JP5076466B2 - Biphenylene derivative, use thereof, and production method thereof - Google Patents

Description

  The present invention relates to a biphenylene derivative that can be developed into an electronic material such as an organic semiconductor, its use, and a production method thereof.

  Organic semiconductor devices typified by organic thin film transistors have recently attracted attention because they have features not found in inorganic semiconductor devices such as energy saving, low cost, and flexibility. An organic thin film transistor is composed of several kinds of materials such as an organic semiconductor active phase, a substrate, an insulating phase, and an electrode. Among them, an organic semiconductor active phase responsible for charge carrier movement has a central role of the device. The semiconductor device performance depends on the carrier mobility of the organic material constituting the organic semiconductor active phase.

  As a method for producing an organic semiconductor active phase, there are generally known a vacuum deposition method in which an organic material is vaporized under a high temperature vacuum, and a coating method in which the organic material is dissolved in an appropriate solvent and applied. ing. Since the coating method can be carried out using a printing technique without using high-temperature and high-vacuum conditions, the manufacturing cost for device fabrication can be greatly reduced, and thus it is an economically preferable process. However, conventionally, there has been a problem that a high-performance material as an organic semiconductor material makes it difficult to form an active phase by coating.

  For example, it has been reported that a crystalline material such as pentacene having a molecular long axis has a carrier mobility as high as that of amorphous silicon and exhibits excellent semiconductor device characteristics (see, for example, Non-Patent Document 1). However, pentacene has low solubility due to its strong cohesiveness, and generally an economical coating method cannot be applied. In addition, attempts have been reported to dissolve polyacene such as pentacene to produce a device by a coating method (see, for example, Patent Document 1). However, in order to dissolve polyacenes that are originally hardly soluble, conditions such as high-temperature heating are reported. In addition, since the pentacene solution is oxidized by air very easily, the application of the coating method is difficult in terms of process and economy. Self-assembled materials such as poly- (3-hexylthiophene) are soluble in solvents, and device fabrication by coating has been reported, but the carrier mobility is one order of magnitude lower than crystalline compounds (for example, There is a problem that the characteristics of the obtained organic semiconductor device are low.

  These organic semiconductor materials are known to exhibit p-type semiconductor characteristics. To construct an energy saving transistor circuit, both p-type and n-type semiconductors are required. It is known that when hydrogen in a p-type organic semiconductor material is replaced with fluorine, a material exhibiting n-type semiconductor characteristics is obtained. For example, perfluoropentacene exhibits n-type semiconductor characteristics (see Non-Patent Document 3, for example). However, there is a problem that a special fluorinating agent is required and the yield of fluorination is low.

  Under such circumstances, biphenylene is a rigid conjugated condensed ring compound and is a compound that can be expected as an organic semiconductor material. Therefore, the following various reports have been made. However, none of these reports have been satisfactory as an organic semiconductor material and a manufacturing method thereof.

  An example in which biphenylenes having a diarylamino substituent are applied to a hole transport layer, an electron transport layer, and a light emitting layer of an organic EL display (see, for example, Patent Document 2). An example of a method for producing a biphenylene derivative by dilithiating a dihalobiphenyl derivative and reacting with zinc chloride and copper (II) chloride (see, for example, Non-Patent Document 4). An example of a method for producing 1,4,5,8-tetraphenylbiphenylene (for example, see Non-Patent Document 5). An example of a method for producing octaphenylbiphenylene from tetraphenylanthraanilic acid by dimerization via tetraphenylbenzyne (see, for example, Non-Patent Document 6). A dibenzobiphenylene derivative and a production method thereof (see, for example, Patent Document 3). Biphenylene derivative as a composition of a cationic polymerization initiator system (see, for example, Patent Document 4).

“Journal of Applied Physics” (USA), 2002, 92, 5259-5263. “Science”, (USA), 1998, 280, 1741-1744. “Journal of American Chemical Society” (USA), 2004, 126, 8138-8140 "Journal of Chemical Society Parkin Transaction 1" (UK), 2001, pp. 159-165 "Tetrahedron Letters", (UK), 1990, 31, 7641-7644 "Journal of American Chemical Society" (USA), 2002, 124, 8035-8041 WO2003 / 016599 Pamphlet JP 2002-43057 A JP 2004-256497 A JP 2005-523348 A

  Therefore, in view of the above-described problems of the prior art, the present invention has a biphenylene derivative having excellent oxidation resistance and capable of forming a semiconductor active phase by a coating method, an oxidation resistant organic semiconductor material using the same, and an organic An object is to provide a thin film and a method for producing the biphenylene derivative simply and economically. The present invention further relates to a dihalobiphenyl derivative which is a precursor compound of the biphenylene derivative.

  As a result of intensive studies to solve the above problems, the present inventors have found a novel biphenylene derivative and a dihalobiphenyl derivative which is a precursor. In addition, the present inventors have found an oxidation-resistant organic semiconductor material comprising the biphenylene derivative and an organic thin film thereof. Furthermore, the inventors have found a production method suitable for producing the biphenylene derivative and have completed the present invention.

The present invention is described in detail below.
(Biphenylene derivative)
The biphenylene derivative of the present invention is represented by the following general formula (1).

(Here, the substituents R ^{1 to} R ⁸ are the same or different and are a hydrogen atom, a fluorine atom, an aryl group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms and substituted with a carbon atom. A bonding group, an alkynyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkyl group having 5 to 20 carbon atoms, or a fluorinated alkyl group having 1 to 20 carbon atoms, provided that R ¹ to R ⁸ cannot simultaneously be a phenyl group, R ² and R ³ cannot simultaneously be a hydrogen atom or a fluorine atom, and R ⁶ and R ⁷ cannot simultaneously be a hydrogen atom or a fluorine atom. Any two or more of the substituents R ^{5 to} R ⁸ are bonded to each other and have a benzene ring having a substituent, a naphthalene ring which may have a substituent, and a substituent. Consisting of an optional triphenylene ring (At least one ring selected from the group can be formed.)
Preferred examples of the substituents R ^{1 to} R ⁸ include a hydrogen atom, an aryl group having 6 to 30 carbon atoms, an alkynyl group having 3 to 20 carbon atoms, an alkyl group having 5 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms. It is a fluorinated alkyl group, and more preferred examples are a hydrogen atom, an alkyl group having 5 to 20 carbon atoms, and a fluorinated alkyl group having 1 to 20 carbon atoms.

Further, when two or more of the substituents R ^{5 to} R ⁸ are bonded to each other to form a ring, the benzene ring having a substituent and the naphthalene ring optionally having a substituent are preferable. And more preferably a naphthalene ring optionally having a substituent.

Examples of combinations of substituents in the biphenylene derivative represented by the general formula (1) of the present invention include the following examples: the substituents R ² , R ³ , R ⁶ , and R ⁷ are the same or different; Hydrogen atom, aryl group having 6 to 30 carbon atoms, heterocyclic group having 2 to 20 carbon atoms having a bonding group on carbon, alkynyl group having 3 to 20 carbon atoms, alkenyl group having 2 to 30 carbon atoms, carbon number 5 -20 alkyl groups and at least one group selected from the group consisting of fluorinated alkyl groups having 1 to 20 carbon atoms, and the substituents R ¹ , R ⁴ , R ⁵ , and R ⁸ are the same. Or, differently, it is a hydrogen atom or a fluorine atom, and any two or more of the substituents R ^{5 to} R ⁸ may be bonded to each other and have a benzene ring having a substituent or a substituent. With naphthalene ring, and substituent Examples of forming at least one or more rings selected from the group consisting of optionally triphenylene ring optionally. In this example, the substituents R ⁶ and R ⁷ may further form a benzene ring having a substituent or a naphthene ring optionally having a substituent, which are bonded to each other. Preferably, the substituents R ² , R ³ , R ⁶ , and R ⁷ are the same or different and are an aryl group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms having a bonding group on the carbon. , And at least one group selected from the group consisting of alkyl groups having 5 to 20 carbon atoms, and the substituents R ¹ , R ⁴ , R ⁵ , and R ⁸ are the same or different and are hydrogen atoms. And an example of at least one group selected from the group consisting of fluorine atoms. In this example, the substituents R ⁶ and R ⁷ can also be bonded to each other to form an optionally substituted naphthalene ring. In particular, the following general formula (2) having a molecular long axis that can be expected to have high semiconductor performance and further having a group (R ² and R ³ ) that makes it possible to improve solubility in a solvent in the molecular long axis direction. It is preferable that it is a structure shown by these.

(Here, the substituents R ² and R ³ have the same meaning as the substituent represented by the general formula (1). The substituents R ⁹ and R ¹⁰ are the same or different and are a hydrogen atom, a fluorine atom, or a carbon number of 1). Represents an alkyl group having ˜20 or a fluorinated alkyl group having 1 to 20 carbon atoms, and n is an integer of 1 or 2.)
The substituent of the general formula (1) of the present invention will be further described.

The aryl group having 6 to 30 carbon atoms in the substituents R ^{1 to} R ⁸ is not particularly limited, and examples thereof include a phenyl group, a p-tolyl group, a p- (n-octyl) phenyl group, and m- (n-octyl) phenyl. Group, p-fluorophenyl group, pentafluorophenyl group, p- (trifluoromethyl) phenyl group, p- (n-perfluorooctyl) phenyl group, p- (trifluoromethyl) tetrafluorophenyl group, p-methoxy Phenyl group, p-phenoxyphenyl group, 1-naphthyl group, 2-naphthyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 1-biphenyleno group, 2-biphenyleno group, biphenyl group, perfluoro Biphenyl group, terphenyl group, (diphenylamino) phenyl group, (diphenylamino) biphenyl group, carbazolyl And a phenyl group, preferably a p- (n-octyl) phenyl group, a p- (trifluoromethyl) phenyl group, a p- (n-perfluorooctyl) phenyl group, a biphenyl group, A perfluorobiphenyl group, particularly preferably a phenyl group, a p- (n-octyl) phenyl group, a p- (trifluoromethyl) phenyl group, and a p- (n-perfluorooctyl) phenyl group.

In the substituents R ^{1 to} R ⁸ , the group which is a heterocyclic group having 2 to 20 carbon atoms and which is substituted and bonded with a carbon atom is not particularly limited. For example, a 2-thienyl group, 5- (n-hexyl)- 2-thienyl group, 5- (n-1-octynyl) -2-thienyl group, 2,2′-bithienyl-5 group, 5 ′-(n-octyl) -2,2′-bithienyl-5 group 2-benzothienyl group, 2-pyridyl group, 3-pyridyl group, tetrafluoropyridyl group, bipyridyl group, quinolyl group, 2-furyl group, 2-benzofuryl group, 1-methyl-2-pyrrolyl group, 1-phenyl 2-indolyl group, 1,3,4-oxadiazolyl-2- group, 1-methyltriazolyl-3- group, triazinyl group, 1-methylpyrazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, 1,3 , 4 And thiadiazolyl-2-group, and the like, preferably 2-thienyl group, 5- (n-hexyl) -2-thienyl group, 2,2′-bithienyl-5-group, 5 ′-(n-octyl) ) -2,2′-bithienyl-5 group, 2-pyridyl group, 3-pyridyl group, tetrafluoropyridyl group, bipyridyl, etc., particularly preferably 2-thienyl group, 5- (n-hexyl) -2. -Thienyl group, 2,2'-bithienyl-5 group.

