JP2589144B2 - Method for producing 2-substituted-cyclohexane-1,4-dione - Google Patents

Description

The present invention is expected to be used as an organic semiconductor.
The present invention relates to a method for producing a compound useful as an intermediate of a 7,7,8,8-tetracyanoquinodimethane (hereinafter, referred to as TCNQ) derivative.

2. Related Art <Complex of TCNQ or its derivative> TCNQ is a yellow crystal having a melting point of 293.5 to 296 ° C. This compound readily accepts one electron to form a stable anion radical.

Donor moiety consisting of cation of nitrogen-containing heterocyclic compound and TC
An organic complex containing an NQ acceptor moiety as a component is useful as a conductive material.

JP-A-61-254561 discloses a cation (D ⁺ ) of a nitrogen-containing heterocyclic compound and an anion radical of TCNQ. Complexes Constituting with Neutral and Neutral TCNQ (TCNQ ⁰ ) Is disclosed.

JP-A-62-468 discloses that a nitrogen-containing heterocyclic compound 2
Kinds of cations (▲ D ⁺ _1１ , 、 D ⁺ ₂ ) and TCNQ anion radical Complexes Constituting with Neutral and Neutral TCNQ (TCNQ ⁰ ) (Where x = 0.1 to 0.9) is disclosed.

JP-A-61-204173 discloses a complex comprising a cation of a nitrogen-containing heterocyclic compound containing a 7-membered ring and TCNQ.

A complex using a methyl-substituted TCNQ is also reported. JP-A-61-282363 discloses a cation (D ⁺ ) of a nitrogen-containing heterocyclic compound and 2-methyl TCNQ (MTCNQ) or
Anion radical of 2,5-dimethyl TCNQ (DMTCNQ) And its complex with neutral substituted TCNQ (MTCNQ ⁰ or DMTCNQ ⁰ ) Is disclosed.

The present applicant has also filed Japanese Patent Application No. 62-16357 (Japanese Patent Application Laid-Open No. 63-185951).
Publication) as a cation (D ⁺ ) of a nitrogen-containing heterocyclic compound
And an anion radical of a TCNQ derivative having alkoxycarbonylethyl groups at the 2- and 5-positions of TCNQ And its complex components And Japanese Patent Application No. 62-16358 (Japanese Patent Application Laid-Open No. 63-185952) discloses a cation (D ⁺ ) of a nitrogen-containing heterocyclic compound.
And a TCNQ derivative (A) having alkoxycarbonylethyl groups at the 2- and 5-positions of TCNQ and an anion radical of TCNQ And its complex components Each has filed a patent application.

<Synthesis method of TCNQ> As a synthesis method of TCNQ, for example, cyclohexane-1,
1,4 obtained by condensing 4-dione with malononitrile
A method of oxidizing -bis- (dicyanomethylene) cyclohexane in pyridine using N-bromosuccinimide or bromine is known.

<Synthesis Method of TCNQ Derivative and Its Intermediate> As described above, TCNQ is an organic compound but has inductive properties. Finding a compound having the following is a study of this kind of organic conductive compound,
This is important for development and practical use. Especially TCNQ,
As described above, the melting point is very high and the organic solvent is insoluble in most organic solvents, so that its usage may be limited. Therefore, finding a similar compound without such disadvantages has important significance.

The following documents are known as methods for synthesizing TCNQ derivatives or intermediates thereof.

"J. Org. Chem., 48 , 3852 (1983)" includes a general formula (R is H or CH ₃ , n is 1 or 2) by oxidizing the compound represented by the general formula Was synthesized from a monosubstituted cyclohexane-1,4-dione represented by Through Are disclosed.

