JPS63225382A - Novel benzoquinone derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I. USE:An organic electronics material, such as an organic semiconductor, capable of readily forming a charge-transfer complex with an electron donor. PREPARATION:A hydroquinone derivative expressed by formula II is oxidized by an oxidizing agent (example; ferrous chloride) to form a compound expressed by formula I. For example, the hydroquinone derivative expressed by formula II is dissolved into an alcohol as an oxidizing agent-dissolving solvent and an alcohol solution of FeCl3 is added thereto, heated while refluxing and left as it is to be cooled. Then water is added thereto and the aimed material precipitated therein is filtered.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel benzoquinone derivative useful as an organic electronic material and a method for producing the same.

[Conventional technology]

Tetracyanoanto-2-quinodimethane and its derivatives have been known as compounds useful as organic electronic materials such as organic semiconductors (for example, JP-A-57-149259).
No. 58-55450, etc.).

These tetracyanoanthraquinodimethanes are compounds having a basic skeleton represented by the following formula and substituted with various substituents.

yc""ON These tetracyanoanthraquinodimethanes are compounds useful as organic electronic materials such as device semiconductors, organic photographic materials, organic conductors, and thermistor materials composed of the corresponding anskiquinones.

In addition, the present inventors succeeded in isolating a charge transfer complex consisting of the natho-2-cyanoquinodimethane and an electron-donating compound as a pure product that is solid at room temperature, and this charge transfer complex is more effective than a simple substance. It was discovered that it is useful as an organic electronic material, and furthermore, at least one of the two benzo-fused metal rings of tetracyanoanthraquinodimethanes was replaced with another heterofused ring, and the two dicyanomethylene groups were replaced with various types. It has also been found that compounds modified with the group are also useful as organic electronic materials (Japanese Patent Application No. 171161/1982).

[Problem that the invention seeks to solve]

As a result of extensive research into analogues of benzoquinone derivatives, which are raw materials for the above-mentioned compounds, the present inventors discovered a novel benzoquinone derivative that can be used in charge transfer complexes.

Therefore, an object of the present invention is to provide a novel inzoquinone-bound conductor and a method for producing the same.

[Means for solving problems]

The present invention provides a method for producing a benzoquinone derivative represented by the following structural formula and the above-mentioned benzoquinone derivative by oxidizing a human quinone derivative represented by the following structural formula with an oxidizing agent.

The benzoquinone derivative of the present invention can be obtained by the following reaction scheme.

? Step (A) is a disodium salt (1) obtained from malonitrile CH2(CN)2, carbon disulfide and sodium hydroxide (J, Org, Chem,...
29, 660 (1969)) with chloranil (I
) in DMI' to form a hydroquinone derivative (I[
This is the process of obtaining I).

Hydroquinone spindle (m) is a yellow-green crystal with a melting point of 384° C. or higher.

Next, the hydroquinone derivative (1) is oxidized to a benzoquinone derivative by the method of the present invention in step (b).

As the oxidizing agent, dicyanodichloro4-p-benzoquinone (DDQ), Na20r207-H2SO, chloride chloride
Iron, etc. can be used.

In the method of using DDQ as an oxidizing agent, it is common to use dioxane or dioxane as a solvent, remove the by-product dihydro form of DDQ (DDHQ), and separate the target product from the p-liquid. Since the raw material hydroquinone derivative is slightly electrolytic in these solvents, DDHQ17) THI' with high solubility is preferred as the solvent;
The desired product can be obtained as a pure product by simply dropping a solution of DDQ into the solution, stirring it at room temperature for several hours, and separating the precipitated crystals from house to house. When dioxane is used as the solvent, the product is DDH
Since it contains impurities such as Q, further purification is necessary, and the reaction does not proceed because the hydroquinone compound (■) is insoluble in benzene.

When using ferrous chloride as an oxidizing agent, an alcoholic solution of li''eC13 is added to a solution of hydroquinone (III) in alcohol, which is a soluble solvent for the oxidizing agent, heated to reflux, and allowed to cool. Afterwards, water may be added and the precipitated target material may be separated in a furnace.

〔Effect of the invention〕

The novel benzoquinone derivatives of the present invention easily form charge transfer complexes with electron donors and can be converted into salts of anions or anion radicals by conventional methods.

Charge transfer complexes of benzoquinone derivatives and salts of anions or anion radicals according to the present invention are organic semiconductors,
It is useful as a conductor and can be used in organic electrophotographic materials.

〔Example〕

E 12.311 (50 mmol) of chloranil (I)
Suspend in 80 d of DMF and cool to 10° C. in a water bath. Disodium salt (1) (J, Org, Ch
em,, 29.

660 (1969)] 1a4
g (99 mmol) dissolved in 50 g J of water was added dropwise to the above DMF solution over 30 minutes, and then at room temperature for 5 minutes.
After stirring for an hour, add 50 ml of water and cool on ice.

The precipitate was taken from house to house, washed with 100 m of water, and then recrystallized from TH1i'-methanol to obtain hydroquinone crystal conductor [phase] 1.
α09F (yield 52%) is obtained. Yellow-green needles.

Melting point>384°C (decomposed).

IRL; JcBr: 1460.1450(8), 2
210?1650 (br), 1360, 1310 (wax 3
200°2930.1690,1180,1100,6
70゜500ge4 Hydroquinone compound ZOII (5,18w
nol) was suspended in 150-anhydrous THE' and DD
Ql, 411 (6,22 mmol, L2 e(1)
A solution of 20114 dissolved in anhydrous THF was added dropwise over 20 minutes. Stir at room temperature for 4 hours and separate the purple crystals.

Yield 1.52.9 (769b). Melting point〉397℃ (min M
); IRLtHHr2203as-"; Mass n7e 384 (M, 100%) Elemental analysis: NS as C,, N4S40□ Calculated value (ch) 43.74 14.57 33
．． 36 Actual value (%) 43.74 1468
33.24゜Example 2 Hydroquinone body (1D10029 (0,26mmoA
') with 8d Geo'Pt'', QC suspended, DDQ70
Add X19 (0.30 mmol.
) 80■ (composition ratio 80%) is obtained.

Example 3 Hydroquinone body (III) 100W (α26 mmo7
) was suspended in 10 m ethanol, and F e Cla
・6H206H2O140α5 mmo42 eq) can be taught. After heating under reflux for 10 minutes, the mixture was allowed to cool, 10 d of water was added, and the mixture was sieved to obtain 80 ml of benzoquinone derivative (yield: 80%).

Claims (1)

[Claims] 1) A benzoquinone derivative represented by the following structural formula. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ 2) The following structural formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The following structural formula is characterized by oxidizing the hydroquinone derivative represented by with an oxidizing agent The method for producing benzoquinone derivatives shown by ▼.