JP6276705B2 - Method for producing halogen compound - Google Patents

Description

  The present invention relates to a method for producing a halogen compound.

  The organic thin-film solar cell that is one aspect of the photoelectric conversion element can omit the high-temperature and high-vacuum process required in the production process of the silicon-based solar cell, and can be inexpensively manufactured only by the coating process. It has attracted attention in recent years.

As a polymer compound used for an organic thin film solar cell, a polymer compound containing a repeating unit represented by the following formula (a) is known (Patent Document 1, Patent Document 2).

The polymer compound containing the repeating unit represented by the formula (a) can be obtained by polymerizing a compound represented by the following formula (b).

  Patent Document 1 discloses a method for producing a compound represented by formula (b) using difluorobenzene as a starting material. Patent Document 2 discloses a method for producing a compound represented by the formula (b) using difluorodiaminobenzene as a starting material.

International Patent Publication WO2011 / 060526A1 International Patent Publication WO2011 / 136311A1

  However, in the manufacturing method described in Patent Document 1, the yield is very low. In the production method described in Patent Document 2, it is necessary to react at a high temperature for a long time in the halogenation step.

  The objective of this invention is providing the manufacturing method of a halogen compound with a high yield by reaction for a short time at comparatively low temperature conditions.

The present invention is as follows.

〔式（Ａ）中、Ｙ^１は硫黄原子、酸素原子、セレン原子、−Ｎ（Ｒ^１）−
又は−Ｃ（Ｒ^２）＝Ｃ（Ｒ^３）−を表す。Ｒ^１、Ｒ^２、およびＲ^３は、同一又は相異なり、水素原子、ハロゲン原子、又は１価の有機基を表す。Ｘ^１およびＸ^２は、同一又は相異なり、窒素原子又は＝ＣＨ−を表す。Ｚ^１およびＺ^２はそれぞれ独立に水素原子、１価の有機基、ハロゲン原子、シアノ基、又はニトロ基を表す。ただし、Ｚ^１およびＺ^２のうちの少なくとも１つはハロゲン原子、フルオロアルキル基、フルオロアリール基 シアノ基、およびニトロ基からなる群から選ばれる基である。〕

〔式（Ｂ）中、Ｑ^１、Ｑ^２およびＱ^３は、同一又は相異なり、水素原子またはハロゲン原子のを表す。ただし、Ｑ^１、Ｑ^２およびＱ^３のうちの少なくとも１つはハロゲン原子を表す。Ｗ^１、Ｗ^２およびＷ^３は、同一又は相異なり、酸素原子または硫黄原子を表す。〕

〔式（Ｃ）中、Ｙ^１、Ｘ^１、Ｘ^２、Ｚ^１およびＺ^２は、前述と同じ意味を表す。Ｕ^１およびＵ^２は、同一又は相異なり、ハロゲン原子を表す。〕[1] A method for producing a halogen compound represented by the following formula (C), wherein a compound represented by the following formula (A) and a compound represented by the following formula (B) are reacted in a solvent.

[In Formula (A), Y ¹ is a sulfur atom, an oxygen atom, a selenium atom, —N (R ¹ ) —
Or -C (R < ² >) = C (R < ³ >)-is represented. R ¹ , R ² , and R ³ are the same or different and each represents a hydrogen atom, a halogen atom, or a monovalent organic group. X ¹ and X ² are the same or different and each represents a nitrogen atom or ═CH—. Z ¹ and Z ² each independently represent a hydrogen atom, a monovalent organic group, a halogen atom, a cyano group, or a nitro group. However, at least one of Z ¹ and Z ² is a group selected from the group consisting of a halogen atom, a fluoroalkyl group, a fluoroaryl group, a cyano group, and a nitro group. ]

[In Formula (B), Q ¹ , Q ² and Q ³ are the same or different and represent a hydrogen atom or a halogen atom. However, at least one of Q ¹ , Q ² and Q ³ represents a halogen atom. W ¹ , W ² and W ³ are the same or different and represent an oxygen atom or a sulfur atom. ]

[In Formula (C), Y ¹ , X ¹ , X ² , Z ¹ and Z ² represent the same meaning as described above. U ¹ and U ² are the same or different and represent a halogen atom. ]

[2] The production method according to [1], wherein the reaction is performed in the presence of an acid.
[3] The production method of the above-mentioned [1] or [2], wherein the solvent is an acid.
[4] The production method of the above-mentioned [2] or [3], wherein the acid is sulfuric acid or fuming sulfuric acid.

