JPS5810553A - Preparation of tetracyanoanthraquinodimethane derivative - Google Patents

Abstract

PURPOSE:To prepare the titled compound useful as an organic semiconductor, etc., in high yield, in a short step, without side reactions, by substituting the ketone group of the Diels-Alder reaction product of a butadiene compound and p-benzoquinone with dicyanomethylene group, and oxidizing the product. CONSTITUTION:Butadiene or 2-monosubstituted or 2,3-disubstituted butadiene and p-benzoquinone are used as the starting material, and are subjected to the Diels-Alder reaction. The oxygen atom of the ketone group of the product is substituted with dicyanomethylene group to obtin 1,4,4a,5,8,8a,9a,10a-octahydro- 11,11,12,12-tetra-cyano-9,10-anthraquinodimethane derivative, which is then oxidized to obtain the objective 11,11,12,12-tetracyano-9,10-anthraquinodimethane derivative of formula (W, X, Y and Z are H or 1-8C hydrocarbon group, provided that W=Y and X=Z or W=Z and X=Y).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 11.11.12,12-tetracyano-9,
The present invention relates to a method for producing a 1o-anthraquinodimethane derivative.

The structure of the 11.11.12.12-tetracyano-9,1o-anthraquinodimethane derivative produced in the present invention is (
1) 5 shown in formula (1) However, w, x, y and Z shall represent one of the groups selected from hydrogen atoms or hydrocarbon groups having 1 to 8 carbon atoms. . Furthermore, W==Y, X=Z
Alternatively, it is assumed that ldW'=Z and x=y, and (the equal sign indicates that the groups represented by W, X, , Y, and Z are equal. These conventions will be used hereinafter as well. )Also,
W and X are groups bonded to the 2- and 3-position carbon atoms of the butadiene derivative used in the present invention, respectively.

These 11.11.12.12-tetracyano-9,
1°-Anthraquinodimethane (hereinafter abbreviated as TCNAQ) derivatives are useful as organic semiconductor compounds.

In addition to these compounds, conventional industrially useful organic semiconductor compounds include 7,7,8.8-tetracyanoquinodimethane (hereinafter abbreviated as TCNQ), 9.9,10.10-
Tetracyano-1,4-natsutaquinodimethane (hereinafter TC
NNQ) and their derivatives have been produced.

(2), (3) and (4), respectively, with TCNQ
, shows the molecular formulas of TCNNO and TCNNAQ. Here, TCNQ, TCNNQ, TCNAQ, and their derivatives have a tetracyanoquinodimethane skeleton represented by formula (5), which determines the characteristics of each compound.

Below margin (2) (3) (4)
(5) Here, the tetracyanoquinodimethane skeleton refers to a skeletal structure consisting of carbon atoms and nitrogen atoms that constitute the molecule of TCNQ.

Among these compounds, methods for producing TCNQ and its derivatives are described in, for example, S. Acker, at, al.
,.

1, kn, Chem, Soc,, 84, 337
0 (1962), RoC, VIFheland, et
, al, , 1.0rg, Chem, ,
40(21), 3101 (1975) and U.S. Pat.
It is described in documents such as No. 15506 specification. For example, TCNQ is prepared using diethyl succinate as the starting material.
, 4-cyclohexanedione, which can be obtained from its reaction with malonitrile. Here, 1,4-
Synthesis of cyclohexanedio/
t, et, al, , T, Org.

Chem, 3, 603 (1939), and subsequent reactions are described in Acker et al.

T by this method by a series of chemical reaction equations (6)
A method for manufacturing CNQ is shown.

7 Below Margin In formula (6), from diethyl succinosuccinate to 1,
When deriving 4-cyclohexanedione, 19
Very strong conditions of 6-200°C must be required. For this purpose, the above-mentioned series of reactions are followed, and TC
There were very big restrictions on getting NQ.

