JP2012219015A - Method for producing chalcogen-containing condensed polycyclic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method which can produce a chalcogen-containing condensed polycyclic compound useful as an organic semiconductor material under mild conditions.SOLUTION: There is provided a method for producing a chalcogen-containing condensed polycyclic compound which comprises a step of reacting a compound (4) represented by formula (4) with an acid to obtain the chalcogen-containing condensed polycyclic compound (5) represented by formula (5). In the formulas, Ris a 1C-20C alkyl group; Zs are each independently a sulfur atom or a selenium atom; Zis an oxygen atom, a sulfur atom, or a selenium atom; R, R, R, and Rare each independently a hydrogen atom, an optionally substituted 1C-30C alkyl group, an optionally substituted 1-30C alkoxyl group, an optionally substituted 6C-30C aryl group, an optionally substituted 7C-30C aralkyl group, an optionally substituted 5C-30C heteroaralkyl group, an optionally substituted 4C-30C heteroaryl group, or a substituted silyl group represented by -Si(R)(wherein Rs are each independently an optionally substituted 1C-30C alkyl group or an optionally substituted 6C-30C aryl group); Xis a halogen atom; and Xis a leaving group.

Description

  The present invention relates to a method 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.

で表される芳香族複素環化合物（１ａ）とN−ハロカルボン酸アミドとを水又はアルコール存在下で反応させて、
下記式（２ａ）

で表される芳香族複素環化合物（２ａ）を得る工程、
芳香族複素環化合物（２ａ）と下記式（３）

で表される芳香族化合物（３）とを反応させて、下記式（４）

で示される化合物（４）を得る工程および
化合物（４）と酸とを反応させて、下記式（５）

で示される含カルコゲン縮合多環式化合物（５）を得る工程を含む、含カルコゲン縮合多環式化合物の製造方法。
(各式中、Ｒ^１は炭素数１〜２０のアルキル基を示し、Ｚ^１はそれぞれ独立に、硫黄原子又はセレン原子を示し、Ｚ^２は酸素原子、硫黄原子又はセレン原子を示す。Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４はそれぞれ独立に、水素原子、置換基を有していてもよい炭素数１〜３０のアルキル基、置換基を有していてもよい炭素数１〜３０のアルコキシ基、置換基を有していてもよい炭素数６〜３０のアリール基、置換基を有していてもよい炭素数７〜３０のアラルキル基、置換基を有していてもよい炭素数５〜３０のヘテロアラルキル基、置換基を有していてもよい炭素数４〜３０のヘテロアリール基、又は、−Ｓｉ（Ｒ^２）_３（Ｒ^２はそれぞれ独立に、置換基を有していてもよい炭素数１〜３０のアルキル基又は置換基を有していてもよい炭素数６〜３０のアリール基を示す。）で表される置換シリル基を示す。Ｘ^１はハロゲン原子を示し、Ｘ^２は脱離基を示す。)
[２] 下記式（１ｂ）

で表される芳香族複素環化合物（１ｂ）とN−ハロカルボン酸アミドとを水又はアルコール存在下で反応させることを特徴とする、下記式（２ｂ）

で表される芳香族複素環化合物（２ｂ）の製造方法。
(各式中、Ｒ^１はそれぞれ独立に炭素数１〜２０のアルキル基を示し、Ｚ^１はそれぞれ独立に、硫黄原子又はセレン原子を示し、Ｚ^２は酸素原子、硫黄原子又はセレン原子を示し、Ｘ^１はそれぞれ独立に、ハロゲン原子を示し、ｍは１〜３の整数を表し、nは１〜３の整数を表す。但し、ｍ＋ｎは２〜４の整数であるものとする。)
[３] ｍは２であり、ｎは２である[２]記載の製造方法。
[４] 一般式（１ｂ）で表される芳香族複素環化合物が下記式（１ａ）で表される芳香族複素環化合物（１ａ）であり、一般式（２ｂ）で表される化合物（２ｂ）が下記式（２ａ）で表される芳香族複素環化合物（２ａ）であることを特徴とする[２]記載の製造方法。

(各式中、Ｒ^１、Ｚ^１、Ｚ^２、及びＸ^１は前記と同じ意味を表す。)
[５] Ｚ^１およびＺ^２がいずれも硫黄原子である[２]〜[４]のいずれかに記載の製造方法。
[６] N−ハロカルボン酸アミドがN−ハロスクシンイミドである[２]〜[４]のいずれかに記載の製造方法。 The present invention provides [1] to [6].
[1] The following formula (1a)

An aromatic heterocyclic compound represented by the formula (1a) and an N-halocarboxylic acid amide in the presence of water or alcohol,
The following formula (2a)

Obtaining an aromatic heterocyclic compound (2a) represented by:
Aromatic heterocyclic compound (2a) and the following formula (3)

Is reacted with an aromatic compound (3) represented by the following formula (4):

And a step of obtaining a compound (4) represented by the following formula (5):

The manufacturing method of a chalcogen condensed polycyclic compound including the process of obtaining the chalcogen condensed polycyclic compound (5) shown by these.
(In each formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, Z ¹ independently represents a sulfur atom or a selenium atom, and 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, an alkyl group having 1 to 30 carbon atoms which may have a substituent, or an alkyl group having 1 to 30 carbon atoms which may have a substituent. An alkoxy group, an optionally substituted aryl group having 6 to 30 carbon atoms, an optionally substituted aralkyl group having 7 to 30 carbon atoms, and an optionally substituted carbon number A heteroaralkyl group having 5 to 30 carbon atoms, a heteroaryl group having 4 to 30 carbon atoms which may have a substituent, or —Si (R ² ) ₃ (R ² each independently has a substituent; Even if it has an alkyl group having 1 to 30 carbon atoms or a substituent, .X ¹ showing a have substituted silyl group represented by.) Of an aryl group having 6 to 30 carbon atoms is a halogen atom, X ² represents a leaving group.)
[2] The following formula (1b)

The aromatic heterocyclic compound (1b) represented by the formula (2b) is reacted with N-halocarboxylic acid amide in the presence of water or alcohol.