  Hereinafter, the present invention will be described in detail.

In formula (A), Y ¹ represents a sulfur atom, an oxygen atom, a selenium atom, —N (R ¹ ) — or —C (R ² ) ═C (R ³ ) —.
R ¹ , R ² , and R ³ are the same or different and each represents a hydrogen atom, a halogen atom, or a monovalent organic group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the monovalent organic group include an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, and a substituted alkyl group. Aryloxy group which may be substituted, arylthio group which may be substituted, arylalkyl group which may be substituted, arylalkoxy group which may be substituted, arylalkylthio group which may be substituted, acyl group, acyloxy group Amide group, imide group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, heterocyclic group, heterocyclic oxy group, heterocyclic thio group, arylalkenyl group, arylalkynyl group or carboxyl Represents a group.
Here, the alkyl group which may be substituted may be linear, branched or cyclic. Carbon number of an alkyl group is 1-30 normally. A halogen atom is mentioned as a substituent. Of the halogen atoms, preferred are a fluorine atom and a chlorine atom, and more preferred is a fluorine atom. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl. Group, hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, nonyl group And chain alkyl groups such as decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group and eicosyl group; and cycloalkyl groups such as cyclopentyl group, cyclohexyl group and adamantyl group.

An example of a substituted alkyl group is a fluoroalkyl group.
Examples of fluoroalkyl groups include partially fluorinated alkyls such as 2,2,2-trifluoroethyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, etc. Groups: perfluoroalkyl groups such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluorobutyl group.

  The alkyl part of the alkoxy group may be linear, branched or cyclic. The alkoxy group may be substituted. Carbon number of an alkoxy group is 1-20 normally. Examples of the substituent include a halogen atom and an alkoxy group. A halogen atom is preferably a fluorine atom. Carbon number of an alkoxy group is 1-20 normally. Specific examples of the optionally substituted alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, Heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy, trifluoromethoxy, pentafluoroethoxy, perfluorobutoxy, perfluoro Examples include a hexyloxy group, a perfluorooctyloxy group, a methoxymethyloxy group, and a 2-methoxyethyloxy group.

  The alkyl part of the alkylthio group may be linear, branched or cyclic. The alkylthio group may be substituted. Carbon number of an alkylthio group is 1-20 normally. A halogen atom is mentioned as a substituent. A halogen atom is preferably a fluorine atom. Specific examples of the alkylthio group which may be substituted include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, tert-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group. Group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group and trifluoromethylthio group.

  An aryl group means the group remove | excluding one hydrogen atom on an aromatic ring from an aromatic hydrocarbon, and the carbon number is 6-60 normally. The aryl group may be substituted. Examples of the substituent include a halogen atom and an alkoxy group. A halogen atom is preferably a fluorine atom. Carbon number of an alkoxy group is 1-20 normally. Specific examples of the optionally substituted aryl group include a phenyl group; a C1-C12 alkylphenyl group; a 1-naphthyl group, a 2-naphthyl group; an alkoxyaryl group such as a C1-C12 alkoxyphenyl group; and pentafluorophenyl. And a fluoroaryl group such as a group (preferably a perfluoroaryl group). Among the C1-C12 alkoxyphenyl groups, a C1-C8 alkoxyphenyl group is preferable, and a C1-C6 alkoxyphenyl group is more preferable. Specific examples of C1-C12 alkoxy, C1-C8 alkoxy and C1-C6 alkoxy include C1-C12 alkoxy, C1-C8 and C1-C6 among the alkoxys exemplified for the above alkoxy group.

