JPH0211585B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () (In the formula, R represents an alkyl group or a cycloalkyl group, and R′ represents a phenyl group, a naphthyl group, an alkyl group, a cycloalkyl group, or an aralkyl group. When R′ is a phenyl group, an alkyl group or a cycloalkyl group , which may be substituted with a phenyl group or an alkoxy group). The quinone derivative represented by the general formula () is a novel compound that has not been previously known. As a result of various studies on quinone derivatives, the present inventors discovered the general formula () (In the formula, R and R' have the same meanings as in the general formula ())
21265: hereinafter referred to as a hydroquinone derivative) by an appropriate method, a quinone derivative represented by the general formula () is produced, and it was discovered that it could be isolated as a compound that exists stably at room temperature
The invention has been completed. The novel quinone derivatives of the present invention are generally isolated as pale yellow crystals. A solution of the substance in an organic solvent is colored yellow and forms adducts with alcohols. It also has a strong oxidizing ability, for example, it quickly performs the following oxidation reactions, Moreover, since it has the characteristic that the produced dye molecules are not subject to oxidative decomposition, it becomes a useful coloring material for, for example, pressure-sensitive and thermal copying paper. Hydroquinone derivatives, which are the starting materials for the compounds of the present invention, are synthesized from dihalogenated dioxoterephthalic acid diesters and sulfinates, for example, in the following manner. There are various methods for producing a new quinone derivative represented by the general formula () by oxidizing the hydroquinone derivative represented by the general formula (). For example,
Dissolves in fuming nitric acid when cold and drains into water after a short time.
Alternatively, a method of heating in a metal oxide-based oxidizing agent and an inert organic solvent is easy to carry out. Examples of the oxidizing agent used to oxidize the hydroquinone derivative represented by the general formula () in an inert organic solvent include nitrogen tetroxide, lead tetracomplex, silver oxide, lead peroxide, nickel peroxide, manganese dioxide, and Compounds such as manganese trioxide are used, but manganese dioxide is usually used frequently. Although the novel quinone derivative represented by the general formula () is a stable compound, it easily reacts with substances having polar groups, so it is preferable to handle it in an inert organic solvent or water. The following hydroquinone derivatives of the general formula () are used as starting materials for the novel quinone derivatives of the present invention. 3,6-dibenzenesulfonyl-2,5-dihydroxyterephthalic acid dimethyl ester, 3,
6-Dibenzenesulfonyl-2,5-dihydroxyterephthalic acid diethyl ester, 3,6-dibenzenesulfonyl-2,5-dihydroxyterephthalic acid dibutyl ester, 3,6-dibenzenesulfonyl-2,5-dihydroxy Terephthalic acid dioctyl ester, 3,6-dibenzenesulfonyl-2,5-dihydroxyterephthalic acid dicyclohexyl ester, 3,6-di-p-toluenesulfonyl-2,5-dihydroxyterephthalic acid dimethyl ester, 3,6-dibenzenesulfonyl-2,5-dihydroxyterephthalic acid dimethyl ester Di-p-toluenesulfonyl-2,5-dihydroxyterephthalic acid diethyl ester, 3,6-di-p-toluenesulfonyl-2,5-dihydroxyterephthalic acid di-isobutyl ester, 3,6-di-
p-toluenesulfonyl-2,5-dihydroxyterephthalic acid di-cyclohexyl ester,
3,6-di-p-toluenesulfonyl-2,5-
Dihydroxyterephthalic acid dibenzyl ester, 3,6-di-p-toluenesulfonyl-2,
5-dihydroxyterephthalic acid di-n-dodecyl ester, 3,6-di-(3',4'-dimethylbenzenesulfonyl)-2,5-dihydroxyterephthalic acid diethyl ester, 3,6-di-(2 ′、
5'-dimethylbenzenesulfonyl)-2,5-dihydroxyterephthalic acid diethyl ester,
3,6-di-(2',4'-dimethylbenzenesulfonyl)-2,5-dihydroxyterephthalic acid diethyl ester, 3,6-di-(pt-butylbenzenesulfonyl)-2,5-di Hydroxyterephthalic acid diethyl ester, 3,6-di-
(p-cyclohexylbenzenesulfonyl)-2,
5-dihydroxyterephthalic acid diethyl ester, 3,6-di-(p-phenylbenzenesulfonyl)-2,5-dihydroxyterephthalic acid diethyl ester, 3,6-di-2-naphthylsulfonyl-2,5- Di-hydroxyterephthalic acid diethyl ester, 3,6-di-p-methoxybenzenesulfonyl-2,5-dihydroxyterephthalic acid diethyl ester, 3,6-di-p-ethoxybenzenesulfonyl-2,5-dihydroxyterephthal acid diethyl ester, 3,6-di-methylsulfonyl-2,5-dihydroxyterephthalic acid diethyl ester, 3,6-di-ethylsulfonyl-2,5-dihydroxyterephthalic acid dimethyl ester, 3,6-di- Ethylsulfonyl-2,5-dihydroxyterephthalic acid diethyl ester, 3,6-di-butylsulfonyl-2,5-dihydroxyterephthalic acid diethyl ester, 3,6-dihexylsulfonyl-2,
5-dihydroxyterephthalic acid diethyl ester, 3,6-dicyclohexylsulfonyl-2,
Examples include 5-dihydroxyterephthalic acid diethyl ester, 3,6-dibenzylsulfonyl-2,5-dihydroxyterephthalic acid diethyl ester, and 3,6-dibenzylsulfonyl-2,5-dihydroxyterephthalic acid dicyclohexyl ester. It will be done. Examples of the novel quinone derivatives of the present invention are shown in Table 1 below, but the present invention is not limited thereto.

