JPH01305048A - Production of 2-substituted-cyclohexane-1,4-dione - Google Patents

Abstract

PURPOSE:To industrially and advantageously obtain the subject compound by reacting cyclohexane-1,4-dione with morpholine and reacting the resultant 1,4- dipyrrolidono-1,3-cyclohexadiene with an unsaturated compound. CONSTITUTION:A compound expressed by formula I is reacted with morpholine to provide a compound expressed by formula II, which is then reacted with a compound expressed by the formula CHR<1>=CR<2>X [R<1> and R<2> are H or CH3; X is COOR<3>, CN or CON(R<4>)2; R<3> is H or alkyl; R<4> is alkyl], preferably in a lower alcohol to industrially and advantageously afford the objective compound expressed by formula III without requiring special raw materials or reaction conditions. Furthermore, a compound expressed by formula V obtained from the above-mentioned compound through a compound expressed by formula IV has the melting point as low as about 80-150 deg.C, exhibits good solubility even in general-purpose solvents, such as methanol, and is capable of forming not only a 1:1 complex but also a 1:2 complex with cations of a nitrogen- containing heterocyclic compound. Thereby, uses as an organic semiconductor is expected.

Description

[Detailed Description of the Invention] Industrial Application Field The present invention is expected to be used as an organic semiconductor.
, 7,8.8-tetracyanoquinodimethane (hereinafter TCN
The present invention relates to a method for producing a compound useful as an intermediate for a derivative (referred to as Q).

Prior Art (Complex of TCNQ or its derivative) TCNQ is a yellow crystal with a melting point of 293.5 to 296° C. This compound easily accepts one electron to form a stable anion radical.

A donor part consisting of a cation of a nitrogen-containing heterocyclic compound and TC
An organic complex containing a part of the acceptor composed of NQ is useful as a conductive material.

JP-A No. 61-254561 discloses a complex D-TCNQ, which consists of a cation (D) of a nitrogen-containing heterocyclic compound, an anion radical of TCNQ (TCNQ?), and neutral TCNQ (TCNQ').・There is a disclosure regarding TCNQ'.

JP-A No. 62-468 describes two types of cations (D, , D) of a nitrogen-containing heterocyclic compound, an anion radical of TCNQ (TCNQ':) and a neutral TCNQ (TCNQ).
Q′ ) as a constituent component (D+”)==(D:
)+-c-TCNQ"・TC:NQ' (However, x=0
．． 1 to 0.8) are disclosed.

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

There has also been a report on a complex using a methyl substituted product of TCNQ, and in JP-A-61-282363, a cation (D ) of a nitrogen-containing heterocyclic compound and a ? -Methyl T CN
cl (MtcNQ) or 2,5-dimethylTC
Anion radical form of N Q (DMTCNQ) D -MTCNQ"・MTCNQ', D, ΦDMTC
NQ"・DMTCNQ' is disclosed.

The present applicant also proposed, in Japanese Patent Application No. 16357/1983, a cation (D) of a nitrogen-containing heterocyclic compound and TCNQ having an alkoxycarbonylethyl group at the 2- and 5-positions.
Regarding the complex D+・A7 which has an anion radical (Ao) of a CNQ derivative as a constituent component, and as in Japanese Patent Application No. 16358/1982, a cation (D) of a nitrogen-containing heterocyclic compound and the 2- and 5-positions of TCNQ are proposed. T having an alkoxycarbonylethyl group in
Patent applications have been filed for the CNQ derivative (A) and the complex D.[A.TCNQI', which contains the 7-ion radical of TCNQ [A-TCNQI' as a constituent component.

(Synthesis method of TCNQ) For example, cyclohexane-
A method is known in which 1,4-bis-(dicyanomethylene)cyclohexane obtained by condensing 1,4-dione with malononitrile is oxidized using N-bromosuccinimide or bromine in pyridine.

(Method for synthesizing TCNQ derivatives and intermediates thereof) As mentioned above, TCNQ is an organic compound but has conductivity, so it is necessary to find a method for synthesizing this compound by another route, or to create a conductive material with a skeleton similar to that of the compound. Finding a compound with
Furthermore, it is important for practical application. In particular, TCNQ has a very high melting point as described above and is insoluble in most organic solvents, which may limit its usage. Therefore, it is important to find a similar compound that does not have these drawbacks.

