the ion exchange resin can be performed multiple times using the same ion exchange resin to treat the purified product, or different ion exchange resins can be used to treat the purified product.

As the ion exchange resin, there can be cited: a cation exchange resin and an anion exchange resin. From the viewpoint of easily setting the mass ratio of the acid component content to the metal component content within the above range by adjusting the content of the metal component, it is preferred to use at least a cation exchange resin. From the viewpoint of being able to adjust the content of the acid component, it is more preferred to use an anion exchange resin together with the cation exchange resin. When both a cation exchange resin and an anion exchange resin are used, the liquid may be passed through a filling portion filled with a mixed resin containing the two resins, or may be passed through a plurality of filling portions filled in each resin.

As the cation exchange resin, a known cation exchange resin can be used, and among them, a gel type cation exchange resin is preferred. Specifically, as the cation exchange resin, there can be exemplified a sulfonic acid type cation exchange resin and a carboxylic acid type cation exchange resin. As the cation exchange resin, commercially available products can be used, for example, AMBERLITE IR-124, AMBERLITE IR-120B, AMBERLITE IR-200CT, ORLITE DS-1, ORLITE DS-4 (all manufactured by ORGANO CORPORATION), DUOLITE C20J, DUOLITE C20LF, DUOLITE C255LFH, DUOLITE C-433LF (all manufactured by Sumika Chemtex Co., Ltd.), DIAION SK-110, DIAION SK1B and DIAION SK1BH (all manufactured by Mitsubishi Chemical Corporation), PUROLITE S957 and PUROLITE S985 (all manufactured by Purolite Corporation), etc.

As the anion exchange resin, a known anion exchange resin can be used, and among them, a gel type anion exchange resin is preferably used. Among them, as the acid component existing in the form of ions in the purified product, there can be listed: inorganic acids from catalysts when producing the purified product and organic acids (for example, reaction raw materials, isomers and by-products) produced after the reaction when producing the purified product. From the perspective of the HSAB (Hard and Soft Acids and Bases: soft and hard acids and bases) rule, the acid component is classified as hard acid to medium hardness acid. Therefore, in order to improve the removal efficiency of the acid components by interaction with the anion exchange resin, it is preferred to use an anion exchange resin containing a base of hard to medium hardness. The anion exchange resin containing a base of hard to medium hardness is preferably at least one anion exchange resin selected from the group consisting of a type I anion exchange resin containing a strong base type having a trimethylammonium group, a type II anion exchange resin containing a slightly weaker strong base type having a dimethylethoxide ammonium group, and anion exchange resins of weak base types such as dimethylamine and diethylenetriamine. Among acid components, for example, organic acids are hard acids, and among inorganic acids, sulfuric acid ions are acids of medium hardness. Therefore, if the above-mentioned strong alkaline or slightly weak strong alkaline anion exchange resin and a weak alkaline anion exchange resin of medium hardness are used together, the content of the acid component can be easily reduced to a preferred range.

As the anion exchange resin, commercially available products can be used, for example, AMBERLITE IRA-400J, AMBERLITE IRA-410J, AMBERLITE IRA-900J, AMBERLITE IRA67, ORLITE DS-2, ORLITE DS-5, ORLITE DS-6 (manufactured by ORGANO CORPORATION), DUOLITE A113LF, DUOLITE A116, DUOLITE A-375LF (manufactured by Sumika Chemtex Co., Ltd.), and DIAION SA12A, DIAION SA10A, DIAION SA10AOH, DIAION SA20A, DIAION WA10 (manufactured by Mitsubishi Chemical Corporation), etc. Among them, examples of the above-mentioned anion exchange resin containing a hard alkaline to medium hardness include: ORLITE DS-6, ORLITE DS-4 (all manufactured by ORGANO CORPORATION), DIAION SA12A, DIAION SA10A, DIAION SA10AOH, DIAION SA20A, DIAION WA10 (all manufactured by Mitsubishi Chemical Corporation), PUROLITE A400, PUROLITE A500, PUROLITE A850 (all manufactured by Purolite Corporation), etc.

Ion adsorption by chelating groups can be performed, for example, using chelating resins having chelating groups. Chelating resins do not release replacement ions when capturing ions, and by not using highly acidic or alkaline chemically active functional groups, secondary reactions with organic solvents that are the target of purification by hydrolysis and condensation reactions can be suppressed. Therefore, more efficient purification can be performed. As chelating resins, there can be listed: resins having chelating groups or chelating ability such as amidoxime, thiourea, thiourea, iminodiacetic acid, amidophosphoric acid, phosphonic acid, aminophosphoric acid, aminocarboxylic acid, N-methylglucamine, alkylamino, pyridine ring, cyclic anthocyanine, phthalocyanine ring and cyclic ether. As the chelating resin, commercially available products can be used, for example: DUOLITE ES371N, DUOLITE C467, DUOLITE C747UPS, SUMICHELATE MC760, SUMICHELATE MC230, SUMICHELATE MC300, SUMICHELATE MC850, SUMICHELATE MC640 and SUMICHELATE MC900 (all manufactured by Sumika Chemtex Co., Ltd.), PUROLITE S106, PUROLITE S910, PUROLITE S914, PUROLITE S920, PUROLITE S930, PUROLITE S950, PUROLITE S957 and PUROLITE S985 (all manufactured by Purolite Corporation), etc.

The method for performing ion adsorption is not particularly limited, and a known method can be used. Typically, there is a method in which the substance to be purified is passed through a filling portion filled with a chelating resin. The ion exchange resin treatment step may be performed by passing the substance to be purified through the same chelating resin multiple times or by passing the substance to be purified through different chelating resins.

The packing part usually includes a container and the ion exchange resin filled in the container. Examples of the container include a column, a cartridge, and a packed tower, and any other container may be used as long as the ion exchange resin can be filled to allow the purified substance to flow therethrough.

[Distillation step] As another purification method, there can be cited: distilling the aforementioned compound itself. There is no particular limitation on the distillation method, and known methods such as atmospheric pressure distillation, reduced pressure distillation, molecular distillation, and water vapor distillation can be used.

[Preferred production method] (Compounds in which RG is benzene) The production method of the compound of formula (Bz) is specifically described. The compound of formula (Bz) is preferably prepared by using a compound represented by formula (MB) as a raw material. The substituents and r1, r2, etc. in the compound are defined as above. ^R1 , R and OH are bonded at any bondable position. However, when r1 and r2 in formula (MB) are in formula (Bz), they are selected so that the total of r1 to r4 is less than the valence of benzene. Examples of the compound of formula (MB) include hydroxybenzaldehyde and the like.

The compound of formula (Bz) can be prepared by various methods, but from the viewpoint of the availability of raw materials and the yield, it is preferably prepared by a method comprising the following steps. A preparation step of preparing the compound of formula (MB), An iodination step of introducing an iodine atom into the aforementioned compound, A protecting group introduction step of introducing a protecting group into the aforementioned compound, and A reduction step of reducing the aforementioned compound.

From the viewpoint of suppressing the formation of by-products, it is preferred to carry out the preparation step, the iodination step, the protecting group introduction step, and the reduction step in sequence.

1) Iodination step As solvents that can be used in the iodination step, there can be listed: a variety of solvents including polar aprotic solvents and protic polar solvents. A single protic polar solvent or a single polar aprotic solvent can be used. Further, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used. Preferably, it is a polar protic solvent or a mixture thereof, and from the viewpoint of suppressing side reactions, a mixture of a polar protic solvent and water is preferred. Solvents are effective but not essential. Suitable polar aprotic solvents are not particularly limited, and include: ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, etc.; ester solvents such as ethyl acetate, γ-butyrolactone, etc.; nitrile solvents such as acetonitrile, hydrocarbon solvents such as toluene, hexane, etc.; amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, hexamethylphosphatamide, hexamethylphosphite triamide, etc.; ketone solvents such as acetone, ethyl methyl ketone, etc.; chlorine solvents such as dichloromethane, chloroform, etc., dimethyl sulfoxide, etc. Dimethyl sulfoxide is preferred. As suitable protic polar solvents, there are no special restrictions, and examples include: water; alcohol solvents such as methanol, ethanol, propanol, butanol, etc.; such as di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol and n-butanol. The amount of solvent used can be appropriately set according to the substrate, catalyst and reaction conditions used, and there is no special restriction, but it is usually more suitable to be 0 to 10,000 parts by mass relative to 100 parts by mass of the reaction raw material. From the perspective of yield, it is preferably 100 to 2,000 parts by mass.

The raw material compound, catalyst and solvent are added to the reactor to form a reaction mixture. Any suitable reactor is used. In addition, the reaction can be carried out by appropriately selecting a batch method, a semi-batch method, a continuous method or the like. There is no particular limitation on the reaction temperature. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst and the desired yield. Generally speaking, the reaction temperature is more suitable at 0°C to 200°C. From the perspective of yield, the reaction temperature is preferably 0°C to 100°C, and more preferably 0°C to 70°C. A reaction temperature of 0°C to 50°C is further preferred. In the reaction of this aspect, the preferred reaction temperature range is 0°C to 100°C. In the iodination step, the ratio of the iodizing agent to the substrate is preferably 0.5 molar times or more, more preferably 1.0 molar times or more, and further preferably 1.5 molar times or more. There is no particular restriction on the reaction pressure. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the choice of catalyst, and the desired yield. An inert gas such as nitrogen can be used, or a suction pump can be used to adjust the pressure. In high-pressure reactions, there are no particular restrictions, but a previous pressure reactor containing a shaking container, a rocker vessel, and a stirring high-pressure and high-temperature autoclave is used. In the reaction of this state, it is preferred that the reaction pressure is reduced pressure to normal pressure, with reduced pressure being preferred. There is no particular restriction on the reaction time. The preferred range varies depending on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. However, most reactions are carried out for less than 6 hours, and the reaction time is generally 15 minutes to 600 minutes. The reaction time range for the reaction in this embodiment is preferably 15 minutes to 600 minutes, and more preferably 15 minutes to 360 minutes. After the reaction is completed, separation and purification can be carried out using appropriate methods previously known. For example, the reaction mixture is poured onto ice water and extracted in a solvent such as ethyl acetate or diethyl ether. Then, the product is recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity compound can be separated and purified by a separation and purification method known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or by a combination of these methods.

When synthesizing a compound represented by the following formula (1), (Bz4), (Bz4-1) or (Bz4-2), from the viewpoint of improving productivity, the iodination step is preferably performed once or twice or more, preferably twice. In addition, when the iodination step is performed once or more, the iodination agent is not particularly limited, and examples thereof include iodine chloride, iodine, N-iodosuccinimide, iodic acid, hydrogen iodide (including hydroiodic acid, hydrogen iodide aqueous solution), etc. Iodine and iodic acid are preferably used. In the iodination step, the ratio of the iodination agent to the substrate is preferably 1.2 molar times or more, more preferably 1.5 molar times or more, and further preferably 2.0 molar times or more. In the second iodination step, it is preferred to use a method of introducing a halogen from an amino group by, for example, the Sandmeier reaction. (In the formula, RG is a group containing at least one cyclic structure, I is an iodine atom, ^R1 is a monovalent functional group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, which may be the same or different, n is an integer of 1 to 5, and m is an integer of 1 to 5.) (wherein I, R, A and Z have the same definitions as in formula (Bz). R1 ^' is a monovalent functional group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, which may be the same or different, but excluding hydroxyl groups. R1', R2', R4' are integers of 0 to 5, and the total of R1', R2', R4' is less than the valence of benzene.)

In formula (Bz4), I, R, A, and Z have the same definitions as above, and R ^1' is a monovalent functional group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, which may be the same or different, but excluding a hydroxyl group, and preferably is not an alkyl group. R ^1' is preferably, for example, an alkoxy group having 1 to 30 carbon atoms, a carboxylic acid group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 2 to 30 carbon atoms, an aldehyde group, a halogen atom other than an iodine atom, a nitro group, an amino group, a cyano group, or a thiol group. Among them, from the viewpoint of the sensitizing effect, etc., R ^1' is preferably a carboxylic acid group, an ester group, or a hydroxyalkyl group. Among these groups, the group that may have a substituent may have a substituent other than a hydroxyl group. R1', R2', and R4' are preferably integers of 0 to 5, more preferably integers of 0 to 3, and particularly preferably integers of 0 to 2. R4' is preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 3. However, the total of R1', R2', and R4' is less than the valence of benzene. (In the formula, I, R, Z and R1 ^' have the same definitions as in formula (Bz4). r1', r2', r4' are integers from 0 to 5, and the total of r1', r2', r4' is less than the valence of benzene.) (Wherein, I has the same definition as in formula (Bz4), r4' is an integer between 0 and 4, and r5' is an integer between 0 and 4.)

2) Protective group introduction step As a solvent that can be used in this step, a variety of solvents including polar aprotic solvents and protic polar solvents are used. A single protic polar solvent or a single polar aprotic solvent can be used. Further, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used. Preferably, it is a polar aprotic solvent or a mixture thereof. The solvent is effective but not necessary. Suitable polar aprotic solvents are not particularly limited, and include: ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, etc.; ester solvents such as ethyl acetate, γ-butyrolactone, etc.; nitrile solvents such as acetonitrile, hydrocarbon solvents such as toluene, hexane, etc.; amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, hexamethylphosphatamide, hexamethylphosphite triamide, etc.; ketone solvents such as acetone, ethyl methyl ketone, etc.; chlorine solvents such as dichloromethane, chloroform, etc., dimethyl sulfoxide, etc. Dimethyl sulfoxide is preferred. As suitable protic polar solvents, there are no particular limitations, and examples thereof include: water; alcoholic solvents such as methanol, ethanol, propanol, butanol; such as di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol and n-butanol. The amount of solvent used can be appropriately set according to the substrate, catalyst and reaction conditions used, and there is no particular limitation, but it is usually more suitable to be 0 to 10,000 parts by mass relative to 100 parts by mass of the reaction raw material. From the perspective of yield, it is preferably 100 to 2,000 parts by mass. As a protective introduction reagent, a protective introduction reagent with various functions is used under the reaction conditions of this embodiment. Examples of suitable protective introduction reagents are not particularly limited, and include, for example: active carboxylic acid derivatives such as acyl halides, acid anhydrides, and dicarbonates; alkyl halides, vinyl alkyl ethers, dihydropyrans, alkyl halides, etc. In the protective group introduction step, the ratio of the protective group introduction agent relative to the substrate is not particularly limited, but is preferably 0.5 molar times or more, more preferably 1.0 molar times or more, and further preferably 1.5 molar times or more. As a catalyst that can be used in the protective step, a protective catalyst having a variety of functions is used under the reaction conditions of this embodiment. Preferably, it is an acid catalyst or an alkaline catalyst. Examples of suitable acid catalysts are not particularly limited, and include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and fluoric acid; organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, ant acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalene disulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, ferric chloride, and boron trifluoride; solid acids such as tungstic acid, tungstic phosphoacid, silicic molybdic acid, or phosphomolybdic acid, etc. These acid catalysts may be used alone or in combination of two or more. Among these, organic acids and solid acids are preferred from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of availability, ease of operation, etc. Examples of suitable alkaline catalysts are not particularly limited, and examples of catalysts containing amines are pyridine, diisopropylethylamine, and ethylenediamine, and examples of non-amine alkaline catalysts include inorganic bases such as metal salts, and potassium salts or acetates are particularly preferred. Suitable catalysts are not particularly limited, and include potassium acetate, potassium carbonate, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydroxide, and magnesium oxide. The non-amine alkaline catalysts of this embodiment are all purchased from, for example, EMScience (Gibbstown or Aldrich (Milwaukee). The amount of the catalyst used can be appropriately set according to the substrate, catalyst and reaction conditions used. Although there is no special limitation, generally speaking, relative to 100 parts by mass of the reaction raw material, it is more suitable to be 1 to 5000 parts by mass. From the perspective of yield, it is preferably 50 to 3000 parts by mass.

In the step of introducing a protecting group, when introducing a protecting group into the hydroxyl group of the compound having a hydroxyl group, it is preferred to use an inorganic base to introduce the protecting group into the hydroxyl group from the viewpoint of improving the yield and scaling up, and it is more preferred to combine an amide solvent and an inorganic base. The inorganic base is not particularly limited, and examples thereof include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, potassium metasilicate, etc. Among these, sodium carbonate and potassium carbonate are preferably used. There is no particular limitation on the amide solvent, and examples thereof include: N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), etc. Among them, DMF is preferred. These can be used alone or in combination of two or more. Although there is no particular limitation, the inventors of the present invention speculate that HCl produced as a by-product in the step of introducing the protecting group participates in the decomposition reaction of the product, but by using an inorganic base, the inorganic base and HCl react, thereby suppressing the decomposition of the product. In addition, it is speculated that by combining the inorganic base with the amide solvent, the component generated by the reaction of the inorganic base with HCl is insoluble in the amide solvent and is discharged from the reaction system, thereby suppressing the decomposition of the product. Examples of the compounds having the aforementioned hydroxyl group into which the protecting group is introduced include compounds wherein ^R1 is a hydroxyl group in the aforementioned formula (Bz) and (Bz4). In addition, in the aforementioned formula (MB), when ^R1 is a hydroxyl group, a protecting group may also be introduced into ^R1 .

The compound to be protected, the catalyst and the solvent are added to the reactor to form a reaction mixture. Any suitable reactor is used. In addition, the reaction can be carried out by appropriately selecting a batch method, a semi-batch method, a continuous method or the like. There is no particular restriction on the reaction temperature. The preferred range varies depending on the concentration of the substrate, the stability of the product formed, the choice of the catalyst and the desired yield. Generally speaking, a temperature of 0°C to 200°C is more suitable. From the perspective of yield, a temperature of 10°C to 190°C is preferred, a temperature of 25°C to 150°C is more preferred, and a temperature of 50°C to 100°C is further preferred. In the reaction of this aspect, the preferred temperature range is 0°C to 100°C. There is no particular restriction on the reaction pressure. The preferred range varies depending on the concentration of the substrate, the stability of the product formed, the choice of catalyst, and the desired yield. Inert gases such as nitrogen and suction pumps can be used to adjust the pressure. In the high-pressure reaction, there is no particular restriction, but a previous pressure reactor containing a shaking container, a rocker vessel, and a stirring high-pressure and high-temperature autoclave is used. In the reaction of this aspect, it is preferred that the reaction pressure is reduced pressure to normal pressure, preferably reduced pressure. There is no particular restriction on the reaction time. The preferred range varies depending on the concentration of the substrate, the stability of the product formed, the choice of catalyst, and the desired yield. However, most reactions are carried out for less than 6 hours, and the reaction time is generally 15 minutes to 600 minutes. In the reaction of this aspect, the reaction time range is preferably 15 minutes to 600 minutes. Separation and purification can be carried out after the reaction is completed using appropriate methods previously known. For example, the reaction mixture is injected onto ice water and extracted in a solvent such as ethyl acetate or diethyl ether. Then, the product is recovered by removing the solvent by evaporation under reduced pressure. The separation and purification method can be performed by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., which are known in the art, or by a combination of these methods to separate and purify the desired high-purity monomer.

3) Reduction step As the solvent that can be used in the reduction step, various solvents including polar aprotic solvents and protic polar solvents are used. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used. A polar aprotic solvent or a mixture thereof is preferred. From the viewpoint of suppressing side reactions, a mixture of polar aprotic solvents and polar protic solvents is preferred as the polar protic solvent, and an alcoholic solvent such as water, methanol, ethanol, propanol, butanol, etc. is further preferred. The solvent is effective but not essential. Suitable polar aprotic solvents are not particularly limited, and include: ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, etc.; ester solvents such as ethyl acetate, γ-butyrolactone, etc.; nitrile solvents such as acetonitrile, hydrocarbon solvents such as toluene, hexane, etc.; amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, hexamethylphosphatamide, hexamethylphosphite triamide, etc.; ketone solvents such as acetone, ethyl methyl ketone, etc.; chlorine solvents such as dichloromethane, chloroform, etc., dimethyl sulfoxide, etc. Dimethyl sulfoxide is preferred. As suitable protic polar solvents, there are no special restrictions, and examples include: water; alcohol solvents such as methanol, ethanol, propanol, butanol, etc.; such as di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol and n-butanol. The amount of solvent used can be appropriately set according to the substrate, reducing agent and reaction conditions used, and there is no special restriction, but it is usually more suitable to be 0 to 10,000 parts by mass relative to 100 parts by mass of the reaction raw material. From the perspective of yield, it is preferably 100 to 2,000 parts by mass.

As the reducing agent, various reducing agents that are functional under the reaction conditions of the present embodiment can be used. Suitable reducing agents are not particularly limited, and include metal hydrides, metal hydride complexes, such as borane dimethyl sulfide, diisobutylaluminum hydroxide, sodium borohydride, lithium borohydride, potassium borohydride, zinc borohydride, tri-s-butyllithium borohydride, tri-s-butylpotassium borohydride, triethyllithium borohydride, lithium aluminum hydroxide, tri-t-butoxylithium aluminum hydroxide, sodium bis(methoxyethoxy)aluminum hydroxide, and the like.

The amount of the reducing agent used can be appropriately set according to the substrate, reducing agent, reaction conditions, etc., and is not particularly limited. However, it is usually preferably 1 to 500 parts by mass relative to 100 parts by mass of the reaction raw material, and preferably 10 to 200 parts by mass from the viewpoint of yield.

As a quenching agent, various quenching agents that are functional under the reaction conditions of this embodiment are used. The quenching agent has the function of inactivating the reducing agent. The quenching agent is an effective but not essential component. As a suitable quenching agent, there is no particular limitation, and examples thereof include: ethanol, ammonium chloride water, water, hydrochloric acid, sulfuric acid, etc. The amount of the quenching agent used can be appropriately set according to the amount of the reducing agent used, and there is no particular limitation, but it is usually more suitable to be 1 to 500 parts by mass relative to 100 parts by mass of the reducing agent, and from the perspective of yield, it is preferably 50 to 200 parts by mass.

The compound to be reduced, the reducing agent and the solvent are added to the reactor to form a reaction mixture. Any suitable reactor is used. In addition, the reaction can be carried out by appropriately selecting a batch method, a semi-batch method, a continuous method or the like. There is no particular restriction on the reaction temperature. The preferred range varies depending on the concentration of the substrate, the stability of the product formed, the selection of the reducing agent and the desired yield. Generally speaking, a temperature of 0°C to 200°C is more suitable. From the perspective of yield, a temperature of 0°C to 100°C is preferred, a temperature of 0°C to 70°C is more preferred, and a temperature of 0°C to 50°C is further preferred. The preferred temperature range is 0°C to 100°C. There is no particular restriction on the reaction pressure. The preferred range varies depending on the concentration of the substrate, the stability of the product formed, the selection of the reducing agent, and the desired yield. Inert gases such as nitrogen and suction pumps can be used to adjust the pressure. In the high-pressure reaction, there is no particular restriction, but a previous pressure reactor containing a shaking container, a rocker vessel, and a stirring high-pressure and high-temperature autoclave is used. In the reaction of this aspect, it is preferred that the reaction pressure is reduced pressure to normal pressure, preferably reduced pressure. There is no particular restriction on the reaction time. The preferred range varies depending on the concentration of the substrate, the stability of the product formed, the selection of the reducing agent, and the desired yield. However, most reactions are carried out for less than 6 hours, and the reaction time is generally 15 minutes to 600 minutes. In the reaction of this aspect, the reaction time ranges preferably from 15 minutes to 600 minutes, and more preferably from 15 minutes to 360 minutes. Separation and purification can be carried out after the reaction is completed using a previously known appropriate method. For example, the reaction mixture is poured onto ice water and extracted in a solvent such as ethyl acetate or diethyl ether. Then, the solvent is removed by evaporation under reduced pressure to recover the product. The desired high-purity compound can be separated and purified by a separation and purification method known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or by a combination of these methods.

In formula (Bz), when R ¹ is a carboxylic acid compound, from the viewpoint of improving productivity, the reduction step preferably includes a step of esterifying the carboxylic acid, and reducing the obtained ester group to convert it into a hydroxymethyl group. For example, when an alkyl ester group is obtained in the step of esterifying the carboxylic acid, the ester group is a structure composed of a carbonyl group derived from a carboxylic acid and an alkoxy group derived from an alcohol. In the esterification step, from the viewpoint of productivity, it is preferred to use an esterifying agent. Carboxylic acid halides and carboxylic anhydrides may also be used as carboxylic acids. Furthermore, in the aforementioned formula (Bz), the compound in which R ¹ is a carboxylic acid is preferably a compound represented by the following formula (Bz5). In addition, a carboxylic acid linked to a group having an electro-attractive property is preferred, and examples thereof include a compound represented by the following formula (Bz5) having an aromatic carboxylic acid having an iodine atom as a substituent. (In the formula, I, Z, ^R1 , A, R, r1 to r4 have the same definitions as in formula (DM1a).)