In the substituents R ^{1 to} R ⁸ , the alkynyl group having 3 to 20 carbon atoms is an alkynyl group not containing a silyl group, such as a methylethynyl group, an isopropylethynyl group, a tert-butylethynyl group, or an (n-octyl) ethynyl group. , (Trifluoromethyl) ethynyl group, (n-perfluorooctyl) ethynyl group, phenylethynyl group, {p- (n-octyl) phenyl} ethynyl group, naphthylethynyl group, anthracenylethynyl group, biphenylenoethynyl group , Biphenylethynyl group, terphenylethynyl group, benzylethynyl group, perfluorophenylethynyl group, {p- (trifluoromethyl) phenyl} ethynyl group, {p- (n-perfluorooctyl) phenyl} ethynyl group, etc. Preferably (n-octyl) ethynyl , (Trifluoromethyl) ethynyl group, phenylethynyl group, {p- (trifluoromethyl) phenyl} ethynyl group, {p- (n-perfluorooctyl) phenyl} ethynyl group, biphenylethynyl group, terphenylethynyl group, etc. It is.

The alkenyl group having 2 to 30 carbon atoms in the substituents R ^{1 to} R ⁸ is not particularly limited. For example, ethenyl group, methylethenyl group, isopropylethenyl group, tert-butylethenyl group, (n-octyl) ethenyl group, (tri Fluoromethyl) ethenyl group, phenylethenyl group, 1,2-difluoro-2-phenylethenyl group, 1,2-dimethyl-2-phenylethenyl group, diphenylethenyl group, triphenylethenyl group, naphthylethenyl group , Anthracenyl ethenyl group, biphenylenoethenyl group, biphenylethenyl group, terphenylethenyl group, benzylethenyl group, phenyl (methyl) ethenyl group, perfluorophenylethenyl group, {p- (trifluoromethyl ) Phenyl} ethenyl group, (n-perfluorooctyl) ethenyl group, etc. It can gel. (N-octyl) ethenyl group, phenylethenyl group and biphenylethenyl group are preferred. The alkenyl group having 2 to 20 carbon atoms may be a trans isomer or a cis isomer, or may be a mixture of any proportion thereof.

The alkyl group having 5 to 20 carbon atoms in the substituents R ^{1 to} R ⁸ is not particularly limited, and examples thereof include a pentyl group, neopentyl group, hexyl group, octyl group, isooctyl group, dodecyl group, and the like. A hexyl group and an octyl group; the fluorinated alkyl group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include a trifluoromethyl group, a trifluoroethyl group, a perfluorooctyl group, and a perfluorododecyl group.

In the substituents R ^{5 to} R ⁸ , any two or more of them are bonded to each other, and a benzene ring having a substituent, a naphthalene ring optionally having a substituent, or triphenylene optionally having a substituent A ring selected from the group consisting of rings can be formed, preferably a benzene ring having a substituent, a naphthalene ring which may have a substituent, and more preferably a substituent. It is a naphthalene ring. The benzene ring having a substituent is, for example, a dimethylbenzene ring, a di (trifluoromethyl) benzene ring, a diphenylbenzene ring or the like, and preferably a diphenylbenzene ring. The naphthalene ring which may have a substituent is, for example, a naphthalene ring, a dimethylnaphthalene ring, a diphenylnaphthalene ring, an anthracene ring, etc., preferably a naphthalene ring or an anthracene ring. The triphenylene ring which may have a substituent is, for example, a triphenylene ring, a decamethyltriphenylene ring, a diphenyltriphenylene ring or the like, preferably a triphenylene ring.

  Specific examples of the biphenylene derivative represented by the general formula (1) of the present invention include the following compounds.

  The substituent of the biphenylene derivative represented by the general formula (2), which is a preferred structure of the biphenylene derivative represented by the general formula (1), will be described.

The substituents R ² and R ³ have the same meaning as the substituent represented by the general formula (1), and the substituents R ⁹ and R ¹⁰ are the same or different and are a hydrogen atom, a fluorine atom, or an alkyl having 1 to 20 carbon atoms. A group or a fluorinated alkyl group having 1 to 20 carbon atoms, n is an integer of 1 or 2;

The substituents R ² and R ³ have the same meaning as the substituent represented by the general formula (1) and are preferably an alkyl group having 5 to 20 carbon atoms or a fluorinated alkyl group having 1 to 20 carbon atoms. Further, either one of R ² and R ³ can be a hydrogen atom.

The substituents R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or a fluorinated alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms; Is not particularly limited, and examples thereof include a methyl group, an ethyl group, a pentyl group, a neopentyl group, a hexyl group, an octyl group, an isooctyl group, and a dodecyl group, preferably a hexyl group and an octyl group; The -20 fluorinated alkyl group is not particularly limited, and examples thereof include a trifluoromethyl group, a trifluoroethyl group, a perfluorooctyl group, and a perfluorododecyl group. In particular, the substituents R ⁹ and R ¹⁰ are preferably hydrogen atoms.

  N is an integer of 1 or 2, and is particularly preferably 1.

  Specific examples of the biphenylene derivative represented by the general formula (2) include the following compounds:

Among the,

Is preferred.
(Dihalobiphenyl derivatives)
Next, the dihalobiphenyl derivative represented by the following general formula (3) used as a raw material for the biphenylene derivative represented by the general formula (1) of the present invention will be described.

(Here, the substituents X ¹ and X ² represent a bromine atom, an iodine atom or a chlorine atom, and the substituents R ^{1 to} R ⁸ have the same meaning as the substituent represented by the general formula (1).)
X < ¹ > -X < ² > in General formula (3) is a bromine atom, an iodine atom, or a chlorine atom, Among them, Preferably it is a bromine atom or an iodine atom, More preferably, it is a bromine atom.

In addition, the substituents R ^{1 to} R ⁸ in the general formula (3) have the same meaning as the substituent represented by the general formula (1), and among them, a hydrogen atom, an aryl group having 6 to 30 carbon atoms, carbon An alkynyl group having 3 to 20 carbon atoms, an alkyl group having 5 to 20 carbon atoms, and a fluorinated alkyl group having 1 to 20 carbon atoms, and more preferable examples are a hydrogen atom, an alkyl group having 5 to 20 carbon atoms, and 1 to 1 carbon atoms. 20 fluorinated alkyl groups.

  Specific examples of the dihalobiphenyl derivative represented by the general formula (3) include the following compounds.

  Among these dihalobiphenylene derivatives represented by the general formula (3), a dihalobiphenyl derivative represented by the following general formula (4) is particularly preferable. The dihalobiphenyl derivative represented by the general formula (4) is used as a raw material for the biphenylene derivative represented by the general formula (2).

(Here, the substituents R ² , R ³ , R ⁹ , and R ¹⁰ are the same as the substituent represented by the general formula (2), and X ¹ and X ² are the substituents represented by the general formula (3). And n is an integer of 1 or 2.
Specific examples of the dihalobiphenyl derivative represented by the general formula (4) include the following compounds.

(3-halo-2-anthracenyl metal reagent)
Next, the 3-halo-2-anthracenyl metal reagent represented by the following general formula (5) used for the production of the dihalobiphenyl derivatives represented by the general formulas (3) and (4) will be described.

(Wherein the substituents R ⁹ , R ¹⁰ , and X ² have the same meaning as the substituent represented by the general formula (4). M is a lithium atom or a copper atom; Mg, B, Zn, Sn, or Cu. A halide, a hydroxide, an alkoxide having 1 to 20 carbon atoms or an alkylated product having 1 to 20 carbon atoms, n is an integer of 1 or 2.)
The substituent of the general formula (5) of the present invention will be further described.

Mg, B, Zn, Sn or Cu halide, hydroxide, C1-C20 alkoxide or C1-C20 alkylated in the substituent M of the general formula (5) is magnesium halide, carbon number 2-20 cyclic or chain dialkoxyboron, C2-20 cyclic or chain dialkylboron, zinc halide, C3-20 trialkyltin or copper halide. Specific examples include: MgCl, MgBr, B (OH) ₂ , B (OMe) ₂ , pinacolate boron, catecholate boron, dimethylboron, bicyclo [3,3,1] nona-9-boron (9-BBN), ZnCl, ZnBr, ZnI, Sn (Bu-n) ₃ or CuCl can be mentioned, among which B (OH) ₂ or ZnCl is preferable.

A preferred example of the substituent M is a lithium atom, B (OH) ₂ .

A preferred example of the substituent X ² is a bromine atom, and n is preferably 1.

  Moreover, as a more specific 3-halo-2-anthracenyl metal reagent represented by the general formula (5) of the present invention, for example, the following compounds may be mentioned.

(Method for producing biphenylene derivative)
Next, a method for producing the biphenylene derivative represented by the general formula (1) of the present invention will be described.

  The biphenylene derivative represented by the general formula (1) of the present invention can be produced by reacting the dihalobiphenyl derivative represented by the general formula (3) with copper or a copper compound.

  The copper or copper compound used in the reaction is not particularly limited as long as it reacts with iodine or bromine. Specific examples include copper, copper (I) chloride, copper bromide (I), copper (I) iodide, copper (II) bromide, and copper (II) iodide, preferably copper. is there. Moreover, even if this copper is an alloy with zinc and / or tin, it can be used without any problem. The shape of the copper and / or copper alloy is preferably powder. This reaction with copper, a copper alloy or a copper compound can be carried out with or without a solvent. When a solvent is used, examples of the solvent include polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile or dimethyl sulfoxide. In the reaction with such copper or copper compound, the amount of copper or copper compound to be used is preferably 1 to 50 equivalents, particularly preferably 5 to 30 equivalents, relative to 1 equivalent of the dihalobiphenyl derivative represented by the general formula (3). The reaction temperature is preferably from 30 to 250 ° C., particularly preferably from 50 to 250 ° C., and the reaction time is preferably from 1 to 120 minutes, particularly preferably from 3 to 80 minutes.

  The reaction is preferably carried out under an inert atmosphere such as nitrogen or argon. The obtained biphenylene derivative represented by the general formula (1) can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

  A more preferable method of the biphenylene derivative represented by the general formula (1) of the present invention will be described.

  The biphenylene derivative represented by the general formula (1) of the present invention can be produced by reacting the dihalobiphenyl derivative represented by the general formula (3) with a copper compound after dilithiation and / or diglynarization.

When dilithiating the dihalobiphenyl derivative represented by the general formula (3), the lithiating agent to be used is particularly limited as long as the halogen X ^{1 to} X ² in the general formula (3) can be substituted with lithium. For example, alkyllithium such as n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, hexyllithium; phenyllithium, p-tert-butylphenyllithium, p-methoxyphenyllithium, p-fluoro Aryl lithium such as phenyl lithium; lithium amide such as lithium diisopropylamide and lithium hexamethyldisilazide; lithium metal such as lithium powder. Alkyl lithium is preferable, and n-butyl lithium, sec-butyl lithium, and tert-butyl lithium are particularly preferable.

Here, dilithiation means that ^two halogens X ¹ and X ² in the general formula (3) are each replaced with lithium.

The amount of the lithiating agent used is a dihalo represented by the general formula (3) in order to convert the halogen of X ^{1 to} X ² of the dihalobiphenyl derivative represented by the general formula (3) into lithium and lithiate it. It is preferably 1.5 to 4 equivalents, more preferably 1.8 to 3 equivalents, and even more preferably 1.9 to 2.6 equivalents per 1 equivalent of the biphenyl derivative.

  The dilithiation reaction is preferably carried out in a solvent. The solvent to be used is not particularly limited, and examples thereof include tetrahydrofuran (hereinafter abbreviated as THF), diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, diglyme, dioxane, toluene, pentane, hexane, cyclohexane and the like, preferably THF, diethyl Ether, methyl tert-butyl ether and dioxane, particularly preferably THF. These solvents may be used alone or as a mixture of two or more.

  The dilithiation reaction temperature is preferably -100 to 60 ° C, particularly preferably -90 to 30 ° C. The reaction time is preferably 1 to 120 minutes, particularly preferably 1 to 60 minutes. The progress of the lithiation reaction can be monitored by taking out a part of the reaction solution, stopping the reaction with water, and then analyzing by gas chromatography.