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

rJ, Org, Chew, 48.3852 (
1983) J synthesizes a monosubstituted cyclohexane-1,4-dione represented by the general formula by oxidizing the compound represented by the general formula (R is H or CH3, n is 1 or 2). , and furthermore, a method for synthesizing from this compound via the following steps is disclosed.

Japanese Patent Application No. 61-208276 filed by the present applicant (
JP-A No. 63-63637) discloses that cyclohexane-1,4-dione is reacted with pyrrolidine to obtain 1,4-divirolidino-1,3-cyclohexadiene, which is then converted into the general formula %. % [In the formula, R', R''H Mataha cH3, X Ha(:
OOR' (R3tfH or alkyl group) or CNI
A method for obtaining a 2,5-substituted cyclohexane-1°4-dione represented by the general formula by reacting it with an unsaturated compound represented by the formula is shown. (However, R', R", and X in this document are partially different from those defined in the present invention.)
JP-A No. 62-26259) describes succinyl succinic acid dialkyl esters represented by the formula [R3 is an alkyl group] and acrylic succinic acid dialkyl esters represented by the general formula % [wherein R+ and Rλ are H or an alkyl group]. A cyclohexane-2,5-dione derivative represented by the general formula is obtained by reacting with an acid or an acrylic acid ester, which is then heated in the presence of a strong acid to form a 2,5-bis( A method for obtaining dicyanomethylene)cyclohexane-1,4-ylene-(3-propionic acids) is shown.

The present applicant has disclosed cyclohexane-1,4
-dione is reacted with pyrrolidine to obtain 1,4-divirolidino-1,3-cyclohexadiene, which is then converted into the general formula % [wherein, R'4*H*ri4*CHi, X hacOOR
By reacting with an unsaturated compound represented by "(R" is H or an alkyl group) or CNI, the general formula [in the formula, R' and X are the same as above, but when R1 is H, X is represented by CNI] 2,5-substituted-cyclohexane-1,4-dione is obtained, this compound is reacted with malontotolyl to obtain NCCM, and this compound is further oxidized to obtain a TCNQ derivative represented by the general formula An application has been filed regarding the method.

Problems to be Solved by the Invention Among the methods for synthesizing TCNQ derivatives or intermediates thereof, rJ,
Org, Chews,, 48.3852 (19
83) The method described in J has problems as an industrial production method because the raw materials used, reaction conditions, etc. are special.

Among the methods for synthesizing TCNQi conductors and intermediates thereof, there is a method in which cyclohexane-1,4-dione is reacted with pyrrolidine to obtain 1,4-divirolidino-1,3-cyclohexadiene, and then this is reacted with an unsaturated compound. In some cases, the product obtained is mainly 2,5-substituted-cyclohexane-1,4-dione, with virtually no mono-substituted product being obtained; therefore, this di-substituted product is reacted with malononitrile and then What is obtained by oxidation is a 2,5-disubstituted TCNQ.

However, according to the research of the present inventors, the cation (D) of the nitrogen-containing heterocyclic compound and the 2°5-substituted T obtained above
When trying to obtain a complex containing the anion radical (8゛) of CNQ as a constituent, only the l:1 complex represented by D+・8″: is obtained, and the complex represented by D+·[A-Al” cannot be obtained.

Therefore, the present inventors obtained l:
We attempted to obtain not only a 1:2 complex but also a 1:2 complex, but as mentioned earlier, the product obtained by reacting cyclohexane-1,4-dione with pyrrolidine is 2,5-substituted-cyclohexane- Since it is a 1°4-dione, monosubstituted T
It was difficult to obtain CNQ derivatives.

The object of the present invention is to provide an industrially advantageous method for producing 2-substituted cyclohexane-1°4-dione, which is an intermediate for obtaining monosubstituted TCNQ derivatives.

