JPS6140222B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the formula () {In formula (), X is a hydrogen atom, a halogen atom,
A lower alkyl group (which may be further substituted with a hydrofuryl group), or a lower alkoxy group (which may be further substituted with a lower alkoxy group, an alkoxyalkoxy group, a phenyl group, a phenoxy group), Y is An acyl group or a methoxycarbonyl group, R ₁ is a hydrogen atom, a lower alkyl group (this can further be a lower alkoxy group, a lower alkoxyalkoxy group, an acyl group, a phenyl group, a phenoxy group, a cyano group, a cyano lower alkoxy group, an acyloxy group, lower alkoxycarbonyl group, lower alkoxyalkoxycarbonyl group,
a hydrofuryl group, a hydroxy group or a lower alkenyl group (which may be substituted with a hydroxyl group or a halogen atom), or a lower alkenyl group, in an aprotic polar solvent such as dimethylformamide, diethylformamide, dimethylsulfoxide, diethylsulfoxide or tetra Using methylene sulfone as a reaction medium and in the presence of an acid binder, the formula () ClCH ₂ COOR ₂ () {In the formula (), R ₂ is a lower alkyl group (this can further be a lower alkoxy group, a lower alkoxyalkoxy group, a phenyl (optionally substituted with a phenoxy group, a benzyloxy group, or a hydrofuryl group)) {In formula (), X, Y and R ₂ represent the above meanings, and R ₃ is a hydrogen atom or - when R ₁ in formula () means a hydrogen atom.
In the CH ₂ COOR ₂ group, when R ₁ means an optionally substituted lower alkyl group or lower alkenyl group, it means R ₁ . } The present invention relates to a method for producing an aromatic amine represented by . That is, the present invention relates to an industrially advantageous improved manufacturing method for obtaining the compound of formula () by reacting the compound of formula () with the compound of formula (). It is well known to those skilled in the art that the compound represented by the above formula () is a useful intermediate for dye synthesis. It is an important compound, especially as a coupling component for disperse dyes. The N-alkylation reaction of amino groups by the reaction of anilines with active halogen compounds is a fairly common reaction, and is conventionally carried out in an appropriate organic solvent such as alcohol, ketone, or ether, or in water in the presence of an acid binder. However, during secondaryization, the by-product of tertiary amine cannot be avoided, and in both cases of secondaryization and tertiaryization, a reaction temperature of 100°C or higher is required, and in the case of esters, When used as a coupling component in dye synthesis, esters tend to decompose in water and at high temperatures in the presence of alkaline acid binders, resulting in large amounts of side reaction products.
There were many problems with the quality and yield of the desired dye. The present inventors have made extensive studies to improve these drawbacks and have discovered the present invention. That is, when dimethylformamide, diethylformamide, dimethyl sulfoxide, diethyl sulfoxide, or tetramethylene sulfone is used as the reaction medium, the reaction proceeds extremely smoothly, and the target compound of the formula () has high purity. Obtained in high yield. Among the compounds represented by the formula () used in the present invention, particularly preferred are compounds represented by the following formula ()'. {In formula ()', X' is preferably the following group: -H, -CH ₃ , -Cl, -OCH ₃ , -
OC ₂ H ₅ , ―OC ₂ H ₄ OCH ₃ , ―OC ₂ H ₄ OC ₂ H ₅ ,

[Formula]-OC ₂ H ₄ OC ₂ H ₄ OCH ₃ ,

【formula】

[Formula] Y′ is preferably the following group: namely,
―COCH ₃ , ―COC ₂ H ₅ ,

[Formula] -COOCH ₃ and R ₁ ' are preferably the following groups: -H, -CH ₃ , -C ₂ H ₅ , -CH ₂ CH
=CH ₂ , -C ₃ H ₇ , -C ₄ H ₉ , -C ₂ H ₄ OCH ₃ , -
C ₂ H ₄ OC ₂ H ₅ , -C ₂ H ₄ OC ₄ H ₉ ,

【formula】

【formula】

[Formula] ―C ₃ H ₆ OCH ₃ , ― C ₃ H ₆ OC ₂ H ₅ , ―C ₄ H ₈ OCH ₃ , ―
C ₂ H ₄ OC ₂ H ₄ OCH ₃ , ―C ₂ H ₄ OC ₂ H ₄ OC ₂ H ₅ , ―
C ₂ H ₄ CN, ―C ₂ H ₄ OC ₂ H ₄ CN, ―C ₂ H ₄ OCOCH ₃ ,
―C ₂ H ₄ COOCH ₃ , ―C ₂ H ₄ COOC ₂ H ₅ , ―
C ₂ H ₄ COOC ₂ H ₄ OCH ₃ ,

