JP2020132537A - Method for generating aryne, and method for producing polyortho-arylene using the same - Google Patents

Abstract

(式中、Ｒ^１は炭素数１から１０のアルコキシ基、または水素原子を示す。二つのＲ^１は同一または相異なっていてもよい。Ｘはハロゲン原子を表す。Ａはペルフルオロアルカンスルホニル基を表す。）で表される２−ハロゲノスルホン酸アリールエステル誘導体と、一般式（３）

(式中、Ｒ^２は炭素数４から１０のヘテロアリール基、炭素数２から６のアルキニル基、アリル基又はベンジル基を示す)で表される有機ケイ素試薬、及びセシウム塩からなるアラインの発生剤とそれを用いたアラインの発生方法、並びにポリオルトアリーレンの製造方法。
【選択図】なしPROBLEM TO BE SOLVED: To provide a method for generating an alignment and a method for producing a polyorthoallylen.
General formula (1)

(Wherein, R ¹ is an alkoxy group or a hydrogen atom. .A two R ¹ good .X be the same or different is representative of a halogen atom perfluoroalkanesulfonyl group, of 1 to 10 carbon atoms A 2-halogenosulfonic acid aryl ester derivative represented by (represented) and a general formula (3).

(In the formula, R ² indicates an organosilicon reagent represented by a heteroaryl group having 4 to 10 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an allyl group or a benzyl group), and an alignment composed of a cesium salt. An agent, a method for generating an alignment using the agent, and a method for producing polyorthoallylen.
[Selection diagram] None

Description

The present invention relates to an alignment generation method in which a 2-halogenosulfonic acid aryl ester derivative and an organosilicon reagent are reacted in the presence of a cesium salt, and a method for producing a polyorthoarylene in which the generation method is carried out in the presence of a copper catalyst.

Polyorthoallylen, in which aromatic rings are continuously bonded at the ortho position, is a next-generation material expected as a conductive material or an orientation material for liquid crystal molecules (Non-Patent Documents 1, 2 and 3). The technique of directly connecting aromatic rings to synthesize a polymer is generally a technique of allowing a catalyst to act on a monomer having a nucleophilic site and an electrophilic site, but in this technique, polymerizing an aromatic ring at the ortho position is not possible. It is said that it cannot be done (Non-Patent Document 4). As a technique for continuously polymerizing aromatic rings at the ortho position, polymerization of aligns disclosed in Non-Patent Document 4 and Patent Document 1 has been reported. In the polymerization, a base is allowed to act on the 2- (trimethylsilyl) phenyltrifurate derivative which is a monomer precursor to generate an align which is a monomer in the reaction system and used for the polymerization, but there are multiple steps in the production of the monomer precursor. It is one of the problems in industrialization that the structure of the monomer precursor that can be used for the polymerization is limited.

Macromolecules, 2011, Vol.44, p.8425−8432. Nature Chemistry, 2011, Vol.3, p.68-73. Journal of the American Chemical Society, 2013, Vol.135, p.14564–14567. Journal of the American Chemical Society, 2015, Vol.137, p.74-77.

Japanese Unexamined Patent Publication No. 2015-214610

An object of the present invention is to provide an alignment generation method using a raw material that is more easily available than the prior art, and a method for producing a polyorthoarylene utilizing the generation method.

As a result of diligent studies in order to solve the above problems, the present inventor was able to generate an alignment by reacting a 2-halogenosulfonic acid aryl ester derivative with an organic silicon reagent in the presence of a cesium salt. The present invention has been completed by finding that it is possible to produce a polyorthoarylene by polymerizing the alignment produced by carrying out this reaction in the presence of a copper salt.

That is, the present invention is composed of the following gist.
[Summary 1]
General formula (1)

(Wherein, R ¹ represents an alkoxy group having 1 to 10 carbon atoms or a hydrogen atom. The .A two R ¹ is representative of the same or different may .X also be a halogen atom general formula (2)

(In the formula, n represents an integer from 1 to 10.) Represents a perfluoroalkanesulfonyl group represented by. 2-halogenosulfonic acid aryl ester derivative represented by) and the general formula (3)

(In the formula, R ² represents a heteroaryl group having 4 to 10 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an allyl group or a benzyl group) and reacting with an organic silicon reagent represented by the presence of a cesium salt. General formula (4)

(In the formula, R ¹ formula represents the same meaning as R ¹ in (1).) METHOD occurrence of alignment represented by.
[Abstract 2]
The method for generating an alignment according to claim 1, wherein the cesium salt is cesium fluoride or cesium carbonate.
[Abstract 3]
How the occurrence of alignment according to claim 1 or 2 R ² is a heteroaryl group having from 4 to 10 carbon atoms.
[Abstract 4]
The method for generating an alignment according to any one of claims 1 to 3, wherein R ² is a 5-thiazolyl group, a 2-thiazolyl group, a 2-thianaftyl group, or a 3-thianaftyl group.
[Abstract 5]
The method for generating an alignment according to any one of claims 1 to 3, wherein R ² is a 5-thiazolyl group or a 3-thianaftyl group.
[Abstract 6]
General formula (4) according to the generation method according to any one of claims 1 to 5 in the presence of a copper salt.

