JPH04273856A - Production of indolenine compound - Google Patents

Abstract

PURPOSE:To obtain a high-purity indolenine compound useful as an intermediate for dye such as cyanine dyestuff, functional dyestuff, etc., from a readily obtainable raw material having no toxicity in high yield, industrially, economically and extremely advantageously. CONSTITUTION:A hydrazine derivative shown by formula I (R is benzene-based or naphthalene-based residue which may be further substituted; m is 1 or 2), preferably naphthalenesulfonic acid-based compound, especially 2- hydrazinonaphthalenesulfonic acid is reacted with isopropyl methyl ketone in the presence of an acid, preferably hydrochloric acid or sulfuric acid or a mixture of the acid and an organic acid such as acetic acid to give an indolenine shown by formula II (A is benzene ring or naphthalene ring which may be further substituted). The compound shown by formula I is preferably used in the form of sulfonate, especially sodium salt.

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new method for producing indolenine compounds useful as intermediates for producing dyes such as cyanine dyes and functional dyes.

0002

[Prior Art] As a conventional method for producing an indolenine compound, a method is known in which an indolenine compound having no sulfonic acid group is sulfonated using a sulfonating reagent (for example, U.S. Pat. No. 3,423,207, Examples 10).

0003

[Problems to be Solved by the Invention] However, in this method, (1) a sulfonic acid group can only be introduced at a specific position; ■A large amount of sulfonation reagent is required and the yield is low. ■Indolenine compound itself or its raw material hydrazine compound, and further traced back to its raw material, amine compound (
(naphthylamine, etc.) are highly toxic and unsuitable for industrial production. In particular, for example, the starting material 2-naphthylamine is a substance whose production is prohibited due to carcinogenic properties and cannot be used industrially. There are several problems.

[0004] In order to solve the above problems, the inventors of the present invention have conducted extensive research and examination, and as a result have arrived at the novel method of the present invention, which solves all the conventional problems at once.

[0005]

[Means for Solving the Problems] The present invention provides general formula (I)
(HO3S)n-R-NHNH2 (I
) [(I) In the formula, R represents a benzene-based or naphthalene-based residue which may be further substituted, and n represents 1 or 2. The following general formula (II) is characterized by reacting a hydrazine derivative represented by ] with isopropyl methyl ketone in the presence of an acid.

embedded image [In formula (II), A represents a benzene ring or naphthalene ring which may be further substituted, and n represents 1 or 2. ) is a method for producing an indolenine compound represented by:

The hydrazine derivative represented by the general formula (I), which is a raw material compound used in the method of the present invention, includes benzene-based and naphthalene-based hydrazine compounds having a sulfone residue, and these are all known compounds. It can be easily obtained by known methods. (For example, Methoden der Organischen Hemy 10 no 2
Volume P169 ~)

Specifically, phenylhydrazine-4-sulfonic acid, phenylhydrazine-3-sulfonic acid, 3-
Methylphenylhydrazine-4-sulfonic acid, 2-hydrazinonaphthalene-5-sulfonic acid, 2-hydrazinonaphthalene-6-sulfonic acid, 2-hydrazinonaphthalene-7-sulfonic acid, 2-hydrazinonaphthalene-4- Sulfonic acid, 1-hydrazinonaphthalene-5-sulfonic acid, 1-hydrazinonaphthalene-7-sulfonic acid, 2-hydrazinonaphthalene-5,7-disulfonic acid, 4-hydrazino-biphenyl-4'-sulfonic acid, Examples include 4-hydrazino-biphenyl ether-4'-sulfonic acid.

The method of the invention is carried out in the presence of an acid. Here, the acid used is an inorganic acid, an organic acid, or a single or a mixture thereof. Specifically, hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, acetic acid, formic acid, propionic acid, Examples include hydriodic acid and strongly acidic ion exchange resins, among which hydrochloric acid and sulfuric acid alone or a mixture of these and an organic acid such as acetic acid are preferably used.

These acids can be used in an anhydrous state or as a diluted aqueous solution, or in a suitable solvent that does not participate in the reaction.
For example, it can also be carried out in alcohols, dioxane, chloroform, etc. However, it is particularly advantageous to work in systems which normally contain 1 to 90% water.

Isopropyl methyl ketone, which is the other raw material of the present invention, is used in an amount equal to or more than the same molar amount as the hydrazine derivative. Preferably 2 to 2 to hydrazine derivatives
The molar ratio is 10.

