JPS59196850A - Production of beta-hydroxypropionitrile - Google Patents

Abstract

PURPOSE:To obtain the titled comound useful as a raw material and synthetic intermediate of organic synthetic chemicals such as pharmaceuticals, agricultural chemicals, etc., in high yield, suppressing the production of by-products, by the hydration reaction of a dilute acrylonitrile in the presence of a strongly basic ion exchange resin catalyst. CONSTITUTION:The objective beta-hydroxypropionitrile is obtained by reacting acrylonitrile having a concentration of <=10wt%, preferably 7-1wt% in an aqueous medium such as water, alcohol, etc. in the presence of a strongly basic ion exchange resin catalyst consisting of a crosslinked polyvinylbenzyl trimethyl ammonium salt (e.g. Amberlite IRA-400) at normal temperature -100 deg.C, preferably 40-80 deg.C. The amount of the catalyst is preferably 5-30wt% based on the reaction liquid, and the catalyst can be used repeatedly.

Description

DETAILED DESCRIPTION OF THE INVENTION (Objective and Background) The present invention provides a method for producing β-hydroxypropionitrile;
In particular, it relates to a method for producing β-hyperoxyprobionitrile by a water utilization reaction of acrylonitrile.

β-Hydroxypropionitrile is the source of many organic synthetic products including pharmaceuticals, agricultural chemicals, and polymeric Ff.
It is a compound useful as an intermediate.

Various methods are conventionally known for producing β-hydroxypropionitrile.

For example, as a raw material ethylene oxy] and "lr"
Method using M (U.S. Pat. No. 2,459,430 dI
) or there is. According to this method, it is relatively easy and t'+-7
β-Hydroxypropionitrile can also be extracted if there is enough available. However, since this method depends on the raw material cyanide having a very large m property, it is severely limited by the manpower of the raw materials.

One of the most economical manufacturing methods is to use dogs as raw materials for synthetic fibers! 11 Several methods have been attempted using hydration of acrylonitrile, which is available at low cost.

For example, β-hydroxypropionitrile is obtained by hydrating acrylonitrile in the liquid phase at room temperature in the presence of a large excess of water and a small amount of an alkali metal hydrobutyride catalyst (U.S. Pat. No. 3,024,267). There is one specification). Although it is RJF's ability to improve the selectivity of β-hydroxypropionitrile by this method, it is essential to keep the reaction rate low, and as a result, the yield can only reach a maximum of 48%. There are major drawbacks as a commercial manufacturing method.
do.

Also, the hydration of acrylokotolyl in the coexistence of a quaternary ammonium hydroxide catalyst and formaldehyde? r Now method (German Patent Publication No. 285.5784)
According to this method, the yield of .beta.-hydroxypropionitrile is on the order of 59.about..delta.9%, but it is still far from being an economical production method.

In this way, in the synthesis reaction of β-hydroxypropionitrile by the hydration reaction of acrylonitrile under a basic catalyst, in addition to the main product β-hydroxypropionitrile, large amounts of hiscyanoethyl ether and acrylamide are produced as by-products. These side reactions result in significantly lower yields, and suppression of these side reactions has become an important issue.

In such a situation, the inventors of wood used acrylonitrile as an industrial raw material, which is manufactured at low cost, as a raw material, and without increasing the yield higher than conventional methods.1) As a result of intensive research to develop an economical one-day production method for nitrile, by using an appropriate strong basic ion exchange resin catalyst at low concentrations of acrylonitrile,
The present invention was achieved by discovering that β-hydroxypropionitrile can be easily obtained in high yield.

(Structure) That is, when producing β-hydroxypropionitrile by the hydration reaction of acrylonitrile, the present invention
A method for producing β-hydroxypropionitrile, characterized in that the concentration of 7crylonitrile in an aqueous medium is 10% by weight or less, and a crosslinked polyvinylhensyltrimethylammonium salt type strongly basic ion exchange resin is used as a catalyst. .

Examples of using strongly basic ion exchange resins as catalysts for cyanethylation reactions have been known, but when applied to β-hydroxypropionitrile, the yields are low. That is, US Pat. No. 2,579,580 proposes a hydration reaction of acrylonitrile using a cross-linked polyvinylpyridinium quaternary salt as a catalyst, but the yield of β-hydroxypropionitrile is 5.8 to 34. 8% and produces a large amount of by-products such as hiscyanoethyl ether (β-hydroxypropioni)
It could not be used as an industrial manufacturing method for Lil.

However, according to the method of the present invention, the formation of by-products such as biscyanoethyl ether is significantly suppressed, and as a result, the selectivity of the target β-hydroxypropionitrile is greatly improved, and the yield of 80% or more is achieved. It becomes possible to reduce the yield by 1-0, and it can become an industrial production method.

The general embodiments of the present invention will be explained below.The hydration reaction of acrylonitrile is carried out in an aqueous medium at an acrylonitrile concentration of IQ% or less, but it is particularly preferable that the acrylonitrile concentration is 7 to 1%. .

As the aqueous medium, for example, water or a mixed solution such as water-flucol, water-dioxane, water-tetrahydrofuran or water-dimethyl sulfoxide is used.
Industrially, reactions using only water are economically advantageous.

When a mixed solvent is used, the ratio of the water-masking machine solvent is preferably about 1:1 to 9=1 (weight ratio).

As a catalyst, a cross-linked polyvinylbenzyltrimethylammonium salt type strongly basic ion exchange resin such as Amberly, IRA-400. Takux 1χ8° Tire Aeon 5A-10, Repachito 500. Toworai 1-A-1 (gel type resin such as 19: Amperist A
-26, Towex MSA-1, Tire Ion PA3
12. Revachit M'P-500, DouOride A'
Macroporous resins such as 181 are preferred.

