JP5735831B2 - Method for producing chalcogen-containing fused polycyclic compound - Google Patents

Description

  The present invention relates to a method for producing a chalcogen-containing fused polycyclic compound. Furthermore, the present invention relates to a compound useful as an intermediate in the process for producing a chalcogen-containing fused polycyclic compound.

  Chalcogen-containing polycyclic compounds have been proposed as organic semiconductor materials useful in the field of organic electronics such as organic thin film transistors (Patent Document 1). As a method for producing a chalcogen-containing fused polycyclic compound, Patent Document 1 discloses a method in which a fused polycyclic compound containing a disulfide bond is heated at about 200 ° C. in the presence of a transition metal catalyst.

International Publication No. 2005/087780

  From an industrial viewpoint, a method for producing a chalcogen-containing condensed polycyclic compound at a milder reaction temperature than before has been demanded.

  Under such circumstances, the present inventors diligently studied, and as a result, reached the following present invention.

で表される化合物を酸と反応させる工程を有する、式（１０）

で表される含カルコゲン縮合多環式化合物の製造方法に関する。 The present invention relates to formula (5)

Having a step of reacting a compound represented by the formula (10) with an acid:

The manufacturing method of the chalcogen containing polycyclic compound represented by these.

In each formula, R ¹ independently represents an alkyl group having 1 to 20 carbon atoms, Z ¹ independently represents a sulfur atom or a selenium atom, Z ² represents an oxygen atom, a sulfur atom or a selenium atom, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a fluorine atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, or an optionally substituted carbon atom. An alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and a substituent; An optionally substituted heteroaralkyl group having 5 to 30 carbon atoms, an optionally substituted heteroaryl group having 4 to 30 carbon atoms, or —Si (R ² ) ₃ (R ² is independently substituted; C1-C30 alkyl which may have a group Or a substituted silyl group represented by.) Which represents an aryl group having 6 to 30 carbon atoms which may have a substituent.

  After reacting the compound represented by formula (5) with an acid, the reaction product and a base are preferably mixed.

で表される化合物を酸化する工程と、該工程で得られた下記式（３ａ）

で表される化合物と下記式（４ａ）

で表される化合物とを縮合する工程と、を含む方法により得られる化合物であることが好ましい。 The compound represented by the formula (5) is represented by the following formula (2a)

And a step of oxidizing the compound represented by formula (3a):

And a compound represented by the following formula (4a)

It is preferable that it is a compound obtained by the method including the process of condensing with the compound represented by these.

で表される化合物（３ｂ）を酸化する工程と、を含む方法により得られる化合物であることも好ましい。 The compound represented by the above formula (5) includes a step of condensing the compound represented by the above formula (2a) and the compound represented by the above formula (4a), and the following formula (3b) obtained in the above step.

It is also preferable that it is a compound obtained by the method including the process of oxidizing the compound (3b) represented by these.

で表される化合物と下記式（４ｂ）

で表される化合物とを縮合する工程と、該工程で得られた式（３ｂ）で表される化合物を酸化する工程と、を含む方法により得られる化合物であることも好ましい。 The compound represented by the above formula (5) is represented by the following formula (2b)

And a compound represented by the following formula (4b)

It is also preferable that it is a compound obtained by the method of condensing the compound represented by these, and the process of oxidizing the compound represented by Formula (3b) obtained at this process.

で表される化合物に含まれる水素原子を、ハロゲン原子、炭素数１〜２０のアルキルスルホネート基又は炭素数６〜２０のアリールスルホネート基に置換する工程を含む方法により得られる化合物であることが好ましい。 The compound represented by the above formula (2a) is represented by the following formula (1):

It is preferable that it is a compound obtained by the method including the process of substituting the hydrogen atom contained in the compound represented by a halogen atom, a C1-C20 alkylsulfonate group, or a C6-C20 arylsulfonate group. .

  The compound represented by the formula (2b) is preferably a compound obtained by a method including a step of substituting a leaving group for a hydrogen atom contained in the compound represented by the formula (1).

で表される基であることが好ましい。 In formulas (2a), (3a), (4a), (2b), (3b), (4b) and (1), R ¹ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , Z ¹ and Z ² is as defined above. X ¹ independently represents a halogen atom, an alkyl sulfonate group having 1 to 20 carbon atoms or an aryl sulfonate group having 6 to 20 carbon atoms, and X ² represents a leaving group. The leaving group X ² has the following formula (6)

It is preferable that it is group represented by these.

Wherein ^{(6), R 10} are each independently, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an aryloxy group having 6 to 20 carbon atoms having 1 to 10 carbon atoms. Two R ¹⁰ in the molecule may be bonded to form a ring structure together with the boron atom.

It is preferable that both Z ¹ and Z ^{2 in the} chalcogen-containing fused polycyclic compound are sulfur atoms.

In the chalcogen-containing fused polycyclic compound, at least one group selected from the group consisting of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, It is an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, and other R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are preferably hydrogen atoms.

で表される各化合物を提供する。 The present invention also provides each compound represented by the above formula (3a), (3b) or (5) and the following formula (10-3):

Each compound represented by is provided.

In formulas (3b) and (5), R ¹² is the same group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms, R ¹¹ , R ¹³ and R ¹⁴ are preferably both hydrogen atoms.

で表される化合物にアルキルリチウムを反応させる第Ｉ’工程と、第Ｉ’工程の反応生成物をアルキルスルフィド化又はアルキルセレニド化する第ＩＩ’工程と、を有する、式（３ｂ）

で表される化合物の製造方法に関する。 The present invention also provides formula (4)

A compound represented by formula (3b), comprising: a step I ′ in which alkyllithium is reacted with an alkyllithium; and a step II ′ in which the reaction product of step I ′ is alkylsulfided or alkylselenylated.

It relates to the manufacturing method of the compound represented by these.

In each formula, R ¹ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , Z ¹ and Z ² are as defined in formula (1), and X ⁵ independently represents a halogen atom.

In the step II ′, after reacting the reaction product of the step I ′ with sulfur or selenium, the formula (11)
R ¹ -X ⁶ (11)
It is preferable that the reaction product of the step I ′ is subjected to alkyl sulfidation or alkyl selenide reaction by reacting an alkyl halide represented by the following formula. In formula (11), R ¹ has the same definition as in formula (3b), and X ⁶ represents a halogen atom.

で表される化合物にハロゲン化剤を反応させる工程を含む方法により得られる化合物であることが好ましい。 The compound represented by the formula (4) has the formula (3)

It is preferable that it is a compound obtained by the method including the process of making a halogenating agent react with the compound represented by these.

で表される化合物と式（４ａ）

で表される化合物とを縮合する工程を含む方法によって得られる化合物であることが好ましい。 The compound represented by the formula (3) is represented by the formula (1c)

And a compound represented by formula (4a)

It is preferable that it is a compound obtained by the method including the process of condensing with the compound represented by these.

In formulas (3) and (1c), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , X ¹ and Z ² have the same definitions as in formulas (5) and (2a).

  According to the production method of the present invention, the chalcogen-containing polycyclic compound can be produced at a milder reaction temperature than before. Moreover, according to this invention, each compound represented by Formula (5), (3a) or (3b) is provided as an intermediate for manufacturing a chalcogen-containing polycyclic compound.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

The production method of the chalcogen-condensed polycyclic compound represented by the following general formula (10) according to the present embodiment (hereinafter sometimes referred to as “chalcogen-condensed polycyclic compound (10)”) is as follows. A step of reacting a compound represented by the formula (5) (hereinafter sometimes referred to as “compound (5)”) with an acid (hereinafter sometimes referred to as “step 4”).
As a manufacturing method of the compound (5) used for the process 4, the method through the following processes 1A, 2A, and 3A can be illustrated.
Step 1A:
A hydrogen atom contained in a compound represented by the following formula (1) (hereinafter sometimes referred to as “compound (1)”) is a halogen atom, an alkyl sulfonate group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. Substitution of 20 aryl sulfonate groups Step 2A:
Step 3A for oxidizing the compound represented by the following formula (2a) obtained in Step 1A (hereinafter sometimes referred to as “compound (2a)”):
The compound represented by the following formula (3a) obtained in step 2A (hereinafter sometimes referred to as “compound (3a)”) and the compound represented by the following formula (4a) (hereinafter referred to as “compound (4a)”. ) "May be noted.)

As another production method of the compound (5) used in the step 4, the following step 3B can be exemplified.
Step 3B:
A step of oxidizing a compound represented by the following formula (3b) (hereinafter sometimes referred to as “compound (3b)”).

  Here, the compound (3b) can be obtained, for example, via the step 1A described above and the step 2B described later, or via the step 1B described later and the step 2C described later.

Step 2B:
A step of condensing compound (2a) obtained in step 1A with compound (4a)

Step 1B:
Step 2C for substituting a leaving group for a hydrogen atom contained in compound (1):
The compound represented by the following formula (2b) obtained in step 1B (hereinafter sometimes referred to as “compound (2b)”) and the compound represented by the following formula (4b) (hereinafter referred to as “compound (4b)”. ) "May be noted.)

When X ¹ of the compound (4b) is a halogen atom, for example, a commercially available halogenated benzene compound or the like may be used as it is, or a benzene compound may be halogenated by a known method to obtain a compound (4b). when X ¹⁾ of the alkyl sulfonate group or an aryl sulfonate group, for example, J. Org. Chem. Soc. , 1999, 64, 3266, a compound (4b) can be obtained by reacting an alkylsulfonic acid anhydride or an arylsulfonic acid anhydride with a compound in which X ¹ of the compound (4b) is a phenolic hydroxyl group. Good.

Hereinafter, step 1A will be described.
First, the compound (1) in step 1A will be described.
R ¹ in the compound (1) represents an alkyl group having 1 to 20 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, 2-ethylhexyl Group, n-heptyl group, n-octyl group, 2-hexyloctyl group, n-nonyl group, n-decyl group, 2-hexyldecyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n -A tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group are mentioned. Preferably methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl Group, n-octyl group, n-nonyl group, and n-decyl group. R ¹ is more preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl, still more preferably methyl, ethyl, n-propyl, and Selected from n-butyl groups.

Z ¹ in the compound (1) independently represents a sulfur atom or a selenium atom. Z ¹ is preferably a sulfur atom. Z ² represents an oxygen atom, a sulfur atom or a selenium atom. Z ² is preferably an oxygen atom or a sulfur atom, and more preferably a sulfur atom.

Examples of the compound (1) include compounds of numbers (1-1) to (1-34) in which Z ¹ , Z ² and R ¹ are combinations exemplified in Table 1.

  As preferred compounds (1), for example, (1-1), (1-2), (1-3), (1-4), (1-5), (1-7), (1-8) ), (1-9), (1-10), (1-12), (1-13), (1-14), (1-16), (1-21), (1-22), (1-24), (1-27), (1-31), or (1-33) compounds, more preferably (1-1), (1-2), (1-5), ( 1-8), (1-10), (1-13), (1-21), (1-27), (1-31), or the compound of (1-33) is mentioned.

As a preparation method of the compound (1) when Z ¹ of the compound (1) is sulfur, for example, the following formula (1a):

（式中、Ｚ^２は上記と同じ意味を示し、Ｘ^５は臭素原子、ヨウ素原子等のハロゲン原子を示す。）で表される化合物（以下、化合物（１ａ）と記すことがある。）にアルキルリチウムを反応させる第Ｉ工程と、第Ｉ工程で得られた反応生成物をアルキルスルフィド化する第ＩＩ工程とを含む調製方法を挙げることができる。

(Wherein, Z ² has the same meaning as described above, and X ⁵ represents a halogen atom such as a bromine atom or an iodine atom) (hereinafter, may be referred to as compound (1a)). A preparation method including Step I in which alkyllithium is reacted and Step II in which the reaction product obtained in Step I is alkylsulfided can be mentioned.

  Examples of the solvent for the above preparation method include aliphatic hydrocarbon solvents such as pentane, hexane, and heptane, aromatic hydrocarbon solvents such as toluene and xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, And ether solvents such as propylene glycol dimethyl ether, and mixed solvents thereof. Pentane, hexane, toluene, diethyl ether, tetrahydrofuran, and cyclopentyl methyl ether are preferable.

  Examples of the alkyl lithium used in Step I include methyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, and phenyl lithium. N-butyllithium, sec-butyllithium, and tert-butyllithium are preferable, and sec-butyllithium, tert-butyllithium, and the like are more preferable.

  The example of the step I will be described more specifically. After dissolving or suspending the compound (1a) in a solvent, for example, −40 ° C. or lower, preferably −55 ° C. to −110 ° C., more preferably − After cooling to a temperature range of 65 ° C. to −100 ° C., 1 to 4 mol, preferably 2 to 4 mol, of alkyl lithium is added to 1 mol of compound (1a), and further 10 minutes in the above temperature range. Stir for ~ 5 hours.

As the step II, for example, the reaction product obtained in the step I is added to the following formula R ¹ —S—S—R ¹
(Wherein R ¹ has the same meaning as described above.)
A dialkyl disulfide represented by the following (hereinafter sometimes simply referred to as dialkyl disulfide) (hereinafter, also referred to as “(I) step”), and
After reacting the reaction product obtained in Step I with sulfur, the formula (11)
R ¹ -X ⁶ (11)
(In the formula, R ¹ represents the same meaning as described above, and X ⁶ represents a halogen atom such as a bromine atom or an iodine atom.)
A step of reacting an alkyl halide represented by formula (hereinafter sometimes referred to as “halogenated alkyl (11)”) (hereinafter sometimes referred to as “step (II)”),
Etc.

