JP2870707B2 - Method for producing 3-butenenitrile - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing 3-butenenitrile useful as a raw material for producing pharmaceuticals.

[0002]

2. Description of the Related Art 3-butenenitrile is converted to 3-halogeno-
Conventional techniques for producing from 1-propenes include the following four.
Two methods are known.

[0003] (A) 3 from allyl bromide and cuprous cyanide
-Method for producing butenenitrile (Org. Snth.
Coll Vol I 46 (1941)).

(B) 3 from allyl chloride and cuprous cyanide
-Method for producing butenenitrile (Org. Snth.
Coll Vol III 852 (1955)).

(C) calcium carbonate, cupric sulfate, water,
A method for producing 3-butenenitrile by dropping hydrogen cyanide into a mixture of 3-chloro-1-propene (J. Orn)
g. Chem, 26 4300 (1961)) .

(D) A method for producing 3-butenenitrile from allyl chloride and sodium cyanide in a mixed solution of a saturated saline solution, cuprous chloride and copper powder under conditions of pH 3 to 4 and an inert atmosphere ( Liebigs Ann.C
chem., 631 , 21, (1960)).

[0007]

However, the method (a) uses expensive cuprous cyanide and allyl bromide, and the reaction is suddenly and suddenly accompanied by danger. Not suitable for industrial production.
The method (b) changes allyl bromide to allyl chloride, but still uses expensive cuprous cyanide .
Reactivity is also not suitable for industrial production is similar to that of (a). The method (c) is relatively excellent as a method for synthesizing 3-butenenitrile, but in this method, 1/2 mol of carbon dioxide gas is generated with respect to 3-butenenitrile, and this gas is entrained. Then, extremely highly toxic hydrogen cyanide goes out of the reaction system, so that it is not easy to recover or remove the hydrogen cyanide. In the method (d), 3-butenenitrile is synthesized from allyl chloride and sodium cyanide using cuprous chloride as a catalyst, but the reaction is carried out in a nitrogen or carbon dioxide atmosphere to prevent oxidation of cuprous. Need to be
Also, large amounts of saturated saline must be used. As described above, all of the above-mentioned methods have problems in industrial implementation.

Accordingly, an object of the present invention is to solve the above problems and to produce 3-butenenitrile easily and easily.

[0009]

The present inventors have conducted intensive studies on a method for producing 3-butenenitrile in order to solve the above-mentioned problems. As a result, the inexpensive formula CH ₂ = CR ¹ -C was obtained.
A compound represented by H ₂ —Cl (wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) (hereinafter referred to as 3-chloro-1-propenes) and cyanide Alkali cyanide, or 3-chloro-1-propenes and hydrogen cyanide and alkali hydroxide in the presence of a specific catalyst,
Easy and easy 3
-It has been found that butenenitrile can be produced, and the present invention has been completed.

That is, the gist of the present invention is as follows.
From the 3-chloro-1-propenes the formula CH ₂ ＣＲCR ¹ -C
H ₂ —CN (wherein R ¹ is a hydrogen atom or a carbon atom
3 represents an alkyl group. In the method for producing 3-butenenitrile represented by the formula (3), 3-butenenitrile is obtained by reacting 3-chloro-1-propene with alkali cyanide under conditions of pH 1 to 5 in the presence of cupric ion. And a method for producing 3-butenenitrile by reacting 3-chloro-1-propenes and hydrogen cyanide with alkali hydroxide in the presence of cupric ion at pH 1-5.

Hereinafter , the present invention will be described in detail.

The formula CH ₂ = CR ¹ -C used in the present invention
H ₂ —Cl (wherein R ¹ is a hydrogen atom or a carbon atom 1
And represents an alkyl group of 1 to 3. Examples of the compound represented by) include 3-chloro-1-propenes such as allyl chloride and 3-chloro-2-methyl-1-propene, and those produced industrially can be used as they are. Is possible.

In the method of the present invention, it is necessary to carry out the reaction in the presence of cupric ion acting as a catalyst, and the cupric ion is a common water-soluble reagent such as cupric sulfate,
It can be obtained by dissolving cupric chloride, cupric nitrate, cupric acetate or the like in water, but it is preferable to use cupric sulfate or cupric chloride. The amount of the water-soluble cupric catalyst to be used is 0.001 times or more mol, preferably 0.004 to 1 mol, of the 3-chloro-1-propene.
Desirably, it is 0.1 mole.

In the present invention, it is necessary to carry out the reaction at a pH of 1 to 5, preferably at a pH of 2 to 4. When the pH is less than 1, the reaction rate is reduced, while when the pH is more than 5, the reaction rate is reduced. When the pH is 7 or more, hydrogen cyanide is polymerized and coloring becomes remarkable. The reaction is stopped because the ions are converted to cupric hydroxide, which is not preferable. After the reaction is stopped, the reaction can be restarted by newly adding an acid to lower the pH to 5 or less, but this is not preferable because of coloring or difficulty in liquid separation. For this reason, an acid is usually added to the reaction system in advance to adjust the pH to the range of 1 to 5. The acid used for this purpose is not particularly limited as long as it does not interfere with the reaction, and hydrochloric acid, sulfuric acid,
Acetic acid and the like can be preferably used, and hydrochloric acid is particularly preferably used.