【table】

[Table] The method of the present invention will be described in detail below with reference to Examples. In the text, parts mean parts by weight. Example 1 Synthesis of 2,5-di-benzenesulfonyl-3,6-dioxoterephthalic acid diethyl ester (Table 1 Compound No. 1) Diethyl 2,5-di-benzenesulfonyl-3,6-dihydroxyterephthalate When 1 part of the ester is added to 5 parts of ice-cooled fuming nitric acid and stirred well, it dissolves rapidly and a reddish-brown gas is observed to be produced. The mixture was stirred for 15 minutes under ice-cooling, then drained into a large amount of ice water, and the precipitated solid was filtered, washed with water, and air-dried. Then, the melting point was
Pale yellow crystals at 213-215°C were obtained with a yield of 80%. The elemental analysis values of this product were as follows. Elemental analysis value (%) C H S Calculated value 54.13 3.79 12.04 Actual value 53.04 4.40 11.82 Also, when a benzene solution of this product was mixed with a benzene solution of a triphenylmethane compound, such as a ryuco crystal violet, the color rapidly developed to blue-purple. . Example 2 2,5-di-p-toluenesulfonyl-3,6
-Synthesis of dioxoterephthalic acid diisobutyl ester (Table 1 Compound No. 5) 2,5-di-p-toluenesulfonyl-3,6
-1 part of dihydroxyterephthalic acid diethyl ester was stirred with 5 parts of manganese dioxide and 20 parts of benzene under reflux for 6 to 7 hours, and at the same time the water produced was removed from the system by an appropriate method. Then, the hot contents were strained, the manganese dioxide residue was washed with hot benzene, the liquid and washing liquid were combined and concentrated, and ligroin was added to precipitate the target product. It was strained, dissolved in benzene, and recrystallized by adding ligroin to give pale yellow crystals with a melting point of 197-199°C. (Yield approximately 80%) Elemental analysis values were as follows. Elemental analysis value (%) C H S Calculated value 58.43 5.23 10.40 Actual value 58.39 5.30 10.36 Example 3 2,5-di-cyclohexylsulfonyl-3,
Synthesis of 6-dioxoterephthalic acid diethyl ester (Compound No. 15 in Table 1) In Example 2, 2,5-di-p-toluenesulfonyl-3,6-dihydroxyterephthalate diethyl was replaced with - Dry silver oxide newly made from silver nitrate and caustic soda instead of manganese dioxide using diethyl cyclohexylsulfonyl-3,6-di-hydroxyterephthalate.
Add 0.7 part, otherwise operate in the same manner as in Example 2,
Pale yellow crystals with a melting point of 190.5-192.5°C were obtained in a yield of about 90%. The elemental analysis values were as follows. Elemental analysis value (%) C H S Calculated value 52.73 6.27 11.73 Actual value 53.01 6.21 11.83 Example 4 Other compounds in Table 1 were synthesized from the corresponding hydroquinone by manganese dioxide oxidation according to the method of Example 2. All of the quinone compounds were obtained in yields in the 80% range, the elemental analysis values were in good agreement with each other, and the coloring properties for triphenylmethane compounds were all good.

Claims (1)

[Claims] 1 General formula () (In the formula, R represents an alkyl group or a cycloalkyl group, and R' represents a phenyl group, a naphthyl group, an alkyl group, an aralkyl group, a cyclohexyl group, or a cyclohexylmethyl group. When R' is a phenyl group, an alkyl group, A novel quinone derivative represented by (optionally substituted with a cycloalkyl group, phenyl group or alkoxy group).