  The aryloxy group usually has 6 to 60 carbon atoms, and the aryl moiety may be substituted. Examples of the substituent include a halogen atom and an alkoxy group. A halogen atom is preferably a fluorine atom. Carbon number of an alkoxy group is 1-20 normally. Specific examples of the optionally substituted aryloxy group include a phenoxy group, a C1-C12 alkoxyphenoxy group, a C1-C12 alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a pentafluorophenoxy group. It is done.

  The arylthio group usually has 6 to 60 carbon atoms, and the aryl moiety may be substituted. Examples of the substituent include a halogen atom and an alkoxy group. A halogen atom is preferably a fluorine atom. Carbon number of an alkoxy group is 1-20 normally. Specific examples of the arylthio group include a phenylthio group, a C1-C12 alkoxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.

The arylalkyl group usually has 7 to 60 carbon atoms, and the aryl moiety may be substituted. Examples of the substituent include a halogen atom and an alkoxy group. A halogen atom is preferably a fluorine atom. Carbon number of an alkoxy group is 1-20 normally.
Specific examples of the optionally substituted arylalkyl group include phenyl-C1-C12 alkyl group, C1-C12 alkoxyphenyl-C1-C12 alkyl group, C1-C12 alkylphenyl-C1-C12 alkyl group, 1-naphthyl. -C1-C12 alkyl group and 2-naphthyl-C1-C12 alkyl group are mentioned.

  The arylalkoxy group usually has 7 to 60 carbon atoms, and the aryl moiety may be substituted. Examples of the substituent include a halogen atom and an alkoxy group. A halogen atom is preferably a fluorine atom. Carbon number of an alkoxy group is 1-20 normally. Specific examples of the optionally substituted arylalkoxy group include a phenyl-C1 to C12 alkoxy group, a C1 to C12 alkoxyphenyl-C1 to C12 alkoxy group, a C1 to C12 alkylphenyl-C1 to C12 alkoxy group, and 1-naphthyl. -C1-C12 alkoxy group and 2-naphthyl-C1-C12 alkoxy group are mentioned.

  The arylalkylthio group usually has 7 to 60 carbon atoms, and the aryl moiety may be substituted. Examples of the substituent include a halogen atom and an alkoxy group. A halogen atom is preferably a fluorine atom. Carbon number of an alkoxy group is 1-20 normally. Specific examples of the optionally substituted arylalkylthio group include phenyl-C1-C12 alkylthio group, C1-C12 alkoxyphenyl-C1-C12 alkylthio group, C1-C12 alkylphenyl-C1-C12 alkylthio group, 1- A naphthyl-C1-C12 alkylthio group and a 2-naphthyl-C1-C12 alkylthio group are mentioned.

  An acyl group means the group remove | excluding the hydroxyl group from the carboxyl group (-COOH) of carboxylic acid, The carbon number is 2-20 normally. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a trifluoroacetyl group, an alkylcarbonyl group which may be substituted with a halogen having 2 to 20 carbon atoms; a benzoyl group, Examples thereof include a phenylcarbonyl group which may be substituted with a halogen such as a pentafluorobenzoyl group.

  An acyloxy group means the group remove | excluding the hydrogen atom from the carboxyl group (-COOH) of carboxylic acid, The carbon number is 2-20 normally. Specific examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

  An amide group means a group obtained by removing one hydrogen atom bonded to a nitrogen atom from an amide, and the carbon number is usually 2 to 20. Specific examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, and a dibenzamide group. , Ditrifluoroacetamide group and dipentafluorobenzamide group.

  An imide group means the group remove | excluding one hydrogen atom couple | bonded with the nitrogen atom from imide, The carbon number is 3-10 normally. Specific examples of the imide group include a succinimide group and a phthalimide group.

