JPS6012352B2 - Manufacturing method of dye intermediate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 4-hydroxynaphthalic acid-N-substituted imides.

More specifically, a 4-mono-substituted naphthalic acid compound represented by the following general formula [1' (Formula '1}, in which X represents a chloro atom, a bromine atom, or a C, ~4 alkoxy group, and R represents the meaning below) N-monosubstituted imide in the presence of methanol, ethanol, propanol or butanol in an aqueous solution of caustic soda or caustic potash at a concentration of 5 to 10% (by weight)
General formula [2] characterized by being hydrolyzed at 130qo
} (Formula (R in 2' is a hydroxyl group, a substituted or unsubstituted amino group,
The present invention relates to a method for producing a 4-hydroxynaphthalic acid-N-substituted imide represented by an alkoxy group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group.

According to known literature, the 4-hydroxynaphthalic acid-N-substituted imide represented by the formula (1) can be produced by any of the following methods.

One method is to react 4-sulfonaphthalic acid or its anhydride with various amines to form 4-sulfonaphthalic acid-N-substituted imide. Kimiaki Hakama produces 4-hydroxynaphthalic acid HN-substituted imide by hydrolysis 39-
28249 Mochiko Sho 42-16303 and Special Kosho 45-2
Another method is to react 4-hydroxynaphthalic acid or anhydride obtained by melting 4-sulfonaphthalic acid or anhydride with an alkali with various amines. -Hydroxynaphthalic acid-N
This is a method described in Samurai Publication No. 39-28250 for producing a -substituted imide. In any of these methods, the starting material is 4-sulfonaphthalic acid or its anhydride. However, it is difficult to produce 4-sulfonaphthalic acid or its anhydride because a large amount of chromium compounds, which tend to be a source of pollution, are used.
The object of the present invention is to industrially produce 4-hydroxynaphthalic acid-N-substituted imide at low cost using 4-halogenonaphthalic acid or its anhydride as a starting material, which has no risk of becoming a source of pollution during its production. It is in.

The following steps are required to produce 4-hydroxynaphthalic acid mono-N-substituted imide from this 4-halogenonaphthalic acid or its anhydride. That is, first 4
-Produce 4-halogenonaphthalic acid-N-substituted imide by reacting various amines with halogenonaphthalic acid or its anhydride, or 4-Produce 4-halogenonaphthalic acid-N-substituted imide by reacting halogenonaphthalic acid or its anhydride with ammonia.4 -Halogenonaphthalic acid imide is reacted with various alkylating agents to produce 4-halogenonaphthalic acid-N-substituted imide, and if necessary, halogen is alkoxylated to produce 4-halogenonaphthalic acid imide.
A step of producing a substituted naphthalic acid-N-substituted imide;
This is a step of hydrolyzing the 4-layer naphthalic acid-N-substituted imide thus obtained.

Of these steps, the former can be achieved without any problem according to known methods, but as for the latter step, there is currently no known method for achieving the objective in an industrially advantageous manner.

That is, for example, known methods for hydrolyzing aromatic halogen derivatives (for example, "Dye Chemistry" by Yutaka Hosoda, Ichigihodo).
If hydrolysis is carried out according to the method described on page 112), a large amount of unreacted substances will remain, making it impossible to obtain satisfactory results. (Refer to reference experiments in Examples 2 and 3) By the above, 4-halogenonaphthalic acid to 4-hydroxynaphthalic acid-N-
It is clear that the biggest and only problem in producing substituted imides lies in the step of producing 4-1-hydroxynaphthalic acid-N-substituted imide from 4-1-substituted naphthalic acid-N-substituted imide.

The present inventors have arrived at the present invention as a result of extensive research into the process for producing 4-hydroxynaphthalic acid-N-substituted imide from this 4-substituted naphthalic acid-N-substituted imide.

According to the method of the present invention, 4-hydroxynaphthalic acid-N-substituted imide can be produced in extremely high yield. That is, when the 4-substituted naphthalic acid-N-substituted imide represented by the general formula m is hydrolyzed in an aqueous caustic alkali solution in the presence of a lower alcohol, the 4-hydride represented by the general formula '21 can be obtained in extremely high yield. It has been found that xinaphthalic acid-N-substituted imides can be obtained. The lower alcohols used here include methanol, ethanol, and n-fu.

