JPS62255465A - Production of 7,7,8,8-tetracyanoquinodimethane, its substituted compound and their intermediate - Google Patents

Abstract

PURPOSE:To produce the titled compound useful as a photosensitive material for electrophotography, etc., on an industrial scale at a low cost from an easily available terephthaloyl cyanide derivative via 1,4-bis(acyloxydicyanomethyl) benzene compound in 3 steps. CONSTITUTION:The objective compound of formula IV useful as an electronic material such as capacitor and heat-sensitive material, etc., or photoconductive composite material can be produced from an easily available raw material in high yield under a condition to facilitate the operation, by (1) reacting a compound of formula I (R1-R4 are H, 1-10C alkyl, 1-10C alkoxy, halogen or CN) with an acid chloride of formula R<5>COCl (R<5> is 1-3C alkyl, phenyl or substituted phenyl) in the presence of a salt of hydrogen cyanide using a phase-transfer catalyst such as crown ether, quaternary ammonium salt or quaternary phosphonium salt, (2) converting the resultant compound of formula II to a compound of formula III by reductive deacyloxylation reaction and (3) subjecting the compound to dehydrogenation reaction with an oxidizing agent.

Description

[Detailed Description of the Invention] [Industrial Application Field] What is the present invention? , 7,8.8-tetracyanoquinodimethane (abbreviated as TGNQ), substituted TCNQ, and a method for producing an intermediate obtained in an intermediate process up to obtaining TCNQ.

TCNQ according to the present invention is an excellent pi (π)-7 acceptor, and forms charge transfer complexes with pi donors such as tetrathiafulvalene (TTF), and also forms TCNQ salts with various cations. These charge transfer complexes and TCNQ
Salts have high electrical conductivity and are useful compounds that are applied to electronic materials such as capacitors and heat-sensitive materials, and photosensitive materials for electrophotography as photoconductive composite materials.

[Prior art] Conventionally, as a method for producing a TCNQ derivative, 1) 1.4-
Synthesis method from cyclohexanedione and malonitrile: D. Nis. Alakar et al.

Journal of the American Chemical Society, No. 84! ! 5.3370 pages (19Ei 2nd year)
[I], S.

Acker et al., J. Am. Chem.
, Soc, 84.3370°1962] 2) Method for synthesis from p-quijilene dihalide: R. C. Leyland et al., Journal of Organic Chemistry, Vol. 40.

3101 pages (1975) [R, C, Wbela
nd et aL, J.

Org, Chew,, 40.3101.1!975
] 3) A method of synthesis from 1,4-cyclohexadiene (Asahi Kasei Patent No. 48-10888) 4) A method of synthesis from p-shortbenzene and malonitrile is known.

[Problems to be Solved by the Invention] However, the above method has the following problems.

In methods 1) and 4), raw materials are difficult to obtain or synthesize, and expensive malononitrile must be used.

In method 2), the reaction route is long and there are steps that must be carried out under anhydrous reaction conditions.

In method 3), it is difficult to obtain or synthesize raw materials, and it is necessary to conduct the reaction under anhydrous reaction conditions.

The reactions 2) and 3) have drawbacks such as the risk of generating hydrogen cyanide when water is mixed.

[Means for solving the problems] In order to improve the shortcomings of the conventional method, the present inventors have developed TC:NQ,
As a result of our intensive efforts to develop new methods for producing substituted TCNQ and their intermediates, we have succeeded in producing highly efficient substituted TCNQ and substituted TCNQ from easily available terephthalic acid chloride derivatives.
and a method for producing intermediates thereof, and have completed the present invention.

The present invention is based on a known method using readily available terephthalic acid chloride derivatives [Niss Yamaguchi et al., Chemical Letters, p. 689, 1985 (S.

Yamaguchi et al., Chew
, Latt, , 889. 1985] is a method for producing TC:NQ, substituted TCNQ, and intermediates thereof using a terephthaloyl cyanide derivative that can be efficiently synthesized as a starting material.

