JPH04139159A - Method for producing n-cyanoethyl aniline compounds - Google Patents

Abstract

PURPOSE:To prepare the subject compound in a high selectivity and in a good yield while preventing the production of by-products and the polymerization of acrylonitrile by reacting an aniline compound with acrylonitrile in the presence of a catalyst comprising zinc hydroxide and/or zinc oxide and an aryl sulfonic acid. CONSTITUTION:When an aniline compound is allowed to react with acrylonitrile to provide a N-cyanoethyl aniline compound, the reaction is performed in the presence of zinc hydroxide and/or zinc oxide and an aryl sulfonic acid (e.g. p-toluene sulfonic acid). In the reaction, the ratio of the sum of zinc hydroxide and/or zinc oxide to the aryl sulfonic acid is preferably approximately 0.5-5wt.%, and the chemical equivalent ratio of zinc hydroxide and/or zinc oxide to the aryl sulfonic acid is preferably approximately 3/1 to 1/3. By the method, the by-production of N,N-dicyanoethyl aniline compounds and the polymerization of the acrylonitrile can be prevented, and the high selectivity and the good yield can be achieved.

Description

Detailed Description of the Invention [Industrial Application Field 1] The present invention relates to a method for producing N-cyanoethylanilines, and more particularly to a method for producing N-cyanoethylanilines by reacting anilines with acrylonitrile. It is.

The N-cyanoethylanilines produced according to the present invention are useful as important intermediates for disperse dyes.

[Conventional technology] The following methods have been reported.

fal A method for reacting anilines and acrylonitrile in the presence of copper acetate [J, Org, Chew,
22.1213 (1957) ] (bl Method of Reacting Anilines and Acrylonitrile in the Coexistence of Transition Metals and Water (Japanese Unexamined Patent Publication No. 56-13325
fc) A method of reacting anilines and acrylonitrile in the presence of zinc chloride, acetic acid and water (Boland Patent No. 9)
(Specification No. 3096) [Problems to be Solved by the Invention] However, among the above manufacturing methods, method a.

Since by-products of N,N-dicyanoethylanilines and polymerization of acrylonitrile occur, the yield of the target N-cyanoethylanilines is low.

Method b suppresses the by-product of N,N-dicyanoethylanilines and the polymerization of acrylonitrile, but the reaction rate is slow and a long reaction time is required to obtain the desired N-cyanoethylanilines. , Multi Ill M 4111
# j I+Rhr I; If 3 m j ! m
1 +'/, m J+ (7, s) In addition, in method C, acetic acid used as a catalyst reacts with anilines to produce acetanilides as by-products, which not only causes a decrease in yield but also may lead to failure of the intended purpose in some cases. For example, in the case of unsubstituted aninone, the boiling point of acetanilide is 147℃15
The boiling point of N-cyanoethylaniline is 15 for Hg.
8~160℃15■ Hg, acetanilide and N
Separation of -cyanoethylaniline is not easy, and in order to obtain N-cyanoethylaniline with good purity, there are problems such as an increase in the number of distillation stages and an increase in the reflux ratio.

An object of the present invention is to provide a simple and efficient method for producing N-cyanoethylanilines. The method for producing cyanoethylanilines is characterized in that zinc hydroxide and/or zinc oxide and arylsulfonic acids are allowed to coexist as catalysts.

Examples of the anilines used in the present invention include the following.

Aniline, 0-toluidine, ■-toluidine, p-toluidine, 〇-ethylaniline, m-ethylaniline, p
-ethylaniline, 0-anisidine, m-anisidine,
p-anisidine, 0-chloroaniline, m-chloroaniline, p-chloraniline, ■-aminoacetanilide, ■-benzoylaminoaniline, 3-amino-4-methoxyanilide, 2.5-dimethoxyaniline, 3-ureidoaniline , 2-methoxy-5-ureidoaniline, 3-ethoxycarbonylaminoaniline, 5-ethoxy-3-methoxyaniline, 2-(2-methoxyethoxy)aniline, 5-acetylamino-2-(2-methoxyethoxy)aniline .