(In the formula, R ¹ represents an alkoxy group having 1 to 20 carbon atoms or a hydrogen atom. The two R ^1, may be the same or different.) To generate aligned represented by, polymerizing the aligned General formula (5)

(In the formula, R ¹ has the same meaning as described above.) A method for producing a polyorthoarylene having a structural unit represented by (in the present specification, it may be referred to as a production method of the present invention).

By using the production method of the present invention, it is possible to generate an alignment using an easily available 2-halogenosulfonic acid aryl ester derivative as a raw material, and to produce a polyorthoallylene.

Hereinafter, embodiments of the present invention will be described in detail. First, the general formulas (1), (2) and (3) will be described together with the explanation of the definitions of R ¹ , X, A and R ² .

The alkoxy group having from 1 carbon atoms represented by R ¹ 10, which may be linear or branched or cyclic, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, pentyloxy group, hexyloxy group, Linear alkoxy group such as heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, isopropoxy group, 1- (2-methylpropyl) oxy group, 2-butyloxy group, tert-butoxy group, 2-ethylhexyloxy group , 3,7-Dimethyloctyloxy group and other branched alkoxy groups, cyclopentyloxy group, cyclohexyloxy group and other cyclic alkoxy groups can be exemplified. R ¹ is preferably an alkoxy group or a hydrogen atom having 1 to 6 carbon atoms, and more preferably a methoxy group or a hydrogen atom in terms of good functions such as solubility, conductivity and orientation of the obtained polymer.
X represents a halogen atom, and iodine atom, bromine atom, chlorine atom, and fluorine atom can be exemplified. Iodine atom and bromine atom are preferable, and iodine atom is more preferable from the viewpoint of good production yield.

The perfluoroalkanesulfonyl group (2) represented by A may be either a linear or branched perfluoroalkanesulfonyl group, and the yields of align (4) and polyorthoallylen (5) are good. Those having n of 1 to 8 are preferable, perfluoro-1-butanesulfonyl group, perfluoro-1-octanesulfonyl group or trifluoromethanesulfonyl group is more preferable, and nonaflate-1-butanesulfonyl group or trifluoromethanesulfonyl group is particularly preferable. Specific 2-halogenosulfonic acid aryl ester derivatives represented by the general formula (1) are (1-1) to (1-12).

(In the formula, Tf represents a trifluoromethanesulfonyl group.)
(1-1), (1-2), (1-3), (1-7) or (1-8) are preferable in terms of good production efficiency in the alignment generation method of the present invention and the production method of the present invention. ..
Specific structures of the organosilicon reagent (3) include, for example, (3-1) to (3-15).

Can be mentioned. From the viewpoint of good production efficiency, (3-1) to (3-7), (3-10) to (3-15) are preferable, and (3-1), (3-3), (3-6), (3-7) is more preferable, and (3-3) and (3-6) are particularly preferable.

Next, the method of generating the alignment of the present invention (also referred to as the method of generating the present invention in the present specification) will be described in detail.

First, the equivalents of the 2-halogenosulfonic acid aryl ester derivative (1) and the organosilicon reagent (3) will be described. The amount of the organic silicon reagent (3) is not particularly limited, but is preferably in the range of 1 to 30 equivalents with respect to the 2-halogenosulfonic acid aryl ester derivative (1) in terms of good reaction yield. It is more preferably in the range of 1-10 equivalents, and even more preferably in the range of 1-6 equivalents.

Examples of the cesium salt used in the generation method of the present invention include cesium fluoride, cesium carbonate, cesium hydroxide and the like, and these may be mixed and used in any ratio. Cesium fluoride, cesium carbonate, or a mixture of cesium fluoride and cesium carbonate is preferable, and cesium fluoride or cesium carbonate is more preferable in terms of good reaction yield. Further, a complexing agent such as crown ether may be added.