  Although the case where sulfur was used as the step II was exemplified in the previous section, the sulfur described in the previous section and the description of the step II described later may be replaced with selenium.

The (I) step of the second step will be described.
Examples of the dialkyl disulfide used in the step (I) include dimethyl disulfide, diethyl disulfide, di-n-propyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, di-n-octyl disulfide, and di- -N-decyl disulfide is mentioned. Preferred are dimethyl disulfide, diethyl disulfide, and di-n-hexyl disulfide, and more preferred are dimethyl disulfide, di-n-hexyl disulfide, and the like.

  In step (I), for example, the reaction product obtained in step I is 1 mol to 4 mol, preferably 2 mol to 4 mol, relative to 1 mol of compound (1a) used in step I. The dialkyl disulfide is added, and the reaction solution is heated to 30 ° C., if necessary, and stirred for 10 minutes to 48 hours.

  In the method for preparing compound (1) by the step I and the step (I), the step I and the step (I) are preferably performed in two steps. In this case, for example, after first dissolving or suspending the compound (1a) in a solvent, for example, −40 ° C. or less, preferably −55 ° C. to −110 ° C., more preferably −65 ° C. to −100 ° C. After cooling to the above temperature range, 1 to 2 mol of alkyl lithium is added to 1 mol of compound (1a), and the reaction solution is further stirred for 10 minutes to 5 hours in the above temperature range (in the step I). To the reaction product obtained in this step, 0.5 mol to 2 mol of dialkyl disulfide is added to 1 mol of compound (1a), and the temperature is raised to 30 ° C. if necessary. A step of stirring the reaction solution for 10 minutes to 48 hours (first time of the step (I)) is performed, and the formula (1b):

（式中、Ｒ^１、Ｚ^２及びＸ^５は上記と同じ意味を示す。）
で表される化合物（以下、化合物（１ｂ）と記すことがある。）を生成させる。続いて、生成した化合物（１ｂ）を含む反応生成物を、例えば、−４０℃以下、好ましくは−５５℃〜−１１０℃、更に好ましくは、−６５℃〜−１００℃の温度範囲に冷却させた後、アルキルリチウムを化合物（１ｂ）１モルに対して、０．５モル〜２モル加え、更に上記温度範囲で１０分〜５時間反応液を攪拌する工程（第Ｉ工程の２回目）を行い、この工程で得られた反応生成物に、化合物（１ｂ）１モルに対して、０．５モル〜２モルのジアルキルジスルフィドを加え、必要に応じて３０℃まで昇温させ、１０分から４８時間反応液を攪拌する工程（（Ｉ）工程の２回目）を行う。

(Wherein R ¹ , Z ² and X ⁵ have the same meaning as described above.)
(Hereinafter, may be referred to as compound (1b)). Subsequently, the reaction product containing the produced compound (1b) is cooled to, for example, −40 ° C. or less, preferably −55 ° C. to −110 ° C., more preferably −65 ° C. to −100 ° C. Then, 0.5 mol to 2 mol of alkyl lithium is added to 1 mol of compound (1b), and the reaction solution is further stirred for 10 minutes to 5 hours in the above temperature range (second step of Step I). Then, 0.5 mol to 2 mol of dialkyl disulfide is added to 1 mol of compound (1b) to the reaction product obtained in this step, and the temperature is raised to 30 ° C., if necessary, from 10 minutes to 48 minutes. A step of stirring the reaction solution for a period of time (second time of step (I)) is performed.

  Here, for example, the compound (1b) may be isolated by performing purification such as distillation, recrystallization, and silica gel chromatography.

  Next, step (II) of step II will be described.

  Examples of the alkyl halide used in the step (II) include methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, -n-propyl bromide, n-propyl iodide, and n-bromide. Butyl, iodide-n-butyl, bromide-n-hexyl, iodide-n-hexyl, bromide-n-octyl, iodide-n-octyl, bromide-n-decyl, iodide-n-decyl , Bromide-n-dodecyl, bromide-n-tetradecyl, and bromide-n-icosyl. Preferred examples include methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, iodinated n-propyl, iodinated n-butyl, and iodinated n-hexyl, iodinated n-decyl. . As a solvent used here, the same thing as the above is mentioned, The thing similar to the above is preferable.

  The sulfur used in the step (II) is preferably pulverized. Sulfur is preferably used as a powder or a suspension dissolved or suspended in the above solvent.

  As the step (II), for example, the reaction product obtained in the step I is set to −40 ° C. or lower, preferably −55 ° C. to −110 ° C., more preferably −65 ° C. to −100 ° C. 1 mol to 6 mol, preferably 2 to 6 mol of sulfur is added in the above temperature range with respect to 1 mol of the compound (1a) used in step I, and the reaction solution is stirred for 10 minutes to 5 hours. In addition, 2 to 4 mol of alkyl halide (11) is added to 1 mol of compound (1a), the temperature is raised to 30 ° C. as necessary, and the reaction solution is stirred for 10 minutes to 48 hours. be able to.

  In the preparation method of the compound (1) by the step I and the step (II), the mixing of the sulfur in the step I and the step (II) was performed in two steps, and then the alkyl halide (11) was mixed. It is preferable to do. In this case, for example, first, the compound (1a) is dissolved or suspended in a solvent and, for example, a temperature of −40 ° C. or lower, preferably −55 ° C. to −110 ° C., more preferably −65 ° C. to −100 ° C. After cooling to the range, 1 to 3 mol of alkyllithium is added to 1 mol of compound (1a), and the reaction solution is further stirred for 10 minutes to 5 hours in the above temperature range (first step of Step I). 1 mol to 3 mol of sulfur is added to 1 mol of compound (1a) to the obtained reaction product, and the reaction solution is stirred for 10 minutes to 5 hours in the same temperature range as in the first step of Step I. (First mixing of sulfur in step (II)). Next, in the reaction product obtained in the first mixing of sulfur in step (II), alkyllithium is added in an amount of 1 mol to 1 mol of compound (1a) in the same temperature range as in the first step of step I. 3 mol is added again, and the reaction solution is stirred for 10 minutes to 5 hours (second time in Step I). Subsequently, 1 mol to 3 mol of sulfur is again added to 1 mol of the compound (1a) to the reaction product obtained in the second step of Step I, and the temperature is raised to 30 ° C. as necessary. The reaction solution is stirred for 5 to 5 hours (the second mixing of sulfur in the step (II)). Furthermore, 2-4 mol of alkyl halide (11) is added to 1 mol of compound (1a) to the reaction product obtained in the second mixing of sulfur in step (II). The temperature is raised to 30 ° C., and the reaction solution is stirred for 10 minutes to 48 hours.

  For the reactive organisms obtained by the step (I) or the step (II) and containing the compound (1b), the compound (1) and the like, for example, post-treatment such as washing with water, drying, and solvent distillation is performed. Further, purification such as distillation, recrystallization, and silica gel chromatography may be performed.

  Next, the compound (2a) obtained in Step 1A will be described.

R ¹ , Z ¹ , and Z ² in the compound (2a) may be the same as those described above, and those similar to the above are preferable. X ¹ represents a halogen atom, an alkyl sulfonate group having 1 to 20 carbon atoms or an aryl sulfonate group having 6 to 20 carbon atoms, and two X ¹ in the same molecule may be the same or different but are the same. It is preferable.

  As a halogen atom, a bromine atom, a chlorine atom, and an iodine atom can be mentioned, for example.

The alkyl sulfonate group having 1 to 20 carbon atoms, an alkyl group and sulfonate group which has carbon atoms which may 20 have a fluorine atom or the like - a group consisting of a (-OSO _2). For example, a methyl sulfonate group, an ethyl sulfonate group, and a trifluoromethyl sulfonate group can be mentioned. The aryl sulfonate group is a group consisting of an alkyl group and an aryl group which may have a fluorine atom and the like and a sulfonate group. For example, a phenyl sulfonate group and p-toluene sulfonate group can be mentioned.

  Of the halogen atom, alkyl sulfonate group, and aryl sulfonate group, a halogen atom is preferable, and a bromine atom and an iodine atom are more preferable.

Examples of the compound (2a) include compounds of numbers (2a-1) to (2a-43) in which Z ¹ , Z ² , R ¹ and X ¹ are combinations exemplified in Table 2 and Table 3. .

  As a preferable compound (2a), the compound numbers described in Tables 2 and 3 are (2a-1), (2a-2), (2a-3), (2a-5), (2a-8), ( 2a-9), (2a-10), (2a-12), (2a-13), (2a-14), (2a-17), (2a-21), (2a-22), (2a- 25), (2a-27), (2a-28), (2a-31), (2a-32), (2a-33), (2a-34), (2a-35), (2a-36) , (2a-37), (2a-38), (2a-39), (2a-40), or (2a-41). More preferably, the compound numbers described in Tables 2 and 3 are (2a-1), (2a-2), (2a-5), (2a-8), (2a-9), (2a-10) , (2a-13), (2a-17), (2a-21), (2a-25), (2a-27), (2a-31), (2a-33), (2a-35), ( The compound which is 2a-36) or (2a-37) is mentioned.

In Step 1A, the hydrogen atom (hydrogen atom at the α-position of Z ² ) contained in compound (1) is substituted with a halogen atom, an alkyl sulfonate group having 1 to 20 carbon atoms, or an aryl sulfonate group having 6 to 20 carbon atoms. The method is not particularly limited. As a method of substituting a hydrogen atom contained in compound (1) with a halogen atom, for example, compound (1) is reacted with a halogenating agent such as N-chlorosuccinimide, N-bromosuccinimide, or N-iodosuccinimide. The method is preferred. The amount of the halogenating agent is preferably 2 to 20 mol, more preferably 2 to 10 mol, per 1 mol of compound (1). Examples of the reaction solvent include aliphatic hydrocarbon solvents such as pentane, hexane, and heptane, aromatic hydrocarbon solvents such as toluene and xylene, such as methylene chloride, chloroform, 1,2-dichloroethane, and 1 Halogenated hydrocarbon solvents such as 1,2-dichloropropane, ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and cyclopentyl methyl ether, and mixed solvents thereof. Preferably, methylene chloride, chloroform, toluene, diethyl ether, tetrahydrofuran, and 1,4-dioxane are mentioned, More preferably, chloroform is mentioned. According to this method, for example, the reaction can easily proceed in the solution at a temperature of about −20 ° C. to 100 ° C. The reaction time is, for example, 10 minutes to 48 hours. After completion of the reaction, the compound (2a) can be obtained by performing general post-treatment and, if necessary, purifying by distillation, recrystallization, silica gel chromatography or the like.

Next, the compound (2b) obtained in the step 1B will be described. R ¹ , Z ¹ and Z ² in the compound (2b) are the same as those described above, and the same are preferable, and two Z ¹ in the same molecule may be the same or different. Are preferably the same. X ² represents a leaving group.

The leaving group ^{X 2,} the compound with the compound (2a) (4a), Compound (2b) and compound (4b), or a leaving group such as a condensation reaction can proceed in the compound (3a) Compound (4a) If it is. For example, a group represented by the following formula (6) is preferable.

In formula (6), each R ¹⁰ independently represents a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, and R ¹⁰ is the same or different. Or two R ¹⁰ may be bonded to form a ring structure together with the boron atom.

  Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, Linear, branched or cyclic such as cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and 1,2-dimethylpropyl group Of the alkyl group. As a C1-C10 alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, n-butoxy group, and n-hexanoxy group are mentioned, for example. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a 1-naphthoxy group, and a 2-naphthoxy group.

When two R ¹⁰ are bonded to form a ring structure with a boron atom, preferred examples include 1,3,2-dioxaborolane ring, 4,4,5,5-tetramethyl-1,3,2-dioxaborolane And a ring, 5,5-dimethyl-1,3,2-dioxaborinane ring, 1,3,2-benzodioxaborol ring, and 9-borabicyclo3,3,1-nonane ring.

  Specific examples of the leaving group include leaving groups represented by the following formulas (7), (8) and (9), in addition to the group of the formula (6).

R ²⁰ in the formula (7) independently represents an alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl. Group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, and n-decyl group. Preferred are a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group, and more preferred are a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. R ²⁰ in formula (7) may be different from each other, but is preferably the same.

X ³ in Formula (8) represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. X ³ is preferably a bromine atom or an iodine atom.

X ⁴ in Formula (9) represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. X ⁴ is preferably a bromine atom or an iodine atom.

Examples of the compound (2b) include compounds of numbers (2b-1) to (2a-52) in which Z ¹ , Z ² , R ¹ and X ² are combinations shown in Table 4 and Table 5.

  As a preferable compound (2b), the compound numbers described in Tables 4 and 5 are (2b-1), (2b-2), (2b-5), (2b-8), (2b-10), ( 2b-12), (2b-13), (2b-15), (2b-17), (2b-19), (2b-30), (2b-33), (2b-38), (2b- 40), (2b-42), (2b-45), (2b-46), (2b-50), or (2b-51). More preferably, the compound numbers are (2b-1), (2b-8), (2b-10), (2b-13), (2b-19), (2b-30), (2b-33), ( 2b-38), (2b-40), (2b-42), (2b-45), (2b-46), (2b-50), or (2b-51).