  The dilithium salt produced by the dilithiation reaction is then reacted with a copper compound. The reaction with the copper compound includes a method of reacting the reaction mixture containing the dilithium salt generated by the lithiation reaction directly using the copper compound, a method of isolating the generated dilithium salt once, and reacting with the copper compound. Any of them may be used.

  The copper compound used for the reaction between the dilithium salt and the copper compound is not particularly limited. For example, copper (II) chloride, copper (II) bromide, copper iodide (II), copper acetate (II), acetylacetonate Examples thereof include divalent copper such as copper (II); monovalent copper such as copper (I) chloride, copper (I) bromide, copper (I) iodide, and copper (I) acetate. Divalent copper is preferable, and copper (II) chloride and copper (II) bromide are particularly preferable.

  The reaction between the produced dilithium salt and the copper compound is preferably carried out in a solvent. The solvent to be used is not specifically limited, For example, the solvent used for the lithiation reaction can be mentioned. The amount of the copper compound to be used is preferably 0.9 to 5 equivalents, particularly preferably 1.0 to 3.5 equivalents, relative to 1 equivalent of the dihalobiphenyl derivative of the general formula (3). The reaction temperature with the copper compound is preferably −100 to 50 ° C., particularly preferably −90 to 30 ° C., and the reaction time is preferably 1 to 30 hours, particularly preferably 1 to 18 hours.

  The production of the biphenylene derivative of the general formula (1) of the present invention is preferably carried out under an inert atmosphere such as nitrogen or argon.

  The biphenylene derivative represented by the general formula (1) thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

  In the case where the dihalobiphenyl derivative represented by the general formula (3) is diglynarized, examples of the Grignard agent to be used include Mg metal or alkyl Grignard reagents such as ethylmagnesium bromide and isopropylmagnesium bromide. However, Mg metal is preferable. The form of the Mg metal is not particularly limited, and examples thereof include a cut shape, a ribbon shape, and a granular shape.

Here, diglynarization means that two halogens X ¹ and X ² in the general formula (3) are each substituted with a magnesium halide.

  For example, in the case of Mg metal, the Grignard agent can be used in the range of 1.8 to 10 equivalents relative to 1 equivalent of the dihalobiphenyl derivative represented by the general formula (3). The Grignard reaction is preferably carried out in a solvent. The solvent to be used is not specifically limited, For example, the solvent used by the lithiation reaction can be mentioned. The temperature of the Grignard reaction is preferably -20 to 80 ° C, and the reaction time is preferably in the range of 1 to 120 minutes.

  The magnesium salt produced by the diglynarization reaction is then reacted with a copper compound. The reaction method with the copper compound and the copper compound to be used can be carried out in the same manner as in the case of reacting the lithium salt produced by the lithiation reaction with the copper compound. The reaction atmosphere and the reaction product can be purified in the same manner.

  In the method for producing the biphenylene derivative of the general formula (1) of the present invention, the dihalobiphenyl derivative of the general formula (3) is dilithiated and / or diglynarized, then reacted with zinc chloride, and then treated with a copper compound. You can also

The biphenylene derivative represented by the general formula (2), which is a preferred structure of the biphenylene derivative represented by the general formula (1), is represented by the general formula (1) from the dihalobiphenyl derivative represented by the general formula (3). It can be obtained from the dihalobiphenyl derivative represented by the general formula (4) by a method similar to the method for obtaining the biphenylene derivative.
(Method for producing dihalobiphenyl derivative)
The dihalobiphenyl derivative represented by the general formula (3), which is a precursor of the biphenylene derivative represented by the general formula (1), can be derived from the dihalobenzene derivative represented by the following general formula (9).

(Here, the substituents X ¹ and R ^{1 to} R ⁴ have the same meaning as the substituent represented by the general formula (3).)
That is, the dihalobiphenyl derivative represented by the general formula (3) can be produced by homocoupling the dihalobenzene derivative represented by the general formula (9) using a lithiating agent or a Grignard agent.

The lithiating agent used for the homocoupling reaction of the dihalobenzene derivative is not particularly limited as long as it can lithiate the halogen X ¹ in the general formula (9). For example, an organic lithium reagent, an organic lithium amide reagent, Mention may be made of lithium metal. Examples of the organic lithium reagent include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, and phenyllithium; examples of the organic lithiumamide reagent include lithium diisopropylamide and lithium hexamethyldisilazide. Etc. Such a lithiating agent is preferably n-butyllithium.

  The lithiation reaction is preferably carried out in a solvent. The solvent to be used is not particularly limited, and examples thereof include THF, diethyl ether, methyl tert-butyl ether, dioxane, toluene, pentane, hexane, cyclohexane, and the like, and preferably THF. These solvents may be used alone or as a mixture of two or more.

  The lithiating agent is preferably 0.3 to 1.2 equivalents, particularly preferably 0.4 to 0.7 equivalents, per 1 equivalent of the dihalobenzene derivative represented by the general formula (9). The temperature of the lithiation reaction is preferably −110 to 40 ° C., particularly preferably −100 to 30 ° C., and the reaction time is preferably 1 to 30 hours, particularly preferably 2 to 20 hours.

On the other hand, the Grignard agent used for the homocoupling reaction of the dihalobenzene derivative represented by the general formula (9) is not particularly limited as long as the halogen X ¹ in the general formula (9) can be Grignard. , Mg metal, or alkyl Grignard reagents such as ethyl magnesium bromide and isopropyl magnesium bromide, and Mg metal is preferable. The form of the Mg metal is not particularly limited, and examples thereof include a cut shape, a ribbon shape, and a granular shape.

  For example, in the case of Mg metal, the Grignard agent is used in the range of 1.8 to 20 equivalents per 1 equivalent of the dihalobenzene derivative represented by the general formula (9). The Grignard reaction is preferably carried out in a solvent. The solvent to be used is not specifically limited, For example, the solvent used by the lithiation reaction can be mentioned. The temperature of the Grignard reaction is preferably -20 to 120 ° C, and the reaction time is preferably 1 to 30 hours.

  The production of the dihalobiphenyl derivative represented by the general formula (3) is preferably carried out under an inert atmosphere such as nitrogen or argon.

  The dihalobiphenyl derivative represented by the general formula (3) thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

  Furthermore, another method for producing the dihalobiphenyl derivative represented by the general formula (3) will be described.

  The dihalobiphenyl derivative represented by the general formula (3) is represented by the following general formula (11) derived from the dihalobenzene derivative represented by the general formula (9) and the dihalobenzene derivative represented by the following general formula (10). -It can be produced by cross-coupling haloaryl metal reagents in the presence of palladium and / or nickel catalysts.

(Here, the substituents X ² and R ^{5 to} R ⁸ have the same meaning as the substituent represented by the general formula (3).)

(Here, M represents a lithium atom or a copper atom; a halide of Mg, B, Zn, Sn or Cu; a hydroxide, an alkoxide or an alkylated product. The substituents X ² , R ^{5 to} R ⁸ are represented by the general formula (3 And the same meaning as the substituent represented by
The substituent M in the general formula (11) is a lithium atom, a copper atom, a halide, hydroxide, alkoxide or alkylated product of Mg, B, Zn, Sn or Cu, and reacts with the palladium and / or nickel catalyst. As long as it is a group that can be substituted with palladium and / or nickel, there is no particular limitation. For example, lithium atom, copper atom, MgCl, MgBr, B (OH) ₂ , B (OMe) ₂ , pinacolato boron, ZnCl, ZnBr, ZnI, Sn (Bu-n) ₃ or CuCl can be mentioned, and B (OH) ₂ or ZnCl is preferable.

  Note that the 2-haloaryl metal reagent represented by the general formula (11) is a dihalobenzene derivative represented by the general formula (10), which is a raw material, for example, a Grignard reagent such as isopropylmagnesium bromide or an organic such as n-butyllithium. After a halogen / metal exchange reaction with a lithium reagent, it can be suitably prepared by reacting with zinc chloride, trimethoxyborane, tri (isopropoxy) borane or the like. The halogen / metal exchange reaction using the Grignard reagent is, for example, the method described in “Journal of Organic Chemistry”, 2000, Vol. 65, pages 4618-4634, and the halogen / metal exchange reaction using an organolithium reagent is For example, the method for lithiation of halogen at −90 ° C. or lower described in “Journal of Chemical Research Synopsis”, 1981, page 185 can also be used.

  The catalyst used for the cross-coupling reaction of the 2-haloaryl metal reagent represented by the general formula (11) and the dihalobenzene derivative represented by the general formula (9) is not particularly limited as long as it is a palladium and / or nickel catalyst. Specific examples of the catalyst include tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium / triphenylphosphine mixture, dichlorobis (triphenylphosphine) palladium, bis (tri-tert-butylphosphine) palladium, palladium acetate / (Tri-tert-butylphosphine) mixture, diacetatobis (triphenylphosphine) palladium, dichloro (1,2-bis (diphenylphosphino) ethane) palladium, palladium acetate / triphenylphosphine Compound, palladium acetate / 2- (dicyclohexylphosphino) -1,1′-biphenyl mixture, dichloro (ethylenediamine) palladium, dichloro (N, N, N ′, N′-tetramethylethylenediamine) palladium, dichloro (N, N, N ′, N′-tetramethylethylenediamine) palladium / triphenylphosphine mixture and the like can include zero-valent or divalent palladium compounds; specific examples of nickel catalysts include dichlorobis (triphenylphosphine) nickel, dichloro ( 1,2-bis (diphenylphosphino) ethane) nickel, dichloro (ethylenediamine) nickel, dichloro (N, N, N ', N'-tetramethylethylenediamine) nickel, dichloro (N, N, N', N'- Tetramethylethylenediamine) Kell / triphenylphosphine mixtures, and bis (1,5-cyclooctadiene) nickel / triphenylphosphine zerovalent mixtures or divalent nickel compounds. Among these, a preferable catalyst is a zero-valent palladium compound, and a particularly preferable catalyst is tetrakis (triphenylphosphine) palladium.

  The amount of the catalyst used in the coupling reaction is preferably in the range of 0.1 to 20 mol% with respect to the dihalobenzene derivative of the general formula (9). The amount of the 2-haloaryl metal reagent of the general formula (11) used is preferably 0.6 to 1.5 equivalents, particularly preferably 0.8 to 1.4 equivalents, relative to 1 equivalent of the dihalobenzene derivative of the general formula (9). More preferably, it can be used in the range of 0.9 to 1.2 equivalents.

  The reaction is preferably carried out in a solvent. Specific examples include THF, diethyl ether, methyl tert-butyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol, N, N-dimethylformamide, N-methylpyrrolidone, diisopropylamine, piperidine, toluene, xylene, hexane, cyclohexane, ethanol, Water etc. can be mentioned, and these solvents may be used alone or as a mixture of two or more. For example, it can also be used in a 2 to 3 component system such as toluene / water or toluene / ethanol / water.

  A base can also be present in the reaction system. The type of base in this case is not particularly limited. For example, inorganic bases such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium phosphate, potassium fluoride; sodium methoxide, sodium tert -Alkoxides such as butoxide and potassium tert-butoxide; amines such as triethylamine, trimethylamine, tributylamine, ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, diisopropylamine, pyridine and the like can be mentioned as suitable ones. . The amount of these bases used is preferably 1.5 to 10.0 equivalents, particularly preferably 2.0 to 8.0 equivalents per 1 equivalent of the dihalobenzene derivative of the general formula (9). . Furthermore, a phase transfer catalyst can be used in combination with these bases. The type of the phase transfer catalyst is not particularly limited, and examples thereof include trioctylmethylammonium chloride, tetrabutylammonium chloride, cetylpyridinium chloride and the like. The amount of these phase transfer catalysts used is preferably from 0.1 to 1.5 equivalents, particularly preferably from 0.2 to 0.8 equivalents, per equivalent of the dihalobenzene derivative of the general formula (9).

