JPS62148461A - Production of 7,7,8,8-tetracyanoquinodimethane and substituted compound and intermediate thereof - Google Patents

Abstract

PURPOSE:To obtain the titled substance by reacting terephtaloyl cyanide with an acid chloride and hydrogen cyanide, subjecting the resultant bis(acyloxydicyanomethyl)benzene to reducing deacyloxylation reaction and dehydrogenating the product. CONSTITUTION:The compound of formula I (R<1>-R<4> are H, alkyl, alkoxy, halogen or cyano) is made to react with an acid chloride of formula R<5>COCl (R<5> is alkyl, phenyl, etc.) and hydrogen cyanide, etc., under ultrasonic radiation to obtain the compound of formula II, which is converted to the compound of formula III by reducing deacyloxylation reaction using metallic powder and a Lewis acid, etc. The objective compound of formula IV can be produced by the dehydrogenation reaction of the compound of formula III with an oxidizing agent (e.g. chlorine, N-halogenosuccinimide, etc.). EFFECT:The objective compound can be produced from an easily available raw material in high yield. USE:Photosensitive material for electrophotography.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention 51111c, 7,7,8,8-tetracyanoquinodimethane (abbreviated as TCNQ), substituted TCNQ and T
The present invention relates to a method for producing an intermediate obtained in an intermediate process up to obtaining CNQ.

TCNQ according to the present invention is an excellent pi (π)-acceptor, and forms a charge transfer complex with a binder donor 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 manufacturing method of TGNCL'J conductor, 1) 1
．． Synthesis method from 4-cyclohexanedione and malonitrile: Di Nis Alacar et al.

Journal of the American Chemical Society, Vol. 84, p. 3370 (1982) [D
, S.

Acker-at al., J. Am. Chem.
, Sac, 84.3370°1962] 2) Synthesis method from p-quidylenedihalide 2009, 2003, 2013, 2003, 2003, 2003, 2013, 2003, 2013, 2003.

Of Organinque Chemistry, Volume 40.

3101 pages (1975) [R, C, Whela
nd et al., J.

Org, Chew, 40.3101.1975]
3) Method of synthesis from 1.4-cyclohexadiene (
Asahi Kasei Patent No. 49-1086Et) 4) A method of synthesis from p-shortbenzene and malononitrile is known.

[Problem to be solved by the invention 1 However, the method described in L has the following problems.

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

In method 2), one 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.

By the way, it has been reported that when benzoic acid chloride and potassium cyanide are reacted under ultrasonic irradiation, a compound with two cyano groups introduced is produced [T. Henaftha et al., Synthesis, p. 637.

1983 (T., Hanafusa et al.
, 5ynthesis 837°1983].

The reaction formula is It is expressed as

There are no examples of applying this method to the synthesis of TCNQ.

[Step F to solve the problem] The present inventors made intensive efforts to develop a new method for producing TCNQ, substituted TCNQ, and their intermediates in order to improve the shortcomings of the conventional method. Efficiency from terephthalate derivatives that can be obtained < TCNQ, substituted TCNQ
and their intermediates as f! We have discovered a method for manufacturing A, and have completed the present invention.

The present invention is based on a known method [Niss Yamaguchi et al., chemical
Letters, 689 pages, 1985 (S.

Yamaguchi et al., Chew, L.
ett,, 689.1985] 't' A terephthaloyl cyanide derivative that can be synthesized efficiently? TCNQ as raw material from E, ffl-converted TCNQ and 111 of them
This is a manufacturing method for one body.

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

i) General formula (■): (1lil, R2, R3, in the formula) 74 are each hydrogen, an alkyl group having 1 to 10 carbon atoms, 1 carbon number
~10 terephthaloyl cyanides represented by flukoxyl, (indicates a halogen atom or a cyano group).

・An acid chloride represented by the general formula (II): R5C0CR(If) (R5 represents an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a substituted phenyl group) and hydrogen cyanide, or a salt thereof, are irradiated with ultrasonic waves. F reaction.

−・General formula (■): (R1, R2, R3, R4, R'' in the formula are the same as above.

) is a compound represented by [! , 4-bis(acyloxydisy7nomethyl)benzene 1.

1i) Compound [1,4 -Bizdici7-methylbenzene 1
How to manufacture.

iii) The compound of general formula (IT) is subjected to a dehydrogenation reaction using an anti-antioxidant agent to form general formula (V): (R1, 1li2. R3, R4 in the formula are the same as above.

) and a method for producing TCNQ and substituted TCNQ.

Specifically, the terephthalic acid chloride used in the present invention includes terephthalic acid chloride; 2-chloroterephthalic acid chloride, 2-bromoterephthalic acid chloride, 12-iodoterephthalic acid chloride, and 2,5-dichloroterephthalic acid chloride.