According to the present invention, usually, water, the above-mentioned water-soluble cupric catalyst, a pH buffer reagent and an acid are introduced into a reactor, and the above-mentioned 3-chloro-1-propene is added thereto. An aqueous solution of alkali cyanide is added dropwise under the condition of pH 1 to 5 in the presence of the compound (1) to react the alkali cyanide with the 3-chloro-1-propenes to synthesize the desired 3-butenenitrile.

Further, water and a water-soluble secondary
A copper catalyst, a pH buffer reagent and an acid were introduced, and 3-chloro-
After adding 1-propenes and hydrogen cyanide, an aqueous solution of alkali hydroxide is added dropwise at pH 1 to 5 in the presence of cupric ion to react the alkali hydroxide with 3-chloro-1-propenes and hydrogen cyanide. Thus, 3-butenenitrile can be synthesized.

These reactions are usually carried out at a temperature in the range of 5 ° C. to 100 ° C., preferably 15 ° C. or higher and the boiling point of the 3-chloro-1-propenes. In this case, the reaction can be carried out at a constant temperature. However, in order to avoid reflux of 3-chloro-1-propenes or hydrogen cyanide, the reaction is carried out at a low temperature, preferably 15 to 30 ° C. at the beginning of the reaction, and then the temperature is gradually increased. It is more preferable to set the temperature at the end of the raising reaction to a temperature near the boiling point of 3-chloro-1-propenes.

Examples of the alkali used for the alkali cyanide and the alkali hydroxide include an alkali metal element and an alkaline earth metal element. In terms of reactivity and post-treatment, usually, sodium cyanide, potassium cyanide and hydroxide are used. Sodium and potassium hydroxide can be used, and sodium cyanide and sodium hydroxide are particularly preferably used. The concentration of these aqueous solutions is not particularly limited, but is generally used at a concentration that facilitates post-treatment. The molar ratio of 3-chloro-1-propenes to alkali cyanide is not particularly limited,
It is preferable to make them equimolar for quantitative reaction.

When the above reaction is carried out using sodium cyanide as the alkali cyanide or sodium hydroxide as the alkali hydroxide, the upper 3-butenenitrile and the lower sodium chloride aqueous solution are separated. Thereby, the separated aqueous solution can be used for the next reaction as it is. A small amount of 3-butenenitrile contained in the aqueous sodium chloride solution can be efficiently recovered by distillation under acidic conditions.

[0020]