  Further, phosphine such as triphenylphosphine can be present in the reaction system. The amount of these phosphines used is preferably 0.9 to 8.0 equivalents, particularly preferably 1.0 to 3.0 equivalents, per 1 equivalent of the palladium and / or nickel catalyst. .

  A copper compound can also be present in the reaction system. The type of copper compound in this case is not particularly limited. For example, monovalent copper such as copper chloride (I), copper bromide (I), copper iodide (I), copper acetate (I); copper chloride (II ), Copper (II) bromide, copper (II) iodide, copper (II) acetate, copper acetylacetonate (II) and the like. Monovalent copper is preferable, and copper (I) iodide is particularly preferable. These copper compounds are preferably used in an amount of 0.3-10.0 equivalents, particularly preferably 0.6-6.0 equivalents, relative to 1 equivalent of the palladium and / or nickel catalyst. .

  The reaction temperature is preferably 10 to 120 ° C., particularly preferably 30 to 100 ° C., and the reaction time can be suitably carried out in the range of 1 to 48 hours.

  The atmosphere of the reaction system in this reaction method and the purification of the obtained dihalobiphenyl derivative represented by the general formula (3) are the same as the method for producing the biphenylene derivative represented by the general formula (1) described above. The method can be used.

  In addition, the dihalobiphenyl derivative represented by the general formula (3) of the present invention is a 2-haloaryl metal reagent derived from a dihalobenzene derivative represented by the general formula (10) and a dihalobenzene derivative represented by the general formula (9). It can also be produced by cross-coupling in the presence of a palladium and / or nickel catalyst. The 2-haloaryl metal reagent is obtained by subjecting a dihalobenzene derivative represented by the general formula (9) as a raw material to a halogen / metal exchange reaction with a Grignard reagent such as isopropylmagnesium bromide or an organic lithium reagent such as n-butyllithium. After carrying out, it can be suitably prepared by reacting with zinc chloride, trimethoxyborane, tri (isopropoxy) borane and the like.

Further, the dihalobiphenyl derivative represented by the general formula (4), which is a precursor of the biphenylene derivative represented by the general formula (2), is produced by the same method as the dihalobiphenyl derivative represented by the general formula (3). Among them, in particular, a 3-halo-2-anthracenyl metal reagent represented by the general formula (5) and a dihalobenzene derivative represented by the following general formula (8) are cross-linked in the presence of a palladium and / or nickel catalyst. It is preferable to produce by coupling reaction. In the general formula (5), the substituents R ⁶ and R ^{7 of the} 2-haloaryl metal reagent represented by the general formula (11) are bonded to each other to form an optionally substituted naphthalene ring. The 3-halo-2-anthracenyl metal reagent shown.

(Here, the substituents R ² , R ³ , and X ¹ have the same meaning as the substituent represented by the general formula (4).)
The catalyst and conditions for producing the dihalobiphenyl derivative represented by the general formula (4) are the dihalobiphenyl derivative represented by the general formula (3), the dihalobenzene derivative represented by the general formula (9) and the general formula (9). The same catalyst and conditions as in the case of cross-coupling the 2-haloaryl metal reagent represented by 11) can be used.
(Method for producing dihalobenzene derivative)
A method for producing the dihalobenzene derivative represented by the general formulas (9) and (10) will be described.

  The dihalobenzene derivatives represented by the general formulas (9) and (10) are, for example, a tetrahalobenzene derivative represented by the following general formula (12) and a reactant represented by the following general formula (13) in the presence of palladium and / or nickel catalyst. It can manufacture by carrying out a cross coupling reaction under.

(Wherein the substituent X ³ represents an iodine atom or a bromine atom, the substituent X ⁴ represents an iodine atom, a bromine atom or a hydrogen atom, and the substituents X ¹ , R ¹ and R ⁴ are represented by the general formula (9) And the same meaning as the substituent represented by.
The substituents X ³ and X ⁴ are preferably iodine atoms.

A-N (13)
(Here, A is a hydrogen atom, a fluorine atom, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms which is substituted with a carbon atom, or an alkynyl group having 3 to 20 carbon atoms. Group, an alkenyl group having 2 to 30 carbon atoms, an alkyl group having 5 to 20 carbon atoms, or a fluorinated alkyl group having 1 to 20 carbon atoms, N is a hydrogen atom, a lithium atom or a copper atom, Mg, B, Zn , Sn or Si halide, hydroxide, alkoxide or alkylated product.)
The substituent A in the general formula (13) is preferably an aryl group having 6 to 30 carbon atoms, an alkyl group having 5 to 20 carbon atoms, or a fluorinated alkyl group having 1 to 20 carbon atoms, more preferably 5 carbon atoms. An alkyl group having ˜20, and a fluorinated alkyl group having 1 to 20 carbon atoms.

The substituent N in the general formula (13) is a hydrogen atom, a lithium atom or a copper atom, a halide, hydroxide, alkoxide or alkylated product of Mg, B, Zn, Sn or Si, and the above palladium and / or nickel catalyst. There is no particular limitation as long as it is a group capable of reacting with palladium and / or nickel or becoming a hydrogen halide in the course of the reaction. For example, MgCl, MgBr, B (OH) ₂ , B (OMe) ₂ , Pinacolato boron, ZnCl, ZnBr, ZnI, Sn (Bu-n) ₃ or Si (Bu-n) ₃ can be mentioned, and B (OH) ₂ or ZnCl is preferable.

  The reactant represented by the general formula (13) is, for example, a halogen / metal exchange reaction of an aryl halogen-substituted product as a raw material with a Grignard reagent such as isopropylmagnesium bromide or an organic lithium reagent such as n-butyllithium. Thereafter, it can be suitably prepared by reacting with zinc chloride, trimethoxyborane or the like.

  One kind or two kinds of reactants represented by the general formula (13) may be used.

  The catalyst used for the cross-coupling reaction of the tetrahalobenzene derivative represented by the general formula (12) and the reactant represented by the general formula (13) is not particularly limited as long as it is a palladium and / or nickel catalyst. The palladium and / or nickel catalyst used when obtaining the dihalobiphenyl derivative shown by General formula (3) from the dihalobenzene derivative shown by (9) and the 2-haloaryl metal reagent shown by General formula (11) is mentioned. be able to. Among these, a preferable catalyst is a zero-valent palladium compound, and a particularly preferable catalyst is tetrakis (triphenylphosphine) palladium.

  The amount of catalyst used in the coupling reaction is preferably in the range of 0.1 to 20 mol% with respect to the tetrahalobenzene derivative of the general formula (12). The amount of the reactant of the general formula (13) used is 1.4 to 3.3 with respect to 1 equivalent of the tetrahalobenzene derivative of the general formula (12) when one kind of the reactant of the general formula (13) is used. 5 equivalents are preferable, particularly preferably 1.6 to 3.0 equivalents, more preferably 1.8 to 2.8 equivalents, and two kinds of the reactants of the general formula (13) are used. In the case, 0.6 to 1.8 equivalents are preferable, particularly 0.7 to 1.5 equivalents, and more preferably 0.8 to 1 equivalent to 1 equivalent of the tetrahalobenzene derivative of the general formula (12). .4 equivalents can be used.

  In the coupling reaction, when two types of reactants of the general formula (13) are used, the two types of reactants can be allowed to exist at the start of the reaction, or the first and second reactants can be present. It is also possible to add the reaction agent after a sufficient time.

  The reaction is preferably carried out in a solvent. Specific examples include THF, diethyl ether, methyl tert-butyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol, N, N-dimethylformamide, N-methylpyrrolidone, triethylamine, diisopropylamine, pyrrolidine, piperidine, toluene, xylene, hexane, Cyclohexane, ethanol, water and the like can be mentioned, and these solvents may be used alone or as a mixture of two or more. For example, it can also be used in a 2 to 3 component system such as toluene / water or toluene / ethanol / water.

  A base can also be present in the reaction system. The type of base in this case is not particularly limited. For example, inorganic bases such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium phosphate, potassium fluoride; sodium methoxide, sodium tert Preferred examples include alkoxides such as butoxide and potassium tert-butoxide; amines such as triethylamine, trimethylamine, tributylamine, diisopropylamine and pyridine. The amount of these bases used is preferably 1.5 to 10.0 equivalents, particularly preferably 2.0 to 8.0 equivalents per 1 equivalent of the tetrahalobenzene derivative of the general formula (12). Can do. Furthermore, a phase transfer catalyst can be used in combination with these bases. The type of the phase transfer catalyst is not particularly limited, and examples thereof include trioctylmethylammonium chloride, tetrabutylammonium chloride, cetylpyridinium chloride and the like. The amount of the phase transfer catalyst used is preferably 0.1 to 1.5 equivalents, particularly preferably 0.2 to 0.8 equivalents per equivalent of the tetrahalobenzene derivative of the general formula (12). .

  Further, phosphine such as triphenylphosphine can be present in the reaction system. The amount of these phosphines used is preferably 0.9 to 8.0 equivalents, particularly preferably 1.0 to 3.0 equivalents, per 1 equivalent of the palladium and / or nickel catalyst. .

  A copper compound can also be present in the reaction system. The type of copper compound in this case is not particularly limited. For example, monovalent copper such as copper (I) chloride, copper (I) bromide, copper (I) iodide, copper (I) acetate; copper chloride ( II), copper (II) bromide, copper (II) iodide, copper (II) acetate, copper acetylacetonate (II) and the like. Monovalent copper is preferable, and copper (I) iodide is particularly preferable. These copper compounds are preferably used in an amount of 0.3-10.0 equivalents, particularly preferably 0.6-6.0 equivalents, relative to 1 equivalent of the palladium and / or nickel catalyst. .

  The reaction temperature is preferably 10 to 120 ° C., particularly preferably 30 to 100 ° C., and the reaction time can be suitably carried out in the range of 1 to 72 hours.

  The position at which a bond is formed by the coupling reaction of the tetrahalobenzene derivative represented by the general formula (12) and the reactant of the general formula (13) can be controlled by the type of halogen.

  That is, since the reactivity of iodine is the highest and the reactivity decreases in the order of bromine and chlorine, the reaction position can be arbitrarily determined by utilizing the reactivity of these halogen types.

Therefore, by synthesizing X ³ and X ⁴ in the general formula (12) with iodine and X ¹ with bromine and / or chlorine, synthesis to the dihalobenzene derivatives represented by the general formulas (9) and (10) is achieved. be able to.

  The production of the dihalobenzene derivative represented by the general formula (9) is preferably carried out under an inert atmosphere such as nitrogen or argon.

  The dihalobenzene derivative represented by the general formula (9) is coupled with 1,2-dichlorobenzene and a Grignard reagent with a nickel catalyst using the method of “Organic Synthesis”, 1978, Vol. 58, pages 127-133. Then, it can be synthesized by dihalogenation using the method of “Organic Letters”, 2004, Vol. 6, pp. 2457-2460.

Among the dihalobenzene derivatives represented by the general formula (10), those in which substituents R ⁶ and R ⁷ are combined to form a ring are described in, for example, “Synthesis”, 1988, pages 628-631. It can also be manufactured by a method.

The dihalobenzene derivative represented by the general formula (9) thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.
(Method for producing 3-halo-2-anthracenyl metal reagent)
A method for producing a 3-halo-2-anthracenyl metal reagent represented by the general formula (5) will be described.

  That is, when a 2,3-dihaloanthracene derivative represented by the following general formula (6) is lithiated using a lithiating agent, a compound in which M in the general formula (5) is a lithium atom can be produced. .