On the other hand, the document by Wheland et al. describes a method for obtaining TCNQ derivatives. This is a benzene derivative,
P from P-xylene derivatives or terephthalic acid derivatives
-xylene...ride, and then a series of reactions to obtain TCNQ derivatives. - For example, a series of reactions leading to TCNQ derivatives from benzene derivatives (
7) In the formula, Me represents a methyl group.

In formula (7), eight reaction steps are required in the process of obtaining the TCNQ derivative from the benzene derivative.

In addition, 1,4-bis(dicyanomethylene)cyclohexane in formula (6) and 1゜4-bis(methoxycarbonyldicyanomethyl)benzene derivatives and 1,4-bis(dicyanomethyl)benzene derivatives in formula (7) are Due to the high polarity of the four cyano groups, it is extremely difficult to dissolve in common solvents. For this reason, a large amount of solvent is required in the final reaction process to obtain TCNQ or its derivatives.

As described above, conventional production methods for obtaining TCNQ or its derivatives require a reaction process under extremely strong conditions or a step consisting of a multi-step reaction process, or the consumption of a large amount of solvent. This is extremely disadvantageous in terms of reaction time, reaction yield, energy or power for promoting the reaction, or consumption of a large amount of solvent.

The method for producing the TCNAQ derivative of the present invention is based on conventional TCN
This is an extremely useful method for producing TCNAQ derivatives that overcomes the above-mentioned drawbacks of the methods for producing Q derivatives.

Here, the features of the structure of the present invention will be explained, and the method of the present invention will be compared with a conventional method for producing TCNQ or its derivative.

The method of the invention consists of three main steps:

a) P-benzoquinone and butadiene or butadiene mono-substituted at the 2-position or di-substituted at the 2- or 3-position (herein, the substituent is a hydrocarbon group having 1 to 8 carbon atoms); A Diels-Alder reaction is carried out using one of these as a starting material.

b) Substituting the oxygen atoms of the ketone groups of the product obtained in a) with dicyanomethylene groups.

c) 1, 4, 4a, 5°8 generated by b)
, 8 a , 9 a , 10 a-octahydro-11゜11.12.12-tetracyano-9,10-
・Oxidizes anthraquinodimethane derivatives.

The present invention achieves TCN by the above-mentioned series of three-step reaction process.
A method for producing an AQ derivative is provided. The method of the invention is illustrated by a series of chemical equations.

NG'”CN NC/C”CN (2)) In these series of reactions, the Diels
The Alder reaction process requires heating at 70-80°C,
Other reaction steps proceed with slight heating or at room temperature or lower. Therefore, the consumption of energy or power for promoting the reaction is extremely small. In addition, all reactions other than the reaction of introducing a dicyanomethylene group in step b) are simple addition reactions or elimination reactions, and almost no side reactions occur throughout the entire process of the present invention. Furthermore, since the reaction process is as few as three steps, the desired TCNAQ derivative can be obtained in high yield.

Also, the 1, 4° 4a, 6,
8,8a,9a,10a-octahydro-11,11,
12,12-tetracyano-9゜10-anthraquinodimethane derivatives are 4a, respectively.

Due to the two cyclic substituents condensed to the carbon atoms at positions 9a, 13a, and 10a, the high polarity of the cyano group is relaxed, making it easily soluble in solvents. For this reason, a large amount of TCNAQ derivative can be produced by using only a small amount of solvent in the process of C).

Table 1 shows 1.4.4a, 5, 8, 8a as examples.

9 a, 10 a-octahydro-11,11,1
2゜The trubility parameter (f
List and compare i (SP value). Here, the sp value is calculated by XG SP=-. Here, d: specific gravity of liquid or crystal ΣG=sum of attractive constants of atomic groups in the molecule M: molecular weight.