2.5-dibromtele, phthalic acid chloride, etc. /\
Logen-substituted terephthalic acid chloride; 2-methylterephthalic acid chloride, 2-ethyl terephthalic acid chloride, 2.5-dimethylterephthalic acid chloride, 2.5-
Alkyl-substituted terephthalic acid chloride such as diethyl terephthalic acid chloride; 2-methoxyterephthalic acid chloride, 2-ethoxyterephthalic acid chloride, 2,5
-Alkoxy-14-substituted terephthalic acid chloride, such as dimethoxyterephthalic acid chloride I, 2,3,5.13
-tetracyano terephthalic acid chloride, etc. can be exemplified.

A known method using terephthalic acid chloride and cupric cyanide [S, YalIlaguchi et al., Chemical Letters, p. 689, 1985]
al.

Chem, Lett, Ei89.1985] to produce a compound represented by general formula (I).

Compound (m) is produced by reacting compound CI) with hydrogen cyanide, or its salts and acid chlorides under ultrasonic irradiation.

([I) (1171. in the formula)72. R3, Ra, 117
5 is the same as above. M represents a metal such as lithium, sodium, potassium, ammonium, copper or silver. ).

In this reaction, ultra-RF irradiation is an essential condition, and without irradiation with ultrasonic waves, the reaction will hardly proceed, making it impossible to obtain compound (III).

Specific examples of the hydrogen cyanide salts used in the present invention include alkali metal salts such as lithium cyanide, sodium cyanide, and potassium cyanide; ammonium dianide; and metal salts such as cyanide 04 and silver cyanide.

The amount of hydrogen cyanide or its salts used per mole of the anti-Jε raw material is in the range of 2 to 10 moles, preferably 3 to 5 moles.

Acid chloride represented by general formula (II) R''C0CR (11) (Rb represents an aryl group, phenyl group or substituted phenyl group having 1 to 3 carbon atoms) used in the present invention Specifically, fatty acid chlorides such as acetyl chloride and propionic acid chloride;
Benzoic acid chloride, 0-toluic acid chloride, m-
) Ruyl chloride resistance, P-toluyl chloride, 2
-Methoxybenzoic acid chloride, 4-methoxybenzoic acid chloride, 0-chlorobenzoic acid chloride, p-chlorobenzoic acid chloride, and various substituted ammonium, ω, and aromatic acid chlorides can be exemplified.

- General formula (II) per mol of compound of general formula (I)
) The usage of the acid chloride is in the range of 2 to 10 mol, preferably 3 to 5 mol.

As a reaction solvent, a solvent that is inert to this reaction and can dissolve compound (I) and the acid chloride is used.Specifically, acetonitrile, dioxane, tetrahydrofuran, ethyl ether, isopropyl ether , dimethylformamide and the like.

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

The frequency of the ultrasonic waves used in the present invention is 20k.
Hz ~500kHz, preferably 20kHz ~1o
It is in the okHz (7) range. The intensity of ultrasound varies depending on the scale of the reaction.

Compound (III) is then subjected to a reductive deacyloxylation reaction using a metal powder and a Lewis acid to produce compound (IT).

What is the reaction formula?

([) (rIr) (R in the formula
1, R2,)73. 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 mole of compound (III) is in the range of 2 to 100 moles, preferably 5 to 20 moles.

Examples of Lewis acids used in this reaction include stannic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; carboxylic acids such as acetic acid and propionic acid; and sulfonic acids such as methanesulfonate acid, benzenesulfonic acid, and pl-ruenesulfonate acid. can do.

The usage state of Lewis acid per t mol of compound (m) is 4 to
200 mol, preferably in the range of 10 to 40 mol.

Specifically, the reaction solvent is acid resistant; tetrahyfuran,
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 in the range of room temperature to 100°C, preferably room temperature to 50°C.

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

Compound (rV) is then dehydrated with an oxidizing agent to produce the target compound (V).

The reaction is expressed by the following formula: %Formula %() (1171.1172.R3,1171+ in the formula is 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.

Use of these oxidizing agents per t mol of compound (rv)
t]: ik is in the range of 1 to 5 mol, preferably 1 to 2 mol.

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

The reaction temperature is 06C to 60C, preferably 0C to 60C.
The temperature range is 30°C.

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

Example 1 Terephthaloyl cyanide (1.0 g, 5.4 mmop
) and Yasu, 0. Fragrant acid chloride (4.0g, 28.5m
The moI was dissolved in acetonitrile (6.5 mN) and potassium cyanide (1.8 g.

27.8+moi') and heated at 50°C for 3.5 hours using a Branson Ultra J''F wave cleaner model 221 (frequency 45kHz).
z, maximum output of 100 W) to irradiate TFLRF waves. After reaction path r.

Dissolve insoluble matter and wash solid matter with acetonitrile.

The solution and the acetonitrile washing solution are condensed together under reduced pressure. C Add ethanol (20 mjl') to the brain fluid and cool with ice water to crystallize. The precipitated crystals are
I will take it. Perform +If crystallization with acetonitrile, 1.
4-bis(dicyanobenzoyloxy)benzene!
, 4 g? ! ) (yield -1 58%).

Examples 2 to 6 The base used in Example 1, 0. The same reaction as in Example 1 was carried out except that the acid chloride shown in Table 1 was used instead of aromatic acid chloride.