Lonogunol, ISo-propanol, butanol, etc. are used, but water-soluble methanol, ethanol, n-
Propanol and lso-propanol are preferred, and methanol and ethanol are particularly preferred. The amount to be used is 5 to 10% (wt%) of the caustic aqueous solution used.
) is desirable, but there is no benefit in using too much; on the other hand, if less than this, the reaction will be incomplete. As the caustic alkali, caustic soda and caustic potash are preferable, and an aqueous solution having a concentration of 5 to 10% (wt%) is preferable. If the concentration of caustic alkali is higher than 10%, undesirable side reactions will proceed, and if it is lower than 5%, the reaction will be difficult to proceed and the yield of the target product will decrease. The reaction temperature is reflux temperature (1
00°C) to 130°C, and if the temperature is higher than 130°C, side reactions occur and the yield decreases. Considering the required reaction time, it is convenient to carry out the reaction in an autoclave at 120-125°C. Once the reaction is complete (the completion of the reaction can be easily confirmed by paper chromatography or thin layer chromatography).

) The resulting clear reddish-brown solution was diluted with the reaction mixture and water and, if necessary, insoluble materials were removed by furnace.The resulting clear reddish-brown solution was acidified with mineral acid and the resulting crystals were separated by furnace to obtain 4-hydroxynaphthalic acid-1N-substituted imide. get. The compound represented by the general formula {11, which is a raw material in the present invention, can be easily produced according to the method described above, but specifically, X is a halogen atom such as chloro or bromine; R represents a hydroxyl group; substituted or unsubstituted ami/groups such as monomethyl group, dimethylamino group, ami/group; alkoxy groups such as methoxy group, ethoxy group; methyl group, ethyl group, n-butyl alkoxyalkyl groups such as methoxyethyl, ethoxyethyl, n-butoxyethyl, iso-propioxyethyl, y-methoxypropyl, y-ethoxypropyl; Hydroxy-substituted alkyl groups such as 8-hydroxyethyl group; alkoxyalkoxy groups such as methoxyshetoxypropyl group, ethoxyshetoxypropyl group, butoxyshetoxypropyl group, ethoxyshetoxyshetyl group, ethoxyshetoxyshetyl group Alkyl group: Aralkyl group such as phenethyl group or benzyl group; Unsubstituted or substituted aminoalkyl group such as 8-aminoethyl group or NON-dimethylpropyl group; Morpholine-substituted alkyl group such as morpholinopropyl group: Represented by the following formula. Substituted alkyl group; [In the formula leg, R2 represents a methyl group, ethyl group, n-propyl group, n-butyl group, or phenyl group.

] and unsubstituted or substituted alkenyl groups such as allyl group, y-methallyl group, and y-phenylallyl group.

The 4-hydroxynaphthalic acid-N-substituted imide thus obtained is extremely useful as an important intermediate for azo dyes and crab light dyes.

The method of the present invention will be explained below with reference to Examples.

(The concentrations of caustic alkali in the Examples are all weight %.) Example 1 4-Chlornaphthalic acid-N-methylimide 9.2 hours,
5. Add 100 ml of 7% caustic soda aqueous solution and 10 ml of methanol to 125 qo while stirring in an autoclave. It was held for a while.

After cooling, 200 g of water was added to dilute. Concentrated hydrochloric acid was added to this reddish-brown and transparent solution until the color of the Congorecid paper clearly turned blue. Yellow crystals were immediately deposited. I continued praying for another hour and retrieved the crystal. After thorough washing with water and drying, crude 4-1-hydroxynaphthalic acid-N-methylimide was obtained for 8.4 days. (Yield 100%). This one is 29
It showed a melting point of 6-8°C. When recrystallized with ethanol, a pure product with a melting point of 300°C or higher was obtained. Example 2 Ethanol 10 was used instead of methanol used in Example 1.
A similar treatment was carried out using 8.3 ml of crude 4-hydroxynaphthalic acid-N-methylimide.

(Yield 98.8%). This product showed a melting point of 296°C. When recrystallized with ethanol, a pure product with a melting point of 300°C or higher was obtained. Reference Experiment 1 100 g of a 7% caustic soda aqueous solution of 9.2 ml of 4-chloronaphthalic acid-N-methylimide was added, and the mixture was heated at 125° C. for 5 hours.

After cooling, 200 ml of water was added to separate the insoluble crystals. This crystal was found to be the raw material 4-chloronaphthalic acid-N-methylimide by the melting point and thin layer chromatography tests. On the other hand, the furnace liquid was subjected to the same post-treatment as in Example 1 to obtain 4.6 days of crude 4-1-hydroxynaphthalic acid-N-methylimide. (Yield 54.5%) Example 3 4-Chlornaphthalic acid-N-methoxypropylimide 12.2 8% caustic potash aqueous solution for 100 minutes and methanol for 10 hours were added under a rope in an autoclave at 120 mm for 5 minutes. Holds time.

