JP3029731B2 - Method for producing primary chrysanthemic nitrile - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing nitrile of primary chrysanthemum which is useful as a synthetic intermediate for agricultural chemicals.

[0002]

2. Description of the Prior Art Nitriles of primary chrysanthemum can be converted into primary chrysanthemic acid, which is an important raw material for agricultural chemicals, by hydrolysis.

[0003] A synthesis reaction of nitrile primary chrysanthemum using phenylprenyl sulfone and senecionitrile as raw materials is already known. For example, Esti NSV Tea
d. Akad. Toim. , Keem. , 38 (4),
238-41 reports a method of reacting phenylprenyl sulfone with sensionitrile in a ratio of 1: 3 in the presence of sodium methoxide or potassium hydroxide in DMSO. However, the reaction yield of this method is at most 50%. Further, this method requires an excessive amount of senecionitrile, but since senecionitrile has a property of being easily polymerized, it is economically disadvantageous to use it excessively.

[0004] Other, as described in JP-B-43-2344, in the presence of a basic substance by reacting the phenyl prenyl sulfone and Seneshionitoriru, resulting Ru methods are known first chrysanthemic acid nitrile . However, in the case of this reaction, expensive basic substances such as metal alkoxides and metal amides are used, and it is necessary to use them in equimolar amounts with phenylprenyl sulfone, which is economically problematic.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for synthesizing nitric acid nitrite using phenylprenyl sulfone and senecionitrile as raw materials, which provides unprecedented economical efficiency and high yield. It is in.

[0006]

Means for Solving the Problems The present inventors have conducted various studies in order to solve the above problems, and as a result, the following formula has been obtained.

[0007]

Embedded image A phenylprenyl sulfone represented by the following formula

[0008]

Embedded image By reacting in a mixed solution of a polar solvent and a solvent for azeotropic dehydration in the presence of a basic substance,

[0009]

Embedded image The present inventors have found that the first nitric acid nitrile represented by the formula (1) can be obtained in high yield, and have reached the present invention.

Specific examples of the basic substance used in the reaction in the [0010] present inventors, sodium hydroxide, alkali metal or alkaline earth hydroxide of a metal, such as potassium hydroxide
Do etc. it is.

[0011] As the polar solvent usable in the reaction, DMS
O, DMF, THF, etc., and azeotropic dehydration solvents include aromatic hydrocarbons such as toluene, saturated hydrocarbons such as hexane and cyclohexane, unsaturated hydrocarbons such as diisobutylene, and ethers such as isopropyl ether. Can be used.

The raw material phenylprenyl sulfone can be synthesized from prenyl chloride and sodium benzenesulfinate, and the reaction solution can be used as it is in the synthesis reaction of nitrile primary chrysanthemum.

[0013] Senecionitrile, another raw material, can be synthesized from methallyl chloride and sodium cyanate.

In order to obtain nitrile primary chrysanthemum in a higher yield, it is preferable to use these raw materials after purification by recrystallization, distillation or the like.

[0015] The reaction can be carried out at a temperature in the range of 30 ° C to 100 ° C, more preferably in the range of 50 ° C to 90 ° C. The preferred amount of the basic substance used is 1 to 3 mol per 1 mol of phenylprenyl sulfone, and it is preferable to use 1 to 2 mol of senecionitrile per 1 mol of phenylprenyl sulfone from the viewpoint of economy. The polar solvent used as the reaction solvent is sufficient as long as it can dissolve phenylprenyl sulfone, that is, 0.5 to 2 times the weight of phenylprenyl sulfone. The solvent for azeotropic dehydration is sufficient as long as water can be azeotropically dehydrated from the system.
It is double weight to 10 times weight.

The reaction is carried out by charging phenylprenyl sulfone, a polar solvent, a solvent for azeotropic dehydration, and a basic substance, and adding sensionitrile to a heated place. At that time, the reaction proceeds by removing water generated from the system by the azeotropic dehydration solvent. The reaction is terminated by the disappearance of phenylprenyl sulfone.

The produced nitric acid nitrite is separated and purified by distillation.

[0018]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. Example 1 A three-necked flask having an inner volume of 300 ml was equipped with a fractionating tube, a thermometer, and a dropping funnel, and then 50% caustic soda water 51.02.
g, 120.5 g of toluene, 80 g of DMSO, and 89.3 g of phenylprenylsulfone, and refluxed under reduced pressure.
Senecionitrile 44.7 at a reduced pressure of 120 mmHg and 71 ° C.
7 g were added dropwise in 5 hours. After performing the reaction for 22 hours, 29 g of water was dehydrated from the system with toluene. The reaction system was neutralized with sulfuric acid, and the precipitated solid was filtered, evaporated, and the solvent was distilled off. The residue was distilled under reduced pressure to obtain 44.96 g of nitrile. The reaction results are as follows
Met.

Phenylprenyl sulfone 100% conversion nitrile nitrous acid selectivity 72.53% Example 2 The polar solvent was changed to DMF and the reaction time was 25 hours.
Was except that reaction was carried out in the same manner as in Example 1. Reaction performance
Was as follows.

[0020] Instead of full E sulfonyl prenyl sulfone 100% conversion first chrysanthemic acid nitrile selectivity of 70.11 percent Example 3 azeotropic dehydration solvent in hexane, and the reaction time 32
The same reaction as in Example 1 was performed except that the time was changed.
The reaction results were as follows.

[0021] except for replacing the full E sulfonyl prenyl sulfone 100% conversion first chrysanthemic acid nitrile selectivity of 67.51% Example 4 basic substance potassium hydroxide was subjected to the same reaction as in Example 1. The reaction results were as follows:
Was.

The full E sulfonyl prenyl sulfone 100% conversion first chrysanthemic acid nitrile selectivity 65.10%

[0023]

According to the present invention, phenylprenyl sulfone and senecionitrile are reacted in a mixed solution of a polar solvent and an azeotropic dehydration solvent in the presence of a basic substance to be useful as an intermediate for the synthesis of pesticides. The first nitric acid nitrile can be produced in a high yield.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-57-2238 (JP, A) JP-A-56-39042 (JP, A) JP-B-43-2344 (JP, B1) (58) Field (Int.Cl. ⁷ , DB name) C07C 255/48 C07C 255/45 C07C 253/30

Claims (1)

(57) [Claims] 1. A compound represented by the following formula (I): And a phenylprenyl sulfone represented by the following formula (II): Wherein Senecionitrile represented by the following formula is reacted in a mixed solution of a polar solvent and a solvent for azeotropic dehydration in the presence of a basic substance: The method for producing a primary chrysanthemic acid nitrile represented by the formula: