JPS58183649A - Preparation of imide compound - Google Patents

Abstract

PURPOSE:To obtain the titled substance useful as a synthetic intermediate for a black pressure-sensitive dyestuff and heat-sensitive dyestuff in high purity and yield without requiring the separation of by-products, etc., by alkylating an aniline compound as a raw material reductively with a ketonic compound. CONSTITUTION:An aniline compound of formula I (X is halogen; R is H or lower alkyl) is catalytically alkylated with a ketonic compound of formula II (R3 and R4 are R1 or R2 or groups convertible into R1 and R2 during the reaction; R1 and R2 are linked through ether or carbonyl bond, cycloalkyl or alkyl which may contain an alkyl or phenyl group; or R1 and R2 together with the C in the ketone form a cycloalkyl, tetralinyl or indanyl) reductively in the presence of a catalyst, e.g. platinum in a solvent, e.g. methanol, at 5-50kg/cm<2>, preferably 10-25kg/cm<2> pressure of the hydrogen at 80-140 deg.C, preferably 110-130 deg.C, to afford the aimed compound of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for making imide compounds.

General formula +11 (wherein, (or 2 may be combined with the carbon of the ketone to form a cycloargyl group, a tetralinyl group, or an indanyl group). It is a compound useful as an intermediate for

Examples of such dyes using an imide compound represented by the general formula (Il) as a raw material include the following.

(3) (4) (5) As a general method for producing the imide compound of general formula (1), for example, the method described in JP-A-55-142693, which describes the same type of dye compound, is considered. be done.

However, since this method alkylates the amino group of 3-chloro-4-aminophenol with alkyl bromide or alkyl tosylate, in addition to the monoalkylated product, dialkylated by-products and unreacted amino compounds remain. Moreover, these are generally difficult to separate, making it impossible to obtain the desired imide compound with good yield and purity.

Furthermore, due to limitations on alkylating agents such as alkyl bromides or alkyl tosylates, the structure of the target imide compound is extremely limited (R).

The inventors of the present invention have conducted intensive studies on an industrially advantageous method for producing the imide compound of general formula (I), and have found that the object can be achieved by reductive alkylation with a ketone compound.

That is, the present invention provides an aniline compound represented by the general formula (Ill (wherein,
3, R4 represents R, , R2 or a group that changes into nitrogen or R2 during the reaction.

R1 and R2 represent an alkyl group which may contain an ether bond, a carbonyl bond, a cycloalkyl group or a phenyl group, or R and R2 together with the carbon of the ketone (7) a cycloalkyl group, A tetralinyl group or an indanyl group may also be formed. ) is characterized by catalytic reductive alkylation with a ketone compound represented by the general formula (II (wherein,
,, R2 have the above meanings. ) This is a method for producing an imide compound shown in the following.

In the present invention, the halogen atom of
Examples include C-C4 alkyl groups such as ethyl, propyl, and butyl groups.

R21 in the general formula @). When R4 is R, R2 may contain one or more ether bonds, carbonyl bonds, cycloalkyl groups, phenyl groups, and alkyl groups in R, R2 (8), Examples of the alkyl group include those having 1 to 8 carbon atoms. Further, the phenyl group may have a substituent such as a lower alkyl group or a halogen atom.

Examples of kllR2 include methyl group, ethyl group, propyl group, isobutyl group, amyl group, methoxymethyl group, methoxyethyl group, ethoxyethyl group, methoxyethoxy group, ethoxyethoxy group, benzyl group, P-
Chlorbenzyl group, phenethyl group, phenylpropyl group, benzyloxymethyl group, phenethyloxymethyl group, benzyloxyethyl group, cyclohexyloxymethyl group, cyclohexyloxyethyl group, acetylmethyl group, acetylethyl group, propionylmethyl group, benzoylmethyl group group, 0-chlorobenzoylmethyl group, etc.

K and R2 may be combined with the carbon of the ketone to form a cycloalkyl group, a tetralinyl group, or an indanyl group, and these groups may be optionally substituted with a substituent (9) such as a lower alkyl group, an alkoxy group, or a halogen group. It may contain atoms.

R31R4 in general formula (III) or R
Examples of such a group include a vinyl group, a propenyl group, a 2-methyl-2-hydroxypropyl group, a 2-methyl-2-methoxypropyl group, and the like. It will be done.

Specific examples of the aniline compound of general formula (n) include the following.

