JPS61129158A - Production of tetracyanoanthraquinodimethane-type charge transfer complex - Google Patents

Abstract

PURPOSE:To obtain a charge-transfer complex which is solid at normal temperature and useful as an organic electronic material, by reacting tetracyanoanthraquinodimethane with an electron-donative compound in a solvent, and removing the solvent from the reaction mixture. CONSTITUTION:The objective compound can be produced by dissolving tetracyanoanthraquinodimethane of formula (R is H, halogen, cyano, nitro, alkoxycarbonyl, alkyl or aryl) and excess electrondonative compound (e.g. benzene, naphthalene, tetrathiafluvalene, etc.) in a mixture of a good solvent of both compounds (e.g. carbon tetrachloride) or dissolving in the good solvent and adding the poor solvent thereto, and removing the solvents from the solution.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a tetracyanoanthraquinodimethane charge transfer complex useful as an organic electronic material.

[Conventional technology]

Tetracyanoanthraquinodimethane and its derivatives are known to be useful compounds as organic electronic materials such as organic semiconductors (for example, JP-A-57-14925
No. 9, No. 58-10554, No. 58-55450, etc.) These tetracyanoanthraquinodimethanes are compounds having the basic skeleton of the following formula and substituted with various substituents.

NOCN These tetracyanoanthraquinodimethanes are compounds useful as organic electronic materials such as organic semiconductors, electrophotographic materials, organic conductors, and thermistor materials, but they have the drawback of low electrical conductivity.

In order to improve this drawback, a method can be considered in which tetracyanoanthraquinodimethane is doped with an electron-donating compound to form a charge transfer complex.

However, although the formation of a charge transfer complex has been confirmed in the conventional solution state, it has not been possible to isolate the charge transfer complex as a solid or crystal. Therefore, the use of such charge transfer complexes has been greatly limited.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a production method capable of isolating a tetracyanoanthraquinodimethane charge transfer complex as a solid or crystal.

[Means and effects for solving the problem] As a result of extensive studies, the present inventors have found that tetracyanoanthraquinodimethane represented by the following general formula is dissolved in a mixed solvent of a soluble solvent for both compounds and a poor solvent, or by adding a poor solvent after dissolving it in a soluble solvent, and then removing the solvent to charge tetracyanoanthraquinodimethane. It was discovered that a mobile complex can be isolated, and the present invention was completed.

In the general formula (Ij, R is a hydrogen atom, a halogen atom,
Represents a cyano group, nitro group, alkoxycarbonyl group, alkyl group or aryl group.

In the production method of the present invention, an electron-donating compound is used in excess of tetracyanoanthraquinodimethane (hereinafter abbreviated as TCNAQ). That is, when using a monocyclic compound such as benzene as an electron donating compound, use more than double the amount as it forms a 1:1 complex with TCNAQ, and use a multi-ring compound such as naphthalene or anthraquinone. In this case, since a complex is formed at 1 mole per 2 moles of TCNAQ, the electron donating compound is used in an amount of A or more.

In the production method of the present invention, the above-mentioned starting material is dissolved in a solvent, a charge transfer complex formation reaction is carried out, and the generated charge transfer complex is then precipitated.

This complex formation reaction proceeds by dissolving the starting material in a solvent, but the solution may be heated if desired. There are two methods for forming and depositing a charge transfer complex.

The first method uses a soluble solvent that easily dissolves both starting materials and forms a charge transfer complex in the solution, and a soluble solvent that easily dissolves the electron-donating compound used in excess of the starting materials. A mixed solvent with a poor solvent that is difficult to dissolve the complex is prepared, both starting materials are dissolved in this mixed solvent, the formation of a charge transfer complex is progressed, and after the reaction is completed, the solution is heated to evaporate the soluble solvent. This is a method in which a charge transfer complex is precipitated, and after being sent from house to house, it is washed with a poor solvent to remove the electron-donating compound contained in the complex. and when the electron-donating compound is relatively poorly soluble in the soluble solvent, in which case a sufficient amount of soluble solvent is used to dissolve the starting material in the mixed solvent.