The amount of cesium salt used is not particularly limited, but is preferably in the range of 1 to 20 equivalents with respect to the 2-halogenosulfonic acid aryl ester derivative (1) in terms of good reaction yield. It is more preferably in the range of equivalents, and even more preferably in the range of 1-6 equivalents.

The generation method of the present invention can be carried out in a solvent. The solvent that can be used is not particularly limited as long as it does not harm the reaction, and is an aliphatic hydrocarbon solvent such as hexane, heptane, decane, or tridecane, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME). , Ether solvent such as tetrahydrofuran (THF), 2-methyl tetrahydrofuran, 1,4-dioxane, dimethoxyethane, aromatic hydrocarbon solvent such as benzene, toluene, xylene, mesitylene, tetraline, ethylene carbonate, propylene carbonate, dimethyl carbonate, Carbonate ester solvents such as diethyl carbonate, ethyl methyl carbonate, 4-fluoroethylene carbonate, ester solvents such as ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, γ-lactone, dimethyl sulfoxide (DMF), dimethyl Amid solvents such as acetoamide (DMAc) and N-methylpyrrolidone (NMP), urea solvents such as N, N, N', N'-tetramethylurea (TMU) and N, N'-dimethylpropylene urea (DMPU), Sulfoxide solvents such as dimethyl sulfoxide (DMSO), alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 2,2,2-trifluoroethanol, etc. Halogen solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, orthodichlorobenzene, bis (2,2,2-trifluoroethyl) = N, N-diisopropylphosphoroamidate (PF-37) ), Fluorine solvent such as phosphate = tris (2,2,2-trifluoroethyl) (TFEP), nitromethane, water and the like can be exemplified, and these may be mixed and used in any ratio.

Of these, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, and an ether solvent are preferable, an aromatic hydrocarbon solvent and an ether solvent are more preferable, and toluene and THF are particularly preferable, in terms of good production yield.

The amount of the solvent used is not particularly limited, but is preferably in the range of 0.1 to 100 mL / mg with respect to the weight of the 2-halogenosulfonic acid aryl ester derivative (1), and is 0.1 to 10 mL / mg. It is more preferable that it is in the range of.

The production method of the present invention is preferably carried out in an atmosphere of an inert gas such as argon gas or nitrogen gas.

The reaction temperature at which the production method of the present invention is carried out is not limited, but it is preferably carried out in the range of −78 ° C. to 200 ° C., more preferably in the range of 0 ° C. to 150 ° C., and 40 ° C. to 130 ° C. It is particularly preferable to carry out within the range of.

The reaction time varies depending on various conditions such as the 2-halogenosulfonic acid aryl ester derivative (1) used, the solvent, and the reaction temperature, but is preferably 0.1 to 100 hours, more preferably 0.5 to 78 hours, and 1 to 48 hours. Time is especially preferred.
As the 2-halogenosulfonic acid aryl ester derivative (1) used in the generation method of the present invention, those produced in the reaction system can also be used. That is, the general formula (6)

(Wherein, ^{R 1} and X are as defined above.)
It is also possible to generate it in a reaction system by allowing a sulfonyl halide to act on it. Examples of the sulfonyl halide that can be used include tetrafluoro-2- (tetrafluoro-2-iodoethoxy) ethanesulfonyl, pentafluoro-1-butanesulfonyl fluoride, pentadecafluoro-1-octanesulfonyl fluoride, and the like. Examples thereof include 2-fluorobenzenesulfonyl chloride, 3-fluorobenzenesulfonyl chloride, 4-fluorobenzenesulfonyl chloride and the like. Tetrafluoro-2- (tetrafluoro-2-iodoethoxy) ethanesulfonyl, pentafluoro-1-butanesulfonyl fluoride, and pentadecafluoro-1-octanesulfonyl fluoride are preferable because of their good reaction yield. Nonatafluoro-1-butanesulfonyl fluorinated, pentadecafluoro-1-octanesulfonyl fluoride are more preferred, and nonafluoro-1-butanesulfonyl fluoride is particularly preferred.

The specific structures represented by the general formula (6) are (6-1) to (6-6).

It is represented by. (6-1), (6-2), (6-3), and (6-5) are preferable in terms of good production efficiency.

Next, the method for producing a polyorthoarylene of the present invention (hereinafter referred to as the production method of the present invention), that is, the method for producing the present invention is carried out to generate an alignment (4), and the alignment (4) is polymerized to generate poly. The method for producing the ortho-allylen (5) will be described in detail.

The production method of the present invention is achieved by carrying out the generation method of the present invention in the presence of a monovalent copper salt. Examples of the copper salt that can be used include copper chloride, copper bromide, copper iodide, and copper cyanide. Copper bromide, copper iodide or copper cyanide is preferable, copper bromide or copper cyanide is more preferable, and copper bromide is particularly preferable, in terms of good reaction yield.