Japanese Patent Application No. 61-208276 filed by the present applicant (Japanese Patent Application
JP-A-63-63637) discloses a compound obtained by reacting cyclohexane-1,4-dione with pyrrolidine. 1,4-dipyrrolidino-1,3-cyclohexadiene represented by the formula: CHR ¹ = CR ² X [wherein R ¹ and R ² are H or CH ₃ , and X is COOR ³ (R ³ is H or an alkyl group) or CN] and an unsaturated compound represented by the general formula A method for obtaining a 2,5-substituted-cyclohexane-1,4-dione represented by (However, R ¹ , R ² ,
X is partially different from that defined in the present invention. Japanese Patent Application No. 60-166080 filed by the present applicant (Japanese Patent Application
No. 62-26259), the formula A dialkyl succinylsuccinate represented by the formula [R ₃ is an alkyl group] is converted to an acrylic acid represented by the general formula CH ₂ CHCHCOOR ₁ or CH ₂ CHCHCOOR ₂ [wherein R ₁ and R ₂ are H or an alkyl group] Reaction with acrylic ester A cyclohexane-2,5-dione derivative represented by
Then, this is heated in the presence of a strong acid to obtain the general formula A method for obtaining 2,5-bis (dicyanomethylene) cyclohexane-1,4-ylene- (3-propionic acid) represented by the following formula:

The present applicant has filed Japanese Patent Application Nos. 61-256254 and 61-25
No. 6255, cyclohexane-1,4-dione is reacted with pyrrolidine to obtain 1,4-dipyrrolidino-1,3-cyclohexadiene, which is then converted to a general formula CH ₂ CRCR ¹ X wherein R ¹ is H or CH ₃ , X is a compound of the general formula by reacting with an unsaturated compound represented by COOR ² (R ² is H or an alkyl group) or CN]. [Wherein R ¹ and X are the same as above, except that when R ¹ is H, X is
CN] to give a 2,5-substituted-cyclohexane-1,4-dione, and reacting this compound with malononitrile. To obtain a compound of the general formula An application has been filed for a method for obtaining a TCNQ derivative represented by

Problems to be Solved by the Invention Among the methods for synthesizing a TCNQ derivative or an intermediate thereof, `` J. Org.
Chem., 48 , 3852 (1983) "has a problem as an industrial production method because the raw materials to be used, reaction conditions and the like are special.

Among the methods for synthesizing TCNQ derivatives and their intermediates, a method of reacting cyclohexane-1,4-dione with pyrrolidine to obtain 1,4-dipyrrolidino-1,3-cyclohexadiene, which is then reacted with an unsaturated compound The product obtained is mainly 2,5-substituted-cyclohexane-1,4-
Diones, monosubstitutes of which are virtually unavailable. Therefore, the disubstituted product is reacted with malononitrile and then oxidized to obtain a 2,5-disubstituted TCNQ.

However, according to the study of the present inventors, the cation (D ⁺ ) of the nitrogen-containing heterocyclic compound was combined with the 2,5-substituted TCNQ obtained above.
Anion radical When trying to obtain a complex having as components, mainly Only the 1: 1 complex shown in is obtained, Cannot be obtained.

Therefore, the present inventors obtained a mono-substituted by 1:
Although it was attempted to obtain not only 1 complex but also 1: 2 complex, as described above, the product obtained by reacting cyclohexane-1,4-dione with pyrrolidine is 2,5-substituted-cyclohexane-. Because of 1,4-dione, it was difficult to obtain a mono-substituted TCNQ derivative.

An object of the present invention is to provide a method for industrially and advantageously producing a 2-substituted-cyclohexane-1,4-dione which is an intermediate for obtaining a mono-substituted TCNQ derivative.

Means for Solving the Problems The present invention employs a formula Reaction of morpholine with cyclohexane-1,4-dione represented by the formula 1,4-Dimorpholino-1,3-cyclohexadiene represented by the formula: CHR ¹ = CR ² X [wherein R ¹ and R ² are H or CH ₃ , and X is COOR ³ (R ³ is H or an alkyl group), CN, or CON (R ⁴ ) ₂ (R ⁴ is an alkyl group)]. Wherein R ¹ , R ² and X are the same as defined above.
A method for producing cyclohexane-1,4-dione. ”As its gist.

Here, when R ¹ , R ² or R ³ is an alkyl group, examples of the alkyl group include methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, cyclohexyl and the like. There are about 10 to about 10 alkyl groups, and industrially, lower alkyl groups having about 1 to 4 carbon atoms, particularly methyl groups, are important.