Specific examples of the compound represented by the following formula (Bz5) are as follows.

The esterification agent used in the esterification step is not particularly limited, and examples thereof include acid catalysts, base catalysts, carbodiimide condensation agents, phosgene derivative condensation agents, etc., preferably acid catalysts, base catalysts, and carbodiimide condensation agents. The acid catalyst and base catalyst are not particularly limited, and the same ones as those mentioned above can be used. The solvent is not particularly limited, and examples thereof include THF, DMSO, chloroform, toluene, etc., preferably THF is used.

The reducing agent used in the step of reducing the ester group to a hydroxyl group is not particularly limited, and examples thereof include boron reducing agents, lithium reducing agents, etc. Preferably, a boron reducing agent such as sodium borohydride and borane is used, and more preferably, a reducing agent is used in combination with calcium chloride or lithium chloride. The solvent is not particularly limited, and examples thereof include THF, DMSO, chloroform, toluene, etc. Preferably, toluene is used, and more preferably, methanol is used in combination. In addition, after the step of esterifying the carboxylic acid, the step of reducing the ester group to a hydroxyl group may be performed without purification.

(RG is a compound of naphthalene) The method for producing the compound of formula (N) is specifically described. The compound of formula (N) is preferably a compound represented by formula (MN) as a raw material. The definitions of the substituents, s3, s4, etc. in the formula are as described above. However, when s3 and s4 in formula (MN) become formula (N), they are selected in such a way that the total of s1 to s4 is less than the valence of naphthalene. ^R1 is not particularly limited, but hydroxyl, amino, nitro, halogen atoms other than iodine atoms, aldehyde groups, etc. can be listed. Specific examples of the compound of formula (MN) are not particularly limited, for example, they can be listed; (ii) hydroxynaphthaldehyde, aminonaphthaldehyde, nitronaphthaldehyde, chlorinated naphthaldehyde, etc.

The compound of formula (N) can be prepared by various methods, but from the perspective of the availability of raw materials and the yield, it is preferably prepared by a method comprising the following steps. From the perspective of the availability of raw materials and the yield, it is preferably prepared by a method comprising the following steps. A preparation step for preparing a compound of formula (MN), An iodination step for introducing an iodine atom into the aforementioned compound, A protective group introduction step for introducing a protective group into the aforementioned compound, and A reduction step for reducing the aforementioned compound.

From the viewpoint of suppressing the formation of by-products, it is preferred to carry out the preparation step, iodination step, protecting group introduction step, and reduction step in sequence. It is further preferred to carry out the preparation step, protecting group introduction step, iodination step, and reduction step in sequence. The solvents and reaction conditions that can be used in each step can be those described in the method for producing a compound wherein RG is benzene.

(Compound in which RG is adamantane) A method for producing a compound of formula (Ad) is described in detail. In this method, it is preferred to use a compound represented by formula (MA) as a raw material. In formula (MA), ^R1 , R", t2, and t3 have the same definitions as in formula (Ad). However, when t2 and t3 in formula (MA) are the same as those in formula (Ad), they are selected so that the total of t1 to t3 is less than the valence of adamantane. The compound is not particularly limited, but examples thereof include adamantantriol and the like.

The compound of formula (Ad) can be prepared by various methods, but from the perspective of the availability of raw materials and yield, it is preferably prepared by a method comprising the following steps. A preparation step for preparing the compound of formula (MA), and An iodination step for introducing an iodine atom.

In addition, as another aspect of the method for producing the compound represented by formula (1), in order to improve productivity, it is preferably a step comprising any one or more steps selected from the following: 1) a step of preparing a compound represented by formula (Ad-A-3-0), 2) a step of preparing a compound represented by formula (Ad-A-3-1), and 3) a step of preparing a compound represented by formula (Ad-A-3-2).

Furthermore, when the step of preparing a compound represented by formula (Ad-A-3-0) is included, it is preferred to include the following steps: 1) preparing a compound represented by formula (Ad-A-3-0), 2) an oxidation step of oxidizing the compound represented by formula (Ad-A-3-0), 3) a step of esterifying the carboxylic acid of the obtained compound, 4) an iodination step of iodination, 5) a step of hydrolyzing the ester group of the obtained compound to convert it into a carboxylic acid group.

The oxidation step of oxidizing the compound represented by formula (Ad-A-3-0) is not particularly limited, but examples thereof include: a method using an oxidant, a method of hydrolyzing a bromide, a method of oxidizing using an imide compound, etc. As the oxidant, there is no particular limitation, and examples thereof include: air, oxygen, ozone, nitric acid, halogens (chlorine, bromine, iodine), potassium nitrate, hypochlorous acid, permanganate, ammonium nitrate, chromic acid, peroxide, Torrance's reagent, ruthenium compounds, etc. It is more desirable to use a ruthenium compound. As the ruthenium compound, there is no particular limitation, and examples thereof include: metallic ruthenium, ruthenium dioxide, ruthenium tetroxide, ruthenium hydroxide, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium sulfate, or hydrates thereof. These can be used alone or in mixture. Among the ruthenium compounds, ruthenium chloride, ruthenium dioxide or hydrates thereof are particularly preferred from the viewpoint of being easy to react with periodate salts or hypochlorous acid used as co-oxidants to generate highly oxidized ruthenium having a highly active catalytic function. As periodate salts, potassium periodate, sodium periodate, and calcium periodate are preferred, and sodium periodate is more preferred. One or more of the oxidants and co-oxidants can be used.

The step of esterifying the carboxylic acid of the compound obtained above may be the same as the esterification step in formula (Bz).

The step of converting the ester group of the compound obtained above into a carboxylic acid group by hydrolysis is not particularly limited, but it is preferably converted into a carboxylic acid group by hydrolysis using an acid catalyst or an alkaline catalyst. From the viewpoint of selective control of hydrolysis, it is preferably to use an alkaline catalyst. The acid catalyst is not particularly limited, and examples thereof include: inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; organic acids such as oxalic acid, ant acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalene disulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, ferric chloride, and boron trifluoride; or solid acids such as tungstic acid, tungstic phosphoacid, silicic molybdic acid, or phosphomolybdic acid. From the perspective of ease of preparation and operability, hydrochloric acid or sulfuric acid is preferably used. The alkali catalyst is not particularly limited, and examples thereof include organic alkali catalysts such as pyridine, quinoline, isoquinoline, α-methylpyridine, β-methylpyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, trimethylamine, triethylamine, tripropylamine, tributylamine, imidazole, N,N-dimethylaniline, and N,N-diethylaniline; and inorganic alkali catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate; inorganic salt catalysts are preferred, and potassium hydroxide and sodium hydroxide are more preferred. In addition, one or more acid catalysts or alkaline catalysts may be used.

The iodination step for iodinating the compound represented by formula (Ad-A-3-0) may be the same as the above-mentioned iodination step.

As another aspect of the method for producing the compound represented by formula (1), in order to improve productivity, it is preferred that the method further comprises: 4) preparing a compound represented by formula (Ad-A-3).

Furthermore, when the step of preparing a compound represented by formula (Ad-A-3) is included, it is preferred to include: 1) preparing a compound represented by formula (Ad-A-3), 2) A reduction step of reducing the compound represented by formula (Ad-A-3).

The reduction step of reducing the compound obtained above may be the same as the above reduction step.

As the solvent that can be used in the iodination step, those listed in the method for producing a compound wherein RG is benzene can be used. In this step, the raw material compound, the catalyst and the solvent are added to a reactor to form a reaction mixture. The reaction conditions and the like can also be the same as those described in the method for producing a compound wherein RG is benzene.

In addition, the iodination step is preferably included in the reaction of obtaining iodinated alkyl using an aqueous hydrogen iodide solution and adamantanol as raw materials, and water is distilled off to concentrate the reaction solution. The hydrogen iodide concentration of the reaction solution is preferably 10% or more, more preferably 25% or more, further preferably 40% or more, particularly preferably 45% or more, and most preferably 50% or more. Moreover, when the reaction solution is separated into two or more phases, the hydrogen iodide concentration of the aqueous phase containing hydrogen iodide is preferably the above concentration.

The adamantanol may have only one hydroxyl group in the molecule or may have two or more. The iodinated hydroxyl group may be any of the primary, secondary, and tertiary groups, but is preferably the secondary or tertiary group, and more preferably the tertiary group.

The adamantanol is preferably represented by the following formula (MA-1). In the formula, ^R1 and R" have the same definitions as in formula (Ad). However, ^R1 is preferably -OH, _-NO2 , or a monovalent group having 1 to 12 carbon atoms which may contain at least one functional group. The functional group is preferably one or more groups selected from the group consisting of a hydroxyl group, an ether group, an ester group, a carboxylic acid group, a halogen atom, _-NO2 , and NLL'. Then, the aforementioned L and L' are independently a hydrogen atom, a hydroxyl group, or a monovalent group having 1 to 12 carbon atoms which may contain at least one functional group.

The amount of hydrogen iodide relative to the iodinated hydroxyl group is preferably 1.01 equivalents or more, more preferably 1.1 equivalents or more, further preferably 1.3 equivalents or more, particularly preferably 1.5 equivalents or more in terms of mass ratio.

When the compound of formula (MA-1) has two or more hydroxyl groups in the molecule, all hydroxyl groups may be iodinated, or one or more hydroxyl groups may remain. As a method for selectively leaving one or more hydroxyl groups, for example, there can be cited the step of performing iodination in a system consisting of a multiphase system including an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent. As an organic solvent, there can be cited a hydrophobic solvent, which refers to a solvent that is not miscible with water in any proportion. When the aqueous phase is derived from an aqueous hydrogen halide solution, the iodination of the hydroxyl group of the aqueous phase is performed in a liquid-liquid two-phase reaction system in which the aqueous hydrogen halide solution and the hydrophobic solvent are separated into an aqueous phase and a hydrophobic solvent phase. In an alcohol having two or more hydroxyl groups, an iodinated alkyl group with one or more hydroxyl groups remaining can be obtained by extracting the iodinated alkyl group with one or more hydroxyl groups remaining from a hydrophobic solvent phase. In addition, by extracting the generated iodinated alkyl group from a hydrophobic solvent phase, a decrease in yield due to side reactions can be suppressed, so the use of a hydrophobic solvent is also effective when all hydroxyl groups are iodinated.

The hydrophobic solvent may or may not be azeotropic with water, but is preferably a hydrophobic solvent that azeotropes with water. Examples of the hydrophobic solvent that azeotropes with water include dichloromethane, chloroform, carbon tetrachloride, nitromethane, 1,2-dichloroethane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, pentane, cyclohexane, hexane, benzene, toluene, o-xylene, m-xylene, p-xylene, isopropylbenzene, nitrobenzene, phenol, s-butanol, cyclopentyl methyl ether, cyclohexanone, etc., and hexane, toluene, o-xylene, m-xylene, and p-xylene are preferably used. In addition, the hydrophobic solvent may be used alone or in combination of two or more.

The amount of the hydrophobic solvent is preferably 50 equivalents or less, more preferably 30 equivalents or less, and even more preferably 20 equivalents or less, based on the mass ratio of the raw material alcohol.

An acid may be used in the reaction. Examples of the acid include sulfuric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, acetic acid, trifluoroacetic acid, citric acid, oxalic acid, apple acid, lactic acid, glycolic acid, succinic acid, chromic acid, and boric acid.

Metal iodides may also be used in combination during the reaction. For example, LiI, NaI, KI, MgI ₂ , CaI ₂ , AlI ₃ and the like are effectively used in combination.

In order to prevent sudden boiling during the reaction, it is preferred to stir the reaction liquid. Various shapes of stirring blades can be appropriately used, for example, flat blades, inclined blades, turbine blades, disc turbine blades, rotary blades, three-swept blades, anchor blades, spiral belt blades, propeller blades, anchor blades, high-efficiency stirring blades, full-area stirring blades, twin star blades, etc.

The stirring speed can be any speed. When a hydrophobic solvent is used and the reaction solution is separated into two liquid-liquid phases, the stirring speed can be a stirring speed that causes the interface to shake, a stirring speed that generates/disperses some oil droplets or water droplets, or a stirring speed that causes a completely dispersed state. In addition, the reaction time of iodination can be shortened by standing and stirring after the substrate and iodizing agent are fed. The standing time is preferably 1 to 48 hours, more preferably 4 to 24 hours, and further preferably 8 to 12 hours.

The reaction temperature is preferably 0 to 150°C, more preferably 20 to 150°C, and further preferably 50 to 120°C. On the other hand, in order to obtain an iodinated alkyl group at a high yield, it is preferred to distill off water during the reaction and concentrate the reaction solution. In order to distill off water, the reaction temperature needs to be set to the boiling point of the reaction solution. When the boiling point is changed by using a hydrophobic solvent, the reaction temperature can be controlled by reducing or increasing the pressure of the reaction.

The reaction temperature can also be controlled by changing the stirring speed. Generally, when a hydrophobic solvent azeotropes with water, the azeotropic point will be lower than the boiling point of the solvent. When a hydrophobic solvent that azeotropes with water is used to separate the reaction liquid into two liquid-liquid phases, as the stirring speed increases, the two phases approach a completely dispersed state. With this, the boiling point also approaches the azeotropic point, so the reaction temperature Can be controlled by stirring speed.

When the reaction solution is concentrated, all the water distilled out by simple distillation may be distilled off, or a necessary amount may be distilled off using a Dean Stark apparatus or the like. However, it is preferred to distill off a necessary amount using a Dean Stark apparatus or the like.

The amount of water to be distilled off is preferably determined in such a way that the concentration of hydrogen iodide is maintained above a predetermined concentration. The above concentration is preferably 15% or more lower than the concentration of hydrogen iodide fed, more preferably 10% or more lower than the concentration of hydrogen halide fed, further preferably 5% or more lower than the concentration of hydrogen iodide fed, and particularly preferably above the concentration of hydrogen iodide fed. In addition, water can be distilled off continuously in a certain amount or in a batch at a predetermined time each time. After the reaction is completed, the purification and separation of the iodinated alkyl is carried out.

In the reaction, monomeric iodine is generated by oxidation of hydrogen iodide. When monomeric iodine remains, it may cause coloring, etc., so it is preferably reduced to hydrogen iodide by a reducing agent. The type of reducing agent is not particularly limited, and examples thereof include sodium sulfite, sodium hydrogen sulfite, phosphinic acid, etc.

As a method for removing the monomeric iodine, in addition to adding an iodide salt to the reaction solution, it is preferably removed by transferring the monomeric iodine to the aqueous layer. As the iodide salt, potassium iodide or the like can be used.

The reducing agent may be added directly to the reaction solution or may be added as an aqueous solution. In addition, the reducing agent may be added in a state where hydrogen iodide remains in the reaction solution or may be added after hydrogen iodide is neutralized with an alkali. The alkali used in the aforementioned neutralization operation is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, and the like.

In the iodination step, a method using a combination of trimethylsilyl chloride, sodium iodide or potassium iodide and adamantanol as a raw material is preferred. The solvent is preferably a polar aprotic solvent, and is not particularly limited. Examples thereof include: ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, etc.; ester solvents such as ethyl acetate, γ-butyrolactone, etc.; nitrile solvents such as acetonitrile, hydrocarbon solvents such as toluene, hexane, etc.; amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, hexamethylphosphatamide, hexamethylphosphite triamide, etc.; ketone solvents such as acetone, ethyl methyl ketone, etc.; chlorine solvents such as dichloromethane, chloroform, etc., dimethyl sulfoxide, etc. Among them, acetonitrile is the best. The ratio of trimethylsilyl chloride to sodium iodide is preferably 1.0 molar times or more, more preferably 1.5 molar times or more, and further preferably 2.0 molar times or more. When acetonitrile is used as the solvent, the reaction temperature is preferably under reflux.

In the iodination reaction using a combination of trimethylsilyl chloride and sodium iodide or potassium iodide, the same methods as those used in the above-mentioned iodination reaction using hydrogen iodide can be used with respect to the concentration method, the type of reducing agent, the stirring speed, the form of the filter, etc.

When an adamantane polyol is used as a raw material, when a plurality of iodine atoms are introduced, hydrogen iodide is preferably used as an iodination agent, and when a single iodine atom is introduced, a combination of trimethylsilyl chloride and sodium iodide or potassium iodide is preferably used as an iodination agent.

When a hydrophobic solvent is used, the hydrophobic solvent phase can be purified by washing with water. For example, pure water, sodium chloride aqueous solution, nitric acid aqueous solution, oxalic acid aqueous solution, sulfuric acid aqueous solution, hydrogen chloride aqueous solution, etc. can be used appropriately for washing. In addition, a hydrophobic solvent can be added after the reaction is completed for washing. The hydrophobic solvent added after the reaction is completed can be the same as the hydrophobic solvent used in the reaction, or it can be different.

Generally, water washing is performed at about room temperature, but if a product precipitates when water washing is performed at room temperature, water washing may be performed while heating. The water washing temperature is preferably below the azeotropic temperature of the hydrophobic solvent and water.

As described above, purification can also be performed by passing the liquid through an ion exchange resin, a chelate resin, a metal removal filter, a microparticle removal filter, etc. The ion exchange resin, the chelate resin, the metal removal filter, and the microparticle removal filter can be used alone or in combination with water washing or the like for purification.

The compound of formula (Ad) can be separated by distillation or crystallization. When the separation is carried out by distillation, the distillation method is not particularly limited, but for example, batch simple distillation, equilibrium flash distillation, batch distillation, continuous distillation, etc. can be appropriately used. In addition, the compound of formula (Ad) can be recovered by distillation, or it can be recovered as a bottom liquid or a bottom liquid.

When separation is performed by crystallization, the hydrophobic solvent used in the reaction may be used as the solvent, or a new solvent may be added. In addition, a single solvent may be used, or two or more solvents may be used in combination.

The mass ratio of the solvent to the compound of formula (Ad) during crystallization is preferably 20 equivalents or less, more preferably 10 equivalents or less, further preferably 5 equivalents or less, and particularly preferably 3 equivalents or less. The ratio of the solvent to the compound of formula (Ad) can be adjusted by distilling off the solvent.

Crystals can be precipitated by adding seed crystals or by cooling the solution without adding seed crystals. In addition, after crystals are precipitated, the slurry is cooled to improve the yield. The cooling rate is preferably 30°C/h or less, more preferably 20°C/h or less, further preferably 10°C/h or less, and particularly preferably 5°C/h or less.

After cooling, the temperature for solid-liquid separation of the slurry is preferably -50 to 40°C, more preferably -20 to 30°C, and further preferably -20 to 10°C. In addition, the retention time from when the slurry temperature reaches the temperature for solid-liquid separation until solid-liquid separation occurs is not particularly limited, but is preferably within 24 hours, and more preferably within 10 hours.

The method for solid-liquid separation is not particularly limited, and for example, suction filtration, centrifugal separation, pressure filtration, etc. can be appropriately used.

In addition, when compound (MA) is iodinated, a base or an oxidizing agent can be used. When the activity of the base or the oxidizing agent is high, compound (Da2) can be synthesized. Examples of the base include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, etc. Examples of the oxidizing agent are not particularly limited, and examples include periodic acid, hydrogen peroxide, predetermined additives (hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, etc.). Furthermore, compound (Da2) can be synthesized by condensing the hydroxyl groups of compound (MA) using a strong acid or the like.

The method for producing compound (B) of the present invention preferably further comprises a step of treating with an adsorbent. In the method for producing compound (B), an adsorbent may be used to remove impurities, or a plurality of filters and adsorbents may be appropriately combined. As the adsorbent, known adsorbents may be listed, for example, inorganic adsorbents such as alumina, activated alumina, silica, silica/alumina and zeolite (synthetic zeolite, etc., others), mica, and mica, as well as organic adsorbents such as activated carbon, molecular sieves, and ion exchange resins. When a clean solid surface comes into contact with an object, the object components are adsorbed onto the surface due to the interaction between the atoms on the solid surface and the object components. These (adsorbents) can use this adsorption to adsorb and remove specific components. Moreover, according to the mode of interaction, adsorption phenomena can be classified into two types: physical adsorption and chemical adsorption. Among them, physical adsorption is the phenomenon of atoms and molecules adsorbed on the solid surface. The main reason for adsorption is the van der Waals force (van der Waals interaction) between gas molecules and surface atoms. Its characteristics are that the specificity caused by the substance is less, the adsorption speed is faster, the adsorption heat is smaller (~20 kJ mol-1), and multi-layer adsorption and reversible desorption will also occur without dissociation. On the other hand, chemical adsorption is the phenomenon of atoms and molecules adsorbed on the surface of solids. The reason for adsorption is the adsorption caused by chemical bond formation and charge transfer interaction. In addition, chemical adsorption is more common on gas molecules and gas atoms such as metals and metal oxides. As its characteristics, it has stronger specificity for substances, slower adsorption speed, larger adsorption heat (hundreds of kJ mol-1), and can only adsorb in a single layer.

Impurities caused by the adsorbent can be removed without particular limitation as long as the compound (B) coexisting with the impurities is brought into contact with the adsorbent. Examples thereof include: adding the adsorbent to the reaction solution (also called silica dispersion), passing the reaction solution through a column filled with the adsorbent, dissolving the compound (B) coexisting with the impurities in an organic solvent and adding the adsorbent, passing the compound (B) coexisting with the impurities through a column filled with the adsorbent, etc. From the viewpoint of productivity, it is preferred to add the adsorbent to the reaction solution. Furthermore, from the viewpoint of selectively removing impurities in the compound (B) and suppressing the mixing of impurities from the adsorbent, it is preferred to use alumina, activated alumina, silica, or silica/alumina as the adsorbent. It is more preferred to use silica or silica/alumina.

2. Composition The aforementioned compound can be used as a composition. The aforementioned compound can be used as a composition for lithography, and thus can be a composition for lithography. Hereinafter, a composition containing the compound will be described by taking a composition for lithography as an example.

When irradiated with radiation, a lithography composition containing the aforementioned compound exhibits a sensitizing effect. Therefore, one aspect of the present embodiment may be a method of using the aforementioned compound to exhibit a sensitizing effect in irradiation of the lithography composition with radiation, preferably using two or more of the aforementioned compounds. The reason is not limited, but the aforementioned compound is believed to be used to promote the absorption of radiation. This effect is particularly evident under extreme ultraviolet (EUV) irradiation. The sensitizing effect has multiple forms, and when a photosensitive layer of a film made using the lithography composition is used as an anti-etching film for lithography, it can be confirmed, for example, as follows. 1) A method in which exposure is performed on the surface without a pattern, and after exposure, a PEB step (a step of performing a heat treatment after exposure) is performed as needed, and a developing step (a step of dissolving and removing the exposed part or the unexposed part by a developer) is performed as needed, and the film thickness of the film obtained by the above is measured. 2) The exposure amount is changed, the film thickness of the obtained film is measured, and the exposure amount when the film thickness changes drastically is defined as the sensitivity in the surface exposure method. 3) When the sensitivity is confirmed on the low exposure side, it can be determined that there is a sensitization effect. In addition, in the method of forming a pattern by exposure, 1) the exposure amount is changed to form a pattern, and the exposure amount that becomes a specified line width after exposure is defined as the sensitivity. 2) When the sensitivity is confirmed on the lower exposure side, it can be determined that there is a sensitization effect. In addition, the lithography composition containing the aforementioned compound is useful for suppressing defects in the resist pattern. In particular, pattern evaluation in extreme ultraviolet (EUV) can also be confirmed by reducing defects such as pitting and bridging. The defect is caused by an exposure state similar to fluctuations in optical exposure or substantial defects due to low exposure, but the anti-etching film avoids the aforementioned fluctuations and defects by promoting absorption with a sensitization effect, thereby reducing the aforementioned defects. When the aforementioned compound is used in the lithography composition, the aforementioned compound can be directly used as a constituent component of the composition. In addition, as another method, the form of a resin (base material (A)) and additives (acid generator (C), crosslinking agent (G), acid diffusion controller (E), other components (F), etc.) containing the aforementioned compound as a partial structure can be processed and these resins and additives can be used as constituent components of a lithography composition.

The lithography composition of the present embodiment comprises a compound represented by formula (1) (hereinafter also referred to as "compound (B)"), and may also comprise other components such as a substrate (A), a solvent (S), an acid generator (C), a crosslinking agent (G), and an acid diffusion control agent (E) as required. Each component is described below.