The substituted amino group means a group in which one or two hydrogen atoms of the amino group are substituted. The substituent is, for example, an alkyl group and an optionally substituted aryl group. Specific examples of the alkyl group and the optionally substituted aryl group are the same as the specific examples of the alkyl group represented by R ¹ and the optionally substituted aryl group. Carbon number of a substituted amino group is 1-40 normally. Specific examples of the substituted amino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, tert -Butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, Cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C1-C12 alcohol Siphenylamino group, di (C1-C12 alkoxyphenyl) amino group, di (C1-C12 alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyrida Dinylamino group, pyrimidylamino group, pyrazylamino group, triazylamino group, phenyl-C1-C12 alkylamino group, C1-C12 alkoxyphenyl-C1-C12 alkylamino group, C1-C12 alkylphenyl-C1-C12 alkylamino group , Di (C1-C12 alkoxyphenyl-C1-C12 alkyl) amino group, di (C1-C12 alkylphenyl-C1-C12 alkyl) amino group, 1-naphthyl-C1-C12 alkylamino group and 2-naphthyl-C1- C12 alkylamino Group, and the like.

The substituted silyl group means a group in which one, two or three hydrogen atoms of the silyl group are substituted, generally a group in which all three hydrogen atoms of the silyl group are substituted. The substituent is, for example, an alkyl group and an optionally substituted aryl group. Specific examples of the alkyl group and the optionally substituted aryl group are the same as the specific examples of the alkyl group represented by R ¹ and the optionally substituted aryl group. Carbon number of a substituted silyl group is 1-60 normally, Preferably it is 1-20. Specific examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilyl group, tribenzylsilyl group, Examples include a diphenylmethylsilyl group, a tert-butyldiphenylsilyl group, and a dimethylphenylsilyl group.

  A substituted silyloxy group is a group in which an oxygen atom is bonded to a substituted silyl group. The definition and specific examples of the substituted silyl group are as described above. Carbon number of a substituted silyloxy group is 1-60 normally, Preferably it is 1-20. Specific examples of the substituted silyloxy group include trimethylsilyloxy group, triethylsilyloxy group, tripropylsilyloxy group, triisopropylsilyloxy group, tert-butyldimethylsilyloxy group, triphenylsilyloxy group, tri-p-xylyl group. Examples thereof include a silyloxy group, a tribenzylsilyloxy group, a diphenylmethylsilyloxy group, a tert-butyldiphenylsilyloxy group, and a dimethylphenylsilyloxy group.

  The substituted silylthio group is a group in which a sulfur atom is bonded to a substituted silyl group. The definition and specific examples of the substituted silyl group are as described above. Carbon number of a substituted silylthio group is 1-60 normally, Preferably it is 1-20. Specific examples of the substituted silylthio group include trimethylsilylthio group, triethylsilylthio group, tripropylsilylthio group, triisopropylsilylthio group, tert-butyldimethylsilylthio group, triphenylsilylthio group, and tri-p-xylyl. Examples thereof include a silylthio group, a tribenzylsilylthio group, a diphenylmethylsilylthio group, a tert-butyldiphenylsilylthio group, and a dimethylphenylsilylthio group.

  The substituted silylamino group is a group in which one or two hydrogen atoms of the amino group are substituted with a substituted silyl group. The definition and specific examples of the substituted silyl group are as described above. Carbon number of a substituted silylamino group is 1-120 normally, Preferably it is 1-20. Specific examples of the substituted silylamino group include trimethylsilylamino group, triethylsilylamino group, tripropylsilylamino group, triisopropylsilylamino group, tert-butyldimethylsilylamino group, triphenylsilylamino group, tri-p-xylyl. Silylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, tert-butyldiphenylsilylamino group, dimethylphenylsilylamino group, bis (trimethylsilyl) amino group, bis (triethylsilyl) amino group, bis (tripropylsilyl) ) Amino group, bis (triisopropylsilyl) amino group, bis (tert-butyldimethylsilyl) amino group, bis (triphenylsilyl) amino group, bis (tri-p-xylylsilyl) amino group, bis (tribe Jirushiriru) amino group, bis (diphenylmethylsilyl) amino group, bis (tert- butyldiphenylsilyl) amino group and bis (dimethylphenylsilyl) and amino group.