That is, according to the present invention, the following manufacturing methods i) and ii) are provided.

i) General formula (I): (R1, R2, R3, RA in the formula are each hydrogen, 1-
It represents an alkyl group having 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogen atom, or a cyan group. ) Terephthaloyl cyanide represented by the general formula (■)
: R5GO11J' (II) (R5 represents an alkyl group having 1 to 3 carbon atoms, a phenyl group or a substituted phenyl group.) In the presence of an acid chloride and a salt of hydrogen cyanide,
The reaction is carried out using a phase transfer catalyst as a catalyst, and R1, R2, R3, R4, and R5 in the general formula (■): C are the same as above.

) A method for producing the compound [1,4-bis(acyloxydicyanomethyl)benzene J].

i) A compound of general formula (III) is obtained by the method of 1) above, and then the compound of general formula (m) is subjected to a reductive membrane acyloxylation reaction to obtain general formula (IV) (71. R2, R3, R4 are the same as above) [1,4-bisdicyanomethylbenzene J] was obtained, and then the compound of general formula (r17) was subjected to a dehydrogenation reaction with an oxidizing agent to obtain general formula (V ): A method for producing TCNQ and substituted TC:NQ represented by (in the formula, R1, R2, R3, R4 are the same as above).

The compound represented by the general formula (I) used as a starting material in method i) can be prepared by a known method [such as Nis Yamaguchi, etc.] using terephthalic acid chloride and cupric cyanide.
Letter, 689 pages, 1985 (S, Yamagu
chi et al, Chem, Lett,
889°1985] to produce a compound represented by general formula (I).

The terephthalic acid dichloride used here specifically includes terephthalic acid dichloride; 2-chloroterephthalic acid dichloride, 2-bromoterephthalic acid dichloride, 2-iodoterephthalic acid dichloride, 2,5-dichloroterephthalic acid dichloride, 2, Halogen-substituted terephthalic acid dichloride such as 5-dibromoterephthalic acid dichloride; alkyl-substituted such as 2-methylterephthalic acid dichloride, 2-ethyl terephthalic acid dichloride, 2,5-dimethylterephthalic acid dichloride, and 2.5-diethyl terephthalic acid dichloride Terephthalic acid dichloride; examples include flukoxy-substituted terephthalic acid dichloride such as 2-methoxyterephthalic acid dichloride, 2-ethoxyterephthalic acid dichloride, 2,5-diethyl terephthalic acid dichloride, 2,3,5.8-tetracyano terephthalic acid dichloride, etc. can do.

Compound (I) is reacted with a salt of hydrogen cyanide and an acid chloride in the presence of a phase transfer catalyst to produce compound (III).

The reaction formula is represented by (m) (In the formula, R1, R2, R3, R4, and 1175 are the same as above. M represents a metal such as lithium, sodium, potassium, ammonium, copper, or silver.)

In this reaction, a phase transfer catalyst is an essential condition for the reaction, and in the absence of a phase transfer catalyst, the reaction will hardly proceed and the target compound (III) cannot be obtained.

Specific examples of the salts of hydrogen cyanide used in the present invention include alkali metal salts such as lithium cyanide, sodium cyanide, and potassium cyanide; ammonium cyanide; metal salts such as copper cyanide and silver cyanide. .

The amount of hydrogen cyanide or its salts to be used per mole of reaction raw materials is in the range of 2 to 10 moles, preferably 3 to 5 moles.

General formula (■) used in the present invention: R5GOCI! (II) (1175 represents an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a substituted phenyl group) Specifically, examples of the acid chloride include fatty acid chlorides such as acetyl chloride and propionic acid chloride;
Benzoic acid chloride, 0-toluic acid chloride, m-
) Toluic acid chloride, p-toluic acid chloride, 2
Examples include various substituted benzoic acid chlorides such as -methoxybenzoic acid chloride, 4-methoxybenzoic acid chloride, 0-chlorobenzoic acid chloride, and p-chlorobenzoic acid chloride.

The amount of the acid chloride represented by the general formula (II) to be used per 1 mol of the compound of the general formula (I) is in the range of 2 to 10 mol, preferably 3 to 5 mol.

Examples of the phase transfer catalyst used in the present invention include crown ethers, quaternary ammonium salts, and phosphonium salts. Specifically, 15-crown-
5,18-crown-6, dicyclohexyl 18-crown-6, dicyclohexyl 24-crown-8, dibenzo 18-crown-6, dibenzo 24-crown-8
crown ethers such as; quaternary ammonium salts such as tetrabutylammonium halide and benzyltriethylammonium halide; and phosphonium salts such as tetrabutylphosphonium halide and methyltriphenylphosphonium halide.

