CN109111463B - Method for producing aromatic compound - Google Patents

Abstract

The present invention relates to a method for producing an aromatic compound, and an object thereof is to provide: a practical process for producing a highly pure BTBT derivative (or DNTT derivative) from easily handled (neither decomposed nor denatured by oxidation in air nor corrosive) starting materials in a simple manner (reaction in one step at 200 ℃ or lower, no generation of corrosive gases). The present inventors have found that a BTBT derivative (or DNTT derivative) can be obtained by a practical method of reacting a specific o-halobenzyl halide derivative (or 3-halo-2- (halomethyl) naphthalene derivative) with elemental sulfur or a sulfur compound, thereby completing the present invention.

Description

Method for producing aromatic compound

Technical Field

The present invention relates to a method for producing an aromatic compound. More specifically, the present invention relates to a method for producing a thiophene ring-condensed aromatic compound. In addition, the present application claims priority to japanese patent application No. 2017-124196, which is applied for 26.6.2017.

Background

An organic thin film transistor (organic TFT) using an organic material for a semiconductor layer does not require a high-temperature heat treatment process in its manufacture, and can be mounted on a resin plastic substrate having poor heat resistance, and thus, research into a flexible display device and a wearable device, which are next-generation electronic devices using these substrates, is expected. Among such organic materials, compounds having a [1] benzothieno [3,2-b ] [1] benzothiophene ring (for example, patent document 1), compounds having a dinaphtho [2, 3-b: a compound having a 2 ', 3' -f ] thieno [3,2-b ] thiophene ring (for example, patent document 2), which has semiconductor characteristics (mobility), since amorphous silicon (hereinafter, the [1] benzothieno [3,2-b ] [1] benzothiophene ring is sometimes referred to as a BTBT (or BTBT ring), the dinaphtho [2, 3-b: 2 ', 3' -f ] thieno [3,2-b ] thiophene ring is sometimes referred to as a DNTT (or DNTT ring), and a compound having a BTBT ring (or DNTT ring) (that is, a compound having a substituent on the BTBT ring (or DNTT ring)) is sometimes referred to as a BTBT derivative (or DNTT derivative)), a method for producing these BTBT derivatives (or DNTT derivatives) in practical (industrial) applications (a method of synthesizing them at low cost and simply and highly pure) has been desired in advance of practical applications of organic TFTs).

In general, BTBT derivatives (or DNTT derivatives) are obtained by: as the former step, "a BTBT ring (or DNTT ring) is constructed (BTBT ring (or DNTT ring) formation reaction is carried out)", and then as the latter step, "a desired substituent is introduced into the BTBT ring (or DNTT ring)" to obtain (when constructing (forming) the BTBT ring (or DNTT ring), the ring may be constructed (formed) so as to have a substituent in advance). The latter step is a commonly known "substituent introduction reaction to an aromatic compound", and on the contrary, the former step has a special feature of forming an aromatic ring. Therefore, in order to produce a BTBT derivative (or DNTT derivative) practically, a practical (low-cost and simple industrial) construction (formation) method of a BTBT ring (or DNTT ring) as a parent skeleton is required.

Patent documents 3 and 4 and non-patent documents 1 and 2 describe the following methods: the BTBT ring (or DNTT ring) is obtained by the reaction of an o-chlorobenzaldehyde derivative with a sulfur compound. However, the o-chlorobenzaldehyde derivative is corrosive and requires special manufacturing equipment. Further, the benzaldehyde derivative is easily oxidized in the air to be decomposed into carboxylic acid, and has a problem in storage stability. Non-patent document 2 describes that a polymer is produced as a by-product by a reaction between an o-chlorobenzaldehyde derivative and a metal hydrosulfide or the like. There is a fear that the polymer by-product having poor solubility has problems in industrial production such as adhesion to a reaction vessel and clogging of piping. In addition, the polymer by-product is likely to remain as an impurity, and there is also a problem that the organic semiconductor must be highly purified. In comparative examples described later, a reproducibility experiment (synthesis) was carried out, and it was confirmed that the purity of the target product was actually low.

Patent document 5 describes the following method: the BTBT ring (or DNTT ring) is obtained by the reaction of a benzaldehyde derivative with a halogenating agent and a sulfur compound. However, the halogenating agent such as thionyl chloride is decomposed in the air to generate hydrogen chloride gas, sulfurous acid gas, and the like, which are highly toxic, and therefore, the operation is difficult. Moreover, since the reaction proceeds at a high temperature, toxic gases such as hydrogen chloride gas and sulfurous acid gas are generated by decomposition of the halogenating agent, which is industrially disadvantageous.

Patent documents 6 and 7 and non-patent documents 3 and 4 describe the following methods: the BTBT ring is obtained by the reaction of benzyl chloride, alpha-dichlorotoluene or alpha, alpha-trichlorotoluene and elemental sulfur. However, heating at a high temperature of 200 ℃ or higher for 10 hours or more is required, which increases the production cost and is industrially disadvantageous. Further, according to patent documents 6 and 7, hydrogen chloride gas and sulfur chloride gas are generated in the reaction. These gases are corrosive and irritant, and therefore, are industrially disadvantageous. In the comparative examples described later, as a result of conducting a reproducibility experiment, when α, α -dichlorotoluene was used, BTBT was not produced at 230 ℃ for 3 hours, and a trace amount of BTBT was produced at 260 ℃ for 3 hours (actually, it was confirmed that a high temperature of 200 ℃ or higher was required for the reaction). In addition, the generation of acid gas was also confirmed by the above-mentioned reproducibility experiment.

Patent documents 8 and 9 and non-patent documents 5 to 7 describe the following methods: a3- (phenylthio) benzo [ b ] thiophene derivative is subjected to intramolecular condensation using a transition metal catalyst to obtain a BTBT ring. However, since an expensive transition metal catalyst is used, the production cost becomes high. Further, the reaction is complicated through multiple steps in order to synthesize the 3- (phenylthio) benzo [ b ] thiophene derivative as a raw material, and therefore, is industrially disadvantageous.