The heterocyclic group means a group obtained by removing one hydrogen atom from a heterocyclic compound, and the carbon number is usually 1-30. Heterocyclic groups may be substituted.
Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, and an aryl group. The definitions and specific examples of the halogen atom, the alkyl group, the alkoxy group, and the aryl group are as described above. A halogen atom is preferably a fluorine atom. Carbon number of an alkyl group and an alkoxy group is 1-20 normally. The carbon number of the aryl group is usually 6-60.
As the heterocyclic compound, an optionally substituted furan, an optionally substituted thiophene, an optionally substituted pyrrole, an optionally substituted pyrroline, an optionally substituted pyrrolidine, a substituted May be an oxazole, an optionally substituted isoxazole, an optionally substituted thiazole, an optionally substituted isothiazole, an optionally substituted imidazole, an optionally substituted imidazoline, a substituted May be an imidazolidine, an optionally substituted pyrazole, an optionally substituted pyrazoline, an optionally substituted prazolidine, an optionally substituted furazane, an optionally substituted triazole, an optionally substituted Good thiadiazole, optionally substituted oxadiazole, substituted Tetrazole, optionally substituted pyran, optionally substituted pyridine, optionally substituted piperidine, optionally substituted thiopyran, optionally substituted pyridazine, optionally substituted Pyrimidine, optionally substituted pyrazine, optionally substituted piperazine, optionally substituted morpholine, optionally substituted triazine, optionally substituted benzofuran, optionally substituted isobenzofuran , Optionally substituted benzothiophene, optionally substituted indole, optionally substituted isoindole, optionally substituted indolizine, optionally substituted indoline, optionally substituted Isoindoline, optionally substituted chromene, optionally substituted Mann, optionally substituted isochroman, optionally substituted benzopyran, optionally substituted quinoline, optionally substituted isoquinoline, optionally substituted quinolidine, optionally substituted benzimidazole , Optionally substituted benzothiazole, optionally substituted indazole, optionally substituted naphthyridine, optionally substituted quinoxaline, optionally substituted quinazoline, optionally substituted quinazolidine, Optionally substituted cinnolines, optionally substituted phthalazines, optionally substituted purines, optionally substituted pteridines, optionally substituted carbazoles, optionally substituted xanthenes, substituted Optionally substituted phenanthridine, optionally substituted phenanthridine Klysine, optionally substituted β-carboline, optionally substituted perimidine, optionally substituted phenanthroline, optionally substituted thianthrene, optionally substituted phenoxathiin, substituted Phenoxazine, which may be substituted, phenothiazine which may be substituted, phenazine which may be substituted, and the like. As the heterocyclic group, an aromatic heterocyclic group is preferable.

〔式（Ｄ）及び式（Ｅ）中、Ａｒ^７は複素環基を表す。〕
複素環基の定義、具体例は前記のとおりである。Examples of the heterocyclic oxy group include a group represented by the formula (D) in which an oxygen atom is bonded to the heterocyclic group. Examples of the heterocyclic thio group include a group represented by the formula (E) in which a sulfur atom is bonded to the heterocyclic group.

[In formula (D) and formula (E), Ar ⁷ represents a heterocyclic group. ]
The definition and specific examples of the heterocyclic group are as described above.

  The heterocyclic oxy group usually has 4 to 60 carbon atoms. Specific examples of the heterocyclic oxy group include thienyloxy group, C1-C12 alkylthienyloxy group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C1-C12 alkylpyridyloxy group, imidazolyloxy group, pyrazolyloxy group, triazolyl group. And a ruoxy group, an oxazolyloxy group, a thiazoleoxy group, and a thiadiazoleoxy group.

  The heterocyclic thio group usually has 4 to 60 carbon atoms. Specific examples of the heterocyclic thio group include thienyl mercapto group, C1-C12 alkyl thienyl mercapto group, pyrrolyl mercapto group, furyl mercapto group, pyridyl mercapto group, C1-C12 alkyl pyridyl mercapto group, imidazolyl mercapto group, pyrazolyl mercapto group. , Triazolyl mercapto group, oxazolyl mercapto group, thiazole mercapto group and thiadiazole mercapto group.