After cooling, 200 ml of water was added to dilute. Concentrated hydrochloric acid was added to the resulting reddish-brown transparent solution until Congo red paper turned blue. The precipitated crystals were collected in a furnace, washed with water, and dried.
．． Two days of crude 4-hydroxynaphthalic acid mono-toxypropylimide was obtained (yield 98.2%) with a melting point of 211-213 pm. Recrystallization with ethanol gave a pure product with a melting point of 214-2170. Reference Experiment 2 In Example 3, when the treatment was carried out in the same manner as in Reference Experiment 1 without adding methanol, 4-hydroxynaphthalic acid-N-methoxypropylimide of 2.6 days was obtained.

(Yield 22.8%) From the comparison of the above-mentioned Reference Experiment 1 and Example 1 and this Reference Experiment and Example 3, it was found that 4-hydroxynaphthalic acid-
The effect of improving the yield of N-substituted imide is striking.

Example 4 4-Chlornaphthalic acid-N-allylimide was added to 10.8 ml of a 7% caustic soda aqueous solution for 100 ml and methanol for 10 ml, and the mixture was kept at 12,000 ℃ for 5 hours under a Takaazusa vacuum.

It was diluted with 250 ml of water after incubation. Concentrated hydrochloric acid was added to the reddish-brown transparent solution from which the insoluble crystals had been separated by furnace, and the precipitated crystals were collected by furnace. After thorough washing with water and drying, 9.6 hours of crude hydroxynaphthalic acid-N-allylimide was obtained (yield: 94%).
). This had a melting point of 256-258°C. Recrystallization with ethanol gave a pure product with a melting point of 259-26ro. Example 5 4-Chlornaphthalic acid-N-ethoxyshetoxychethylimide 13.9 ml was added with 100 ml of a 7% aqueous sodium chloride solution and 10 ml of methanol, and kept at 120 qo under sea bream Azusa for 5 hours.

After 200 minutes of use, concentrated hydrochloric acid was added to the reddish-brown transparent solution diluted with water until it turned Congo red paper blue. A yellow candy-like substance was immediately released. When this product was kept cooled on ice for 3 hours, yellow crystals were precipitated. The crystals were collected in a furnace to obtain crude 4-hydroxynaphthalic acid-N-ethoxyshethyl imide in 11.2 hours. (Yield 85%) Melting point was 85-90 qo. When this product is recrystallized with ethanol, the melting point is 119-121.
A pure product with a temperature of 5°C was obtained. Example 6 4-Methoxynaphthalic acid-N-methylimide 12.1
In the evening, add 7% caustic soda aqueous solution 125 minutes and methanol 12 hours.
．． The autoclave was heated for 5 hours and kept under the light for 5 hours at 12yo.

After cooling the reaction solution, it was made acidic with sulfuric acid. The precipitated crystals were collected in a furnace to obtain 10.9 g of pale yellow 4-hydroxynaphthalic acid-N-methylimide. (Yield: 100%) This product had a melting point of 300% or higher. Example 7 4-Chlornaphthalic acid-N-(8-hydroxyethyl)imide 8.22, 8% caustic soda aqueous solution 75 hours, n
- 7.5 liters of propyl alcohol was charged into an autoclave and held at 11,500 mph for 6 hours at sea.

After cooling, 200 g of water was added and insoluble substances were removed by filtration.
Concentrated hydrochloric acid was added to the resulting reddish-brown transparent solution until the Congo red paper turned clearly blue. The precipitated crystals are taken out in a furnace 5
．． Crude 4-1-hydroxynaphthalic acid-N-(8-hydroxyethyl)imide was obtained over 4 hours. (Yield: 70%) When this product was recrystallized from ethanol, a pure product with a melting point of 241-3°C was obtained. Example 8 4-Chlornaphtha,-ruic acid-N
- To 7.4 days of hydroxyimide, 75 days of a 7% caustic soda solution and 7.5 days of methanol were added, and the mixture was kept at 125 quarts under a rope for 5 hours.

After cooling, sulfuric acid was added to the reddish-brown transparent reaction solution to make it acidic. The precipitated crystals were collected in a furnace to obtain 6.3 g of green-yellow 4-hydroxynaphthalic acid mono-hydroxyimide. (
Yield: 91.3%) This product simultaneously melted and decomposed at temperatures above 300°C. Hereinafter, the desired product shown in Column B was obtained from the raw material shown in Column A by a method similar to Examples 1 to 8.

Claims (1)

[Claims] 1 The following general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In formula (1), X is a chlorine atom, a bromine atom, or C_1_
4-substituted naphthalic acid-N-substituted imide represented by ~_4 alkoxy group, R represents the meaning below) at a concentration of 5 to 10% (by weight) in the presence of methanol, ethanol, propanol or butanol. General formula (2), which is characterized by being hydrolyzed at 100 to 130°C in caustic soda or aqueous caustic potash solution ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In formula (2), R is a hydroxyl group, a substituted or unsubstituted amino group , an alkoxy group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group).