3-Chlor-4-aminophenol 3-chloro-4-aminoanisole 3-chloro-4-aminophenetol 3-bromo-4-aminophenol 3-bromo-4-aminoaninol 3-iodo 4-aminophenol 3 -Fluoro-4-aminephenol Specific examples of the ketone compound having the general formula @) include the following.

Cyclohexanone, cyclopentanone, β-(]0) tetralone, 2-indanone, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methoxyacetone, 4-methoxy-2-butanone, diacetone alcohol, 4-methoxy-4- Methyl-2-pentanone, dimethoxyacetone, 3-cyclohexyloxy-2-pentanone, 4-7enyl-2-butanone, dibenzyl ketone, acetylacetone, benzoylacetone, acetonyl acetone, methyl vinyl ketone, followed by the reductive alkylation of the present invention. An outline for carrying out the reaction will be explained. Aniline compound of general formula (II),
The ketone compound of the general formula, a reaction solvent, and a catalyst are placed in an autoclave, and reduced with hydrogen under pressure and heat.

The ketone compound is used in a molar ratio of 1 or more, preferably 1 to 2 molar relative to the aniline compound as a raw material.

Examples of reaction solvents include alcohols such as methanol, impropanol, 2-methoxyethanol, and 2-ethoxyethanol, ethers of polyhydric alcohols such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; Dioxane etc. can be used. Moreover, the ketone compound used in the reaction can also be used as a solvent.

The catalyst is platinum or palladium-based, especially platinum on a carrier is effective, and a platinum catalyst slightly poisoned with a sulfur compound is preferred.

In the present invention, 1 to 30
The addition of a molten organic acid, such as acetic acid, is preferred at F to prevent dehalogenation.

The reaction is carried out under a pressure of 5 to 50 Kli'/cm2 of hydrogen, preferably 10 to 25 Kli'/cm2, at 80 to 140°C.
Preferably it is carried out at 110 to 130°C. Once the theoretical amount of hydrogen has been absorbed and consumed, a state is reached where no more hydrogen is absorbed and unreacted aniline compounds also disappear.

To isolate the target product, the contents of the autoclave are filtered to remove the catalyst, the solvent or excess ketone is removed by distillation or steam distillation, and soluble substances are removed by treatment with water or hot water. .

For further purification, methods such as recrystallization from toluene, n-hexane, etc., or vacuum distillation can be employed.

According to the method of the present invention, an imide compound in which the α-position carbon of the alkyl group bonded to the imino group is a tertiary carbon can be obtained industrially in higher yield and purity than conventional methods.

By using the imide compound obtained in this way, it is possible to improve the purity and yield of the above-mentioned (Kl) pigment compounds, which could only be obtained in a mixture with by-products that are difficult to separate using conventional methods. You can get it at

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Cyclo (13
) Xanone 57. OF, ethanol 100 F, 3-chloro-4-aminophenol? 1.89. After charging 3 and 5 titanium glacial acetic acid platinum/carbon catalysts and purging with hydrogen, the temperature was raised to 120° C. and reductive alkylation was performed at a hydrogen pressure of 20 Kl/ci. By injecting hydrogen several times in response to hydrogen consumption, a 1 molar ratio of hydrogen to chloraminophenol was consumed. After cooling to 60° C., the contents were filtered to remove the catalyst, and after washing with a small amount of ethanol, ethanol was removed from the P solution by distillation. After adding water 11 to the distillation residue and stirring, the crystals were filtered, washed with water, and dried.

2-10-4-hydroxy-N-cyclohexylaniline 110.8F (melting point 115-117C) was obtained. This is recrystallized from toluene and has a melting point of 116-1
White crystals at 17°C were obtained. The elemental analysis values and mass spectrum values were consistent with the calculated values.

Example 2 Cyclopentanone 25.2f, (+A
S 100y of ethanol, 43.19ml of 3-chloro-4-aminophenol, 2v of glacial acetic acid, and 2F of 5% platinum/carbon catalyst were charged, and after replacing with hydrogen, the temperature was raised to 120°C, and
Reductive alkylation was carried out at a hydrogen pressure of 0 Q/cm2.

By injecting hydrogen several times in response to hydrogen consumption, a 1 molar ratio of hydrogen to chloraminophenol was consumed. After cooling to 60°C, the contents were filtered to remove the catalyst.
After washing with a small amount of ethanol, ethanol was removed from the p liquid by distillation.