[Compound (B)] The composition in this embodiment includes one or more compounds (B). Although not limited, it is preferred that the composition includes two or more compounds (B). When two or more compounds (B) are included, there is a tendency to reduce etching defects as shown in the examples described below. The reason for reducing etching defects is not clear, but it is believed that, for example, the mutual solubility of the compound (B) in the composition is improved, and there is a possibility of reducing fine defects during film formation. RG of compound B is preferably a group derived from benzene, naphthalene or adamantane that may have a substituent. When two or more compounds B are included, the groups derived from RG may be the same or different.

There is no limit to the amount of compound (B) incorporated, but when there is a compound (B) with a smaller amount of incorporation (the compound is referred to as compound (B')), from the perspective of the improvement effect of etching defects, the amount of compound (B') is preferably 1 ppm or more, and more preferably 10 ppm or more, in the total amount of all compounds (B). In addition, when there is a compound (B) with the largest amount of incorporation (the compound is referred to as compound (B")), from the perspective of improving sensitivity, the content of compound (B'") having a lower iodine atom content in the molecule than that of compound (B") is preferably 40% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less, in the total amount of all compounds (B).

In one embodiment, in compound (B), when the monomer compound with more iodine atoms is set as H, the monomer compound with less iodine atoms is set as L, and the dimer compound is set as D, the following combination can be exemplified. H/L (mass ratio, the same below) = (97~99.999): (3~0.001) Furthermore, the following combinations are more preferred. Furthermore, the following combinations are more preferred. In addition, the following combinations are particularly preferred.

The method of mixing two or more compounds (B) is not limited, and the two or more compounds (B) may be mixed or may be simultaneously synthesized as a mixture in the process of synthesizing the compound (B).

More preferred aspects of compound (B) are as follows. 1) A combination of a compound represented by formula (1) as a reference compound and a compound having a smaller number of iodine atoms than the compound represented by formula (1) as the reference compound (preferably a compound represented by formula (BP0-1) described later). 2) A combination of a compound represented by formula (1) as a reference compound and a polymer of the compound represented by formula (1) (preferably a compound represented by formula (DM0-1) described above). 3) A combination of a compound represented by formula (1) as a reference compound, the compound having a smaller number of iodine atoms, and the polymer. In addition, the compound having a smaller number of iodine atoms may be a compound containing no iodine atoms.

The composition, by including the compound represented by the formula (DM0-1), can be assumed to have a higher effect on ensuring the stability over time caused by inorganic substances and inorganic components, and it can be assumed that the capture effect of the factor components is higher, resulting in improved stability over time. In addition, as another preferred embodiment, the composition, by including the compound represented by the formula (BP0-1), can be assumed to be more effective in ensuring the stability over time due to the difference in redox potential with the compound represented by the formula (1), and it can be assumed that the stability over time is improved, which is caused by natural oxidation and the deterioration of coexisting substances over time.

The compound represented by formula (DM0-1) is as described above. The compound represented by formula (DM0-1) is preferably a compound represented by the aforementioned formula (DM1a), (Dn1) or (Da1), or the following formula (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x) or (Ba1-eb). (In the formula, Z, I, ^R1 , A, R, r1 to r4 have the same definitions as in formula (DM1a).) (In the formula, Z, R ¹ , A, R, r1 to r4 have the same definitions as in formula (DM1a).) (In the formula, I, ^R1 , A, R", Q, s1-s4 have the same definitions as in formula (Dn1).) (In the formula, R ¹ , A, R”, Q, s2 to s4 have the same definitions as in formula (Dn1). (In the formula, I, R ¹ , R”, R ^d , t1 to t3 have the same definitions as in formula (Da1).) (In the formula, R ¹ , R”, R ^d , t2~t3 have the same definitions as in formula (Da1).) (In the formula, I, R ¹ , R”, R ^d , t1 to t3 have the same definitions as in formula (Da1).) (In the formula, I, R ¹ , R”, R ^d , t1 to t3 have the same definitions as in formula (Da1).) (In the formula, I, R ¹ , R”, R ^d , t1 to t3 have the same definitions as in formula (Da1).)

Examples of the compound having a smaller number of iodine atoms include the compound represented by formula (BP0-1).

RG, I, ^R1 have the same definitions as in formula (1). n' is an integer from 0 to 5 and less than n, preferably an integer from 0 to 3. When the composition contains compounds represented by formula (DM0-1) and formula (BP0-1), n' in formula (BP0-1) is preferably an integer obtained by subtracting 1 from the value of n' in formula (DM0-1). m' is an integer from 1 to 5 and less than m. When n' is 1 to 5, the compound of formula (BP0-1) is a type of compound represented by formula (1).

The compound represented by formula (BP0-1) is preferably represented by the following formula. In the formula, R, R ¹ , R ″, A, r1~r4, s2~s3, t2~t3 are defined as above. a1 and r4a are integers of 0~4, and a1 and r4a are numbers satisfying a1+r4a≤r4. r4 is defined as above, but preferably has the same meaning as r4 in formula (Bz). s1b is an integer of 0~6, and is an integer satisfying s1b≤(s1-1). s1 is defined as above, but preferably has the same meaning as s1 in formula (N). t1b is an integer of 0~9, and is an integer satisfying t1b≤(t1-1). t1 is defined as above, but preferably has the same meaning as t1 in formula (Ad).

In addition, the compound represented by formula (BP0-1) is preferably represented by the following formula (BP1a-Dt), (Bn1-Dt) or (Ba1-Dt). (In the formula, Z, R, ^R1 , A, r1, r2, r3, and r4a have the same meanings as in formula (BP1a).) (In the formula, R ¹ , R ”, A, s2 to s4 have the same definitions as in formula (Bn1). (In the formula, R ¹ , R ″, t2, and t3 have the same definitions as in formula (Ba1).)

A composition using a compound represented by formula (1) in combination with a compound represented by formula (DM0-1) or formula (BP0-1) has excellent storage stability. The reason is not limited, but it is speculated that the compound represented by formula (DM0-1) or formula (BP0-1) captures factor substances and factor components that deteriorate storage stability in stereo or electronically. From this point of view, the lower limit of the total amount of the compounds represented by formula (DM0-1) and formula (BP0-1) relative to the entire compound represented by formula (1) is preferably 1 ppm or more, more preferably 2 ppm or more, further preferably 5 ppm or more, and particularly preferably 10 ppm or more. The upper limit of the total amount is preferably 10000 ppm or less, more preferably 8000 ppm or less, further preferably 5000 ppm or less, and particularly preferably 3000 ppm or less.

When the composition further contains a compound represented by formula (DM0-1), it is preferred that the compounds represented by formula (1) and formula (DM0-1) satisfy the following relationship. 0.1≧[amount of compound of formula (DM0-1) (mol)]÷[amount of compound of formula (1) (mol)]≧0.000001

When the composition further includes a compound represented by formula (DM0-1) and a compound represented by formula (BP0-1), it is preferred that the compounds represented by formula (1), formula (DM0-1), and formula (BP0-1) satisfy the following relationship. 0.1≧([total amount of the compound of formula (DM0-1) and the compound of formula (BP0-1) (mol)])÷[amount of the compound of formula (1) (mol)]≧0.000001

In addition to the above effects, from the viewpoint of improving the heat resistance of the compound, it is preferred to use a compound represented by formula (DM0-1), more preferably a compound represented by (DM1a), (Dn1), (Da1), (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x) or (Ba1-eb). Among them, dimers are particularly preferred.

In addition to the above effects, from the perspective of miscibility, when the composition contains a compound B different from the compound represented by formula (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), (Ba1-eb), formula (BP1a-Dt), (Bn1-Dt) or (Ba1-Dt), the compound represented by formula (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), (Ba1-eb), formula (BP1a-Dt), (Bn1-Dt) or (Ba1-Dt) preferably has the same parent nucleus as the compound B.

In addition to the above effects, from the viewpoint of improving the dissolution stability of the compound, it is preferred to use a compound represented by formula (BP0-1), and it is preferred to use a compound having fewer iodine atoms, such as a compound represented by formula (BP1a), (Bn1) or (Ba1). Even when the compound represented by formula (BP1a), (Bn1) or (Ba1) does not contain an iodine atom, the expected effect can be obtained. In this aspect, Z in formula (BP1a) may not contain I. The preferred compound will be described below.

The compound represented by formula (BP1a) is preferably a compound represented by formula (BP1b).

In formula (BP1b), I, R, ^R1 , A, and Z are the same as those defined in formula (BP1a), and a11 and a12 are integers between 0 and 2 satisfying a11+a12≤r4. r4 is defined as above, but preferably has the same meaning as r4 in formula (Bz) (hereinafter, the same).

The compound represented by formula (BP1b) is preferably a compound represented by formula (BP1c1).

In formula (BP1c1), I, R, R ¹ , A, and Z have the same definitions as in formula (BP1a), and a11 and a12 are integers between 0 and 1 satisfying a11+a12≤r4.

The compound represented by formula (BP1c1) is preferably a compound represented by formula (BP1d11).

In formula (BP1d11), I, R, R ¹ , A, and Z have the same definitions as in formula (BP1a), and a11 and a12 are integers between 0 and 1 satisfying a11+a12≤r4.

The compound represented by formula (BP1c1) is preferably a compound represented by formula (BP1d12).

In formula (BP1d12), I, R, ^R1 , and Z are the same as defined in formula (BP1a), and a11 and a12 are integers of 0 to 1 satisfying a11+a12≤r4. A' is a group having a protecting group, and is represented by -ORa ^{- ORb} , -O-CO- ^ORb , or -ORa ^- CO- ^ORb , or -ORa ^- O-CO- ^Rb . ^Ra is a linear or branched alkyl group having 1 to 3 carbon atoms. ^Rb is a monovalent linear, branched, or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group that forms a ring together with an adjacent oxygen atom. ^Ra and a cyclic structure including ^Ra can be formed. However, A' is present at least 1.

The compound represented by formula (BP1b) is preferably a compound represented by formula (BP1c2).

In formula (BP1c2), I, R, R ¹ , A, and Z have the same definitions as in formula (BP1a), and a11 and a12 are integers between 0 and 1 satisfying a11+a12≤r4.

The compound represented by formula (BP1c2) is preferably a compound represented by formula (BP1d21).

In formula (BP1d21), I, R, R ¹ , A, and Z have the same definitions as in formula (BP1a), and a11 and a12 are integers between 0 and 1 satisfying a11+a12≤r4.

The compound represented by formula (BP1c1) is preferably a compound represented by formula (BP1d22).

In formula (BP1d22), I, R, and ^R1 are the same as those defined in formula (BP1a), and a11 and a12 are integers between 0 and 1 satisfying a11+a12≤r4. A' is the same as defined in formula (BP1d12).

The compound represented by formula (BP1b) is preferably a compound represented by formula (BP1c3).

In formula (BP1c3), I, R, R ¹ , A, and Z have the same definitions as in formula (BP1a), and a11 and a12 are integers between 0 and 1 satisfying a11+a12≤r4.

The compound represented by formula (BP1c3) is preferably a compound represented by formula (BP1d31).

In formula (BP1d31), I, R, R ¹ , A, and Z have the same definitions as in formula (BP1a), and a11 and a12 are integers between 0 and 1 satisfying a11+a12≤r4.

The compound represented by formula (BP1b) is preferably a compound represented by formula (BP1c4).

In formula (BP1c4), I, R, R ¹ , A, and Z have the same definitions as in formula (BP1a), and a11 and a12 are integers between 0 and 1 satisfying a11+a12≤r4.

The compound represented by formula (BP1c4) is preferably a compound represented by formula (BP1d41).

In formula (BP1d41), I, R, and ^R1 are the same as those defined in formula (BP1a), and a11 and a12 are integers between 0 and 1 satisfying a11+a12≤r4. A' is the same as defined in formula (BP1d12).

The compound represented by formula (Bn1) is preferably a compound represented by formula (Bn1a).

In formula (Bn1a), I, R ¹ , R″, and A have the same definitions as in formula (Bn1). x' and y' are each 0 or 1, and for x and y in formula (1n), (x'+y')≤(x+y-1) is satisfied.

The compound represented by formula (Bn1a) is preferably a compound represented by formula (Bn1b1).

In formula (Bn1b1), I, R ¹ , R″, and A are the same as those defined in formula (Bn1). x′ and y′ are each 0 or 1, and for x and y in formula (1n), (x′+y′)≤(x+y-1) is satisfied. s4′ is the same as defined above.

The compound represented by formula (Bn1b1) is preferably a compound represented by formula (Bn1c11).

In formula (Bn1c11), I, R ¹ , R″, and A have the same definitions as in formula (Bn1). x' and y' are each 0 or 1, and for x and y in formula (1n), (x'+y')≤(x+y-1) is satisfied.

The compound represented by formula (Bn1b1) is preferably a compound represented by formula (Bn1c12).

In formula (Bn1c12), R ¹ and R" have the same meanings as in formula (Bn1), and A' has the same meanings as in formula (BP1d12).

The compound represented by formula (Bn1a) is preferably a compound represented by formula (Bn1b2).

In formula (Bn1b2), I, R ¹ , R″, and A are the same as defined in formula (Bn1). x″ is 0 or 1. s4′ is the same as defined above.

The compound represented by formula (Bn1b2) is preferably a compound represented by formula (Bn1c21).

In formula (Bn1c21), R ¹ and R" have the same meanings as in formula (Bn1), and A' has the same meanings as in formula (BP1d12).

The compound represented by formula (Bn1a) is preferably a compound represented by formula (Bn1b3).

In formula (Bn1b3), I, R ¹ , R″, and A are the same as those defined in formula (Bn1). x′ and y′ are each 0 or 1, and for x and y in formula (1n), (x′+y′)≤(x+y-1) is satisfied. s4′ is the same as defined above.

The compound represented by formula (Bn1b3) is preferably a compound represented by formula (Bn1c31).

In formula (Bn1c31), R ¹ and R" have the same meanings as in formula (Bn1), and A' has the same meanings as in formula (BP1d12).

The compound represented by formula (Bn1b3) is preferably a compound represented by the following formula (Bn1c32).

In formula (Bn1c32), R ¹ and R" have the same meanings as in formula (Bn1), and A' has the same meanings as in formula (BP1d12).

The compound represented by formula (Ba1) is preferably a compound represented by formula (Ba1a).

In formula (Ba1a), I, ^R1 , and R" have the same definitions as in formula (Ba1). 1c1, 1c2, and 1c3 are integers of 0 or 1 satisfying (1c1+1c2+1c3)≤t1b. t1b has the same definition as above, and preferably has the same meaning as t1b in formula (Ba1) (hereinafter, the same).

The compound represented by formula (Ba1a) is preferably a compound represented by formula (Ba1b).

In formula (Ba1b), I, R”, and R ¹ have the same definitions as in formula (Ba1a). 1c1, 1c2, and 1c3 are integers of 0 or 1 that satisfy (1c1+1c2+1c3)≤t1b.

The compound represented by the formula (Ba1b) is preferably a compound represented by the following formula (Ba1c11).

In formula (Ba1c11), I, R”, and R ¹ have the same definitions as in formula (Ba1a). 1d1 and 1d2 are integers of 0 or 1 that satisfy (1d1+1d2)≤t1b.

The compound represented by formula (Ba1b) is preferably a compound represented by the following formula (Ba1c12).

In formula (Ba1c12), I, R'', and ^R1 have the same definitions as in formula (Ba1a), and 1e1, 1e2, and 1e3 are integers of 0 or 1 that satisfy (1e1+1e2+1e3)≤t1b.

As compound B, it is preferred that the compound to which a solvent is added is included in the composition. Examples of the compound to which a solvent is added include compounds represented by the following formula (Ba1-tl), (Ba1-x) or (Ba1-eb). (In the formula, I, R ¹ , R”, R ^d , t1 to t3 have the same definitions as in formula (Da1).) (In the formula, I, R ¹ , R”, R ^d , t1 to t3 have the same definitions as in formula (Da1).) (In the formula, I, R ¹ , R”, R ^d , t1 to t3 have the same definitions as in formula (Da1).)

Examples of the compounds represented by formula (DM0-1) and formula (BP0-1) that do not contain an iodine atom are shown below.

[Substrate (A)] In this embodiment, the so-called substrate (A) refers to a compound other than compound (B) and can be used as a material for an anti-etching agent. The substrate (A) can be a resin. For example, the so-called substrate (A) refers to a substrate that can be used as an anti-etching agent for g-line, i-line, KrF excimer laser (248nm), ArF excimer laser (193nm), extreme ultraviolet (EUV) lithography (13.5nm), and electron beam (EB) (for example, a substrate for lithography, a substrate for an anti-etching agent). Examples of the substrate (A) include phenol novolac type resins, cresol novolac type resins, hydroxystyrene resins, (meth)acrylic resins, hydroxystyrene-(meth)acrylic acid copolymers, cycloolefin-maleic anhydride copolymers, cycloolefin-vinyl ether-maleic anhydride copolymers, and inorganic anti-corrosion agent materials having metal elements such as titanium, tin, einsteinium, zirconium, and the like, and their derivatives. Among these, from the viewpoint of the shape of the resulting anti-corrosion pattern, preferred are phenol novolac type resins, cresol novolac type resins, hydroxystyrene resins, (meth)acrylic resins, hydroxystyrene-(meth)acrylic copolymers, and inorganic anti-corrosion materials having metal elements such as titanium, tin, einsteinium, zirconium, and the like, and their derivatives.

From the viewpoint of reducing defects in the film formed using the composition and obtaining a good pattern shape, the weight average molecular weight of the substrate (A) is preferably 2000 to 49900, more preferably 2000 to 29900, and further preferably 2000 to 14900. The weight average molecular weight can be obtained by measuring the weight average molecular weight in terms of polystyrene using GPC.

[Solvent (S)] The solvent in this embodiment can be any solvent that can dissolve compound (B), and a known solvent can be used appropriately. Specific examples of the solvent include: ethylene glycol monoalkyl ether acetates; ethylene glycol monoalkyl ethers; propylene glycol monoalkyl ether acetates (e.g. propylene glycol monomethyl ether acetate); propylene glycol monoalkyl ethers; lactic acid esters; aliphatic carboxylic acid esters; other esters; aromatic hydrocarbons; ketones; amide 3:9; lactones, etc. Specific examples of these include: those disclosed in Patent Document 1.

The solvent used in the present embodiment is preferably a safe solvent, more preferably at least one selected from PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), CHN (cyclohexanone), CPN (cyclopentanone), 2-heptanone, anisole, butyl acetate and ethyl lactate, and further preferably at least one selected from PGMEA, PGME, CHN, CPN and ethyl lactate.

In the present embodiment, the amount of the solid component and the amount of the solvent are not particularly limited, but relative to the total mass of the solid component and the solvent, it is preferably that the solid component is 1-80 mass% and the solvent is 20-99 mass%, more preferably that the solid component is 1-50 mass% and the solvent is 50-99 mass%, further preferably that the solid component is 2-40 mass% and the solvent is 60-98 mass%, and particularly preferably that the solid component is 2-10 mass% and the solvent is 90-98 mass%. In addition, the total mass of the solid component (including the sum of the solid components of any components used, such as the substrate (A), the compound (B), the acid generator (C), the crosslinking agent (G), the acid diffusion control agent (E) and other components (F), the same applies hereinafter) is taken as the amount of the solid component.

[Acid Generator (C)] The composition of the present embodiment preferably contains one or more acid generators (C). The acid generator (C) refers to a material that directly or indirectly generates an acid by irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray and ion beam. As the acid generator (C), for example, those described in International Publication No. 2013/024778 can be used. Two or more acid generators (C) may also be used in combination.

The amount of the acid generator (C) used is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, further preferably 3 to 30% by mass, and particularly preferably 10 to 25% by mass, based on the total mass of the solid component. By using the acid generator (C) within the above range, a pattern profile with high sensitivity and low edge roughness tends to be obtained.

[Crosslinking agent (G)] The composition of the present embodiment preferably contains one or more crosslinking agents (G). The crosslinking agent (G) can crosslink at least one of the substrate (A) and the compound (B). The crosslinking agent (G) causes the substrate (A) to undergo intramolecular crosslinking or intermolecular crosslinking in the presence of an acid generated from the acid generator (C). Examples of such acid crosslinking agents include compounds having one or more groups (hereinafter referred to as "crosslinking groups") that can crosslink the substrate (A). As a crosslinking agent (G) having such a crosslinking group, for example, those described in International Publication No. 2013/024778 can be used. Two or more crosslinking agents (G) may also be used in combination.

In this embodiment, the amount of the crosslinking agent (G) used is preferably 0.5-50% by mass, more preferably 0.5-40% by mass, further preferably 1-30% by mass, and particularly preferably 2-20% by mass in the total mass of the solid component. When the mixing ratio of the crosslinking agent (G) is 0.5% by mass or more, the effect of suppressing the solubility of the anti-corrosion film in the alkaline developer is improved, the residual film rate is reduced, and there is a tendency to suppress the swelling and meandering of the pattern. On the other hand, when it is 50% by mass or less, there is a tendency to suppress the decrease in heat resistance as an anti-corrosion agent.

[Acid diffusion control agent (E)] The composition of this embodiment may contain an acid diffusion control agent (E). The acid diffusion control agent (E) has the function of controlling the diffusion of the acid generated from the acid generator by radiation in the anti-etching film and preventing undesirable chemical reactions in the unexposed area. By using the acid diffusion control agent (E), the storage stability of the composition of this embodiment tends to be improved. In addition, by using the acid diffusion control agent (E), the resolution of the thin film formed using the composition of this embodiment can be improved. In addition, by using an acid diffusion control agent (E), the variation of the line width of the resist pattern caused by the variation of the post-exposure development delay before radiation irradiation and the post-exposure development delay after radiation irradiation can be suppressed, which tends to improve the process stability. Examples of the acid diffusion control agent (E) include radiation-decomposable alkaline compounds described in International Publication No. 2013/024778. Two or more acid diffusion control agents (E) may also be used in combination.

The amount of the acid diffusion control agent (E) blended is preferably 0.001 to 49% by mass of the total mass of the solid component, more preferably 0.01 to 10% by mass, further preferably 0.01 to 5% by mass, and particularly preferably 0.01 to 3% by mass. When the amount of the acid diffusion control agent (E) blended is within the above range, it tends to prevent a decrease in resolution, deterioration of pattern shape, scale fidelity, etc. Further, even if the post-exposure development delay from electron beam irradiation to heating after radiation irradiation becomes longer, the deterioration of the shape of the upper layer of the pattern can be suppressed. In addition, when the blending amount is less than 10% by mass, it tends to prevent a decrease in sensitivity, developability of unexposed areas, etc. Furthermore, by using such an acid diffusion controller, the storage stability of the resist composition is improved, and while the resolution is improved, the variation in line width of the resist pattern caused by the variation in the post-exposure development delay before radiation irradiation and the post-exposure development delay after radiation irradiation can be suppressed, which tends to improve process stability.

[Other components (F)] The composition of this embodiment may contain one or more but not more than one additive as other components (F). (Dissolution promoter) When the solubility of the solid component in the developer is too low, the dissolution promoter increases its solubility and appropriately increases the dissolution rate of the aforementioned compound during development. As the aforementioned dissolution promoter, it is preferably a low molecular weight one, for example: a low molecular weight phenolic compound. As a low molecular weight phenolic compound, for example: bisphenols, tris(hydroxyphenyl)methane, etc. can be listed. Two or more dissolution promoters can also be used in combination.

The amount of the dissolution promoter blended is appropriately adjusted depending on the type of the solid component used, but is preferably 0-49% by mass, more preferably 0-5% by mass, further preferably 0-1% by mass, and particularly preferably 0% by mass, based on the total mass of the solid component.

(Dissolution control agent) When the solubility of the solid component in the developer is too high, the dissolution control agent controls its solubility and appropriately reduces the dissolution rate during development. As such a dissolution control agent, it is preferred that it does not undergo chemical changes during the steps of firing, radiation irradiation, and development of the anti-corrosion coating.

There is no particular limitation on the dissolution control agent, and examples thereof include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthylene; ketones such as acetophenone, benzophenone, and phenylnaphthophenone; sulfones such as methylphenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone. Two or more dissolution control agents may be used in combination. The amount of the dissolution control agent blended is appropriately adjusted depending on the type of the aforementioned compound used, but is preferably 0 to 49% by mass of the total mass of the solid component, more preferably 0 to 5% by mass, further preferably 0 to 1% by mass, and particularly preferably 0% by mass.

(Sensitizer) The sensitizer absorbs the energy of the irradiated radiation and transfers the energy to the acid generator (C), thereby increasing the amount of acid generated and improving the apparent sensitivity of the anti-corrosion agent. Examples of such sensitizers include benzophenones, diacetyl, pyrene, phenanthryl, fluorene, etc. Two or more sensitizers may also be used in combination. The amount of the sensitizer blended is appropriately adjusted depending on the type of the aforementioned compound used, but is preferably 0-49% by mass of the total solid content, more preferably 0-5% by mass, further preferably 0-1% by mass, and particularly preferably 0% by mass.