で表される基に置換する方法としては、例えば、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，２００６，１２８，９０３４記載の方法に準拠して、化合物（１）にＢｕＬｉを作用させた後、２−イソプロポキシ−４，４，５，５−テトラメチル−１，３，２−ジオキサボロランと反応させる方法がある。 The method for substituting the hydrogen atom of compound (1) with a leaving group is not particularly limited. The following formula, which is one of the groups represented by formula (6) as the leaving group

As a method for substitution with a group represented by Am. Chem. Soc. , 2006, 128, 9034, after allowing BuLi to act on compound (1), 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and There is a method of reacting.

In addition, after obtaining a compound in which two X ¹ in the compound (2a) are bromine atoms by Step 1A, Appl. Poly. Sci. , 2009, 114, 1278, after allowing BuLi to act on compound (2a), 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and By the reaction method, the compound (2a) substituted with the group represented by the above formula can be obtained.

Examples of the method for substituting the hydrogen atom in the compound (2a) with a leaving group represented by the formula (7) and in which R ²⁰ is a methyl group include: Am. Chem. Soc. , 2003, 125, 13173, there is a method in which BuLi is allowed to act on compound (1) and then reacted with trimethyltin chloride. In Step 1A, a compound in which two X ¹ 's in the compound (2a) are bromine atoms was obtained. Org. Chem. , 1984, 49, 5250, by reacting BuLi with compound (2a) and then reacting with trimethyltin chloride, R ²⁰ represented by the formula (7) is a methyl group. The compound (2a) substituted by the leaving group which is can be obtained.

As a method for substituting the hydrogen atom in the compound (2a) with a group represented by the formula (8) as a leaving group, for example, in Step 1A, two X ¹ in the compound (2a) are bromine atoms. After obtaining the compound, Phys. Chem. In accordance with the method described in B, 2009, 113, 8214, the compound (2a) was substituted with a leaving group represented by the formula (8) and X ³ being a bromine atom by the method of allowing metal magnesium to act. Compound (2a) can be obtained.

As a method for substituting the hydrogen atom in the compound (2a) with a group represented by the formula (9) as a leaving group, for example, in Step 1A, two X ¹ in the compound (2a) are bromine atoms. After obtaining the compound, Am. Chem. Soc. , 2003, 125, 3867, a compound represented by formula (9) and substituted with a leaving group in which X ⁴ is a bromine atom by a method in which metal zinc is allowed to act on compound (2a) (2a) can be obtained.

Next, step 2A and step 3B will be described. The method for oxidizing compound (2a) or compound (3b) in step 2A or step 3B is not particularly limited. As a method for oxidizing compound (2a) or compound (3b), for example, compound (2a) or compound (3b) is converted into hydrogen peroxide, m-chloroperbenzoic acid, perbenzoic acid, peracetic acid, tert-butylhydro Examples thereof include peroxides and peroxides such as cumene hydroperoxide, and a method of reacting with an oxidizing agent such as quinone compounds such as 2,3-dichloro-5,6-dicyano-p-benzoquinone. As the oxidizing agent, hydrogen peroxide, m-chloroperbenzoic acid, perbenzoic acid, peracetic acid, and peroxides such as tert-butyl hydroperoxide are preferable, and hydrogen peroxide is more preferable. According to this method, for example, the reaction can easily proceed at a temperature of −20 ° C. to 100 ° C., preferably 0 ° C. to 80 ° C. The amount of the oxidizing agent is, for example, 1 mol to 5 mol, preferably 1.5 mol to 3 mol, relative to 1 mol of the compound (2a) or the compound (3b). When the amount of the oxidizing agent is 5 mol or less, the progress of peroxidation (for example, oxidation to -SO ₂ -in the case of a sulfur atom (-S-)) can be suppressed. Examples of the reaction solvent include water, acetic acid, for example, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, for example, halogen such as methylene chloride, chloroform, 1,2-dichloroethane, and 1,2-dichloropropane. Hydrocarbon solvents, for example, alcohol solvents such as methanol, ethanol, isopropanol, and n-butanol, and mixed solvents thereof can be exemplified. Alcohol solvents such as methanol, ethanol and isopropanol or acetic acid are preferred, and acetic acid is more preferred.

  Since both the reaction of step 2A and step 3B can be performed at about the above temperature range and at normal pressure, the desired compound (3a) or compound (5) is obtained in mild conditions and in high yield. Can do.

Examples of the compound (3a) include compounds of numbers (3a-1) to (3a-41) in which Z ¹ , Z ² , R ¹ and X ¹ are combinations shown in Table 6.

  Preferable compounds (3a) include the numbers (3a-1), (3a-2), (3a-3), (3a-5), (3a-8), (3a-10), (3a-12) ), (3a-13), (3a-14), (3a-17), (3a-21), (3a-22), (3a-25), (3a-27), (3a-31), (3a-33), (3a-35), (3a-36), (3a-37), (3a-38), (3a-39), (3a-40), or (3a-41). Compounds. More preferably, the compound (3a) has the numbers (3a-1), (3a-2), (3a-8), (3a-10), (3a-13), (3a-17), (3a -21), (3a-25), (3a-27), (3a-31), (3a-33), or (3a-35).

  Next, step 2B, step 2C, and step 3A will be described. Step 2B is a step of condensing compound (2a) with compound (4a) described later to obtain compound (3b), and step 2C is a process of condensing compound (2b) with compound (4b) described later to obtain compound ( 3b), and step 3A is a step of condensing compound (3a) with compound (4a) described later to obtain compound (5). Hereinafter, this condensation reaction may be collectively referred to.

Compound ^{X 2} in (4a) and compound (2b), when the group represented by the formula (6), condensation reaction, for example, the presence of a transition metal catalyst and a base, for example, 0 ° C. to 150 DEG ° C. approximately The reaction can easily proceed in the solution within the above temperature range. Since all of the present condensation reactions can be carried out in the above temperature range and at normal pressure, compound (3b) or compound (5) can be obtained in mild conditions and in high yield.

  Examples of the transition metal catalyst used in the condensation reaction include a palladium catalyst and a nickel catalyst. As the paradymium catalyst, a commercially available one may be used, one prepared in advance from a palladium compound and a phosphine compound, or a palladium compound and a phosphine compound may be used in the reaction system of this condensation reaction. May be prepared.

  Examples of the palladium catalyst include tetrakis (triphenylphosphine) palladium (0), bis (acetate) bis (triphenylphosphine) palladium (II), bis [1,2-bis (diphenylphosphino) ethane] palladium (0 ), [1,2-bis (diphenylphosphino) ethane] dichloropalladium (II), dibromobis (triphenylphosphine) palladium (II), dichlorobis (dimethylphenylphosphine) palladium (II), dichlorobis (methyldiphenylphosphine) palladium (II), dichlorobis (tricyclohexylphosphine) palladium (II), dichlorobis (triethylphosphine) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorobi [Tris (2-methylphenyl) phosphine] palladium (II), tetrakis (methyldiphenylphosphine) palladium (0), tetrakis (tricyclohexylphosphine) palladium (0), and dichlorobis (1,1′-diphenylphosphinoferroce Nyl) palladium (II).

  Examples of the palladium compound used for the preparation of the paradymium catalyst include zero-valent palladium such as tris (dibenzylideneacetone) dipalladium (0) and tris (dibenzylideneacetone) dipalladium (0) / chloroform adduct. Compounds containing, for example, palladium (II) acetate, palladium (II) chloride, palladium (II) bromide, palladium (II) iodide, (bicyclo [2.2.1] hepta-2,5-diene) dichloro Palladium (II), (2,2′-bipyridyl) dichloropalladium (II), bis (acetonitrile) chloronitropalladium (II), bis (benzonitrile) dichloropalladium (II), bis (acetonitrile) dichloropalladium (II) Dichloro (1,5-cyclooctadiene) palladium (I ), Dichloro (ethylenediamine) palladium (II), dichloro (N, N, N ′, N′-tetramethylenediamine) palladium (II), dichloro (1,10-phenanthroline) palladium (II), palladium (II) acetyl Examples thereof include compounds containing divalent palladium such as acetonate, palladium (II) hexafluoroacetylacetonate, palladium (II) nitrate, palladium (II) sulfate, and palladium (II) trifluoroacetate. Palladium (II) acetate, palladium (II) chloride, and tris (dibenzylideneacetone) dipalladium (0) are mentioned. As the palladium compound, a commercially available product is usually used.

  Examples of the phosphine compound used for the preparation of the paradium catalyst include triphenylphosphine, tris (2-methylphenyl) phosphine, tris (3-methylphenyl) phosphine, tris (4-methylphenyl) phosphine, tris (pentafluorophenyl) phosphine , Tris (4-fluorophenyl) phosphine, tris (2-methoxyphenyl) phosphine, tris (3-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, Tri (3-chlorophenyl) phosphine, tri (4-chlorophenyl) phosphine, tri-n-butylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, 1,2-diphenylphosphinoethane 1,3-diphenylphosphinopropane, 1,4-diphenylphosphinobutane, 1,2-dicyclohexylphosphinoethane, 1,3-dicyclohexylphosphinopropane, 1,4-dicyclohexylphosphinobutane, 1,2-dimethyl Phosphinoethane, 1,3-dimethylphosphinopropane, 1,4-dimethylphosphinobutane, 1,2-diethylphosphinoethane, 1,3-diethylphosphinopropane, 1,4-diethylphosphinobutane, 1 , 2-diisopropylphosphinoethane, 1,3-diisopropylphosphinopropane, 1,4-diisopropylphosphinobutane, tri-2-furylphosphine, 2- (dicyclohexylphosphino) biphenyl, 2- (di-tert-butyl) Phosphino) biphenyl, 2-di- ert-Butylphosphino-2′-methylbiphenyl, 2- (dicyclohexylphosphino-2′-6′-dimethoxy, 1,1′-biphenyl, 2- (dicyclohexylphosphino) -2 ′-(N, N- Dimethylamino) biphenyl, 2-dicyclohexylphosphino-2′-methyl-biphenyl, 2- (dicyclohexylphosphino) -2 ′, 4 ′, 6′-tri-isopropyl 1,1′-biphenyl, 1,1′- Examples thereof include bis (diphenylphosphino) ferrocene and 1,1′-bis (di-isopropylphosphino) ferrocene, etc. As such phosphine compounds, commercially available ones may be used or according to known methods. The amount of the phosphine compound used is, for example, 0 with respect to 1 mol of the palladium compound. .5 mol to 10 mol, preferably 1 mol to 5 mol.

  Examples of the nickel catalyst used in the condensation reaction include dichlorobis (1,1′-diphenylphosphinoferrocenyl) nickel (II), dichlorobis (diphenylphosphino) nickel (II), dichloronickel (II), and Diiodine nickel (II) may be mentioned.

  The amount of the transition metal catalyst used is, for example, 0.0005 mol to 0.5 mol as a transition metal atom with respect to 1 mol of the compound (2a), the compound (3a) or the compound (4b).

  This condensation reaction is preferably performed in the presence of a reaction solvent. Examples of the reaction solvent include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, tert-butyl methyl ether, and ethylene glycol dimethyl ether, N, N Amide solvents such as dimethylformamide and N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, and water. A reaction solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it. The solvent is preferably used after deaeration. Alternatively, some or all of the compounds used in the reaction may be dissolved or suspended in the reaction solvent and then degassed by a method such as nitrogen bubbling. The usage-amount of the reaction solvent is 0.5 mass part-200 mass parts with respect to 1 mass part of a compound (2a), a compound (3a), or a compound (4b), Preferably it is 2 mass parts-100 masses. Part.

  This condensation reaction is preferably performed in the presence of a base. Examples of the base include lithium hydroxide, sodium hydroxide, potassium hydroxide, thallium hydroxide, barium hydroxide, lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, Sodium-tert-butoxide, potassium-tert-butoxide, lithium carbonate, sodium carbonate, potassium carbonate, thallium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, and potassium phosphate are used. The amount of the base to be used is at least 0.5 mol, preferably at least 1 mol, per 1 mol of compound (2a), compound (3a) or compound (4b).

  This condensation reaction may be performed in the presence of a phase transfer catalyst. Examples of the phase transfer catalyst include quaternary ammonium salts such as tetraalkyl ammonium halide, tetraalkyl ammonium hydrogen sulfate, and tetraalkyl ammonium hydroxide, preferably tetra-n-butyl ammonium halide. And benzyltriethyl ammonium halide. The reaction atmosphere can be carried out in the air, but it is preferably carried out under an inert gas such as nitrogen or argon.

  The reaction temperature of this condensation reaction can mention the range of 0 to 150 degreeC, for example. The reaction time of this condensation reaction can mention the range of 1 minute-96 hours, for example. After completion of the condensation reaction, for example, the obtained reaction mixture and an aqueous ammonium chloride solution are mixed, and if necessary, an extraction process is performed by adding an organic solvent insoluble in water, and the obtained organic layer is concentrated and necessary. The compound (5) or the compound (3b) can be obtained by performing purification means such as column chromatography, distillation, recrystallization, and recycle gel permeation chromatography according to the above.

The compounds (4a) and (4b) used in Step 3A and Step 2B will be described. Examples of X ² in the compound (4a) include the same as those described above, and those similar to the above are preferable. Examples of X ¹ in the compound (4b) include the same as those described above, and those similar to the above are preferable.