The amount of phase transfer catalyst used relative to compound (n) is 0.0
0.001 mole to 0.5 mole, preferably 0.005 to 0.1 mole.

Examples of the reaction solvent include acetonitrile; ethers such as dioxane, tetrahydrofuran, and ethyl ether; halogenated hydrocarbons such as methylene chloride, chloroform, and dichloroethane; and aromatic compounds such as benzene and toluene.

The reaction temperature is room temperature to 100°C, preferably room temperature to 100°C.
The temperature range is 50°C.

In order to obtain the desired TCNQ, compound (III)
is subjected to a reductive deacyloxylation reaction with a metal powder and a Lewis acid to produce compound (IV).

The reaction formula is (m) (IV) (R1 in the formula
, R2, R3, R4, and R5 are the same as above. ).

Specific examples of the metal powder used in this reaction include metals such as zinc magnesium, aluminum, iron, lead, and nickel.

The amount of metal powder used per 1 mol of compound (III) is in the range of 2 to 100 mol, preferably 5 to 20 mol.

Specifically, the Lewis acids used in this reaction include hydrochloric acid, sulfuric acid,
Mineral acids such as nitric acid and phosphoric acid; Carboxylic acids such as acetic acid and propionic acid; methanesulfonic acid, benzenesulfonic acid,
Examples include sulfonic acids such as p-toluenesulfonic acid.

The amount of Lewis acid used per 1 mol of compound (III) is in the range of 4 to 200 mol, preferably 10 to 40 mol.

Specifically, the reaction solvent is acetic acid; tetrahydrofuran;
Examples include ethers such as dioxane, ethyl ether, and isopropyl ether; water; alcohols such as methanol, ethanol, and isopropyl alcohol; and aromatic hydrocarbons such as benzene toluene.

The reaction temperature is room temperature to 100°C, preferably room temperature to 100°C.
The temperature range is 50°C.

The reductive deacyloxylation reaction is not limited to the above method.

Next, compound (IV) is subjected to a dehydrogenation reaction with an oxidizing agent,
The target compound (V) is produced.

The reaction is expressed by the following formula: %Formula %() (R1, R2, R3, and R4 in the formula are the same as above).

Specific examples of the oxidizing agent used in this reaction include halogens such as chlorine, bromine, and bromine water; and N-halogenosuccinimides such as N-chlorsuccinimide, N-bromsuccinimide, and N-iodosuccinimide. I can do it.

The amount of these oxidizing agents used per i mole of compound (rv) is in the range of 1 to 5 moles, preferably 1 to 2 moles.

Examples of the reaction solvent include water, acetonitrile, methanol, and the like.

The reaction temperature is 0°C to 60°C, preferably 0°C to 3°C.
It is in the range of 0°C.

[Example 1] Next, the method of the present invention will be specifically explained with reference to Examples.

Example 1 Terephthaloyl cyanide (5.0 g, 27 mmoi'
) and benzoic acid chloride (20.0g, 143mmo
Dissolve j2) in acetonitrile (50+*j), potassium cyanide (9.0 g, 138 mmof) and 1
8-Crown-6 (0,38g.

1.38 mmai') and stirred at room temperature for 6 hours.

After the reaction is completed, insoluble matter is separated by furnace, and solid matter is washed with acetonitrile. The filtrate and acetonitrile wash are concentrated together under reduced pressure. Add ethanol (100+5
Add i)) and cool with ice water to crystallize. The precipitated crystals are collected in a furnace. This was recrystallized from acetonitrile to obtain 5.4 g of 1,4-bis(dicyanobenzoyloxymethyl)benzene (yield: 45%).

Examples 2 to 6 Table 1 was used instead of benzoyl chloride used in Example 1.
The same reaction as in Example 1 was carried out except that the acid chloride shown in Example 1 was used.

Table 1 Examples 7 to 10 The same reaction as in Example 1 was carried out except that the substituted terephthaloyl cyanide shown in Table 2 was used instead of the terephthaloyl cyanide used in Example 1.

Table 2 Examples 11 to 15 The same reaction as in Example 1 was carried out except that the hydrocyanate shown in Table 3 was used instead of the potassium cyanide used in Example 1.

