JPH0692959A - Salt of anionic radial of benzoquinone derivative - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as an organic electrophotographic material, a capacitor material, a low resistance heat-sensitive element, a sensor material, etc. CONSTITUTION:The salt of an anionic radical of a benzoquinone derivative expressed by formula I (rings A and B are heterocyclic ring such as formula II; when either is this heterocyclic ring, the other may be formula III) with a cation such as Li<+>, (CH3CH2)4N<+> or formula IV, e.g. a compound expressed by formula V. This compound expressed by formula I is obtained by reacting BTDTQ with lithium iodide.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel anion radical salt of a benzoquinone derivative useful as an organic electrophotographic material.

[0002]

2. Description of the Related Art Tetracyanoanthraquinodimethane and its derivatives have been conventionally known as compounds useful as organic electronic materials such as organic semiconductors (see, for example, JP-A-57).
No. 149259, No. 58-55450, etc.). The tetracyanoanthraquinodimethanes are compounds having a basic skeleton represented by the following formula and substituted with various substituents.

[0003]

[Chemical 5]

These tetracyanoanthraquinodimethanes are compounds synthesized from the corresponding anthraquinones and are useful compounds as organic electronic materials such as organic semiconductors, organic photographic materials, organic conductors and thermistor materials. Further, the present inventors have succeeded in isolating a charge transfer complex composed of the tetracyanoquinodimethanes and an electron donating compound as a solid pure product at room temperature, and this charge transfer complex is more excellent than a simple substance. It was found to be useful as an organic electronic material, and at least one of the two benzo-condensed rings of tetracyanoanthraquinodimethanes was replaced with another hetero-condensed ring,
Further, they have found that compounds obtained by modifying two dicyanomethylene groups into various groups are also useful as organic electronic materials (JP-A-62-33157).

[0005]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The inventors of the present invention have conducted extensive research on a related compound of a benzoquinone derivative which is a raw material of the above compound, and as a result, found that a novel anion radical salt of a benzoquinone derivative is similar to an organic electronic material. It was found to be useful as Therefore, it is an object of the present invention to provide novel anion radical salts of benzoquinone derivatives.

[0006]

[Means for Solving the Problems] That is, the present invention is
The following general formula (I)

[Chemical 6] (In the formula, ring A and ring B are independent of each other,

[Chemical 7] Represents a heterocycle, and when one represents this heterocycle, the other is

[Chemical 8] Is good. ) An anion radical of a benzoquinone derivative represented by the formula

[Chemical 9] It provides a salt with a cation selected from

Specific examples of the benzoquinone derivative represented by the general formula (I) are shown below by structural formulas.

[0008]

[Chemical 10]

Among the compounds of the above-mentioned specific examples, the compound represented by the formula (3) is novel, and the production steps and literatures including it are shown below.

[0010]

[Chemical 11]

[0011]

[Chemical 12]

[0012]

[Chemical 13]

[0013]

[Chemical 14]

[0014]

[Chemical 15]

[0015]

[Chemical 16]

[0016]

[Chemical 17]

[0017]

[Chemical 18]

[0018]

[Chemical 19]

[0019]

[Chemical 20]

[0020]

[Chemical 21]

Examples of the counter cation of the anion radical of the benzoquinone derivative represented by the general formula (I) of the present invention include the following.

[0022]

[Chemical formula 22]

Among these counter cations, L
i ⁺ , EtN ⁺ (tetraethylammonium ion),
NMPy ⁺ (N-methylpyridinium ion), NMo
-P ⁺ (N-methyl-o-phenanthrolinium ion), NMQ ⁺ (N-methylquinolinium ion) and NMA ⁺ (N-methylacridinium ion) can be preferably used. A method for producing a salt is shown by the following formula when lithium iodide is used. ^{3LiI + 2Q → 2Li + Q -} + Li + + I 3 - Li + Q - + D + X - → D + Q - + Li + + X - ( wherein, Q is with benzoquinone derivative, D ⁺ is a cationic salt to be exchanged, X ^- is the It is a counter anion.)

That is, first, the benzoquinone derivative represented by the general formula (I) is dissolved in an inert organic solvent (acetonitrile or the like) by heating, if desired, and equimolar or more, preferably an excess amount with respect to the benzoquinone derivative. A solution of metal iodide (LiI, NaI, KI, etc.) (preferably a solution in the above-mentioned inert organic solvent) is added,
By allowing to cool, an anion radical salt in which the counter cation is an alkali metal cation (Li ⁺ , Na ⁺ , K ⁺ ) is obtained, and then, if desired, a salt of another counter cation is formed by a salt exchange reaction of the alkali metal cation salt. To get In the case of a salt exchange reaction, a solution obtained by dissolving an alkali metal cation salt in an inert organic solvent is added with a solution containing an excessive amount of the salt of the cation to be exchanged, then cooled, and the precipitated crystals may be filtered and washed. .