Patent document 10 describes the following method: the 2- [2- (methylthio) phenyl ] benzo [ b ] thiophene derivative is subjected to intramolecular condensation using a strong acid as a solvent to obtain a BTBT ring. However, since a large amount of strong acid is used, it is necessary to treat the acid waste liquid. Further, the reaction is complicated by a plurality of steps in order to synthesize the 2- [2- (methylthio) phenyl ] benzo [ b ] thiophene derivative as a raw material, and therefore, the reaction is industrially disadvantageous.

Patent document 11 and non-patent document 8 describe the following methods: butyl lithium is allowed to act on a 3-bromo-2- (2-bromophenyl) benzo [ b ] thiophene derivative, and then bis (phenylsulfonyl) sulfide is allowed to act thereon to perform intramolecular condensation, thereby obtaining a BTBT ring. However, butyl lithium reacts with moisture in the air to cause ignition, and therefore, handling is difficult. Further, the reaction is complicated by a plurality of steps for synthesizing a 3-bromo-2- (2-bromophenyl) benzo [ b ] thiophene derivative as a raw material, and therefore, the reaction is industrially disadvantageous.

Patent document 12 and non-patent documents 9 and 10 describe the following methods: the sulfur compound is allowed to act on the iodonium salt derivative to give a BTBT ring. However, the reaction is complicated through multiple steps in order to synthesize the iodonium salt derivative as a raw material, and therefore, is industrially disadvantageous.

The following methods are described in patent documents 13, 14, 15, 17, and 18 and non-patent documents 11, 15, 18, 19, and 21: cyclization of the stilbene derivative gives a BTBT ring. However, the reaction is complicated through multiple steps in order to synthesize the stilbene derivative as a raw material, and thus, is industrially disadvantageous.

Non-patent documents 12 to 14 describe the following methods: the sulfur compound is allowed to act on the bis (2-bromophenyl) acetylene derivative to cause intramolecular condensation thereof, thereby obtaining a BTBT ring. However, in order to synthesize a bis (2-bromophenyl) acetylene derivative as a raw material, the reaction is complicated through multiple steps, and therefore, is industrially disadvantageous.

Patent document 16 describes the following method: elemental iodine is allowed to act on a bis [2- (methylthio) phenyl ] acetylene derivative to cause intramolecular condensation thereof, thereby obtaining a BTBT ring. However, in order to synthesize a bis [2- (methylthio) phenyl ] acetylene derivative as a raw material, the reaction is complicated through multiple steps, and therefore, is industrially disadvantageous.

Non-patent document 17 describes the following method: the phosphorus ylide derivative is thermally decomposed at 850 ℃ to obtain the BTBT derivative. However, since a high temperature such as 850 ℃ is required, it cannot be said that this method is a practical method for producing a BTBT derivative. Further, the synthesis of the phosphorus ylide derivative as a raw material is industrially disadvantageous because the reaction is complicated through multiple steps.

Non-patent document 20 describes the following method: a base is allowed to act on the dithiocarbamate derivative, thereby obtaining a BTBT ring. However, in order to synthesize the dithiocarbamate derivative as a raw material, the reaction is complicated through multiple steps, and thus, is industrially disadvantageous.

Non-patent document 22 describes the following method: phosphorus pentasulfide was allowed to act on diphenylethanedione, thereby obtaining a BTBT ring. However, the yield was as low as 3.9%, which was not a practical method for producing BTBT rings.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2012/121393

Patent document 2: international publication No. 2012/115236

Patent document 3: japanese patent laid-open publication No. 2010-275192

Patent document 4: japanese laid-open patent publication No. 2015-030727

Patent document 5: japanese patent laid-open No. 2008-290963

Patent document 6: U.S. Pat. No. 3278552

Patent document 7: U.S. Pat. No. 3433874

Patent document 8: international publication No. 2014/030700

Patent document 9: japanese laid-open patent publication No. 2016 (Japanese patent application laid-open Specification) -

Patent document 10: japanese patent laid-open publication No. 2011-256144

Patent document 11: japanese patent laid-open publication No. 2011-184309

Patent document 12: chinese laid-open publication No. 105820098

Patent document 13: international publication No. 2015/028768

Patent document 14: japanese laid-open patent publication No. 2009-062302

Patent document 15: japanese laid-open patent publication No. 2010-202523

Patent document 16: japanese laid-open patent publication No. 2009-196975

Patent document 17: japanese laid-open patent publication No. 2009-073780

Patent document 18: international publication No. 2009/113599

Non-patent document

Non-patent document 1: journal of Materials Chemistry C, 2016, Vol.4, p.6742

Non-patent document 2: tetrahedron Letters, 2011, volume 52, page 285

Non-patent document 3: collection of Czechloroslavak Chemical Communications, 2002, volume 67, page 645

Non-patent document 4: journal of the American Chemical Society, 2012, volume 134, page 16548

Non-patent document 5: tetrahedron Letters, 2014, volume 55, page 4175

Non-patent document 6: journal of the American Chemical Society, 2013, volume 135, page 13900

Non-patent document 7: angewandte Chemie International Edition 2015, volume 54, page 5772

Non-patent document 8: tetrahedron, 2016, volume 72, page 8085

Non-patent document 9: chemical Communications, 2017, volume 53, page 2918

Non-patent document 10: organic Letters, 2016, volume 18, page 5756

Non-patent document 11: zhurnal organic heskoi Khimii, 1980, Vol.16, page 425

Non-patent document 12: european Journal of Organic Chemistry 2011, page 7331

Non-patent document 13: journal of Heterocyclic Chemistry 1998, volume 35, page 725

Non-patent document 14: journal of Materials Chemistry C, 2016, volume 4, page 5981

Non-patent document 15: tetrahedron Letters, 2010, Vol 51, page 5277

Non-patent document 16: collection of Czechosvak Chemical Communications, 2009, volume 74, page 785

Non-patent document 17: synlett, 1995, page 53

Non-patent document 18: zhurnal organic heskoi Khimii, 1980, Vol.16, page 430

Non-patent document 19: journal of Organic Chemistry, 1993, volume 58, page 5209

Non-patent document 20: angewandte Chemie, International Edition 2010, volume 49, page 4751

Non-patent document 21: journal of Organic Chemistry, 2013, volume 78, page 7741

Non-patent document 22: phosphorus, Sulfur and Silicon 2002, volume 177, page 2725

Disclosure of Invention

Problems to be solved by the invention

In view of the background described above, an object of the present invention is to provide: a practical method for constructing a BTBT ring (or DNTT ring) (which has a small number of reaction steps, does not generate corrosive gas, and has a low reaction temperature) and a method for producing a BTBT derivative (or DNTT derivative) are provided which are capable of easily providing a target substance with high purity by using a raw material which is easy to handle (which is not decomposed or deteriorated by oxidation or the like in the air, and which is not corrosive).