(Surfactant) The surfactant improves the coating properties, streaks, and anti-corrosion agent developing properties of the composition of the present embodiment. The surfactant may be an anionic surfactant, a cationic surfactant, a non-ionic surfactant, or an amphoteric surfactant. As a preferred surfactant, there can be listed: non-ionic surfactants. Non-ionic surfactants have good affinity with the solvent used to prepare the composition of the present embodiment, and can further enhance the effect of the composition of the present embodiment. As examples of non-ionic surfactants, there can be listed: polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyethylene glycol, etc., but there are no special restrictions. These surfactants may also be commercial products as described in Patent Document 1. The amount of surfactant blended is appropriately adjusted depending on the type of the aforementioned solid component used, but is preferably 0-49% by mass of the total mass of the solid component, more preferably 0-5% by mass, further preferably 0-1% by mass, and particularly preferably 0% by mass.

(Organic carboxylic acid or phosphorus oxygen-containing acid or derivative thereof) Organic carboxylic acid or phosphorus oxygen-containing acid or derivative thereof (hereinafter also referred to as "acid or derivative") has the effect of preventing sensitivity degradation, improving the shape of the anti-etching agent pattern or improving the stability of the shelf life. As organic carboxylic acid, for example, malonic acid described in Patent Document 1 can be listed. As phosphorus oxygen-containing acid or derivative thereof, derivatives such as phosphonic acid or its ester described in Patent Document 1 can be listed. Among these, phosphonic acid is particularly preferred.

The aforementioned acid or derivative may be used alone or in combination of two or more thereof. The amount of the acid or derivative blended is appropriately adjusted depending on the type of the aforementioned compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, further preferably 0 to 1% by mass, and particularly preferably 0% by mass, based on the total mass of the solid component.

(Other additives) Furthermore, the composition of the present embodiment may contain additives other than the above-mentioned components as required. Examples of such additives include dyes, pigments, and bonding aids. For example, when dyes or pigments are formulated, it is preferable because the latent image of the exposed part is visualized and the effect of the halo during exposure is alleviated. In addition, when bonding aids are formulated, it is preferable because the adhesion to the substrate can be improved. Furthermore, examples of other additives include anti-halo agents, storage stabilizers, defoaming agents, shape modifiers, etc., specifically 4-hydroxy-4'-methylchalcone, etc.

[Ratio of each component in the composition] In the composition of this embodiment, the amount of compound B is preferably 10ppm~10% by mass in the total mass of the solid components of the composition. The total mass of the solid components in the present invention refers to the sum of the solid components of any components used, including the substrate (A), compound (B), acid generator (C), crosslinking agent (G), acid diffusion control agent (E) and other components (F). The mass ratio of the substrate (A) to the compound (B) is preferably 3:97~99.5:0.5, and more preferably 10:90~99:1. When the mass ratio is within this range, it has a tendency to suppress exposure deviation in the high sensitivity and depth direction. The aforementioned mass ratio is more preferably 30:70~98:2, and further preferably 50:50~97:3.

In the composition of the present embodiment, the total amount of the substrate (A) and the compound (B) is preferably 50-99.4% by mass of the total mass of the solid component, more preferably 55-95% by mass, further preferably 60-95% by mass, and particularly preferably 70-95% by mass. When the total amount of the substrate (A) and the compound (B) is the above content, there is a tendency that the resolution is further improved and the line edge roughness (LER) is further reduced.

In the composition of the present embodiment, the mass ratio (mass %) of (A)/(B)/(C)/(G)/ (E)/(F) relative to the total mass of the solid components of the composition of the present embodiment is: preferably 1.5~99.0/0.2~96.4/0.001~49/0~49/0.001~49/0~49, more preferably 5~98.5/0.5~89/1~40/0~40/0.01~10/0~5, further preferably 15~97.5/1~69/3~30/0~30/0.01~5/0~1, particularly preferably 25~96.5/1.5~50/3~30/0~30/0.01~3/0.

The proportion of each component is selected from various ranges so that the total is 100% by mass. When the above-mentioned proportion is adopted, the sensitivity, resolution, developing property and other performances tend to be more excellent. The so-called "solid content" refers to the components excluding the solvent, and the so-called "total solid content mass" refers to the total of the components excluding the solvent from the components constituting the composition, which is set to 100% by mass.

The composition of the present embodiment is usually prepared by dissolving each component in a solvent to form a uniform solution, and then filtering through a filter with a pore size of about 0.2 μm, etc., as required.

[Physical properties of the composition, etc.] The composition of this embodiment can form an amorphous film by spin coating. In addition, the composition of this embodiment can be applied to a general semiconductor manufacturing process. In addition, depending on the type of developer used, the composition of this embodiment can be used to produce either a positive resist pattern or a negative resist pattern.

The lithography composition containing the compound (B) exhibits an excellent sensitization effect in EUV exposure. Therefore, the present invention also provides a method for enhancing the sensitivity of the lithography composition in EUV exposure. As described above, in the sensitization method, it is preferred to use two or more compounds (B).

The residual amount of metal impurities in the composition is preferably less than 1 ppm, more preferably less than 100 ppb, further preferably less than 50 ppb, further preferably less than 10 ppb, and most preferably less than 1 ppb relative to the composition. In particular, for metal species such as Fe, Ni, Sn, Zn, Cu, Sb, W, and Al, which are classified as transition metals, when the residual amount of the above metals is more than 1 ppm, there is a concern that it may become a factor causing the material to be modified and deteriorated over time due to the interaction with other compounds. In addition, for alkaline metals and alkaline metals such as Na, K, Ca, and Mg, when the residual amount is more than 1 ppm, the metal residue cannot be sufficiently reduced when the semiconductor resin is used in the production step using the compound, and there is a concern that it may become a factor of reduced yield due to defects and performance degradation caused by the residual metal in the semiconductor manufacturing step. [Example]

[Measurement method] [Nuclear magnetic resonance (NMR)] The structure of the compound was confirmed by NMR measurement under the following conditions using a nuclear magnetic resonance device "Avance500III spectrometer" (product name, manufactured by Bruker). [1H-NMR measurement] Frequency: 500 MHz Solvent: CDCl3 or d6-DMSO Internal standard: TMS Measurement temperature: 23°C [13C-NMR measurement] Frequency: 125 MHz Solvent: CDCl3 or d6-DMSO Internal standard: Use the solvent used Measurement temperature: 23°C

[Molecular weight] The molecular weight of the compound was measured by liquid chromatography-mass spectrometry (LC-MS) using Acquity UPLC/MALDI-Synapt HDMS manufactured by Waters.

[Example 1] Compounds using benzene as a parent core The compound was produced according to the following process. The reaction was carried out under a nitrogen flow.

(Synthesis of compound 1-2) Immerse a flask equipped with a stirrer and a cooling tube in an ice water bath, add 40 g (0.11 mol) of compound 1-1 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 120 mL of acetone into the flask and stir. The internal temperature at this time is 4°C. Then, 15.6 g (1.1 equivalents relative to compound 1-1) of diisopropylethylamine (DIPEA) is added dropwise to the flask. After the addition of diisopropylethylamine is completed, 12.3 g (1.2 equivalents relative to compound 1-1) of chloromethyl ethyl ether is added dropwise, and the reaction is carried out for 2 hours under a nitrogen flow. After the reaction is completed, 120 mL of water is added to the flask to obtain a precipitate. Subsequently, the mixture was filtered and washed with water, and then further washed with methanol, filtered and dried to obtain compound 1-2. The yield was 84%. The formation was confirmed by NMR and LC-MS. The molecular weight was 432.

(Synthesis of Compound 1-2 2) Immerse a flask equipped with a stirrer and a cooling tube in an ice water bath, add 40 g (0.11 mol) of Compound 1-1 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 80 mL of dimethylformamide into the flask and stir. The internal temperature at this time is 4°C. Then, add 15.2 g of potassium carbonate (1.0 equivalent to Compound 1-1) to the flask. After the addition of potassium carbonate, add 12.3 g of chloromethyl ethyl ether (1.2 equivalent to Compound 1-1) dropwise, and react for 1 hour under a nitrogen flow. After the reaction is completed, add 180 mL of water to the flask to obtain a precipitate. Subsequently, the mixture was filtered and washed with water, and then further washed with methanol, filtered and dried to obtain compound 1-2. The yield was 89%.

(Synthesis of compound 1-3) Immerse a flask equipped with a stirrer and a cooling tube in an ice water bath, and add 33 g of compound 1-2 and 100 mL of dehydrated ethanol into the flask. The internal temperature at this time is 3°C. Then, add 2.88 g of NaBH ₄ (less than 1.0 equivalent relative to compound 1-2) in batches within 1 hour. Thereafter, continue the reaction under a nitrogen flow for 45 minutes. Then, add 78 g of 5% ammonium chloride (reagent produced by FUJIFILM Wako Pure Chemical Corporation) and 100 g of water, filter, wash with water and dry to obtain compound 1-3. The yield is 85%. The formation is confirmed by NMR and LC-MS. The molecular weight is 434.

[Example 1a] Compound 2 with benzene as the parent nucleus Add 16 g (65 mmol) of 5-iodovanillin to 60 ml of acetone and ice-cool. After adding 8.2 g (63 mmol) of diisopropylethylamine under nitrogen, 6.4 ml (0.84 mol) of chloromethyl ethyl ether was added dropwise at below 12°C. Stir at 3°C for 15 minutes and slowly add 100 ml of water. Filter to obtain the precipitate and wash with water. Suspend the obtained solid in 70 ml of methanol, stir and filter. Dry the solid at room temperature and use in the next step. Add 15 ml of ethanol to 2 g of the solid and ice-cool. Add 225 mg (5.9 mmol) of sodium borohydride in batches over 5 minutes. Continue the reaction for 30 minutes and add 20 ml of water. After adding 400 mg (7.5 mmol) of ammonium chloride, 20 ml of water was added dropwise. After adding ethyl acetate for extraction, it was dried with sodium sulfate, and the organic solvent was distilled off by an evaporator to obtain compound 2. The formation was confirmed by NMR and LC-MS. The molecular weight is 338.

[Example 1b] Compound 3 with benzene as the parent nucleus Similar to Example 1, 9.38 g of ethyl vinyl ether was used instead of 12.3 g of chloromethyl ethyl ether to obtain compound 3. As another method, 100 ml of dichloromethane was added to 22 g (60 mmol) of 4-hydroxy-3,5-diiodobenzaldehyde and ice-cooled. After adding 43.2 g (600 mmol) of ethyl vinyl ether under a nitrogen environment, 1.5 g (6 mmol) of polytoluene sulfonate pyridinium salt was added at below 10°C. Subsequently, the mixture was stirred at 20°C for 24 hours and 100 ml of water was added. After extraction with dichloromethane, the organic layer was dried with sodium sulfate, and the organic solvent was distilled off by an evaporator to obtain an ethoxyethyl protected compound. Add 25 ml of ethanol to 4.5 g (10 mmol) of the protected compound and cool with ice. Add 113 mg (3 mmol) of sodium borohydride in batches over 5 minutes. Continue the reaction for 30 minutes and add 20 ml of water. Add 240 mg (4.5 mmol) of ammonium chloride and then drop 20 ml of water. Add ethyl acetate for extraction, dry with sodium sulfate, and distill off the organic solvent with an evaporator to obtain compound 3. The formation was confirmed by NMR and LC-MS. The molecular weight is 448.

[Example 1c] Compound 4 with benzene as the nucleus Similar to Example 1b, 50.5 g of 3,4-dihydro-2H-pyran was used instead of 43.2 g of ethyl vinyl ether to obtain Compound 4. The formation was confirmed by NMR and LC-MS. The molecular weight was 460.

[Example 1d] Compound 5 with benzene as the nucleus Similar to Example 1, 14.2 g of di-tert-butyl dicarbonate was used instead of 12.3 g of chloromethyl ethyl ether to obtain Compound 5. The formation was confirmed by NMR and LC-MS. The molecular weight was 474.

[Example 1e] Compound 6 with benzene as the parent nucleus In the same manner as in Example 1, 3,5-diiodo-4-hydroxybenzyl alcohol was obtained. 3,5-diiodo-4-hydroxybenzyl alcohol and THF were added, stirred and dissolved, and then phosgene (2 equivalents relative to the raw material, 20% toluene solution, manufactured by Merck) was added dropwise under nitrogen atmosphere and ice-cooling. The mixture was further stirred for 2 hours under ice-cooling. The mixture was further stirred at 25°C for 12 hours. Then, nitrogen was bubbled for 2 hours, and the carbonate (1e0) was obtained by reduced pressure concentration. The obtained carbonate (1e0) was placed in chloroform and stirred and dissolved under ice-cooling. Further, 1-methylcyclopentanol (1.2 equivalents relative to the aforementioned (1e0)) was added dropwise under ice cooling and stirred. Further, pyridine (1.2 equivalents relative to the aforementioned (1e0)) was added dropwise under ice cooling and stirred. After stirring for 1 hour, stirring was performed at 25°C for 12 hours. Then, ion exchange water was added and the organic phase was recovered. The obtained organic phase was washed with 5% baking soda water, and then washed with ion exchange water 5 times, and compound 6 was obtained by reduced pressure concentration. The formation was confirmed by NMR and LC-MS. The molecular weight is 502.

[Example 1f] Compound 7 with benzene as the nucleus Similar to Example 1, 10.5 g of chloromethyl methyl ether was used instead of 12.3 g of chloromethyl ethyl ether to obtain Compound 7. The formation was confirmed by NMR and LC-MS. The molecular weight was 420.

[Example 1g] Compound 8 with benzene as the parent core The compound was prepared according to the following process. The reaction was carried out under a nitrogen flow.

A 200L glass-lined reaction vessel connected to a reflux tube was treated, 10kg of 4-aminobenzyl alcohol and 100L of methanol were added, and the mixture was stirred at 220rpm for 1 hour under a nitrogen flow to dissolve. 21kg of iodine was added. 10L of water was added and ice-cooled, and 9.2kg of 30wt% hydrogen peroxide was added dropwise. Thereafter, the mixture was stirred at 24°C and 70rpm for 24 hours. Then, 10L of a 10wt% sodium sulfite aqueous solution was added while stirring at 120rpm, and then 3.5L of pure water was added, and the precipitate formed was recovered by filtration separation. After drying, 5kg of compound 8 was obtained. The formation was confirmed by NMR and LC-MS. The molecular weight was 249.

[Example 1h] Compound 9 with benzene as the parent core The compound was prepared according to the following process. The reaction was carried out under a nitrogen flow.

A 200 L glass-lined reaction vessel connected to a reflux tube was used, and 10 kg of compound (8) and 20 L of methanol were added, and the mixture was stirred at 220 rpm for 1 hour under a nitrogen flow to dissolve. 1.2 aq. of concentrated hydrochloric acid was added and ice-cooled, and 1.1 aq. of a 40 wt% aqueous sodium nitrite solution was added dropwise. Thereafter, the mixture was stirred at 24°C and 70 rpm for 24 hours. Then, an aqueous potassium iodide solution was added at 120 rpm, and 7.0 L of pure water was added, and the precipitate formed was recovered by filtration separation. After drying, 5 kg of compound 9 was obtained. The formation was confirmed by NMR and LC-MS. The molecular weight was 360.

[Example 1i] Compound 10 (1) with benzene as the core The compound was prepared according to the following process. The reaction was carried out under a nitrogen flow.

Using a 200 mL flask connected to a reflux tube, add 760 mg of lithium aluminum hydroxide and 100 mL of superdehydrated THF, and stir at 220 rpm for 1 hour under a nitrogen flow. Further, 10 g of 2,3,5-triiodobenzoic acid is gradually added in 10 portions over 40 minutes. Thereafter, stir at 24°C and 70 rpm for 24 hours. Add 3500 mL of pure water, and filter and separate by filtration to recover the formed precipitate. After drying, 0.4 g of compound 10 (yield 4%) is obtained. The formation is confirmed by NMR and LC-MS. The molecular weight is 486.

[Example 1j] Compound 10 (2) with benzene as the nucleus Except for using sodium borohydride instead of lithium aluminum hydride, 0.1 g of compound 10 was obtained in the same manner as Example 1i (yield: 1%).

[Example 1k] Compound 10 (3) with benzene as the parent core The compound was prepared according to the following process. The reaction was carried out under a nitrogen flow.

[Esterification step] Add 5 g of 2,3,5-triiodobenzoic acid, 50 mL of toluene, and 0.01 mL of dimethylformamide to a flask connected to a reflux tube and ice-cool. Then, add 2.38 g (2.0 equivalents) of sulfinyl chloride dropwise and heat to room temperature. Stir at room temperature for 2 hours, then heat to 60°C and stir for 2 hours. Then, add 3.2 g (10 equivalents) of methanol and react for 2 hours. The reaction solution was concentrated under reduced pressure, 25 mL of water and sodium carbonate were added to make it alkaline, 50 mL of ethyl acetate was added, and after stirring at room temperature for 30 minutes, 25 mL of water was added for separation, the aqueous layer was removed and the organic layer was concentrated, and then hexane was added and filtered and dried to obtain 4.6 g of methyl 2,3,5-triiodobenzoate (yield: 90%). The formation was confirmed by NMR and LC-MS. The molecular weight was 514. [Reduction step] 0.90 g (1.05 equivalents) of calcium chloride and 30 mL of ethanol were added to a container connected to a reflux tube, and 0.64 g (2.2 equivalents) of sodium borohydride was added under ice cooling. Add 4 g of methyl 2,3,5-triiodobenzoate obtained in the above esterification step, stir at room temperature for 1.5 hours, and stir at 40°C for 1.5 hours. After the reaction is completed, add 90 mL of water, and further add hydrochloric acid to adjust the pH to 3-4. Then, add ethyl acetate to extract the organic layer, dehydrate and concentrate, add hexane and filter, wash and dry with chloroform to obtain a crude product of compound 10, and purify the crude product by column chromatography to obtain 3.0 g of compound 10 (yield 80%). Compared with Example 1i, the yield of compound 10 is greatly improved.

[Example 11] Compound 10 (4) with benzene as the nucleus 15 g of 2,3,5-triiodobenzoic acid, 150 mL of toluene, 20 g of methanol (20 equivalents), and 1.8 g of sulfuric acid (0.6 equivalents) were added to a container connected to a reflux tube, and the esterification step of Example 1k was carried out under reflux conditions. After 8 hours, 1.8 g of sulfuric acid (0.6 equivalents) was added and the reaction was carried out for 16 hours. After cooling, the mixture was washed with 100 mL of water, 100 mL of a 10% sodium carbonate aqueous solution was added, and the mixture was further washed with 100 mL of water. After concentration, hexane was added, and the mixture was filtered and dried. By changing the mixture to 7.2 g of methyl 2,3,5-triiodobenzoate (yield 46.7%), 3.2 g of compound 10 (85%) was obtained.

[Example 1m] Compound 10 (5) with benzene as the nucleus In the same manner as Example 1k, lithium chloride was used instead of calcium chloride to obtain 2.1 g of compound 10 (yield 55%).

[Example 1n] Compound 10 (6) with benzene as the nucleus In the same manner as Example 1k, 2 mL of methanol was added without using calcium chloride to obtain 1.4 g of compound 10 (yield 40%).

[Example 1o] Compound 10 (7) with benzene as the nucleus In the same manner as Example 1k, instead of using calcium chloride, lithium aluminum hydride was used instead of sodium borohydride to obtain 0.6 g of compound 10 (yield 15%).

(Synthesis Example L1) [Iodination step]

A 100L glass-lined reaction vessel connected to a reflux tube was used to feed 700g of 4-hydroxybenzaldehyde, 4900ml of methanol, and 1260mL of pure water, and stirred at 220rpm for 1 hour under a nitrogen flow to dissolve. Further, 1590g of sodium bicarbonate was gradually added 10 times within 10 minutes, and 3200g of iodine was gradually added 10 times within 40 minutes. At this time, the liquid temperature rose to 47°C, and foaming was observed. The internal temperature was maintained at 46°C by a hot water bath and stirred for 8 hours. At the time point of stirring for 5 hours, 300g of iodine was added. After that, it was stirred at 24°C and 70rpm for 24 hours. Then, 21 L of 6M hydrochloric acid aqueous solution was added dropwise at 120 rpm over 1 hour, and the mixture was stirred for 30 minutes. Then, 2.3 L of 20 wt% sodium sulfite aqueous solution was added while stirring, and 3.5 L of pure water was further added, and the formed precipitate was recovered by filtration separation. After further rinsing with 2 L of methanol, 4-hydroxy-3,5-diiodobenzaldehyde (1880 g) was obtained with a yield of 87%.

[Protective group introduction step]

Using a 100L glass-lined reaction vessel connected to a reflux tube, 1822g of 4-hydroxy-3,5-diiodobenzaldehyde and 3650mL of dehydrated dimethylformamide (DMF) were added in an ice bath under a nitrogen flow, and stirred with a stirring paddle to dissolve. Then, while stirring in an ice bath, 673g of potassium carbonate (1.0 equivalent relative to the substrate) was added, and further stirred for 60 minutes. Using a dropping funnel, 553g of chloromethyl ethyl ether (1.2 equivalent relative to the substrate) was added dropwise to the stirred reaction solution over 60 minutes, and further stirred in an ice bath for 30 minutes. Then, 7.2 L of pure water was added under ice bath, stirred for 60 minutes, and the formed precipitate was recovered by filtration. The recovered solid was suspended and stirred in 5.8 L of methanol under ice bath for 30 minutes, and then filtered to obtain a white solid (2450 g) of the protected compound as the target. The yield was 99%. The formation was confirmed by NMR and LC-MS. The molecular weight was 432.

[Reset steps]

Using a 20L separable flask, fill it with ethanol (5L) under an ice bath, and gradually add 2450g of the protective body obtained in the previous step and suspend it. Under a nitrogen flow, add 50g of sodium borohydride in batches of 5g each time over 60 minutes while stirring. After further stirring for 1 hour under an ice bath, 842g of a 5% by mass aqueous solution of ammonium chloride was added dropwise over 15 minutes. Under ice cooling, the resulting reaction solution was gradually added to 21L of pure water and stirred for 30 minutes. After filtering and separating the precipitate gradually formed during stirring, it was further rinsed with 5L of pure water. The obtained precipitate was dissolved in 10.5 L of ethyl acetate, and then washed three times with 3.5 L of 10% by mass NaCl aqueous solution. After the obtained ethyl acetate solution was recovered, 200 g of magnesium sulfate was further added and suspended for 30 minutes. The filtrate obtained by filtration separation was concentrated to a concentration of 50% by mass ± 5%, and 9 L of heptane was further added for crystallization. The crystals separated by filtration were further rinsed with cold heptane and dried to obtain 1680 g of compound (1-3) with a yield of 77% and an LC purity of 99.8%. The formation was confirmed by NMR and LC-MS. The molecular weight was 434.

(Synthesis Example L1-1) The obtained precipitate was dissolved in 10.5 L of ethyl acetate, and 50 g of silica gel was added to disperse the silica gel. The organic phase was recovered by filtration. The other operations were the same as those in Synthesis Example L1. 1660 g of compound (1-3) was obtained with a yield of 76% and a high purity of LC purity > 99.9%.

(Synthesis Example L2)

The same [iodination step], [protecting group introduction step], and [reduction step] as those in Synthesis Example L1 were performed except that salicylic aldehyde was used instead of 4-hydroxybenzaldehyde and the iodination step was set to the following iodination step L2 to obtain compound (1-4). The formation was confirmed by NMR and LC-MS. The molecular weight before and after the reduction step changed from 432 to 434.

[Iodination step L2] A 100L glass-lined reaction vessel connected to a reflux tube was used to feed 700g of salicylic aldehyde, 5700ml of ethanol, and 1164g of iodine. The mixture was heated in a water bath at an internal temperature of 40°C under a nitrogen flow, and stirred at 220rpm for 1 hour to dissolve. 2490g of a 20% by mass aqueous iodic acid solution was then slowly added dropwise over 60 minutes. The internal temperature was then raised to 50°C and stirring was continued for 2 hours. Next, 2.3L of a 20wt% aqueous sodium sulfite solution was added while stirring, and then 7.6L of pure water was added, and the formed precipitate was recovered by filtration separation. After further rinsing with 5L of pure water, the product was dried to obtain 2-hydroxy-3,5-diiodobenzaldehyde (2046g) with a yield of 95.5%.

(Synthesis Example L3) Except that vanillin (4-hydroxy-3-methoxybenzaldehyde) was used instead of 4-hydroxybenzaldehyde and the iodination step was set to the following [iodination step L3], the same [iodination step], [protecting group introduction step], and [reduction step] as in Synthesis Example L1 were performed to obtain the target compound (1-5). The formation was confirmed by NMR and LC-MS. The molecular weight before and after the reduction step changed from 336 to 338.