Then, by distillation under reduced pressure, the boiling point was 142-143℃/1.5m.
57.7 y of 2-chloro-4-hydroxy-N-cyclopentylaniline (white crystal) of mHg was obtained.

The melting point was 68-69°C.

Example 3 β-tetralone 14.6F, methanol 50v 13-chloro-4-aminophenol 14.4F.

Reductive alkylation was carried out at 120° C. in the same manner as in Example 1 using 3 g of glacial acetic acid and 1.5 g of 5% platinum/carbon catalyst. After consuming hydrogen at a molar ratio of 1 to chloraminophenol, the contents were passed through to remove the catalyst, and the F solution was distilled to remove methanol. Add boiling water 11 to the remainder and stir, then separate the oil layer (26.8 $'), which is recrystallized from the same amount of toluene and has a melting point of 81-8.
2-chloro-4-hydroxy-N-(β-tetralinyl)aniline 23.8 P (white crystals) was obtained at 3°C.

Example 4 Acetone 13.9y, ethanol 40F, β-chloro-
Reductive alkylation of 4-aminophenol was carried out with 1 molar ratio of hydrogen to chloraminophenol at 120 °C in an autoclave using 1.22 F of 2S, qy1 glacial acetic acid and 0.8 F of 5T platinum/carbon catalyst. Ta. F the catalyst
After separating the ethanol and distilling off the ethanol, it was washed with boiling water and the separated oil was reconsolidated with JiR from a small amount of toluene to produce 2-chloro-4-hydroxy-N-isopropylaniline with a melting point of 85-86°C. 20y (white crystals) was obtained.

Example 5 In place of acetone in Example 4, diacetone alcohol 25.69 or diacetone alcohol methyl ether 28°6F was used, and the rest was subjected to reductive alkylation, post-treatment and recrystallization in the same manner. f and 24 S
'2-chloro-4-hydroxy-N-isopropylaniline was obtained, respectively. The melting point was 85-86°C.

The structure of this compound was confirmed from FD mass spectrum and NMR spectrum.

Example 6 Reductive alkylation with hydrogen was carried out at 120<0>C using 3-pentanone 130F, 3-chloro-4-aminephenol 43.19, acetic acid 3V and 5T platinum/carbon catalyst 22.

After removing the catalyst and excess 3-pentanone and washing with water, the oil was distilled under reduced pressure. Boiling point 120-121'C/1°2mm
One cup of 2-chloro-4-hydroxy-N-(1-ethylpropyl)aniline 51M' (17) was obtained. It is oily.

Example 7 Methyl isobutyl ketone 150F, 3-chloro-4-aminophenol 71.8f! , 5V of glacial acetic acid and 2V of 5T platinum/carbon catalyst in an autoclave at 120°C.
Reductive alkylation was carried out using hydrogen. The catalyst was separated from P, methyl isobutyl ketone was distilled off by steam distillation, and the oily part was separated and distilled under reduced pressure.

2-chloro-4-hydroxy=N-(2,4-dimethylbutyl) with boiling point 136-137°C/2 mm H7
Aniline 80.61' (white crystals) was obtained.

The melting point was 64-65.5°C.

Example 8 Dibenzyl ketone 42. IP, 3-chloro-4-tinominophenol 2B, 79, acetic acid 3, ethanol 100
120 using V and 5T platinum/carbon catalysts.
Reductive alkylation was carried out with hydrogen at °C. The catalyst and ethanol were removed, washed with water, and then recrystallized from toluene. Melting point 9
5(18) 2-chloro-4-hydroxy-N-(1-phenylmethyl-2-phenylethyl)aniline at ~97°C 63°5
9 (white crystals) was obtained.

Example 9 22.2 g of 4-phenyl-2-butanone, 3-chloro-
4-Aminophenol 21.59. Using 3f acetic acid, 40y ethanol and 5t platinum/carbon catalyst 29,
Reductive alkylation was carried out with hydrogen at 120°C. After removing the catalyst and ethanol, it was washed with water and distilled under reduced pressure to obtain 2-chloro-4-hydroxy-N-(1-methyl-3-phenylpropyl)aniline with a boiling point of 146-147°C/1.5 #Im th. I got it.

Example 10 Acetylacetone 45.09.3-chloro-4-tinominophenol 43. IF, acetic acid 3F, ethanol 100
Reductive alkylation was carried out with hydrogen at 120° C. using 5% platinum/carbohydrate and Bonn catalyst 22. After removing the catalyst and ethanol, it was washed with water and recrystallized from toluene.