Means for solving the problems

The present inventors have conducted intensive studies and found that: the present inventors have completed the present invention by constructing a BTBT ring (or DNTT ring) by reacting a compound represented by the general formula (2) with elemental sulfur or a sulfur compound to obtain a BTBT derivative (or DNTT derivative) represented by the general formula (1).

(in the formulae, m represents 0 or 1, R¹Represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a cyano group, a nitro group, a carbonyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, or an aryl group (R)¹Optionally the same or different, respectively. ) And X and Y represent a halogen atom (X and Y are optionally the same as or different from each other). ). )

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a highly pure BTBT derivative (or DNTT derivative) can be produced easily (without generation of a corrosive gas by a reaction in one step at 200 ℃ or lower) using a raw material which is easy to handle (which is not decomposed or deteriorated by oxidation or the like in the air, and which is not corrosive). Therefore, a practical method for producing a BTBT derivative (or DNTT derivative) at low cost can be provided.

Detailed Description

The production method of the present invention will be explained below. The manufacturing scheme of the present invention is as follows.

(wherein, R¹M, X and Y are as defined above, n represents 6 when m is 1, and n represents 4 when m is 0. )

(with respect to R)¹)

In the general formula (2) of the present invention, R¹A hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group, an amino group, a cyano group, a nitro group, a carbonyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, or an aryl group, and a plurality of R' s¹May be the same or different from each other.

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a n-hexyl group, a 1-methylpentyl group, a 4-methyl-2-pentyl group, a 3, 3-dimethylbutyl group, a 2-ethylbutyl group, a n-heptyl group, a 1-methylhexyl group, a cyclohexylmethyl group, a n-octyl group, a tert-octyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a 2-propylpentyl group, a n-nonyl group, a 2, 2-dimethylheptyl group, a 2, 6-dimethyl-4-heptyl group, a 3,5, 5-trimethylhexyl group, a n-decyl group, a n-undecyl group, a 1-methyldecyl group, a n-dodecyl group, a n-tridecyl group, a 1-hexylheptyl group, a n-tetradecyl group, a n-pentadecyl group, a n-hexadecyl group, A straight-chain, branched or alicyclic alkyl group such as an n-heptadecyl group, an n-octadecyl group or an n-eicosyl group, and these alkyl groups may be substituted with a halogen atom (for example, a trifluoromethyl group).

Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a n-pentyloxy group, an isopentyloxy group, a neopentyloxy group, a n-hexyloxy group, a 1-methylpentyloxy group, a 4-methyl-2-pentyloxy group, a 3, 3-dimethylbutyloxy group, a 2-ethylbutoxy group, a n-heptyloxy group, a 1-methylhexyloxy group, a cyclohexylmethoxy group, a n-octyloxy group, a tert-octyloxy group, a 1-methylheptyloxy group, a 2-ethylhexyloxy group, a 2-propylpentyloxy group, a n-nonyloxy group, a 2, 2-dimethylheptyloxy group, a 2, 6-dimethyl-4-heptyloxy group, a 3,5, 5-trimethylhexyloxy group, a n-decyloxy group, a 1-methyldecyloxy group, a n-dodecyloxy group, a n-butyloxy group, a, Straight-chain, branched-chain and alicyclic alkoxy groups such as n-tridecyloxy group, 1-hexylheptyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group and n-eicosyloxy group.

Examples of the alkylthio group having 1 to 20 carbon atoms include a methylthio group, an ethylthio group, a n-propylthio group, an isopropylthio group, a n-butylthio group, an isobutylthio group, a n-pentylthio group, an isopentylthio group, a neopentylthio group, a n-hexylthio group, a 1-methylpentylthio group, a 4-methyl-2-pentylthio group, a 3, 3-dimethylbutylthio group, a 2-ethylbutylthio group, a n-heptylthio group, a 1-methylhexylthio group, a cyclohexylmethylthio group, a n-octylthio group, a t-octylthio group, a 1-methylheptylthio group, a 2-ethylhexylthio group, a 2-propylpentylthio group, a n-nonylthio group, a 2, 2-dimethylheptylthio group, a 2, 6-dimethyl-4-heptylthio group, a 3,5, 5-trimethylhexylthio group, a n-decylthio group, a n-undecylthio group, a 1-methyldecylthio group, a n-dodecylthio group, Straight-chain, branched-chain, and alicyclic alkylthio groups such as n-tridecylthio, 1-hexylheptylthio, n-tetradecylthio, n-pentadecylthio, n-hexadecylthio, n-heptadecylthio, n-octadecylthio, and n-eicosylthio.

The aryl group means an aromatic hydrocarbon group or a heteroaromatic group, and these groups may have an alkyl group or a halogen substituent as a substituent.