Means for Solving the Problems The present invention provides ``1,4-dimorpholino-1,3-cyclohexadiene represented by the formula by reacting cyclohexane-1,4-dione represented by the formula with morpholine, and then In addition, the general formula % formula % [In the formula, R, R, Httf:, CH3, X, GOO
R3 (R3H or an alkyl group), CM, or C0N(R')h, (R4 is an alkyl group)] is reacted with the general formula [R' in the formula, A method for producing a 2-substituted cyclohexane-1,4-dione represented by
” is its gist.

When R, R or R is an alkyl group, the argyl group has 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, cyclohexyl, etc. Among them, lower alkyl groups having about 1 to 4 carbon atoms, particularly methyl groups, are important from an industrial perspective.

As described above, the method of the present invention includes the first step of reacting cyclohexane-1,4-dione with morpholine to obtain 1,4-dimorpholino-1,3-cyclohexadiene; generated l.

4-dimorpholino-1,3-cyclohexadiene is reacted with an unsaturated compound to produce 2-substituted-cyclohexane-1,
and a second stage reaction to obtain 4-dione.

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

The reaction temperature is preferably reflux, and the reaction is allowed to proceed while removing water by-produced during the reaction from the system. A catalyst is not particularly required, but an acid such as p-toluenesulfonic acid can also be used to accelerate the reaction.

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

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

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

After removing the solvent and residual morpholine from the reaction product solution of the first stage reaction, the reaction proceeds to the second stage reaction. In this case, the produced dienamine can be isolated and used, or the next reaction can be carried out simply by expelling the solvent etc. after the reaction is completed.

Strategy 12 Fuzuki JL [As the solvent in the second stage reaction, methanol,
Ethanol, propatool, acetonitrile, dimethylformamide, etc. are used, and lower alcohols are particularly suitable. The selection of the solvent is important; for example, if dioxane is used as the solvent, the yield of the desired 2-substituted-cyclohexane-1,4-dione will be low.

Specific examples of the unsaturated compound include acrylic acid alkyl ester, methacrylic acid alkyl ester, acrylonitrile, methacrylonitrile, N,N-dialkyl acrylamide, N,N-dialkyl methacrylamide, and the like.

The amount of unsaturated compound used is 1, 4 shown by formula (IT)
-Dimorpholino-1,3-cyclohexadiene is preferably selected from the range of 1 to 2 mol per mol of cyclohexadiene.

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

Isolation of this compound can be accomplished by vacuum distillation, other conventional purification methods,
This is done by taking isolation measures.

To obtain the malononitrile monosubstituted TCNQ derivative, first, the 2-substituted-cyclohexa7-1.4 represented by the formula (m) obtained above is
- Reacting the dione with malononitrile.

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

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

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

The amount of malononitrile used is usually 2 moles per mole of 2-substituted-cyclohexane-1,4-dione represented by formula (m), but there is no problem even if malononitrile is used in excess.

After the reaction is completed, the precipitated crystals may be collected and purified by a conventional method.

This reaction yields 2-substituted cyclohexane-1,4-bis(dicyanomethylene) represented by the general formula % [wherein R', R'' and X are the same as above].

Mono TCN Yukiko 2-substituted cyclohexane-1,4-bis(dicyanomethylene) represented by the formula (rV) obtained in this way
is oxidized with bromine or N-bromosuccinimide, a monosubstituted TCNQ derivative, i.e., 2-
Substituted-7,7,8,8-tetracyanoquinodimethane (monosubstituted TCNQ derivative) is obtained.

The oxidation reaction is carried out in an inert gas atmosphere using N-bromosuccinimide or bromine, usually in acetonitrile or other medium, and in the presence of pyridine or other basic substance 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 determined by the formula (
2-substituted-cyclohexane-1,4- represented by rV)
The amount is usually 1 to 5 mol per mol of bis(dicyanomethylene).

After the reaction is completed, the solvent is expelled or, if necessary, water is added to the system to precipitate a precipitate, followed by purification by a conventional method.

The monosubstituted TCNQ derivative represented by formula (V) has a low melting point of about 80 to about 150° C. and exhibits good solubility in general-purpose solvents such as methanol, as shown in the examples below.