[Iodination step L3] In a 30L glass reaction vessel, add 1300g (8.55mol) of vanillin (4-hydroxy-3-methoxybenzaldehyde) and 5.6L of methanol, blow nitrogen into the reaction vessel at a flow rate of 200mL/min and start stirring. After confirming that the vanillin is dissolved, add 2.6L of ion exchange water and 635g (6mol) of sodium carbonate, and stir at room temperature of 22°C for 3 hours. After adding 2600g (10.3mol) of iodine in batches and stirring at room temperature of 22°C for 20 hours, add 16.6% sodium sulfite aqueous solution until the solution is decolorized and the system reaches alkalinity, add 4.3L of water and stir for 1 hour. The precipitated solid was filtered, rinsed, re-slurried and dried with a suction filter to obtain 1900 g of a white solid. The results of liquid chromatography-mass spectrometry (LC-MS) analysis showed a molecular weight of 278. In addition, when ¹ H-NMR was measured under the above-mentioned measurement conditions, it was confirmed that it had the chemical structure of 4-hydroxy-5-iodo-3-methoxybenzaldehyde. The LC purity at 254 nm was 99.8%, and the GPC purity was 99.9%. The formation was confirmed by NMR and LC-MS. The molecular weight is 338.

(Synthesis Example L4) Except that 1420 g of ethyl vanillin was used instead of 1300 g of vanillin, the same [iodination step], [protecting group introduction step], and [reduction step] as those in Synthesis Example L3 were performed to obtain compound (1-6).

(Synthesis Example L5)

Compound (1-7) was obtained by carrying out the same [iodination step], [protecting group introduction step] and [reduction step] as in Synthesis Example L1 except that 3-hydroxybenzaldehyde was used instead of 4-hydroxybenzaldehyde.

[Iodination step] Use a 100L glass-lined reaction vessel connected to a reflux tube, add 700g of 3-hydroxybenzaldehyde, 4900ml of methanol, and 1260mL of pure water, and stir at 220rpm for 1 hour under a nitrogen flow to dissolve. Further, after gradually adding 730g of sodium bicarbonate in 10 times over 10 minutes, 1480g of iodine was gradually added in 10 times over 40 minutes. At this time, the liquid temperature rose to 47°C and foaming was observed. Stir for 8 hours while maintaining the internal temperature at 46°C in a hot water bath. At the time point of stirring for 5 hours, add 300g of iodine. Thereafter, stir for 24 hours at 24°C and 70rpm. Then, 21L of 6M hydrochloric acid aqueous solution was added dropwise at 120rpm within 1 hour, and the mixture was stirred for 30 minutes. Then, 2.3L of 20wt% sodium sulfite aqueous solution was added while stirring, and 3.5L of pure water was further added, and the formed precipitate was recovered by filtration separation. After further rinsing with 2L of methanol, 3-hydroxy-4-iodobenzaldehyde (1237g) was obtained, with a yield of 86%.

[Protective group introduction step] Using a 100L glass-lined reaction vessel connected to a reflux tube, 1237g of 3-hydroxy-4-iodobenzaldehyde and 3650mL of dehydrated dimethylformamide (DMF) were added in an ice bath under a nitrogen flow, and stirred with a stirring paddle to dissolve. Then, while stirring in an ice bath, 689g of potassium carbonate (1.0 equivalent relative to the substrate) was added, and further stirred for 60 minutes. Using a dropping funnel, 565g of chloromethyl ethyl ether (1.2 equivalent relative to the substrate) was added dropwise to the stirred reaction solution over 60 minutes, and further stirred in an ice bath for 30 minutes. Then, 7.2 L of pure water was added under ice bath, stirred for 60 minutes, and the formed precipitate was recovered by filtration. The recovered solid was suspended and stirred in 5.8 L of methanol under ice bath for 30 minutes, and then filtered to obtain a white solid (1511 g) as the protective body of the target. The yield was 99%. The formation was confirmed by NMR and LC-MS. The molecular weight was 306.

[Reduction step] Use a 20L separable flask, fill it with ethanol (5L) under ice bath, and gradually add 1511g of the protective body obtained in the previous step and suspend it. Under nitrogen flow, add 50g of sodium borohydride in batches of 5g each time over 60 minutes while stirring. After further stirring for 1 hour under ice bath, 842g of 5% by mass ammonium chloride aqueous solution is added dropwise over 15 minutes. Under ice cooling, the obtained reaction solution is gradually added to 21L of pure water and stirred for 30 minutes. After filtering and separating the precipitate gradually formed during stirring, it is further rinsed with 5L of pure water. The obtained precipitate was dissolved in 10.5 L of ethyl acetate and then washed three times with 3.5 L of 10% by mass NaCl aqueous solution. After the obtained ethyl acetate solution was recovered, 200 g of magnesium sulfate was further added and suspended for 30 minutes. The filtrate obtained by filtration separation was concentrated to a concentration of 50% by mass ± 5% and further added with 9 L of heptane for crystallization. The crystals separated by filtration were further rinsed with cold heptane and dried to obtain 1171 g of compound (1-7) with a yield of 77% and an LC purity of 99.8%. The formation was confirmed by NMR and LC-MS. The molecular weight changed from 306 to 308 before and after the reduction step.

(Synthesis Example L6) Using 3,4-dihydroxybenzaldehyde as a raw material, the protective group introduction step of Synthesis Example L3 was carried out. However, the amount of diisopropylmethylamine and chloromethyl ethyl ether was set to 2 times the amount of 3,4-dihydroxybenzaldehyde. Then, the following [iodination step L6] was carried out. Then, the [reduction step] was carried out in the same manner as Synthesis Example L3 to obtain compound (1-8). The formation was confirmed by NMR and LC-MS. The molecular weight before and after the reduction step changed from 380 to 382.

[Iodination step L6]

In a 30L glass reaction vessel, 2172g (8.55mol) of 3,4-diethoxymethoxybenzaldehyde and 5.6L of methanol as raw materials were added, and nitrogen was blown into the reaction vessel at a flow rate of 200mL/min and stirring was started. After confirming that the raw materials were dissolved, 2.6L of ion exchange water and 634g (5.99mol) of sodium carbonate were added, and stirring was carried out at room temperature of 22°C for 3 hours. Then, 2609g (10.3mol) of iodine was added, and the reaction vessel was stirred at room temperature of 22°C for 12 hours, and then a 16.6% sodium sulfite aqueous solution was added until the solution decolorized, and 4.3L of water was added and stirred for 1 hour. The precipitated solid was filtered, rinsed, re-slurried and dried with a suction filter to obtain 2438 g of a white solid. The results of liquid chromatography-mass spectrometry (LC-MS) analysis showed a molecular weight of 380. In addition, when ¹ H-NMR was measured under the above-mentioned measurement conditions, it was confirmed that it had a chemical structure of 3,4-diethoxymethoxy-5-iodobenzaldehyde. The LC purity at 254 nm was 99.5%, and the GPC purity was 99.9%.

(Synthesis Example L7) Using 2,4,6-trihydroxybenzaldehyde as a raw material, the protective group introduction step of Synthesis Example L3 was carried out. However, the amount of diisopropylmethylamine and chloromethyl ethyl ether was set to 3 times the amount of 2,4,6-trihydroxybenzaldehyde. Then, the same [iodination step] as Synthesis Example L3 was carried out. Next, the [reduction step] was carried out in the same manner as Synthesis Example L3 to obtain compound (1-9). The formation was confirmed by NMR and LC-MS. The molecular weight before and after the reduction step changed from 580 to 582.

(Synthesis Example L8) Using 3,5-dihydroxybenzaldehyde as a raw material, the protective group introduction step of Synthesis Example L3 was carried out. However, the amount of diisopropylmethylamine and chloromethyl ethyl ether was set to 2 times the amount of 3,5-dihydroxybenzaldehyde. Then, the same [iodination step] as Synthesis Example L3 was carried out. Next, the [reduction step] was carried out in the same manner as Synthesis Example L3 to obtain compound (1-10). The formation was confirmed by NMR and LC-MS. The molecular weight before and after the reduction step changed from 380 to 382.

(Synthesis Example BPL1) [Protective group introduction step BPL1P]

Using a 100L glass-lined reaction vessel connected to a reflux tube, 700g of 4-hydroxybenzaldehyde and 3650mL of dehydrated dimethylformamide (DMF) were added in an ice bath under a nitrogen flow, and stirred with a stirring paddle to dissolve. Then, while stirring in an ice bath, 822g of diisopropylethylamine was added dropwise with a dropping funnel over 30 minutes, and further stirred for 60 minutes. 553g of chloromethylethyl ether (1.2 equivalents relative to the substrate) was added dropwise to the stirred reaction solution using a dropping funnel over 60 minutes, and further stirred for 30 minutes in an ice bath. Then, 7.2 L of pure water was added under ice bath, stirred for 60 minutes, and the formed precipitate was recovered by filtration. The recovered solid was suspended and stirred in 5.8 L of methanol under ice bath for 30 minutes, and then separated by filtration to obtain the target compound (BPL1P) (1012 g) as a white solid. The yield was 98%. The formation was confirmed by NMR and LC-MS. The molecular weight was 180.

[Reset step BPL1R]

Using a separable flask of 20L, fill it with ethanol (5L) under an ice bath, and gradually add 1012g of the protective body BPL1P obtained in the previous step and suspend it. Under a nitrogen flow, add 50g of sodium borohydride in batches at a rate of 5g each time over 60 minutes while stirring. After further stirring under an ice bath for 1 hour, 842g of a 5% by mass aqueous solution of ammonium chloride was added dropwise over 15 minutes. Under ice cooling, the resulting reaction solution was gradually added to 21L of pure water and stirred for 30 minutes. After filtering and separating the precipitate gradually formed during stirring, it was further rinsed with 5L of pure water. The obtained precipitate was dissolved in 10.5 L of ethyl acetate, and then washed three times with 3.5 L of 10% by mass NaCl aqueous solution. After the obtained ethyl acetate solution was recovered, 200 g of magnesium sulfate was further added and suspended for 30 minutes. The filtrate obtained by filtration separation was concentrated to a concentration of 50% by mass ± 5%, and 9 L of heptane was further added for crystallization. The crystals separated by filtration were further rinsed with cold heptane and dried to obtain compound (BPL1R) (716 g) with a yield of 70% and a purity of 99.6%. The formation was confirmed by NMR and LC-MS. The molecular weight is 182.

(Synthesis Example BPL1b) After THF was added to 4-hydroxybenzyl alcohol and stirred to dissolve, phosgene (2 equivalents relative to the raw material, 20% toluene solution, manufactured by Merck) was added dropwise under nitrogen atmosphere and ice-cooling, and further stirred for 2 hours under ice-cooling. Stirring was further performed at 25°C for 12 hours. Then, nitrogen was bubbled for 2 hours, and then the carbonate body (1be0) was obtained by reduced pressure concentration. The obtained carbonate body (1be0) was placed in chloroform and stirred to dissolve under ice-cooling. 1-Methylcyclopentanol (1.2 equivalents relative to the aforementioned (1be0)) was further added dropwise under ice-cooling and stirred. Pyridine (1.2 equivalents relative to the aforementioned (1be0)) was further added dropwise under ice-cooling and stirred. After stirring for 1 hour, stir at 25°C for 12 hours. Then, add ion-exchange water and recover the organic phase. The obtained organic phase is washed with 5% baking soda water, washed with ion-exchange water 5 times, and concentrated under reduced pressure to obtain compound (BPL1b). The formation is confirmed by NMR and LC-MS. The molecular weight is 250.

(Synthesis Example BPL2) (BPL2P) and (BPL2R) were synthesized in the same manner as Synthesis Examples BPL1-4 except that salicylic aldehyde was used instead of 4-hydroxybenzaldehyde as a raw material. The formation of (BPL2R) was confirmed by NMR and LC-MS. The molecular weight was 182.

(Synthesis Example BPL3) (BPL3P) and (BPL3R) were obtained in the same manner as Synthesis Example BPL1 except that 3-hydroxybenzaldehyde was used as the raw material. The formation of (BPL3R) was confirmed by NMR and LC-MS. The molecular weight was 182.

(Synthesis Example DML1) [Iodination Step DML1D]

A 100L stainless steel reaction vessel connected to a reflux tube was used, 700g of 4-hydroxybenzaldehyde and 4900ml of methanol were added, and stirred at 220rpm for 1 hour under a nitrogen flow to dissolve. The reaction vessel was ice-cooled, and a sodium hydroxide aqueous solution prepared by dissolving 757g of sodium hydroxide in 1260mL of pure water was gradually added to the reaction vessel, and 3200g of iodine was gradually added in 10 portions over 60 minutes. The internal temperature was maintained at 60°C by a hot water bath and stirred for 8 hours. Then, 21L of a 6M hydrochloric acid aqueous solution was added dropwise at 120rpm under ice-cooling over 1 hour, and stirred for 30 minutes. Next, 2.3 L of a 20 wt% sodium sulfite aqueous solution was added while stirring, and then 3.5 L of pure water was added, and the precipitate formed was recovered by filtration separation. The obtained solid was purified by column chromatography using silica gel, thereby obtaining DML1D (840 g) with a yield of 30%. The formation was confirmed by NMR and LC-MS. The molecular weight was 494.

[Protective group introduction step DML1P]

Using a 100L glass-lined reaction vessel connected to a reflux tube, 840g of DML1D and 1680mL of dehydrated dimethylformamide (DMF) were added in an ice bath under a nitrogen flow, and stirred with a stirring paddle to dissolve. Then, while stirring in an ice bath, 380g of diisopropylethylamine was added with a dropping funnel over 30 minutes, and further stirred for 60 minutes. 255g of chloromethylethyl ether (1.2 equivalents relative to the substrate) was added dropwise to the stirred reaction solution over 60 minutes using a dropping funnel, and further stirred for 30 minutes in an ice bath. Then, 7.2 L of pure water was added under ice bath, stirred for 60 minutes, and the formed precipitate was recovered by filtration. The recovered solid was suspended and stirred in 5.8 L of methanol under ice bath for 30 minutes, and then separated by filtration to obtain 996 g of the target protected compound DML1P as a white solid. The yield was 96%. The formation was confirmed by NMR and LC-MS. The molecular weight was 610.

[Reset step DML1R]

Using a separable flask of 20L, fill it with ethanol (5L) under an ice bath, and gradually add 996g of the prepared protective body DML1P body and suspend it. Under a nitrogen flow, add 19g of sodium borohydride in batches of 3g each time over 60 minutes while stirring. After further stirring for 1 hour under an ice bath, 350g of a 5wt% ammonium chloride aqueous solution is added dropwise over 15 minutes. Under ice cooling, the resulting reaction solution is gradually added to 8L of pure water and stirred for 30 minutes. After filtering and separating the precipitate gradually formed during stirring, it is further rinsed with 2L of pure water. The obtained precipitate was dissolved in 4L of ethyl acetate, and then washed three times with 1.5L of 10wt% NaCl aqueous solution. After the obtained ethyl acetate solution was recovered, 80g of magnesium sulfate was further added and suspended for 30 minutes. The filtrate obtained by filtration separation was concentrated to a concentration of 50wt%±5%, and 9L of heptane was further added for crystallization. The crystals separated by filtration were further rinsed with cold heptane and dried to obtain 701g of compound DML1R with a yield of 70% and a purity of 99.2%. The formation was confirmed by NMR and LC-MS. The molecular weight is 614.

(Synthesis Example DML2R)

DML2R was synthesized in the same manner as in Synthesis Example DML1 except that 4-hydroxybenzaldehyde was used as a raw material, the type of protective agent was changed to ethyl vinyl ether, and the [Protective Group Introduction Step] was changed to the method described below. The formation of DML2R was confirmed by NMR and LC-MS. The molecular weight was 642.

[Protective group introduction step] Using a 100L glass-lined reaction vessel connected to a reflux tube, 840g of DML1D body and 1680mL of dehydrated tetrahydrofuran (THF) were added in an ice bath under a nitrogen flow, and stirred with a stirring paddle to dissolve. Then, while stirring in an ice bath, 80g of PPTS (pyridinium salt-p-toluenesulfonic acid) was added over 30 minutes, and further stirred for 60 minutes. 294g of ethyl vinyl ether (1.2 equivalents relative to the functional group equivalent) was added dropwise to the stirred reaction solution over 60 minutes, and further stirred at 35°C for 60 minutes. Then, 7.2 L of pure water was added under ice bath, and after stirring for 60 minutes, 2 L of ethyl acetate and 5 L of pure water were added to the recovered organic phase and stirred. The organic phase was recovered and concentrated under reduced pressure to obtain 833 g of white solid of the target protected substance DML2P. The yield was 81%. The formation was confirmed by NMR and LC-MS. The molecular weight was 638.

(Synthesis Example DML3R) DML3R was synthesized in the same manner as Synthesis Example DML2 except that 4-hydroxybenzaldehyde was used as a raw material, the type of protective agent was set to 3,4-dihydropyran, and the [Protective Group Introduction Step] was changed to the method described below. The formation was confirmed by NMR and LC-MS. The molecular weight was 666.

(Synthesis Example DML4R) DML4R was synthesized in the same manner as Synthesis Example DML1 except that 4-hydroxybenzaldehyde was used as a raw material, the type of protective agent was set to 3,4-dihydropyran, and the [Protective Group Introduction Step] was changed to the method described below. The formation was confirmed by NMR and LC-MS. The molecular weight was 698.

[Protective group introduction step] Using a 100L glass-lined reaction vessel connected to a reflux tube, 840g of DML1D body and 1680mL of dehydrated tetrahydrofuran (THF) were added in an ice bath under a nitrogen flow, and stirred with a stirring paddle to dissolve. Then, while stirring in an ice bath, 10g of DMAP (dimethylaminopyridine) (0.05 equivalents relative to the substrate) was added within 10 minutes, and further stirred for 30 minutes. 890g of di-tert-butyl dicarbonate (1.2 equivalents relative to the functional group equivalents) was added dropwise to the stirred reaction solution within 60 minutes, and further stirred for 120 minutes under ice cooling. After confirming the disappearance of the raw material by TLC (thin layer chromatography), add 1000 mL of n-heptane while cooling, and while confirming that the internal temperature is below 10°C under ice cooling, add 2800 mL of 1N hydrochloric acid dropwise, and stir for 30 minutes. After recovering the upper organic phase, wash it with 7 L of 5% baking soda water (once) and 7 L of ion exchange water (three times), add 50 g of silica gel to disperse it, and recover the organic phase by filtration. After adding 200 ppm of MQ (methylquinone) to the matrix, push out and concentrate it with n-heptane (40°C), and confirm that no THF flows out. After that, high-purity IPA (Kanto Chemical EL-IPA) was used for further push out and concentration. After further adding high-purity IPA to dissolve until the target substance was dissolved at 40°C, an equal amount of ion exchange water as IPA was added dropwise, and crystallization was further performed by ice cooling for about 1 hour to recover the target substance. 811g of white solid of the target protected body DML4P was obtained. The yield was 69%. The formation was confirmed by NMR and LC-MS. The molecular weight was 694.

(Synthesis Example DML5R) DML5R was synthesized in the same manner as Synthesis Example DML1 except that 3-hydroxybenzaldehyde was used as a raw material. The formation was confirmed by NMR and LC-MS. The molecular weight was 614.

(Synthesis Example DML6R) DML6R was synthesized in the same manner as Synthesis Example DML1 except that vanillin was used as a raw material. The formation was confirmed by NMR and LC-MS. The molecular weight was 674.

(Synthesis Example DML7R) DML7 was synthesized in the same manner as Synthesis Example DML1 except that 3,4-dihydroxybenzaldehyde was used as a raw material. However, in the step of introducing the protecting group, the amount of diisopropylmethylamine and chloromethyl ethyl ether was set to 2 times that of 3,4-dihydroxybenzaldehyde as a raw material. The formation was confirmed by NMR and LC-MS. The molecular weight was 762.

(Synthesis Example DML8R) DML8R was synthesized in the same manner as Synthesis Example DML1 except that ethyl vanillin was used as a raw material. The formation was confirmed by NMR and LC-MS. The molecular weight was 702.

(Synthesis Example DML9R) DML9R was synthesized in the same manner as Synthesis Example DML1 except that 2-hydroxybenzaldehyde was used as the raw material. The formation was confirmed by NMR and LC-MS. The molecular weight was 614.

(Synthesis Example DML10R) The compound was produced according to the following process. The reaction was carried out under a nitrogen flow to obtain DML10R. The formation was confirmed by NMR and LC-MS. The molecular weight was 496.

A 200L glass-lined reaction vessel connected to a reflux tube was treated, 10kg of 4-aminobenzyl alcohol and 100L of methanol were added, and the mixture was stirred at 220rpm for 1 hour under a nitrogen flow to dissolve. 21kg of iodine was added. 10L of water was added and ice-cooled, and 9.2kg of 30wt% hydrogen peroxide was added dropwise. Thereafter, the mixture was stirred at 24°C and 70rpm for 24 hours. Then, 10L of a 10wt% sodium sulfite aqueous solution was added while stirring at 120rpm, and then 3.5L of pure water was added, and the formed precipitate was recovered by filtration separation. The obtained solid was purified by column chromatography using silica gel to obtain 1kg of DML10R.

(Synthesis Example DML11R) The compound was prepared according to the following process. The reaction was carried out under a nitrogen flow to obtain DML11R. The formation was confirmed by NMR and LC-MS. The molecular weight was 718.

A 200L glass-lined treatment reaction vessel connected to a reflux tube was used, and 10kg of DML10R and 20L of methanol were added, and stirred at 220rpm for 1 hour under a nitrogen flow to dissolve. 1.2aq. of concentrated hydrochloric acid was added, ice-cooled, and 1.1aq. of 40wt% sodium nitrite aqueous solution was added dropwise. Thereafter, stirring was performed at 24°C and 70rpm for 24 hours. Then, potassium iodide aqueous solution was added at 120rpm, and 7.0L of pure water was further added, and the formed precipitate was recovered by filtration separation. After drying, 4kg of DML11R was obtained.

(Synthesis Example DML1e) Using the compound (1-4) obtained in Synthesis Example L2, the [reduction step] of Synthesis Example L1 was carried out to obtain compound (1-4a). The formation was confirmed by NMR and LC-MS. The molecular weight was 376. In a 200 mL container connected to a reflux tube, 5 g (13.3 mmol) of the obtained compound (1-4a) and 100 mL of toluene were added, and the reaction was carried out under reflux conditions for 1 hour. The mixture was separated by column chromatography to obtain 0.4 g (0.55 mmol) of compound 1-4b. The formation was confirmed by NMR and LC-MS. The molecular weight was 734. Next, using compound 1-4b, the [protecting group introduction step] of Synthesis Example L1 was carried out to obtain compound (DML1e). The formation was confirmed by NMR and LC-MS. The molecular weight is 850.

[Example 2] Compounds using naphthalene as the parent nucleus The compound was produced according to the following process. The reaction was carried out under a nitrogen flow.

(Synthesis of Compound 2-2) Into a flask equipped with a stirrer and a cooling tube, add 50 g of Compound 2-1 (manufactured by FUJIFILM Wako Pure Chemical Corporation), 600 mL of ethanol, and 2.8 mL of 98% sulfuric acid (0.2 equivalents relative to Compound 2-1). Stir the contents under reflux for 14 hours to carry out the esterification reaction. Then, neutralize with 10.6 g of sodium bicarbonate (a reagent manufactured by FUJIFILM Wako Pure Chemical Corporation) and distill off the ethanol, then add ethyl acetate and water to extract the organic phase, wash with sodium bicarbonate, dehydrate with sodium sulfate, distill off the solvent, and perform suspension washing and drying with acetone to obtain Compound 2-2. The yield is 64%.

(Synthesis of Compound 2-3) Into a flask equipped with a stirrer and a cooling tube, add 34 g of Compound 2-2, 48 g (1.2 equivalents relative to Compound 2-2) of iodine, 20 g of sodium bicarbonate, 160 mL of methanol, and 16 mL of water. Stir the contents at room temperature for 5 hours to carry out the iodination reaction. Then, add 50 mL of methanol, add sodium bisulfite until the color of iodine disappears, filter, wash with water, and then suspend and wash with methanol, filter and dry to obtain Compound 2-3. The yield is 97%. The formation is confirmed by NMR and LC-MS. The molecular weight is 342.