As described above, the method of the present invention comprises a first-stage reaction of reacting cyclohexane-1,4-dione with morpholine to obtain 1,4-dimorpholino-1,3-cyclohexadiene, The second step is a reaction in which an unsaturated compound is reacted with the obtained 1,4-dimorpholino-1,3-cyclohexadiene to obtain a 2-substituted-cyclohexane-1,4-dione.

Reaction of the first step As a solvent in the reaction of the first step, benzene,
A solvent azeotropic with water, such as toluene or xylene, is used.

The reaction temperature is preferably under reflux, and the reaction proceeds while removing water by-produced during the reaction out of the system. A catalyst is not particularly required, but an acid such as p-toluenesulfonic acid can be used to promote the reaction.

The reaction system comprises the resulting dienamine represented by formula (II),
That is, it is advantageous to keep the atmosphere of an inert gas such as nitrogen in order to prevent the oxidation of 1,4-dimorpholino-1,3-cyclohexadiene.

The amount of morpholine used is at least 1 mol per mol of cyclohexane-1,4-dione represented by the formula (I), and is particularly preferably selected from the range of 1.5 to 3 mol.

The reaction time is often, for example, about 1 to 3 hours.

After removing the solvent and residual morpholine from the reaction product liquid of the first-stage reaction, the process proceeds to the second-stage reaction.
In this case, the produced dienamine can be used after isolation, or the next reaction can be carried out continuously only by removing the solvent or the like after the completion of the reaction.

Second-Step Reaction As a solvent in the second-step reaction, methanol, ethanol, propanol, acetonitrile, dimethylformamide, or the like is used, and a lower alcohol is particularly optimal. The choice of the solvent is important. For example, when dioxane is used as the solvent, the yield of the objective 2-substituted-cyclohexane-1,4-dione is low.

Specific examples of the unsaturated compound include alkyl acrylate, alkyl methacrylate, acrylonitrile, methacrylonitrile, N, N-dialkylacrylamide, N, N-dialkylmethacrylamide and the like.

The amount of the unsaturated compound used is 1,4-
It is preferable to select from a range of 1 to 2 mol per 1 mol of dimorpholino-1,3-cyclohexadiene.

The reaction is carried out under reflux for about 3 to 24 hours, and then about 2 molar equivalents of water are added to cyclohexane-1,4-dione, and the hydrolysis reaction is continued under reflux for about 1 to 2 hours. The 2-substituted-cyclohexane-1,4-dione represented by (III) is obtained. This is the target compound of the present invention.

Isolation of this compound is accomplished by distillation under reduced pressure and other conventional purification and isolation procedures.

Reaction with malononitrile In order to obtain the mono-substituted TCNQ derivative, first, the 2-substituted-cyclohexane-1,4-dione represented by the formula (III) obtained above is reacted with malononitrile.

The reaction is usually performed in a solvent such as water, alcohol, water / alcohol.

At the time of the reaction, a small amount of a catalyst such as β-alanine, glycine, and ammonium acetate is allowed to coexist.

It is sufficient to carry out the reaction under heating (for example, 40 to 60 ° C.) for about 1 to 5 hours.

The amount of malononitrile used is 2 represented by the formula (III).
2-substituted cyclohexane-1,4-dione
Usually, the molar amount is used, but malononitrile may be used in excess.

After completion of the reaction, the precipitated crystals may be analyzed and purified by a conventional method.

This reaction gives the general formula Wherein R ¹ , R ² and X are the same as defined above.
Cyclohexane-1,4-bis (dicyanomethylene) is obtained.

Synthesis of Mono-Substituted TCNQ Derivative The 2-substituted-cyclohexane-1,4-bis (dicyanomethylene) represented by the formula (IV) thus obtained is oxidized with bromine or N-bromosuccinimide to obtain mono-substituted TCNQ derivative. Substituted TCNQ derivatives, that is, the general formula Wherein R ¹ , R ² and X are the same as defined above.
7,7,8,8-Tetracyanoquinodimethane (monosubstituted TCNQ derivative) is obtained.