  The arylalkenyl group usually has 8 to 20 carbon atoms. Specific examples of the arylalkenyl group include a styryl group.

  The arylalkynyl group usually has 8 to 20 carbon atoms. Specific examples of the arylalkynyl group include a phenylacetylenyl group.

Y ¹ is preferably a sulfur atom, an oxygen atom, —N (R ¹ ) — or —C (R ² ) ═C (R ³ ) —, more preferably a sulfur atom or an oxygen atom, still more preferably It is a sulfur atom.

In formula (A), X ¹ and X ² are the same or different and represent a nitrogen atom or ═CH—. X ¹ and X ² are preferably nitrogen atoms.

In formula (A), Z ¹ and Z ² each independently represent a hydrogen atom, a monovalent organic group, a halogen atom, a cyano group, or a nitro group. However, at least one of Z ¹ and Z ² is a group selected from a halogen atom, a fluoroalkyl group, a fluoroaryl group, a cyano group, or a nitro group.
Z ¹ and Z ² each independently represent a monovalent organic group, a halogen atom, a cyano group, or a nitro group, and at least one of Z ¹ and Z ² is a fluorine atom, a fluoroalkyl group, a cyano group, or a nitro group A group selected from groups is preferred.

Examples of the monovalent organic group include the same monovalent organic groups as those described above. Z ¹ and Z ² are preferably an optionally substituted alkyl group (preferably a fluoroalkyl group, more preferably a perfluoroalkyl group), an optionally substituted alkoxy group, and an optionally substituted aryl group ( Preferably a fluoroaryl group, more preferably a perfluoroaryl group), an optionally substituted aryloxy group, an optionally substituted arylalkoxy group, a halogen atom, a cyano group, or a nitro group, more preferably A halogen atom, a cyano group, or a nitro group, more preferably a halogen atom. Of the halogen atoms, a fluorine atom is more preferred.

Examples of the compound represented by the formula (A) include compounds represented by the following formulas (1) to (240).

  As the compound represented by the formula (A), among the above (1) to (240), (1), (2), (6), (24), (41), (42), (64 ), (65), (121), (122), (201), (202), (224), (225), more preferably (1), (2), (6), (24). , (41), (42), (64), (121), (122), (201), (202), (224), (225), more preferably (1), (41), (121) and (201), more preferably (1) and (41).

  In the method for producing a halogen compound of the present invention, the compound represented by the formula (A) to be reacted in a solvent may be used alone or in combination of two or more.

In formula (B), Q ¹ , Q ² and Q ³ are the same or different and represent either a hydrogen atom or a halogen atom. However, at least one of Q ¹ , Q ² and Q ³ represents a halogen atom. The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a bromine atom.

W ¹ , W ² and W ³ are the same or different and each represents an oxygen atom or a sulfur atom. W ¹ , W ² and W ³ are preferably oxygen atoms.

U ¹ and U ² are the same or different and represent a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a bromine atom.

Examples of the compound represented by the formula (B) include compounds represented by the following formulas (501) to (540).

  The compound represented by the formula (B) is preferably (501), (502), (503), (506), (507), (508) among the above (501) to (540). More preferred are (501), (502), (506) and (507), and particularly preferred is (502).

  In the method for producing a halogen compound of the present invention, the compound represented by the formula (B) to be reacted in a solvent may be used alone or in combination of two or more.