Examples of the aryl group include an aromatic hydrocarbon group having an unsubstituted or alkyl group as a substituent, such as a phenyl group, a naphthyl group, an azulenyl group, an acenaphthyl group, an anthracenyl group, a phenanthryl group, a tetracenyl group, a pyrenyl group, a chrysenyl group, a perylenyl group, a biphenyl group, a p-terphenyl group, a quaterphenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2, 4-xylyl group, a 2, 6-xylyl group, a mesityl group, a 2,3,5, 6-tetramethylphenyl group, a 4-ethylphenyl group, a 4-n-propylphenyl group, a 4-isopropylphenyl group, a 4-n-butylphenyl group, a 4-n-pentylphenyl group, a 4-n-hexylphenyl group, a 4-decylphenyl group, a 4-stearylphenyl group, and a 9, 9-dihexylfluorenyl group;

an aromatic hydrocarbon group having a halogen such as a fluorine atom, a chlorine atom or a bromine atom as a substituent, such as a 4-fluorophenyl group, a 2, 6-difluorophenyl group, a 4-chlorophenyl group or a 2,3,4,5, 6-perfluorophenyl group;

heteroaromatic groups such as pyridyl, pyrrolyl, thienyl, benzothienyl, benzoxazolyl, benzothiazolyl, oxadiazolyl, dibenzooxazolyl, and dibenzothienyl;

a heteroaromatic group having an alkyl group as a substituent, such as 2-methylthiophenyl, 2-butylthienyl, or 2-hexylthienyl; and the like.

(regarding X and Y)

In the general formula (2), X and Y may be the same or different from each other, and each represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and preferably each represents a fluorine atom, a chlorine atom or a bromine atom.

(specific Compound represented by the general formula (2))

Specific examples of such a compound represented by the general formula (2) include: o-chlorobenzyl chloride, o-bromobenzyl chloride, o-iodochlorobenzyl chloride, 2, 3-dichlorochlorobenzyl chloride, 2, 4-dichlorochlorobenzyl chloride, 2, 5-dichlorochlorobenzyl chloride, 2, 6-dichlorochlorobenzyl chloride, 2-chloro-3-fluorobenzyl chloride, 2-chloro-4-fluorobenzyl chloride, 2-chloro-5-fluorobenzyl chloride, 2-chloro-6-fluorobenzyl chloride, 2-chloro-3-bromobenzyl chloride, 2-chloro-4-bromobenzyl chloride, 2-chloro-5-bromobenzyl chloride, 2-chloro-6-bromobenzyl chloride, 2-chloro-3-iodochlorobenzyl chloride, 2-chloro-4-iodochlorobenzyl chloride, 2-chloro-5-iodochlorobenzyl chloride, 2-chloro-6-iodochlorobenzyl chloride, 2, 3-dibromochlorobenzyl chloride, 2-chloro-3-iodochlorobenzyl chloride, 2-chloro-4-iodochlorobenzyl chloride, 2-chloro-5-iodochlorobenzyl chloride, 2, 3-dibromochlorobenzyl chloride, 2-halochlorobenzyl derivatives (chloro-2-halobenzyl derivatives) such as 2, 4-dibromochlorobenzyl, 2, 5-dibromochlorobenzyl, 2, 6-dibromochlorobenzyl, 2-bromo-3-fluorobenzyl, 2-bromo-4-fluorobenzyl, 2-bromo-5-fluorobenzyl, 2-bromo-6-fluorobenzyl, 2-bromo-3-chlorobenzyl, 2-bromo-4-chlorobenzyl chloride, 2-bromo-5-chlorobenzyl chloride, 2-bromo-6-chlorobenzyl chloride, 2-bromo-3-iodochlorobenzyl, 2-bromo-4-iodochlorobenzyl chloride, 2-bromo-5-iodochlorobenzyl chloride, and 2-bromo-6-iodochlorobenzyl chloride;

o-chlorobenzyl bromide, o-bromobenzyl bromide, o-iodobromobenzyl, 2, 3-dichlorobromobenzyl, 2, 4-dichlorobromobenzyl, 2, 5-dichlorobromobenzyl, 2, 6-dichlorobromobenzyl, 2-chloro-3-fluorobenzyl bromide, 2-chloro-4-fluorobenzyl bromide, 2-chloro-5-fluorobenzyl bromide, 2-chloro-6-fluorobenzyl bromide, 2-chloro-3-bromobenzyl bromide, 2-chloro-4-bromobenzyl bromide, 2-chloro-5-bromobenzyl bromide, 2-chloro-6-bromobenzyl bromide, 2-chloro-3-iodobromobenzyl bromide, 2-chloro-4-iodobromobenzyl bromide, 2-chloro-5-iodobromobenzyl bromide, 2-chloro-6-iodobromobenzyl bromide, 2, 3-dibromobromobenzyl bromide, 2-chloro-4-iodobromobenzyl bromide, 2-chloro-5-iodobromobenzyl bromide, 2-chloro-6-iodobromobenzyl bromide, 2-halobromobenzyl derivatives (bromo-2-halobenzyl derivatives) such as 2, 4-dibromobromobenzyl, 2, 5-dibromobromobenzyl, 2, 6-dibromobromobenzyl, 2-bromo-3-fluorobromobenzyl, 2-bromo-4-fluorobromobenzyl, 2-bromo-5-fluorobromobenzyl, 2-bromo-6-fluorobromobenzyl, 2-bromo-3-chlorobromobenzyl, 2-bromo-4-chlorobromobenzyl, 2-bromo-5-chlorobromobenzyl, 2-bromo-6-chlorobromobenzyl, 2-bromo-3-iodobromobenzyl, 2-bromo-4-iodobromobenzyl, 2-bromo-5-iodobromobenzyl, and 2-bromo-6-iodobromobenzyl;

o-chloroiodobenzyl, o-bromoiodobenzyl, o-iodobenzyl, 2, 3-dichloroiodobenzyl, 2, 4-dichloroiodobenzyl, 2, 5-dichloroiodobenzyl, 2, 6-dichloroiodobenzyl, 2-chloro-3-fluoroiodobenzyl, 2-chloro-4-fluoroiodobenzyl, 2-chloro-5-fluoroiodobenzyl, 2-chloro-6-fluoroiodobenzyl, 2-chloro-3-bromoiodobenzyl, 2-chloro-4-bromoiodobenzyl, 2-chloro-5-bromoiodobenzyl, 2-chloro-6-bromoiodobenzyl, 2-chloro-3-iodobenzyl, 2-chloro-4-iodobenzyl, 2-chloro-5-iodobenzyl, 2-chloro-6-iodobenzyl, 2, 3-dibromoiodobenzyl, 2-chloro-3-iodobenzyl, 2-haloiodobenzyl derivatives (iodo 2-halobenzyl derivatives) such as 2, 4-dibromoiodobenzyl, 2, 5-dibromoiodobenzyl, 2, 6-dibromoiodobenzyl, 2-bromo-3-fluoroiodobenzyl, 2-bromo-4-fluoroiodobenzyl, 2-bromo-5-fluoroiodobenzyl, 2-bromo-6-fluoroiodobenzyl, 2-bromo-3-chloroiodobenzyl, 2-bromo-4-chloroiodobenzyl, 2-bromo-5-chloroiodobenzyl, 2-bromo-6-chloroiodobenzyl, 2-bromo-3-iodobenzyl, 2-bromo-4-iodoiodobenzyl, 2-bromo-5-iodobenzyl, and 2-bromo-6-iodobenzyl;