The second method is to dissolve the starting material in a soluble solvent to allow the charge transfer complex formation reaction to proceed, and then add a poor solvent to precipitate the charge transfer complex, which is then distributed to individual customers. This method is used when the boiling point of the soluble solvent is higher than the boiling point of the poor solvent, and the poor solvent is added and mixed in an amount sufficient to precipitate the reaction product.

In these two methods 9, when dissolving the starting materials, it is possible to dissolve both starting materials in a solvent in advance and then mix them, or to add both starting materials directly to the solvent and mix. It's okay. If it is difficult to dissolve, heat as appropriate.

The charge transfer complex of TCNAQ and an electron donating compound isolated by the method of the present invention is an antagonistic solid with a melting point in the range of 300'C to 300'C, and has a characteristic characteristic of the complex. color, and is colored purple, yellow, orange, green, etc.

Such complexes do not show a clear or no trace of the constituent electron-donating compounds (e.g., 2-CN -TCN
AQ-TTF complex and 2-C00GH3-TCN
AQ-TTF complex) and is therefore expected to have high electrical conductivity.

T represented by general formula (1) used in the production method of the present invention
Among CNAQ, those in which R represents a cyan group, a chlorine atom, a methyl group, or a methoxycarbonyl group at the 2-position are particularly preferred. Examples of electron-donating compounds include aromatic compounds such as bezene, naphthalene, anthracene, pyrene, and Krylene, P-phenyl diamine and similar condensed ring type aromatic amines, and tetrathiafulvalene (
Examples include sulfur-containing electron-donating compounds such as TTF), tetrathiatetracene (TTT), and tetramethyltetrathiafulvalene (TMTSF).

As for the solvent used, soluble solvents include chlorinated hydrocarbon solvents such as methylene chloride and dichlorobutane, which easily promote charge transfer complex formation reactions, and acetone, and poor solvents include alcohols and carbon tetrachloride. etc.

〔Example〕

Examples of the charge transfer complex of the present invention are listed below.

In addition, in the following examples, infrared absorption spectrum (IR)
was measured using the KBr tablet method, and nuclear magnetic resonance was measured using the KBr tablet method.
R) is measured as a CDCl3 solution.

Also, during melting point measurement, once the sample decomposes and becomes a powder,
For molten samples, both the decomposition point and melting point are listed.

Example 1 2-CN-TCNAQ-anthracene complex (2:1)2
-cyano-11,11,12,12-tetracyano-9
, 100rn9 of 10-anthraquinodimethane and 54rn9 of anthracene (corresponding to a 2-fold excess) in 2rnl of acetone and 3m7 of carbon tetrachloride! When the solution is dissolved in a mixed hot solvent and gradually concentrated to 1.5 ml while heating, purple crystals are precipitated. At this time, anthracene crystals may precipitate at the same time, but in that case carbon tetrachloride is added to dissolve only the anthracene. The purple crystals are filtered hot and washed with hot carbon tetrachloride.

Yield 98rn9° Melting point 245-250°C.

Elemental analysis - C28H1°N, as HN Calculated value (% > 80.37 2.89 16.74
Actual measurement value (excellent) 80,20 2.77 16.48 mR
:Figure 1.

Implementation f3iIJ 2 2-CtJ-TCNAQ-benzene complex (L:1) 2-
cyano-11,11,12,12-tetracyano-9,
100 wL9 of 10-anthraquinodimethane is heated and dissolved in excess benzene. After cooling to room temperature, the precipitated crystals are separated from P and washed with benzene.

Yield 73m9° Melting point 140-150°C (decomposition), 2
60°C (melting).

Elemental analysis HN as 27H13'5 Calculated value (% > 79.59 3.22 17.19 Actual value (%) 79,59 3.19 17.21 The title complex was prepared by adding 2-CN-TCNAQ to benzene and It can also be obtained by dissolving and then heating to 40-50'C under reduced pressure to remove all the p/zene.

Example 3 2-ON-TCNAQ-naphthalene complex (2:1) 2-
cyano-11, 11,12, 12-tetracyano-9,
10-anthraquinodimethane 100m9 and naphthalene 1
Dissolve oomy in 3 ml of 1,2-dichloro1tane and gradually concentrate to 5 ml of Q while heating. The precipitated orange crystals are separated and washed with hot carbon tetrachloride. Yield 7
8mg. Melting point 160°C (decomposition), 278-285 min melting).