The manufacturing method of the aromatic heterocyclic compound (2b) 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, and Z ² represents an oxygen atom, a sulfur atom or a selenium atom. X ¹ independently represents a halogen atom, m represents an integer of 1 to 3, n represents an integer of 1 to 3, provided that m + n is an integer of 2 to 4).
[3] The production method according to [2], wherein m is 2 and n is 2.
[4] The aromatic heterocyclic compound represented by the general formula (1b) is the aromatic heterocyclic compound (1a) represented by the following formula (1a), and the compound (2b) represented by the general formula (2b) ) Is an aromatic heterocyclic compound (2a) represented by the following formula (2a).

(In each formula, R ¹ , Z ¹ , Z ² , and X ¹ represent the same meaning as described above.)
[5] The production method according to any one of [2] to [4], wherein Z ¹ and Z ² are both sulfur atoms.
[6] The production method according to any one of [2] to [4], wherein the N-halocarboxylic acid amide is N-halosuccinimide.

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

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

  The aromatic heterocyclic compound represented by the general formula (2a) (hereinafter sometimes referred to as the compound (2a)) is an aromatic heterocyclic compound represented by the general formula (1a) (hereinafter referred to as the compound (1a). ) And N-halocarboxylic acid amide in the presence of water or alcohol.

First, the compound (1a) will be described. R ¹ in the compound (1a) 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 (1a) 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 N-halocarboxylic acid amide used in the method for producing the aromatic heterocyclic compound (2a) represented by the formula (2a) by reacting the compound (1a) with an N-halocarboxylic acid amide include N-chloro N-haloacetamides such as acetamide, N-bromoacetamide, N-iodoacetamide, N-chlorosuccinimide, N-bromosuccinimide, N-halosuccinimides such as N-iodosuccinimide, N-chlorophthalimide, N-bromophthalimide N-halophthalimides such as N-iodophthalimide, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethyl 1,3-dihalohydantoins such as hydantoinPreferably, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, N-chlorophthalimide, N-bromophthalimide, and N-iodophthalimide are used, and more preferably, N-bromosuccinimide is used.

With respect to the use amount of N-halocarboxylic acid amide, for example, 0.5 mol to 15 mol, preferably 0.7 mol to 10 mol, more preferably 1 mol to 8 mol, per 1 mol of compound (1a) is there. If the amount of N-halocarboxylic acid amide used is too small, the reaction is not completed, and if the amount used is too large, side reactions proceed.
The N-halocarboxylic acid amide may be charged at once, or may be charged in several times according to the progress of the reaction.

  The reaction between compound (1a) and N-halocarboxylic acid amide is carried out in the presence of water or alcohol. In the reaction, water or alcohol may be added to the reaction solvent before starting the reaction, or may be added to the reaction solvent after starting the reaction. Moreover, you may use water or alcohol as a reaction solvent. When water or alcohol is added to the reaction solvent, the amount is usually 1 to 200 times by weight, preferably 2 to 150 times by weight, more preferably 5 to 100 times by weight with respect to the reaction solvent. Examples of the alcohol include methanol, ethanol, isopropanol, and n-butanol.

  As the reaction solvent, in addition to water or alcohol, for example, aliphatic hydrocarbon solvents such as pentane, hexane, and heptane, aromatic hydrocarbon solvents such as toluene and xylene, methylene chloride, chloroform, 1,2-dichloroethane, 1, Examples include halogenated hydrocarbon solvents such as 2-dichloropropane, ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, cyclopentylmethyl ether, and mixed solvents thereof.

  The amount of the reaction solvent to be used is generally 1 to 500 times by weight, preferably 2 to 300 times by weight, more preferably 5 to 200 times by weight with respect to compound (1a). The reaction temperature is generally −78 ° C. to the boiling point of the solvent, preferably −40 ° C. to the boiling point of the solvent, more preferably 0 ° C. to the boiling point of the solvent. The reaction time can be in the range of 1 minute to 96 hours. After completion of the reaction, the compound (2a) can be obtained by performing general post-treatment and, if necessary, purification by distillation, recrystallization, silica gel chromatography or the like.

  In this reaction, a base may be added after reacting compound (1a) with N-halocarboxylic acid amide.

  Examples of the base include sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate and the like, preferably sodium carbonate.

  The amount of the base added is, for example, from 1 mol to 100 mol, preferably from 2 mol to 80 mol, more preferably from 5 mol to 50 mol, per 1 mol of compound (1a).

Subsequently, a condensation reaction between the aromatic heterocyclic compound represented by the general formula (2a) and the aromatic compound represented by the general formula (3) (hereinafter sometimes referred to as compound (3)) will be described.
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in the compound (3) may each independently have a hydrogen atom, a C 1-30 alkyl group which may have a substituent, or a substituent. A good C1-C30 alkoxy group, an optionally substituted aryl group having 6-30 carbon atoms, an optionally substituted aralkyl group having 7-30 carbon atoms, 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 Represents a C1-C30 alkyl group which may have a substituent, or a C6-C30 aryl group which may have a substituent.