[Formula] - C ₂ H ₄ OH, - C ₂ H ₄ Cl,

【formula】

【formula】

【formula】

[Formula] In the above formula (), R ₂ is preferably the following group: -CH ₃ , -C ₂ H ₅ , -
C ₃ H ₇ , ―C ₄ H ₉ , ―C ₂ H ₄ OCH ₃ , ―C ₂ H ₄ OC ₂ H ₅ ,
―C ₂ H ₄ OC ₃ H ₇ , ―C ₂ H ₄ OC ₄ H ₉ , ―C ₃ H ₆ OCH ₃ ,
―C ₂ H ₄ OC ₂ H ₄ OCH ₃ , ―C ₂ H ₄ OC ₂ H ₄ OC ₂ H ₅ ,

【formula】

【formula】

【formula】

[Formula] Among the compounds represented by the above formula (), particularly preferred industrially are the compounds represented by the formula ()'. {In formula ()′, X″ is -H, -OCH ₃ , -
OC ₂ H ₅ , ―OC ₂ H ₄ OCH ₃ , ―Cl, ―
OC ₂ H ₄ OC ₂ H ₄ OCH ₃ ,

[Formula] Y″ is -COCH ₃ , -COC ₂ H ₅ , -COOCH ₃

[Formula], R ₂ ′ is -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -C ₄ H ₉ , -C ₂ H ₄ OCH ₃ , and R ₃ ' is -H, -CH ₃ , -C ₂ H ₅ , -CH ₂ CH=
CH ₂ , ―C ₂ H ₄ OCH ₃ , ―C ₂ H ₄ CN,

[Formula]. The amount of the reaction medium may be arbitrary, but it is preferably used about 0.1 to 10 times, more preferably about 0.5 to 3 times, the amount of the raw material amine represented by formula (). In the production of the compound represented by formula (), the reaction is preferably carried out using a stoichiometric amount or a slight excess of the monochloroacetic acid derivative in the presence of an acid binder at 50°C to 180°C, more preferably 70°C to 130°C. The addition of a small amount of alkali metal iodide has the effect of accelerating the reaction and gives favorable results. Examples of the acid binder include soda carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, magnesium oxide, calcium oxide, magnesium hydroxide, and calcium hydroxide. The reaction is monitored by gas chromatography, and when the reaction is completed, it is cooled, the precipitated salt is filtered and washed with a small amount of solvent, and the washings can be combined and used as they are in the coupling reaction. The present invention will be specifically described below with reference to Examples. Example 1 2-methoxy-5-acetylamino-aniline
75.6g (0.42g-mol), dimethylformamide
75.6g, anhydrous potassium carbonate 31.9g (0.23g-mol),
A mixture of 4.2 g of potassium iodide and 50.1 g (0.46 g-mol) of monochloroacetic acid methyl ester was
The mixture was stirred at ℃ for 3 hours. A portion of the reaction solution was collected, dissolved in methanol, and analyzed by gas chromatography to obtain the following results. 2-methoxy-5-acetylamino-aniline: 2.7%, 2-methoxy-5-acetylamino-N(methoxycarbonylmethyl)aniline:
92.1%, 2-methoxy-5-acetylamino-
N,N-bis-(methoxycarbonylmethyl)aniline: 5.2%. The reaction mixture was cooled, precipitated potassium chloride was separated, and the residue was washed with a small amount of methanol. After combining the washing liquids, methanol and dimethylformamide are distilled and recovered to obtain 2-methoxy-5-acetylamino-N-(methoxycarbonylmethyl).
Crystals containing aniline as the main component were obtained. This product can be used as is for dye synthesis without purification, and the desired product can be obtained in high yield and quality. Comparative Example A reaction was carried out at 80 to 85° C. for 4 hours in the same manner as in Example 1, except that nitrobenzene was used instead of dimethylformamide. Analysis of the reaction solution by gas chromatography was as follows. 2-Methoxy-5-acetylamino-aniline: 90%, 2-methoxy-5-acetylamino-
N-(methoxycarbonylmethyl)aniline: 5
%, 2-methoxy-5-acetylamino-N-
(Hydroxycarbonylmethyl)aniline: 5%
Therefore, almost no alkylation reaction took place. Further, the reaction temperature was raised to 180 to 185° C. and the results were as follows, in which the number of hydroxycarbonylmethyl groups resulting from hydrolysis of methoxycarbonylmethyl groups increased significantly. 2-methoxy-5-acetylamino-aniline: 12.5%, 2-methoxy-5-acetylamino-N-(methoxycarbonylmethyl)aniline:
20.2%, 2-methoxy-5-acetylamino-
N,N-bis-(methoxycarbonylmethyl)aniline: 5.2%, 2-methoxy-5-acetylamino-N-(hydroxycarbonylmethyl)aniline: 50.2%, 2-methoxy-5-acetylamino-N,N- Bis-(hydroxycarbonylthyl)aniline: 11.9%. Example 2 2-methoxy-5-acetylamino-aniline
75.6g (0.42g-mol), dimethylformamide
75.6g, anhydrous potassium carbonate 63.8g (0.46g-mol),
A mixture of 4.2 g of potassium iodide and 100.2 g (0.92 g-mol) of monochloroacetic acid methyl ester was
Stirred at ~125°C for 10 hours. A portion of the reaction solution was taken, dissolved in methanol, and tested by gas chromatography with the following results. 2-methoxy-5-acetylaminoaniline;
trace, 2-methoxy-5-acetylamino-N
-(methoxycarbonylmethyl)aniline; 2.4
%, 2-methoxy-5-acetylamino-N,N
-Bis(methoxycarbonylmethyl)aniline;
97.0%. The reaction mixture was cooled, the precipitated potassium chloride was separated, and the residue was washed with a small amount of methanol. Methanol and dimethylformamide are distilled and recovered to produce high-purity 2-methoxy-5-acetylamino-N,N.
-Bis(methoxycarbonylmethyl)aniline was obtained. Example 3 In Example 2, 75.6 g of dimethylformamide
Instead, 75.6 g of dimethyl sulfoxide was used and stirred at 135 to 140°C for 6 hours. The results of gas chromatography analysis were 2-methoxy-5-acetylaminoaniline; trace, 2-methoxy-
5-acetylamino-N-(methoxycarbonylmethyl)aniline: 1.8%, 2-methoxy-5-
Acetylamino-N,N-bis(methoxycarbonylmethyl)aniline; 98.1%. Example 4 15 g (0.1 g-mol) of 3-acetylamino-aniline, 10 g of tetramethylene sulfone, 12 g of magnesium hydroxide and 33.6 g (0.22 g-mol) of monochloroacetic acid methoxyethyl ester were mixed to give 150 g.
After reacting at ~155°C for 6 hours, the precipitated magnesium chloride was filtered off, washed with a small amount of acetone, and the washings were combined to recover the acetone by distillation. ) A mixture consisting of 4.3% aniline and 95.7% 3-acetylamino-N,N-bis(methoxyethoxycarbonylmethyl)aniline was obtained. Example 5 3-acetylamino-N-β-cyanoethylaniline 20.3 g (0.1 g-mol), diethylformamide 42 g, magnesium oxide 4.84 g (0.12 g-mol),
Monochloroacetic acid, finethyl ester 23.8g
(0.12 g-mol) and 1 g of potassium iodide,
The reaction was carried out at 120-125°C until no starting material was detected by gas chromatography. It took about 20 hours. After cooling, the filtered mass was washed with a small amount of acetone, and the washing liquid was combined and used as it was for dye synthesis. That is, the aqueous layer was cooled and acidified with hydrochloric acid, and a separately prepared p-nitroaniline diazotization reaction solution (p-nitroaniline 13.8 g, equivalent to 0.1 mole) was added while cold, and the mixture was buffered with sodium acetate and coupled. Complete the process, remove the precipitated dye, and
47.7 g of -nitro-3'-acetylamino-4'-N-β-cyanoethyl-N-(β-phenoxyethoxycarbonylmethyl)amino-azobenzene was obtained. Examples 6-25 The results shown in Table 1 were obtained according to Examples 1-5.