β-Hydroquine propionitrile can be obtained in the same manner by using crosslinked polyvinylbenzylhydroxyethyldimethylammonium'b 47, crosslinked polyvinylpyridinium salt type and crosslinked polyethyltrimethylammonium methacrylate type ion exchange resin, but the selectivity is low. Since the yield is low, the yield is significantly reduced and the preferred catalyst is not suitable for use in the present invention.

Although there is no restriction on the use of immersion, for example, in the case of a batch reaction, it is preferable to use 5 to 30% by weight of the reaction solution in view of reaction time and other considerations.

Although the catalyst can be reused any number of times, in order to maintain its activity it is preferable to wash it with an alkaline solution once every 3 to 10 uses.

The reaction temperature can be carried out between Hatata temperature and 100"C, but from the viewpoint of reaction rate and prevention of catalyst deterioration, it is particularly recommended to set the temperature between 40 and 80"C.
C is preferred.

The reaction time varies depending on the acrylonitrile concentration, catalyst concentration, reaction temperature, etc., but the reaction time is 15 minutes to 15 minutes for batchwise reaction.
6 hours, preferably about 1 minute to 6 hours for continuous reaction.

The reaction force V is for batch reaction, semi-batch reaction and continuous reaction 14'
, , etc. may be used, but continuous reaction is preferable from an industrial perspective.

Separation and purification of β-hydroxypropionitrile from the reaction mixture can be easily carried out by extraction with an organic solvent and distillation of the extract.

Any extraction bath agent can be used as long as it dissolves β-hydroxypropionitrile and is difficult to mix with water, but especially butyronitrile, ethyl acetate, methyl imbutyl ketone, cyclo t-xanone, methicyl oxide, etc. used.

The present invention will be explained more fundamentally using Examples below.
The present invention is not limited to these Examples in any way.

Example 1 Temperature gauge 1, stirrer, cooling condenser and extraction draw I
・Amberlite TRA-400 (O
Add 12 g of Type H) and 91 g of water, and heat to 70'C+. Add 2.5 g of acrylonitrile using a dropwise draw 1.
%), and the reaction was carried out between two seeds at 70°C with stirring.

After the reaction was completed, it was cooled to room temperature, the catalyst was filtered off, and a portion of the reaction solution was collected and analyzed using a gas chromatography method.Results 2
．． 8 g of β-hydroquine propionitrile, 0.1 g of acrylamide (yield: 43%) and 0.07 g of hiscyanoethyl ether (yield: 24%).
2%) were confirmed S.

Examples 2 to 4 Experiments were conducted in the same manner as in Example 1, except that the catalyst and reaction time were changed, and the results shown in Table F were obtained.

BCE: Biscyanoethyl ether Comparative Examples 1 to 2 Hydroxylation as a catalyst]・lium or crosslinked polyvinylhenzylhydroxyethyl dinotyl ammonium L, 11
, A-type strong salt ion exchange resin Amberly)・IR
An experiment was conducted in exactly the same manner as in Example 1 except that A-410(O)l type) was used, and the results shown in the following table were obtained.

Comparative Example 3 An experiment was conducted in exactly the same manner as in Example 1, except that 15 g of acrylonitrile and 80 g of water were used (acrylonitrile concentration: 15.8%).

Example 5 Jakentoy 1 anti 1 heart saving (capacity j4 (4150mJ2,
length 18cm, inner 13.5cm)
Filled with 100g of IRA-400 (OH;
Inside the Jakent, warm water at 0°C was circulated using a pump.

2.5-fold fj% preheated to 70°C in a raw material tank
An acrylonitrile aqueous solution was dripped from 11 parts of the reaction tube in a flow of 10 m272 minutes. t: Approximately 8 between station 11 and 111f
．． It was 6 minutes.

reaction,? The yield of β-hydroxypropionitrile was 82% as determined by gas chromatographic analysis of the reaction B compound, which produced 55 parts.

One sample of the reaction mixture was extracted with 500 g of mesityl oxide, and the extract was distilled to give 26
71 tons of 5g of β-hydroxypropionitrile were collected. Yield 79%, product line point 116-1 l 8
°C/20mmHg.

EXAMPLE In a reactor similar to Example 1, Revachit 1-M-500 (
OHJt! ! ) 24 g and 90 g of water to make 70
Heat to ℃. Add 6 g of acrylonitrile dropwise (acrylonitrile concentration 6.3%),
The reaction was allowed to proceed for 15 minutes at 75°C with stirring. reaction path r
After cooling to room temperature and filtering off the catalyst, a portion of the reaction solution was taken and analyzed by gas chromatography, which confirmed the production of 6.4 g of β-hydroxypropionitrium.

Yield: 80%; 0.2 g of acrylamide (yield: 3%) and hiscyanoethyl ether as secondary substances; 1. og (yield-
4-14%) was confirmed.

(Effects) As is clear from the examples, when the method of the present invention is used, β-hydroxypropionyltrimethylammonium can be obtained with a yield of 80% or more, and crosslinked polyhinylhensyltrimethylammonium I), j-type strong Compared to the case where a catalyst other than a basic/f-on exchange resin is used or the acrylonitrile concentration in the aqueous medium is 10% or more, the yield is increased or the amount of by-products is reduced.

Applicant: Tokagaku Jogyo Co., Ltd. Attorney: Shoji Aoma

Claims (1)

[Claims] When producing β-hydroxypropionitrile by the water utilization reaction of acrylonitrile, the concentration of acrylonitrile in the aqueous medium is 10% by weight or less, and the cross-linked polyhinyl pencyl trimethyl ammonium salt type strong salt solution (
Use ion exchange resin 4! β- to be +61
Product V of Hydroxypropioni I.Ril.