When carrying out the method of the present invention, the general formula (
Although the hydrazine derivative I) can be used as a free sulfonic acid, it has been found that it is particularly preferable to use it in the form of a neutral salt such as sodium or potassium. In this case, the free sulfonic acid in the reaction system can be maintained in a neutral salt state by the action of an alkali such as sodium acetate or sodium carbonate, and then used for the reaction.

[0012] The reaction of the present invention is carried out under atmospheric pressure or under increased pressure.
This is usually carried out by suitably mechanically mixing the raw materials with or without heating. The temperature in the case of heating is usually 50°C to 120°C, preferably 60 to 100°C.

The reaction of the present invention involves the following general formula (III) produced by the reaction of a hydrazine derivative and isopropyl methyl ketone.

Although it is presumed that the reaction proceeds through the hydrazone compound represented by the following formula, it is not necessary to isolate the intermediate hydrazone compound and carry out the subsequent treatment.

The progress of the reaction of the present invention can be monitored by TLC or LC,
It can be tracked by suitable analytical means such as GC. The reaction products may be separated by conventional work-up means such as salting out, filtration, dilution, concentration, extraction, distillation, amine extraction, etc.

The indolenine compound represented by the general formula (II), which is the object of the present invention, is usually obtained in the form of a free acid, but in some cases, by neutralization, it can be converted into an alkali metal salt, an amine salt, etc. It can also be obtained in salt form.

[0016]

Effects of the Invention According to the method of the present invention, a hydrazine derivative having a sulfonic acid group at a specified position is used as a raw material,
The desired indolenine compound represented by the general formula (II) can be produced with high purity and high yield in an industrially and economically very advantageous manner. In particular, the raw material hydrazine compound and the further raw material amine compound have high industrial value because they are non-toxic and easily available compounds.

[0017]

[Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Crystalline sodium acetate was added to a mixture of 3.0 parts of 2-hydrazinonaphthalene-6-sulfonic acid, 4.05 parts of isopropyl methyl ketone (4 molar ratio) and 10 parts of water at 45°C.
2.7 parts followed by 60 parts by weight of glacial acetic acid. Next, 6 parts of concentrated hydrochloric acid was added, and the mixture was stirred at 75° C. for 10 hours. 100 parts by weight of isopropanol is added, and the precipitate is filtered off and washed with isopropanol. Columnar white crystal 3
．． I got 8 copies. As a result of LC analysis, the purity was 99.2% and the yield was 99.5%.

This product was poured into water, and sodium bicarbonate was added to dissolve it. Salt was added to the activated carbon-treated filtrate, and N
Crystals of a salt were obtained and acidified with acetic acid again in water to obtain crystals. Elemental analysis values, proton NMR, 13C-NMR, FD
- An indolenine compound of the following formula was confirmed by MS.

[C5]

Example 2 3.0 parts of 2-hydrazinonaphthalene-6-sulfonic acid used in Example 1 was replaced with 2-hydrazinonaphthalene-6-sulfonic acid.
Using 5-sulfonic acid, otherwise carrying out in exactly the same manner, the following formula

[C6] An indolenine compound represented by was obtained.

Example 3 The same procedure was repeated except that 3.0 parts of 2-hydrazinonaphthalene-6-sulfonic acid used in Example 1 was replaced with 2.37 parts of 4-hydrazinobenzenesulfonic acid. ,
2.78 parts of 2,3,3-trimethylindolenine-5-sulfonic acid were obtained.

Example 4-6 Table 1 shows the results obtained by changing the conditions of Example 1 as shown in the following table.

[Table-1]

Claims (5)

[Claims] Claim 1: General formula (I) (HO3S)n-R-NHNH2 (I
) [(I) In the formula, R represents a benzene-based or naphthalene-based residue which may be further substituted, and n represents 1 or 2. [In formula (II), A may be further substituted] [Formula (II), A may be further substituted] It represents a benzene ring or a naphthalene ring, and n represents 1 or 2. ] A method for producing an indolenine compound represented by 2. The method for producing an indolenine compound according to claim 1, wherein the hydrazine derivative represented by the general formula (I) is used as a sulfonic acid salt. 3. The method for producing an indolenine compound according to claim 2, wherein a sodium salt is used as the sulfonic acid salt. 4. The method for producing an indolenine compound according to claim 1, wherein the hydrazine derivative represented by formula (I) is a naphthalenesulfonic acid compound. 5. The method for producing an indolenine compound according to claim 4, wherein the naphthalene sulfonic acid compound is 2-hydrazinonaphthalene sulfonic acid. 0001