The oxidation reaction is usually carried out in acetonitrile or other medium using N-bromosuccinimide or bromine in an inert gas atmosphere, and pyridine and other basic substances are present in the system.

It is sufficient to carry out this reaction at 0 ° C. to 80 ° C. for about 0.1 to 8 hours.

The amount of bromine or N-bromosuccinimide used is usually 1 to 5 mol per 1 mol of the 2-substituted-cyclohexane-1,4-bis (dicyanomethylene) represented by the formula (IV).

After completion of the reaction, the solvent is driven off or, if necessary, water is added to the system to precipitate a precipitate, which is then purified by a conventional method.

The mono-substituted TCNQ derivative represented by the formula (V) has a low melting point of about 80 to about 150 ° C.
It also has good solubility in general-purpose solvents such as methanol.

Manufacture of a complex Donor part comprising a cation of a nitrogen-containing heterocyclic compound,
An organic complex containing a monosubstituted TCNQ derivative represented by the formula (V) and an acceptor moiety as components is produced as follows.

Examples of the nitrogen-containing heterocyclic compound (D) include pyridine, quinoline, isoquinoline, imidazole, picoline, dipyridyl, pyridazine, pyrazine, benzimidazole, benzothiazole, thiazole, phenanthroline, morpholine, pyrazole, isoxazole, hexamethylenetetramine, Compounds having a skeleton such as 4-diazabicyclo [2,2,2] octane, phenylpyridine, and styrylpyridine are used. Especially pyridine, quinoline,
Compounds having a skeleton of isoquinoline or imidazole are important.

When an alkyl iodide or an alkyl bromide is reacted with the nitrogen-containing heterocyclic compound (D), the corresponding N-alkyl onium cation (D ⁺ ), that is, an N-alkyl pyriumium cation or an N-alkyl quinolium cation , N
-Alkylisoquinolinium cation, N-alkylimidazolium cation and the like are obtained in the form of halide. These N-alkyl onium cations (D ⁺ )
Is represented by the following general formula.

Here, R 'is hydrogen or an alkyl group having about 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a se
c-butyl group, amyl group, hexyl group, octyl group and the like. R 'is particularly preferably an alkyl group having 1 to 4 carbon atoms.

Organic Complex The organic complex of the present invention comprises an N-alkylonium cation (D ⁺ ) of the nitrogen-containing heterocyclic compound (D) and an anion radical of the monosubstituted TCNQ derivative represented by the formula (V). And a component represented by the general formula Or Indicated by

Is preferably produced by the following method.

That is, the solvent solution of the N-alkylonium iodide or bromide and the solvent solution of the lithium complex of the compound (V) are mixed in a heated state, and after cooling, the formed crystals are separated and, if necessary, washed, dry.

The 1: 2 complex represented by is preferably produced by the following method.

That is, the solvent solution of the N-alkylonium iodide or bromide and the solvent solution of the compound (V) are mixed in a heated state, and after cooling, the formed crystals are separated, washed and dried if necessary.

As the solvent or cleaning agent in the above, for example,
Alcohol (methanol, ethanol, n-propanol, isopropanol, etc.), ketone (acetone, methyl ethyl ketone, etc.), nitrile (acetonitrile, etc.), ester (methyl acetate, ethyl acetate, etc.), ether (dimethyl ether, tetrahydrofuran, etc.), hydrocarbon (hexane) Etc.), one or two organic solvents such as cellosolve
Mixtures of more than one species are used. TCNQ is limited in the type of solvent, whereas compound (V) dissolves in a general-purpose solvent, so that the solvent has a wide range of options.

Since the formed 1: 1 complex or 1: 2 complex shows high conductivity while having only organic compounds as constituents,
Applications such as conductive paints, conductive inks, conductive plastics, conductive rubber, high-performance conductive films, electrodes, liquid crystal display tubes, solar cells, high-density memories, nonlinear optical materials, biological elements, solid electrolytes and capacitors Useful for

Action The following is a summary of the series of reactions described in detail above.