  The “alkyl group having 1 to 30 carbon atoms” of the “alkyl group having 1 to 30 carbon atoms which may have a substituent” may be linear, branched or 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. More preferably, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, -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, Examples thereof include alkyl groups having 1 to 16 carbon atoms such as 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” include a halogen atom and an alkoxy group having 1 to 30 carbon atoms.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

  Examples of the alkoxy group having 1 to 30 carbon atoms include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, and 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 Group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-icosyloxy group, n-henicosyloxy group, n-docosyloxy group, n-tricosyloxy group, n-tetracosyl group Oxy group, n-pentacosyloxy group, n-hexacosyloxy group, n-heptacosyloxy group, n-octacosyloxy group Group, n- Nonakoshiruokishi group, and n- triacontyl group and the like.

  As the substituent that the “optionally substituted alkyl group having 1 to 30 carbon atoms” 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” of the “optionally substituted alkoxy group having 1 to 30 carbon atoms” include, for example, a methoxy group, an ethoxy group, an n-propoxy group, and an 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, n -Henicosyloxy group, n-docosyloxy group, n-tricosyloxy group, n-tetracosyloxy group, n-pentacosyloxy group, n Hexa cosyl group, n- hepta cosyl 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 “optionally substituted alkoxy group having 1 to 30 carbon atoms” include halogen atoms such as fluorine atom, chlorine atom and bromine atom, alkoxy group having 1 to 30 carbon atoms, carbon Examples thereof include an aryl group having 6 to 30 carbon atoms, 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.

  Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the aralkyl group having 7 to 30 carbon atoms include groups represented by the following general formula. n1 shows the integer of 1-14, n2 and n3 show the integer of 1-10.

  The heteroaryl group having 4 to 30 carbon atoms means a group in which at least one carbon atom contained in the aromatic ring of the aryl group is replaced with a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a selenium atom. For example, thienyl group, furyl group, thiazolyl group, thieno [3,2-b] thienyl group, fluoro [3,2-b] furyl group, thieno [3,2-b] furyl group, benzo [b] Examples include a thienyl group and a 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 are preferable.

  The heteroaralkyl group having 5 to 30 carbon atoms means a group in which at least one carbon atom contained in the aromatic ring of the aralkyl group is replaced with a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a selenium atom. Examples of the heteroaralkyl group include a group represented by the following general 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.

  More preferably, the following general formula can be mentioned. 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.

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

  The “aryl group” of the “optionally substituted aryl group having 6 to 30 carbon atoms” is preferably monocyclic or bicyclic, more preferably phenyl group, 1-naphthyl group, 2 -A naphthyl group is mentioned.

  Examples of the substituent of the “optionally substituted aryl group having 6 to 30 carbon atoms” include a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, for example, an alkyl having 1 to 20 carbon atoms. A group having 1 to 20 carbon atoms, 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. Can be mentioned. The hydrogen atom contained in the substituent may be replaced with a fluorine atom.

  Examples of the “aryl group optionally having a substituent” include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and perfluorophenyl.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl. Group, n-decyl 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 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-nonacosyl group Group, and n-triacontyl group.

Examples of the substituent of “optionally substituted aralkyl group having 7 to 30 carbon atoms” include halogen atoms such as fluorine atom, chlorine atom and bromine atom, for example, alkyl group having 1 to 20 carbon atoms. And an alkoxy group having 1 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.
The hydrogen atom contained in the substituent alkyl group, alkoxy group, aralkyl group, heteroaryl group or heteroaralkyl group may be replaced by a fluorine atom.

  As the substituent of the “optionally substituted aralkyl group having 7 to 30 carbon atoms”, a fluorine atom is preferable.

  Examples of the “optionally substituted aralkyl group having 7 to 30 carbon atoms” include, for example, the following general formula:

（ｎ１は１〜２４の整数を示し、ｎ２及びｎ３は１〜２０の整数を示す。）で表される炭素数７〜３０のアラルキル基、又は下記一般式；

(N1 represents an integer of 1 to 24, n2 and n3 represent an integer of 1 to 20), or an aralkyl group having 7 to 30 carbon atoms, or the following general formula;

（ｎ４及びｎ５は１〜２４の整数を示し、ｎ６は１〜２３の整数を示す。）で表される炭素数７〜３０の置換基を有するアラルキル基が挙げられる。

(The n4 and n5 show the integer of 1-24, n6 shows the integer of 1-23.) The aralkyl group which has a C7-30 substituent represented by this is mentioned.

  Examples of the “optionally substituted heteroaryl group having 4 to 30 carbon atoms” include thienyl group, furyl group, thiazolyl group, thieno [3,2-b] thienyl group, and fluoro [3,2]. -B] furyl group, thieno [3,2-b] furyl group, benzo [b] thienyl group, benzo [b] furyl group and the like. As the heteroaryl group, a thienyl group, a thiazolyl group, a thieno [3,2-b] thienyl group, a benzo [b] thienyl group, a benzo [b] furyl group, more preferably the following chemical formula

で表わされる基が挙げられる。

The group represented by these is mentioned.

  Examples of the substituent of the “optionally substituted heteroaryl group having 4 to 30 carbon atoms” include halogen atoms such as fluorine atom, chlorine atom and bromine atom, for example, alkyl having 1 to 20 carbon atoms. A group, an alkoxy group having 1 to 20 carbon atoms, 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, a heteroaralkyl group having 5 to 30 carbon atoms, and the like. Can be mentioned. 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, Examples include 5-fluoro-2-thienyl group, 5-hexyl-2-thienyl group, 4-hexyloxy-2-thienyl group, and the like.

  Examples of the substituent of the “optionally substituted heteroaralkyl group having 5 to 30 carbon atoms” include, for example, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, for example, an alkyl having 1 to 20 carbon atoms. Group, an alkoxy group having 1 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a heteroaryl group having 4 to 30 carbon atoms, a heteroaralkyl group having 5 to 20 carbon atoms, and the like. The hydrogen atom contained in the substituent may be replaced with a fluorine atom.