(Synthesis of compound 2-4) Immerse a flask equipped with a stirrer and a cooling tube in an ice water bath, add 50 g of compound 2-3 and 150 mL of acetone into the flask and stir. The internal temperature at this time is 4°C. Then, 20.8 g (1.1 equivalents relative to compound 2-3) of diisopropylethylamine is added dropwise to the flask. After the addition of diisopropylethylamine is completed, 14.7 g of chloromethyl ethyl ether is added dropwise and the reaction is carried out for 1 hour. After the reaction is completed, 300 g of ethyl acetate and 500 g of water are added and the organic phase is extracted. The solvent of the extracted organic phase is distilled off and separated by column chromatography to obtain compound 2-4. The yield is 70%. The formation is confirmed by NMR and LC-MS. The molecular weight is 400.

(Synthesis of Na-1) Except for using 6,7,8-trimethoxynaphthalene-2-carboxaldehyde instead of 4-hydroxybenzaldehyde, the iodination step and reduction step were carried out in the same manner as in Synthesis Example L1 to obtain compound Na-1. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight changed from 372 to 374 before and after the reduction step.

(Synthesis of Na-2) Compound Na-2 was obtained in the same manner as in Synthesis Example L1 except that 2-hydroxy-1-naphthaldehyde was used instead of 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of (Na-2-1) was 298. In addition, the molecular weight changed from 356 to 358 before and after the reduction step to generate (Na-2).

(Synthesis of Na-3) Compound Na-3 was obtained in the same manner as in Synthesis Example L1 except that 2-hydroxynaphthalene-6-carboxaldehyde was used instead of 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of (Na-3-1) was 298. In addition, the molecular weight changed from 356 to 358 before and after the reduction step to generate (Na-3).

(Synthesis of Na-4) Compound Na-4-3 was obtained in the same manner as Example 2 except that 3-hydroxy-2-naphthoic acid was used instead of compound 2-1. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of (Na-4-2) was 342, and the molecular weight of (Na-4-3) was 400.

(Synthesis of Na-5) Compound Na-5 was obtained in the same manner as in Synthesis Example L1 except that 1-hydroxy-2-naphthaldehyde was used instead of 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight changed from 356 to 358 before and after the reduction step to generate (Na-5).

(Synthesis of Na-6) Compound Na-6 was obtained in the same manner as in Synthesis Example L1 except that 4-hydroxy-2-naphthaldehyde was used instead of 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight changed from 356 to 358 before and after the reduction step to generate (Na-6).

(Synthesis of Na-7) Compound Na-7 was obtained in the same manner as in Synthesis Example L1 except that 4-hydroxy-2-naphthaldehyde was used instead of 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight changed from 356 to 358 before and after the reduction step to generate (Na-7).

(Synthesis of Na-8) Compound Na-8 was obtained in the same manner as in Synthesis Example L1 except that 4-hydroxy-1-naphthaldehyde was used instead of 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight changed from 356 to 358 before and after the reduction step to generate (Na-8).

(Synthesis of Na-9) Compound Na-9 was obtained in the same manner as in Synthesis Example L1 except that 5-hydroxy-2-naphthaldehyde was used instead of 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight changed from 356 to 358 before and after the reduction step to generate (Na-9).

(Synthesis of Na-10) Compound Na-10 was obtained in the same manner as in Synthesis Example L1 except that 8-hydroxy-2-naphthaldehyde was used instead of 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight changed from 356 to 358 before and after the reduction step to generate (Na-10).

(Synthesis of Na-11) Compound Na-11 was obtained in the same manner as in Synthesis Example L1 except that 8-hydroxy-1-naphthaldehyde was used instead of 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight changed from 356 to 358 before and after the reduction step to generate (Na-11).

(Synthesis of Na-12) Compound Na-12 was obtained in the same manner as Example 2 (Synthesis of Compound 2-4), except that 1-hydroxy-2-naphthalenecarboxylic acid was used instead of compound 2-1. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of the generated (Na-12) was changed from 342 to 400 by introducing a protecting group.

(Synthesis of Na-13) Compound Na-13 was obtained in the same manner as Example 2 (Synthesis of Compound 2-4), except that 4-hydroxy-2-naphthalenecarboxylic acid was used instead of Compound 2-1. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of the generated (Na-13) was changed from 342 to 400 by introducing a protecting group.

(Synthesis of Na-14) Compound Na-14 was obtained in the same manner as Example 2 (Synthesis of Compound 2-4) except that 4-hydroxy-2-naphthalenecarboxylic acid was used instead of Compound 2-1. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of the generated (Na-14) was changed from 342 to 400 by introducing a protecting group.

(Synthesis of Na-15) Compound Na-15 was obtained in the same manner as Example 2 (Synthesis of Compound 2-4) except that 5-hydroxy-1-naphthalenecarboxylic acid was used instead of Compound 2-1. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of the generated (Na-15) was changed from 342 to 400 by introducing a protecting group.

(Synthesis of Na-16) Compound Na-16 was obtained in the same manner as Example 2 (Synthesis of Compound 2-4) except that 5-hydroxy-2-naphthalenecarboxylic acid was used instead of Compound 2-1. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of the generated (Na-16) was changed from 342 to 400 by introducing a protecting group.

(Synthesis of Na-17) Compound Na-17 was obtained in the same manner as Example 2 (Synthesis of Compound 2-4) except that 8-hydroxy-2-naphthalenecarboxylic acid was used instead of compound 2-1. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of the generated (Na-17) was changed from 342 to 400 by introducing a protecting group.

(Synthesis of Na-18) Compound Na-18 was obtained in the same manner as Example 2 (Synthesis of Compound 2-4) except that 8-hydroxy-1-naphthalenecarboxylic acid was used instead of compound 2-1. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of the generated (Na-18) was changed from 342 to 400 by introducing a protecting group.

(Synthesis of Na-19) Compound Na-19 was obtained in the same manner as in Synthesis Example L1 except that 6-hydroxy-2-naphthaldehyde was used instead of 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight changed from 356 to 358 before and after the reduction step to generate (Na-19).

[Synthesis Example DMN2-3P] The following reaction was carried out.

(Synthesis of Compound 2-2) Compound 2-2 was obtained by the same method as Example 2. The formation was confirmed by NMR and LC-MS. The molecular weight was 216.

(Synthesis of compound DMN2-3) Into a flask equipped with a stirrer and a cooling tube, add 34 g of compound 2-2, 48 g (1.2 equivalents relative to compound 2-2) of iodine, 10 g of sodium bicarbonate, 160 mL of methanol, and 16 mL of water. Stir the contents at 40°C for 5 hours to carry out the iodination reaction. Then, add 50 mL of methanol, add sodium bisulfite until the iodine color disappears, filter, wash with water, and then suspend and wash with methanol, filter and dry to obtain compound DMN2-3. The formation was confirmed by NMR and LC-MS. The molecular weight is 682.

(Synthesis of compound DMN2-3P) Immerse a flask equipped with a stirrer and a cooling tube in an ice water bath, add 50 g of compound DMN2-3 and 150 mL of acetone into the flask and stir. The internal temperature at this time is 4°C. Then, add 20.8 g (1.1 equivalents relative to DMN2-3) of diisopropylethylamine dropwise into the flask. After the addition of diisopropylethylamine is complete, add 14.7 g of chloromethyl ethyl ether dropwise and react for 1 hour. After the reaction is complete, add 300 g of ethyl acetate and 500 g of water and extract the organic phase. Distill off the solvent of the extracted organic phase, separate by column chromatography, and obtain compound DMN2-3P. The formation was confirmed by NMR and LC-MS. The molecular weight is 798.

[Synthesis Example BPN2-3P] The following reaction was carried out.

(Synthesis of Compound 2-2) Compound 2-2 was obtained by the same method as Example 2.

(Synthesis of compound BPN2-3P) Immerse a flask equipped with a stirrer and a cooling tube in an ice water bath, add 15.8 g of compound 2-2 and 150 mL of acetone into the flask and stir. The internal temperature at this time is 4°C. Then, 20.8 g (1.1 equivalents relative to compound 2-2) of diisopropylethylamine is added dropwise to the flask. After the addition of diisopropylethylamine is completed, 14.7 g of chloromethyl ethyl ether is added dropwise and the reaction is carried out for 1 hour. After the reaction is completed, 300 g of ethyl acetate and 500 g of water are added and the organic phase is extracted. The solvent of the extracted organic phase is distilled off and separated by column chromatography to obtain compound BPN2-3P. The formation is confirmed by NMR and LC-MS. The molecular weight is 274.

(Synthesis of DMNa-1-1) Compound DMNa-1-1 was synthesized in the same manner as in Synthesis Example DMN2-3 except that 6,7,8-trimethoxynaphthalene-2-carboxaldehyde was used instead of compound 2-2. The formation was confirmed by NMR and LC-MS. The molecular weight was 744.

[Synthesis Example DMNa2-1R] Compound DMNa-2-1 was synthesized in the same manner as Synthesis Example DMN2-3, except that 2-hydroxy-3-naphthaldehyde was used instead of compound 2-2. The formation was confirmed by NMR and LC-MS. The molecular weight was 594. Next, compound DMNa2-1P was synthesized in the same manner as the synthesis of compound DMN2-3P, except that compound DMNa-2-1 was used instead of compound DMN2-3. The formation was confirmed by NMR and LC-MS. The molecular weight was 710. Further, compound DMNa-2-1R was obtained in the same manner as the synthesis of compound 1-3, except that compound DMNa2-1P was used instead of compound 1-2. The formation was confirmed by NMR and LC-MS. The molecular weight was 714.

[Synthesis Example BPNa2-1R] Compound BPNa2-1P was obtained in the same manner as compound DMN2-3P except that 2-hydroxy-3-naphthaldehyde was used instead of compound DMN2-3. The formation was confirmed by NMR and LC-MS. The molecular weight was 230. Furthermore, compound BPNa-2-1R was obtained in the same manner as compound 1-3 except that compound BPNa2-1P was used instead of compound 1-2. The formation was confirmed by NMR and LC-MS. The molecular weight was 232.

(Synthesis of compound DMNa-3-1R) Compound DMNa-3-1 was obtained in the same manner as in the synthesis example DMN2-3 except that 2-hydroxynaphthalene-6-carboxaldehyde was used instead of compound 2-2. The formation was confirmed by NMR and LC-MS. The molecular weight was 594. Next, compound DMNa3-1P was obtained in the same manner as in the synthesis of compound DMN2-3P except that compound DMNa-3-1 was used instead of compound DMN2-3. The formation was confirmed by NMR and LC-MS. The molecular weight was 710. Further, compound DMNa-3-1R was obtained in the same manner as in the synthesis of compound 1-3 except that compound DMNa3-1P was used instead of compound 1-2. The formation was confirmed by NMR and LC-MS. The molecular weight was 714.

[Synthesis Example DMNa-2b-1R] The following reaction was performed.

Compound DMNa-2b-1 was obtained in the same manner as the iodination step DML1D except that 2-hydroxy-3-naphthaldehyde was used instead of 4-hydroxybenzaldehyde. The formation was confirmed by NMR and LC-MS. The molecular weight was 594. Next, compound Na-2b-1P was obtained in the same manner as the protecting group introduction step DML1P except that compound DMNa-2b-1 was used instead of 5-iodovanillin. The formation was confirmed by NMR and LC-MS. The molecular weight was 710. Further, compound DMNa-2b-1R was obtained in the same manner as the reduction step DML1R except that compound DMNa-2b-1P was used instead of DML1P. The formation was confirmed by NMR and LC-MS. The molecular weight was 714.

[Synthesis Example: Synthesis of DMNa-3-2R] The following reaction was performed.

The iodination step, the protective group introduction step, and the reduction step were carried out in the same manner as in Synthesis Example DMNa-2-1, except that 2-hydroxynaphthalene-6-carboxaldehyde was used instead of 2-hydroxy-3-naphthaldehyde as the raw material to obtain compound DMNa-3-2R. The formation was confirmed by NMR and LC-MS. The molecular weight was 714.

(Synthesis of DMNa-4-2P) Compound Na-4-1 was obtained in the same manner as the synthesis of compound 2-2, except that 3-hydroxy-2-naphthoic acid was used instead of compound 2-1. Next, compound DMNa-4-2 was obtained in the same manner as the iodination step in Synthesis Example DMNa-2-1, except that compound Na-4-1 was used instead of compound 2-2. The formation was confirmed by NMR and LC-MS. The molecular weight was 682. Further, the compound was subjected to the same protective group introduction step as in Synthesis Example DMNa-2-1 to obtain compound DMNa-4-2P. The formation was confirmed by NMR and LC-MS. The molecular weight was 798.

[Example 3] Compounds using adamantane as a parent core (Synthesis 1 of Compound 3-2) The compound was prepared according to the following process.

A flask equipped with a stirrer and a cooling tube was immersed in an oil bath, and 80 g of compound 3-1 (manufactured by Mitsubishi Gas Chemical Co., Ltd., 0.43 mol) and 2.5 L of toluene were added to the flask and stirred. Next, 400 g (1.72 mol) of a 55% aqueous hydrogen iodide solution was added to the flask. The internal temperature was set at 83-89°C and the reaction was carried out for 32 hours. Furthermore, 50 g of a 55% aqueous hydrogen iodide solution was added to the flask. The internal temperature was set at 83-89°C and the reaction was carried out for 16 hours.

In another container, add 22.5 mL of 10% sodium sulfite aqueous solution and 1720 mL of water, and then slowly inject the above reaction solution. When 2 g of sodium sulfite and 1 L of ethyl acetate are further added, separate the organic phase from the aqueous phase. Further add water and separate the liquid to obtain an organic phase (oil phase). Concentrate the organic phase, add 500 mL of toluene, and place in a refrigerator overnight.

The organic phase was filtered and washed with cold toluene and hexane to obtain 145 g of a wet cake. The wet cake was dried under reduced pressure at 40°C for 2.5 hours to obtain 138 g of light red crystals. Then, the crystals were mixed with 1.3 L of ethyl acetate and heated to 70°C to dissolve. The ethyl acetate solution was cooled to room temperature. 650 mL of 0.5% sodium sulfite aqueous solution was added to the liquid, stirred, separated, and the ethyl acetate phase was taken out.

Add 650 mL of water to the ethyl acetate phase, stir and separate. Take out the ethyl acetate phase again, add magnesium sulfate and stir for 30 minutes, and leave it in the refrigerator for two nights. Since crystals will precipitate after standing, heat to dissolve them and cool them to room temperature again. Filter the cooled mixture to obtain magnesium sulfate and filtrate. At this time, wash the magnesium sulfate with ethyl acetate. The obtained filtrate is concentrated and further dried at 40°C under reduced pressure for 9 hours to obtain 128 g of white crystals of compound 3-2 with a purity of 99.2% (yield of 72%). The formation was confirmed by NMR and LC-MS. The molecular weight is 404. At the time point when the reflux reaction was completed, the yield of the compound 3-1 in which only one hydroxyl group was converted to iodine was less than 1%, and the yield of the compound in which three hydroxyl groups were converted to iodine was less than 1%.

(Synthesis 2 of Compound 3-2) Immerse a flask equipped with a stirrer, cooling tube, and Dean-Stark tube in an oil bath, add 308 g of toluene to 21 g of 1,3,5-adamantantriol, and further add 78.6 g of a 55 wt% aqueous solution of hydrogen iodide. While distilling and discharging 26 g of water in a Dean-Stark tube at 105-110°C, reflux for 3 hours and then cool to room temperature. After adding 177.5 g of water, add 10 g of a 10% aqueous solution of sodium sulfite. Then, add 61.4 g of a 6% aqueous solution of sodium hydroxide for neutralization. After that, the reaction solution was filtered to filter out a toluene solution and 31 g of crystals, and the toluene solution was washed twice with 88 g of 3 wt% oxalic acid, and then washed five times with 88 g of water to obtain 255 g of a toluene solution. 341 g of ethyl acetate was added to 31 g of the filtered crystals to dissolve them, and then 85 g of water and 0.4 g of a 10% sodium sulfite aqueous solution were added to wash the solution. Furthermore, the solution was washed six times with 85 g of water to obtain 316 g of an ethyl acetate solution. 255g of toluene solution and 316g of ethyl acetate solution containing crystals were concentrated under reduced pressure, the precipitated crystals were filtered out, and then dried under reduced pressure at 50°C to obtain 40.9g of white crystalline compound 3-2 with a purity of 99.3% and a yield of 89%. At the time point when the reflux reaction was completed, the yield of the compound in which only one hydroxyl group of compound 3-1 was converted to iodine was <1%, and the yield of the compound in which three hydroxyl groups were converted to iodine was <1%.

(Synthesis 3 of Compound 3-2) A flask equipped with a stirrer, a cooling tube, and a Dean-Stark tube was immersed in an oil bath, 102 g of toluene was added to 7 g of 1,3,5-adamantantriol, and 26.6 g of a 55 wt% aqueous hydrogen iodide solution was further added, and the mixture was allowed to stand for 12 hours. Thereafter, 8.5 g of water was distilled out and discharged from the Dean-Stark tube at 102-108°C, and the mixture was refluxed for 1 hour and then cooled to room temperature. After 59 g of water was added, 8 g of a 10% aqueous sodium sulfite solution was added. Thereafter, the reaction solution was filtered to filter out 12 g of toluene solution and crystals, and the toluene solution was washed with 29 g of water 5 times to obtain 85 g of toluene solution. After adding 122g of ethyl acetate to 12g of filtered crystals to dissolve them, 28g of water and 0.4g of 10% sodium sulfite aqueous solution were added for liquid separation and washing. Furthermore, 85g of water was used for liquid separation and washing 6 times to obtain 105g of ethyl acetate solution. 85g of toluene solution and 105g of ethyl acetate solution were concentrated under reduced pressure, and the precipitated crystals were filtered and dried under reduced pressure at 50°C to obtain 13.7g of white crystalline compound 3-2 with a purity of 99.3% (yield of 91%). At the time point when the reflux reaction was completed, the yield of the compound in which only one hydroxyl group of compound 3-1 was converted to iodine was <1%, and the yield of the compound in which three hydroxyl groups were converted to iodine was 2%.

(Synthesis 3-2 of Compound 3-2) Except for adding 50 g of silica gel to the obtained ethyl acetate solution 105 g to disperse the silica gel and recovering the organic phase by filtration, the other operations were the same as those of Synthesis 2 of Compound 3-2 to obtain 13.5 g of Compound (3-2) with a yield of 90% and a high purity of LC purity of >99.9%.

(Synthesis 4 of Compound 3-2) Immerse a flask equipped with a stirrer, cooling tube, and Dean-Stark tube in an oil bath, add 17.8 g of water to 21 g of 1,3,5-adamantantriol, and further add 78.6 g of a 55 wt% aqueous hydrogen iodide solution and stir. While distilling out 28 g of water in a Dean-Stark tube at 115-120°C and discharging, reflux reaction is performed for 2 hours and then cooled to room temperature. After adding 100 g of water, 15 g of a 10% aqueous sodium sulfite solution is added. Thereafter, the reaction solution is filtered to filter out 45 g of crystals. After adding 220 g of ethyl acetate to the filtered 45 g of crystals to dissolve them, 110 g of water and 4.8 g of a 10% aqueous sodium sulfite solution are added to separate and wash. Furthermore, 110 g of water was used for 8 times of liquid separation and washing to obtain 165 g of ethyl acetate solution. The obtained ethyl acetate solution was concentrated under reduced pressure, and the precipitated crystals were filtered out and dried under reduced pressure at 50°C to obtain 41.9 g of white crystalline compound 3-2 with a purity of 99.1% and a yield of 91%. At the time point when the reflux reaction was completed, the yield of the compound in which only one hydroxyl group of compound 3-1 was converted to iodine was 1%, and the yield of the compound in which three hydroxyl groups were converted to iodine was 2%.

(Synthesis 5 of Compound 3-2) Except for the additional steps of dissolving the obtained precipitate in 10.5L of ethyl acetate, adding 50g of silica gel to disperse the silica gel, and recovering the organic phase by filtration, the other operations were the same as those of Synthesis Example L1 to obtain 1660g of Compound (1-3) with a yield of 76% and a high purity of >99.9%.

(Synthesis of Ad-A-1) Add 1278 g of acetonitrile to 150 g of 1,3,5-adamantantriol and stir. Add 177 g of trimethylsilyl chloride under nitrogen at room temperature, and further add 244 g of sodium iodide (2 equivalents relative to 1,3,5-adamantantriol) in batches. Set the bath temperature to 85°C and react for 6 hours, then cool overnight. Add 1625 g of water, and then add 79 g of a 10% aqueous sodium sulfite solution. Use an evaporator to reduce pressure and concentrate until the internal volume becomes 2.2 kg, and add 700 g of toluene. Stir at room temperature for 14 hours and filter. Wash the solid twice with 150 ml of acetonitrile. Dry under reduced pressure at 30°C to obtain 132 g of solid. The formation was confirmed by NMR and LC-MS. The molecular weight is 294.

(Synthesis of Ad-A-2) Add 100 ml of dehydrated N-methylpyrrolidone (NMP) to 24 g of 1-iodoadamantan-3,5-diol and ice-cool. Add 10 g of chloroacetyl chloride dropwise at below 5°C. Set the bath temperature to 60°C and react for 1 hour. Add ice to which 4% hydrochloric acid has been added while stirring the reaction solution. Extract with 200 ml of ethyl acetate and wash with 100 ml of 2% hydrochloric acid and 100 ml of water. Dehydrate with saturated saline and sodium sulfate, distill off the solvent with an evaporator, and purify with silica gel column chromatography. Obtain 18.8 g of solid. Confirm the formation with NMR and LC-MS. Molecular weight is 371.

(Synthesis of Ad-2-2) Compound Ad-2-2 was obtained in the same manner as Example 1 except that compound Ad-2-1 was used instead of compound 3-1. The formation was confirmed by NMR and LC-MS. The molecular weight was 420.

(Synthesis of Ad-2-3) 10 g of Ad2-2 was dissolved in 30 ml of THF, and after ice cooling, 7.7 g of succinic acid chloride was added dropwise. After the addition was completed, the reaction was carried out at 60°C for 2 hours. THF was distilled off from the reaction solution, toluene was added to the residue, and the precipitated solid was filtered to obtain 11 g of Ad-2-3. The formation was confirmed by NMR and LC-MS. The molecular weight is 657.

(Synthesis of Ad-2-4) 10g of Ad-2-2 was dissolved in 50ml of THF, and after ice cooling, 7.7g of succinic acid chloride was added dropwise. After the addition was completed, the reaction was carried out at 60°C for 2 hours. After the reaction solution was returned to room temperature, 40ml of 15% sodium carbonate was added dropwise and stirred for 1 hour. 7ml of concentrated hydrochloric acid was added dropwise to the reaction solution, and the precipitated solid was filtered to obtain 10g of Ad-2-4. The formation was confirmed by NMR and LC-MS. The molecular weight is 620.

(Synthesis of Ad-A-3) The compound was produced according to the following scheme.

(Synthesis of Ad-A-3-1) To a suspension of 30 g (153 mmol) of Ad-A-3-0 (3-hydroxy-1-adamantan carboxylic acid) in acetonitrile-water (1:1, 300 mL) were added 600 mg (2.54 mmol, 1.7 mol%) of ruthenium (III) chloride hydrate (ruthenium content: 42.8%), 1.2 mL (15 mmol, 10 mol%) of pyridine, and 60.0 g (280 mmol, 1.8 equivalents) of sodium periodate. After stirring at 70°C for 15 hours, acetone was added to the reaction solution and filtered. The filtrate was concentrated and the resulting residue was washed with acetone to obtain 20.0 g of a crude product of Ad-A-3-1 (GC purity: 68%). It can be used in the next step without purification.

(Synthesis of Ad-A-3-2) To a solution of 20.0 g of the crude product of Ad-A-3-1 in methanol (300 mL), 18 mL (289 mmol) of iodomethane and 25 mL (167 mmol) of 1,8-diazabicyclo[5.4.0]-7-undecene were added. After stirring at 60°C for 5 hours, the reaction solution was concentrated. The residue was subjected to silica gel column chromatography to obtain 18.7 g (82.6 mmol) of Ad-A-3-2.

(Synthesis of Ad-A-3) To a methanol (100 mL) solution of 21.4 g (94.5 mmol) of Ad-A-3-2, an aqueous solution (100 mL) of 4.6 g (115 mmol, 1.2 equivalents) of sodium hydroxide was added. After stirring at 60°C for 12 hours, the reaction solution was concentrated. 200 mL of 57% hydroiodic acid was added to the residue, and stirred at 60°C for 18 hours. After cooling to room temperature, the reaction solution was added to an aqueous solution of sodium sulfite. The solid was filtered and washed with water and toluene. It was reprecipitated from methanol-water to obtain 22.8 g (70.8 mmol) of Ad-A-3. The formation was confirmed by NMR and LC-MS. ¹ H-NMR:δ (ppm)(d-DMSO):12.3(1H, -COOH), 4.9(1H, -OH), 1.2~2.5 (13H, =CH-, -CH ₂ -), molecular weight is 322.