"halo-2-halobenzyl" derivatives having an alkyl group optionally substituted with a halogen atom, such as 2-chloro-4-methylchlorobenzyl, 2-chloro-4-ethylchlorobenzyl, 2-chloro-4-propylchlorobenzyl, 2-chloro-5-methylchlorobenzyl, 2-chloro-5-ethylchlorobenzyl, 2-chloro-5-propylchlorobenzyl, 2-chloro-5-butylchlorobenzyl, 2-chloro-3-trifluoromethylchlorobenzyl, and 2-chloro-5-trifluoromethylchlorobenzyl;

"halogenated 2-halobenzyl" derivatives having an aryl group such as 2-chloro-5- (3-pyridyl) chlorobenzyl and 2-chloro-5- (4-pyridyl) chlorobenzyl;

"halogenated 2-halobenzyl" derivatives having a hydroxyl group or an alkoxy group, such as 2-chloro-5-hydroxychlorobenzyl, 2-chloro-5-methoxychlorobenzyl, 2-chloro-5-ethoxychlorobenzyl, and 2-chloro-5-butoxychlorobenzyl;

2-chloro-5-cyanobenzyl chloride, 2-chloro-4-dimethylaminochlorobenzyl, 2-chloro-5-nitrochlorobenzyl, 2-chloro-5-methylthiochlorobenzyl, etc.;

3-halo-2- (halomethyl) naphthalene derivatives such as 3-chloro-2- (chloromethyl) naphthalene; and the like, but are not limited thereto.

(elemental sulfur and sulfur compounds)

The production method of the present invention is characterized by reacting a compound represented by the above general formula (2) with elemental sulfur or a sulfur compound. The elemental sulfur includes an allotrope of sulfur represented by the chemical composition S (linear or cyclic S)_q(q is an integer of 2 or more)) or a mixture of allotropes. Examples of the sulfur compound include hydrogen sulfide, sulfide salts, hydrosulfide salts, oxygen-containing anion salts of sulfur, and dithio compounds.

Examples of the sulfide salt or hydrosulfide salt include:

hydrosulfides such as aqueous or anhydrous sodium hydrosulfide, aqueous or anhydrous potassium hydrosulfide, or aqueous or anhydrous calcium hydrosulfide;

sulfides such as aqueous or anhydrous sodium sulfide, aqueous or anhydrous potassium sulfide, or aqueous or anhydrous calcium sulfide;

polysulfides such as aqueous or anhydrous sodium polysulfide, aqueous or anhydrous potassium polysulfide, or aqueous or anhydrous calcium polysulfide; and the like.

Examples of the salt of sulfur with an oxyanion include:

bisulfates such as sodium bisulfate, potassium bisulfate, calcium bisulfate, magnesium bisulfate, and ammonium bisulfate;

sulfates such as sodium sulfate, potassium sulfate, calcium sulfate, magnesium sulfate, and ammonium sulfate;

bisulfites such as sodium bisulfite, potassium bisulfite, calcium bisulfite, magnesium bisulfite, and ammonium bisulfite;

sulfites such as sodium sulfite, potassium sulfite, calcium sulfite, magnesium sulfite, and ammonium sulfite;

thiosulfate such as sodium thiosulfate, potassium thiosulfate, calcium thiosulfate, magnesium thiosulfate, ammonium thiosulfate, and the like;

sodium dithionite such as sodium dithionite;

persulfates such as sodium peroxodisulfate, potassium peroxodisulfate, and ammonium peroxodisulfate; and so on.

The salt of the sulfur oxyanion may be an anhydride or a hydrate.

Examples of the dithio compound include:

sodium dimethyldithiocarbamate, potassium dimethyldithiocarbamate, calcium dimethyldithiocarbamate, titanium dimethyldithiocarbamate, zinc dimethyldithiocarbamate, tin dimethyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldithiocarbamate, silver dimethyldithiocarbamate, nickel dimethyldithiocarbamate, sodium diethyldithiocarbamate, potassium diethyldithiocarbamate, calcium diethyldithiocarbamate, titanium diethyldithiocarbamate, zinc diethyldithiocarbamate, tin diethyldithiocarbamate, copper diethyldithiocarbamate, iron diethyldithiocarbamate, silver diethyldithiocarbamate, nickel diethyldithiocarbamate, sodium diisopropyldithiocarbamate, potassium dimethyldithiocarbamate, copper dimethyldithiocarbamate, nickel diethyldithiocarbamate, zinc diethyldithiocarbamate, copper diethyldithiocarbamate, iron diethyldithiocarbamate, silver diethyldithiocarbamate, nickel diethyldithiocarbamate, potassium diisopropyldithiocarbamate, zinc dimethyldithiocarbamate, copper dimethyldithiocarbamate, zinc dimethyldithiocarbamate, copper diethyldithiocarbamate, iron diethyldithiocarbamate, silver diethyldithiocarbamate, nickel diethyldithiocarbamate, zinc dimethyldithiocarbamate, calcium dithiocarbamate, zinc dimethyldithiocarbamate, zinc dimethyldithiocarbamate, calcium dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc dimethyldithiocarbamate, Calcium diisopropyldithiocarbamate, titanium diisopropyldithiocarbamate, zinc diisopropyldithiocarbamate, tin diisopropyldithiocarbamate, copper diisopropyldithiocarbamate, iron diisopropyldithiocarbamate, silver diisopropyldithiocarbamate, nickel diisopropyldithiocarbamate, sodium dibutyldithiocarbamate, potassium dibutyldithiocarbamate, calcium dibutyldithiocarbamate, titanium dibutyldithiocarbamate, zinc dibutyldithiocarbamate, tin dibutyldithiocarbamate, copper dibutyldithiocarbamate, iron dibutyldithiocarbamate, silver dibutyldithiocarbamate, nickel dibutyldithiocarbamate, sodium dibenzyldithiocarbamate, potassium dibenzyldithiocarbamate, calcium dibenzyldithiocarbamate, zinc dibutyldithiocarbamate, iron dibutyldithiocarbamate, dibutyltin dithiocarbamate, silver dibutyldithiocarbamate, nickel dibutyldithiocarbamate, sodium dibenzyldithiocarbamate, potassium dibenzyldithiocarbamate, calcium dibenzyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dithiocarbamate, zinc dibutyldithiocarbamate, zinc dithiocarbamate, zinc dibutyl dithiocarbamate, zinc dithiocarbamate, zinc, Metal salts of dithiocarbamic acid such as titanium dibenzyldithiocarbamate, zinc dibenzyldithiocarbamate, tin dibenzyldithiocarbamate, copper dibenzyldithiocarbamate, iron dibenzyldithiocarbamate, silver dibenzyldithiocarbamate, and nickel dibenzyldithiocarbamate;