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in the compounds (4a) and (4b) are each independently a hydrogen atom, a fluorine atom, an optionally substituted alkyl group having 1 to 30 carbon atoms or a substituted group. An optionally substituted alkoxy group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, and an optionally substituted group having 7 to 30 carbon atoms. An aralkyl group, an optionally substituted heteroaralkyl group having 5 to 30 carbon atoms, an optionally substituted heteroaryl group having 4 to 30 carbon atoms, or —Si (R ² ) ₃ (R ² each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent). Represents a substituted silyl group.

  The alkyl group having 1 to 30 carbon atoms in the present embodiment may be any of linear, branched, and cyclic. Specific examples of the alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, and neopentyl group. N-hexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group, 2-hexyloctyl group, n-nonyl group, n-decyl group, 2-hexyldecyl group, n-undecyl group, n- Dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, n-henicosyl group, n- Docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonakosi Group, n-triacontyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like, preferably methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t -Butyl group, n-pentyl group, neopentyl group, n-hexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, 2-hexyldecyl group, n- Examples include undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group. And more preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclohexyl. 2-ethylhexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, 2-hexyloctyl group, n-tetradecyl group C1-C16 alkyl groups, such as a group, n-pentadecyl group, n-hexadecyl group, cyclohexyl group, and cycloheptyl group.

  Examples of the substituent of the “optionally substituted alkyl group having 1 to 30 carbon atoms” in the present embodiment include a fluorine atom and an alkoxy group having 1 to 30 carbon atoms.

  As the substituent that the “optionally substituted alkyl group having 1 to 30 carbon atoms” in the present embodiment has, a fluorine atom is preferable. Examples of the alkyl group having 1 to 30 carbon atoms having a fluorine atom include a perfluorohexyl group, a perfluorooctyl group, a perfluorodecyl group, a perfluorododecyl group, and a perfluorotridecyl group.

  Examples of the alkoxy group having 1 to 30 carbon atoms in the present embodiment include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, and an n-heptyloxy group. , N-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group N-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-icosyloxy group, n-henicosyloxy group, n-docosyloxy group, n-tricosyloxy group N-tetracosyloxy group, n-pentacosyloxy group, n-hexacosyloxy group, n-heptacosyloxy group Group, n- oct cosyl group, can be exemplified n- Nonakoshiruokishi group, and n- triacontyl group. Preferably, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n- Decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group , N-octadecyloxy group, n-nonadecyloxy group, n-icosyloxy group, etc., and an alkoxy group having 1 to 20 carbon atoms.

  Examples of the substituent of the “optionally substituted alkoxy group having 1 to 30 carbon atoms” in the present embodiment include a fluorine atom, an alkoxy group having 1 to 30 carbon atoms, and an alkyl group having 6 to 30 carbon atoms. Examples thereof include an aryl group, an aralkyl group having 7 to 30 carbon atoms, a heteroaryl group having 4 to 30 carbon atoms, and a heteroaralkyl group having 5 to 30 carbon atoms. The hydrogen atom contained in the substituent may be replaced with a fluorine atom.

  As the substituent that the “optionally substituted alkoxy group having 1 to 30 carbon atoms” in the present embodiment has, a fluorine atom is preferable. Examples of the alkoxy group having 1 to 30 carbon atoms having a substituent include, for example, a perfluorohexyloxy group, a perfluorooctyloxy group, a perfluorodecyloxy group, a perfluorododecyloxy group, a perfluorotridecyloxy group, and a methoxy group. An ethoxyethoxy group etc. are mentioned.

  As the aryl group of the “aryl group having 6 to 30 carbon atoms which may have a substituent” in the present embodiment, a monocyclic or bicyclic aryl group can be exemplified. A preferred aryl group is phenyl. Group, 1-naphthyl group, 2-naphthyl group and the like.

  Examples of the substituent in the “aryl group having 6 to 30 carbon atoms which may have a substituent” in the present embodiment include a fluorine atom, an alkyl group having 1 to 20 carbon atoms, and a carbon atom having 1 to 20 carbon atoms. Examples thereof include an alkoxy group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, and a heteroaralkyl group having 5 to 20 carbon atoms. A hydrogen atom contained in the substituent may be replaced with a fluorine atom.

  As the “optionally substituted aryl group having 6 to 30 carbon atoms”, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, perfluorophenyl, and the like are preferable.

で表わされる基が挙げられる。 Examples of the heteroaryl group of the “optionally substituted heteroaryl group having 4 to 30 carbon atoms” in the present embodiment include a thienyl group, a furyl group, a thiazolyl group, and thieno [3,2-b]. Examples include thienyl group, fluoro [3,2-b] furyl group, thieno [3,2-b] furyl group, benzo [b] thienyl group, and benzo [b] furyl group. As the heteroaryl group, a thienyl group, a thiazolyl group, a thieno [3,2-b] thienyl group, a benzo [b] thienyl group, and a benzo [b] furyl group, more preferably the following chemical formula

The group represented by these is mentioned.

  Examples of the substituent of the “optionally substituted heteroaryl group having 4 to 30 carbon atoms” include a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and carbon. Examples thereof include an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a heteroaryl group having 4 to 30 carbon atoms, and a heteroaralkyl group having 5 to 30 carbon atoms. The hydrogen atom contained in the substituent may be replaced with a fluorine atom.

  Examples of the “optionally substituted heteroaryl group having 4 to 30 carbon atoms” include 2-thienyl group, 2-thieno [3,2-b] thienyl group, 2-benzo [b] thienyl group, 5-fluoro-2-thienyl group, 5-hexyl-2-thienyl, 4-hexyloxy-2-thienyl group and the like are preferable.

（ｎ１は１〜１４の整数を示し、ｎ２及びｎ３は１〜１０の整数を示す。）
で表される基が挙げられる。 Examples of the aralkyl group of the “aralkyl group having 7 to 30 carbon atoms which may have a substituent” in the present embodiment include the following formulas:

(N1 shows the integer of 1-14, n2 and n3 show the integer of 1-10.)
The group represented by these is mentioned.

  Examples of the substituent in the “aralkyl group having 7 to 30 carbon atoms which may have a substituent” in the present embodiment include a fluorine atom, an alkyl group having 1 to 20 carbon atoms, and a carbon atom having 1 to 20 carbon atoms. Examples thereof include an alkoxy group, an aralkyl group having 7 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, and a heteroaralkyl group having 5 to 20 carbon atoms. The hydrogen atom contained in the substituent alkyl group, alkoxy group, aralkyl group, heteroaryl group, and heteroaralkyl group may be replaced with a fluorine atom.

  As the substituent that the “aralkyl group having 7 to 30 carbon atoms which may have a substituent” in the present embodiment has, a fluorine atom is preferable.

（ｎ４及びｎ５は１〜２４の整数を示し、ｎ６は１〜２３の整数を示す。）
で表される基が挙げられる。 Examples of the “substituted aralkyl group having 7 to 30 carbon atoms” include, for example, the following formula:

(N4 and n5 show the integer of 1-24, n6 shows the integer of 1-23.)
The group represented by these is mentioned.

（ｎ４は１〜２６の整数を示し、ｎ５は１〜２４の整数を示し、ｎ６は１〜２２の整数を示す。）
で表されるヘテロアラルキル基を挙げることができる。 In the present embodiment, the heteroaralkyl group of the “heteroaralkyl group having 5 to 30 carbon atoms which may have a substituent” means that at least one carbon atom contained in the aromatic ring of the aralkyl group is a nitrogen atom, oxygen A group substituted by a hetero atom such as an atom, a sulfur atom, and a selenium atom means a heteroaralkyl group, for example,

(N4 represents an integer of 1 to 26, n5 represents an integer of 1 to 24, and n6 represents an integer of 1 to 22.)
The heteroaralkyl group represented by these can be mentioned.

（ｎ４は１〜２６の整数を示し、ｎ５は１〜２４の整数を示し、ｎ６は１〜２２の整数を示す。）
で表される基である。 More preferably, the heteroaralkyl group is represented by the following formula:

(N4 represents an integer of 1 to 26, n5 represents an integer of 1 to 24, and n6 represents an integer of 1 to 22.)
It is group represented by these.

  Examples of the substituent of the “optionally substituted heteroaralkyl group having 5 to 30 carbon atoms” in the present embodiment include a fluorine atom, an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms. Examples thereof include an alkoxy group, an aralkyl group having 7 to 30 carbon atoms, a heteroaryl group having 4 to 30 carbon atoms, and a heteroaralkyl group having 5 to 20 carbon atoms. The hydrogen atom contained in the substituent may be replaced with a fluorine atom.

（ｎ４は１〜２６の整数を示し、ｎ５は１〜２４の整数を示し、ｎ６は１〜２２の整数を示す。）
で表される基を挙げることができる。 As the substituent of the “optionally substituted heteroaralkyl group having 5 to 30 carbon atoms”, a fluorine atom is preferable. As the “optionally substituted heteroaralkyl group having 5 to 30 carbon atoms”, for example, the following formula

(N4 represents an integer of 1 to 26, n5 represents an integer of 1 to 24, and n6 represents an integer of 1 to 22.)
The group represented by these can be mentioned.

The substituted silyl group in the present embodiment is represented by the following formula: —Si (R ² ) ₃
(In the formula, each R ² independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent.)
It is group represented by these. Here, the total number of carbon atoms of the three alkyl groups or aryl groups bonded to the silicon atom in the substituted silyl group is 3 to 30. The alkyl group or the aryl group has a maximum of 28 carbon atoms. Some or all of the hydrogen atoms of the alkyl group or aryl group may be replaced by fluorine atoms.

  Specific examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tri (i-propyl) silyl group, t-butyldimethylsilyl group, dimethylhexylsilyl group, and dimethyldodecylsilyl group.

Examples of the compound (4a) include compounds of numbers (4a-1) to (4a-280) in which R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and X ² are combinations exemplified in Tables 7 to 23. be able to.

  As a preferable compound (4a), the numbers described in Tables 7 to 23 are (4a-1), (4a-2), (4a-3), (4a-6), (4a-8), (4a -11), (4a-13), (4a-15), (4a-16), (4a-17), (4a-20), (4a-21), (4a-24), (4a-26) ), (4a-29), (4a-32), (4a-42), (4a-43), (4a-44), (4a-45), (4a-46), (4a-47), (4a-48), (4a-49), (4a-50), (4a-51), (4a-52), (4a-54), (4a-56), (4a-57), (4a -59), (4a-60), (4a-61), (4a-62), (4a-63), (4a-64), (4a-65), (4a-66), (4a- 7), (4a-68), (4a-69), (4a-70), (4a-71), (4a-72), (4a-73), (4a-74), (4a-75) , (4a-76), (4a-77), (4a-78), (4a-79), (4a-80), (4a-81), (4a-83), (4a-84), ( 4a-85), (4a-86), (4a-87), (4a-88), (4a-92), (4a-95), (4a-96), (4a-97), (4a- 98), (4a-99), (4a-100), (4a-101), (4a-103), (4a-104), (4a-105), (4a-107), (4a-109) , (4a-110), (4a-112), (4a-114), (4a-124), (4a-128), (4a-129), (4a- 34), (4a-135), (4a-137), (4a-138), (4a-139), (4a-143), (4a-147), (4a-149), (4a-151) (4a-156), (4a-159), (4a-164), (4a-169), (4a-177), (4a-196), (4a-197), (4a-198), ( 4a-201), (4a-203), (4a-205), (4a-207), (4a-208), (4a-210), (4a-219), (4a-225), (4a- 228), (4a-234), (4a-235), (4a-237), (4a-239), (4a-246), (4a-249), (4a-251), (4a-253) , (4a-259), (4a-269), (4a-270), (4a-2 71), (4a-272), (4a-274), (4a-276), (4a-278), or (4a-280).

  More preferably, the compound (4a) has the numbers described in Tables 7 to 23 as (4a-1), (4a-2), (4a-3), (4a-6), (4a-42), (4a-43), (4a-44), (4a-45), (4a-46), (4a-47), (4a-48), (4a-49), (4a-50), (4a -51), (4a-52), (4a-54), (4a-56), (4a-57), (4a-59), (4a-64), (4a-73), (4a-78) ), (4a-80), (4a-92), (4a-95), (4a-101), (4a-103), (4a-104), (4a-105), (4a-107), (4a-109), (4a-110), (4a-112), (4a-114), (4a-124), (4a-128), (4a-12) ), (4a-156), (4a-196), (4a-197), (4a-269), (4a-272), (4a-274), or (4a-276). .

Examples of the compound (4b) include compounds of numbers (4b-1) to (4b-251) in which R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and X ¹ are combinations exemplified in Tables 24 to 38. be able to.

