JPS61251675A - Production of naphtho(2.3-d)thiazole-4,9-dione compound - Google Patents

Abstract

PURPOSE:To obtain the titled compound in high yield, by reacting a 2-amino-3- chloro-1,4-naphthoquinone compound with sodium sulfide in a water-soluble polar organic solvent in an inert gas atmosphere, and reacting the reaction product with an aldehyde in the presence of an acid catalyst. CONSTITUTION:A 2-amino-3-halo-1,4-naphthoquinone compound (e.g. 2-amino-3- chloro-1,4-naphthoquinone, etc.) is made to react with a sulfide (e.g. alkali metal sulfide, ammonium sulfide, etc.) in a water-soluble inert polar solvent such as water-soluble N,N-dialkyl-substituted acid amide, N,N-dialkyl-substituted phosphoric acid triamide, etc., in an inert gas atmosphere and the obtained reaction mixture containing 2-amino-3-mercapto-1,4-naphthoquinone compound is made to react with an aldehyde in the presence of an acid catalyst such as acetic acid to obtain the titled compound. EFFECT:The reaction can be carried out at a high concentration and the objective product can be produced in high yield and purity. USE:An antiseptic agent, wood preservative and dye.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to naphtho(2,3-d)thiazole-4,9
-Regarding a method for producing a dione compound.

``Prior Art'' Naphtho(2,3-d)thiazole-4,9-dione compounds are useful as fungicides, wood preservatives, or dyes, but the production method has not been Only a method has been disclosed in which -chloro-1,4-naphthoquinone is reacted with sodium sulfide in all water, and then an aldehyde is added and the reaction is carried out in the presence of an acetic acid catalyst.

``Problems to be solved by the invention'' However, this method has the drawbacks of low product purity and low yield, and requires high reaction temperature, and in addition, when increasing the reaction concentration, acid is added. It is not used industrially because the reaction intermediate becomes insoluble in water and precipitates out, making stirring difficult, and the product forms lump-like blocks, making it possible to carry out the reaction only at dilute reaction concentrations. It is not possible.

As a result of research into methods to overcome the drawbacks of such conventional methods, the present inventors discovered that 2-amino-3-chloro-1, 2-amino-3-chloro-1,
The 4-naphthoquinone compound and sodium sulfide are reacted, and then the resulting reaction mixture containing the sodium salt of the 2-amino-3-mercapto-1,4-naphthoquinone compound is reacted with an aldehyde in the presence of an acid catalyst such as acetic acid. Naphtho(2,3-d)thiazole-4,
The present invention was completed by discovering that a 9-dione compound can be obtained.

[Means and actions for solving the problems] The present invention has the following features:
-amino-3-halo-1,4-naphthoquinone compound,
The resulting 2-amino-3 was reacted with a sulfide in an inert gas atmosphere in the presence of an inert water-soluble polar solvent
-Nut(2,3-d)thiazole- characterized by reacting a reaction mixture containing a mercap)-1,4-naphthoquinone compound with an aldehyde in the presence of an acid catalyst.
It consists in a method for producing a 4,9-dione compound.

2-amino-3-halo-1 of the raw materials used in the present invention.
As the 4-naphthoquinone compound, in addition to compounds in which the benzene ring is unsubstituted, compounds in which the benzene ring is substituted can also be used. Examples of unsubstituted compounds include 2-amino-3-chloro-1,4-naphthoquinone, 2-amino-3-chloro-1,4-naphthoquinone,
-Amino-3-bromo-1,4-naphthoquinone and the like. The substituted compound is a compound having an inactive substituent on the benzene ring in this reaction, and is
．． It may be substituted at any of the 8-positions, and examples of the substituent include an alkyl group, an alkoxy group, an amino group, and a halogen. Examples include 2,6-diami2-3-chloro-1,4-naphthoquinone, 2-amino-3
-chloro-5-methoxy-1,4-naphthoquinone.

The sulfide used in the present invention includes 2-amino-3-
Substitutes for the halogen group of halo-1,4-naphthoquinone compounds 0 For example, alkali metal sulfides such as sodium sulfide and potassium sulfide; alkali metal hydrosulfides such as sodium bisulfide and potassium bisulfide; ammonium sulfide. It will be done.

The amount of sulfide to be used is preferably at least equimolar to the raw material.Sulfide may also be used in the form of a hydrate such as sodium sulfide nonahydrate.

The inert water-soluble polar solvent used in the present invention includes:
It is inert in the reaction, and its water solubility may mean that it dissolves in water to the extent that it dissolves in water, but it may not be completely miscible (for example, N.