The amount of acrylonitrile used is 0.3 to 2.0 mol, preferably 0.5 to 1.3 mol, per 1 mol of aniline.

The arylsulfones used in the present invention include, for example, benzene, naphthalene, anthracene, phenanthrene sulfonic acid, disulfonic acid, trisulfonic acid, tetrasulfonic acid, etc., and these benzene nuclei have an alkyl group,
It may have one or more substituents of a cycloalkyl group, an amino group, a hydroxyl group, a halogen group, a nitro group, and a fluorinated alkyl group.

Specifically, examples of benzenesulfonic acids include benzenesulfonic acid, l)-toluenesulfonic acid, o-t
-Luenesulfonic acid, ■-Toluene or sulfonic acid, xylene sulfonic acids, trimethylbenzenesulfonic acid, phenolsulfonic acids, benzenedisulfonic acids, benzenetrisulfonic acids, methylbenzenesulfonic acids, phenoldisulfonic acids, cresolsulfonic acids, chlorobenzenesulfonic acids Acids, fluorobenzenesulfonic acids, trifluoromethylbenzenesulfonic acids, bromobenzenesulfonic acids, dichlorobenzenesulfonic acids, chlorotoluenesulfonic acids, phenoltrisulfonic acid, oxytoluenesulfonic acid +J Todoroki Shoko
-12 1+1 ”'I ++, -shi...+
No Isshiki +, 1/+ Auto S No 1 No Includes fluoronic acid, nitrobenzenesulfonic acids, nitrotoluenesulfonic acids, nitroxylenesulfonic acids, dinitrobenzenesulfonic acids, dinitrotoluenesulfonic acids, cyclohexylbenzenesulfonic acids, aminobenzenesulfonic acids, etc. .

Examples of naphthalenesulfonic acids include α-naphthalenesulfonic acids, β-naphthalenesulfonic acids, 1.5-
naphthalenedisulfonic acid, 2.5-naphthalenedisulfonic acid, 2.6-naphthalenedisulfonic acid, 1.3.5-
Naphthalene trisulfonic acid, 2.5.7-naphthalene trisulfonic acid, 2.4.6-naphthalene trisulfonic acid, 2.4.6.8-naphthalene tetrasulfonic acid, N
W acid, Schaefer acid, croseic acid, Tobias acid, R
acid, G acid, naphthionic acid, 2S acid, H acid, γ acid, J acid,
Amino G acid, Friend acid, peric acid, 5-naphthylamine-1-sulfonic acid, l-naphthylamine-8-sulfonic acid, l-naphthylamine 4.8-disulfonic acid 51-naphthylamine-2,4,8-to+ I L+ ”ノ#
I-+7 hand I+, a;
-Nitronaphthalene-■-sulfonic acid, 1-bito-naphthalene-3-sulfonic acid, 1-nitronaphthalene-4-
Sulfonic acid, ■-Nitronaphthalene 5-sulfonic acid, 2
-Nitronaphthalene-5-sulfonic acid, 1-nitronaphthalene-6-sulfonic acid, l-nitronaphthalene-7
-sulfonic acid, l-nitronaphthalene-8-sulfonic acid, 2-nitronaphthalene-8-sulfonic acid, 6-methyl-1-nitronaphthalene-5-sulfonic acid, 8-methyl-1-nitronaphthalene-5- Sulfonic acid, 5-methyl-1-nitronaphthalene-8-sulfonic acid, 7-methyl-1-nitronaphthalene-8-sulfonic acid, 1.3=dinitronaphthalene-5-sulfonic acid, 1.5-dinitronaphthalene- 3-sulfonic acid, 1,8-dinitronaphthalene-3-sulfonic acid, 1,8-dinitronaphthalene-
4-sulfonic acid, 1-nitronaphthalene-3,6-disulfonic acid, l-nitronaphthalene-3,7-disulfonic acid, l-nitronaphthalene-3,8-disulfonic acid, ■-
Nitronaphthalene-4,8-disulfonic acid, 2-nitronaphthalene-4,8-disulfonic acid, ■-Nitronaphthalene-5,8-disulfonic acid, l-nitronaphthalene-
Examples include 3,6,8-1-disulfonic acid and 1-nitronaphthalene-4,6,8-trisulfonic acid.