  As a preferable compound (4b), the numbers described in Tables 24-38 are (4b-1), (4b-2), (4b-3), (4b-6), (4b-8), (4b -10), (4b-11), (4b-13), (4b-15), (4b-16), (4b-17), (4b-20), (4b-21), (4b-24) ), (4b-26), (4b-29), (4b-32), (4b-42), (4b-43), (4b-44), (4b-45), (4b-46), (4b-47), (4b-48), (4b-49), (4b-50), (4b-51), (4b-52), (4b-53), (4b-54), (4b -55), (4b-56), (4b-57), (4b-59), (4b-60), (4b-61), (4b-62), (4b-63), (4b 64), (4b-65), (4b-66), (4b-67), (4b-68), (4b-69), (4b-70), (4b-71), (4b-72) , (4b-73), (4b-74), (4b-75), (4b-76), (4b-77), (4b-78), (4b-79), (4b-80), ( 4b-81), (4b-82), (4b-83), (4b-84), (4b-85), (4b-86), (4b-87), (4b-88), (4b- 92), (4b-95), (4b-96), (4b-97), (4b-99), (4b-100), (4b-101), (4b-103), (4b-105) , (4b-106), (4b-107), (4b-108), (4b-110), (4b-114), (4b-115), (4b-11) ), (4b-119), (4b-121), (4b-122), (4b-127), (4b-129), (4b-130), (4b-135), (4b-139), (4b-140), (4b-148), (4b-158), (4b-165), (4b-166), (4b-167), (4b-168), (4b-169), (4b -171), (4b-172), (4b-173), (4b-174), (4b-176), (4b-177), (4b-178), (4b-182), (4b-183) ), (4b-185), (4b-187), (4b-188), (4b-190), (4b-195), (4b-199), (4b-205), (4b-207), (4b-208), (4b-210), (4b-211), (4b-214) ), (4b-217), (4b-219), (4b-220), (4b-221), (4b-223), (4b-224), (4b-225), (4b-227), (4b-228), (4b-229), (4b-233), (4b-234), (4b-240), (4b-241), (4b-242), (4b-243), (4b -245), (4b-247), (4b-248), (4b-249), or (4b-251).

  More preferably, the compound (4b) has the numbers described in Tables 24-38 as (4b-1), (4b-2), (4b-3), (4b-6), (4b-42), (4b-43), (4b-44), (4b-45), (4b-46), (4b-47), (4b-48), (4b-49), (4b-50), (4b -51), (4b-52), (4b-54), (4b-56), (4b-57), (4b-59), (4b-64), (4b-73), (4b-78) ), (4b-92), (4b-95), (4b-118), (4b-165), (4b-166), (4b-167), (4b-168), (4b-185), (4b-205), (4b-207), (4b-208), (4b-210), (4b-243), (4b-245), or (4 Selected from -247) compounds wherein.

The compound (3b) obtained in Step 2B or Step 2C will be described. Examples of Z ¹ , Z ² , R ¹ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in the compound (3b) include the same as those described above, and those similar to the above are preferable. As the compound (3b) obtained in Step 2B or Step 2C, R ¹ , Z ¹ , Z ² , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are numbers that are combinations exemplified in Table 39 to Table 60 ( The compounds of 3b-1) to (3b-445) can be mentioned.

  As the compound (3b) obtained in Step 2B or Step 2C, the following compounds (3b-446) to (3b-452) can be further exemplified.

  As the compound (3b), the numbers (3b-1), (3b-2), (3b-3), (3b-5), (3b-6), (3b-8), (3b- 10), (3b-16), (3b-17), (3b-18), (3b-24), (3b-28), (3b-31), (3b-35), (3b-37) , (3b-41), (3b-42), (3b-49), (3b-51), (3b-52), (3b-56), (3b-57), (3b-58), ( 3b-68), (3b-73), (3b-81), (3b-82), (3b-83), (3b-84), (3b-85), (3b-86), (3b- 87), (3b-88), (3b-89), (3b-90), (3b-91), (3b-93), (3b-94), (3b-95), (3b-96) (3b-98), (3b-101), (3b-103), (3b-107), (3b-108), (3b-110), (3b-112), (3b-113), (3b -114), (3b-122), (3b-127), (3b-137), (3b-140), (3b-142), (3b-148), (3b-150), (3b-159) ), (3b-160), (3b-161), (3b-166), (3b-167), (3b-177), (3b-178), (3b-181), (3b-184), (3b-186), (3b-202), (3b-203), (3b-207), (3b-212), (3b-213), (3b-223), (3b-225), (3b -228), (3b-230), (3b-239), (3b-243), 3b-246), (3b-248), (3b-257), (3b-260), (3b-269), (3b-271), (3b-279), (3b-291), (3b- 298), (3b-299), (3b-300), (3b-302), (3b-308), (3b-314), (3b-320), (3b-321), (3b-325) , (3b-327), (3b-331), (3b-332), (3b-334), (3b-341), (3b-344), (3b-350), (3b-362), ( 3b-375), (3b-376), (3b-380), (3b-380), (3b-390), (3b-393), (3b-394), (3b-398), (3b- 399), (3b-404), (3b-410), (3b-416), ( 3b-434), (3b-435), (3b-436), (3b-437), (3b-439), (3b-441), (3b-442), (3b-443), or (3b -445).

  More preferably, the compound (3b) has the numbers (3b-1), (3b-2), (3b-5), (3b-6), (3b-17), (3b-18), (3b -35), (3b-37), (3b-81), (3b-82), (3b-83), (3b-84), (3b-85), (3b-86), (3b-87) ), (3b-89), (3b-90), (3b-93), (3b-96), (3b-98), (3b-103), (3b-112), (3b-140), (3b-142), (3b-148), (3b-150), (3b-159), (3b-167), (3b-177), (3b-178), (3b-181), (3b -184), (3b-202), (3b-203), (3b-207), (3b-223), (3b-225), (3b 230), (3b-239), (3b-298), (3b-299), (3b-300), (3b-302), (3b-308), (3b-325), (3b-327) , (3b-331), (3b-332), (3b-375), (3b-376), (3b-380), (3b-381), (3b-399), (3b-437), ( 3b-439) or (3b-441).

で表される化合物（以下、「化合物（４）」と記すことがある）にアルキルリチウムを反応させる第Ｉ’工程と、第Ｉ’工程で得られた反応生成物をアルキルスルフィド化する第ＩＩ’工程とを含む方法を挙げることができる。 As a different production method of the compound (3b), a compound represented by formula (4)

Step I ′ in which alkyllithium is reacted with a compound represented by the formula (hereinafter sometimes referred to as “compound (4)”), and Step II in which the reaction product obtained in Step I ′ is alkylsulfided. And a method including a process.

Z ² , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in the formula (4) are the same as the symbols in the chemical formulas already mentioned. X ⁵ is each independently a halogen atom, preferably a bromine atom or an iodine atom.

  Specifically, the production of the compound (3b) by this method comprises the step I of reacting the compound (1a) with alkyllithium and the step II of alkylsulfating the reaction product obtained in the step I. What is necessary is just to perform on the conditions similar to the preparation method of the compound (1) containing.

  Although the case where sulfur was used as the step II was exemplified in the previous item, the sulfur described in the previous item and the description of the step II 'described later may be replaced with selenium.

  As step II ′, as in step II, for example, a reaction product obtained in step I ′ is reacted with a dialkyl disulfide (hereinafter sometimes referred to as (I ′) step). In addition, a step of reacting the reaction product obtained in the step I ′ with sulfur and then reacting with an alkyl halide (11) (hereinafter sometimes referred to as a step (II ′)), and the like. Can be mentioned.

Preferable specific examples of compound (4) include numbers (4-1) to (4-251) in which R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and X ⁵ are combinations exemplified in Tables 61 to 75. Can be mentioned.

  As the compound (4), the numbers (4-1), (4-2), (4-3), (4-6), (4-8), (4-10), (4- 11), (4-13), (4-15), (4-16), (4-17), (4-20), (4-21), (4-24), (4-26) , (4-29), (4-32), (4-42), (4-43), (4-44), (4-45), (4-46), (4-47), ( 4-48), (4-49), (4-50), (4-51), (4-52), (4-53), (4-54), (4-55), (4- 56), (4-57), (4-59), (4-60), (4-61), (4-62), (4-63), (4-64), (4-65) , (4-66), (4-67), (4-68), (4-69), (4-70), (4-7) ), (4-72), (4-73), (4-74), (4-75), (4-76), (4-77), (4-78), (4-79), (4-80), (4-81), (4-82), (4-83), (4-84), (4-85), (4-86), (4-87), (4 -88), (4-92), (4-95), (4-96), (4-97), (4-99), (4-100), (4-101), (4-103) ), (4-105), (4-106), (4-107), (4-108), (4-110), (4-114), (4-115), (4-118), (4-119), (4-121), (4-122), (4-127), (4-129), (4-130), (4-135), (4-139), (4 -140), (4-148), (4-158), 4-165), (4-166), (4-167), (4-168), (4-169), (4-171), (4-172), (4-173), (4- 174), (4-176), (4-177), (4-178), (4-182), (4-183), (4-185), (4-187), (4-188) , (4-190), (4-195), (4-199), (4-205), (4-207), (4-208), (4-210), (4-211), ( 4-214), (4-217), (4-219), (4-220), (4-221), (4-223), (4-224), (4-225), (4- 227), (4-228), (4-229), (4-233), (4-234), (4-240), (4-241), (4-242), (4-243) ), (4-245), (4-247), (4-248), (4-249), or (4-251).

  More preferably, the compound (4) has the numbers (4-1), (4-2), (4-3), (4-6), (4-42), (4-43), (4 -44), (4-45), (4-46), (4-47), (4-48), (4-49), (4-50), (4-51), (4-52) ), (4-54), (4-56), (4-57), (4-59), (4-64), (4-73), (4-78), (4-92), (4-95), (4-118), (4-165), (4-166), (4-167), (4-168), (4-185), (4-205), (4 -207), (4-208), (4-210), (4-243), (4-245), or (4-247).

で表される化合物（以下、「化合物（３）」と記すことがある）にハロゲン化剤を反応させる工程を含む方法によって得ることができる。当該工程の具体的な方法としては、工程１Ａにおける化合物（１）に代えて化合物（３）を用いること以外は、工程１Ａのハロゲン化剤を用いる方法と同様に行えばよい。式（３）中、Ｚ^２、Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４は式（４）と同義である。 Compound (4) is represented, for example, by the formula (3)

It can obtain by the method including the process of making a halogenating agent react with the compound (henceforth "compound (3)") represented. A specific method for this step may be the same as the method using the halogenating agent in Step 1A, except that Compound (3) is used instead of Compound (1) in Step 1A. In formula (3), Z ² , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ have the same meaning as in formula (4).

で表される化合物（以下、化合物（１ｃ）と記すことがある）と式（４ａ）

で表される化合物（化合物（４ａ））とを縮合する工程を含む方法によって得ることができる。当該工程の具体的な方法としては、上述の工程３Ａにおける、化合物（３ａ）に代えて化合物（１ｃ）を用い、化合物（５）に代えて化合物（３）を得ること以外は、工程３Ａと同様に行えばよい。式中、Ｚ^２、Ｘ^１、Ｘ^２、Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４は、上記各式と同義である。 Compound (3) is represented, for example, by the formula (1c)

A compound represented by the formula (hereinafter sometimes referred to as compound (1c)) and formula (4a)

It can obtain by the method including the process of condensing with the compound (compound (4a)) represented by these. As a specific method of this step, Step 3A and Step 3A are used except that Compound (1c) is used instead of Compound (3a) in Step 3A and that Compound (3) is obtained instead of Compound (5). The same may be done. In the formula, Z ² , X ¹ , X ² , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are as defined above.

Examples of the compound (3) include compounds in which X ^{5 in} the compounds (4) of the numbers (4-1) to (4-251) is substituted with a hydrogen atom.

The compound (5) obtained in Step 3A or Step 3B, that is, the compound (5) used in Step 4 will be described. Examples of Z ¹ , Z ² , R ¹ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in the compound (5) include the same as those described above, and those similar to the above are preferable. In the compound (5), two R ¹² are preferably the same as each other. Examples of the compound (5) include compounds of numbers (5-1) to (5-445) exemplified in Tables 76 to 97.

  As the compound (5), compounds of numbers (5-446) to (5-452) represented by the following chemical formulas can be further exemplified.

  As the compound (5), the numbers described in Tables 76 to 97 are preferably (5-1), (5-2), (5-3), (5-5), (5-6), (5 -8), (5-10), (5-16), (5-17), (5-18), (5-24), (5-28), (5-31), (5-35) ), (5-37), (5-41), (5-42), (5-49), (5-51), (5-52), (5-56), (5-57), (5-58), (5-68), (5-73), (5-81), (5-82), (5-83), (5-84), (5-85), (5 -86), (5-87), (5-88), (5-89), (5-90), (5-91), (5-93), (5-94), (5-95) ), (5-96), (5-98), (5-101), (5-103), (5-107) (5-108), (5-110), (5-112), (5-113), (5-114), (5-122), (5-127), (5-137), (5 -140), (5-142), (5-148), (5-150), (5-159), (5-160), (5-161), (5-166), (5-167) ), (5-177), (5-178), (5-181), (5-184), (5-186), (5-202), (5-203), (5-207), (5-212), (5-213), (5-223), (5-225), (5-228), (5-230), (5-239), (5-243), (5 -246), (5-248), (5-257), (5-260), (5-269), (5-271), (5-279), (5-291), (5-2) 8), (5-299), (5-300), (5-302), (5-308), (5-314), (5-320), (5-321), (5-325) , (5-327), (5-331), (5-332), (5-334), (5-341), (5-344), (5-350), (5-362), ( 5-375), (5-376), (5-380), (5-381), (5-390), (5-393), (5-394), (5-398), (5- 399), (5-404), (5-410), (5-416), (5-434), (5-435), (5-436), (5-437), (5-439) , (5-441), (5-442), (5-443), or (5-445).