  As the substituent of the “optionally substituted heteroaralkyl group having 5 to 30 carbon atoms”, a fluorine atom is preferable. Examples of the “heteroaralkyl group having 5 to 30 carbon atoms which may have a substituent” include groups represented by the following general 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 trialkylsilyl group in the “trialkylsilyl group having 3 to 30 carbon atoms which may have a fluorine atom” is a total of 3 to 30 carbon atoms of three alkyl groups bonded to a silicon atom. It is a certain silyl group. The maximum number of carbon atoms of one alkyl group bonded to a silicon atom is 28, which is an alkyl group having 1 to 30 carbon atoms which may be substituted with a fluorine atom. The trialkylsilyl group substituted with a fluorine atom means a group in which part or all of the hydrogen atoms in the alkyl group bonded to the silicon atom are replaced with fluorine atoms. Specific examples of the trialkylsilyl group include trimethylsilyl group, triethylsilyl group, tri (i-propyl) silyl group, t-butyldimethylsilyl group, dimethylhexylsilyl group, and dimethyldodecylsilyl group.

X ² in the compound (3) represents a leaving group. X ² may be any leaving group capable of allowing the condensation reaction between compound (3) and compound (2a) to proceed. For example, a group represented by the following general 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 general 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. A bromine atom and an iodine atom are preferable.

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. A bromine atom and an iodine atom are preferable.

  In the compound (3), as a method for producing a compound having the group of the formula (6) as a leaving group, for example, the method described in page 80, Experimental Chemistry Course 24 Organic Synthesis VI (Edited by The Chemical Society of Japan), page 80 Can be manufactured.

  In the compound (3), as a method for producing a compound having the group of the formula (7) as a leaving group, for example, the method described in the 4th edition Experimental Chemistry Course 24 Organic Synthesis VI (Edited by The Chemical Society of Japan) page 189 is used. Can be manufactured.

  In the compound (3), as a method for producing a compound having the group of the formula (8) as a leaving group, for example, the method described in the 43rd edition Experimental Chemistry Course 24 Organic Synthesis VI (Edited by Chemical Society of Japan) page 43 Can be manufactured.

  In the compound (3), as a method for producing a compound having the group of the formula (9) as a leaving group, for example, the method described in page 4 of Experimental Chemistry Course 25 Organic Synthesis VII (Edited by Chemical Society of Japan) page 401 is used. Can be manufactured.

Examples of compound (3) include compounds (3-1) to (3-280) exemplified in Table 1.

波線は結合手を意味する。

A wavy line means a bond.

Preferably, (3-1), (3-2), (3-3), (3-6), (3-8), (3-11), (3-13), (3-15) , (3-16), (3-17), (3-20), (3-21), (3-24), (3-26), (3-29), (3-32), ( 3-42), (3-43), (3-44), (3-45), (3-46), (3-47), (3-48), (3-49), (3- 50), (3-51), (3-52), (3-54), (3-56), (3-57), (3-59), (3-60), (3-61) , (3-62), (3-63), (3-64), (3-65), (3-66), (3-67), (3-68), (3-69), ( 3-70), (3-71), (3-72), (3-73), (3-74), (3-75), (3- 6), (3-77), (3-78), (3-79), (3-80), (3-81), (3-83), (3-84), (3-85) , (3-86), (3-87), (3-88), (3-92), (3-95), (3-96), (3-97), (3-98), ( 3-99), (3-100), (3-101), (3-103), (3-104), (3-105), (3-107), (3-109), (3- 110), (3-112), (3-114), (3-124), (3-128), (3-129), (3-134), (3-135), (3-137) , (3-138), (3-139), (3-143), (3-147), (3-149), (3-151), (3-156), (3-159), ( 3-164), (3-169), (3 177), (3-196), (3-197), (3-198), (3-201), (3-203), (3-205), (3-207), (3-208) , (3-210), (3-219), (3-225), (3-228), (3-234), (3-235), (3-237), (3-239), ( 3-246), (3-249), (3-251), (3-253), (3-259), (3-269), (3-270), (3-271), (3- 272), (3-274), (3-276), (3-278), and (3-280).
More preferably, (3-1), (3-2), (3-3), (3-6), (3-42), (3-43), (3-44), (3-45) ), (3-46), (3-47), (3-48), (3-49), (3-50), (3-51), (3-52), (3-54), (3-56), (3-57), (3-59), (3-64), (3-73), (3-78), (3-80), (3-92), (3 -95), (3-101), (3-103), (3-104), (3-105), (3-107), (3-109), (3-110), (3-112) ), (3-114), (3-124), (3-128), (3-129), (3-156), (3-196), (3-197), (3-269), (3-272), (3-274), (3-276) It is.

X ² of the compound (3) is, when the group represented by formula (6), condensation reaction, for example, the presence of a transition metal catalyst and a base, for example, within a temperature range of about 0 ° C. to 150 DEG ° C. The reaction can easily proceed in solution.
Examples of the transition metal catalyst used in the condensation reaction include a palladium catalyst or a nickel catalyst. As the palladium catalyst, a commercially available catalyst may be used, or a catalyst prepared by bringing a palladium compound and a phosphine compound into contact with each other in advance may be used. May be prepared in.

  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), dichlorobis [tri (2-Methylphenyl) phosphine] palladium (II), tetrakis (methyldiphenylphosphine) palladium (0), tetrakis (tricyclohexylphosphine) palladium (0), and dichlorobis (1,1′-diphenylphosphinoferrocenyl) Palladium (II) etc. are mentioned.