An organic complex comprising a donor part consisting of a cation of a nitrogen-containing heterocyclic compound and an acceptor part consisting of a monosubstituted TCNQ derivative represented by Formula 1 (V) is produced as follows. Ru.

Examples of the nitrogen-containing heterocyclic compound (D) include pyridine, quinoline, inquinoline, imidazole, picoline, dipyridyl, pyridazine, pyrazine, benzimidazole, benzothiazole, thiazole, phenanthroline, morpholine, pyrazole, inoxazole, hexamethylenetetramine, 1 .4-diazabicyclo[2,2,2]
Compounds having skeletons such as octane, phenylpyridine, and styrylpyridine are used. Particularly important are compounds having a pyridine, quinoline, inquinoline or imidazole skeleton.

If this nitrogen-containing heterocyclic compound (D) is reacted with an alkyl iodide or an alkyl bromide, the corresponding N-alkylonium cation (D), i.e., an N-alkylpyridinium cation, an N-alkylquinolinium cation, is produced. , N-alkylisoquinolinium cation, N-furkylimidazolium cation, etc. can be obtained in the form of a halide.

These N-alkylonium cations (D) are represented by the following general formula.

Here, R' is hydrogen or an alkyl group having about 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 5e
As Rl, which is a c-butyl group, amyl group, hexyl group, octyl group, etc., an alkyl group having 1 to 4 carbon atoms is particularly preferable.

The organic complex of the present invention comprises the above-mentioned nitrogen-containing heterocyclic compound (D)
It consists of an N-alkylonium cation (D ) and an anion radical (v7) of a monosubstituted TCNQ derivative represented by the above formula (V), and has the general formula %D"・vl. The 1:1 complex shown is preferably prepared by the following method.

That is, a solvent solution of N-alkylonium iodide or bromide and a solvent solution of the lithium complex of 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 D".[V-Vl" is preferably produced by the following method.

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

Examples of the solvents or cleaning agents mentioned above include alcohols (methanol, ethanol, n-propertool, impropertool, etc.), ketones (acetone, methyl ethyl ketone, etc.), nitriles (acetonitrile, etc.), esters (methyl acetate, ethyl acetate, etc.). ), ethers (dimethyl ether, tetrahydrofuran, etc.), hydrocarbons (hexane, etc.), cellosolve, etc., or a mixture of two or more of them is used. While the type of solvent used for TCNQ is limited, compound (V) is soluble in general-purpose solvents, so there is a wide range of solvent choices.

The formed l:1 complex or 1:2 complex exhibits high conductivity even though it consists only of organic compounds, so it can be used in conductive paints, conductive inks, conductive plastics, conductive rubber, high Functional conductive films, electrodes, liquid crystal display tubes, solar cells, high-density memory, nonlinear optical materials, biological devices,
Useful in applications such as solid electrolytes and capacitors.

Action The series of reactions detailed above can be summarized as follows.

■ (I) Ten morpholine → (II) 0 (II) + CHR'=CR"-X H2
O(m)? ■ (m) + NC-GHz-C; N → (IT)
■ (IT) - Exsanguination. (V) Reactions (1) and (2) correspond to the production method of the present invention.

Among the compounds (III) obtained by the reaction (2).

Compounds where X is 10000 or other than -COOCR3, for example, the substituent at the 2-position is -(Oh)zCN, -(GHz
)zcON(CH3)2 is a new substance.

Of the compound (rV) obtained by the reaction (2), X is -
Compounds other than COOH or 10,000 lb are new substances.

In the compound (V) obtained by the reaction (2), X is -C
Compounds other than OOH or -coocn3 are new substances.

Example Next, the present invention will be further explained with reference to Examples.

Hereinafter, "%" means % by weight unless otherwise specified.

■ and m Example 1 <First stage reaction> This reaction corresponds to the reaction formula (■) described in the section of the effect.

Cyclohexane-1,4-dione (I) 42.0g
(0,375 mol) and morpholine 97.9 g (1,1
(24 mol) was reacted for 3.5 hours using toluene 2001 as a solvent while introducing nitrogen gas under reflux and expelling by-produced water from the system.

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

(Second-stage reaction) This reaction corresponds to reaction formula (2) described in the section on action.