Margin below +1 Table 1 Comparison of sp values Generally speaking, the solubility of a crystalline organic substance in a solvent is determined by the presence of a common functional group in both substances and the fact that the sp values are comparable. 1,4゜4a, 5,8,8a
, 9a, 10a-octahydro-11,11,12,1
Good solubility of 2-tetracyano-911o-anthraquinodimethane in acetonitrile and 1,4-bis(
The poor solubility of dicyanomethylene)cyclohexane in acetonitrile can also be understood from the sp values shown in Table 1.

Furthermore, since P-benzoxin and butadiene or their derivatives, which are the starting materials of the present invention, can be obtained at low cost and in large quantities, this also contributes to the production of TCNAQ derivatives at extremely low cost.

Furthermore, the present invention will be explained by dividing into each process.

Step a) P-benzoquinone and butadiene or a derivative thereof are dissolved in benzene or ethanol as a solvent, and the reaction is carried out by heating to 70 to 80°C. The reaction proceeds smoothly even when quinhydrone, which is disclosed in German Patent No. 2,162,949, is used in place of P-benzoquinone.

The reaction of introducing a dicyanomethylene group represented by the process (9) of b) is a method also used when synthesizing TCNQ,
For example, D.S., Acker, et al.
, .

1, Am, Chem, SOC,, 84, 3370
(1962) and others describe a method similar to the present invention.

Margin 18' ■ (9) Process C) The final process of the present invention is the process (1) obtained in process b).
o) 1, 4, 4a, 5. s.

8a, 9a, 10a-octahito o-11, 11°12
．． This is a process of oxidizing a 12-tetracyano-9,1o-anthraquinodimethane derivative.

(1o) This reaction can be carried out at room temperature or lower by using a combination of halogen and a base as an oxidizing agent.19 In this process, the formation reaction of the TCNAQ derivative is carried out at the 4o-position, the 9a-position, the 8o-position, and the 1-position in equation (10), respectively.
The reaction can be divided into a reaction in which a double bond is formed between a pair of two carbon atoms at the 0a position and a dehydrogenation reaction.

In the former reaction, hydrogen atoms bonded to carbon atoms at positions 4a, 8a, 9a, and 10a are more easily eliminated than hydrogen atoms bonded to carbon atoms from the 1st to 8th positions. This can be interpreted as being caused by the fact that

The reasons for this include the following factors. First of all 1,4°4a,5,8.8a,9a,10a-octahydro-11,11,12,12-tetrahydro-9
゜1o-Anthraquinodimethane derivatives 4a and 8a.

The hydrogen atoms on the carbons at positions 9a and 10a have electrons that are shared with the bonded carbon atoms through the double bond of the dicyanomethylene group, and the strong electron attraction force of the cyan group causes the carbon atoms to being pulled toward For this reason, hydrogen atoms on carbon atoms in the 1st to 8th positions are more easily desorbed as protons.

Furthermore, stabilization of the double bonds formed between the carbon atoms at the 4a and 9a positions and between the 8a and 10a positions due to the hyperconjugation effect is also considered to be a major factor. Such an effect is well known in organic synthetic chemistry as the 5aytzeff rule.

In addition, in the latter reaction, halogen atoms are added to the carbon atoms at the 2, 3, 6, and 7 positions, and then the halogen atoms are added to the 1 and 2 positions, respectively.
Hydrogen halide is eliminated from the four carbon atoms at positions 3 and 4, positions 5 and 6, and positions 7 and 8, and a double bond is formed between these carbon atoms. You will understand when it is completed.

The above reaction ff1 (11) is schematically shown.

Margins below (11) (12) /C\NCCN (11) A in formula (11) represents no-rogen. However, in the present invention, the existence of intermediates represented by (11) and (2) has not been confirmed.

The present invention will be explained in more detail below by giving examples of production of TCNAO derivatives.

TCNAQ derivatives were prepared by the procedure described below.

i) Synthesis of 1.4.4a,6,8.8a,9a,10a-octahydro-9,1o-anthraquinone derivatives From 0.6 mol of P-benzoquinone and 1.2 mol of butadiene or its derivative. 4,4a.