N. such as N-dimethylformamide thylacetamide. N-dialkylacylamide; sulfoxide such as dimethylsulfoxide (DMSO); hexamethylphosphoric triamide (HMPA)
) and other N,N-dialkylphosphoric acid triamides: ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether,
Chain or ring ethers such as diethylene glycol diethyl ether, tetrahydrofuran, dioxane, trioxane; methanol, ethanol, propatool, t
- Examples include alcohols such as butanol. Moreover, there is no problem even if it is a mixture of these solvents.

The amount of these solvents to be used is generally about 1 to about 100 times the weight of the raw materials, preferably about 3 to about IO times the weight of the raw materials.

As the aldehyde in the present invention, any substituent other than the aldehyde group may be used as long as it is inactive in the reaction.6For example, formaldehyde, acetaldehyde, acrolein, crotonaldehyde, acrolein dimer, benzaldehyde, P-cyanobenzaldehyde, etc. corresponding to this substituent, respectively unsubstituted, 2-methyl-22-vinyl-22-(α-propenyl)-12-(2'-oxy-3''-cyclohexenyl)
-12-phenyl- and 2-(P-cyanophenyl)-
A substituted naphtho(2,3-d)thiazole-4,9-dione compound is obtained.

The amount of aldehyde used may be 1.0 to 2.0 times the mole of the raw material, preferably 1.1 to 1.5 times the mole.Aldehyde can also be used in an aqueous solution such as 37χ formalin. .

In the present invention, the acid catalyst is preferably a so-called Brønsted acid that can donate protons, and may be an inorganic or organic acid as long as it promotes the reaction.For example, acetic acid, propionic acid, succinic acid, glutaric acid, adipic acid. ,
Aliphatic carboxylic acids such as malic acid, citric acid, and maleic acid; Aromatic carboxylic acids such as benzoic acid and phthalic acid; Sulfonic acids such as para-toluenesulfonic acid and methanesulfonic acid; Minerals such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid Examples include acids and acid salts such as sodium hydrogen sulfate, but carboxylic acids such as acetic acid are preferred.

The amount of acid catalyst used is generally equal to or more than the equivalent amount to neutralize sulfides such as soda sulfide, as this acid catalyst neutralizes sulfides such as soda sulfide. The amount is about 1605 times or more, usually about 1.05 to about 1.5 times, preferably about 1.1 to about 1.3 times the equivalent. however,
There is no problem in neutralizing the amount equivalent to the neutralization equivalent with another acid.

In the present invention, the reaction between the 2-amino-3-halo-1,4-naphthoquinone compound and the sulfide is generally carried out at room temperature to boiling point reflux, usually 20 to 100°C, preferably 40 to 70°C.
, and may be under normal pressure or pressurization.

Further, the condensation reaction between the 2-aminol-3-mercabuto-1,4-naphthoquinone compound and the aldehyde is generally carried out at room temperature to boiling point reflux, usually at 30 to 100°C, preferably at 40 to 80°C.
C, and may be under normal pressure or pressurization.

The invention generally operates as follows.

Dissolve the 2-amino-3-halo-1,4-naphthoquinone compound in a predetermined amount of solvent, replace the air with an inert gas such as nitrogen, and dissolve the 2-amino-3-halo-1,4-naphthoquinone compound by replacing the air with an inert gas such as nitrogen. A predetermined amount of sulfide such as , ) is added, and the mixture is reacted with stirring at a predetermined temperature for 0.5 to 3 hours. A predetermined amount of aldehyde and a predetermined amount of acid catalyst were added to this reaction mixture, and while stirring,
The reaction is allowed to proceed at a predetermined temperature for about 1 to about 5 hours. The product obtained by this reaction is nut(2,3-d)thiazole-
It is a reduced form of a 4,9-dione compound (4,9-dihydroxynaphtho(2,3-d)thiazole), and this compound can be removed from air during subsequent processing in the case of small amounts of reaction or dilute concentrations. The naphtho(2,3-d)thiazole-4,9-dione compound can be sufficiently oxidized by oxygen in the reactor, but in the case of large-scale reaction or high concentration, most of the products are reduced. Since it exists in the form of quinhydrone or quinhydrone, it can be oxidized with an appropriate oxidizing agent.

Examples include air, molecular oxygen such as oxygen; peroxides such as hydrogen peroxide, and the like. However, it is also possible to obtain this compound in reduced form, but in that case all work-up must be carried out under an inert gas.