Elemental analysis - HN as C26H N5 Calculated value (Coefficient 1 79.38 2.82 17.80 Actual value (%l 79.45 3.03 17.52
Example 4 2-ON-TCNAQ-funinanthrene complex (2:L)
2-cyano-11,11,12,12-tetracyano-
Dissolve 9,10-anthraquinodimethane toom9 and 54 ml of heptadnanthrene in 3 rnl of 1,2-dichloroethane, heat and gradually concentrate to 1 ml, and then add 5 ml of ethanol Q. After cooling, the precipitated orange crystals are separated from each other and washed with hot ethanol. Yield 98m9° Melting point 240-241°C0 Elemental analysis: HN calculated value as C28H□2NS (Coefficient 1 80.37 2.89 16.74
Actual value (knowledge) 80.64 2.92 16.82 Example 5゜2- ON -TCNAQ-pyrene complex (2:1) 2-
cyano-11,11,12,12-tetracyano-9,
100mg of 10-anthraquinodimethane and 61m of pyrene
Dissolve 9 in 3 ml of 1',2-dichloroethane, concentrate to 2'fnl while heating, and then add 1 ml of carbon tetrachloride. After cooling, the precipitated purple crystals are separated from each other and washed with hot carbon tetrachloride. Yield 88■. Melting point 271-272°C.

Calculated value Ugu 1 80.92 2.81 16.27
Actual measurement 1st shift (ch) 8L18 2.98 16.2
6 Example 6 2 + Cl-TCNAQ-benzene complex (1:1) 2
-chloro-11,11,12,12-tetracyano-9
, 100 m9 of 10-anthraquinodimethane is heated and dissolved in benzene. Cool to room temperature, separate the precipitated crystals, and wash with benzene. Yield 60m9゜Melting point 110-
120°C (decomposition) + 271°C (melting).

Calculated value (ch) 74,91 3.17 13,78
8.64 Actual value (ch) 74.81 3.14
13.44 8.5ONMR: Figure 2.

The title complex can also be obtained analogously to Example 2 by removing all benzene.

Example 7 2-C1-TCNAQ-naphthalene complex (2:1) 2-
Chloro-11,11,12,12-tetracyano-9,
10-Anthraquinodimethane 50■ and naphthalene 100
%' in methylene chloride l tnl and add ethanol while heating. After cooling, the precipitated yellow crystals are separated and washed with hot carbon tetrachloride. Yield: 8In9゜Melting point: 16
0-180°C (decomposition), 265-268°C (melting)
.

Calculated value (%1 74.54 2.75 13.91 8
．． 80 Actual value (coefficient 1 74.54 2.97 13.7
5 9.08 Example 8 2- C1-TCNAQ-anthracene complex (2:1)
2-chloro-11,11,12,12-tetracyano-
9,10-anthraquinodimethane 50In9 and anthracene 261n9 are heated and dissolved in 2 ml of methylene chloride, and carbon tetrachloride is added. Concentrate while heating until purple crystals precipitate, and leave to cool. The purple crystals are taken from house to house and washed with hot carbon tetrachloride. Yield 26'mgo Melting point 224-225°C0
Actual value (%) 75.59 3.01 13.11
8.60 Example 9 2-C1-TCNAQ-phenanthrene complex (2:1
) 50 ml of 2-chloro-11,11,12,12-tetracyano-9,10-anthraquinodimethane and 26 ml of tophenanthrene are dissolved with heating in 772 ml of methichloride, and ethanol is added. Concentrate while heating until orange crystals precipitate, and leave to cool. Remove the orange crystals from door to door and wash them with hot ethanol. Yield 46m9° Melting point 220-221°C0 Calculation f Direct (%l 75.79 2.83 13.09
8.28 actual measurement part) 75.71 2.93 13.
12 8.47 Example 10 2-Cl-TCNAQ-pyrene complex (2:1) 2-chloro-11,11,12,12-tetracyano-9,10
- 50 ml of anthraquinodimethane and 30 rnl of pyrene are dissolved by heating in 2 rnl of methylene chloride and concentrated until purple crystals are precipitated. After cooling, the purple crystals are separated and washed with hot carbon tetrachloride. Yield 45■. Melting point 239-240°C.