Table 1 Examples 7 to IO 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 Example 16 1.4-bis(dicyanobenzoyloxymethyl)henzea (100 mg, 0.22 mmoi') was dissolved in acetic acid (
lhjl+) and tetrahydrofuran (10si))
Zinc powder (0.15 g, 2.3 mm
oi') and stir for 30 minutes at room temperature. After the reaction is completed, insoluble materials are separated. The filtrate was decompressed under reduced pressure (1
．． 27 mg of 4-bisdicyanomethylbenzene was obtained (yield: 0%).

Examples 17-20 Except for using substituted 1,4-bis(dicyanobenzoyloxymethyl)benzene shown in Table 4 instead of 1,4-bis(dicyanobenzoyloxymethyl)benzene used in Example 16. , the same reaction as in Example 16 was carried out.

Table 4 Examples 21 to 24 The same reaction as in Example 1B was carried out except that the metal powder shown in Table 5 was used instead of the zinc powder used in Example 16.

Table 5 Examples 25 to 29 The same reaction as in Example 16 was carried out except that 5 mmoi' of the acid shown in Table 6 was used instead of the acetic acid used in Example 16.

Table-6 Example 30 1,4-bisdicyanomethylbenzene (1,0g.

Add bromine (0.84g, 5.3+smo) to water (30+sf) and stir while cooling with water.
i'). After stirring for 30 minutes, the solids are filtered out and washed twice with water. After drying the solid, crystallization was performed with methylene chloride to give TCNQ of 0.8.
4g was obtained (yield 85%).

Examples 31 to 34 '4k Same as Example 30 except that the substituted 1,4-bisdicyanomethylbenzene shown in Table 7 was used instead of the 1,4-bisdicyanomethylbenzene used in Example 30. The following reaction was carried out to obtain substituted CNQ. replacement TCNQ
The yield is also listed in Table-7.

Table-7 Example 35 1,4-bisdicyanomethylbenzene (1,0g.

4.8 mmoi)) was dissolved in acetonitrile (50 mA'), and N-iodosuccinimide (1.6 g
, 7.2 mmof') and stir for 30 minutes. After the reaction is completed, water (100 ij) is added, and the precipitated crystals are separated by furnace. After washing the crystals with water, dry them. Recrystallization was performed with methylene chloride to obtain 0.84 g of TCNQ (yield: 85
%).

Examples 36 to 37 Example 35 except that the oxidizing agent shown in Table 8 was used instead of N-iodosuccinimide used in Example 35.
The same reaction as above was carried out to obtain TCNQ. Table 8 shows the yield.
Also listed in

Table 8 [Effects of the Invention] As shown in Section L, according to the present invention, the synthesis conditions for easy synthesis are achieved by using a terephthaloyl cyanide derivative that is easy to obtain or synthesize as a starting material. by TCN
Q, substituted TCNQ and their intermediates can be obtained in high yields. It will be useful in the future for electrophotographic photosensitive materials, etc. as a photoconductive composite material; TCNQ, which is expected to rapidly increase in 1"L,
The present invention is of great significance in the sense that it provides a novel industrial manufacturing method for substituted TCNQ.

Claims (8)

[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.) By reacting acid chloride and hydrogen cyanide or their salts under ultrasonic irradiation, the general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (R^1, R^2, R^3 in the formula , R^4 is hydrogen, an alkyl group having 1 to 10 carbon atoms, and 1 carbon number, respectively.
~10 alkoxyl groups, halogen atoms or cyano groups. R^5 represents an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a substituted phenyl group. ) A method for producing the compound [1,4-bis(acyloxydicyanomethyl)benzene]. (2) The method according to claim 1, wherein the hydrocyanate is an alkali metal salt, an alkali metal salt, ammonium cyanide, or a transition metal salt. (3) General formula (III): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (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. R^5 represents an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a substituted phenyl group. ) By subjecting the compound represented by the formula to a reductive deacyloxylation reaction, the general formula (IV): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (R^1, R^2, R^ in the formula 3, R^4 is each hydrogen, an alkyl group having 1 to 10 carbon atoms, and 1 carbon number
~10 alkoxyl groups, halogen atoms or cyano groups. ) A method for producing the compound [1,4-bisdicyanomethylbenzene]. (4) The method according to claim 3, wherein the reductive deacyloxy reaction is carried out using a metal powder-Lewis acid. (5) The method according to claim 4, wherein the Lewis acid is a mineral acid, a carboxylic acid, or a sulfonic acid. (6) Metal powder is zinc, magnesium, aluminum,
The method of claim 4, wherein iron is used. (7) General formula (IV): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (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. ) By subjecting the compound represented by the formula to a dehydrogenation reaction with an oxidizing agent, the general formula (V): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (R^1, R^2, R^3, R^4 is each hydrogen, an alkyl group having 1 to 10 carbon atoms, and 1 carbon number.
~10 alkoxyl groups, halogen atoms or cyano groups. ) A method for producing 7,7,8,8-tetracyanoquinodimethane, which is a target compound represented by the following formula, and a substituted product thereof. (8) The method according to claim 7, wherein chlorine, bromine, bromine water, or N-halogenosuccinimide is used as the oxidizing agent.