  Examples of the palladium compound include tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) / chloroform adduct, palladium (II) acetate, palladium (II) chloride, (bicyclo [2 2.1] hepta-2,5-diene) dichloropalladium (II), (2,2′-bipyridyl) dichloropalladium (II), bis (acetonitrile) chloronitropalladium (II), bis (benzonitrile) dichloro Palladium (II), bis (acetonitrile) dichloropalladium (II), dichloro (1,5-cyclooctadiene) palladium (II), dichloro (ethylenediamine) palladium (II), dichloro (N, N, N ′, N ′ -Tetramethylenediamine) palladium (II), dichroic (1,10-phenanthroline) palladium (II), palladium (II) acetylacetonate, palladium (II) bromide, palladium (II) hexafluoroacetylacetonate, palladium (II) iodide, palladium (II) nitrate, Examples include palladium (II) sulfate and palladium (II) trifluoroacetate, and preferably palladium (II) acetate, palladium (II) chloride, and tris (dibenzylideneacetone) dipalladium (0). As the palladium compound, a commercially available product is usually used.

  Examples of phosphine compounds include triphenylphosphine, tris (2-methylphenyl) phosphine, tris (3-methylphenyl) phosphine, tris (4-methylphenyl) phosphine, tris (pentafluorophenyl) phosphine, and 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-diphenylphosphino Lopan, 1,4-diphenylphosphinobutane, 1,2-dicyclohexylphosphinoethane, 1,3-dicyclohexylphosphinopropane, 1,4-dicyclohexylphosphinobutane, 1,2-dimethylphosphinoethane, 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-butylphosphino) biphenyl, 2- Di-tert-butylphosphino-2 -Methylbiphenyl, 2- (dicyclohexylphosphino-2'-6'-dimethoxy, 1,1'-biphenyl, 2- (dicyclohexylphosphino) -2 '-(N, N-dimethylamino) biphenyl, 2-dicyclohexyl Phosphino-2′-methyl-biphenyl, 2- (dicyclohexylphosphino) -2 ′, 4 ′, 6′-tri-isopropyl 1,1′-biphenyl, 1,1′-bis (diphenylphosphino) ferrocene, And 1,1′-bis (di-isopropylphosphino) ferrocene, etc. As such a phosphine compound, a commercially available one may be used, or one produced according to a known method may be used. The amount of the phosphine compound used is preferably, for example, 0.5 mol to 10 mol with respect to 1 mol of the palladium compound. It is 1 mol-5 mol.

  Examples of the nickel catalyst used in this condensation reaction include dichlorobis (1,1′-diphenylphosphinoferrocenyl) nickel (II), dichlorobis (diphenylphosphino) nickel (II), dichloronickel (II), An example is iodonickel (II).

  The usage-amount of a transition metal catalyst is 0.0005 mol-0.5 mol in conversion of a metal with respect to 1 mol of compounds (3).

  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; water. A reaction solvent may be used independently and may be used in mixture of 2 or more types. 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 a reaction solvent is 0.5 mass times-200 mass times with respect to a compound (2a), for example, Preferably it is 2 mass times-100 mass times.

  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 (3).

  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 tetraalkylammonium halide, tetraalkylammonium hydrogensulfate, and tetraalkylammonium hydroxide, preferably tetra-n-butyl halide. Examples include ammonium and benzyltriethyl ammonium halide. Although the atmosphere of the reaction can be performed in the air, it is preferable to carry out the reaction under an inert gas such as nitrogen or argon because the catalyst used may be deteriorated.

  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 (4) can be obtained by performing purification means such as column chromatography, distillation, recrystallization, and recycle gel permeation chromatography.

Examples of compound (4) include compounds (4-1) to (4-452) exemplified in Table 2.

波線は結合手を意味する。

A wavy line means a bond.

The compound (4) is preferably (4-1), (4-2), (4-3), (4-5), (4-6), (4-8), (4-10). , (4-16), (4-17), (4-18), (4-24), (4-28), (4-31), (4-35), (4-37), ( 4-41), (4-42), (4-49), (4-51), (4-52), (4-56), (4-57), (4-58), (4- 68), (4-73), (4-81), (4-82), (4-83), (4-84), (4-85), (4-86), (4-87) , (4-88), (4-89), (4-90), (4-91), (4-93), (4-94), (4-95), (4-96), ( 4-98), (4-101), (4-103), (4-107), (4-108), (4-1 0), (4-112), (4-113), (4-114), (4-122), (4-127), (4-137), (4-140), (4-142) , (4-148), (4-150), (4-159), (4-160), (4-161), (4-166), (4-167), (4-177), ( 4-178), (4-181), (4-184), (4-186), (4-202), (4-203), (4-207), (4-212), (4- 213), (4-223), (4-225), (4-228), (4-230), (4-239), (4-243), (4-246), (4-248) , (4-257), (4-260), (4-269), (4-271), (4-279), (4-291), (4-298), (4-299), ( -300), (4-302), (4-308), (4-314), (4-320), (4-321), (4-325), (4-327), (4-331) ), (4-332), (4-334), (4-341), (4-344), (4-350), (4-362), (4-375), (4-376), (4-380), (4-381), (4-390), (4-393), (4-394), (4-398), (4-399), (4-404), (4 -410), (4-416), (4-434), (4-435), (4-436), (4-437), (4-439), (4-441), (4-442) ), (4-443), and (4-445).

More preferably, (4-1), (4-2), (4-5), (4-6), (4-17), (4-18), (4-35), (4-37) ), (4-81), (4-82), (4-83), (4-84), (4-85), (4-86), (4-87), (4-89), (4-90), (4-93), (4-96), (4-98), (4-103), (4-112), (4-140), (4-142), (4 -148), (4-150), (4-159), (4-167), (4-177), (4-178), (4-181), (4-184), (4-202 ), (4-203), (4-207), (4-223), (4-225), (4-230), (4-239), (4-298), (4-299), (4-300), (4-302), (4-3 8), (4-325), (4-327), (4-331), (4-332), (4-375), (4-376), (4-380), (4-381) , (4-399), (4-437), (4-439), (4-441).