6,8,8a,9a,10a-octahydro-9°1o-anthraquinone derivatives were obtained.

The butadiene derivatives used were 2-methylbutadiene, 2,
3-dimethylbutadiene, 2-ethylbutadiene, 2.
3-diethylbutadiene, 2-7'ropylbutadiene,
2-butylbutadiene, 2-pentylbutadiene, 2-
Hexylbutadiene, 2-octylbutadiene, 2-phenylbutadiene 23 7.2-(4-methylphenyl)butadiene.

The reaction was carried out by dissolving P-benzoquinone and each of the above-mentioned butadiene derivatives in habenine, heating to 70° C. and refluxing. The yields varied somewhat depending on the type of derivative, but all yields were above 85%.

1j) Synthesis of TCNAQ derivatives 1, 4.4a, 6, 8.8a obtained in 1).

0.2 mol of each of the 9a, 10a-octahydro-9,1o-anthraquinone derivatives and 0.24 mol of malonitrile were each separately dissolved in 3omg of benzene and mixed with 12fil of acetic acid and 4ml. of ammonium acetate was added thereto, and the mixture was refluxed for 3 hours while stirring. After this, the solution was cooled, filtered, and recrystallized from acetonitrile to give 1,4,4a, 6,8°8a, 9a, 10
a-octahydro-11,11°12.12. -tetracyano-9,1o-anthraquinodimethane derivative was obtained.

Of these compounds, 0.1 mole of each was collected and cooled to 0°C with 0.12 mole of bromine.
ml! of acetonitrile, and the reaction system was purged with nitrogen gas. An additional 26 ml of pyridine was added, and the solution was stirred for 1 hour while being maintained at 0°C, and cooling water was added to precipitate crystals. After filtration, recrystallize from acetonitrile to obtain the second
Each TCNAQ derivative shown in the table was obtained. Although the yield varies somewhat depending on the type of derivative,
All were 90% or more. In addition, throughout the entire reaction process of 1) and 11) of this example, each T CNA
The yields of the Q derivatives were all 75% or higher.

Margin below 6 Table 2 Types of TCNAQ derivatives If a butadiene derivative other than 2,3-dimethylfuridiene and 2,3-diethylbutadiene was used as a starting material in this example, Table 2 shows the types of TCNAQ derivatives. Two stereoisomers were obtained for each derivative as shown. For these isomers, the desired final product 2,
After separating the 6-disubstituted product and the 2,7-disubstituted product, the identification of both isomers is performed by measuring the dipole moment, and the compound with a dipole moment of 0 is
, 6-disubstituted product.

Claims (2)

[Claims] (1) A Diels-Alder reaction is performed using butadiene or a mono-substituted product of butadiene at the 2-position or a dis-substituted product at the 2- and 3-positions and P-benzoquinone as a starting material, and the resulting product is obtained. The oxygen atom of the ketone group was replaced with a dicyanomethylene group, and then the 1,4.4a,5,8゜8a,9a,10a-octahydro-11,11゜12.12- Tetracyano
By oxidizing a 9,10-anthraquinodimethane derivative, 11.11.1'2.
1. A method for producing a tetracyanoanthraquinodimethane derivative, which comprises obtaining a 12-tetracyano-9,1o-anthraquinodimethane derivative. However, w, x, y and Z each represent a hydrogen atom or one of the groups selected from hydrocarbon groups having 1 to 8 carbon atoms. Furthermore, let W-Y, x=Z or W=Z, x=Y be Rumo's (equal signs are w, x
, indicating that the groups represented by y and Z are equal). Moreover, W and X are groups bonded to the 2nd and 3rd position carbon atoms of the butadiene derivative, respectively. (2) The method for producing a tetracyanoanthraquinodimethane derivative according to claim 1, wherein the oxidation is carried out using a halogen and a base.