(Synthesis of Ad-A-4)

Using a 300 mL flask connected to a reflux tube, add 0.4 mg of aluminum lithium hydride and 100 mL of superdehydrated THF, and stir at 220 rpm for 1 hour under a nitrogen flow. Furthermore, 3.2 g of Ad-A-3 is gradually added in 10 portions over 40 minutes. Thereafter, stir at 24°C and 70 rpm for 24 hours. Add 100 mL of pure water, and filter separate by filtration to recover the formed precipitate. After drying, 0.3 g of Ad-A-4 is obtained (yield 10%). The formation is confirmed by NMR and LC-MS. ¹ H-NMR:δ(ppm)(d-DMSO):4.9 (1H, -OH), 4.2(1H, -CH ₂ O H ), 1.0~2.5(15H, =CH-, -CH ₂ -), molecular weight is 308.

[Synthesis Example DMA1P] Compound using adamantane as a parent core The compound was prepared according to the following process.

A flask equipped with a reflux tube and a Dean-Stark tube was immersed in an oil bath, and 80 g of compound 3-1 (Mitsubishi Gas Chemical Co., Ltd., 0.43 mol) and 2.5 L of o-xylene were added to the flask and stirred. Then, 400 g (1.72 mol) of a 55% aqueous hydrogen iodide solution was added to the flask. The internal temperature was set at 125°C and the reaction was carried out for 3 hours. Thereafter, the mixture was stirred in a water bath at 25°C for 1 hour.

Add 2.5 L of ion exchange water to the reaction vessel to separate it into an organic phase and an aqueous phase. After the organic phase is recovered, it is washed three times with 1 L of 5% baking soda water and 1 L of ion exchange water. After the organic phase is recovered and concentrated, 35 g of a white solid (DMA1a) is obtained. The formation is confirmed by NMR and LC-MS. The molecular weight is 570.

In a 3L flask connected to a reflux tube and a Dean-Stark tube, 35g of DMA1a (0.06mol) and 182.5mL of dehydrated toluene were added under a nitrogen flow, and stirred with a stirring paddle to dissolve. Then, 12g of methanesulfonic acid was added and dissolved while stirring over 30 minutes. Furthermore, 7.4g of succinic anhydride (1.2 equivalents relative to the substrate) was added to the stirred reaction solution over 60 minutes, and the internal temperature was set to 100°C and stirred for 2 hours. After that, it was cooled to room temperature, 360mL of pure water was added, and after liquid separation, the toluene phase was recovered. Furthermore, after washing with 360 mL of 0.5% sodium bicarbonate aqueous solution, washing was performed three times with 350 mL of ion exchange water, and the recovered toluene phase was concentrated under reduced pressure to obtain 20.6 g of a white solid of the protected DMA1aP form as the target substance. The yield was 50%. The formation was confirmed by NMR and LC-MS. The molecular weight was 670.

[Synthesis Example DMA2] Compounds using adamantane as a parent core The compound was produced according to the following process. (Synthesis of DMA2a)

A flask equipped with a reflux tube and a Dean-Stark tube was immersed in an oil bath, and 87.9 g of compound Ad-2-1 (0.43 mol) and 2.5 L of toluene were added to the flask and stirred. Then, 400 g (1.72 mol) of a 55% aqueous hydrogen iodide solution was added to the flask. The internal temperature was set at 100°C and the reaction was carried out for 3 hours. Thereafter, the mixture was stirred in a water bath at 25°C for 1 hour.

2.5 L of ion exchange water was added to the reaction vessel to separate it into an organic phase and an aqueous phase. After the organic phase was recovered, it was washed three times with 1 L of 5% baking soda water and 1 L of ion exchange water. After the organic phase was recovered and concentrated, 37 g of a white solid (DMA2a) was obtained. The formation was confirmed by NMR and LC-MS. The molecular weight was 602.

(Synthesis of DMA2aP)

Using a 3L flask connected to a reflux tube and a Dean-Stark tube, 37g (0.06mol) of (DMA1a) and 182.5mL of dehydrated toluene were added under a nitrogen flow, and stirred with a stirring paddle to dissolve. Then, 12g of methanesulfonic acid was added and dissolved while stirring over 30 minutes. Furthermore, 7.4g of succinic anhydride (1.2 equivalents relative to the substrate) was added to the stirred reaction solution over 60 minutes, and the internal temperature was set to 100°C and stirred for 2 hours. After that, it was cooled to room temperature, 360mL of pure water was added, and after liquid separation, the toluene phase was recovered. Furthermore, after washing with 360 mL of 0.5% sodium bicarbonate aqueous solution, washing was performed three times with 350 mL of ion exchange water, and the recovered toluene phase was concentrated under reduced pressure to obtain 23.8 g of a white solid compound (DMA2aP) as the target substance. The yield was 55%. The formation was confirmed by NMR and LC-MS. The molecular weight was 702.

(Synthesis of DMA1aP2)

Add 140 ml of dehydrated NMP to 47.1 g of DMA1a and ice-cool. Add 10 g of chloroacetyl chloride dropwise below 5°C. Set the bath temperature to 60°C and react for 1 hour. Add ice to which 4% hydrochloric acid has been added while stirring the reaction solution. Extract with 200 ml of ethyl acetate and wash with 100 ml of 2% hydrochloric acid and 100 ml of water. After dehydration with saturated brine and sodium sulfate, use an evaporator to distill off the solvent and purify with silica gel column chromatography. 29.6 g of solid DMA1aP2, the target substance, is obtained with a yield of 79.7%. The formation is confirmed by NMR and LC-MS. The molecular weight is 679.

(Synthesis of DMA2aP2)

Add 140 ml of THF to 49.1 g of DMA2a and cool with ice. Add 14 g of succinic acid chloride dropwise at a temperature below 5°C. Set the bath temperature to 60°C and react for 2 hours. After the addition is complete, react at 60°C for 2 hours. Distill THF from the reaction solution, add toluene to the residue, and recover 46.9 g of the precipitated solid by filtration to obtain DMA2aP2 as the target substance with a yield of 79.8%. Confirm the formation by NMR and LC-MS. The molecular weight is 721.

(Synthesis of DMA3a)

DMA3-2 was obtained in the same manner as the synthesis of Ad-A-3-2, except that 60 g (258 mmol) of 55% aqueous hydrogen iodide solution was used instead of 18 mL (289 mmol) of methyl iodide. Next, DMA3-2 was used instead of AdA-3-2 to obtain DMA3a in the same manner as the synthesis of Ad-A-3. The formation was confirmed by NMR and LC-MS. The molecular weight was 626.

(Synthesis of DMA4a)

DMA4a was obtained in the same manner as Ad-A-4 using DMA3a instead of AdA-3. The formation was confirmed by NMR and LC-MS. The molecular weight was 598.

(Synthesis of DAMA1-tl) DAMA1-t1 was obtained in the same manner as (Synthesis 2 of Compound 3-2) except that hydrogen iodide:sulfuric acid = 1:1 was used instead of hydrogen iodide. The formation was confirmed by NMR and LC-MS. The molecular weight was 384.

(Synthesis of DAMA1-mx) DAMA1-mx was obtained in the same manner as DAMA1-tl except that m-xylene was used instead of toluene. The formation was confirmed by NMR and LC-MS. The molecular weight was 398.

(Synthesis of DAMA1-eb) DAMA1-eb was obtained in the same manner as DAMA1-tl except that ethylbenzene was used instead of toluene. The formation was confirmed by NMR and LC-MS. The molecular weight was 398.

[Examples 4 to 7, 7A to 7C] Composition for lithography (substrate A) Dissolve 0.5 g of 4-hydroxystyrene, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylate, and 1.5 g of hydroxyadamantyl methacrylate in 45 mL of tetrahydrofuran, and add 0.20 g of azobisisobutyronitrile. After refluxing for 12 hours, add the reaction solution dropwise into 2 L of n-heptane. The precipitated polymer is filtered, separated, and dried under reduced pressure to obtain a white powdery polymer MAR represented by the following formula (MAR). The weight average molecular weight (Mw) of this polymer is 11,500, and the degree of dispersion (Mw/Mn) is 1.90. In addition, according to the results of ¹³ C-NMR measurement, the composition ratio (molar ratio) in the following formula (MA1) is a:b:c:d=60:10:15:15. Although the following formula (MAR) is briefly described in order to express the ratio of each structural unit, the arrangement order of each structural unit is random, and each structural unit forms an independent block, and it is not a block copolymer. For the carbon of the main chain directly bonded to benzene in the unit having benzene; for the carbonyl carbon of the ester bond of the methacrylate-based unit (2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, and hydroxyadamantyl methacrylate), the molar ratio was calculated based on the respective integral ratios.

(Composition) Compound 1-3 synthesized in Example 1, compound 2-3 and compound 2-4 synthesized in Example 2, compound 3-2 synthesized in Example 3, compound 8 synthesized in Example 1g, compound 9 synthesized in Example 1h, and compound 10 synthesized in Example 1i were used as compound B to prepare the composition shown in Table 1. The following were used for the acid generator, acid diffusion control agent, and organic solvent. Acid generator: Triphenylsulfonium nonafluorobutane sulfonate (TPS-109) manufactured by Midori Kagaku Co., Ltd. Acid diffusion control agent: Tri-n-octylamine (TOA) manufactured by Kanto Chemical Organic solvent: Propylene glycol monomethyl ether acetate (PGMEA) manufactured by Kanto Chemical

[Evaluation method] (Pattern evaluation of EB anti-etching agent pattern (pattern formation)) After preparing the anti-etching agent composition according to the composition of Table 1, it was spin-coated on a clean silicon wafer and then pre-exposure baked (PB) on a hot plate at 110°C to form an anti-etching film with a thickness of 50nm. The obtained anti-etching film was irradiated with an electron beam with a line and space setting of 1:1 at a spacing of 50nm using an EB drawing device (ELS-7500, manufactured by ELIONIX Co., Ltd.). After the irradiation, the anti-etching film was heated at 110°C for 90 seconds and immersed in a TMAH 2.38 mass% alkaline developer for 60 seconds for development. Afterwards, the anti-etching film was cleaned with ultrapure water for 30 seconds and dried to form an anti-etching agent pattern.

(Evaluation of the shape of the resist pattern) The cross-sectional shape of the obtained 50 nm L/S (1:1) resist pattern was observed using an electron microscope (S-4800) manufactured by Hitachi Ltd. The shape of the resist pattern after development was evaluated by evaluating the half-value width of the pattern cross section at a position 10% of the pattern height from the surface of the silicon wafer, with those less than +10% of the half-value width being "A" and those greater than +10% of the half-value width being "C". (Anti-etching pattern defects) In addition, regarding the anti-etching pattern defects after development, the number of spherical foreign particles was used as an index for the anti-etching pattern with a length of 1μm. (Evaluation criteria) S: Number of spherical foreign particles = 0 A: 0 < Number of spherical foreign particles ≤ 5 C: 5 < Number of spherical foreign particles (Electron beam drawing sensitivity) The minimum electron beam energy that can be drawn without pattern inversion is set as "electron beam drawing sensitivity", and those that are equal to or higher than Comparative Example 1 are evaluated as "A", and those that are lower than Comparative Example 1 are evaluated as "C".

[Examples 8-11] EUV Exposure Sensitivity, Etching Defects (EUV Exposure Sensitivity) The compositions prepared in Examples 4-7 and 7A-7C were spin coated on a silicon wafer and then baked at 110°C for 60 seconds to form a photoresist layer with a film thickness of 100 nm. In the composition of Comparative Example 3, Compound 3-1 was used instead of Compound 1-3 of Example 4. Next, an extreme ultraviolet (EUV) exposure device "EUVES-7000" (product name, manufactured by Litho Tech Japan Corporation) was used to increase the exposure dose from 1mJ/ ^cm2 to 80mJ/ ^cm2 in steps of 1mJ/cm2 each time, and ^then a maskless exposure was performed. The exposure was then baked (PEB) at 110°C for 90 seconds and developed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds to obtain a wafer with 80 shots of exposure performed on the wafer. The film thickness of each obtained exposure area was measured by an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), and the profile data of the film thickness relative to the exposure amount was obtained. The exposure amount when the slope of the film thickness change relative to the exposure amount was the maximum was calculated as the sensitivity value (mJ/ ^cm2 ) and used as an indicator of the EUV sensitivity of the resist.

(Etching defect evaluation) The composition used for EUV exposure sensitivity measurement was applied to an 8-inch silicon wafer with a 100nm thick oxide film formed on the outermost layer, and baked at 110°C for 60 seconds to form a photoresist layer with a film thickness of 100nm. Then, the wafer was subjected to emission exposure on the entire surface using an extreme ultraviolet (EUV) exposure device "EUVES-7000" (product name, manufactured by Litho Tech Japan Corporation) at an exposure amount less than 10% of the EUV sensitivity value obtained in the above EUV sensitivity evaluation, and then baked (PEB) at 110°C for 90 seconds, developed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and subjected to emission exposure for 80 shots on the entire surface of the wafer to obtain a wafer.

(Etching defects) For the exposed wafers that have been manufactured, the etching device "Telius SCCM" (product name, manufactured by Tokyo Electron Ltd.) is used to perform etching processing using _CF4 /AR gas until the oxide film is etched to 50nm. For the wafers manufactured by etching, defect evaluation is performed using the defect inspection device "Surfscan SP5" (product name, manufactured by KLA Corporation), and the number of pyramidal defects above 19nm is set as the indicator of etching defects. (Evaluation criteria) A: The number of pyramidal defects ≤ 10 B: 10 < the number of pyramidal defects ≤ 80 C: 80 < the number of pyramidal defects ≤ 400 D: 400 < the number of pyramidal defects

(Time-dependent change in etching defect evaluation) The composition used for the above etching defect evaluation was placed at room temperature for 7 days, and the etching defect evaluation was performed again. If the change in EUV sensitivity before and after the placement was less than 6%, it was evaluated as "G", and if it was more than 6%, it was evaluated as "N".

[Example 12] Acid-purified compound 3-2 (Treatment 1: Purification with acid) In a 1000 mL four-necked flask (bottomless type), add 150 g of a PGMEA solution (10 mass %) containing compound 3-2, and heat to 80°C while stirring. Then, add 37.5 g of an oxalic acid aqueous solution (pH 1.3), stir for 5 minutes, and let stand for 30 minutes. The oil phase and the water phase are separated, and the water phase is removed. After repeating this operation once, add 37.5 g of ultrapure water to the obtained oil phase, stir for 5 minutes, let stand for 30 minutes, and remove the water phase. After repeating this operation three times, the flask was heated to 80°C and the pressure in the flask was reduced to below 200 hPa to concentrate and remove residual water and PGMEA. After that, EL grade PGMEA (reagent produced by Kanto Chemical Co., Ltd.) was diluted and the concentration was adjusted to 10% by mass to obtain a PGMEA solution of compound 3-2 with a reduced metal content.

(Treatment 2: Treatment without using acid) In the same manner as in Example 12, except that ultrapure water was used instead of the aqueous oxalic acid solution, a PGMEA solution of compound 3-2 adjusted to a concentration of 10 mass % was obtained.

The contents of various metals in the 10 mass % PGMEA solution of the untreated compound 3-2, the 10 mass % PGMEA solution of the compound 3-2 after treatment 1, and the 10 mass % PGMEA solution of the compound 3-2 after treatment 2 were measured by ICP-MS. The measurement results are shown in the following table.

(EUV exposure sensitivity, etching defects) Similar to Example 8, the purified compound 3-2 was used to measure EUV exposure sensitivity and etching defects. The measurement results are shown in the following table.

[Example 13] Synthesis of aldehydes with benzene as the nucleus The compound was produced by the following process. The reaction was carried out under a nitrogen flow.

(Synthesis of Compound 1-1, Compound 1-1a, and Compound 1-1b) 150 g (1.2 mol) of 4-hydroxybenzaldehyde and 1 L of methanol (Kanto Chemical) were weighed and added to a 3 L three-neck flask equipped with a stirrer and a nitrogen flow. The flask was immersed in a water bath set at 40°C, and heated while stirring under a nitrogen flow, and 200 mL of water was added. When the internal temperature reached 34°C, 309.4 g (3.7 mol) of sodium bicarbonate (NaHCO ₃ ) was added in batches.

When the internal temperature reached 38°C, 654.5 g (2.6 mol) of iodine (I ₂ ) was added in portions while paying attention to foaming, and stirred at 40°C for 3 hours. The flask was then cooled with water, and a sodium sulfite aqueous solution (Na ₂ SO ₃ ) was added dropwise until the reaction solution turned yellow-white.

Add 3L of water to a container with a stirrer, inject the above reaction solution and stir for 15 minutes. Filter the precipitate and wash it with 500mL of water. Add the filtrate to a container with a stirrer, add 1L of water and stir for 15 minutes. Filter the precipitate and wash it with 300mL of water.

Add the filtrate to a container with a stirrer, add 500 mL of methanol and stir for 15 minutes. Filter the precipitate and wash with 150 mL of methanol. Use column chromatography (spherical silica 60N manufactured by Kanto Chemical Co., Ltd.) and gradient separate the precipitate with a developing solvent of ethyl acetate:hexane in a ratio of 1:9 to 9:1 to obtain compound 1-1, compound 1-1a, and compound 1-1b, with the relative value ratio of each amount being about 1:0.9:0.5. The molecular weight of each component of the mixture was measured by LC-MS, and the molecular weight of compound 1-1 was 374, compound 1-1a was 248, and compound 1-1b was 494.

(Synthesis of Compound 1-3a and Compound 1-3b) Compound 1-3a was obtained from Compound 1-1a via Compound 1-2a by the same method as in Example 1. Compound 1-3b was obtained from Compound 1-1b via Compound 1-2b.

(Synthesis of a mixture of compounds 1-2, 1-2a, 1-2b, compounds 1-3, 1-3a, 1-3b) By the same method as in Example 1, a mixture of compounds 1-2, 1-2a, 1-2b was obtained from a mixture of compounds 1-1, 1-1a, 1-1b. Furthermore, a mixture of compounds 1-3, 1-3a, 1-3b was obtained from a mixture of compounds 1-2, 1-2a, 1-2b. The molecular weights of the components of the mixture were determined by LC-MS, and the molecular weights of the components 1-2a, 1-3a, 1-3a, 1-3b, 1-3b, and 1-3b were 306, 308, 610, and 614, respectively.

[Examples 14-18] Evaluation of EUV exposure sensitivity and etching defects As in Example 4, the following compound was used as compound B to prepare the composition. The table shows the mass ratio of each compound contained in the composition. EUV exposure sensitivity and etching defects were evaluated in the same way as in Example 8. However, the etching defects were evaluated according to the following criteria. (Evaluation criteria) S: Number of pyramidal defects ≤ 6 A’: 6 < Number of pyramidal defects ≤ 10 B: 10 < Number of pyramidal defects ≤ 80 C: 80 < Number of pyramidal defects ≤ 400 D: 400 < Number of pyramidal defects

(Synthesis Example BPL1Rc) Using a 100L glass-lined reaction vessel connected to a reflux tube, 700g of 4-hydroxybenzaldehyde and 1600mL of dehydrated tetrahydrofuran (THF) were added in an ice bath under a nitrogen flow, and stirred with a stirring paddle to dissolve. Then, while stirring in an ice bath, 80g of PPTS (pyridinium salt-p-toluenesulfonic acid) was added within 30 minutes, and further stirred for 60 minutes. 500g of ethyl vinyl ether (1.2 equivalents relative to the functional group equivalent) was added dropwise to the stirred reaction solution within 60 minutes, and further stirred at 35°C for 60 minutes. Then, 7.2 L of pure water was added under ice bath, stirred for 60 minutes, and the organic phase was recovered. 2 L of ethyl acetate and 5 L of pure water were added to the recovered organic phase and stirred, and then the organic phase was recovered and concentrated by reduced pressure to obtain 840 g of white solid of the target protected substance BPL1Pc. The yield was 75%. The formation was confirmed by NMR and LC-MS. The molecular weight was 194.

The obtained BPL1Pc was used as a raw material to obtain BPL1c in the same manner as the reduction step BPL1R. The formation was confirmed by NMR and LC-MS. The molecular weight was 196.

(Synthesis Example BPL3R) BPL3R was obtained in the same manner as Synthesis Example BPL1 using 4-hydroxy-3-methoxybenzaldehyde as a raw material. The formation was confirmed by NMR and LC-MS. The molecular weight was 212.

(Synthesis Example BPL4R) BPL4R was obtained in the same manner as Synthesis Example BPL1 using 4-hydroxy-3-ethoxybenzaldehyde as a raw material. The formation was confirmed by NMR and LC-MS. The molecular weight was 226.

(Synthesis Example DML1bR) DML1bR was obtained in the same manner as Synthesis Example DML1 using iodic acid instead of iodine. The formation was confirmed by NMR and LC-MS. The molecular weight was 362.

(Synthesis Example Na-0b) In Example L1, 6-hydroxy-2-naphthaldehyde was used instead of 4-hydroxy-3,5-diiodobenzaldehyde, and the [protecting group introduction step] was performed, and then the [reduction step] was performed to obtain compound Na-0b. The formation was confirmed by NMR and LC-MS. The molecular weight was 232.

(Synthesis Example Na-0c) In the synthesis of compound 2-4 in Example 2, compound 2-2 was used instead of compound 2-3 to obtain compound Na-0c. The formation was confirmed by NMR and LC-MS. The molecular weight was 274.

(Synthesis Example Na-2b) In Example L1, 2-hydroxy-1-naphthaldehyde was used instead of 4-hydroxy-3,5-diiodobenzaldehyde, and the [protecting group introduction step] was performed, and then the [reduction step] was performed to obtain compound Na-2b. The formation was confirmed by NMR and LC-MS. The molecular weight was 232.

(Synthesis Example DMNa2-1bR) DMNa2-1bR was obtained in the same manner as Synthesis Example DMN2-1 using iodic acid instead of iodine. The formation was confirmed by NMR and LC-MS. The molecular weight was 463.

(Synthesis Example DMN2-3cP) Using iodic acid instead of iodine, DMN2-3c was obtained in the same manner as Synthesis Example DMN2-3. Subsequently, using DMN2-3c instead of DMN2-3, the compound DMN2-3cP was obtained in the same manner as DMN2-3P. The formation was confirmed by NMR and LC-MS. The molecular weight was 547.

(Synthesis Example Ad-A-2b) Using 1,3,5-adamantantriol instead of 1-iodoadamantan-3,5-diol, Ad-A-2b was obtained in the same manner as the synthesis of Ad-A-2. The formation was confirmed by NMR and LC-MS. The molecular weight was 414.

(Synthesis Example Ad-A-2c) Using 1,3,5-adamantantriol instead of Ad2-2, Ad-A-2c was obtained in the same manner as the synthesis of Ad-2-3. The formation was confirmed by NMR and LC-MS. The molecular weight was 540.

(Synthesis Example Ad-A-2d) Using 1,3,5-adamantantriol instead of Ad2-2, Ad-A-2d was obtained in the same manner as the synthesis of Ad-2-4. The formation was confirmed by NMR and LC-MS. The molecular weight was 484.

(Synthesis Example Ad-2-3b) Using 1,3,5,7-adamantanetrol instead of Ad-A-1, Ad-2-3b was obtained in the same manner as the synthesis of Ad-A-2. The formation was confirmed by NMR and LC-MS. The molecular weight was 506.

(Synthesis Example DMA1bP) Using iodic acid instead of hydrogen iodide, DMA1b was obtained in the same manner as the synthesis of DMA1a. The formation was confirmed by NMR and LC-MS. The molecular weight was 350. Next, using DMA1b instead of DMA1a, a mixture of DMA1bP and DMA1bP2 was obtained in the same manner as the synthesis of DMA1aP. It was purified and separated by column chromatography to obtain DMA1bP and DMA1bP2. The formation was confirmed by NMR and LC-MS. The molecular weight of DMA1bP was 656, and the molecular weight of DMA1bP2 was 194.

From the above results, it can be seen that the compounds of this embodiment can, for example, provide lithography compositions that have high sensitivity to EUV exposure and few defects while maintaining a good pattern shape, and have industrial applicability.

[Example 19-1] Evaluation was performed in the same manner as in Examples 4 and 8, except that Compound B described in the following table was used instead of Compound 1-3 described in Example 14, and the baking temperature after exposure as the evaluation conditions was set to 100°C and 120 seconds. As a result, as shown in the following table, good evaluation results similar to those of Examples 4 and 8 were confirmed for both the resist pattern and EUV exposure sensitivity.