The chalcogen-containing polycyclic compound represented by the general formula (5) (hereinafter sometimes referred to as the compound (5)) can be obtained by reacting the compound (4) with an acid. Specific examples of the acid include trifluoromethanesulfonic acid, methanesulfonic acid, sulfuric acid, phosphoric acid, a mixture of phosphoric acid and diphosphorus pentoxide, and hydrochloric acid. Preferred are trifluoromethanesulfonic acid, methanesulfonic acid, sulfuric acid, and hydrochloric acid. The acid to be used may be diluted with water if necessary.

The compound (4) is charged into the acid as it is or diluted in a solvent such as chloroform, and the mixture is stirred at about -20 ° C to 100 ° C for about 1 minute to 48 hours. 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, for example, the reaction mixture may be mixed with water, and the precipitated solid may be filtered off. After mixing with water, if necessary, a solvent may be added, and the organic layer may be separated and concentrated. . The compound (5) can be obtained by performing usual purification means such as column chromatography, distillation, recrystallization, and recycle gel permeation chromatography as necessary.

  Alternatively, compound (5) can be obtained by reacting compound (4) with an acid and then subjecting the resulting onium cation intermediate to a base treatment. In this case, an onium cation intermediate obtained by reacting the compound (4) with an acid, mixing with water, filtering the precipitated solid, or mixing with water and then adding a solvent to separate the organic layer. If necessary, a base such as an organic base such as pyridine and triethylamine is added in the presence of a solvent, and the mixture is stirred 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 (5) can be obtained by performing a usual purification means such as column chromatography, distillation, recrystallization, recycle gel permeation chromatography or the like as necessary.

Examples of compound (5) include compounds (5-1) to (5-452) exemplified in Table 3.

波線は結合手を意味する。

A wavy line means a bond.

The compound (5) is preferably (5-1), (5-2), (5-3), (5-5), (5-6), (5-8), (5-10) , (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), (5-177), (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), (5-298), (5-299), (5-300) , (5-302), (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), (5-398), (5-399), (5- 04), (5-410), and (5-416).
More preferably, (5-1), (5-2), (5-5), (5-6), (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), (5-177), (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), (5-302), (5-325), (5-327), (5-331), (5-332), (5-375), (5-376), (5-380), (5-381), (5 399), and the like.

  According to the production method of the present invention, an aromatic heterocyclic compound represented by the general formula (1b) (hereinafter sometimes referred to as compound (1b)) and N-halocarboxylic acid amide are present in the presence of water or alcohol. The aromatic heterocyclic compound represented by the general formula (2b) (hereinafter sometimes referred to as the compound (2b)) can be obtained.

First, the compound (1b) will be described. R ¹ in the compound (1b) represents the same meaning as described above.

Z ¹ in the compound (1b) represents the same meaning as described above. Z ¹ is preferably a sulfur atom. Z ² in the compound (1b) represents the same meaning as described above. Z ² is preferably an oxygen atom or a sulfur atom, and more preferably a sulfur atom.

Examples of compound (1b) include compounds (1-1) to (1-42) exemplified in Table 4. In this illustration, for convenience, the compound (1b) is represented by the following formula.

  Preferred compounds (1b) include (1-1), (1-3), (1-6), (1-9), (1-12), (1-13), (1-14), (1-15), (1-16), (1-17), (1-18), (1-19), (1-24), (1-25), (1-26), (1 -27), (1-28), (1-29), (1-32), (1-35), (1-36), (1-38), and (1-40).

  More preferably, the compound (1b) is (1-12), (1-13), (1-14), (1-15), (1-16), (1-17), (1-18) ), (1-19), (1-24), (1-25), (1-26), (1-27), and (1-29).

  The reagent, amount used, reaction temperature, reaction time, etc. used in the method for producing the aromatic heterocyclic compound represented by formula (2b) by reacting compound (1b) with N-halocarboxylic acid amide are the same as described above. Can be done.

  m represents an integer of 1 to 3, and n represents an integer of 1 to 3. However, m + n is an integer of 2-4. Preferably, m is 2 and n is 2.

Examples of compound (2b) include compounds (2-1) to (2-62) exemplified in Table 5. In this illustration, for convenience, the compound (2b) is represented by the following formula.

  Preferred compounds (2b) include (2-1), (2-3), (2-4), (2-9), (2-10), (2-13), (2-17), (2-21), (2-22), (2-23), (2-24), (2-25), (2-27), (2-28), (2-29), (2 -37), (2-39), (2-40), (2-42), (2-43), (2-44), (2-46), (2-47), (2-49) ), (2-52), (2-58).

  The compound (2b) is more preferably (2-17), (2-22), (2-23), (2-24), (2-25), (2-29), (2-37). ), (2-39), (2-40), (2-42), (2-43), (2-46), and (2-49).