(I) + morpholine → (II) _{(III) + NC-CH 2} -CN → (IV) The reaction of and corresponds to the production method of the present invention.

Among the compounds obtained by the reaction (III) of, X is -COOH or -COOCH ₃ other compounds, for example 2-position of the substituent _{- (CH 2) 2 CN,} - (CH 2) 2 CON (CH 3 The compound of ₂ ) is a novel substance.

In the compound (IV) obtained by the reaction of
COOH or -COOCH ₃ other compounds are novel substances.

In the compound (V) obtained by the reaction of
COOH or -COOCH ₃ other compounds are novel substances.

EXAMPLES Next, the present invention will be further described with reference to examples. Hereinafter, “%” means “% by weight” unless otherwise specified.

Synthesis of Compounds (II) and (III) Example 1 <First-Step Reaction> This reaction corresponds to the reaction formula described in the section of action.

42.0 g (0.375 mol) of cyclohexane-1,4-dione (I) and 97.9 g (1.124 mol) of morpholine were added to toluene 20
Using 0 ml of the solvent as a solvent, the reaction was carried out for 3.5 hours while introducing nitrogen gas under reflux and driving out by-product water out of the system.

After the reaction was completed, the system was cooled, and the precipitated crystals were filtered, washed with toluene, and dried to obtain 77.56 g of 1,4-dimorpholino-1,3-cyclohexadiene (II). The yield was 82.7%.

<Reaction of Second Stage> This reaction corresponds to the reaction formula described in the section of action.

57.7 g (0.23 mol) of 1,4-dimorpholino-1,3-cyclohexadiene (II) obtained above and 19.8 g of methyl alkylate
(0.23 mol) was dissolved in 200 ml of methanol and reacted under reflux for 2 hours. Subsequently, 23.1 g of water was added and hydrolysis was carried out for 1 hour.

After cooling, 200 ml of water was added, and the mixture was extracted with chloroform. After washing the chloroform layer with a 10% hydrochloric acid aqueous solution and water,
The solvent was driven off from the chloroform layer to obtain 19.9 g of oil. Purification was performed by Kugel distillation (0.5 mmHg, oven temperature 120-140 ° C).

Thereby, 3- (2,5-dioxocyclohexyl)
-Methyl (III) propionate was obtained. The yield is 1,4
43.6% based on dimorpholino-1,3-cyclohexadiene (II).

Example 2 In the second stage reaction of Example 1, 23.08 ethyl acrylate was used instead of 19.8 g (0.23 mol) of methyl acrylate.
g. (0.23 mol), except that 27.26
g of oil was obtained. Purification was performed similarly.

Thereby, 3- (2,5-dioxocyclohexyl)
-Ethyl propionate (III) was obtained. The yield is 1,4
55.8% based on dimorpholino-1,3-cyclohexanediene (II).

Example 3 To 6.40 g of ethyl 3- (2,5-dioxocyclohexyl) -propionate obtained in Example 2 was added 110 g of water and 98% H2.
0.32 g of ₂ SO ₄ was added, and the mixture was reacted under reflux for 3.5 hours while expelling water / methanol out of the system, and then concentrated. After cooling, the precipitated crystals were filtered, washed and dried to obtain 4.77 g of colorless crystals.

This crystal is 3- (2,5-dioxocyclohexyl)-
It was propionic acid (III).

Example 4 To 3.68 g of 3- (2,5-dioxocyclohexyl) -propionic acid obtained in Example 3 was added 12.2 g of n-propanol and 0.18 g of 98% H ₂ SO ₄ and reacted under reflux for 1.0 hour. I let it.

After expelling excess n-propanol, water was added, followed by chloroform extraction, and then chloroform was expelled from the chloroform layer to obtain 3.19 g of the desired product. Purification was performed in the same manner as in the purification operation of the second stage reaction in Example 1.

Thereby, 3- (2,5-dioxocyclohexyl)
-N-propyl (III) propionate was obtained.