57.7 g (0.23 mol) of 1,4-dimorpholino-1,3-cyclohexadiene (u) obtained above and 19.8 g (0.23 mol) of methyl acrylate were dissolved in methanol 2001 and refluxed. The mixture was allowed to react for 2 hours.

Subsequently, 23.1 g of water was added and hydrolysis was carried out for 1 hour.

After cooling, water 2001 was added and extraction was performed with chloroform. After washing the chloroform layer with a 10% aqueous hydrochloric acid solution and water, the solvent was expelled from the chloroform layer to obtain 19.9 g.
of oil was obtained. Purification was carried out by Kugel distillation (0.5 mmH
g, oven temperature 120-140°C).

This results in 3-(2,5-dioxocyclohexyl)
-Methyl propionate (III) was obtained. The yield is
1.4-dimorpholino-l,3-cyclohexadiene (
■) It was 43.6% based on the standard.

Example 2 The same operation as in Example 1 except that 23.08 g (0.23 mol) of ethyl acrylate was used instead of 18.8 g (0.23 mol) of methyl acrylate. 27.28g of oil was obtained. Purification was performed in the same manner.

This results in 3-(2,5-dioxocyclohexyl)
- Ethyl propionate (m) was obtained. The yield is 1.
4-dimorpholino-1,3-cyclohexane diene (I
l) It was 55.8% based on the standard.

Example 3 To 8.40 g of ethyl 3-(2,5-dioxocyclohexyl)-propionate obtained in Example 2, 110 g of water and 0.32 g of 98% H, SO-cooled, were added, and the mixture was refluxed.

After reacting for 3.5 hours while expelling water/methanol from the system, it was concentrated. After cooling, filter the precipitated crystals,
After washing and drying, 4.77 g of colorless crystals were obtained.

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

Example 4 3.88 g of 3-(2,5-dioxocyclohexyl)-propionic acid obtained in Example 3 was added with 1 n-propatool.
Add 2.2 g and 98% H2SO + 0.18 g,
The reaction was carried out under reflux for 1.0 hour.

After expelling the excess n-proper tool, add water,
After extraction with chloroform, chloroform was expelled from the chloroform layer to obtain 3.19 g of the desired product. Purification was performed in the same manner as the purification operation for the second stage reaction of Example 1.

Add to this, 3-(2,5-dioxocyclohexyl)
-n-propyl propionate (m) was obtained.

Example 5 In the second stage reaction of Example 1, the same operation was carried out except that 12.21 g (0.23 mol) of acrylonitrile was used instead of 19.8 g (0.23 mol) of methyl acrylate. , 8.15 g of oil was obtained. Purification was performed in the same manner.

This results in 2-(2,5-dioxocyclohexyl)
-cyanoethane (III) was obtained. Yield "4" is 1.
4-dimorpholino-1,3-cyclohexane diene (I
I) It was 16.2% based on the standard.

The reactions in the examples were carried out successively from the reactions of reaction formulas ○ and ① described in the section 1. Effects.

Cyclohexane-1,4-dione (r) 112.1
g (1.0 mol) and morpholine 117.8 g (2
.

After 1.5 hours of reaction, toluene and remaining morpholine were removed from the system, and 400 sl of ethanol and 148.7 g (1.5 mol) of N,N-dimethylacrylamide were added. After 6 hours of reaction under reflux, , ethanol was removed, water 5001 was added, and chloroform extraction was performed.

After washing the chloroform layer with a 10% He-based aqueous solution, the chloroform was removed to obtain 130.8 g of crystals. Purification was performed by vacuum distillation to obtain 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).

Mono-substituted products obtained in Examples 1 to 6 above, i.e. 2
The characteristic values of -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 21.34 g (0,1 mol) of pyrrolidine
3 mol) was reacted for 2.5 hours using toluene 451 as a solvent while introducing nitrogen gas under reflux and expelling by-product water from the system.

Excess pyrrolidine and toluene are expelled and methanol 4
01 and 31 g (1.1 mol) of methyl acrylate Elf were added and reacted under reflux for 2 hours.