【table】

【table】

Claims (1)

[Claims] 1 Formula () [In formula (), X is a hydrogen atom, a halogen atom,
A lower alkyl group (which may be further substituted with a hydrofuryl group), or a lower alkoxy group (which may be further substituted with a lower alkoxy group, an alkoxyalkoxy group, a phenyl group, or a phenoxy group), Y is an acyl group or a methoxycarbonyl group, R ₁ is a hydrogen atom, a lower alkyl group (this can further be a lower alkoxy group, a lower alkoxyalkoxy group, an acyl group, a phenyl group, a phenoxy group, a cyano group, a cyano lower alkoxy group, an acyloxy group) , lower alkoxycarbonyl group, lower alkoxyalkoxycarbonyl group,
(optionally substituted with a hydrofuryl group, a hydroxy group or a halogen atom) or a lower alkenyl group. ] The aniline derivative represented by is reacted with dimethylformamide, diethylformamide, dimethyl sulfoxide, diethyl sulfoxide or tetramethylene sulfone in the presence of an acid binder.
Formula () ClCH ₂ COOR ₂ () [In formula (), R ₂ is a lower alkyl group (which is further substituted with a lower alkoxy group, a lower alkoxyalkoxy group, a phenyl group, a phenoxy group, a benzyloxy group or a hydrofuryl group)] ). ] Formula () characterized by reacting with a monochloroacetic acid derivative represented by [In the formula (), X, Y and R ₂ represent the above meanings, and R ₃ is a hydrogen atom or - when R ₁ in the formula () means a hydrogen atom.
When R ₁ in the CH ₂ COOR ₂ group means an optionally substituted lower alkyl group or lower alkenyl group, it means R ₁ in formula (). ] A method for producing an aromatic amine represented by