  More preferably, the compound (5) has the numbers (5-1), (5-2), (5-5), (5-6), (5-17), (5-18), (5 -35), (5-37), (5-81), (5-82), (5-83), (5-84), (5-85), (5-86), (5-87) ), (5-89), (5-90), (5-93), (5-96), (5-98), (5-103), (5-112), (5-140), (5-142), (5-148), (5-150), (5-159), (5-167), (5-177), (5-178), (5-181), (5 -184), (5-202), (5-203), (5-207), (5-223), (5-225), (5-230), (5-239), (5-298) ), (5-299), (5-300), ( -302), (5-308), (5-325), (5-327), (5-331), (5-332), (5-375), (5-376), (5-380) ), (5-381), (5-399), (5-437), (5-439), or (5-441).

  Step 4 is a step of reacting compound (5) with an acid. Specific examples of the acid include trifluoromethanesulfonic acid, methanesulfonic acid, sulfuric acid, phosphoric acid, and a mixture of the above acids. Preferred are trifluoromethanesulfonic acid, methanesulfonic acid and sulfuric acid. If necessary, the acid may be diluted with water or the like.

Step 4 will be specifically described. For example, the compound (5) is added to the acid as it is or after being diluted with a solvent such as chloroform, and then added at a temperature of about -20 ° C to 100 ° C for about 1 minute to 48 hours. Stir. At this time, the reaction may be performed in the presence of a dehydrating agent such as P ₂ O ₅ . After completion of the reaction, the reaction mixture is mixed with water, an organic solvent is added as necessary, and the organic layer is separated. The obtained solution (organic layer) may be used as it is, but preferably after concentration, a base such as an organic base such as pyridine or triethylamine is added, and the compound (5) and the base are mixed. The compound (5) and the base are preferably mixed at a temperature from 50 ° C. to the boiling point of the solvent, for example, for 1 minute to 48 hours.

  Then, a general post-treatment is performed, and the compound (10) can be obtained by performing a usual purification means such as column chromatography, distillation, recrystallization, and recycle gel permeation chromatography as necessary. .

  Before performing the post-treatment, step 4 may be further repeated as necessary.

  Step 4 can proceed under mild conditions. In addition, step 4 can be performed at a temperature lower than 100 ° C. The chalcogen-containing polycyclic compound (10) useful as an organic semiconductor material can be produced under milder conditions than before.

In the chalcogen-containing polycyclic compound (10) thus obtained, at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is an alkyl group having 1 to 30 carbon atoms and an alkoxy having 1 to 30 carbon atoms. It is preferably a group, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 4 to 30 carbon atoms. More preferably, R ¹¹ , R ¹³ and R ¹⁴ are hydrogen atoms, and R ¹² is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. Carbon number of the alkyl group and alkoxy group in R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is preferably 4-16. The chalcogen-containing fused polycyclic compound (10) having such a long-chain alkyl group or alkoxy group is preferable because the coating processability for film formation tends to be improved.

  Specific examples of the chalcogen-containing fused polycyclic compound (10) include compounds of numbers (10-1) to (10-445) exemplified in Table 98 to Table 116.

  Examples of the chalcogen-containing condensed polycyclic compound (10) include compounds of numbers (10-446) to (10-452) represented by the following chemical formulas.

  As preferable compound (10), for example, the numbers are (10-1), (10-2), (10-3), (10-5), (10-6), (10-8), (10- 10), (10-35), (10-37), (10-41), (10-42), (10-49), (10-51), (10-52), (10-56) , (10-57), (10-58), (10-68), (10-73), (10-81), (10-82), (10-83), (10-84), ( 10-85), (10-86), (10-87), (10-88), (10-89), (10-90), (10-91), (10-93), (10- 94), (10-95), (10-96), (10-98), (10-101), (10-103), (10-107), (10-108), ( 0-110), (10-112), (10-113), (10-114), (10-177), (10-178), (10-181), (10-184), (10- 186), (10-202), (10-203), (10-207), (10-212), (10-213), (10-223), (10-225), (10-228) , (10-230), (10-239), (10-243), (10-246), (10-248), (10-257), (10-260), (10-269), ( 10-271), (10-279), (10-291), (10-298), (10-299), (10-300), (10-302), (10-325), (10- 327), (10-331), (10-332), (10-334), ( 0-341), (10-344), (10-350), (10-362), (10-375), (10-376), (10-380), (10-381), (10- 398), (10-399), (10-404), (10-410), or (10-416).

  More preferably, the compound (10) has the numbers (10-1), (10-2), (10-5), (10-6), (10-35), (10-37), (10 -81), (10-82), (10-83), (10-84), (10-85), (10-86), (10-87), (10-89), (10-90) ), (10-93), (10-96), (10-98), (10-103), (10-112), (10-177), (10-178), (10-181), (10-184), (10-202), (10-203), (10-207), (10-223), (10-225), (10-230), (10-239), (10 -298), (10-299), (10-300), (10-302), (10-325), (10-327), ( 0-331), (10-332), (10-375), (10-376), (10-380), is selected from compounds which are (10-381), or (10-399).

  Hereinafter, the present invention will be described more specifically with reference to examples.

Reference Example <Synthesis of 3,4-dimethylsulfanylthiophene>
3,4-Dibromothiophene (0.30 g, 1.2 mmol) was dissolved in 6 mL of diethyl ether, cooled to −78 ° C., and then at the same temperature, a pentane solution containing 1.59 M of t-BuLi (0.78 mL, 1.2 mmol) was added dropwise. Further, after stirring at the same temperature for 30 minutes, sulfur powder (0.04 g, 1.2 mmol) was added, and the mixture was stirred at the same temperature for 30 minutes. Under the same temperature, a pentane solution (0.78 mL, 1.2 mmol) containing 1.59 M of t-BuLi was dropped again and stirred for 30 minutes. Thereafter, sulfur powder (0.04 g, 1.2 mmol) was added, and the mixture was stirred at the same temperature for 30 minutes, then gently warmed to room temperature and stirred as it was for 1 hour. The solution was cooled to 0 ° C., methyl iodide (0.39 g, 2.7 mmol) was added, the temperature was slowly raised to room temperature, and the mixture was stirred for 2 hours. Thereafter, water and chloroform were added, the organic layer was separated, and the aqueous layer was extracted with chloroform. The organic layer was dried over magnesium sulfate and then concentrated to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (chloroform: hexane = 1: 1) to obtain 0.19 g of 3,4-dimethylsulfanylthiophene (yield 87%).
¹ H-NMR (CDCl ₃ , δ ppm): 7.02 (s, 2H), 2.46 (s, 6H)

(1) Bis (5-hexylbenzo [4,5] thieno) [3,2-c: 2 ′, 3′-e] thiophene (represented by formula (10), wherein R ¹¹ , R ¹³ and R ¹⁴ are Synthesis of a chalcogen-containing fused polycyclic compound in which a hydrogen atom, R ¹² is an n-hexyl group, and Z ¹ and Z ² are all sulfur atoms

Production Example 1 (Process 1)
Synthesis of 2,5-dibromo-3,4-dimethylsulfanylthiophene 3,4-Dimethylsulfanylthiophene (0.18 g, 1.0 mmol) was dissolved in 10 mL of chloroform, and N-bromosuccinimide 0. 38 g was gradually added at room temperature (about 20 ° C.). The resulting mixture was further stirred at room temperature for 4 hours, water was added, and the mixture was separated into an organic layer and an aqueous layer. The organic layer was washed with saturated brine and dried over magnesium sulfate. The organic layer after drying was concentrated to obtain a crude product. The obtained crude product was purified by silica gel column chromatography to obtain 0.26 g of 2,5-dibromo-3,4-dimethylsulfanylthiophene (yield 77%).
¹ H-NMR (CDCl ₃ , δ ppm): 2.41 (s, 6H)

Production Example 2 (Process 2B)
Synthesis of 2,5-bis (4-n-hexylphenyl) -3,4-dimethylsulfanylthiophene 2,5-dibromo-3,4-dimethylsulfanylthiophene (2.2 g, 6.6 mmol) was added to tetrahydrofuran (THF) Dissolve in 270 mL, and add 4-n-hexyl-1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene (4.74 g, 16) to the resulting solution. 4 mmol), and aqueous sodium carbonate (2.0 M, 89 mL). The resulting mixture was bubbled with nitrogen at room temperature. PdCl ₂ (dppf) (0.54 g, 0.7 mmol) was added to the mixture, and the mixture was stirred at 85 ° C. for 7 hours. The resulting reaction solution was cooled to room temperature, and an aqueous ammonium chloride solution was added. Then, it was separated into an aqueous layer and an organic layer. The product contained in the aqueous layer was extracted with THF and mixed with the organic layer. The mixed organic layer was washed with water and a saturated aqueous sodium chloride solution and then dried over magnesium sulfate. Thereafter, the reaction solution was concentrated to obtain a crude product. The obtained crude product was fractionated using a silica gel column and preparative gel permeation chromatography to obtain 2,5-bis (4-n-hexylphenyl) -3,4-dimethylsulfanylthiophene as 1. 88 g was obtained (yield 51%).
¹ H-NMR (CDCl ₃ , δ ppm): 7.60 (d, J = 8.4 Hz, 4H), 7.25 (d, J = 8.4 Hz, 4H), 2.65 (t, J = 7) .6 Hz, 4H), 2.31 (s, 6H), 1.71-1.60 (m, 4H), 1.40-1.29 (m, 12H), 0.90 (t, J = 6) .8Hz, 6H)

Production Example 3 (Process 3B)
Synthesis of 2,5-bis (4-n-hexylphenyl) -3,4-dimethylsulfinylthiophene 2,5-bis (4-n-hexylphenyl) -3,4-dimethylsulfanylthiophene (1.40 g, 2 0.8 mmol) was dissolved in 70 mL of acetic acid, and 35% aqueous hydrogen peroxide (0.60 g, 6.2 mmol) was added dropwise thereto at room temperature. After completion of the dropwise addition, the obtained reaction solution was heated to 50 ° C. and further stirred at the same temperature for 5.5 hours. In the middle, 0.3 g of 35% hydrogen peroxide solution was added. Next, after cooling a reaction liquid to room temperature, saturated sodium hydrogencarbonate aqueous solution and chloroform were added, and it isolate | separated into the organic layer and the water layer. The product contained in the aqueous layer was extracted with chloroform and mixed with the organic layer. The mixed organic layer was dried over magnesium sulfate and then concentrated to obtain a crude product. The obtained crude product was washed with hexane to obtain 0.99 g of 2,5-bis (4-n-hexylphenyl) -3,4-dimethylsulfinylthiophene (yield 66%).
¹ H-NMR (CDCl ₃ , δ ppm): 7.45 (d, J = 8.1 Hz, 1.6H), 7.36 (d, J = 8.1 Hz, 2.4H), 7.28-7 .24 (m, 4H), 3.28 (s, 3.6H), 3.09 (s, 2.4H), 2.70-2.63 (m, 4H), 1.70-1.53 (M, 4H), 1.42-1.28 (m, 12H), 0.92-0.87 (m, 6H)
MS-FD: 528 (M +)

Production Example 4 (Process 4)
Synthesis of bis (5-hexylbenzo [4,5] thieno) [3,2-c: 2 ′, 3′-e] thiophene 2,5-bis (4′-n-hexylphenyl) -3,4- Dimethylsulfinylthiophene (0.30 g, 0.6 mmol) and P ₂ O ₅ (0.03 g, 0.2 mmol) were dissolved in 10.3 mL of trifluoromethanesulfonic acid to obtain a reaction solution. The temperature of the solution was raised to 50 ° C., and the mixture was stirred at the same temperature for 3 hours and then cooled to room temperature to obtain a reaction solution. The reaction solution was added to 103 mL of water, and the precipitated solid was filtered off. After the precipitated solid was washed with water, the obtained solid was dissolved in 90 mL of pyridine, and stirred for 10 hours while heating until the obtained solution was refluxed. After cooling the solution to room temperature, water and chloroform were added to the solution. The obtained organic layer and aqueous layer were separated, and the organic layer was dried over magnesium sulfate and then concentrated to obtain a crude product. The obtained crude product was purified using a silica gel column and gel permeation chromatography to obtain bis (5-hexylbenzo [4,5] thieno) [3,2-c: 2 ′, 3′-e. ] 0.08 g of thiophene was obtained (yield 31%).
¹ H-NMR (CDCl ₃ , δ ppm): 7.65 (d, J = 7.3 Hz, 2H), 7.57 (d, J = 1.0 Hz, 2H), 7.19 (dd, J = 7) .3, 1.0 Hz, 2H), 2.73 (t, J = 7.0 Hz, 4H), 1.73-1.63 (m, 4H), 1.40-1.29 (m, 12H) 0.90 (t, J = 6.8 Hz, 6H)

Production Example 5 (Step 2A)
Synthesis of 2,5-dibromo-3,4-dimethylsulfinylthiophene 2,5-dibromo-3,4-dimethylsulfanylthiophene (2.34 g, 7.0 mmol) was dissolved in 150 mL of acetic acid, and the resulting solution was dissolved. After dropwise addition of 35% aqueous hydrogen peroxide (0.78 g, 8.0 mmol), the resulting reaction solution was heated to 60 ° C. and stirred at the same temperature for 12 hours. In the middle, 0.77 g of 35% hydrogen peroxide solution was added. After completion of the reaction, the obtained reaction solution was cooled to room temperature, a saturated aqueous sodium bicarbonate solution and chloroform were added and mixed, and then separated into an organic layer and an aqueous layer. The organic layer was dried over magnesium sulfate and then concentrated to obtain a crude product. The obtained crude product was purified using a silica gel column to obtain 1.65 g of 2,5-dibromo-3,4-dimethylsulfinylthiophene (yield 64%).
¹ H-NMR (CDCl ₃ , δ ppm): 3.21 (s, 2.4H), 3.09 (s, 3.6H)