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

室温下、３，４−ジメチルスルファニルチオフェン（２．５０ｇ、１４．２ｍｍｏｌ）のジオキサン（２６７ｍＬ）溶液にＮ−ブロモスクシンイミド（３．８５ｇ、２１．６ｍｍｏｌ）を加え、６時間撹拌した。その後、さらにＮ−ブロモスクシンイミド（０．９６ｇ、５．３９ｍｍｏｌ）を追加し、２時間攪拌した。この反応マスに水（１１５ｍＬ）およびＮ−ブロモスクシンイミド（３．８５ｇ、２１．６ｍｍｏｌ）を追加し、同温度にて２時間攪拌した。その後、さらにＮ−ブロモスクシンイミド（３．８５ｇ、２１．６ｍｍｏｌ）をさらに追加し、４時間３０分攪拌した。反応終了後、この反応混合物を飽和炭酸ナトリウム水溶液（１５０ｍＬ）に加え、酢酸エチルで有機層を抽出した。水、飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、エバポレーターにて溶媒を留去した。得られた粗生成物をシリカゲルカラム（展開溶媒：クロロホルム−酢酸エチル）にて精製することで、２，５−ジブロモ−３，４−ジメチルスルフィニルチオフェンを０．７３ｇ得た。（収率１４％）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δｐｐｍ）：３．２１（ｓ，２．４Ｈ）、３．０９（ｓ，３．６Ｈ） <Synthesis 1 of 2,5-dibromo-3,4-dimethylsulfinylthiophene>

N-bromosuccinimide (3.85 g, 21.6 mmol) was added to a dioxane (267 mL) solution of 3,4-dimethylsulfanylthiophene (2.50 g, 14.2 mmol) at room temperature, and the mixture was stirred for 6 hours. Thereafter, N-bromosuccinimide (0.96 g, 5.39 mmol) was further added and stirred for 2 hours. Water (115 mL) and N-bromosuccinimide (3.85 g, 21.6 mmol) were added to the reaction mass, and the mixture was stirred at the same temperature for 2 hours. Thereafter, N-bromosuccinimide (3.85 g, 21.6 mmol) was further added, and the mixture was stirred for 4 hours 30 minutes. After completion of the reaction, the reaction mixture was added to a saturated aqueous sodium carbonate solution (150 mL), and the organic layer was extracted with ethyl acetate. The extract was washed with water and saturated brine, dried over magnesium sulfate, and the solvent was distilled off with an evaporator. The obtained crude product was purified with a silica gel column (developing solvent: chloroform-ethyl acetate) to obtain 0.73 g of 2,5-dibromo-3,4-dimethylsulfinylthiophene. (14% yield)
¹ H-NMR (CDCl ₃ , δ ppm): 3.21 (s, 2.4H), 3.09 (s, 3.6H)

室温下、３，４−ジメチルスルファニルチオフェン（８３ｍｇ、０．４７ｍｍｏｌ）のジオキサン（１１．６ｍＬ）および水（５．０ｍＬ）溶液にＮ−ブロモスクシンイミド（３３６ｍｇ、１．８９ｍｍｏｌ）を加え、４時間４０分撹拌した。その後、さらにＮ−ブロモスクシンイミド（１６８ｍｇ、０．９５ｍｍｏｌ）を追加し、２時間攪拌した。この反応マスの一部を引き抜き、飽和炭酸ナトリウム水溶液により処理、有機層をＧＣ分析したところ、２，５−ジブロモ−３，４−ジメチルスルフィニルチオフェンの生成を確認した。 <Synthesis 2 of 2,5-dibromo-3,4-dimethylsulfinylthiophene>

N-bromosuccinimide (336 mg, 1.89 mmol) was added to a solution of 3,4-dimethylsulfanylthiophene (83 mg, 0.47 mmol) in dioxane (11.6 mL) and water (5.0 mL) at room temperature for 4 hours. Stir for minutes. Thereafter, N-bromosuccinimide (168 mg, 0.95 mmol) was further added and stirred for 2 hours. A part of the reaction mass was extracted, treated with a saturated aqueous sodium carbonate solution, and the organic layer was analyzed by GC. As a result, it was confirmed that 2,5-dibromo-3,4-dimethylsulfinylthiophene was formed.

２，５−ジブロモ−３，４−ジメチルスルフィニルチオフェン（０．０８ｇ、０．２ｍｍｏｌ）をＴＨＦ９ｍＬに溶解し、得られる溶解液に４−ｎ−ヘキシル−1−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼン（０．１７ｇ、０．６ｍｍｏｌ）、及び炭酸セシウム水溶液（２．０Ｍ、２．９ｍＬ）を加える。得られる混合液を室温にて窒素でバブリングし、ＰｄＣｌ_２（ｄｐｐｆ）（０．０９ｇ、０．０１ｍｍｏｌ）を加え、さらに、８０℃まで昇温して１６時間撹拌する。得られる反応液を室温まで冷却後、塩化アンモニウム水溶液を加え、有機層及び水層に分離する。水層はＴＨＦで抽出し、有機層と混合する。混合される有機層を水を飽和塩化ナトリウム水溶液で洗浄し、次いで硫酸マグネシウムで乾燥し、濃縮し粗生成物を得る。得られる粗生成物を、薄層クロマトグラフィーを用いて分取することによって、以下のスペクトルを有する２，５−ビス（４’−ｎ−ヘキシルフェニル）−３，４−ジメチルスルフィニルチオフェンを得る。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δｐｐｍ）：７．４５（ｄ，Ｊ＝８．１Ｈｚ，２．５Ｈ）、７．３６（ｄ，Ｊ＝８．１Ｈｚ，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） <Synthesis of 2,5-bis (4-n-hexylphenyl) -3,4-dimethylsulfinylthiophene>

2,5-Dibromo-3,4-dimethylsulfinylthiophene (0.08 g, 0.2 mmol) was dissolved in 9 mL of THF, and 4-n-hexyl-1- (4,4,5,5- Add tetramethyl-1,3,2-dioxaborolan-2-yl) benzene (0.17 g, 0.6 mmol) and aqueous cesium carbonate (2.0 M, 2.9 mL). The resulting mixture is bubbled with nitrogen at room temperature, PdCl ₂ (dppf) (0.09 g, 0.01 mmol) is added, and the mixture is further heated to 80 ° C. and stirred for 16 hours. After cooling the resulting reaction liquid to room temperature, an aqueous ammonium chloride solution is added to separate it into an organic layer and an aqueous layer. The aqueous layer is extracted with THF and mixed with the organic layer. The combined organic layer is washed with saturated aqueous sodium chloride solution, then dried over magnesium sulfate and concentrated to give the crude product. The resulting crude product is fractionated using thin layer chromatography to obtain 2,5-bis (4′-n-hexylphenyl) -3,4-dimethylsulfinylthiophene having the following spectrum.
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)