Table 3 Examples 18 to 18 The same reaction as in Example 1 was carried out except that the solvent shown in Table 4 was used instead of acetonitrile used in Example 1.

Table-4 Examples 18 to 27 Table-5 instead of 18-crown-6 used in Example 1
The same reaction as in Example 1 was conducted except that the phase transfer catalyst shown in Example 1 was used.

Table-5 Example 28 1,4-bisdicyanomethylbenzene (1,0g.

Add bromine (0.84 g, 5.3 mmoi) to water (30 mi') and stir while cooling with water.
'). After stirring for 30 minutes, the solids are filtered out and washed twice with water. After drying the solid matter,
Recrystallize with methylene chloride to obtain 0.84g of TCNQ.
(yield 85%).

Examples 29 to 32 Same as Example 2B except that the substituted 1,4-bisdicyanomethylbenzene shown in Table 6 was used instead of the 1,4-bisdicyanomethylbenzene used in Example 2s. The reaction was carried out to obtain substituted TGNQ. The yield of substituted TCNQ is also listed in Table 6.

Table-6 Example 33 1,4-bisdicyanomethylbenzene (1,0g.

Dissolve 4.8 liters of moj7) in acetonitrile (5011 liters) and add N-iodosuccinimide (1.6 g,
7.2 mmoR) and stir for 30 minutes. After the reaction was completed, water (100mi) was added and the precipitated crystals were separated by 7p.
Separate. After washing the crystals with water, dry them. Recrystallization was performed with methylene chloride to obtain 0.84 g of TCNQ (yield: 85%).
).

Examples 34-35 Example 33 except that the oxidizing agent shown in Table 7 was used instead of N-iodosuccinimide used in Example 33.
The same reaction as above was carried out to obtain TCNQ. Table 7 shows the yield.
Also listed in

Table 7 [Effects of the Invention] As described above, according to the present invention, by using a terephthaloyl cyanide derivative that is easy to obtain or synthesize as a starting material, TCNQ
, substituted TC:NQ and their intermediates can be obtained in high yields. electronic materials such as capacitors and heat-sensitive materials;
The present invention is of great significance in the sense that it provides a new industrial method for producing TGNQ and substituted TCNQ, which are expected to be used in rapidly increasing amounts in the future as photoconductive composite materials for electrophotographic photosensitive materials and the like.

Claims (3)

[Claims] (1) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1, R^2, R^3, R^4 are each hydrogen, 1 to 10 Alkyl group having a carbon number of 1
~10 alkoxyl groups, halogen atoms or cyano groups. ) Terephthaloyl cyanide represented by the general formula (II): R^5COCl(II) (R^5 represents an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a substituted phenyl group.) In the presence of acid chloride and hydrogen cyanide salts,
The reaction is carried out using a phase transfer catalyst as a catalyst, and the general formula (III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (R^1, R^2, R^3, R^4, R^5 is the same as above.) [1,4-bis(acyloxydicyanomethyl)benzene and its substituted products]
How to manufacture. (2) The method according to claim 1, wherein a crown ether, a quaternary ammonium salt, or a quaternary phosphonium salt is used as the phase transfer catalyst. (3) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1, R^2, R^3, R^4 are each hydrogen, 1 to 10 Alkyl group having a carbon number of 1
~10 alkoxyl groups, halogen atoms or cyano groups. ) Terephthaloyl cyanide represented by the general formula (II): R^5COCl(II) (R^5 represents an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a substituted phenyl group.) In the presence of acid chloride and hydrogen cyanide salts,
The reaction is carried out using a phase transfer catalyst as a catalyst, and the general formula (III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (R^1, R^2, R^3, R^4, R^5 is the same as above.) [1,4-bis(acyloxydicyanomethyl)benzene and its substituted products]
Then, by subjecting the compound represented by general formula (III) to a reductive deacyloxylation reaction, general formula (IV): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (R in the formula ^1, R^2, R^3, and R^4 are the same as above.) is obtained, and then the compound represented by general formula (IV) is subjected to a dehydrogenation reaction with an oxidizing agent to obtain the general formula (V): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (R^1, R^2, R^3, R^4 in the formula are the same as above.) 7, 7, 8 , 8-tetracyanoquinodimethane and its substituted product.