Example 5 In the second stage reaction of Example 1, 12.21 g of acrylonitrile was used instead of 19.8 g (0.23 mol) of methyl acrylate.
g (0.23 mol), except that 6.15 g
Oil was obtained. Purification was performed similarly.

Thereby, 2- (2,5-dioxocyclohexyl)
-Cyanoethane (III) was obtained. The yield was 16.1 based on 1,4-dimorpholino-1,3-cyclohexanediene (II).
2%.

Example 6 This reaction is a continuation of the reaction of the reaction formula and the reaction described in the section of action.

112.1 g (1.0 mol) of cyclohexane-1,4-dione (I) and 117.8 g (2.5 mol) of morpholine were mixed with 450 ml of toluene.
The reaction was carried out while introducing nitrogen gas under reflux and driving out by-product water out of the system using ml as a solvent.

After the reaction for 1.5 hours, toluene and residual morpholine were removed from the system, and the mixture was refluxed under the addition of 400 ml of ethanol and 148.7 g (1.5 mol) of N, N-dimethylacrylamide.
After reacting for an hour, ethanol was removed, 500 ml of water was added, and chloroform extraction was performed.

The chloroform layer was washed with a 10% aqueous HCl solution to remove chloroform, and 130.8 g of crystals were obtained. Purification by vacuum distillation gave colorless crystals.

This crystal is 2- (2,5-dioxocyclohexyl)-
It was dimethylcarbamoylethane, and the yield was 26.3% based on cyclohexane-1,4-dione (I).

The mono-substituted product obtained in the above Examples 1 to 6, ie,
The characteristic values of the 2-substituted-cyclohexane-1,4-dione (III) are shown in Table 1 below.

Comparative Example 1 Cyclohexane-1,4-dione (I) 11.21 g (0.1 mol) and pyrrolidine 21.34 g (0.3 mol) were mixed with toluene 45 m
Using 1 as a solvent, the reaction was carried out for 2.5 hours while introducing nitrogen gas under reflux and driving out by-product water out of the system.

Drive off excess pyrrolidine and toluene and remove methanol
40 ml and 8.61 g (0.1 mol) of methyl acrylate were added and reacted under reflux for 2 hours.

Subsequently, 10 ml of water was added, and the mixture was refluxed for 1 hour to hydrolyze. Purification was performed in the same manner as in the purification operation of the second stage reaction in Example 1. The product obtained by Kugel distillation is cyclohexane-1,4-dione (I) as a raw material, and distilled 2,5-bis [2- (methoxycarbonyl) ethyl] cyclohexane-1, Only 4-dione was obtained, and only a trace of methyl (III) 3- (2,5-dioxocyclohexyl) -propionate, a monosubstituted product, was obtained.

Comparative Example 2 In Comparative Example 1, dioxane was used in place of methanol as a solvent in the subsequent reaction.

Although the presence of the mono-substituted product was confirmed by gas chromatography mass spectrum, the amount was very small. The main product was a di-substituted product, and a large amount of the starting material cyclohexane-1,4-dione (I) was recovered.

Synthesis of Compounds (IV) and (V) The present invention relates to a method for obtaining compound (II) from compound (I) and then obtaining compound (III). Obtaining and further obtaining compound (V) from compound (IV) are out of the scope of the present invention, but specific examples thereof will be given for reference.

<Synthesis of Compound (IV)> The following reaction corresponds to the reaction formula described in the section of action.

Example 5a 1.0 g (6.1 mmol) of 2- (2,5-dioxocyclohexyl) -cyanoethane (III) obtained in Example 5, water 5.
9 g, methanol 3.5 g, β-alanine 10.1 mg mixed, 40
Warmed to ° C. Then, a methanol solution of 0.81 g (12.3 mmol) of malononitrile was added, and the mixture was reacted at 40 to 50 ° C for 1.5 hours. After cooling, the precipitated crystals were filtered, washed with water, washed with methanol, and then dried to give 1.12 g (4.3 mmol) of white powdery crystalline 2- [2,5-bis (dicyanomethylene) cyclohexyl] -cyanoethane ( IV) was obtained.