Production Example 6 (Step 3A)
Synthesis of 2,5-bis (4-n-hexylphenyl) -3,4-dimethylsulfinylthiophene Dissolve 2,5-dibromo-3,4-dimethylsulfinylthiophene (0.08 g, 0.2 mmol) in 9 mL of THF. 4-n-hexyl-1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene (0.17 g, 0.6 mmol), And aqueous cesium carbonate (2.0 M, 2.9 mL) were added. The obtained mixture was bubbled with nitrogen at room temperature, PdCl ₂ (dppf) (0.09 g, 0.01 mmol) was added, and the mixture was further heated to 80 ° C. and stirred for 16 hours. The resulting reaction solution was cooled to room temperature, and then an aqueous ammonium chloride solution was added to separate it into an organic layer and an aqueous layer. The product contained in the aqueous layer was extracted with THF and mixed with the organic layer. The combined organic layer was washed with water and saturated aqueous sodium chloride solution, then dried over magnesium sulfate, and concentrated to obtain a crude product. The obtained crude product was fractionated using thin layer chromatography to obtain 0.05 g of 2,5-bis (4′-n-hexylphenyl) -3,4-dimethylsulfinylthiophene ( Yield 41%).
¹ H-NMR (CDCl ₃ , δ ppm): 7.45 (d, J = 8.1 Hz, 2.5H), 7.36 (d, J = 8.1 Hz, 1.5H), 7.28-7 .24 (m, 4H), 3.28 (s, 2.3H), 3.09 (s, 3.7H), 2.70-2.63 (m, 4H), 1.70-1.53 (M, 4H), 1.42-1.28 (m, 12H), 0.92-0.87 (m, 6H)

(2) Bis (5-pentyloxybenzo [4,5] thieno) [3,2-c: 2 ′, 3′-e] thiophene (represented by formula (10), R ¹¹ , R ¹³ and R Synthesis of chalcogen-condensed polycyclic compound wherein ¹⁴ is a hydrogen atom, R ¹² is an n-pentyloxy group, and three Z are sulfur atoms. A chalcogen-containing polycyclic compound was synthesized according to the following synthesis route.

Production Example 7
Synthesis of 1-n-pentyloxy-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene 1-bromo-4-n-pentyloxybenzene (25 g, 103 mmol) was dissolved in 500 mL of diethyl ether, and the resulting solution was cooled to -78 ° C. To this solution, 117 mL of a t-BuLi / pentane solution (manufactured by Kanto Chemical Co., Ltd., t-BuLi concentration 1.76 M) was added dropwise at −78 ° C. over 45 minutes, and the mixture was further stirred for 30 minutes at the same temperature. The temperature was raised to 0 ° C. over 1 hour and the mixture was stirred at 0 ° C. for 1 hour. The obtained reaction solution was cooled again to -78 ° C, and 2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (31.2 mL, 154 mmol) was added dropwise to the same temperature. The mixture was further stirred for 3 hours, then warmed to room temperature, and stirred at room temperature for 3 hours. Saturated saline and ether were added to the resulting reaction solution to separate into an organic layer and an aqueous layer. The organic layer was washed with water, dried over magnesium sulfate, and concentrated to obtain a crude product. The obtained crude product was purified with a silica gel column to give 1-n-pentyloxy-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene. (Yield 98%) was obtained.
¹ H-NMR (CDCl ₃ , δ ppm): 7.74 (d, J = 8.6 Hz, 2H), 6.88 (d, J = 8.6 Hz, 2H), 3.97 (t, J = 6) .5 Hz, 2H), 1.73-1.81 (m, 2H), 1.20-1.50 (m, 4H), 1.33 (s, 12H), 0.93 (t, J = 7) .0Hz, 3H)

Production Example 8 (Step 2A)
Synthesis of 2,5-bis (4-n-pentyloxyphenyl) -3,4-dimethylsulfanylthiophene 2,5-dibromo-3,4-dimethylsulfanylthiophene (9 g, 27 mmol) was obtained by dissolving in THF 1000 mL. 4-n-pentyloxy-1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene (21.1 g, 72.7 mmol) and carbonic acid Aqueous sodium solution (2.0 M, 364 mL) was added. The resulting mixture was then bubbled with nitrogen at room temperature. PdCl ₂ (dppf) (2.2 g, 2.7 mmol) was added to the mixture, and the mixture was heated to 85 ° C. and stirred at the same temperature for 4.5 hours. The resulting reaction solution was cooled to room temperature, and then an aqueous ammonium chloride solution was added to separate it into an organic layer and an aqueous layer. The product contained in the aqueous layer was extracted with THF and mixed with the organic layer. The combined organic layer was washed successively with water and saturated aqueous sodium chloride solution, dried over magnesium sulfate and concentrated to obtain a crude product. The obtained crude product was purified using a silica gel column to obtain 13.7 g of 2,5-bis (4-n-pentyloxyphenyl) -3,4-dimethylsulfanylthiophene (yield: 100). %).
¹ H-NMR (CDCl ₃ , δ ppm): 7.60 (d, J = 8.6 Hz, 4H), 6.95 (d, J = 8.6 Hz, 4H), 4.00 (t, J = 6) .5 Hz, 4H), 2.96 (s, 6H) 1.76-1.84 (m, 4H), 1.38-1.48 (m, 8H), 0.94 (t, J = 7. 0Hz, 6H)

Production Example 9 (Step 3A)
Synthesis of 2,5-bis (4-n-pentyloxyphenyl) -3,4-dimethylsulfinylthiophene To 250 mL of acetic acid, 2,5-bis (4-n-pentyloxyphenyl) -3,4-dimethylsulfanylthiophene ( 5 g, 10 mmol) was added, and the resulting mixture was heated to 50 ° C. and dissolved, and then cooled to room temperature. To this solution, 35% aqueous hydrogen peroxide (2.1 g, 22 mmol) was added and stirred at room temperature. Thereafter, a small amount of 35% aqueous hydrogen peroxide was repeatedly added until 2,5-bis (4-n-pentyloxyphenyl) -3,4-dimethylsulfanylthiophene was not confirmed by NMR, for a total of 3.9 g. Of 35% hydrogen peroxide was added. A saturated aqueous sodium hydrogen carbonate solution was added to the resulting reaction solution, and the organic matter was extracted with chloroform. The extracted organic layer was dried over magnesium sulfate and concentrated to obtain 5.3 g of 2,5-bis (4-n-pentyloxyphenyl) -3,4-dimethylsulfinylthiophene (99% yield). .
¹ H-NMR (CDCl ₃ , δ ppm): 7.46 (d, J = 8.6 Hz, 1.9H), 7.38 (d, J = 8.6 Hz, 2.1H), 6.94-6 .98 (m, 4H), 3.98-4.03 (m, 4H), 3.25 (s, 3.2H), 3.09 (s, 2.8H), 1.70-1.90 (M, 4H), 1.30-1.50 (m, 8H), 0.94 (t, J = 7.0 Hz, 6H)

Production Example 10 (Process 4)
Synthesis of bis (5-pentyloxybenzo [4,5] thieno) [3,2-c: 2 ′, 3′-e] thiophene A solution obtained by adding 1.3 g of P ₂ O _{5 to} 211 mL of methanesulfonic acid was 0. After cooling to ° C., a chloroform solution (211 mL) containing 2,5-bis (4-n-pentyloxyphenyl) -3,4-dimethylsulfinylthiophene (12.5 g, 23.5 mmol) was added dropwise over 30 minutes. . The resulting reaction solution was heated to 50 ° C. and stirred for a total of 12 hours. The reaction solution after stirring was added to 2111 mL of water, and the mixture was separated into an organic layer and an aqueous layer. The organic layer was washed with water and concentrated. To the obtained oil, 1877 mL of pyridine was added and stirred for 4 hours while refluxing. After cooling the obtained pyridine solution to room temperature, water and chloroform were added and liquid-separated into the organic layer and the water layer. The organic layer was dried over magnesium sulfate and concentrated to give a crude product. In the silica gel column chromatography of the obtained crude product, after removing the component eluted with a developing solvent of hexane / chloroform = 3/1, the developing solvent was changed to ethyl acetate, and the eluted component was recovered. 1 g of a mixture was obtained.

A solution obtained by adding 0.7 g of P ₂ O _{5 to} 120 mL of methanesulfonic acid was cooled to 0 ° C., and then a solution obtained by dissolving 7.1 g of the obtained mixture in 120 mL of chloroform was added dropwise over 15 minutes. The resulting reaction solution was heated to 50 ° C. and further stirred at the same temperature for 4 hours. The resulting reaction solution was added to 1200 mL of water and separated into an aqueous layer and an organic layer, and then the organic layer was washed with water and the organic layer was concentrated. To the obtained oil, 1000 mL of pyridine was added and stirred for 2.5 hours while refluxing.

The resulting pyridine solution was cooled to room temperature and concentrated, and further water and chloroform were added to separate the aqueous layer and the organic layer. The obtained organic layer was dried over magnesium sulfate and concentrated. The oil obtained was purified by a silica gel column and subsequently recrystallized from toluene to give bis (5-pentyloxybenzo [4,5] thieno) [3,2-c: 2 ′, 3′-e] thiophene. 0.43 g was obtained (yield 4%).
¹ H-NMR (CDCl ₃ , δ ppm): 7.72 (d, J = 8.6 Hz, 2H), 7.36 (s, 2H), 7.05 (d, J = 8.6 Hz, 2H), 4.05 (t, J = 6.5 Hz, 4H), 1.80-1.90 (m, 4H), 1.38-1.56 (m, 12H), 0.96 (t, J = 7) .3Hz, 6H)

Different production examples of 2,5-bis (4-n-hexylphenyl) -3,4-dimethylsulfinylthiophene (Production Examples 11 to 13)

Production Example 11
Production Example of 2,5-bis (4-hexylphenyl) thiophene 2,5-Dibromothiophene (15.0 g, 62.0 mmol) was dissolved in 300 mL of THF, and 4-hexyl-1- (4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene (48.25 g, 167.4 mmol) and aqueous sodium carbonate (2.0 M, 387.5 mL), Bubbling with nitrogen at room temperature gave a suspension. To this suspension, PdCl ₂ (dppf) · dichloromethane complex (5.06 g, 6.2 mmol) was added and stirred at 40 ° C. for 6 hours. After cooling the obtained reaction solution to room temperature, the organic layer was separated, the product contained in the aqueous layer was further extracted with chloroform, and the organic layer and the chloroform layer were combined and concentrated. Chloroform was added to the obtained concentrate, and the resulting chloroform layer was washed with water, dried over magnesium sulfate, and concentrated to obtain a crude product. The crude product was purified by a silica gel column (developing solvent: hexane) and then recrystallized (recrystallization solvent: hexane) to obtain 5.70 g of 2,5-bis (4-hexylphenyl) thiophene. (Yield 23%).
The analysis results of the obtained 2,5-bis (4-hexylphenyl) thiophene are as follows.
¹ H-NMR (CDCl ₃ , δ ppm): 7.53 (d, J = 8.1 Hz, 4H), 7.23 (s, 2H), 7.19 (d, J = 8.1 Hz, 4H), 2.61 (t, J = 7.6 Hz, 4H), 1.68-1.57 (m, 4H), 1.40-1.25 (m, 12H), 0.89 (t, J = 6) .8Hz, 6H)
HRMS (EI): 404.2535 (M +). Calcd for C ₂₈ H ₃₆ S: 404.2538.

Production Example 12
Production example of 3,4-dibromo-2,5-bis (4-hexylphenyl) thiophene (compound (4-6)) 2,5-bis (4-) obtained according to Production Example 11 and Production Example 11 Hexylphenyl) thiophene (9.90 g, 24.47 mmol) was dissolved in 79 mL of chloroform. The solution was cooled to 0 ° C., a chloroform solution (4 mL) containing bromine (7.97 g, 49.87 mmol) was added dropwise, and the mixture was further stirred at the same temperature for 3.5 hours. A sodium thiosulfate aqueous solution was added to the obtained reaction solution, and the organic layer obtained by liquid separation was washed successively with water and saturated brine, dried over magnesium sulfate, and concentrated to obtain a crude product. By purifying the obtained crude product by silica gel column chromatography (developing solvent: hexane), 3,4-dibromo-2,5-bis (4-hexylphenyl) thiophene (compound (4-6)) was obtained. 11.80 g was obtained (yield 86%).
The analysis results of the obtained compound (4-6) are as follows.
¹ H-NMR (CDCl ₃ , δ ppm): 7.57 (d, J = 8.1 Hz, 4H), 7.27 (d, J = 8.1 Hz, 4H), 2.66 (t, J = 7) .6 Hz, 4H), 1.71-1.60 (m, 4H), 1.40-1.26 (m, 12H), 0.90 (t, J = 6.8 Hz, 6H)
HRMS (EI): 560.0722 (M +). Calcd for C ₂₈ H ₃₄ Br ₂ S: 560.0748.