(Here, the substituents R ⁹ , R ¹⁰ , and X ² have the same meaning as the substituent represented by the general formula (5). N is an integer of 1 or 2.)
Further, after the lithiation, a reactant represented by the following general formula (7) can be reacted to produce a compound in which M is other than a lithium atom.

MY (7)
Here, the substituent M has the same meaning as the substituent other than lithium represented by the general formula (5). The substituent Y is a hydrogen atom, an iodine atom, a bromine atom, a chlorine atom, or an alkoxy having 1 to 20 carbon atoms. Group, or pinacolato boron.)
When the 2,3-dihaloanthracene derivative represented by the general formula (6) is lithiated, as long as the lithiating agent to be used can replace one halogen atom in the general formula (6) with lithium It is not specifically limited, For example, alkyl lithium, such as n-butyl lithium, sec-butyl lithium, tert-butyl lithium, methyl lithium, hexyl lithium; phenyl lithium, p-tert-butylphenyl lithium, p-methoxyphenyl lithium, p -Aryl lithium such as fluorophenyl lithium; lithium amide such as lithium diisopropylamide and lithium hexamethyldisilazide; lithium metal such as lithium powder. Alkyl lithium is preferable, and n-butyl lithium, sec-butyl lithium, and tert-butyl lithium are particularly preferable.

  The amount of the lithiating agent used is preferably 0.9 to 5.0 equivalents, particularly preferably 1.5 to 4.4, per 1 equivalent of the 2,3-dihaloanthracene derivative represented by the general formula (6). It can be used in the range of 0 equivalent, more preferably 1.8 to 3.5 equivalent.

  The lithiation reaction is preferably carried out in a solvent. The solvent to be used is not particularly limited, and examples thereof include THF, diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, diglyme, dioxane, toluene, pentane, hexane, cyclohexane and the like, preferably THF, diethyl ether, methyl tert-butyl ether. Yes, particularly preferably THF. These solvents may be used alone or as a mixture of two or more.

  The lithiation reaction temperature is preferably -90 to -30 ° C, more preferably -85 to -50 ° C, and particularly preferably -85 to -70 ° C. The reaction time is preferably 1 to 100 minutes, particularly preferably 5 to 60 minutes. The progress of the lithiation reaction can be monitored by taking out a part of the reaction solution, stopping the reaction with water, and then analyzing by gas chromatography.

  The lithium salt produced by the lithiation reaction is then reacted with a reactant represented by general formula (7). The reaction with such a reactive agent is a method of reacting the reaction mixture containing the lithium salt produced by the lithiation reaction by directly using the reactant, a method of isolating the produced lithium salt and then reacting with the reactant. Any of them may be used.

  The reactant used for the reaction of the lithium salt with the reactant is not particularly limited, and examples thereof include magnesium chloride, magnesium bromide, tri (isopropoxy) boron, trimethoxyboron, (pinacolato) boron chloride, (pinacolato) boron, Bis (pinacolato) diboron, chloride (catecholate) boron, (dimethyl) boron chloride, bicyclo [3,3,1] nona-9-boron chloride (9-BBN chloride), zinc chloride, zinc bromide, zinc iodide, Examples thereof include tributyltin chloride, copper (I) chloride, copper (II) chloride, copper (I) bromide, copper (II) bromide and the like. Tri (isopropoxy) boron and zinc chloride are preferable, and tri (isopropoxy) boron is particularly preferable.

  The reaction between the formed lithium salt and the reactant is preferably carried out in a solvent. The solvent to be used is not specifically limited, For example, the solvent used for the lithiation reaction can be mentioned. The amount of the reactant used is preferably 1.0 to 4.0 equivalents, particularly preferably 1.1 to 3.5 equivalents, relative to 1 equivalent of the 2,3-dihaloanthracene derivative of the general formula (6). . The reaction temperature with the reactant is preferably -90 to 50 ° C, particularly preferably -85 to 30 ° C, and the reaction time is preferably 1 to 30 hours, particularly preferably 1 to 18 hours.

  The production of the 3-halo-2-anthracenyl metal reagent of the general formula (5) of the present invention is preferably carried out under an inert atmosphere such as nitrogen or argon.

  The 3-halo-2-anthracenyl metal reagent represented by the general formula (5) thus obtained may be used as it is by treating with dilute hydrochloric acid, extracting with an organic solvent such as toluene or diethyl ether, and concentrating. For example, it can be purified by column chromatography or recrystallization. Alternatively, it can be used simply by concentrating.

  The 3-halo-2-anthracenyl metal reagent represented by the general formula (5) is, for example, 2,3-dibromoanthracene synthesized by the method described in “Synthesis”, 1988, pages 628-631 Can also be manufactured.

  In the above lithiation, for example, in the case of 1,2-dihalobenzene or 2,3-dihalonaphthalene, dimerization proceeds immediately when butyllithium is reacted at −78 ° C. or higher, and dihalobiphenyl or dihalobinaphthyl. (For example, “Journal of Organic Chemistry”, 1957, Vol. 22, pp. 447-449, or “Bretin of Chemical Society of Japan”, 2005, Vol. 78, 142-146. page). In order to suppress the dimerization, a low temperature of −90 ° C. or lower, preferably −100 ° C. or lower is required, which is not preferable economically and practically. However, in the case of the 2,3-dihaloanthracene derivative of the general formula (6), dimerization is not possible even when lithiated at -85 to -70 ° C, compared to 1,2-dihalobenzene or 2,3-dihalonaphthalene. It was found that by using 1.8 to 3.5 equivalents of a lithiating agent, a compound in which M in the general formula (5) is lithium can be obtained with good yield. Furthermore, it came to discover that the 3-halo-2-anthracenyl metal reagent shown by General formula (5) can be manufactured by making this Lithium compound and the reaction agent shown by General formula (7) react.

In addition, when M is a cyclic dialkoxyboron such as a copper atom, ZnBr, or pinacolatoboron among 3-halo-2-anthracenyl metal reagents represented by the general formula (5) of the present invention, the general formula ( 6) without necessarily undergoing lithiation of the 2,3-dihaloanthracene derivative represented by, for example, the 2,3-dihaloanthracene derivative of the general formula (6) and copper powder or zinc powder, or , 3-Dihaloanthracene derivative and bis (pinacolato) diboron can also be produced by a cross-coupling reaction in the presence of a palladium and / or nickel catalyst.
(Oxidation-resistant organic semiconductor materials)
Next, an oxidation resistant organic semiconductor material containing the biphenylene derivative represented by the general formula (1) of the present invention will be described. The oxidation-resistant organic semiconductor material is excellent in solubility in a solvent and oxidation resistance, and has suitable coating properties.

  The solvent used for dissolving the biphenylene derivative represented by the general formula (1) of the present invention is preferably a halogen-based solvent containing halogen such as chlorine, such as o-dichlorobenzene, chlorobenzene, 1,2-dichloroethane, 1,1. , 2,2-tetrachloroethane, chloroform; ether solvents containing 1 to 2 oxygens, such as THF, dioxane; aromatic hydrocarbon solvents such as toluene, xylene; ester solvents such as ethyl acetate, γ-butyrolactone; amide solvents such as N, N-dimethylformamide, N-methylpyrrolidone; and the like. These solvents may be used alone or as a mixture of two or more. Among them, preferred is toluene or o-dichlorobenzene.

  By mixing and stirring the above-mentioned solvent and the biphenylene derivative represented by the general formula (1), a solution of an oxidation-resistant organic semiconductor containing the biphenylene derivative represented by the general formula (1) can be prepared. The temperature in this case is preferably 10 to 200 ° C, particularly preferably 20 to 190 ° C. The concentration of the resulting solution can vary depending on the solvent and temperature, and is preferably 0.01 to 10.0% by weight. The solution can be prepared in air, but is preferably prepared in an inert atmosphere such as nitrogen or argon.

  Evaluation of the oxidation resistance of the oxidation-resistant organic semiconductor material containing the biphenylene derivative represented by the general formula (1) can be performed by a method in which the solution is brought into contact with air for a predetermined time. First, the solvent to be used is degassed in advance to remove dissolved oxygen. The contact time with air is suitably 0.5 minutes to 3 hours. The progress of oxidation can be performed by changing the color of the solution and detecting the oxide by gas chromatography and gas chromatography-mass spectrum (GCMS) analysis.

The solution of the oxidation-resistant organic semiconductor material containing the biphenylene derivative represented by the general formula (1) of the present invention has a relatively high cohesiveness because the biphenylene derivative itself represented by the general formula (1) used has an appropriate cohesiveness. Since it can be dissolved in a solvent at a low temperature and has oxidation resistance, it can be suitably applied to the production of an organic thin film by a coating method. That is, since it is not necessary to strictly remove air from the atmosphere, the coating process can be simplified. The coating can be carried out in the air, but is preferably performed under a nitrogen stream in consideration of drying of the solvent. In order to obtain suitable coating properties, the viscosity of the solution of the oxidation-resistant organic semiconductor material containing the biphenylene derivative represented by the general formula (1) of the present invention may be in the range of 0.005 to 20 poise. preferable.
(Organic thin film)
Next, an organic thin film using an oxidation-resistant organic semiconductor material containing a biphenylene derivative represented by the general formula (1) of the present invention will be described. Such an organic thin film can be produced by applying the above-mentioned oxidation-resistant organic semiconductor material solution to a substrate.

  The production of a thin film by coating on a substrate can be carried out by vaporizing the solvent by a method such as heating, air flow, and natural drying after the oxidation-resistant organic semiconductor material solution is coated on the substrate. The concentration of the compound of the general formula (1) in the solution is not particularly limited, and is preferably 0.01 to 10.0% by weight, for example. There is no particular limitation on the coating temperature, and for example, it can be suitably carried out between 20 ° C. and 200 ° C. The specific method of application is not particularly limited, and known methods such as spin coating, cast coating, and dip coating can be used. Further, it can be produced by using a printing technique such as screen printing, ink jet printing, or gravure printing. The material of the substrate to be used is not particularly limited, and various crystalline and non-crystalline materials can be used. Further, the substrate may be made of an insulating or dielectric material. Specific examples include plastic substrates such as polyethylene terephthalate, polymethyl methacrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol; glass, quartz, aluminum oxide, silicon, silicon oxide, tantalum dioxide, An inorganic material substrate such as tantalum pentoxide or indium tin oxide; a metal substrate such as gold, copper, chromium, or titanium can be preferably used. Further, the surfaces of these substrates can be used even if they are modified with silanes such as octadecyltrichlorosilane and octadecyltrimethoxysilane. Drying of the solvent after coating can be removed at normal pressure or reduced pressure, or may be performed by heating. Furthermore, crystal growth of the biphenylene derivative represented by the general formula (1) of the present invention can be controlled by adjusting the evaporation rate of the solvent. The film thickness of the thin film obtained by application to the substrate is not particularly limited, and is preferably 1 nm to 100 μm, particularly preferably 10 nm to 20 μm.

Since the biphenylene derivative represented by the general formula (1) of the present invention has a molecular structure with high plane rigidity, it can be expected to give excellent semiconductor characteristics. In particular, when the substituents R ⁶ and R ⁷ in the general formula (1) are naphthalene rings which may be bonded to each other, they can be easily dissolved in a solvent such as toluene and in a solution state. It is not oxidized by air. Therefore, a semiconductor thin film can be easily formed by a coating method. Therefore, the biphenylene derivative represented by the general formula (1) of the present invention is used for an organic semiconductor active phase of a transistor such as an electronic paper, an organic EL display, a liquid crystal display, or an IC tag, and further an organic EL display material and an organic semiconductor laser material. It can be used as an organic thin film solar cell material or a photonic crystal material.