Subsequently, 101 liters of water was added and the mixture was refluxed for 1 hour for hydrolysis. Purification was performed in the same manner as the purification operation for the second stage reaction of Example 1. What was obtained by Kugel distillation was the raw material cyclohexane-1,4-dione (I), and from the residue was the disubstituted product 2,5-bis[2-(methoxycarbonyl)ethylcocyclohexane-1, Only 4-dione was obtained, and only traces of the monosubstituted methyl 3-(2,5-dioxocyclohexyl)-propionate (■) were 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 monosubstituted product was confirmed by gas chromatography mass spectrometry, the amount was extremely small. The main product was a di-substituted product, and a large amount of the raw material cyclohexane-1,4-dione (I) was also recovered.

■ and V Since the present invention relates to a method for obtaining compound (II) from compound (I) and then obtaining compound (m),
Although obtaining compound (IV) from compound (III) and further obtaining compound (V) from compound (rV) are outside the scope of the present invention, specific examples of these will also be given for reference. .

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

Example 5a 1.0 g (8.1 mmol) of 2-(2,5-dioxocyclohexyl)-cyanoethane (m) obtained in Example 5, 5.8 g of water, 3.5 g of methanol, lO β-alanine, 1 mg was mixed and heated to 40°C. Then, a methanol solution of 0.81 g (12.3 mmol) of malonitrile 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 and methanol, and dried to yield 1.12 g (4.3 mmol) of 2-[2,5-bis(dicyanomethylene)cyclohexyl] as a white powder crystal. - Cyanoethane (IV) was obtained.

Example 6a 2.11 g of 2-(2,5-dioxocyclohexyl)-dimethylcarbamoylethane (I[[) obtained in Example 6
(10.0 mmol), 7.2 g of water, 4.0 g of methanol.
2 g of β-alanine and 20.0 layer g of β-alanine were mixed and heated to 40°C. Next, 1.33 g of malononitrile (20,
Add a methanol solution of 3 mmol) and heat to 40-50°C.
The reaction was carried out for 1.5 hours. After cooling, the precipitated crystals were filtered, washed with water and methanol, and dried.
g (5.4 mmol) of 2-[2
, 5-bis(dicyanomethylene)cyclohexyl]-dimethylcarbamoylethane l) was obtained.

Examples 1a to 4a Methyl 3-(2,5-dioxocyclohexyl)-propionate obtained in Example 1, 3-(2,5-Dioxocyclohexyl)-propionate obtained in Example 2
-Dioxocyclohexyl)-propionate ethyl, 3-(2,5-dioxocyclohexyl) obtained in Example 3
-propionic acid, Example 5a except that n-propyl 3-(2,5-dioxocyclohexyl)-propionic acid obtained in Example 4 was used as mono-substituted-cyclohexane-1,4-dione (m) or similarly to 6a, the corresponding 2-substituted-cyclohexane-1,4-bis(dicyanomethylene)l), i.e., 2-[2,5-bis(dicyanomethylene)cyclohexyl]-methoxycarbonylethane (Example 1a), 2-[2,5-bis(dicyanomethylene)cyclohexylgoethoxycarbonylethane (Example 2a), 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 2-substituted-cyclohexane-1,4-bis(dicyanomethylene) (IV) obtained in Examples 1a to 8a above.

<Synthesis of Compound (V)> The following reaction corresponds to the reaction formula (2) described in the section of action.

Example 5b 2-[2,5-bis(dicyanomethylene)cyclohexyl]-cyanoethane (IV) obtained in Example 5a 1.0
0 g (3.83 mm, mol) and acetonitrile 29.
9g were mixed and heated to 70°C. Bromine 1.24g (
7.77 mmol) was added dropwise, followed by 1.2 mmol of pyridine.
1 g (15.3 mmol) was added dropwise. 70-75℃
After reacting for 15 minutes, the mixture was cooled and the acetonitrile was removed under reduced pressure. Water and methanol were added, the crystals were filtered, washed with methanol, and dried.
mmol) of yellow 41-color crystalline 2-(1-cyanoethyl)-7,7,8,8-tetracyanoquinodimethane (V)
I got it.