[Example 19-2] Evaluation was performed in the same manner as in Examples 4 and 8, except that Compound B1 described in the following table was used instead of Compound 1-3 described in Example 14, and the baking temperature after exposure as the evaluation conditions was set to 100°C and 120 seconds. As a result, as shown in the following table, good evaluation results similar to those of Examples 4 and 8 were confirmed for both the resist pattern and EUV exposure sensitivity.

[Example 20-1] Except that Compound B1 and Compound B2 listed in the following table were used in place of Compound 1-3 and Compound 1-3a in the following proportions, the EUV sensitivity and etching defect evaluation were performed in the same manner as in Examples 14 to 18.

[Example 20-2] Except that Compound B1 and Compound B2 listed in the following table were used in place of Compound 1-3 and Compound 1-3a in the following proportions, the EUV sensitivity and etching defect evaluation were performed in the same manner as in Examples 14 to 18.

[Example 21] Except that the compound shown in the following table was used instead of compound 3-2, the compound after treatment 1 or treatment 2 was obtained in the same manner as in Example 12, and the EUV sensitivity and etching defects were evaluated. As a result, as in Example 12, it was confirmed that any compound had good results for EUV sensitivity and etching defects.

[Example 22] According to the method of Example 4, prepare the following composition. (Value: parts by mass)

The composition was subjected to a time test under the following conditions, and the state of the liquid after the test was evaluated by absorbance using a spectrophotometer. Specifically, the spectrum of the sample after the time test was measured in the visible light region, and the "average value A1 of the absorbance at 450nm, 550nm, and 650nm" was obtained, and the difference ΔA between it and the "average value A0 of the absorbance at 450nm, 550nm, and 650nm" before the start of the test was calculated for evaluation.

As a result, in any composition, by using the compound B2 in a predetermined amount, it was found that the increase in absorbance in the spectroscopic spectrum after the time test was suppressed. Compared with L1-NA using only one compound, the composition using the compound B2 in a predetermined amount had a lower ΔA value. From these results, it was found that the stability over time was improved by the composition.

[Example 23] According to the method of Example 4, the following composition was prepared (value: mass parts). The time stability of the composition was evaluated in the same way as in Example 22.

As a result, it was found that in any composition, by using the compound B2 in a predetermined amount together, the increase in absorbance in the spectroscopic spectrum after the time test was suppressed. From these results, it was found that the stability over time was improved by the composition.

[Example 24] According to the method of Example 4, the following composition was prepared (value: mass parts). The time stability of the composition was evaluated in the same way as in Example 22.

As a result, it was found that in any composition, by using the compound B2 in a predetermined amount together, the increase in absorbance in the spectroscopic spectrum after the time test was suppressed. From these results, it was found that the stability over time was improved by the composition.

[Example 25]

The following composition (value: parts by mass) was prepared according to the method of Example 4. The temporal stability of the composition was evaluated in the same manner as in Example 22.

As a result, it was found that in any composition, by using the compound B2 in a predetermined amount together, the increase in absorbance in the spectroscopic spectrum after the time test was suppressed. From these results, it was found that the stability over time was improved by the composition.

[Example 26] According to the method of Example 4, the following composition was prepared (value: mass parts). The time stability of the composition was evaluated in the same way as in Example 22.

As a result, it was found that in any composition, by using the compound B2 in a predetermined amount together, the increase in absorbance in the spectroscopic spectrum after the time test was suppressed. From these results, it was found that the stability over time was improved by the composition.

[Example 27] According to the method of Example 4, the following composition was prepared (value: mass parts). The time stability of the composition was evaluated in the same way as in Example 22.

As a result, it was found that in any composition, by using the compound B2 in a predetermined amount together, the increase in absorbance in the spectroscopic spectrum after the time test was suppressed. From these results, it was found that the stability over time was improved by the composition.

[Example 28] Except that Compound B1 and Compound B2 in Example 22 were replaced with the compounds listed in the table below, a time-dependent test was performed in the same manner as in Example 22. As a result, similarly to Example 22, in any composition, by using Compound B2 in combination at a predetermined amount, it was found that the increase in absorbance in the spectroscopic spectrum after the time-dependent test was suppressed.

The time test was conducted in the same manner as in Example 23 except that Compound B1 and Compound B2 in Example 23 were replaced with the compounds shown in the following table. As a result, similarly to Example 23, in any composition, by using Compound B2 in a predetermined amount, it was found that the increase in absorbance in the spectroscopic spectrum after the time test was suppressed.

As a result, it was found that in any of the above compositions, by using a predetermined amount of compound B2 together, the increase in absorbance in the spectroscopic spectrum after time testing was suppressed. From these results, it was found that the composition improves the stability over time.

[Example 29] Except that Compound B1 and Compound B2 of Example 22 were replaced with the compounds listed in the table below, a time-dependent test was performed in the same manner as in Example 22. As a result, similarly to Example 22, in any composition, by using Compound B2 in combination at a predetermined amount, it was found that the increase in absorbance in the spectroscopic spectrum after the time-dependent test was suppressed.

As a result, it was found that in any of the above compositions, by using a predetermined amount of compound B2 together, the increase in absorbance in the spectroscopic spectrum after time testing was suppressed. From these results, it was found that the composition improves the stability over time.

The time test was conducted in the same manner as in Example 23 except that Compound B1 and Compound B2 in Example 23 were replaced with the compounds shown in the following table. As a result, similarly to Example 23, in any composition, by using Compound B2 in a predetermined amount, it was found that the increase in absorbance in the spectroscopic spectrum after the time test was suppressed.

As a result, it was found that in any of the above compositions, by using a predetermined amount of compound B2 together, the increase in absorbance in the spectroscopic spectrum after time testing was suppressed. From these results, it was found that the composition improves the stability over time.

Claims (61)

A compound represented by the following formula (1): (wherein, RG is a group containing at least one cyclic structure, I is an iodine atom, ^R1 is a monovalent functional group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, which may be the same or different, n is an integer of 1 to 5, and m is an integer of 1 to 5). The compound of claim 1, wherein the aforementioned RG is a group derived from benzene, naphthalene, anthracene, pyrene, a heteroaromatic ring or a polycyclic aliphatic ring which may have a substituent, and the aforementioned ^R1 is one selected from: ^Rf selected from the group consisting of a hydroxyl group and an ether group having a protecting group, and ^Rg , a alkyl group having 0 to 30 carbon atoms which may have a substituent. The compound of claim 2, wherein the aforementioned R ^f is R ^f' selected from the group consisting of one or more hydroxyl groups and ether groups having a protecting group that can be removed by acid, base or heat. The compound of claim 1, wherein RG is a group derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene or adamantane which may have a substituent. The compound of claim 4, wherein RG is a group derived from benzene, naphthalene or adamantane which may have a substituent. The compound of claim 1, wherein R ¹ is selected from -OR ² , -COOR ³ , -CH ₂ -OR ⁴ or -CHO, wherein R ² is a hydrogen atom, an alkyl group with 1 to 30 carbon atoms which may have a substituent, or an aryl group with 1 to 30 carbon atoms, R ³ is a hydrogen atom, an alkyl group with 1 to 29 carbon atoms which may have a substituent, or an aryl group with 1 to 29 carbon atoms, and R ⁴ is a hydrogen atom, an alkyl group with 1 to 29 carbon atoms which may have a substituent, or an aryl group with 1 to 29 carbon atoms. The compound of claim 1, wherein R ¹ has a protecting group. The compound of claim 1, which is represented by any one of the following formulae: (wherein, Z is I, ^R1 or a linking group for forming a dimer, I and ^R1 have the same definitions as in formula (1), A is a group having a protecting group, R is an organic group that is not a functional group, ^R1 , A, and R are bonded at positions where they can be bonded, r1 to r4 are integers of 0 to 5, and the total of r1 to r4 in one benzene is less than the valence of benzene); (wherein, I, A, and ^R1 are defined as above, R" is a hydrogen atom or an organic group other than ^R1 , s1 is 1 to 7, s2 to s3 are 0 to 7, and s4 is an integer of 1 to 7; however, the total of s1 to s4 is less than the valence of naphthalene, and at least one of s2 and s3 is selected so as to be 1 or more); (wherein, I, ^R1 , and R" are defined as above, t1 is an integer from 1 to 10, t2 is an integer from 1 to 9, and t3 is an integer from 1 to 14; however, the total of t1 to t3 is less than the valence of adamantane). The compound of claim 8, which is represented by any one of the following formulae: (wherein, I, Z, R, ^R1 and A have the same meanings as in formula (Bz)); (wherein, I, R ¹ , A, and R" are the same as those defined in formula (N); x and y are 0 or 1, but at least one of them is 1; s4' represents the number of R" that can be combined with the 1, 7, and 8 positions of naphthalene, which is an integer of 1 to 3); (wherein, I, R ¹ , and R" have the same definitions as in formula (Ad), one of D is I, and the other of D is R ¹ ). The compound of claim 9, which is represented by any one of the following formulae: (wherein, I, Z, R, R ¹ , and A have the same definitions as in formula (Bz)); (wherein, I, R ¹ , R ″, A, x, y, s4 ′ have the same meanings as in formula (n)); (wherein, I, R ¹ , and R" have the same definitions as in formula (Ad)). The compound of claim 8, wherein the aforementioned R ¹ is a hydroxyl group, a carboxylic acid group, an ester group or a hydroxyalkyl group, when the aforementioned A is A' represented by -OR ^a -OR ^b (R ^a is a linear or branched alkyl group having 1 to 3 carbon atoms; R ^b is a monovalent linear or branched alkyl group having 1 to 3 carbon atoms, or a cyclic alkyl group, or a divalent cyclic alkyl group that forms a ring together with an adjacent oxygen atom), the number of said A's is 1 or more. The compound of claim 5, wherein RG is a group derived from benzene which may have a substituent. The compound of claim 1, wherein when RG is a benzene-containing group and there are multiple R ^1s , the R ^1s do not include a combination of an alkoxy group (except for a protecting group) and an aldehyde group, a combination of the alkoxy group and a hydroxyl group, and a combination of a hydroxyl group and an aldehyde group; when RG is a naphthalene-containing group and there are multiple R ^1s , the R ^1s do not include a combination of a hydroxyl group and a carboxylic acid group. The compound of claim 12 is represented by the following formula (Bz4): (wherein, I, R, A and Z have the same definitions as in formula (Bz); R1 ^' is a monovalent functional group other than a hydroxyl group, which may be the same or different, has a carbon number of 0 to 30 and does not contain a polymerizable unsaturated bond; r1', r2', r4' are integers of 0 to 5, and the total of r1', r2', r4' is less than the valence of benzene). The compound of claim 14 is represented by the following formula (Bz4-1): (wherein, I, R, Z and ^R1' have the same definitions as in formula (Bz4); r1', r2', r4' are integers from 0 to 5, and the total of r1', r2', r4' is less than the valence of benzene). The compound of claim 15, which is represented by the following formula (Bz4-2): (wherein, I has the same definition as in formula (Bz4), r4' is an integer between 0 and 4, and r5' is an integer between 0 and 4). The compound of claim 15, which is represented by any one of the following formulae; . The compound of claim 12, which is represented by any one of the following formulae: (wherein, I, R, Z, A and ^R1 have the same definitions as in formula (Bz); A' is a group having a protecting group, represented by ^-ORa - ^ORb , -O-CO- ^ORb or -ORa ^- CO- ^ORb ; ^Ra is a linear or branched alkyl group having 1 to 3 carbon atoms; ^Rb is a monovalent linear or branched alkyl group having 1 to 3 carbon atoms, or a cyclic alkyl group, or a divalent cyclic alkyl group that forms a ring together with an adjacent oxygen atom). The compound of claim 12, which is represented by any one of the following formulae: (wherein, I, ^R1 and A have the same definitions as in formula (Bz); A' is a group having a protecting group, represented by ^-ORa - ^ORb , -O-CO- ^ORb or -ORa ^- CO- ^ORb ; ^Ra is a linear or branched alkyl group having 1 to 3 carbon atoms; ^Rb is a monovalent linear or branched alkyl group having 1 to 3 carbon atoms, or a cyclic alkyl group, or a divalent cyclic alkyl group that forms a ring together with an adjacent oxygen atom; Z' is I, ^R1 or a hydrogen atom). The compound of claim 5, wherein RG is a group derived from naphthalene which may have a substituent. The compound of claim 20, which is represented by any one of the following formulae: (wherein, I, R ¹ , R ″, A, x, y, and s4′ have the same definitions as in formula (n)). The compound of claim 21, which is represented by any one of the following formulae: (wherein, I, ^R1 and R" have the same definitions as in formula (n); A' is a group having a protecting group, represented by ^-ORa - ^ORb , -O-CO- ^ORb or -ORa ^- CO- ^ORb ; ^Ra is a linear or branched alkyl group having 1 to 3 carbon atoms; ^Rb is a monovalent linear or branched alkyl group having 1 to 3 carbon atoms, or a cyclic alkyl group, or a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom). The compound of claim 22, wherein the aforementioned R ¹ is a hydroxyl group, a carboxylic acid group, an ester group or a hydroxyalkyl group. The compound of claim 21, which is represented by any one of the following formulae: (wherein, I, R ¹ , A, A′, x, and y have the same meanings as in formula (n)). The compound of claim 5, wherein RG is a group derived from adamantane which may have a substituent. The compound of claim 25, which is represented by any one of the following formulae: (wherein, I, R ¹ , and R" have the same definitions as in formula (Ad)). The compound of claim 26, wherein the aforementioned R ¹ is a hydroxyl group, a carboxylic acid group, an ester group or a hydroxyalkyl group. The compound of claim 27, which is represented by any one of the following formulae: (wherein, I and R ¹ have the same definitions as in formula (Ad)). A composition comprising the compound of claim 1. A composition as claimed in claim 29, which is used for lithography. The composition of claim 30 comprises two or more compounds represented by the aforementioned formula (1). The composition of claim 29, further comprising a compound represented by the following formula (DMO-1) or the following formula (BP0-1) or a combination thereof: (wherein, RG, I, ^R1 have the same definitions as in formula (1), Q is a group or a single bond caused by a group that binds molecules, n' is an integer from 0 to 5 and less than n, m' is an integer from 1 to 5 and less than m, and b is an integer from 1 to 4). The composition of claim 32, wherein the compound represented by the aforementioned formula (DM0-1) is a compound represented by the following formula (DM1a), (Dn1) or (Da1), and the compound represented by the aforementioned formula (BP0-1) is a compound represented by the following formula (BP1a), (Bn1) or (Ba1): (wherein, Z is I, ^R1 or a linking group for forming a dimer, I and ^R1 have the same definitions as in formula (1), A is a group having a protecting group, R is an organic group that is not a functional group, ^R1 , A, and R are bonded at positions where they can be bonded, r1 to r4 are integers of 0 to 5, and the total of r1 to r4 in one benzene is less than the valence of benzene); (wherein, I, ^R1 , and A are the same as defined in formula (DM1a), R" is a hydrogen atom or an organic group other than ^R1 , I, ^R1 , A, and R" are bonded at a bondable position, Q is the same as defined in formula (DM0-1), s1 is 1 to 7, s2 to s3 are 0 to 7, and s4 is an integer of 1 to 7; however, the total of s1 to s4 is less than the valence of naphthalene, and is selected so that any one of s2 and s3 is 1 or more; nd is an integer of 1 to 4); (wherein, I and ^R1 have the same definitions as in formula (Dn1), R" is a hydrogen atom or an organic group other than ^R1 , ^Rd is a single bond or -O- (ether bond), t1 is an integer of 1 to 10, t2 is an integer of 1 to 9, and t3 is an integer of 1 to 13; however, the total of t1 to t3 is less than the valence of diamond); (wherein, I, Z, R, ^R1 , A have the same definitions as in formula (DM1a), r1, r2, r3 are integers ranging from 0 to 5, a1 and r4a are integers ranging from 0 to 4, a1 and r4a satisfy a1+r4a≤r4; wherein, r4 has the same definition as in formula (DM1a)); (wherein, I, ^R1 , R", and A have the same definitions as in formula (Dn1) and (Da1), s2-s4 have the same definitions as in formula (Dn1), s1b is an integer from 0 to 6 and is an integer satisfying s1b≤(s1-1); wherein s1 has the same definition as in formula (Dn1)); (wherein, I, ^R1 , and R" have the same definitions as in formula (Dn1) and (Da1), t2 and t3 have the same definitions as in formula (Da1), t1b is an integer from 0 to 9 and satisfies t1b≤(t1-1); and t1 has the same definition as in formula (Da1)). The composition of claim 32, which comprises the compound represented by the aforementioned formula (DM0-1). As claimed in claim 34, the compounds represented by formula (1) and formula (DM0-1) satisfy the following relationship: 0.1≧[amount of compound of formula (DM0-1) (mol)]÷[amount of compound of formula (1) (mol)]≧0.000001. The composition of claim 32, which comprises a compound represented by formula (BP0-1). The composition of claim 36, wherein the compound represented by formula (BP0-1) is: a compound represented by formula (BP1a) wherein Z is not I, a compound represented by formula (Bn1), or a compound represented by formula (Ba1). The composition of claim 32, wherein the compounds represented by formula (1), formula (DM0-1), and formula (BP0-1) satisfy the following relationship: 0.1≧([the total amount of the compound of formula (DM0-1) and the compound of formula (BP0-1) (mol)])÷[the amount of the compound of formula (1) (mol)]≧0.000001. The composition of claim 33, wherein the compound represented by the aforementioned formula (DM0-1) is a compound represented by the following formula (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x) or (Ba1-eb), and the compound represented by the aforementioned formula (BP0-1) is a compound represented by the following formula (BP1a-Dt), (Bn1-Dt) or (Ba1-Dt): (wherein, Z, R, R ¹ , A, r1, r2, r3, and r4a have the same meanings as in Formula (BP1a)); (wherein, Z, I, R ¹ , A, R, r1 to r4 have the same definitions as in formula (DM1a)); (wherein, Z, R ¹ , A, R, r1 to r4 have the same definitions as in formula (DM1a)); (wherein, R ¹ , R ”, A, s2 to s4 have the same definitions as in formula (Bn1)); (wherein, I, R ¹ , A, R”, Q, s1 to s4 have the same definitions as in formula (Dn1)); (wherein, R ¹ , A, R”, Q, s2 to s4 have the same definitions as in formula (Dn1)); (wherein, R ¹ , R ″, t2, t3 have the same definitions as in formula (Ba1)); (wherein, I, R ¹ , R ″, R ^d , t1-t3 have the same definitions as in formula (Da1)); (wherein, R ¹ , R ″, R ^d , t2-t3 have the same definitions as in formula (Da1)); (wherein, I, R ¹ , R ″, R ^d , t1-t3 have the same definitions as in formula (Da1)); (wherein, I, R ¹ , R ″, R ^d , t1-t3 have the same definitions as in formula (Da1)); (wherein, I, R ¹ , R″, R ^d , t1 to t3 have the same definitions as in formula (Da1)). The composition of claim 30, wherein RG in the aforementioned formula (1) is a group derived from benzene which may have a substituent. The composition of claim 30, wherein RG of the aforementioned formula (1) is a group derived from naphthalene which may have a substituent. The composition of claim 30, wherein RG in formula (1) is a group derived from adamantane which may have a substituent. The composition of claim 29 exhibits a sensitizing effect when exposed to radiation. The composition of claim 29, wherein the content of metal impurities is less than 1 ppm. A method for exhibiting a sensitizing effect, which is a method for exhibiting a sensitizing effect when a lithographic composition is irradiated with radiation using the compound of claim 1. The method of claim 45, wherein two or more of the aforementioned compounds are used. A method for producing the compound of claim 1, comprising the step of introducing an iodine atom or an ^R1 group into the compound containing the aforementioned RG group. A method for producing a compound according to claim 1, which is a method for producing a compound represented by the aforementioned formula (1), wherein the compound represented by the aforementioned formula (1) is represented by formula (Bz), (wherein, I, Z, R ¹ , A, R, r1-r4 are the same as those defined in formula (DM1a)); the preparation method comprises: 1) preparing a compound represented by formula (MB); (wherein, I, ^R1 , R, r1, r2 are the same as defined in formula (Bz), and ^R1 , R, OH are bonded at any bondable position); 2) an iodination step of iodinating the compound; 3) a protecting group introduction step of introducing a protecting group into the compound; and 4) a reduction step of reducing the compound. A method for producing a compound according to claim 48, wherein the aforementioned step of introducing a protecting group comprises the step of introducing a protecting group into the hydroxyl group of formula (MB) using an inorganic base. A method for producing a compound according to claim 1, which is a method for producing a compound represented by the aforementioned formula (1), wherein the compound represented by the aforementioned formula (1) is represented by formula (Bz), (wherein, I, Z, R ¹ , A, R, r1 to r4 have the same definitions as in formula (DM1a)); the preparation method comprises: 1) preparing a compound represented by formula (Bz4), (wherein, I, R, A, and Z have the same definitions as in formula (Bz), R1 ^' is a monovalent functional group other than a hydroxyl group, which may be the same or different, has a carbon number of 0 to 30 and does not contain a polymerizable unsaturated bond, r1', r2', and r4' are integers of 0 to 5, and the total of r1', r2', and r4' is less than the valence of benzene); 2) the iodination step of iodizing the compound is performed once or twice or more. A method for producing a compound according to claim 1, which is a method for producing a compound represented by the aforementioned formula (1), wherein the compound represented by the aforementioned formula (1) is represented by formula (Bz), (wherein, I, Z, R ¹ , A, R, r1 to r4 have the same definitions as in formula (DM1a)); the preparation method comprises: 1) preparing a compound represented by formula (Bz5); (wherein, I, Z, ^R1 , A, R, r1-r4 have the same definitions as in formula (DM1a)); 2) a step of esterifying the carboxylic acid of the compound represented by formula (Bz5); 3) a step of reducing the obtained ester group to convert it into a hydroxymethyl group. A method for producing a compound according to claim 1, which is a method for producing a compound represented by the aforementioned formula (1), wherein the compound represented by the aforementioned formula (1) is represented by formula (N), (wherein, I, R ¹ , A, and R" are the same as those defined in formula (Dn1) and (Bn1), however, I, R ¹ , R" and A are bonded at any bondable position, s1 is 1 to 7, s2 to s3 are 0 to 7, and s4 is an integer of 1 to 7; however, the total of s1 to s4 is less than the valence of naphthalene, and is selected in such a way that any one of s2 and s3 is 1 or more); the production method comprises: 1) preparing a compound represented by formula (MN); (wherein, R ¹ , R", s3 and s4 have the same meanings as in formula (N)); 2) an iodination step of iodizing the compound; 3) a protecting group introduction step of introducing a protecting group into the compound; and 4) a reduction step of reducing the compound. A method for producing a compound according to claim 1, which is a method for producing a compound represented by the aforementioned formula (1), wherein the compound represented by the aforementioned formula (1) is represented by formula (Ad), (wherein, I, R ¹ , and R” are the same as those defined in formula (Da1); I, R ¹ , and R” are bonded at any position where they can be bonded; t1 is an integer of 1 to 10, t2 is an integer of 1 to 9, and t3 is an integer of 1 to 14; however, the total of t1 to t3 is less than the valence of adamantane); the preparation method comprises: 1) preparing a compound represented by formula (MA); (wherein, R ¹ , R", t2, and t3 have the same meanings as in formula (Ad)); 2) subjecting the compound to an iodination step. A method for producing a compound as claimed in claim 53, wherein the iodination step comprises: a step of performing iodination on a system consisting of a multiphase system comprising an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent. A method for producing a compound as claimed in claim 53, wherein the iodination step comprises a step of concentrating the reaction solution while distilling off water during the reaction. The method for producing the compound of claim 53, wherein the iodination step comprises the step of feeding the substrate and the iodination agent and then standing for 1 to 48 hours. A method for preparing a compound as claimed in claim 1, comprising any one or more steps selected from: 1) a step of preparing a compound represented by formula (Ad-A-3-0); 2) a step of preparing a compound represented by formula (Ad-A-3-1); and 3) a step of preparing a compound represented by formula (Ad-A-3-2), . A method for preparing the compound of claim 57, comprising: 1) preparing a compound represented by formula (Ad-A-3-0); 2) an oxidation step of oxidizing the compound represented by formula (Ad-A-3-0); 3) a step of esterifying the carboxylic acid of the obtained compound; 4) a step of hydrolyzing the ester group of the obtained compound to convert it into a carboxylic acid; 5) an iodination step of iodination. The manufacturing method of any one of claims 47 to 58 further comprises a step of treating with an adsorbent. The compound of claim 1, which is represented by the following formula (Ad-A-3): . The compound of claim 1 is represented by the following formula (Ad-A-4): .