  Provided are a biphenylene derivative having excellent oxidation resistance and capable of forming a semiconductor active phase by a coating method and its use. Furthermore, in the production method of the present invention, a biphenylene derivative having a substituent introduced therein can be produced, and a novel organic semiconductor material can be provided.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited only to these Examples.

For identification of the product, ¹ H NMR spectrum and mass spectrum were used. The ¹ H NMR spectrum was measured using JEOL GSX-270WB (270 MHz) manufactured by JEOL. Mass spectrum (MS) was measured by electron impact (EI) method (70 electron volts) by directly introducing a sample using JEOL JMS-700 manufactured by JEOL. UV-vis (ultraviolet visible absorbance) spectrum analysis was measured using UV-3100 manufactured by Shimadzu Corporation.

  For confirmation of the progress of the reaction, etc., gas chromatography and gas chromatography-mass spectrum (GCMS) analysis were used.

Gas chromatography analyzer Shimadzu GC14B
Column J & W Scientific, DB-1, 30m
Gas chromatography-mass spectrum analyzer Perkin Elmer Auto System XL (MS part; Turbomass Gold)
Column J & W Scientific, DB-1,30
X-ray diffraction measurement was performed under the following conditions.

Equipment RAD-C made by Rigaku Denki
X-ray CuKα ray (using graphite monochromator), 50 kV, 200 mA
Conditions θ-2θ scan, 3 ≦ 2θ ≦ 70 °, scan speed = 4.8 ° / min,
Continuous scan Measurement every 0.04 ° A commercially available dehydrated solvent was used as the solvent for reaction.

Synthesis Example 1 (Synthesis of 1,2-dibromo-4,5-diiodobenzene)
1,2-Dibromo-4,5-diiodobenzene was synthesized as follows according to “Sinlet”, 2003, pp. 29-34.

  Periodic acid 36.9 g (162 mmol) and sulfuric acid 150 ml were added to a 1 l three-necked flask equipped with a mechanical stirrer. After the periodic acid was dissolved, 80.7 g (486 mmol) of potassium iodide was added little by little. The temperature of the content was cooled to 0 ° C., and 75.0 g (318 mmol) of 1,2-dibromobenzene (manufactured by Wako Pure Chemical Industries) was added. The resulting mixture was stirred at 0 ° C. for 30 minutes. The reaction mixture was poured into ice and then filtered to remove the solid. The solid was recrystallized twice from THF / methanol to obtain white crystals of 1,2-dibromo-4,5-diiodobenzene (76.2 g, yield 49%).

¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.03 (s, 2H).
Synthesis Example 2 (Synthesis of 1,2-dibromo-4,5-diphenylbenzene)
Under a nitrogen atmosphere, 3.074 g (6.30 mmol) of 1,2-dibromo-4,5-diiodobenzene synthesized in Synthesis Example 1 in a 200 ml Schlenk reaction vessel, tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 600 mg (0.519 mmol) and 1.920 g (15.7 mmol) of phenylboronic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added. Further, 50 ml of toluene, 13 ml of ethanol, and an aqueous solution consisting of 4.007 g (37.8 mmol) of sodium carbonate and 16 ml of water were added. Heat to 82 ° C. and stir for 24 hours. After cooling to room temperature, toluene and water were added for phase separation. The organic phase was concentrated, and the resulting residue was dissolved in 26 ml of toluene, 1.0 ml of 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at room temperature for 2 hours. The toluene solution was washed twice with water, the organic phase was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (solvent, hexane), and then 1,2-dibromo-4,5-diphenylbenzene white A solid was obtained (1.953 g, 80% yield).

¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.67 (s, 2H), 7.24-7.13 (m, 6H), 7.12-6.90 (m, 4H).
MS m / z: 388 (M ⁺ , 100%), 308 (M ⁺ -Br, 23), 228 (
M ⁺ -2Br, 53).
Synthesis Example 3 (Synthesis of 1,2-dibromo-4,5-bis {4- (trifluoromethyl) phenyl} benzene)
Under a nitrogen atmosphere, 3.70 g (13.6 mmol) of 4-iodobenzotrifluoride and 28 ml of THF were added to a 100 ml Schlenk reaction vessel. The solution was cooled to −30 ° C., and 21 ml (13.6 mmol) of a THF solution of isopropyl magnesium bromide (manufactured by Kanto Chemical Co., Ltd., 0.65 M) was added dropwise. After aging for 30 minutes, 13 ml (13 mmol) of a diethyl ether solution of zinc chloride (manufactured by Sigma-Aldrich, 1.0 M) was added dropwise at that temperature. After gradually warming to room temperature, the produced pale yellow slurry was concentrated under reduced pressure. To the obtained maroon viscous material, 2.22-g (4.55 mmol) of 1,2-dibromo-4,5-diiodobenzene synthesized in Synthesis Example 1 and tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 174 mg (0.15 mmol) and 56 ml of THF were added. After carrying out the reaction at 65 ° C. for 4 hours, the reaction was stopped by cooling the vessel with water and adding 6 ml of 3N hydrochloric acid. Toluene and sodium chloride were added, and after phase separation, the organic phase was washed twice with water. The whole was concentrated under reduced pressure, and the solvent was distilled off. The obtained residue was dissolved in 15 ml of toluene, 0.23 ml of 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at room temperature for 2 hours. The toluene solution was washed twice with water, the organic phase was concentrated under reduced pressure, and the resulting residue was filtered through a column packed with silica gel (10 g) (solvent, hexane). The filtrate was concentrated under reduced pressure, and the resulting residue was subjected to vacuum distillation using a glass tube oven, and a fraction at 150 to 200 ° C. was taken out at 19 Pa (1.22 g). Further, this fraction was recrystallized and purified from heptane to obtain 1,2-dibromo-4,5-bis {4- (trifluoromethyl) phenyl} benzene crystals (842 mg, yield 35%).

¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.69 (s, 2H), 7.51 (d, J = 8.3 Hz, 2H), 7.20 (d, J = 8.1 Hz, 2H) ).
^{MS m / z: 524 (M} +, 52%), 444 (M + -Br, 10), 376 (M + - (Br + CF 3) +1,64), 364 (M + -2Br, 100).
Example 1 (Synthesis of 4,5,4 ′, 5′-tetraphenyl-2,2′-dibromo-1,1′-biphenyl) [Synthesis of dihalobiphenyl derivative]
Under a nitrogen atmosphere, 717 mg (1.85 mmol) of 1,2-dibromo-4,5-diphenylbenzene synthesized in Synthesis Example 2 and 14 ml of THF were added to a 100 ml Schlenk reaction vessel. This solution was cooled to −78 ° C., and 0.58 ml (0.92 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Inc., 1.59 M) was added dropwise. After raising the temperature to room temperature overnight, the produced solid was filtered out and washed with water. The obtained crude solid was recrystallized from toluene to obtain the desired white solid (481 mg, 84% yield).

¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.76 (s, 2H), 7.43 (s, 2H), 7.26-7.11 (m, 20H).
MS m / z: 616 (M ⁺ , 100%), 536 (M ⁺ -Br, 8), 456 (M ⁺ -2Br, 38).
The structural formula of the obtained 4,5,4 ′, 5′-tetraphenyl-2,2′-dibromo-1,1′-biphenyl is shown below.

Example 2 (Synthesis of 4,5,4 ′, 5′-tetrakis {4- (trifluoromethyl) phenyl} -2,2′-dibromo-1,1′-biphenyl) [Synthesis of dihalobiphenyl derivative]
Under a nitrogen atmosphere, 764 mg (1.46 mmol) of 1,2-dibromo-4,5-bis {4- (trifluoromethyl) phenyl} benzene synthesized in Synthesis Example 3 and 15 ml of THF were added to a 100 ml Schlenk reaction vessel. This solution was cooled to −78 ° C., and 0.46 ml (0.73 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) was added dropwise. After raising the temperature to room temperature overnight, saturated brine and toluene were added. The phases were separated and the organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase was filtered and concentrated under reduced pressure, and the resulting crude solid was recrystallized from hexane to obtain the desired white solid (214 mg, 33% yield).

¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.80 (s, 2H), 7.53 (dd, J = 12.2 Hz, 7.8 Hz, 8H), 7.43 (s, 2H), 7.29 (dd, J = 12.2 Hz, 7.8 Hz, 8H).
MS m / z: 888 (M ⁺ , 100%), 808 (M ⁺ -Br, 11), 728 (M ⁺ -2Br, 44).
The structural formula of the obtained 4,5,4 ′, 5′-tetrakis {4- (trifluoromethyl) phenyl} -2,2′-dibromo-1,1′-biphenyl is shown below.

Example 3 (Synthesis of 4,5,4 ′, 5′-tetrakis {4- (trifluoromethyl) phenyl} -2,2′-dibromo-1,1′-biphenyl) [Synthesis of dihalobiphenyl derivative]
Under a nitrogen atmosphere, 254 mg (0.48 mmol) of 1,2-dibromo-4,5-bis {4- (trifluoromethyl) phenyl} benzene synthesized in Synthesis Example 3 and 4 ml of THF were added to a 100 ml Schlenk reaction vessel. The solution was cooled to −10 ° C., and 0.65 ml (0.53 mmol) of a THF solution of isopropyl magnesium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., 0.81 M) was added dropwise. After aging for 1 hour, 0.5 ml (0.5 mmol) of a diethyl ether solution of zinc chloride (manufactured by Sigma-Aldrich, 1.0 M) was added dropwise. After gradually raising the temperature to room temperature, the produced slurry was concentrated under reduced pressure. To the obtained solid, 230 mg (0.44 mmol) of 1,2-dibromo-4,5-bis {4- (trifluoromethyl) phenyl} benzene synthesized in Synthesis Example 3 and tetrakis (triphenylphosphine) palladium ( Tokyo Chemical Industry Co., Ltd.) 41 mg (0.035 mmol) and THF 10 ml were added. The reaction was carried out at 67 ° C. for 40 hours. After cooling to room temperature, toluene and water were added for phase separation. The organic phase was concentrated, and the resulting residue was dissolved in 5 ml of toluene, 0.1 ml of 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at room temperature for 2 hours. The toluene solution was washed twice with water, the organic phase was concentrated under reduced pressure, and saturated brine and toluene were added to the resulting residue. The phases were separated and the organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase was filtered and concentrated under reduced pressure, and the resulting residue was filtered through a column packed with silica gel (solvent, hexane). The obtained crude solid was recrystallized from hexane to obtain the objective white solid (175 mg, yield 45%).

Example 4 (Synthesis of 2,3,6,7-tetraphenylbiphenylene) [Synthesis of biphenylene derivative]
In a nitrogen atmosphere, 253 mg (0.410 mmol) of 4,5,4 ′, 5′-tetraphenyl-2,2′-dibromo-1,1′-biphenyl synthesized in Example 1 and THF12. 5 ml was added. After cooling this solution to −75 ° C., 0.62 ml (0.99 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Inc., 1.59 M) was added dropwise. After stirring at −75 ° C. for 60 minutes, 168 mg (1.25 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The temperature was slowly raised to room temperature over 10 hours, and a 1N hydrochloric acid aqueous solution and toluene were added. The phases were separated and the organic phase was further washed with water and dried over anhydrous sodium sulfate. The organic phase was filtered and concentrated under reduced pressure, and the resulting crude solid was recrystallized from toluene to obtain the desired yellow crystals (103 mg, 55% yield).

¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.26-7.14 (m, 12H), 7.14-7.06 (m, 8H), 6.79 (s, 4H).
MS m / z: 457 (M ^{++ 1,} 51%), 456 (M ⁺ , 100%), 379 (M ⁺ -Ph, 3%), 228 (M ⁺ / 2, 7%).
The structural formula of the obtained 2,3,6,7-tetraphenylbiphenylene is shown below.