dimethyl ammonium dithiocarbamate, tetramethyl ammonium dimethyl dithiocarbamate, tetraethyl ammonium dimethyl dithiocarbamate, tetrabutyl ammonium dimethyl dithiocarbamate, diethyl ammonium dithiocarbamate, tetramethyl ammonium diethyl dithiocarbamate, tetraethyl ammonium diethyl dithiocarbamate, tetrabutyl ammonium diethyl dithiocarbamate, diisopropyl ammonium dithiocarbamate, tetramethyl ammonium diisopropyl dithiocarbamate, tetraethyl ammonium diisopropyl dithiocarbamate, tetrabutyl ammonium diisopropyl dithiocarbamate, dibutyl ammonium dithiocarbamate, tetramethyl ammonium dibutyl dithiocarbamate, tetraethyl ammonium dibutyl dithiocarbamate, tetrabutyl ammonium dibutyl dithiocarbamate, dibenzyl ammonium dithiocarbamate, tetramethyl ammonium dibenzyl dithiocarbamate, tetrabutyl ammonium dibutyl dithiocarbamate, tetrabutyl ammonium dibenzyl dithiocarbamate, tetrabutyl ammonium dimethyl dithiocarbamate, tetrabutyl ammonium diisopropyl ammonium dithiocarbamate, or dimethyl dithiocarbamate, Organic salts of dithiocarbamic acids such as tetraethylammonium dibenzyldithiocarbamate, tetraisopropylammonium dibenzyldithiocarbamate and tetrabutylammonium dibenzyldithiocarbamate;

metal salts of xanthic acid such as sodium ethyl xanthate, potassium ethyl xanthate, sodium propyl xanthate, potassium propyl xanthate, sodium isopropyl xanthate, potassium isopropyl xanthate, sodium butyl xanthate, potassium butyl xanthate, sodium pentyl xanthate, potassium pentyl xanthate, sodium hexyl xanthate, and potassium hexyl xanthate;

xanthates disulfide such as diethyl xanthate disulfide, diisopropyl xanthate disulfide, dipropyl xanthate disulfide, dibutyl xanthate disulfide, diamyl xanthate disulfide, and dihexyl xanthate disulfide;

tetraalkylthiurams such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetraisopropylthiuram disulfide, and tetrabutylthiuram disulfide; and so on.

In the present invention, when the compound represented by the general formula (2) is reacted with the above-mentioned dithiocarbamate, a dithiocarbamate can be produced in the reaction system as the first stage, and the compound represented by the general formula (2) can be added to the same reaction system as the second stage to react. For example, when sodium N, N-diethyldithiocarbamate is used, sodium N, N-diethyldithiocarbamate can be formed by reacting diethylamine with carbon disulfide in the presence of sodium hydroxide as the first stage, and the compound represented by the general formula (2) can be added to the same reaction system as the second stage to react.

Similarly, in the present invention, when the compound represented by the general formula (2) is reacted with the above xanthic acid, the xanthic acid may be generated in the reaction system as the first stage, and the compound represented by the general formula (2) may be added to the same reaction system and reacted as the 2 nd stage. For example, when sodium ethylxanthate is used, sodium ethoxide and carbon disulfide may be reacted to form sodium ethylxanthate as a first stage, and the compound represented by the general formula (2) may be added to the same reaction system and reacted as a second stage.

Among the above sulfur compounds, from the viewpoint of improving reactivity,

preferably hydrosulfides such as aqueous or anhydrous sodium hydrosulfide, aqueous or anhydrous potassium hydrosulfide, or aqueous or anhydrous calcium hydrosulfide;

sulfides such as aqueous or anhydrous sodium sulfide, aqueous or anhydrous potassium sulfide, or aqueous or anhydrous calcium sulfide;

polysulfides such as aqueous or anhydrous sodium polysulfide, aqueous or anhydrous potassium polysulfide, or aqueous or anhydrous calcium polysulfide;

oxygen-containing anion salts of sulfur such as sodium thiosulfate and ammonium thiosulfate; further, in order to improve reactivity and obtain a high yield, it is particularly preferable

Hydrosulfides such as aqueous or anhydrous sodium hydrosulfide, aqueous or anhydrous potassium hydrosulfide, or aqueous or anhydrous calcium hydrosulfide;

and oxygen-containing anion salts of sulfur such as sodium thiosulfate and ammonium thiosulfate.

(specific Compound represented by the general formula (1))

Specific examples of the compound represented by the general formula (1) include, but are not limited to, the following compounds.

(Synthesis conditions of the present invention)

The amount of the elemental sulfur or sulfur compound used is usually 1 to 30 moles, preferably 1 to 15 moles, and more preferably 1.2 to 6 moles, based on the compound of the general formula (2).