Example 6a 2.11 g (10.0 g) of 2- (2,5-dioxocyclohexyl) -dimethylcarbamoylethane (III) obtained in Example 6.
Mmol), water 7.2 g, methanol 4.2 g, β-alanine 2
0.0 mg was mixed and heated to 40 ° C. Then, a methanol solution of 1.33 g (20.3 mmol) of malononitrile was added, and the mixture was reacted at 40 to 50 ° C for 1.5 hours. After cooling, the precipitated crystals were filtered, washed with water, washed with methanol, and dried to give 1.65 g (5.4 mmol) of 2- [2,
5-bis (dicyanomethylene) cyclohexyl] -dimethylcarbamoylethane (IV) was obtained.

Examples 1a-4a Methyl 3- (2,5-dioxocyclohexyl) -propionate obtained in Example 1, 3- (2,5) obtained in Example 2
-Dioxocyclohexyl) -ethyl propionate, 3- (2,5-dioxocyclohexyl) obtained in Example 3
Example 5a or propionic acid, except that n-propyl 3- (2,5-dioxocyclohexyl) -propionate obtained in example 4 was used as mono-substituted-cyclohexane-1,4-dione (III). As in 6a, the corresponding 2-substituted-cyclohexane-1,4-bis (dicyanomethylene)
(IV), that is, 2- [2,5-bis (dicyanomethylene) cyclohexyl] -methoxycarbonylethane (Example 1a), 2- [2,5-bis (dicyanomethylene) cyclohexyl] -ethoxycarbonylethane (imp. Example 2
a), 2- [2,5-bis (dicyanomethylene) cyclohexyl] -hydroxycarbonylethane (Example 3a), 2
-[2,5-bis (dicyanomethylene) cyclohexyl]
-N-Propoxycarbonylethane (Example 4a) was obtained.

Table 2 shows the characteristic values of the 2-substituted-cyclohexane-1,4-bis (dicyanomethylene) (IV) obtained in Examples 1a to 6a.

<Synthesis of Compound (V)> The following reaction corresponds to the reaction formula described in the section of action.

Example 5b 1.00 g (3.8 g) of 2- [2,5-bis (dicyanomethylene) cyclohexyl] -cyanoethane (IV) obtained in Example 5a
3 mmol) and 29.9 g of acetonitrile, and heated to 70 ° C. 1.24 g (7.77 mmol) of bromine were added dropwise, followed by 1.21 g (15.3 mmol) of pyridine. 70-75
After reaction at 15 ° C. for 15 minutes, the mixture was cooled and acetonitrile was expelled under reduced pressure. Water and methanol were added, and the crystals were filtered, washed with methanol, and dried to give 0.79 g (3.07 mmol) of 2- (2-cyanoethyl) -7,7,7 as a yellow-orange crystal.
8,8-Tetracyanoquinodimethane (V) was obtained.

Example 6b 2.60 g (8.50 mmol) of 2- [2,5-bis (dicyanomethylene) cyclohexyl] -dimethylcarbamoylethane (IV) obtained in Example 6a, 35.0 g of acetonitrile,
0.86 g in the same manner as in Example 5b except that 2.82 g (17.6 mmol) of bromine and 2.68 g (33.9 mmol) of pyridine were used.
(2.8 mmol) of yellow-orange crystalline 2- [2- (dimethylcarbamoyl) ethyl] -7,7,8,8-tetracyanoquinodimethane (V) was obtained.

Examples 1b to 4b 2- [2,5-bis (dicyanomethylene) cyclohexyl] -ethoxycarbonylethane obtained in Example 1b, 2- [2,5-bis (dicyanomethylene) cyclohexyl] obtained in Example 2a -Ethoxycarbonylethane, Example 3a
The 2- [2,5-bis (dicyanomethylene) cyclohexyl] -hydroxycarbonylpropylethane obtained in the above, and the 2- [2,5-bis (dicyanomethylene) cyclohexyl] -n-propoxycarbonylethane obtained in Example 4a. 2-
The corresponding 2-substituted-7,7,8,8-tetracyanoquinodimethane was prepared in the same manner as in Example 5b or 6b except that it was used as substituted-cyclohexane-1,4-bis (dicyanomethylene) (IV). (V), that is, 2- (2-methoxycarbonylethyl) -7,7,8,8-tetracyanoquinodimethane (Example 1b), 2- (2-ethoxycarbonylethyl)
-7,7,8,8-tetracyanoquinodimethane (Example 2b),
2- (2-hydroxycarbonylethyl) -7,7,8,8-
Tetracyanoquinodimethane (Example 3b), 2- (2-n
-Propoxycarbonylethyl) -7,7,8,8-tetracyanoquinodimethane (Example 4b) was obtained.