Additionally, there are anthracene sulfonic acid, phenanthrene sulfonic acid, and the like. These arylsulfonic acids can be used alone or in combination of two or more.

The amount of catalyst used is such that the sum of zinc hydroxide and/or zinc oxide and arylsulfonic acid is 0.1 to 20% of the aniline.
% by weight, preferably 0.5-5% by weight. The ratio of zinc hydroxide and/or zinc oxide to the arylsulfonic acids is 571 to 1/4 in chemical equivalent ratio, preferably 3/l to 1
/3.

The reaction temperature is 40-160°C, preferably 60-140°C.
It is ℃. At temperatures below 40°C, the reaction takes a long time, and 160°C
If the temperature is higher than 0.degree. C., some side reactions such as polymerization of acrylonitrile occur, and the yield of N-cyanoethylanilines tends to decrease.

The reaction time is greatly influenced by the amount of catalyst and the reaction temperature, but is generally conveniently in the range of 1 to 20 hours, preferably 3 to 13 hours.
It's time.

In the present invention, organic solvents such as benzene, toluene, ethers, ethylene glycol dimethyl ether, water, etc. can be used as the reaction heating medium, but the use of these heating mediums generally reduces the reaction rate and is not suitable for industrial use. is disadvantageous.

After the reaction is completed, N-cyanoethylanilines with good yield and high purity can be obtained by carrying out appropriate catalyst removal such as water washing and filtration, followed by distillation purification or crystallization.

[Effect 1] In the present invention, it can be assumed that zinc hydroxide and/or a neutralized salt of zinc oxide and arylsulfonic acid exhibits catalytic activity.

This suppresses the by-product of N,N-dicyanoethylanilines and the polymerization of acrylonitrile, and dramatically increases the reaction rate.

[Example 1: IIL-★Dn day t,'e t* a-+, 7 jl
t -(1,% y Jc e-1- will be explained as tension r-, but the present invention is not limited to the following examples.

Example 1 Aniline 20 (LIg (2.15 mol), acrylonitrile 94.0 g fl, 77 mol), p~toluenesulfonic acid 4.2 g and zinc hydroxide 0.8 g were charged into a glass reactor, and while stirring. 90-10 when heated
The temperature was maintained at 0°C and the reaction was carried out for 10 hours.

The composition of the reaction product according to GC analysis was 94% acrylonitrile, 18.49% aniline, 78.52% N-cyanoethylaniline, and 0.60% N,N-dicyanoethylaniline.

After washing with 10% NaaSO + aqueous solution and then simple distillation under reduced pressure to remove unreacted acrylonitrile and aniline, N-cyanoethylaniline 235.
5 g (purity 99.5%) was obtained, and the yield was 91.0% based on acrylonitrile.

Comparative Example 1 Aniline 624.8 gf 6.71 mol), acetic acid steel 18.
0g and yt-7hII rq -L II f
l ReCA C-LJ no x ++, 1 f
-9rT9Q and raise the temperature while stirring to 100
The temperature was maintained at ~110°C and the reaction was carried out for 3 hours.

The reaction solution composition according to GC analysis was acrylonitrile 0.3
3%, aniline 26.72%, N-cyanoethylaniline 69.25%, N,N-dicyanoethylaniline3.
0.6% and other by-products 0.64%.

