JP3151687B2 - Method for synthesizing 4-amino-o-quinone derivative and 3-amino-6-arylazophenol derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to 4-amino-o-quinone derivatives useful as intermediates for medical chemicals, dyes and dyes for thermal transfer materials, and 3-amino-6 useful as dyes and dyes for thermal transfer materials. -A method for synthesizing an arylazophenol derivative.

[0002]

2. Description of the Related Art Conventionally, a synthesis method for obtaining a diazo dye from an o-quinone derivative and a hydrazine derivative in an acetic acid solvent has been known.
J. Chem. (Indian Journal of Chemistry) 2 (6), p. 232 (1964).
Also, as a method for synthesizing a 4-amino-o-quinone derivative,
A method of reacting catechol with an amine compound in methanol in the presence of silver (I) oxide is described in Ber. (Berichte) 89,2768.
Page (1956).

Therefore, referring to the above synthesis method, catechol and an amine compound are isolated as a 4-amino-o-quinone derivative in methanol in the presence of silver (I) oxide and reacted with an arylhydrazine to obtain A 3-amino-6-arylazophenol derivative can be obtained. However, this synthesis method is effective when the 4-amino-o-quinone derivative to be isolated is stable. -o
-Not only is the quinone derivative decomposed, but also by-products are produced during the synthesis reaction, which leads to a decrease in the synthesis yield of the 4-amino-o-quinone derivative, which is not preferred. In addition, the reaction is a two-stage reaction, and requires a step of isolating the intermediate 4-amino-o-quinone derivative, which is not preferable because it increases the production cost. Further, silver oxide (I) is expensive and is not preferred in terms of cost.

Further, a method of obtaining a synthetic intermediate 4-amino-o-catechol derivative from catechol, amines and sodium iodate is described in J. Chem. Soc. (Journal of the.
Chemical Society), page 859 (1958), but is not preferred for the same reasons as in the above synthesis method.

[0005]

An object of the present invention is to synthesize a 4-amino-o-quinone derivative from a catechol and an amine compound in a high yield in the presence of an acid and an oxidizing agent, and further condense the 3-amino-o-quinone derivative with an arylhydrazine compound. An object of the present invention is to provide a method for synthesizing a 6-arylazophenol derivative with high yield.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to provide a method for reacting catechol with an amine compound in the presence of an acid and an oxidizing agent.
This was achieved by a method for synthesizing -o-quinone derivatives and a method for synthesizing 3-amino-6-arylazophenol derivatives by reacting catechol with an amine compound in the presence of an acid and an oxidizing agent and condensing with an arylhydrazine compound.

Hereinafter, the present invention will be described in more detail.

The oxidizing agent used in the present invention is silver oxide
(I), sodium iodate, potassium permanganate, hydrogen peroxide, iodine, osmium tetroxide, sodium hypochlorite and the like are preferred. The oxidizing agent may be added in an amount of 1 to 3 times the molar amount of catechol, and particularly preferably 1.5 to 2.5 times the molar amount because a higher yield can be obtained.

The acid used in the present invention includes acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, hydrochloric acid, nitric acid, sulfuric acid,
Phosphoric acid and the like are preferable, and two or more kinds can be used as a mixture.

The solvent used in the present invention is not particularly limited, but is not particularly limited as long as it does not react with the arylhydrazine compound in the reaction using the arylhydrazine compound. Representative solvents include methanol, ethanol, toluene, and the like. Xylene, chloroform, dioxane, tetrahydrofuran and the like are preferable, and an acid used for the reaction may be used as a solvent. The amount of the solvent is not particularly limited as long as it is an amount sufficient to stir the catechol and the amine compound.

If the reaction temperature is too low, the reaction is slow, and if the reaction temperature is too high, by-products increase, so that the reaction temperature is preferably -10 to 60 ° C, particularly preferably 0 to 20 ° C.

Representative specific examples of the 4-amino-o-quinone derivative and 3-amino-6-arylazophenol derivative according to the present invention are shown below, but are not limited thereto.

[0013]

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R ₁ R ₂ R ₁ R ₂ I-1 CH ₃ C ₆ H ₅ I-5 C ₆ H ₁₃ C ₆ H ₅ I-2 C ₂ H ₅ C ₂ H ₅ I-6 C ₂ H ₅ 3 -CH ₃ -C ₆ H ₄ I-3 HC ₄ H ₉ I-7 C ₂ H ₅ 2-CH ₃ OC ₆ H ₄ I-4 HC ₆ H ₅ I-8 CH ₃ 4-CO ₂ C ₂ H ₅ -C ₆ H ₄

[0015]

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[0016]

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[0017]

[0018]

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[0019]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1-1 (Synthesis of Compound I-1) 300 g of acetic acid was added to 10 g of catechol, 10 g of N-methylaniline was added, and an aqueous solution of 13 g of sodium iodate was added with stirring.
130 cc was dropped. After stirring for 1 hour, the reaction solution was added dropwise to 1000 cc of water, whereby black crystals of 4-N-methylanilino-o-quinone were precipitated (89% yield). Example 1-2 Instead of N-methylaniline of Example 1-1, diethylamine, butylamine, aniline, N-hexylaniline,
When a similar reaction was performed using N-ethyl-m-toluidine, N-ethyl-o-anisidine, and ethyl 4-methylaminobenzoate, the corresponding compounds I-2, I-3, I-4, I
-5, I-6, I-7 and I-8 were obtained at a yield of 60%, 54%, 82%, 70% and 82%.
%, 72% and 78%.