These elemental sulfur and sulfur compounds may be used alone or in combination, and the amount of the sulfur compound to be used in the combination is preferably within the above-mentioned range relative to the total mole number of the compound of the general formula (2).

The reaction temperature is not particularly limited as long as the reaction is carried out at a temperature within the range of room temperature to 300 ℃, preferably 80 to 250 ℃. Below 80 ℃ the reaction is slow and therefore impractical, and above 250 ℃ the product sometimes decomposes.

The reaction solvent may be omitted, and is preferably used from the viewpoint of stirring efficiency and reaction uniformity. As the reaction solvent, known and commonly used reaction solvents can be used, and if they are exemplified, the following are mentioned:

hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, nonane, decane, dodecane, octadecane, cyclohexane, methylcyclohexane, and tetrahydronaphthalene;

halogen-based solvents such as dichloromethane, chloroform, dibromomethane, dichloroethane, dibromoethane, 1, 2-trichloroethane, dichloropropane and dibromopropane;

aromatic solvents such as toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, n-butylbenzene, n-pentylbenzene, n-hexylbenzene, decahydronaphthalene, chlorobenzene, o-dichlorobenzene, 1,2, 4-trichlorobenzene, bromobenzene, bromonaphthalene, and the like;

ketone solvents such as acetone, 2-butanone, methyl isobutyl ketone, and cyclohexanone;

ether solvents such as diethyl ether, tetrahydrofuran, diisopropyl ether, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and diphenyl ether;

ester-based solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, and propylene glycol methyl ether acetate;

amide solvents such as N-methyl-2-pyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide;

urea solvents such as 1, 3-dimethyl-2-imidazolidinedione and N, N' -dimethylpropyleneurea;

sulfoxide solvents such as dimethyl sulfoxide and sulfolane; and the like.

Among the above solvents, solvents having a boiling point of 80 ℃ or higher are preferable, and polar solvents such as ether solvents, amide solvents, sulfoxide solvents, etc., hydrocarbon solvents, and aromatic solvents are particularly preferable from the viewpoint of reaction yield.

(other additives)

In the production method of the present invention, an additive may be added to efficiently progress the reaction. If this is the case, then:

bicarbonates such as sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate;

carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate;

phosphates such as sodium salts of phosphoric acid, disodium hydrogen phosphate, trisodium phosphate, potassium phosphate, calcium phosphate, diammonium hydrogen phosphate;

hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide,

Fluorides such as potassium fluoride, cesium fluoride and tetrabutylammonium fluoride;

alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide;

tertiary amines such as trimethylamine, triethylamine, tributylamine, diisopropylethylamine, N-methylmorpholine, N-methylpyrrolidine, N-methylpiperidine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, and 1, 4-diazabicyclo [2.2.2] octane;

pyridine derivatives such as pyridine, picoline, ethylpyridine, propylpyridine, butylpyridine, t-butylpyridine, 2, 3-lutidine, 2, 4-lutidine, 2, 5-lutidine, 2, 6-lutidine, 3, 5-lutidine, 2-methyl-5-ethyl-pyridine, 2, 6-diisopropylpyridine, and 2, 6-di-t-butylpyridine; and the like.

Among the above additives, bicarbonate, carbonate, and hydroxide salts are preferable from the viewpoint of improving the reaction yield.

Examples

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.

(confirmation of purity)

The purity of the target was evaluated from the peak area ratio on the chromatogram by measuring with a high performance liquid chromatograph (hereinafter, may be abbreviated as HPLC. the apparatus is constituted by a system controller SCL-10ADVP, a liquid feeding unit LC-10ADvp, a column box CTO-10ASVP, an autosampler SIL-10ADVP, and a detector SPD-M10 AVP). As the column, a Kinetex5 μm column (stationary phase: C18, particle system: 5 μm, length: 100mm, inner diameter: 4.6mm) manufactured by Phenomenex corporation was used, and the flow rate: 1.0 ml/min, eluent: acetonitrile/water/tetrahydrofuran 50/50/0 → 50/0/50 (linear gradient: 10 min), measurement time: 20 minutes, detection wavelength: 340nm, column temperature: sample introduction at 40 ℃: the measurement was performed under the condition of 1 uL. The tetrahydrofuran (stabilizer-free) solution (0.1 wt%) of the dried sample was subjected to filtration (pore size: 0.22um) to prepare an assay solution.

(measurement of Hydrogen ion index)

The hydrogen ion index (pH) was determined by using a pH test paper 2600-100A manufactured by Whatman.

(example 1)

A20 mL two-necked flask was charged with 1.3g (8.1mmol) of o-chlorobenzyl chloride, 0.97g (12mmol) of 70% sodium hydrosulfide and 4mL of dimethyl sulfoxide, and the mixture was stirred at 180 ℃ for 2 hours. The reaction mixture was cooled to room temperature, 2mL of methanol was added, and the precipitated solid was filtered. The obtained solid was washed with water and acetone to obtain 0.32g (yield: 33%) of BTBT as pale yellow crystals. The HPLC purity (340nm) was 99.77%.

¹H-NMR(400MHz，CDCl₃)：7.85-7.95ppm(m，4H)、7.39-7.50ppm(m，4H)。

(example 2)

The same procedures as in example 1 were repeated except for using 1.1g (7.6mmol) of o-fluorobenzyl chloride instead of the o-chlorobenzyl chloride in example 1 to obtain 0.22g (yield: 24%) of BTBT as pale yellow crystals. The HPLC purity (340nm) was 99.20%.

(example 3)

The same procedures as in example 1 were repeated except for using 1.6g (7.8mmol) of o-chlorobenzyl bromide instead of the o-chlorobenzyl chloride in example 1 to obtain 0.16g (yield: 17%) of BTBT as pale yellow crystals. HPLC purity (340nm) was 99.00%.

(example 4)

The same operation as in example 1 was carried out except that N, N-dimethylformamide was used instead of dimethyl sulfoxide in example 1, to obtain 0.16g (yield: 17%) of BTBT as pale yellow crystals.