Example 5 (Synthesis of 2,3,6,7-tetrakis (p-trifluoromethylphenyl) biphenylene) [Synthesis of biphenylene derivative]
4,5,4 ′, 5′-tetrakis {4- (trifluoromethyl) phenyl} -2,2′-dibromo-1,1′-biphenyl synthesized in Example 2 in a 100 ml Schlenk reaction vessel under nitrogen atmosphere 162 mg (0.182 mmol) and 5.6 ml THF were added. After cooling this solution to -75 ° C, 0.24 ml (0.38 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Inc., 1.59 M) was added dropwise. After stirring at −75 ° C. for 60 minutes, 64 mg (0.48 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The temperature was slowly raised to room temperature over 10 hours, and a 1N hydrochloric acid aqueous solution and toluene were added. The phases were separated and the organic phase was further washed with water and dried over anhydrous sodium sulfate. The organic phase was filtered and concentrated under reduced pressure, and the resulting crude solid was recrystallized from toluene to obtain the desired yellow crystal (58 mg, 44% yield).

¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.48 (d, J = 8.1 Hz, 8H), 7.20 (d, J = 8.0 Hz, 8H), 6.81 (s, 4H) ).
MS m / z: 729 (M ^{+ +1,} 55%), 728 (M ⁺ , 100%), 364 (M ⁺ / 2, 5%).
The structural formula of the obtained 2,3,6,7-tetrakis (p-trifluoromethylphenyl) biphenylene is shown below.

Example 6 (Synthesis of 2,3,6,7-tetraphenylbiphenylene) [Synthesis of biphenylene derivative]
Under nitrogen atmosphere, 112 mg (0.182 mmol) of 4,5,4 ′, 5′-tetraphenyl-2,2′-dibromo-1,1′-biphenyl synthesized in Example 1 in a 20 ml Schlenk reaction vessel and copper powder 323 mg (5.08 mmol) (Sigma-Aldrich) was added. After stirring for 20 minutes, the reaction vessel was immersed in an oil bath at 230 ° C. After reacting at this temperature for 30 minutes, hot toluene extraction was performed. The toluene solution was cooled to room temperature. The precipitated solid was filtered to obtain yellow crystals of the target product (19 mg, yield 23%).

Example 7 (Oxidation resistance evaluation)
Under a nitrogen atmosphere, 10.4 g of toluene was added to a 100 ml Schlenk container, and dissolved oxygen was removed by repeating the cycle consisting of freezing (liquid nitrogen) -depressurization-nitrogen replacement-thawing three times. Thereto was added 10.5 mg of yellow crystals of 2,3,6,7-tetraphenylbiphenylene obtained in Example 4 and dissolved by heating at 110 ° C. to obtain a yellow transparent solution. Next, the stopper at the top of the Schlenk container was opened, air was introduced by contacting with external air for 1 hour, and the mixture was further stirred at 110 ° C. There were no new peaks due to oxidation in gas chromatography and gas chromatography-mass spectrum (GCMS) analysis.

Comparative Example 1
Under a nitrogen atmosphere, 28.9 g of toluene was added to a 100 ml Schlenk container, and dissolved oxygen was removed by repeating the cycle consisting of freezing (liquid nitrogen), reduced pressure, nitrogen substitution and thawing three times. When 3.0 mg of pentacene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and heated to 110 ° C. and dissolved, a reddish purple solution was obtained. Next, when the upper stopper of the Schlenk container was opened and air was introduced for 1 hour, the color of the solution changed to red pink. The mixture was further stirred at 110 ° C. From gas chromatography and gas chromatography-mass spectrum (GCMS) analysis, it was found that 6,13-pentacenequinone was produced.

  Further, when air was introduced into the solution with stirring at 110 ° C. for 1 hour, the color of the solution changed to pink. Gas chromatographic analysis showed increased production of 6,13-pentacenequinone.

Example 8 (Preparation of organic thin film)
Under a nitrogen atmosphere, 7.2 mg of 2,3,6,7-tetraphenylbiphenylene obtained in Example 4 was mixed with toluene (10.2 g), stirred at 80 ° C. for 1 hour, 2, 3, 6, A clear yellow solution of 7-tetraphenylbiphenylene was prepared.

  A quartz substrate having a concave surface was heated to 80 ° C. in an air atmosphere, and the above solution was applied onto the substrate using a dropper and dried under normal pressure to produce an organic thin film having a thickness of 480 nm. As a result of analyzing the components of the organic thin film by gas chromatography, there was no peak other than 2,3,6,7-tetraphenylbiphenylene, and it was not oxidized. Therefore, it was found that an organic thin film of 2,3,6,7-tetraphenylbiphenylene can be produced without being oxidized in the air.

  As a result of measuring the X-ray diffraction of the obtained organic thin film, a diffraction peak of a (00n) plane (n = 1 to 4) having an inter-plane distance of 1.36 nm was obtained, and it was found to be a crystalline film. .

  The X-ray diffraction pattern is shown in FIG.

  X-ray diffraction of only the quartz substrate used here was measured, but the peak intensity was weak and did not affect the X-ray diffraction peak of the organic thin film of 2,3,6,7-tetraphenylbiphenylene.

  The X-ray diffraction pattern of the quartz substrate is shown in FIG.

  From these results, the organic thin film was suitable for an organic semiconductor device.

Synthesis Example 4 (Synthesis of 2-phenyl-5-bromo-4-biphenylboronic acid)
Under a nitrogen atmosphere, 755 mg (1.95 mmol) of 1,2-dibromo-4,5-diphenylbenzene synthesized in Synthesis Example 2 and 12 ml of THF were added to a 100 ml Schlenk reaction vessel. The solution was cooled to −100 ° C., and 1.3 ml (2.1 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) was added dropwise. After aging for 30 minutes, 472 mg (2.51 mmol) of tri (isopropoxy) boron (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at that temperature. After gradually warming to room temperature, 3N hydrochloric acid was added and the phases were separated. The organic phase was concentrated under reduced pressure to obtain 680 mg of a white solid.

Example 9 (Synthesis of 4 ′, 5′-diphenyl-2,2′-dibromo-1,1′-naphthobiphenyl) [Synthesis of dihalobiphenyl derivative]
2,3-Dibromoanthracene was synthesized as follows according to “Synthesis”, 1988, pp. 628-630.

  Under a nitrogen atmosphere, 0.5 g (1.49 mmol) of 6,7-dibromo-1,4-dihydroanthracene was dissolved in 100 ml of benzene in a 300 ml Schlenk reaction vessel. Dichlorodicyanobenzoquinone 0.60 g (2.51 mmol) was added, and the mixture was stirred for 4 hours under reflux conditions. The produced insoluble hydroquinone was filtered off while hot and removed from the solution. When the obtained solution was cooled to room temperature, a yellow solid of 2,3-dibromoanthracene precipitated. After filtration, drying and concentration under reduced pressure, 180 mg of a yellow solid was obtained (180 mg, 48% yield).

¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.33 (s, 2H), 8.31 (s, 2H), 7.98 (dd, J = 6.6 Hz, 3.2 Hz, 2H), 7.50 (dd, J = 6.6 Hz, 3.2 Hz, 2H).
^{The 1} H NMR spectrum is shown in FIG.

  Under a nitrogen atmosphere, 194 mg of 2-phenyl-5-bromo-4-biphenylboronic acid synthesized in Synthesis Example 4 in a 100 ml Schlenk reaction vessel, 144 mg (0.43 mmol) of 2,3-dibromoanthracene, tetrakis (triphenylphosphine) palladium (Tokyo Chemical Industry Co., Ltd.) 25 mg (0.022 mmol), toluene 4.0 ml, and ethanol 0.9 ml were added. Further, a solution consisting of 273 mg (2.58 mmol) of sodium carbonate and 1.1 ml of water was added, and the mixture was reacted at 85 ° C. for 10 hours. After cooling to room temperature, toluene and brine were added for phase separation, and the organic phase was washed with brine. The organic phase was concentrated under reduced pressure, the solvent was distilled off, and further heated and dried under vacuum. The obtained residue was dissolved in toluene, 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.04 ml) was added, and the mixture was stirred at room temperature for 2 hours. This solution was washed with water, and the organic phase was concentrated under reduced pressure. The residue was dissolved with hexane and chloroform and passed through a column packed with silica gel. The eluate was concentrated, and the resulting crude solid was washed with hexane to obtain the desired product (124 mg, yield 51%).

MS m / z: 564 (M ⁺ , 100%), 484 (M ⁺ -Br, 11), 404 (M ⁺ -2Br, 31).
The structural formula of the obtained 4 ′, 5′-diphenyl-2,2′-dibromo-1,1′-naphthobiphenyl is shown below.

Example 10 (Synthesis of 3-bromo-2-anthracenyl lithium) [Synthesis of 3-halo-2-anthracenyl metal reagent]
Under a nitrogen atmosphere, 443 mg (1.32 mmol) of 2,3-dibromoanthracene and 46 ml of THF were added to a 100 ml Schlenk reaction vessel. This solution was cooled to −83 ° C., and 2.5 ml (4.0 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Inc., 1.59 M) was added dropwise. After aging for 30 minutes, a mixture of 1673 mg (6.59 mmol) of iodine and 8 ml of THF was added dropwise at that temperature. After gradually warming to room temperature, 3N hydrochloric acid was added and the phases were separated. The organic phase was concentrated under reduced pressure to give a yellow solid (269 mg, 53% yield).

¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.62 (s, 1H), 8.33 (s, 1H), 8.30 (s, 1H), 8.29 (s, 1H), 7 .99 (dd, J = 6.6 Hz, 3.2 Hz, 2H), 7.50 (dd, J = 6.6 Hz, 3.2 Hz, 2H).
^{The 1} H NMR spectrum is shown in FIG.

MS m / z: 384 (M ^{+ +1,} 99%), 382 (M ⁺ −1,100), 255 (M ⁺ −1−I, 14), 176 (M ⁺ −I−Br, 88).
From the above, it was found that 3-bromo-2-iodoanthracene was produced, and thus 3-bromo-2-anthracenyl lithium was synthesized.

  The structural formula of synthesized 3-bromo-2-anthracenyl lithium is shown below.

Example 11 (Synthesis of 3-bromo-2-anthracenylboronic acid) [Synthesis of 3-halo-2-anthracenyl metal reagent]
Under a nitrogen atmosphere, 299 mg (0.890 mmol) of 2,3-dibromoanthracene and 31 ml of THF were added to a 100 ml Schlenk reaction vessel. The solution was cooled to −83 ° C., and 1.7 ml (2.7 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) was added dropwise. After aging for 15 minutes, 595 mg (3.16 mmol) of tri (isopropoxy) boron (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at that temperature. After gradually warming to room temperature, 3N hydrochloric acid was added and the phases were separated. The organic phase was concentrated under reduced pressure to obtain 332 mg of a yellow solid.

  The structural formula of the obtained 3-bromo-2-anthracenylboronic acid is shown below.

Example 12 (Synthesis of 4 ′, 5′-di (n-hexyl) -2′-iodo-2-bromo-1,1′-naphthobiphenyl) [Synthesis of dihalobiphenyl derivative]
1,2-di (n-hexyl) benzene is obtained from 1,2-dichlorobenzene and n-hexylmagnesium bromide with reference to the method of “Organic Synthesis”, 1978, Vol. 58, pages 127-133. 2-Di (n-hexyl) -4,5-diiodobenzene is 1,2-di (n-hexyl) benzene by referring to the method of “Organic Letters”, 2004, Vol. 6, pp. 2457-2460. This was synthesized as follows by diiodination.