Example 1-3 The same reaction was carried out using hydrogen peroxide, potassium permanganate and sodium hypochlorite in place of the sodium iodate of Example 1-1. I−
The yields of 1 were 70%, 68% and 72%, respectively.

Example 1-4 (Synthesis of Compound I-9) The same reaction was carried out using 4-methylcatechol instead of catechol of Example 1-1, and it was found that 4-N-methylanilino-5- was obtained. Methyl-o-quinone was obtained in a yield of 80%.

Example 1-5 A similar reaction was carried out using 10 cc of hydrochloric acid and 290 cc of methanol instead of 300 cc of acetic acid added to the catechol of Example 1-1, and the yield of compound I-1 was 68%. Was.

Example 2-1 (Synthesis of Compound II-1) 300 g of acetic acid was added to 10 g of catechol, 10 g of N-methylaniline was further added, and an aqueous solution of 13 g of sodium iodate was added with stirring.
130 cc was dropped. After completion of the dropwise addition, the reaction system was cooled to 10 ° C., and 100 g of an acetic acid solution of 10 g of 2-hydrazinopyridine was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, acetic acid was distilled off under reduced pressure, the residue was extracted with ethyl acetate, washed with a saturated aqueous solution of potassium carbonate and brine, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. did. The residue was recrystallized from acetonitrile to obtain 24 g of 3-N-methylanilino-6- (2-pyridyl) azophenol red crystals (yield 87%).

Example 2-2 In place of N-methylaniline in Example 2-1, aniline and N-methylaniline were used.
Hexylaniline, N-ethyl-m-toluidine, N-ethyl-
A similar reaction was performed using o-anisidine, ethyl 4-methylaminobenzoate, 3-chloro-N-propylaniline, and 4-dimethylcarbamoyl-N-methylaniline, and the corresponding compounds II-2 and II, respectively. -3, II-4, II-5, II-
6, II-7, II-8 were obtained in a yield of 70%, 64%, 89%, 66%, 73%, 68%.
%, 59%.

Example 2-3 A similar reaction was carried out using hydrogen peroxide, potassium permanganate and sodium hypochlorite in place of the sodium iodate of Example 2-1. II−
The yields of 1 were 60%, 58% and 65%, respectively.

Example 2-4 (Synthesis of Compound II-9) A similar reaction was carried out using 4-methylcatechol instead of catechol of Example 2-1 to obtain 3-N-methylanilino-4- Methyl-6- (2-pyridyl) azophenol yield 72
%.

Example 2-5 A similar reaction was carried out using 3-bromo-6-hydrazinopyridine and 2-hydrazino-4-methylpyridine instead of 2-hydrazinopyridine in Example 2-1. However, corresponding compounds II-10 and II-11 were obtained in 75% and 78% yield. Example 2-6 The same reaction was carried out using 10 cc of hydrochloric acid, 290 cc of methanol, 10 cc of nitric acid and 290 cc of ethanol, 10 cc of sulfuric acid and 290 cc of tetrahydrofuran instead of 300 cc of acetic acid added to the catechol of Example 2-1. The yields of -1 were 51%, 45%, and 48%, respectively.

[0029]

Industrial Applicability According to the present invention, 4-amino-o-quinone derivatives useful as intermediates for medical chemicals, dyes, and dyes for thermal transfer materials, and 3-amino-6-use useful as dyes and dyes for thermal transfer materials An arylazophenol derivative can be obtained easily and in good yield.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Daiwa Komamura 1st Sakuramachi, Hino-shi, Tokyo Konica Co., Ltd. Examiner, Koji Ito (56) References Tetrahedron, 1990, Vol. 46, No. 2, pages 661-670 (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 225/28 C07C 221/00 C07D 213/76 CASREACT (STN)

Claims (2)

(57) [Claims] 1. A method of reacting catechol with an amine compound in the presence of an acid and an oxidizing agent.
A method for synthesizing quinone derivatives. 2. A method for synthesizing a 3-amino-6-arylazophenol derivative, comprising reacting catechol with an amine compound in the presence of an acid and an oxidizing agent, and subsequently condensing the reaction with an arylhydrazine compound.