(example 5)

The same operation as in example 1 was carried out except that N, N-dimethylacetamide was used instead of dimethylsulfoxide in example 1, to obtain 0.15g (yield: 16%) of BTBT as pale yellow crystals.

(example 6)

The same procedures as in example 1 were carried out except for using N-methyl-2-pyrrolidone instead of dimethyl sulfoxide in example 1 to obtain 0.25g (yield 26%) of BTBT as pale yellow crystals.

(example 7)

The same procedures as in example 1 were carried out except for using 1, 3-dimethyl-2-imidazolidinone instead of dimethyl sulfoxide in example 1 to obtain 0.15g (yield 16%) of BTBT as pale yellow crystals.

(example 8)

The same procedures as in example 1 were repeated except for using 1.4g (12mmol) of 48% sodium hydrosulfide instead of 0.97g (12mmol) of 70% sodium hydrosulfide in example 1 to obtain 0.30g (yield 31%) of BTBT as pale yellow crystals.

(example 9)

The same procedures as in example 1 were carried out except for using 0.15g (1.9mmol) of 70% sodium hydrosulfide and 0.32g (10mmol) of elemental sulfur in place of 0.97g (12mmol) of 70% sodium hydrosulfide in example 1, to obtain 0.17g (yield: 18%) of BTBT as pale yellow crystals.

(example 10)

The same procedures as in example 1 were repeated except for using 3.0g (12mmol) of sodium thiosulfate pentahydrate instead of 0.97g (12mmol) of 70% sodium hydrosulfide in example 1 to obtain 0.27g (yield 28%) of BTBT as pale yellow crystals.

Comparative example 1

According to the method described in patent document 3, 1.0g (7.1mmol) of o-chlorobenzaldehyde, 1.1g (14mmol) of 70% sodium hydrosulfide and 20mL of N-methyl-2-pyrrolidone are placed in a 100mL two-neck flask, and stirred at 180 ℃ for 3 hours. The reaction mixture was cooled to room temperature, and then added to 100mL of a saturated aqueous ammonium chloride solution, and the precipitated solid was filtered. The obtained solid was washed with water and acetone to obtain 0.31g of BTBT as pale yellow crystals (yield 36%). The HPLC purity (340nm) was 97.27%.

Comparative example 2

According to the method described in patent document 4, 1.4g (10mmol) of o-chlorobenzaldehyde, 4.9g (22mmol) of sodium N, N-diethyldithiocarbamate trihydrate, and 21mL of N-methyl-2-pyrrolidone are charged into a 100mL two-neck flask, and the temperature is raised to 180 ℃ over 4 hours while stirring. Further, the mixture was stirred at the same temperature for 15 hours. The reaction mixture was cooled to room temperature, 50mL of a saturated aqueous ammonium chloride solution was added, and the precipitated solid was filtered. The obtained solid was washed with water and acetone to obtain 0.52g of BTBT as pale yellow crystals (yield 43%). The HPLC purity (340nm) was 95.84%.

Comparative example 3

According to the method described in example 7 of patent document 6, 1.25g (7.8mmol) of α, α -dichlorotoluene and 0.27g (8.3mmol) of sulfur were charged into a 10mL two-necked flask, and the mixture was stirred at 230 ℃ for 3 hours. The reaction solution was cooled to room temperature, and the obtained black solid was analyzed by HPLC, and as a result, BTBT production was not confirmed.

Gas is generated in the reaction, and water absorbing the gas shows strong acidity (pH 1).

Comparative example 4

According to the method described in example 7 of patent document 6, 1.25g (7.8mmol) of α, α -dichlorotoluene and 0.27g (8.3mmol) of sulfur were charged into a 10mL two-necked flask, and the mixture was stirred at 260 ℃ for 3 hours. The reaction solution was cooled to room temperature, and the obtained black solid was purified by silica gel column chromatography (developing solvent: chloroform) to obtain 0.018g of BTBT as pale yellow crystals (yield 1.0%).

Gas is generated in the reaction, and water absorbing the gas shows strong acidity (pH 1).

As described in examples, it is understood that the target product obtained by the production method of the present invention has a high purity of 99% or more. On the other hand, the target product obtained by the production methods of the prior art shown in comparative examples 1 and 2 was less than 99%, which was inferior in purity.

In addition, o-chlorobenzyl chloride, o-chlorobenzyl bromide and o-fluorobenzyl chloride used in the examples as the raw material corresponding to the general formula (2) were not deteriorated by leaving in the atmosphere. On the other hand, it was confirmed that o-chlorobenzaldehyde used in comparative examples 1 and 2 was changed from a liquid to a solid by leaving it in the atmosphere.

According to the conventional production methods of comparative examples 3 and 4, high temperatures of 200 ℃ or higher were required for obtaining BTBT, and acid gas was generated during the reaction. On the other hand, in examples 1 to 10, which are the production methods of the present invention, BTBT was obtained at 200 ℃ or lower, and no gas was generated during the reaction.

As described above, according to the present invention, it is possible to form a BTBT ring (or a DNTT ring) by an industrially advantageous and simple method (a method having characteristics such as one step, a low-temperature reaction, and no generation of acidic and corrosive gases) using a raw material which is easy to handle (which is not deteriorated or decomposed by oxidation or the like in the air, and which is not corrosive). By using the thus obtained compound having a BTBT ring (or DNTT ring) as a starting material and further introducing a substituent, a desired BTBT derivative (or DNTT derivative) can be produced.

Industrial applicability

The thiophene ring-condensed aromatic compound (BTBT derivative or DNTT derivative) obtained by the production method of the present invention can be used, for example, as a material for an organic semiconductor or a raw material for a material for an organic semiconductor.

Claims (1)

1. A method for producing a compound represented by the general formula (1),

reacting a compound represented by the general formula (2) with a hydrosulfide salt or a thiosulfate salt,

in the formulae, m represents 0 or 1, R¹Represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a cyano group, a nitro group, a carbonyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, or an aryl group, R¹Optionally the same or different, X and Y represent a halogen atom, and X and Y are optionally the same or different from each other.