Calculated value (chil 76.45 2.75 12.74
8.06 actual value excellent) 73,29 2.91 12.
70 8.36 Example 11 1-Cl-TCNAQ-pyrene complex (2:L) 1-chloro-11,11,12,12-tetracyano-9,10
-Anthraquinodimethane 25mg and pyrene 1oo1n9
Dissolve in 15 ml of hot chloroform. The solution is concentrated under reduced pressure and the remaining red solid is suspended in 3 ml of carbon tetrachloride, filtered and washed twice with 2 ml of hot carbon tetrachloride.

Yield 10m9° Melting point 160°C (decomposition), 210. −
260'C (melting).

Actual measurement part) 76.13 2.98 12.42 8
．． 47 Example 12゜2-ON-TCNAQ-TTF complex (2:l)2
- Schiff/-11,11,,12,12-Tetrasia/
-9,10-anthraquinodimethane 82m9 and TTF
Dissolve 50■ in 2 ml of hot methylene chloride, 1.5 mA!
Concentrate to After cooling, the precipitated green crystals are separated and washed with carbon tetrachloride. Yield 11■. Melting point 239-242
°C (decomposition).

Actual value part 1 66.24 2.14 16.30 L
3.58 Example 13 2- Cl-TCNAQ -TTF complex α; 1) 2-Cl-11,11+ 12 + 12- Tet7 Schiff / -9,10-Anthraquinodimethane 85 mg and TTF5o1n9 were mixed with hot methylene chloride. Dissolve in 3 ml and add 1 ml of carbon tetrachloride.

Concentrate to 1 rnl, allow to cool, and collect the precipitated green crystals from person to person. Yield 29rn9° Melting point 222-224°c0 Actual value c%) 63.01 2.30 12.71 1
4.59 8.36 Example 14 2-COOMe-TCNAQ-TTF complex (2:
1) 2-methoxycarbonyl-11,11,12,12
-tetracyano-9,10-anthraquinodimethane 90
Dissolve m9 and TTF50 in 2rnl of hot methylene chloride and concentrate to 1ml. After cooling, the precipitated dark blue crystals are separated and washed with carbon tetrachloride. Yield 20rn9° Melting point 247-251°C (decomposition).

Actual value ($1 64.54 2.73 12.05 1
3.85 Example 15 2-CH3-TCNAQ-TTF complex (2:1) 2-methyl-11,11,12,12-tetracyano-9,1
80m9 of 0-anthraquinodimethane and TTF5Qm9 are dissolved in 2ml of hot methylene chloride and concentrated to lrttl. After cooling, the precipitated green crystals are separated and washed with carbon tetrachloride. Yield 20m9° Melting point 200-270°C (
Disassembly).

Calculation (direct) 68.55 2.88 L3.3
2 15.25 Actual value (ch) 68.24 3.05
13.22 15.17 Example 16 2-CH3-TCNAQ-benzene complex (1:1) 2-
Methyl-11,11,12,12-tetracyano-9,
Recrystallization of 10-anthraquinodimethane from benzene produces the title complex. Melting point 90-95°C (decomposition)
.

285-287°C (melting).

Calculated value (chi) 8L, 80 4.07 14.1
3 Actual measurement value (chi) 81.98 4.35 14.
29 Example 17゜2-0H3-TCNAQ-7 engineered nanthrene complex (2:1
) 100rn9 of 2-methyl-11,11,12,12-tetracyano-9,10-anthraquinodimethane and 730m9 of 7-enanthine were dissolved in hot methanol, and 1 mA'
Concentrate with i. After cooling, the precipitated yellow crystals are separated and washed with a mixed solvent of methanol and carbon tetrachloride (1:1).

Yield 26■. Melting point 250-255°C.