The compound represented by the formula (A) and the compound represented by the formula (B) are reacted in a solvent. The reaction is preferably performed in the presence of an acid from the viewpoint of yield improvement. That is, it is preferable to react the compound represented by Formula (A) with the compound represented by Formula (B) in an acidic solvent. Examples of the method for performing the reaction in the presence of an acid include a method using an acid as a solvent and a method of adding an acid.
The acid may be an inorganic acid or an organic acid. Examples of the inorganic acid include sulfuric acid, fuming sulfuric acid, nitric acid, hydrochloric acid and the like. The concentration of sulfuric acid is usually 1% to 100% by weight, preferably 50% to 100% by weight, and more preferably 90% to 100% by weight. The concentration of nitric acid is usually 1% to 100% by weight, preferably 50% to 100% by weight, and more preferably 90% to 100% by weight. The fuming sulfuric acid means one obtained by dissolving sulfur trioxide in 100% by weight sulfuric acid. The concentration of sulfur trioxide is preferably 1% to 60%, more preferably 5% to 30% with respect to the weight of 100% by weight sulfuric acid. Examples of the organic acid include aromatic carboxylic acid, aliphatic carboxylic acid, aromatic sulfonic acid, and aliphatic sulfonic acid. Aromatic carboxylic acids include benzoic acid, salicylic acid, phthalic acid and the like. Examples of the aliphatic carboxylic acid include acetic acid, monofluoroacetic acid, difluoroacetic acid, and trifluoroacetic acid. Examples of the aromatic sulfonic acid include benzene sulfonic acid and toluene sulfonic acid. Examples of the aliphatic sulfonic acid include methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid. These acids may be used alone or in combination of two or more.

  The acid is preferably sulfuric acid, fuming sulfuric acid or aromatic sulfonic acid, more preferably 90 to 100% by weight sulfuric acid or fuming sulfuric acid.

  Preferred examples of the solvent other than the acid include aliphatic solvents and halogen solvents. Examples of the aliphatic solvent include hexane, heptane, cyclohexane, and the like. Examples of the halogen solvent include chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane and the like.

  The temperature at the time of reacting the compound represented by the formula (A) and the compound represented by the formula (B) is usually -50 ° C to 80 ° C, preferably -20 ° C to 50 ° C.

  The time for reacting the compound represented by the formula (A) and the compound represented by the formula (B) is usually 1 minute to 10 hours, preferably 30 minutes to 8 hours, more preferably 1 hour. ~ 5 hours.

  When the compound represented by the formula (A) and the compound represented by the formula (B) are reacted, the ratio of the substance amount of the compound represented by the formula (A) and the compound represented by the formula (B) is usually [Compound represented by formula (A)] / [compound represented by formula (B)], which is 1 / 0.5 to 1/20 (mol / mol), preferably 1 / 0.0. It is 8 to 1/10 (mol / mol).

  After the reaction, the compound represented by the formula (C) can be obtained by performing usual post-treatment such as, for example, putting the reactant into ice water and then extracting with an organic solvent and distilling off the solvent. The product can be isolated and purified by methods such as chromatographic fractionation and recrystallization.

  The compound represented by the formula (C) obtained by the production method of the present invention is preferably used as a raw material for producing an organic semiconductor material, and the obtained organic semiconductor material is used as an electroluminescence element or an organic thin film solar cell element. When used for an organic thin film transistor element or the like, an organic element having high characteristics can be obtained.

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

Example 1
(Bromination reaction using dibromoisocyanuric acid)

In a 100 mL flask, put 500 mg (2.90 mmol) of the compound represented by the formula (F) {FBT (5,6-difluoro-2,1,3-benzothiadiazole)} and 10 mL of sulfuric acid (98 wt%). A homogeneous solution was obtained. To this solution, 915 mg (3.19 mmol) of dibromoisocyanuric acid was added at room temperature, and the mixture was stirred at 40 ° C. for 2 hours. When the reaction mass was analyzed by HPLC (High Performance Liquid Chromatography), it was confirmed that the raw material remained. Therefore, 460 mg (1.60 mmol) of dibromoisocyanuric acid was added to the reaction mass, and the mixture was further stirred at 40 ° C. for 3 hours. The reaction mass was cooled to room temperature and then poured onto ice. After the ice melted, the mixture was extracted 3 times with 50 mL of chloroform. The organic layer was washed once with 50 mL of an aqueous sodium bicarbonate solution and once with 50 mL of water. The organic layer was dried over magnesium sulfate and filtered, and then the filtrate was concentrated with an evaporator. The obtained crude product was recrystallized and purified with methanol, and the target compound represented by the formula (G) {FBTBR (4,7-dibromo-5,6-difluoro-2,1,3-benzothiadiazole)} 620 mg (1.88 mmol, 64.8%) was obtained. When measured by HPLC, the content of the by-product represented by the following formula (I) in the product was 0.01% or less (value obtained by area percentage method).