After washing with 1O% NazSO4 aqueous solution, simple distillation under reduced pressure was performed in the same manner as in Example 1 to remove unreacted acrylonitrile and aniline, and 504.3 g of N-cyanoethylaniline (purity 97.6%) was obtained as the main distillate. The yield was 69.1% based on acrylonitrile. 1.3% of N,N-dicyanoethylaniline was contained as an impurity.

Example 2 200.0 g + 1.87 mol of 1m-toluidine), 79.2 g + 1.49 mol of acrylonitrile), 3.6 g of p-phenolsulfonic acid, and 0-8 g of zinc hydroxide were charged into a glass reactor, and the temperature was raised while stirring. 90~9
The reaction was carried out for 10 hours while maintaining the temperature at 7°C.

The reaction product liquid composition according to GC analysis is acrylonide nor 0.
．． 59%, -1-toluidine 17.31%, N-cyanoethyl m-toluidine 80.16%, and N,N-dicyanoethyl I-toluidine 0.91%.

After carrying out the same treatment as in Example 1, unreacted acrylonitrile and -toluidine were removed by simple distillation under reduced pressure, and 222.5 g of N-cyanethyl m-toluidine was obtained as the main fraction.
(purity 99.6%) was obtained. The yield was 93.2% based on acrylonitrile.

Comparative Example 2 4 g of toluidine (8 g f3.74 mol), 200.3 g f3.74 mol) of acrylonitrile, 12.0 g of zinc chloride, 8.5 g of acetic acid, and 40 g of water were charged into a glass reactor and heated while stirring. Warm to 105-115
The temperature was maintained at ℃ and allowed to react for 10 hours.

The reaction solution composition according to GC analysis is acrylonitrile 1, 16
%, m-toluidine 9.57%, aceto l-toluiside 1.12%, N-cyanoethyl m-toluidine 83.7
2%, N,N-dicyanoethyl ts-toluidine 1.9
It was 6%.

The same treatment as in Example 1 was carried out, unreacted acrylonitrile and aniline were removed by simple distillation under reduced pressure, and N-
Cyanoethyl m-toluidine 368.9 (purity 96.4
%) was obtained. This product contained 1.64% aceto-l-toluicide as an impurity.

The yield was 61.6%.

Example 3 Kaku-anisidine 20 (LOgfl, 62 mol), acrylonitrile 68.8 g fl, 30 mol), 2.
7.0 g of 4.6-dolinitrobenzenesulfonic acid and 0.8 g of zinc hydroxide were charged into a glass reactor, and the temperature was raised while stirring to maintain the temperature at 95 to 100° C., and the reaction was carried out for 10 hours.

The reaction solution composition according to GC analysis was acrylonitrile 1.0
1%, intestinal-anisidine 17.68%, N-cyanoethyl l-anisidine 8100%, and N,N-dicyanoethyl-anisidine 0.31%.

The same treatment as in Example 1 was carried out, and unreacted acrylonitrile and -anisidine were removed by simple distillation under reduced pressure to obtain 1 g of N-cyanoethyl toluidine 21O (purity 99.3%) as the main distillate. The yield is as follows: Acrylonide Comparative Example 3: 200.0 g (1,62 mol) of anisidine, 68.8 g + 1.30 mol of acrylonitrile), 1 mol of zinc chloride
0.0g and 20.0g of water were charged into a glass reactor,
The temperature was raised while stirring and maintained at 95 to 98°C, and the reaction was allowed to proceed for 10 hours.

The reaction solution composition according to GC analysis was acrylonitrile 16,
14%, l-anisidine 54.86%, and N-cyanoethylnieanisidine 29.00%. Since the reaction rate was low, no further treatment was performed.

Example 4 200.0 g (1.65 mol) of p-ethylaniline, 87.5 g + 1.65 mol of acrylonitrile), 2.0 g of zinc hydroxide, and 8.0 g of l-naphthalenesulfonic acid were charged into a glass reactor and stirred. While raising the temperature, it reaches 92~
The temperature was maintained at 97°C and the reaction was carried out for 9 hours.