2-chloro-4-hydroxy-N- with a melting point of 62-64°C
(1-Methyl-2-acetylethyl)aniline 25F (
White crystals) were obtained.

Boiling point 133-135°C/3 rnm Hg.

Example 11 Methoxyacetone 20 y, 3-chloro-4-aminophenol 32.6 y, ethanol 100v1 acetic acid 2 y
and 5L16 platinum/carbon catalyst 2f, reductive alkylation was carried out with hydrogen at 120°C. After removing the catalyst and ethanol, it was washed with water and then recrystallized with toluene.

1 point 2-chloro-4-hydroxy-N at 82-83℃
-(1-methyl-2-methoxyethyl)aniline 25F
(white crystals) were obtained.

Example 12 Reductive alkylation was carried out in the same manner as in Example II, using 4-methoxy-2-butanone 25.5 F instead of methoxyacetone.

After removing the catalyst and ethanol, the oily 3-
Chlor-4-(neemethyl-3-methoxypropylamino)phenol 30F was obtained.

Example 13 Cyclohexanone 2B, 5f, methanol 1002.
12 using 39.42 kg of 3-chloro-4-aminoanisole, 1.52 kg of glacial acetic acid and 22 kg of platinum/carbon catalyst.
Reductive alkylation was carried out with hydrogen at 0°C. After removing the catalyst and methanol, the product was washed with water and then recrystallized from n-hexane. 2-chloro-4=methoxy-N-cyclohexylaniline 5 (1 (white crystals) with a melting point of 47-48°C
I got it.

Example 14 Instead of cyclohexanone in Example 13, methyl ethyl ketone is used to consume a 1 molar ratio of hydrogen to amine, or methyl vinyl ketone is used to consume a 2 molar ratio of hydrogen to amine. By consuming oily 2-chlor-4-methoxic
-methylpropyl)aniline (21) was obtained.

Example 15 Cyclohexanone 16°2P1 Ethanol 40P13-
Bromo-4-aminophenol 28.2 f.

Reductive alkylation was carried out with hydrogen at 120° C. using 0.92% of glacial acetic acid and 0.59% of platinum/carbon catalyst.

After removing the catalyst and ethanol, the product was washed with water and then recrystallized from toluene and n-hexane. White crystal, melting point 10
36.2f'E- of 2-bromo-4-hydroxy-N-cyclohexylaniline was obtained at 3-104°C.

Example 16 Substitute for 3-bromo-4-aminophenol in Example 15, 3-bromo-4-aminoanisole 30.
Similar reductive alkylation was carried out using 3F. After removing the catalyst and ethanol, wash with boiling water to remove the oily 2
-Bromo-4-methoxy-N-cyclohexylaniline (35%) was obtained.

(29 characters) Procedural amendment 1. Indication of small matter Patent Application No. 66489 of 1989 2, Name of invention Process for producing imide compound 3, Department of amendment 'JIl! 1. What relationship Patent applicant 5-15 Kitahama, Higashi-ku, Osaka (209) Representative of Sumitomo Chemical Co., Ltd. 1 D Formula % Formula % (1) 6. Contents of amendment (1) Line 8 of page 9 of the specification , “methogishethoxy group”
The text has been corrected to read "MethoA-jethoxyethyl group."

(2) “Ethoxyethogycy group” on page 9, lines 8-9.
I corrected it to read "ethoxyethoxyethyl group."

(3) On page 11, lines 6-7, "3-cyclohexyloxy-2-pentanone" has been replaced with "4-Schiffr7
J＼Gishiro A-C-2-Butanone” is corrected.

(IL) On page 16, line 1θ, “β-” is
r: Correct as 3-J.

I"2 (to 2)

Claims (1)

[Scope of Claims] An aniline compound represented by the general formula (II) (wherein, X represents a halogen atom and k represents a hydrogen atom or a lower alkyl group) , R4 represents a group that can change during the reaction, R2 or k, or R2 represents an alkyl group which may contain an ether bond, a carbonyl bond, a cycloalkyl group or a phenyl group. or R2 may be combined with the carbon of the ketone (1) to form a cycloalkyl group, a tetralinyl group, or an indanyl group. The general formula (II (wherein R, R□, R2
represents the above-mentioned meaning).