Example 8b 2-[2,5-bis(dicyanomethylene)cyclohexyl]-dimethylcarbamoylethane (obtained in Example 6a)
IV) Same as Example 5b except that 2JOg (8.50 mmol), 35.0 g of acetonitrile, 2.82 g of bromine (17.8 mmol), and 2.88 g of pyridine (33.9 mmol) were used. 0.88 g (2
, 8 mmol) of 2-(2-(dimethylcarbamoyl)ethyl]-7.7,8.8-tetracyanoquinodimethane CV'') in the form of yellow-orange crystals was obtained.

Examples 1b-4b 2-[2,5-bis(dicyanomethylene]cyclohexyl]-methoxycarbonylethane obtained in Example 1a, 2-[2,5-bis(dicyanomethylene)cyclohexyl] obtained in Example 2a -ethoxycarbonylethane, 2-[2,5-bis(dicyanomethylene) obtained in Example 3a
cyclohexyl]-hydroxycarbonylpropylethane, 2-[2,5-bis(dicyanomethylene)cyclohexyl]-n-propoxycarbonylethane obtained in Example 4a to 2-substituted-cyclohexane-1,4-bis(dicyanomethylene) Example 5b except that it was used as (■)
or similarly to 6b, corresponding 2-substituted-7,7,
8,8-tetracyanoquinodimethane (V), i.e.
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 (Execution N5b), 2-
(2-n-propoxycarbonylethyl)-7,7°8.8-tetracyanoquinodimethane (Example 4b) was obtained.

2-substituted-7°7.8 obtained in Examples 1b to 6b above
．． The characteristic values of 8-tetracyanoquinodimethane (V) are
Shown in the table.

By reacting "Chu 1" with colored pyridine, quinoline, inquinolin, pyridine, or pyrimidine with equimolar amounts of methyl iodide, ethyl iodide, n-propyl iodide, or n-butyl iodide, the following N-iodide Flukylonium (D-gar) was obtained.

DtI-N-methylpyridinium iodide D-■-N-ethylpyridinium iodide D3" I-N-n-propylpyridinium iodide D4" I-N-ethylquinolium iodide D-I-iodide N-n -Butylquinolium D('
I-N-ethylisoquinolium iodide D7'' I-N-n-propyl inquiturium iodide 1:1 complex and 1:2s using these N-flukylonium iodides as donors by the following method manufactured a body.

(1:1 complex) A lithium complex of compound (V) is dissolved in acetonitrile by heating, and N-alkylonium iodide (DI) is added to the solution.
An acetonitrile solution prepared by heating and dissolving was mixed, and the mixture was left to cool at room temperature. The precipitated crystals were collected by filtration, washed with ethanol, and then vacuum dried 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> Compound (V) was dissolved in acetonitrile under heating, and an acetonitrile solution in which N-alkylonium iodide (DI) was dissolved under heating was mixed therewith, and the mixture was allowed to cool at room temperature. The precipitated crystals were collected by filtration, washed with acetonitrile, and then dried in vacuum to obtain a 1:2 complex.

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

Effects of the Invention According to the present invention, by reacting compound (I) with morpholine to obtain compound (II), and then reacting this with an unsaturated compound, compound (m), which is a monosubstituted compound, can be obtained. 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) forms not only a 1:1 complex but also a 1:1 complex with the cation of a monosubstituted nitrogen-containing heterocyclic compound.
:2 complexes can be formed.

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

Claims (1)

[Claims] 1. Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) By reacting cyclohexane-1,4-dione with morpholine, the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( II) 1,4-dimorpholino-1,3-cyclohexadiene represented by C.O.
General formula ▲ characterized by reacting an unsaturated compound represented by OR^3 (R^3 is H or an alkyl group), CN, or COH (R^4)_2 (R^4 is an alkyl group)] There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) A method for producing 2-substituted cyclohexane-1,4-dione represented by [R^1, R^2, and X in the formula are the same as above]. 2. 1,4-dimorpholino-1,3 represented by formula (II)
2. The method according to claim 1, wherein the reaction between -cyclohexadiene and an unsaturated compound represented by the general formula CHR^1=CR^2X is carried out in a lower alcohol.