The reaction product thus obtained is obtained by distilling off the solvent under normal pressure or reduced pressure, adding about 10 to 30 times the weight of water to the residue, and treating it at about 20 to 50°C for about 60 minutes with stirring. , filter, and the resulting filter cake is washed with water and dried. If necessary, recrystallization is performed to obtain a highly pure naphtho(2,3-d)thiazole-4,9-dione compound.

"Effects of the Invention" The present invention enables the reaction to be carried out at a much higher concentration than the conventional method using an aqueous medium, and with high purity and high yield. , 9-dione compounds can be obtained, which has extremely industrially valuable effects.

"Example" Next, the present invention will be explained in detail with reference to Examples. However, unless otherwise specified, "%" and "part" used in this specification are "overlapping %" and "overlapping %". Indicates "parts by weight".

Example 1 15.0 g of 2-amino-3-chloro-1,4-naphthoquinone (
72゜3-101), sodium sulfide 9-hydrate salt 17.4
g (72.5 gmol) and 150 sl of DMF were charged and reacted at 45° C. for 1 hour under a nitrogen stream to prepare sodium salt of 2-amino-3-mercabuto-1,4-naphthoquinone. First, 8.0 g (98.7 m+*o1) of formalin (37χ) was added dropwise to this reaction mixture, and then 5.0 g (83.3 sso1) of acetic acid was added dropwise thereto, followed by a reaction at 70° C. for 4 hours. After distilling off 120 ml of DMF from this reaction solution under reduced pressure, 200 ml of water was added, and the mixture was thoroughly stirred at 50°C for about 1 hour. The resulting crystals were filtered, thoroughly washed with water, and dried. 15.7 g of crude crystals of naphtho[2,3-d)thiazole-4,9-dione with a purity of 89.0χ were obtained. The yield was 89.9 molX.

Example 2 2-amino-3-chloro-1,4-naphthoquinone 45.
0g (216,9ms+o1), sodium sulfide nonahydrate 52.5g (218,8m+*o1), formalin 24.0g (296,1sso1), and acetic acid 15.0g
The same procedure as in Example 1 was carried out except that (249,9peng-o1) was used to obtain 46.7 g of naphtho[2°3-d]thiazole-4,9-dione with a purity of 86.1χ.

The yield was 86.2+solχ.

Example 3 Nuts (2,3-
d) Thiazole-4,9-dione 32.2 sections were obtained.

The yield was 83.9 olx.

Example 4 2-amino-3-chloro-1,4-naphthoquinone 8.7
0g<41.9wrmo1), sodium sulfide nonahydrate 10.2g (42.5sso1), D as solvent
M F 120+l and ethanol 80g+1. 6 ml of crotonaldehyde (90x aqueous solution) and 4 ml of acetic acid
．． 2-(α-propenyl)-naphtho(2,3-d)thiazole-4,9-dione 7 with a purity of 94χ was prepared in the same manner as in Example 1, except that 0g was used and the reaction temperature was 40°C. .9g was obtained. The yield was 69.5 intestines.

Example 5 6.5 g of p-cyanobenzaldehyde (49.6 ms+
2-(p-cyanophenyl)-naphtho(2,3-d)thiazole-4,9 with a purity of 91χ was prepared in the same manner as in Example 4, except that the reaction temperature was 70°C.
-8.9 g of dione was obtained. The yield was 61.2 mol.

Comparative example

Claims (8)

[Claims] (1) A 2-amino-3-halo-1,4-naphthoquinone compound is reacted with a sulfide in an inert gas atmosphere in the presence of an inert water-soluble polar solvent, and then the resulting 2-amino- A method for producing a naphtho[2,3-d]thiazole-4,9-dione compound, which comprises reacting a reaction mixture containing a 3-mercapto-1,4-naphthoquinone compound with an aldehyde in the presence of an acid catalyst. . (2) The method according to claim 1, wherein the 2-amino-3-halo-1,4-naphthoquinone compound is 2-amino-3-chloro-1,4-naphthoquinone. (3) The method according to claim 1, wherein the inert water-soluble polar solvent is a water-soluble N,N-dialkyl-substituted acid amide, N,N-dialkyl-substituted phosphoric acid triamide, alcohol, sulfoxide, or ether. . (4) The method according to claim 1, wherein the sulfide is a compound capable of substituting a halo group of a 2-amino-3-halo-1,4-naphthoquinone compound. (5) The method according to claim 1, wherein the sulfide is an alkali metal sulfide, an alkali metal hydrosulfide, or ammonium sulfide. (6) The method according to claim 1, wherein the acid catalyst is a Bronsted acid. (7) The method according to claim 1, wherein the acid catalyst is a carboxylic acid. (8) The method according to claim 7, wherein the carboxylic acid is acetic acid.