Example 2
(Bromination reaction using dibromoisocyanuric acid)

  A 100 mL flask was charged with 1.00 g (5.81 mmol) of the compound represented by formula (F) and 20 mL of fuming sulfuric acid (sulfur trioxide content: 30%) to obtain a homogeneous solution. To this solution, 2.40 g (8.37 mmol) of dibromoisocyanuric acid was added at room temperature, and the mixture was stirred at 40 ° C. for 2.5 hours. After confirming disappearance of the raw material peak by HPLC, the reaction mass was cooled to room temperature and poured into ice. After the ice melted, the mixture was extracted 3 times with 100 mL of chloroform. The organic layer was washed once with 100 mL of aqueous sodium bicarbonate solution and once with 100 mL of water. The organic layer was dried over magnesium sulfate and filtered, and then the filtrate was concentrated with an evaporator. The obtained crude product was recrystallized and purified with methanol to obtain 977 mg (2.96 mmol, 51.0%) of the desired compound represented by the formula (G). When measured by HPLC, the content of the by-product represented by the formula (I) in the product was 0.01% (value obtained by area percentage method) or less.

(Comparative Example 1)

  In a 100 mL flask, 2.00 g (11.6 mmol) of the compound (FBT) represented by the formula (F) and 0.20 g (3.58 mmol) of iron powder were placed, and the flask was heated to 90 ° C. To this flask, 31 g (194 mmol) of bromine was added dropwise over 1 hour. After the dropping, the reaction solution was stirred at 90 ° C. for 38 hours. Thereafter, the flask was cooled to room temperature (25 ° C.) and diluted with 100 mL of chloroform. The obtained solution was poured into 300 mL of 5 wt% aqueous sodium sulfite solution and stirred for 1 hour. The organic layer of the obtained mixture was separated with a separatory funnel, and the aqueous layer was extracted with chloroform three times. The obtained extract was mixed with the organic layer, and the mixed solution was dried over sodium sulfate. After filtration, the filtrate was concentrated with an evaporator and the solvent was distilled off. The obtained yellow solid was dissolved in 90 mL of methanol heated to 55 ° C., and then cooled to 25 ° C. The precipitated crystals were collected by filtration, and then dried under reduced pressure at room temperature (25 ° C.) to obtain 1.50 g (4.55 mmol, 39%) of the compound (FBTBR) represented by the formula (G). When measured by HPLC, the by-product represented by the formula (I) was contained in 1.25% (value obtained by area percentage method).

  The method for producing a halogen compound of the present invention is extremely useful because a halogen compound can be obtained in a high yield in a short time under relatively low temperature conditions.

Claims (4)

A method for producing a halogen compound represented by the following formula (C), wherein a compound represented by the following formula (A) and a compound represented by the following formula (B) are reacted in a solvent.

[In Formula (A), Y ¹ represents a sulfur atom or an oxygen atom . X ¹ and X ² represent a nitrogen atom. Z ¹ and Z ² represent a fluorine atom. ]

[In formula (B), Q ¹ , Q ² and Q ³ are the same or different and each represents a hydrogen atom or a halogen atom. However, at least one of Q ¹ , Q ² and Q ³ represents a halogen atom. W ¹ , W ² and W ³ are the same or different and represent an oxygen atom or a sulfur atom. ]

[In Formula (C), Y ¹ , X ¹ , X ² , Z ¹ and Z ² represent the same meaning as described above. U ¹ and U ² are the same or different and represent a halogen atom. ]   The process according to claim 1, wherein the reaction is carried out in the presence of an acid.   The production method according to claim 1 or 2, wherein the solvent is an acid.   The method according to claim 2 or 3, wherein the acid is sulfuric acid or fuming sulfuric acid.