The amount of the copper salt used is not particularly limited, but the degree of polymerization of the polyorthoarylene (5) can be changed by changing the amount of the copper salt with respect to the 2-halogenosulfonic acid aryl ester derivative (1). , Can be appropriately selected according to the degree of polymerization of the target polymer. Usually, it is preferably 0.001 to 1 equivalent, more preferably 0.01 to 0.1 equivalent, relative to the 2-halogenosulfonic acid aryl ester derivative (1).

The production method of the present invention can also be carried out in the presence of a tertiary phosphorus compound or carbene compound. Examples of the tertiary phosphorus compound that can be used include triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tri-o-tolylphosphine, trioctylphosphine, 9, 9-Dimethyl-4,5-bis (diphenylphosphino) xanthene, 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphino) ferrocene, tert-butyldiphenylphosphine, 2- (diphenylphosphino) -2'-(N, N-dimethylamino) biphenyl, bis (diphenylphosphine) methane, 1,4-bis (diphenylphosphine) butane, tri (2-furyl) phosphine, tris (2,5-kisilyl) Examples thereof include phosphine and bis (diphenylphosphino) -1,1'-binaphthyl. Examples of the carbene compound that can be used include 1,3-bis (2,6-diisopropylphenyl) imidazol-2-iriden, 1,3-bis (2,6-diisopropylphenyl) imidazolidine-2-iriden, 1, Examples thereof include 3-di-tert-butylimidazol-2-imidazole, 1,3-dimesityl imidazole-2-imidazole and the like.

The amount of the tertiary phosphorus compound or carbene compound used is not particularly limited, but is preferably 0.01 to 10 equivalents, and more preferably 0.1 to 5 equivalents, relative to the copper salt.

Polyorthoallylen (5) can be obtained by subjecting it to conventional treatment after completion of the production method of the present invention. If necessary, purification may be performed by precipitation, filtration, dialysis, column chromatography, preparative HPLC, Soxhlet extraction, or the like.

As the 2-halogenosulfonic acid aryl ester derivative (1), a commercially available product may be used, and it is described in the literature (Chemical Communications, Vol. 46, pp. 7028-7030, 2010, The Journal of Organic Chemistry, Vol. 80, 11460-11467, 2015). Year) may be prepared according to the method.

The organosilicon reagent (3) may be a commercially available product, or may be prepared according to the method described in the literature (Nature, Vol. 518, pp. 80-84, etc.).

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

The monomer obtained in the example was structurally analyzed by ^{1 1} H-NMR measurement. The molecular weight and molecular weight distribution of the polymers obtained in the examples were estimated by Gel Permeation Chro, attografy (GPC) measurement. Commercially available reagents were used.
<NMR measurement conditions>
Measuring device: Bruker ASCEND ^TM ADVANCE III HD (400MHz)
Measuring solvent: Deuterated chloroform (CDCl ₃ )
Internal standard substance: Tetramethylsilane <TGA measurement conditions>
Measuring device: SII Co., Ltd. EXSTAR6000 TGA / DTA6200
Sample container: Aluminum pan Measurement atmosphere: Nitrogen T _d3 , T _{d5 and} T _d10 represent 3%, 5% and 10% weight loss temperatures, respectively.
[Example 1]

Toluene (5 mL) was added to a mixture of cesium fluoride (0.458 g) and 18-crown-6 ether (1.571 g), and the solvent was distilled off under reduced pressure. There 1,3-diphenylisobenzofuran (0.406 g), 2-iodophenyltrifluoromethanesulfonic acid ester (0.350 g) and tetrahydrofuran (5 mL), 3-trimethylsilylbenzo [3,2-b] thiophene ( 0.309 g) and hexadecane (0.227 g) as an internal standard were added, and the mixture was stirred at 60 ° C. for 21 hours. A saturated aqueous ammonium chloride solution was added to the reaction solution to stop the reaction, and the mixture was extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered. The solvent was distilled off under reduced pressure to obtain a brown solid (1.08 g, 80%). Write the name of what the solid was in the text. The yield was determined based on ^{1 1} H-NMR spectrum.
^{1 1} H-NMR (CDCl ₃ , 400 MHz) δ7.94 (d, J = 7.0 Hz, 4H), 7.60 (t, J = 7.4 Hz, 4H), 7.49 (t, J = 7. 4Hz, 2H), 7.36 (dd, J = 3.0Hz, 5.2Hz, 4H), 7.03 (dd, J = 3.0Hz, 5.2Hz, 4H).