Production Example 13
Production Example of 2,5-bis (4-hexylphenyl) -3,4-dimethylsulfanylthiophene (Compound (3b-6)) 3,4-Dibromo-2,5-bis (4-hexylphenyl) under a nitrogen atmosphere ) Thiophene (1.00 g, 1.78 mmol) was dissolved in 22 mL of THF and cooled to -78 ° C. To the solution, a 1.55 M pentane solution (1.72 mL, 2.67 mmol) of t-BuLi was added dropwise and stirred at −78 ° C. for 30 minutes (step I ′ above). Sulfur powder (0.069 g, 2.15 mmol) was added to the reaction solution obtained in Step I ′ and stirred for 1 hour (step V ′). To the reaction solution obtained in Step V ′, a 1.55 M pentane solution (1.72 mL, 2.67 mmol) of t-BuLi was added dropwise, stirred for 30 minutes, and then sulfur powder (0.063 g, 1.96 mmol). Was added. After stirring at the same temperature for 1 hour, the temperature was gradually raised to room temperature, and the mixture was stirred as it was for 1 hour (step VI ′). The reaction solution obtained in Step VI ′ was cooled to 0 ° C., iodomethane (0.606 g, 4.27 mmol) was added, and the mixture was slowly warmed to room temperature and stirred for 2 hours. Water and chloroform were added to the resulting reaction solution for liquid separation. The obtained organic layer was washed with water, dried over magnesium sulfate, and concentrated by an evaporator to obtain a crude product. The obtained crude product was purified by a silica gel column and preparative gel permeation chromatography, whereby 2,5-bis (4-hexylphenyl) -3,4-dimethylsulfanylthiophene (compound (3b-6)) ) Was obtained (yield 51%).
The analysis results of the obtained compound (3b-6) are as follows.
¹ H-NMR (CDCl ₃ , δ ppm): 7.60 (d, J = 8.4 Hz, 4H), 7.25 (d, J = 8.4 Hz, 4H), 2.65 (t, J = 7) .6 Hz, 4H), 2.31 (s, 6H), 1.71-1.60 (m, 4H), 1.40-1.29 (m, 12H), 0.90 (t, J = 6) .8Hz, 6H)
HRMS (EI): 496.2281 (M +). _{Calcd for C 30 H 40 S 3} : 496.2292.

で表される２，５−ビス（４−エチルフェニル）−３，４−ジメチルスルフィニルチオフェン（１５．４ｇ、３７．０ｍｍｏｌ）の白色結晶を収率９５％で得た。
得られた２，５−ビス（４−エチルフェニル）−３，４−ジメチルスルフィニルチオフェンの分析結果は以下の通りである。
^１Ｈ−ＮＭＲ（δ、ＣＤＣｌ_３）： １．２９（ｔ×ｄ、６Ｈ）、３．１０（ｓ、３Ｈ）、３．２８（ｓ、３Ｈ）、７．２９（ｄ×ｄ、４Ｈ）、７．３７（ｄ、２Ｈ）、７．４６（ｄ、２Ｈ） Bis (5-ethylbenzo [4,5] thieno) [3,2-c: 2 ′, 3′-e] thiophene (Production Example of Compound (10-3) (Production Examples 14 and 15))
Production Example 14
(Production example of 2,5-bis (4-ethylphenyl) -3,4-dimethylsulfinylthiophene)
2,5-bis (4-ethylphenyl) -3,4-dimethylsulfanylthiophene (15.0 g, 39.0 mmol) was dissolved in acetic acid 600 mL at 70 ° C., and the resulting solution was dissolved at the same temperature at 35. An aqueous solution containing 4% by weight of hydrogen peroxide (7.7 g, 79.9 mmol as hydrogen peroxide) was added dropwise over 1 hour, followed by stirring at the same temperature for 10 hours. Next, 150 mL of an aqueous sodium sulfite solution (20 wt%) was added at 70 ° C., and the mixture was stirred at the same temperature for 1 hour. After cooling the obtained reaction liquid to room temperature, chloroform 500mL was added and it isolate | separated into the organic layer and the water layer. The product contained in the aqueous layer was extracted twice with 150 mL of chloroform and mixed with the organic layer. The mixed organic layer was washed with 300 mL of water three times, an aqueous sodium hydroxide solution (20 wt%) was added at room temperature to adjust the aqueous layer to pH 10-12, and further stirred at room temperature for 30 minutes. After that, the organic layer and the aqueous layer were separated. To the obtained organic layer, 300 mL of water and an aqueous sulfuric acid solution (5% by weight) were added to adjust the aqueous layer to pH 6-8, and the organic layer and the aqueous layer were separated. The separated organic layer was dried over magnesium sulfate and concentrated to obtain a crude product. By purifying the resulting crude product by recrystallization from n-heptane, the following formula

A white crystal of 2,5-bis (4-ethylphenyl) -3,4-dimethylsulfinylthiophene (15.4 g, 37.0 mmol) represented by the following formula was obtained in a yield of 95%.
The analysis results of the obtained 2,5-bis (4-ethylphenyl) -3,4-dimethylsulfinylthiophene are as follows.
¹ H-NMR (δ, CDCl ₃ ): 1.29 (t × d, 6H), 3.10 (s, 3H), 3.28 (s, 3H), 7.29 (d × d, 4H) 7.37 (d, 2H), 7.46 (d, 2H)

Production Example 15
(Bis (5-ethylbenzo [4,5] thieno) [3,2-c: 2 ′, 3′-e] thiophene (Production Example of Compound (10-3))
After adding 20 mL of 97% sulfuric acid to a flask equipped with a stirrer and a thermometer, and replacing the system with nitrogen, the sulfuric acid was cooled to 0 ° C. The 2,5-bis (4-ethylphenyl) -3,4-dimethylsulfinylthiophene (2.00 g, 4.80 mmol) obtained in Preparation Example 14 was added to the cooled sulfuric acid, and the temperature of the mixture exceeded 2 ° C. The reaction solution was added little by little over 30 minutes and further stirred at 0 ° C. for 6 hours. In another flask equipped with a stirrer and a thermometer, 150 mL of water was charged, and the reaction solution was added to this water. The reaction solution was added little by little so that the temperature of the mixture of water and the reaction solution did not exceed 20 ° C. The obtained reaction solution was allowed to stand at 5 ° C. for 18 hours and then filtered, and the filtered product was washed with water, an aqueous sodium hydrogen carbonate solution (5% by weight), water and methanol in this order. The obtained filtered product was added to toluene, an aqueous sodium carbonate solution (5% by weight) was added, and the mixture was dissolved at 70 ° C. to separate into an organic layer and an aqueous layer. The organic layer was further washed twice with water at 70 ° C. and then concentrated to obtain a crude product. By purifying the resulting crude product by recrystallization from toluene, the formula (10-3)

で表されるビス（５−エチルベンゾ［４，５］チエノ）［３，２−ｃ：２’，３’−ｅ］チオフェン（化合物（１０−３）、１．０６ｇ、３．０１ｍｍｏｌ）の白黄色結晶を収率６３％で得た。
得られた化合物（１０−３）の分析結果は以下の通りである。
^１Ｈ−ＮＭＲ（δ、ＣＤＣｌ_３）： １．３２（ｔ、６Ｈ）、２．８０（ｑ、４Ｈ）、７．２８（ｄ、２Ｈ）、７．７０（ｓ、２Ｈ）、７．７６（ｄ、２Ｈ）
ＬＣ−ＨＲＭＳ（ＡＰＰＩ＋）：ｃａｌｃｄ ｆｏｒ Ｃ_２０Ｈ_１６Ｓ_３、３５２．０４０８；ｆｏｕｎｄ ３５２．０４０６

Bis (5-ethylbenzo [4,5] thieno) [3,2-c: 2 ′, 3′-e] thiophene (compound (10-3), 1.06 g, 3.01 mmol) represented by white Yellow crystals were obtained with a yield of 63%.
The analysis result of the obtained compound (10-3) is as follows.
¹ H-NMR (δ, CDCl ₃ ): 1.32 (t, 6H), 2.80 (q, 4H), 7.28 (d, 2H), 7.70 (s, 2H), 7.76 (D, 2H)
_{LC-HRMS (APPI +):} calcd for C 20 H 16 S 3, 352.0408; found 352.0406

  According to the production method of the present invention, a chalcogen-containing polycyclic compound can be produced under milder conditions than before.

Claims (13)

Formula (5)

[Wherein R ¹ independently represents an alkyl group having 1 to 20 carbon atoms, Z ¹ independently represents a sulfur atom or a selenium atom, Z ² represents an oxygen atom, a sulfur atom or a selenium atom, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a fluorine atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, or an optionally substituted carbon atom. An alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and a substituent; An optionally substituted heteroaralkyl group having 5 to 30 carbon atoms, an optionally substituted heteroaryl group having 4 to 30 carbon atoms, or —Si (R ² ) ₃ (R ² is independently substituted; C1-C30 alkyl which may have a group Or a substituted silyl group represented by.) Which represents an aryl group having 6 to 30 carbon atoms which may have a substituent. ]
Having a step of reacting a compound represented by the formula (10) with an acid:

[Wherein, Z ¹ , Z ² , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are as defined above]. ]
The manufacturing method of chalcogen containing polycyclic compound represented by these. The production method according to claim 1, wherein the acid is sulfuric acid. The method according to claim 1 or 2 , wherein the reaction product and a base are mixed after reacting the compound of the formula (5) with the acid. The compound represented by the formula (5) is
Following formula (2a)

[Wherein, R ¹ , Z ¹ and Z ² have the same meanings as described above. X ¹ each independently represents a halogen atom, an alkyl sulfonate group having 1 to 20 carbon atoms or an aryl sulfonate group having 6 to 20 carbon atoms. ]
A step of oxidizing the compound represented by:
Formula (3a) obtained in the above step

[Wherein, R ¹ , Z ¹ , Z ² and X ¹ are as defined above. ]
And a compound represented by formula (4a)

[Wherein, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are as defined above. X ² represents a leaving group. ]
A step of condensing the compound represented by:
The production method according to any one of claims 1 to 3, wherein the compound is obtained by a method comprising: The compound represented by the formula (5) is
Formula (2a)

[Wherein, R ¹ , Z ¹ and Z ² have the same meanings as described above. X ¹ each independently represents a halogen atom, an alkyl sulfonate group having 1 to 20 carbon atoms or an aryl sulfonate group having 6 to 20 carbon atoms. ]
And a compound represented by formula (4a)

[Wherein, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are as defined above. X ² represents a leaving group. ]
A step of condensing the compound represented by:
Formula (3b) obtained in the above step

[Wherein, R ¹ , Z ¹ , Z ² , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ have the same meaning as described above. ]
A step of oxidizing the compound represented by:
The production method according to any one of claims 1 to 3, wherein the compound is obtained by a method comprising: The compound represented by the formula (5) is
Formula (2b)

[Wherein, R ¹ , Z ¹ and Z ² have the same meanings as described above. X ² represents a leaving group. ]
And a compound represented by formula (4b)

[Wherein, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are as defined above. X ¹ each independently represents a halogen atom, an alkyl sulfonate group having 1 to 20 carbon atoms or an aryl sulfonate group having 6 to 20 carbon atoms. ]
A step of condensing the compound represented by:
Formula (3b) obtained in the above step

[Wherein, R ¹ , Z ¹ , Z ² , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ have the same meaning as described above. ]
A step of oxidizing the compound represented by:
The production method according to any one of claims 1 to 3, wherein the compound is obtained by a method comprising: The compound represented by the formula (2a) is
Following formula (1)

[Wherein, R ¹ , Z ¹ and Z ² have the same meanings as described above. ]
A step of substituting a hydrogen atom contained in the compound represented by a halogen atom, an alkyl sulfonate group having 1 to 20 carbon atoms or an aryl sulfonate group having 6 to 20 carbon atoms,
The production method according to claim 4 or 5 , wherein the compound is obtained by a method comprising: The compound represented by the formula (2b) is
Following formula (1)

[Wherein, R ¹ , Z ¹ and Z ² have the same meanings as described above. ]
A step of substituting a leaving group for a hydrogen atom contained in the compound represented by:
The method according to claim 6 , wherein the compound is obtained by a method comprising: The leaving group has the formula (6)

[Wherein, R ¹⁰ independently represents a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. Two R ¹⁰ in the molecule may be bonded to form a ring structure together with the boron atom. ]
The production method according to any one of claims 4 to 8 , wherein the leaving group is represented by the following formula. Method of any one of claims 1-9, characterized in that Z ¹ and Z ² are each a sulfur atom. At least one group selected from the group consisting of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or It is a C7-30 aralkyl group, and other R < ¹¹ >, R < ¹² >, R < ¹³ > and R < ¹⁴ > are hydrogen atoms, The manufacturing method as described in any one of Claims 1-10 characterized by the above-mentioned. Formula (5)

[Wherein R ¹ independently represents an alkyl group having 1 to 20 carbon atoms, Z ¹ independently represents a sulfur atom or a selenium atom, Z ² represents an oxygen atom, a sulfur atom or a selenium atom,
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a fluorine atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, or an optionally substituted carbon atom. An alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and a substituent; An optionally substituted heteroaralkyl group having 5 to 30 carbon atoms, an optionally substituted heteroaryl group having 4 to 30 carbon atoms, or —Si (R ² ) ₃ (R ² is independently substituted; A substituted silyl group represented by: an alkyl group having 1 to 30 carbon atoms which may have a group or an aryl group having 6 to 30 carbon atoms which may have a substituent. ]
A compound represented by R ¹² in the formula (5) is the same group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms, and R ¹¹ , R ¹³ and R The compound according to claim 12, wherein all ¹⁴ are hydrogen atoms.