  Under a nitrogen atmosphere, 2.7 ml (24.0 mmol) of 1,2-dichlorobenzene, 66 mg (0.12 mmol) of nickel chloride {bis (diphenylphosphino) propane}, and 18 ml of diethyl ether were added to a 200 ml Schlenk reaction vessel. The mixture was cooled to 0 ° C., and 30 ml (60 mmol) of a diethyl ether solution of n-hexylmagnesium bromide (manufactured by Sigma-Aldrich, 2.0M) was added dropwise. After 6 hours of reaction at 35 ° C., 3N hydrochloric acid was added to stop the reaction. Extracted with diethyl ether and the organic phase was washed with water and saturated aqueous sodium bicarbonate. It dried with calcium chloride and concentrated the solvent under reduced pressure. The residue was distilled under reduced pressure (0.15 mmHg, 100 ° C.) to obtain a liquid of 1,2-di (n-hexyl) benzene (5.43 g, yield 85%).

  Under a nitrogen atmosphere, in a 100 ml Schlenk reaction vessel, 5.43 g (20.5 mmol) of 1,2-di (n-hexyl) benzene, 2.00 g (8.76 mmol) of periodic acid dihydrate, 7.18 g of iodine (28.3 mmol), 11.4 ml acetic acid, 2.3 ml water, and 0.34 ml sulfuric acid were added. After stirring at 70 ° C. for 7 hours, 1.00 g of periodic acid dihydrate, 3.33 g of iodine, 6.0 ml of acetic acid, 1.2 ml of water, and 0.20 ml of sulfuric acid were added, and the mixture was stirred at 70 ° C. for 8 hours. Stir. After cooling to room temperature, an aqueous sodium hydrogen sulfite solution was added to stop the reaction. Extraction was performed with dichloromethane, and the organic phase was washed with water and then dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (hexane), followed by hexane recrystallization at −78 ° C. to obtain 1,2-di (n-hexyl) -4,5. -Diiodobenzene was obtained (7.40 g, yield 72%).

¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.60 (s, 2H), 2.47 (t, J = 7.6 Hz, 4H), 1.60-1.18 (m, 16H), 0.89 (t, J = 6.8 Hz, 6H).
^{The 1} H NMR spectrum is shown in FIG.

  In a 100 ml Schlenk reaction vessel under a nitrogen atmosphere, 332 mg of 3-bromo-2-anthracenylboronic acid obtained in Example 11 and 347 mg of 1,2-di (n-hexyl) -4,5-diiodobenzene (0 .696 mmol), tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 41 mg (0.035 mmol), toluene 10 ml, and ethanol 2.6 ml were added. Further, a solution consisting of 295 mg (2.78 mmol) of sodium carbonate and 3.2 ml of water was added, and the mixture was reacted at 80 ° C. for 8 hours. After cooling to room temperature, toluene and brine were added for phase separation, and the organic phase was washed with brine. The organic phase was concentrated under reduced pressure, the solvent was distilled off, and further heated and dried under vacuum. The obtained residue was dissolved in toluene, 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.2 ml) was added, and the mixture was stirred at room temperature for 2 hours. This solution was washed with water, and the organic phase was concentrated under reduced pressure. The residue was dissolved in the residue and purified by column chromatography packed with silica gel (solvent; hexane: chloroform = 10: 1) to obtain the desired product (280 mg, yield 64%).

¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.40 (s, 1H), 8.38 (s, 1H), 8.35 (s, 1H), 8.06-7.96 (m, 2H), 7.85 (s, 1H), 7.73 (s, 1H), 7.53-7.46 (m, 2H), 7.12 (s, 1H), 2.68-2.50. (M, 4H), 1.70-1.22 (m, 16H), 0.98-0.78 (m, 6H).
^{The 1} H NMR spectrum is shown in FIG.

MS m / z: 628 (M ^{+ +1,} 100%), 626 (M ⁺ −1, 97), 487 (M ⁺ + 2—C ₁₀ H ₂₂ , 12), 485 (M ⁺ —C ₁₀ H ₂₂ , 12 ), 359 (M ⁺ + 1-C ₁₀ H ₂₂ -I, 5), 279 (M ⁺ + 1-C ₁₀ H ₂₂ -I-Br, 22).
The structural formula of the obtained 4 ′, 5′-di (n-hexyl) -2′-iodo-2-bromo-1,1′-naphthobiphenyl is shown below.

Example 13 (Synthesis of 2,3-diphenylnaphthobiphenylene) [Synthesis of biphenylene derivative]
Under a nitrogen atmosphere, 110 mg (0.19 mmol) of 4 ′, 5′-diphenyl-2,2′-dibromo-1,1′-naphthobiphenyl synthesized in Example 9 and 7 ml of THF were added to a 100 ml Schlenk reaction vessel. After cooling this solution to −75 ° C., 0.29 ml (0.46 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Inc., 1.59 M) was added dropwise. After stirring at −75 ° C. for 60 minutes, 77 mg (0.57 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The temperature was slowly raised to room temperature over 10 hours, and a 1N hydrochloric acid aqueous solution and toluene were added. The phases were separated and the organic phase was further washed with water and dried over anhydrous sodium sulfate. The organic phase was filtered and concentrated under reduced pressure, and the resulting crude solid was recrystallized from toluene to obtain the desired yellow crystals (32 mg, yield 42%).

MS m / z: 404 (M ⁺ , 100%), 202 (M ⁺ / 2, 4).
The structural formula of the obtained 2,3-diphenylnaphthobiphenylene is shown below.

Example 14 Synthesis of 2,3-di (n-hexyl) naphthobiphenylene [Synthesis of biphenylene derivative]
Under a nitrogen atmosphere, 278 mg (0.443 mmol) of 4 ′, 5′-di (n-hexyl) -2′-iodo-2-bromo-1,1′-naphthobiphenyl synthesized in Example 12 in a 100 ml Schlenk reaction vessel. And 9.5 ml of THF were added. After cooling this solution to -90 ° C, 0.68 ml (1.1 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Inc., 1.59 M) was added dropwise. After stirring at −90 ° C. for 15 minutes, 214 mg (1.59 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The temperature was slowly raised to room temperature over 10 hours, and 3N hydrochloric acid and toluene were added. The phases were separated and the organic phase was further washed with water and dried over anhydrous sodium sulfate. The organic phase was filtered and concentrated under reduced pressure, and the resulting residue was washed with hexane to obtain the desired yellow solid (22 mg, 12% yield).

¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.91 (s, 2H), 7.80 (dd, J = 6.3 Hz, 3.2 Hz, 2H), 7.38 (dd, J = 6 .3 Hz, 3.2 Hz, 2H), 6.99 (s, 2H), 6.89 (s, 2H), 2.54 (t, J = 7.6 Hz, 4H), 1.63-1.24 (M, 16H), 0.91 (t, J = 7.1 Hz, 6H).
^{The 1} H NMR spectrum is shown in FIG.

MS m / z: 421 (M ^{+ +1,} 35%), 420 (M ⁺ , 100), 279 (M ⁺ + 1-C ₁₀ H ₂₂ , 55), 210 (M ⁺ / 2, 1).
The structural formula of the obtained 2,3-di (n-hexyl) naphthobiphenylene is shown below.

Example 15 (Oxidation resistance evaluation)
Under a nitrogen atmosphere, 8.4 g of toluene was added to a 100 ml Schlenk container, and dissolved oxygen was removed by repeating the cycle of freezing (liquid nitrogen) -depressurization-nitrogen replacement-thawing three times. Thereto was added 6.7 mg of a yellow solid of 2,3-di (n-hexyl) naphthobiphenylene obtained in Example 14, and the mixture was dissolved by heating at 110 ° C. to obtain a yellow transparent solution. Next, the stopper at the top of the Schlenk container was opened, air was introduced by contacting with external air for 1 hour, and the mixture was further stirred at 110 ° C. There were no new peaks due to oxidation in gas chromatography and gas chromatography-mass spectrum (GCMS) analysis.

Example 16 (Preparation of organic thin film)
Under a nitrogen atmosphere, 8.2 mg of 2,3-di (n-hexyl) naphthobiphenylene obtained in Example 14 was mixed with toluene (10.2 g), and stirred at 80 ° C. for 1 hour. A yellow transparent solution of (n-hexyl) naphthobiphenylene was prepared.

  A quartz substrate having a concave surface was heated to 80 ° C. in an air atmosphere, and the above solution was applied onto the substrate using a dropper and dried under normal pressure to produce an organic thin film having a thickness of 670 nm. As a result of analyzing the components of this organic thin film by gas chromatography, there was no peak other than 2,3-di (n-hexyl) naphthobiphenylene, and it was not oxidized. Therefore, it was found that an organic thin film of 2,3-di (n-hexyl) naphthobiphenylene can be produced without being oxidized even in the air.

  As a result of measuring X-ray diffraction of the obtained organic thin film, it was found that the organic thin film had crystallinity because a sharp diffraction line was observed. The broad peak is derived from the quartz substrate used.

  The X-ray diffraction pattern is shown in FIG.

  The UV-vis spectrum is shown in FIG. Since the maximum absorption wavelength was 450 nm, the optical band gap was 2.76 eV.

  From the X-ray diffraction pattern and the UV-vis spectrum, the organic thin film enables charge carrier movement and is suitable for an organic semiconductor device.

X-ray diffraction pattern of organic thin film of Example 8 X-ray diffraction pattern of the quartz substrate of Example 8 ¹ H NMR spectrum of 2,3-dibromoanthracene in Example 9 (CDCl ₃ , 22 ° C.) ¹ H NMR spectrum (CDCl ₃ , 22 ° C.) of 3-bromo-2-iodoanthracene of Example 10 ¹ H NMR spectrum (CDCl ₃ , 22 ° C.) of 1,2-di (n-hexyl) -4,5-diiodobenzene in Example 12 ¹ H NMR spectrum (CDCl ₃ , 22 ° C.) of 4 ′, 5′-di (n-hexyl) -2′-iodo-2-bromo-1,1′-naphthobiphenyl of Example 12 ¹ H NMR spectrum (CDCl ₃ , 22 ° C.) of 2,3-di (n-hexyl) naphthobiphenylene of Example 14 X-ray diffraction pattern of organic thin film of Example 16 UV-vis spectrum of the organic thin film of Example 16

Claims (8)

A biphenylene derivative represented by the following general formula (2) .

(Here, the substituents R ² and R ³ are the same or different and represent a hydrogen atom, a phenyl group, or an alkyl group having 5 to 20 carbon atoms. The substituents R ⁹ and R ¹⁰ are the same or different and represent a hydrogen atom, Represents an alkyl group having 1 to 20 carbon atoms, and n is 1.) The biphenylene derivative according to claim 1, which is 2,3-diphenylnaphthobiphenylene or 2,3-di (n-hexyl) naphthobiphenylene . An oxidation-resistant organic semiconductor material comprising the biphenylene derivative according to claim 1. An organic thin film comprising the oxidation-resistant organic semiconductor material according to claim 3 . The method for producing a biphenylene derivative according to claim 1 or 2 , wherein a dihalobiphenyl derivative represented by the following general formula (4) is dilithiated or diglynarized and then reacted with a copper compound .

(Here, the substituents R ² , R ³ , R ⁹ , and R ¹⁰ have the same meaning as the substituent represented by the general formula (2), and X ¹ and X ² represent a bromine atom, an iodine atom, or a chlorine atom. And n is 1.) The dihalobiphenyl derivative is 4 ′, 5′-diphenyl-2,2′-dibromo-1,1′-naphthobiphenyl or 4 ′, 5′-di (n-hexyl) -2′-iodo-2-bromo. The method for producing a biphenylene derivative according to claim 5, which is -1,1′-naphthobiphenyl. The method for producing a biphenylene derivative according to claim 5 or 6, wherein the copper compound is a divalent copper compound . The method for producing a biphenylene derivative according to claim 7, wherein the divalent copper compound is copper chloride (II) or copper bromide (II).

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