EXAMPLES The present invention will be specifically described with reference to the following examples. Example 1 In a 1 liter glass reactor equipped with a pH meter, thermometer, cooler, stirrer, and liquid supply tube, cupric sulfate pentahydrate was added.
75 g, monosodium phosphate dihydrogen dihydrate 2.64 g, water 71.9 g, and concentrated hydrochloric acid 23.8 g were charged and stirred to adjust to 25 ° C. In this reactor, allyl chloride 248.
1 g (3.242 mol) was added. 529.7 g (3.242 mol) of a 30% aqueous solution of sodium cyanide
For 3 hours while controlling the pH of the reaction solution within the range of 3-4.
It was added dropwise over 0 minutes. During this time, the temperature of the reaction solution was gradually raised from the initial 25 ° C., and adjusted to 43 ° C. at the end of the dropping of the aqueous sodium cyanide solution. The reaction solution was cooled to 25 ° C., and the generated salt and water were separated to obtain 213.5 g of an organic layer.
The aqueous layer (648.5 g) was distilled to separate the distillate up to 100 ° C., and an organic layer (9.6 g) was recovered. These organic layers 22
The content of allyl cyanide in 3.1 g was 92.2%, and the yield from allyl chloride was 94.6%. The proton chemical shift in the product NMR (CDCl ₃ solution) was 3.14 ppm (d, 2H).
33 ppm (d, 1H), 5.47 ppm (d, 1H),
5.73 ppm (m, 1H). Example 2 In a 500 ml glass reactor equipped with the same equipment as in Example 1 , 1.13 g of cupric sulfate pentahydrate and disodium borate 2 were added.
2.5 g of hydrogen decahydrate, 43.1 g of water, and 7.14 g of concentrated hydrochloric acid were charged, and the mixture was stirred and adjusted to 20 ° C. To this reactor, 74.43 g (0.973 mol) of allyl chloride and 26.3 g (0.973 mol) of hydrogen cyanide were added.
While controlling the pH of the reaction solution in the range of 3 to 4, 155.7 g (0.973 mol) of 25% sodium hydroxide was added dropwise over 6 hours and 20 minutes. During this time, the temperature of the reaction solution was initially 20 ° C.
And the temperature was adjusted to 43 ° C. at the end of the dropping of the aqueous sodium hydroxide solution. The reaction solution was cooled to 25 ° C., and the generated salt and water were separated to obtain 63.3 g of an organic layer.
247 g of the aqueous layer was distilled to separate a distillate up to 100 ° C., and 3.1 g of an organic layer was recovered. These organic layers 66.
The content of 4 g of allyl cyanide was 93.2%.
The yield from allyl chloride was 94.8%. The proton chemical shift in the product NMR (CDCl ₃ solution) was 3.14 ppm (d, 2H), 5.33 ppm.
(D, 1H), 5.47 ppm (d, 1H), 5.73 pp
m (m, 1H). Example 3 In a 500 ml glass reactor equipped with the same equipment as in Example 1, 3.48 g of cupric sulfate pentahydrate and monosodium phosphate 2 were added.
Hydrogen dihydrate 1.85 g, water 66.8 g, and concentrated hydrochloric acid 9.
28 g was charged, and the mixture was stirred and adjusted to 26 ° C. The reactor was charged with 3-chloro-2-methyl-1-propene 135.9.
5 g (1.501 mol) were added. 245.0 g (1.500 mol) of a 30% aqueous solution of sodium cyanide
For 5 hours for 6 hours while controlling the pH of the reaction solution in the range of 3 to 5.
It was added dropwise over 0 minutes. During this time, the temperature of the reaction solution was gradually raised from the initial temperature of 26 ° C., and adjusted to 56 ° C. at the end of the dropping of the aqueous sodium cyanide solution. The reaction solution was cooled to 25 ° C., and the organic layer from which the saline solution was separated was distilled to obtain a distillate of 66 ° C./64 mmHg and 95.08 g of 3-methyl-3-butenenitrile. The yield from 3-chloro-2-methyl-1-propene was 94.6%. The NMR (CDCl
₃ solution) has a chemical shift of 1.85 ppm
(S, 3H), 3.06 ppm (s, 2H), 5.01 pp
m (s, 1H) and 5.10 ppm (s, 1H). Example 4 1.13 g of cupric sulfate pentahydrate and monosodium phosphate 2 were placed in a 300 ml glass reactor equipped with the same equipment as in Example 1.
0.79 g of hydrogen dihydrate, 21.6 g of water, and 7.1 g of concentrated hydrochloric acid were charged, and the mixture was stirred and adjusted to 40 ° C. To this reactor, 74.4 g (0.972 mol) of allyl chloride was added. Further, 158.9% aqueous sodium cyanide solution 158.9
1 g (0.972 mol) was added dropwise for 6 hours and 30 minutes while controlling the pH of the reaction solution in the range of 2 to 4. Of allyl cyanide
The yield was 92.7%.

[0021] The ratio Comparative Examples 1 to 300ml glass reactor equipped with a similar device as in Example 1, the second copper pentahydrate 1.3g, phosphate monosodium dihydrogen dihydrate 0.79g sulfate, water 21.6g And concentrated hydrochloric acid7.
1 g was charged, stirred and adjusted to 40 ° C. To this reactor, 74.4 g (0.972 mol) of allyl chloride was added. Further, a 30% aqueous sodium cyanide solution was added
The solution was added dropwise for 6 hours and 30 minutes while controlling the pH within the range of 6.5 to 7.5. However, the obtained reaction solution was black-brown, difficult to separate, and contained polymer-like solids.

[0022]

According to the present invention, inexpensive 3-chloro-1
-3-butenenitrile can be easily and safely produced from propenes and alkali cyanide, or from 3-chloro-1-propenes and hydrogen cyanide and alkali hydroxide.

Claims (2)

(57) [Claims] 1. A formula ^{_{CH 2 = CR 1 -CH 2 -Cl}} ( wherein, R ¹ is. Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) wherein CH ₂ = CR ¹ from the compounds represented by −
CH ₂ —CN (wherein R ¹ is a hydrogen atom or carbon atom 1)
And represents an alkyl group of 1 to 3. In the process for producing 3-butenenitrile represented by the formula: CH ₂ ＣＲCR ¹ —CH ₂ —C ₂ under the condition of pH ¹ to 5 in the presence of cupric ion.
1. A method for producing 3-butenenitrile, which comprises reacting an alkali cyanide with a compound represented by l. 2. A formula ^{_{CH 2 = CR 1 -CH 2 -Cl}} ( wherein, R ¹ is. Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) wherein CH ₂ = CR ¹ from the compounds represented by −
CH ₂ —CN (wherein R ¹ is a hydrogen atom or carbon atom 1)
And represents an alkyl group of 1 to 3. In the process for producing 3-butenenitrile represented by the formula: CH ₂ ＣＲCR ¹ —CH ₂ —C ₂ under the condition of pH ¹ to 5 in the presence of cupric ion.
A method for producing 3-butenenitrile, which comprises reacting an alkali hydroxide with the compound represented by 1 and hydrogen cyanide.