[0025]

INDUSTRIAL APPLICABILITY The salt of the present invention is useful as an organic electronic material, and can be used as an organic electrophotographic material, a capacitor material, a low resistance thermosensitive element, a sensor material and the like. For example, when it is used as a charge transporting material for an electrophotographic photoreceptor, it can be used together with a binder resin such as polycarbonate or polyester to form a charge transporting layer, or it can be contained in a charge generating layer together with a charge generating material.

[0026]

EXAMPLES The present invention will be specifically described below with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited thereto. Reference example: Synthesis of benzoquinone derivative represented by formula (3)

[0027]

[Chemical formula 23]

12.3 g (50 mmol) of chloranil (I) was added to 18
Suspend in 0 ml dimethylformamide (DMF) and cool to 10 ° C in an ice bath. Malon nitrile CH
(CN) ₂ C ₂ S ₂ Na ₂ [J. Org. Chem., 2 prepared from ₂ (CN) ₂ , carbon disulfide and sodium hydroxide.
9 , 660 (1969)] A solution prepared by dissolving 18.4 g (99 mmol) in 50 ml of water was added dropwise to the above DMF solution over 30 minutes, and then stirred at room temperature for 5 hours, and then 50 ml of water was added and ice-cooled. To do. The precipitate was separated by filtration, washed with 100 ml of water, and recrystallized from tetrahydrofuran (THF) -methanol to give the following compound.

[0029]

[Chemical formula 24]

10.09 g of the hydroquinone derivative represented by
(Yield 52%), yellow green needle crystals (melting point> 384 ° C.). 2.0 g (5.18 mmol) of this hydroquinone derivative was suspended in 150 ml of anhydrous THF, and dicyanodichloro-
20% of p-benzoquinone 1.41 g (6.22 mmol, 1.2 equivalents)
A solution in ml of dry THF is added dropwise over 20 minutes.
Stir for 4 hours at room temperature and filter off the purple crystals. Yield: 1.52 g (76%); Melting point: 397 ° C. or higher (decomposition); IR (KBr tablet method): 2203 cm ^-1 (CN); Mass: m / e 384 (M ⁺ , 100%); Elemental analysis: C Calculated as ₁₄ N ₄ S ₄ O ₂ (%): C 43.74 N 14.57 S 33.76, found (%): C 43.74 N 14.68 S 33.24.

Example 1

[Chemical 25]

BTDTQ (4) 38 mg (0.1 mmol) 40
A solution of 50 mg (0.39 mmol) of lithium iodide dissolved in 5 ml of acetonitrile was added to the solution, which was dissolved in dry acetonitrile by heating. After allowing to cool, black green needle crystals were filtered off and washed with acetonitrile to obtain the title salt. Black-green needles. Melting point> 355 ° C (decomposition). Elemental analysis: calculated as LiC ₈ S ₆ O ₂ .2H ₂ O (%): C 26.44 H 1.11 S 52.93, measured value (%): C 26.98 H 1.31 S 50.08.

Example 2

[Chemical formula 26]

The title salt was obtained in the same manner as in Example 1 except that BTDTQ (4) was replaced with BDTIQ (2). Blue-violet powder. Melting point> 400 ° C (decomposition). IR (KBr tablet method): 2228 cm ^-1 (CN); Elemental analysis: Calculated as LiC ₁₄ N ₄ S ₄ O ₂ (%): C 42.96 H 0.00 N 14.32, measured value (%): C 42.17 H 0.15 N 14.39.

Example 3

[Chemical 27]

33 mg (0.1 mmol) of the salt prepared in Example 1
Is dissolved in 20 ml of dry acetonitrile by heating, and NMA ⁺
CH ₃ SO ₄ ^- addition of a solution of salt 100mg of (0.33 mmol) was dissolved in acetonitrile 5 ml. After allowing to cool, the precipitated brown crystals are filtered off and washed with acetonitrile and ether to give 40 mg of the title salt. Melting point: 230-255 ° C (decomposition). Elemental analysis: calculated as C ₂₂ H ₁₂ NS ₆ O ₂ (%): C 51.34 H 2.35 N 2.72, found (%): C 50.59 H 2.22 N 2.67.

Example 4 Conductivity of Anion Radical Salt The salt of the present invention consisting of a combination of a cation and a benzoquinone derivative shown in Table 1 below was pelletized by a two-terminal method or a four-terminal method and their specific resistance values ( ρ / c
m). The results are shown in Table 1.

[0038]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07D 495/04 101 9165-4C 111 9165-4C // G03G 5/06 9221-2H 376 9221-2H

Claims (1)

[Claims] 1. The following general formula (I): (In the formula, ring A and ring B are independent of each other, and When one of the heterocycles is represented by the other, the other is Is good. An anion radical of a benzoquinone derivative represented by the formula: A salt with a cation selected from.