２，５−ビス（４’−ｎ−ヘキシルフェニル）−３，４−ジメチルスルフィニルチオフェン（０．３０ｇ、０．６ｍｍｏｌ）、及びＰ_２Ｏ_５（０．０３ｇ、０．２ｍｍｏｌ）をトリフルオロメタンスルホン酸１０．３ｍＬに溶解させ反応液を得る。該溶解液を５０℃まで昇温し、同温度にて３時間撹拌し、続いて室温まで冷却し、反応液を得る。反応液を水１０３ｍＬに加え、析出した固体をろ別する。析出する固体を水で洗浄後、得られる固体をピリジン９０ｍＬに溶解し、得られる溶解液を還流するまで加熱しながら１０時間撹拌する。溶解液を室温まで冷却し、溶解液に水及びクロロホルムを加える。得られる有機層及び水層を分離し、有機層を硫酸マグネシウムで乾燥してから、濃縮し、粗生成物を得る。得られた粗生成物をシリカゲルカラム及びゲルパーミネーションクロマトグラフィーを用いて精製することによって、以下のスペクトルを有するビス（５−ヘキシルベンゾ［４，５］チエノ）［３，２−ｃ：２’，３’−ｅ］チオフェンを得る。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δｐｐｍ）：７．６５（ｄ，Ｊ＝７．３Ｈｚ，２Ｈ）、７．５７（ｄ，Ｊ＝１．０Ｈｚ，２Ｈ）、７．１９（ｄｄ，Ｊ＝７．３，１．０Ｈｚ，２Ｈ）、２．７３（ｔ，Ｊ＝７．０Ｈｚ，４Ｈ）、１．７３−１．６３（ｍ，４Ｈ）、１．４０−１．２９（ｍ，１２Ｈ）、０．９０（ｔ，Ｊ＝６．８Ｈｚ，６Ｈ） 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 added to trifluoromethanesulfone. Dissolve in 10.3 mL of acid to obtain a reaction solution. The solution is heated to 50 ° C., stirred at the same temperature for 3 hours, and then cooled to room temperature to obtain a reaction solution. The reaction solution is added to 103 mL of water, and the precipitated solid is filtered off. After the precipitated solid is washed with water, the obtained solid is dissolved in 90 mL of pyridine, and the resulting solution is stirred for 10 hours while being heated to reflux. Cool the solution to room temperature and add water and chloroform to the solution. The obtained organic layer and aqueous layer are separated, and the organic layer is dried over magnesium sulfate and then concentrated to obtain a crude product. The resulting crude product is purified using a silica gel column and gel permeation chromatography to give bis (5-hexylbenzo [4,5] thieno) [3,2-c: 2 ′ having the following spectrum: , 3′-e] thiophene.
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)

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

Claims (6)

The following formula (1a)

An aromatic heterocyclic compound represented by the formula (1a) and an N-halocarboxylic acid amide in the presence of water or alcohol,
The following formula (2a)

Obtaining an aromatic heterocyclic compound (2a) represented by:
Aromatic heterocyclic compound (2a) and the following formula (3)

Is reacted with an aromatic compound (3) represented by the following formula (4):

And a step of obtaining a compound (4) represented by the following formula (5):

The manufacturing method of a chalcogen condensed polycyclic compound including the process of obtaining the chalcogen condensed polycyclic compound (5) shown by these.
(In each formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, Z ¹ independently represents a sulfur atom or a selenium atom, and 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, an alkyl group having 1 to 30 carbon atoms which may have a substituent, or an alkyl group having 1 to 30 carbon atoms which may have a substituent. An alkoxy group, an optionally substituted aryl group having 6 to 30 carbon atoms, an optionally substituted aralkyl group having 7 to 30 carbon atoms, and an optionally substituted carbon number A heteroaralkyl group having 5 to 30 carbon atoms, a heteroaryl group having 4 to 30 carbon atoms which may have a substituent, or —Si (R ² ) ₃ (R ² each independently has a substituent; Even if it has an alkyl group having 1 to 30 carbon atoms or a substituent, .X ¹ showing a have substituted silyl group represented by.) Of an aryl group having 6 to 30 carbon atoms is a halogen atom, X ² represents a leaving group.) The following formula (1b)

The aromatic heterocyclic compound (1b) represented by the formula (2b) is reacted with N-halocarboxylic acid amide in the presence of water or alcohol.

The manufacturing method of the aromatic heterocyclic compound (2b) 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, and Z ² represents an oxygen atom, a sulfur atom or a selenium atom. X ¹ independently represents a halogen atom, m represents an integer of 1 to 3, n represents an integer of 1 to 3, provided that m + n is an integer of 2 to 4). The manufacturing method according to claim 2, wherein m is 2 and n is 2. 4. The aromatic heterocyclic compound represented by the general formula (1b) is the aromatic heterocyclic compound (1a) represented by the following formula (1a), and the compound (2b) represented by the general formula (2b) is It is an aromatic heterocyclic compound (2a) represented by Formula (2a), The manufacturing method of Claim 2 characterized by the above-mentioned.

(In each formula, R ¹ , Z ¹ , Z ² , and X ¹ represent the same meaning as described above.) The process according to any one of claims 2 to 4 Z ¹ and Z ² are each a sulfur atom. The production method according to claim 2, wherein the N-halocarboxylic acid amide is N-halosuccinimide.