[Examples 2 to 17]
The same operation as in Example 1 was repeated, and a verification experiment was conducted in which an alignment was generated using the organosilicon reagents, bases, and additives shown in Table 1. Table 1 shows the results of Examples 1 to 17. The occurrence of alignment is described in the literature (Journal of the American Chemical Society, 2008, Vol. 130, p.472-480. (For example, p.474, lines 19-40 in the second column), According to the method of Journal of the American Chemical Society, 2017, Vol. 139, p.8416-8419. (For example, line 4 in the second column of p.8417 to line 18 in the first column of p.8418). confirmed.

It was confirmed that alignment occurred in the reaction system in Examples 1 to 17.
[Example 18]

Toluene (5 mL) was added to a mixture of cesium fluoride (0.399 g) and 18-crown-6 ether (0.071 g), and the solvent was distilled off under reduced pressure. There, 2-iodophenyltrifluoromethanesulfonic acid ester (0.298 g) and tetrahydrofuran (9 mL), copper bromide (0.026 g), 5-trimethylsilylthiazole (0.200 g), and hexadecane (0.192 g) as an internal standard were added. ) Was added, and the mixture was stirred at 60 ° C. for 19 hours. The reaction solution was diluted with methanol and filtered, and the obtained solid was washed with water and methanol to obtain a white solid (0.048 g, 75%). IR (ATR, cm ^-1 ) 3076,1471,1369,1302,125,1157,1113,974,893,869,802,758,611. T _d3 = 186 ° C., T _d5 = 211, T _d10 = 270.
[Example 19]

Toluene (5 mL) was added to a mixture of cesium carbonate (0.663 g), cesium fluoride (0.335 g), and 18-crown-6 ether (0.056 g), and the solvent was evaporated under reduced pressure. There, 2-iodophenol (0.220 g) and tetrahydrofuran (10 mL), copper bromide (0.032 g), 5-trimethylsilylthiazole (0.631 g), nonafluoro-1-butanesulfonylfloride (0.598 g), Hexadecane (0.231 g) was added as an internal marker, and the mixture was stirred at 70 ° C. for 18 hours. The reaction solution was diluted with methanol and filtered, and then the obtained solid was washed with water and methanol to obtain a black solid (0.052 g, 73%). IR (ATR, cm ^-1 ) 3078, 168, 1635, 1558, 1541, 1489, 1458, 1338, 1230, 1151, 1111, 899, 870, 806, 760, 613. T _d3 = 117 ° C., T _d5 = 135, T _d10 = 217.

Also describe the availability of the method of generation of the present invention. The polyorthophenylene provided by the present invention is expected as a novel compound useful for electronic devices such as organic EL and liquid crystal displays as a conductive material and a molecular orientation material.

Claims (6)

General formula (1)

(Wherein, R ¹ represents an alkoxy group having 1 to 10 carbon atoms or a hydrogen atom. The .A two R ¹ is representative of the same or different may .X also be a halogen atom general formula (2)

(In the formula, n represents an integer from 1 to 10.) Represents a perfluoroalkanesulfonyl group represented by. 2-halogenosulfonic acid aryl ester derivative represented by) and the general formula (3)

(In the formula, R ² represents a heteroaryl group having 4 to 10 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an allyl group or a benzyl group) and reacting with an organic silicon reagent represented by the presence of a cesium salt. General formula (4)

(In the formula, R ¹ formula represents the same meaning as R ¹ in (1).) METHOD occurrence of alignment represented by. The method for generating an alignment according to claim 1, wherein the cesium salt is cesium fluoride or cesium carbonate. How the occurrence of alignment according to claim 1 or 2 R ² is a heteroaryl group having from 4 to 10 carbon atoms. The method for generating an alignment according to any one of claims 1 to 3, wherein R ² is a 5-thiazolyl group, a 2-thiazolyl group, a 2-thianaftyl group, or a 3-thianaftyl group. The method for generating an alignment according to any one of claims 1 to 3, wherein R ² is a 5-thiazolyl group or a 3-thianaftyl group. General formula (4) according to the generation method according to any one of claims 1 to 5 in the presence of a copper salt.

(In the formula, R ¹ represents an alkoxy group having 1 to 20 carbon atoms or a hydrogen atom. The two R ^1, may be the same or different.) To generate aligned represented by, polymerizing the aligned General formula (5)

(In the formula, R ¹ has the same meaning as described above.) A method for producing a polyorthoallylen having a structural unit represented by the above.