Elemental analysis” Actual value as C28H15N4 (H) 82.71 3.9L 14.
02 Example 18 2-0H3-TCNAQ-pyrene complex (2:1) 2-methyl-11,11,12,12-tetracyano-9,1
801n9 of 0-anthraquinodimethane and 64cm of pyrene are dissolved in hot carbon tetrachloride and concentrated to 5 ml. Next, 1 rnl of carbon tetrachloride is added, and the precipitated red crystals are separated. Yield: 74m9° Melting point: 226-227°C0 Elemental analysis Actual value as 2C29H□5N4 (%1 83.19 3.85 13.49
Implementation 1] 19 TCNAQ-2,3,5,6-tetramethyl-p-phenylenediamine complex (L:1) 11 , 11 , 12 , 12-tetracyano-9,1
0-Anthraquinodimethane 25m9 and 2.3.5.6-
Tetramethyl-p-phenylenediamine 135 ~ is dissolved in a mixture of 2 Qrnl of hot methylene chloride and 2 ml of hot acetone. The solution was concentrated under reduced pressure, the remaining green solid was suspended in 3 ul of carbon tetrachloride, filtered, and heated with 2 d of carbon tetrachloride.
Wash 3 times with Yield 2orrui, melting point 165-30
0°C (decomposition).

Elemental analysis: Actual value as C3oH24N6) 76.86. 5.07 18.1
3rd construction R: Figure 3.

Example m 2- C1-TCNAQ -2,3,5,6-titramethyl-P-phenylenediamine complex (1:1) 2-chloro-11,11,12,12-tetracyano-
9,10-anthraquinodimethane 100■ and 2.3.5
．． Dissolve 48 ml of 6-titramethyl-P-phenylenediamine in 3 ml of hot methylene chloride and concentrate to 2.5 ml. After cooling, the precipitated green crystals are separated and washed with methylene chloride. Yield: 57 mg. Melting point 198-200'
C (decomposition).

Elemental analysis: CHtJ as C3oH23C4N6
C1 Calculated value (%l 71.63 4.61 16.70
7.05 Actual value (chi) 71,48 4.4L L
6,69 7.45 Example 21 2-CH3-TCNAQ-2,3,5,6-tetramethyl-p-phenylenediamine complex (1:1) 2-methyl-11,ICl3.12-tetramethyl-p-phenylenediamine complex (1:1) 7/
100 m9 of -9,10-anthraquinodimethane; 2.
3.5.6-Titramethyl-P-7 enylenediamine 5
Dissolve 2m9 in 1ml of hot methylene chloride and add 1rrLl of carbon tetrachloride.

Gradually concentrate to 1 ml while heating, and after cooling, the precipitated dark blue crystals are separated and washed with a methylene chloride-carbon tetrachloride mixture.

Yield: 96 mg. Melting point 185-188°C (decomposed).

Elemental analysis: Actual value (%) as C3□H26N6 76.53 5.46 17.2
3 [Effects of the Invention] The present invention provides a method for producing a charge transfer complex that is solid at room temperature and is composed of a tetracyanoanthraquinodimethane derivative and an electron donating compound. The complexes are useful as a variety of organic electronic materials, such as organic semiconductors, electrophotographic charge transport or charge generating materials, conductors, resistors, or thermistor materials. That is, according to the charge transfer complex of the present invention, for example, it is possible to create an organic electronic material consisting only of a crystalline complex, and it is also possible to exhibit stable characteristics by dispersing the complex in a binding substance, etc. I can do it.

[Brief explanation of the drawing]

FIGS. 1 to 3 are infrared absorption spectra or nuclear magnetic resonance spectral diagrams of Examples of the tetracyanoanthraquinodimethane complexes of the present invention, respectively.

Claims (1)

[Claims] General formula I ▲ Numerical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkoxycarbonyl group, an alkyl group, or an aryl group. represent. ] Tetracyanoanthraquinodimethane and excess electron-donating compound are dissolved in a mixed solvent of a solvent in which both compounds are soluble and a poor solvent, or a poor solvent is added after dissolving both compounds in a soluble solvent. 1. A method for producing a charge transfer complex of tetracyanoanthraquinodimethane and an electron-donating compound, which comprises removing the solvent.