The reaction solution composition according to GC analysis was acrylonitrile 1.6
5%, p-ethylaniline 5.29%, N-cyanoethyl p-ethylaniline 91.84%, and N,N dicyanoethyl-ethylaniline 1.22%.

After removing unreacted acrylonitrile and p-ethylaniline, 261.3 g of N-cyanoethyl p-aniline (purity 99.4%) was obtained as the main fraction. The yield was 93.5% based on acrylonitrile.

Comparative Example 4 200.0 g (1.65 mol) of p-ethylaniline, 70.0 g (1.32 mol) of acrylonitrile), 10.0 g of l-naphthalenesulfonic acid, and 20.0 g of water were charged into a glass reactor and heated while stirring. 90-95 warm
The temperature was maintained and the reaction was carried out for 15 hours.

The reaction solution composition according to GC analysis was acrylonitrile 16,
90%, p-ethylaniline 5120%, and N-cyanoethyl p-ethylaniline 30.81%. Since the reaction rate was low, no further treatment was performed.

Example 5 Aniline 200.4g (2.15 mol), acrylonitrile 148.0gf2.79 mol), p-xylene-
8-5 g of 2-sulfonic acid and 2.0 g of zinc oxide were placed in a glass reactor, and the temperature was raised while stirring to reach a temperature of 95-10
The temperature was maintained at 5°C and the reaction was carried out for 10 hours.

The reaction solution composition according to GC analysis was acrylonitrile 7.2
4%, aniline 3.18%, N-cyanoethylaniline 86.96%, N,N dicyanoethylaniline 2.14%
%Met.

After carrying out the same treatment as in Example 1 and removing unreacted acrylonitrile and aniline by simple distillation under reduced pressure, 260.6 g of N-cyanoethylaniline (purity 98.
9%).

Comparative Example 5 Aniline 205.9g (2.21 mol), acrylonitrile 93.6g (1.76 mol), zinc hydroxide 3.0
g and 7.0 g of oxalic acid were charged into a glass reactor, and the temperature was raised while stirring to maintain the temperature at 95 to 100° C., and the reaction was carried out for 10 hours.

The reaction solution composition according to GC analysis was acrylonitrile 23,
17%, aniline 72.34%, and N-cyanoethylaniline 4.49%.

Comparative Example 6 Aniline 203.0g f2.18 mol), acrylonide nor 92. (Ig (1,73 mol), zinc hydroxide 3
．． 0g and benzoic acid 7. Pour Og into a glass reactor, raise the temperature while stirring and keep it at 95-105℃, and heat it for 10 minutes.
Allowed time to react.

The reaction solution composition according to GC analysis was 13.
63%, aniline 57.69%, and N-cyanoethylaniline 28.56%.

Comparative Example 7 Aniline 205.9 gf2.2 t mol), acrylonitrile 93.6 g (1,76 mol), zinc hydroxide 3.0
g and 7.0 g of 85% phosphoric acid into a glass reactor,
The temperature was raised while stirring and maintained at 95 to 100°C, and the reaction was carried out for 10 hours.

The reaction solution composition according to GC analysis was acrylonitrile 21.
16%, aniline 74.29%, and N-cyanoethylaniline 4.55%.

[Effect of the invention 1 As described above, according to the present invention, N,N-diethylanilines can be prepared by reacting anilines with acrylonitrile in the presence of zinc hydroxide and/or zinc oxide and arylsulfonic acid. Polymerization of by-products and acrylonitrile is suppressed, and the desired N-cyanoethylanilines can be produced with high selectivity and good yield.

Claims (1)

[Claims] (1) By reacting anilines and acrylonitrile, N
- A method for producing N-cyanoethylanilines, which comprises coexisting zinc hydroxide and/or zinc oxide with an arylsulfonic acid as a catalyst.