Table 3 shows the characteristic values of the 2-substituted-7,7,8,8-tetracyanoquinodimethane (V) obtained in Examples 1b to 6b.

Synthesis of Complex By reacting pyridine, quinoline, isoquinoline or pyrimidine with an equimolar amount of methyl iodide, ethyl iodide, n-propyl iodide or n-butyl iodide, the following N-alkylonium iodide (D ⁺ I ^-) was obtained.

D ₁ ⁺ I ^- iodide N- methylpyridinium D ₂ ⁺ I ^- iodide N- ethylpyridinium D ₃ ⁺ I ^- iodide N-n-propyl-Ili pyridinium D ₄ ⁺ I ^- iodide N- ethyl Keno potassium D ₅ ⁺ I ^- iodide N-n-propyl isoquinolizinyloxy tumefaciens these iodide N- alkyl-onium ^- iodide N-n-butyl-quinolinone potassium D ₆ ⁺ I ^- iodide N- ethyl isoquinolizinyloxy imidazolium D ₇ ⁺ I The 1: 1 complex and the 1: 2 complex were produced by the following method using as a donor.

<1: 1 complex> compound lithium complex (V) was dissolved with heating in acetonitrile, to which iodide N- alkyl-onium (D ⁺ I ^-) were mixed warming dissolved in acetonitrile solution, allowed to stand at room temperature Cool. The precipitated crystals were collected by filtration, washed with ethanol, and dried under vacuum to obtain a 1: 1 complex.

Complex production conditions, yield and properties of the obtained 1: 2 complex,
The characteristics are shown in Table 4.

<1: 2 Complex> The compound (V) was dissolved in acetonitrile by heating, and an acetonitrile solution in which N-alkylonium iodide (D ⁺ I ⁻ ) was dissolved by heating was mixed, and the mixture was allowed to cool at room temperature. The precipitated crystals were collected by filtration, washed with acetonitrile, and dried under vacuum to obtain a 1: 2 complex.

Complex production conditions, yield and properties of the obtained 1: 1 complex,
The characteristics are shown in Table 5.

Effect of the Invention According to the present invention, compound (I) is reacted with morpholine to obtain compound (II), and then reacted with an unsaturated compound to obtain monosubstituted compound (III). it can.

This method is industrially advantageous because it does not require special raw materials or special reaction conditions.

The compound (V) produced from the obtained compound (III) via the compound (IV) is not only a 1: 1 complex but also a 1: 2 complex with a cation of a monosubstituted nitrogen-containing heterocyclic compound. Complexes can be formed.

Therefore, the present invention greatly contributes to the field of organic semiconductors.

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Claims (2)

(57) [Claims] (1) Expression Reaction of morpholine with cyclohexane-1,4-dione represented by the formula 1,4-Dimorpholino-1,3-cyclohexadiene represented by the formula: CHR ¹ = CR ² X [wherein R ¹ and R ² are H or CH ₃ , and X is COOR ³ (R ³ is H or an alkyl group), CN, or CON (R ⁴ ) ₂ (R ⁴ is an alkyl group)]. Wherein R ¹ , R ² and X are the same as defined above.
A method for producing cyclohexane-1,4-dione. 2. The 1,4-dimorpholino represented by the formula (II)
The reaction of the unsaturated compounds represented by 1,3-cyclohexadiene and the general formula CHR ¹ = CR ² X, process of claim 1, characterized in that a lower alcohol.