JPS59163352A - Production of serine - Google Patents

Abstract

PURPOSE:To produce serine in high yield, by reacting cupric glycinate with formaldehyde in the presence of a basic catalyst and quaternary ammonium ion. CONSTITUTION:Serine is produced by reacting cupric glycinate with formaldehyde in the presence of a basic catalyst (e.g. NaOH). The reaction is carried out in the presence of a quaternary ammonium ion [e.g. quaternary lower alkyl ammonium ion (e.g. tetramethylammonium ion)]. The concentration of the quaternary ammonium ion is preferably 0.01-0.1%, and the ion can be produced by adding a quaternary ammonium salt or quaternary ammonium hydroxide to the reaction liquid. The amount of formaldehyde is preferably 0.1-10pts. per 1pt. of cupric glycinate. The reaction is carried out at 30-150 deg.C for 0.5-5hr.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for producing serine from glycine and pormaldehyde. More specifically, the present invention relates to a method for producing serine which is characterized in that when producing serine by reacting glycine steel with pormaldehyde, the reaction is carried out in the presence of quaternary ammonium ions.

Serine is a type of amino acid, and many methods have been known for synthesizing serine, among which a method in which glycine steel and formaldehyde are reacted in a basic aqueous solution is known (Japanese Patent Publication No. 34-2964). . However, the method using glycine steel has a low yield of serine and has not been put into practical use yet.

The present inventors have conducted various studies regarding this reaction with the aim of improving the serine Ω yield, and have found that the serine yield increases when the reaction is carried out in the presence of quaternary ammonium ions. found that it is possible to improve

In the method of the invention, the reaction is carried out in the presence of quaternary ammonium ions. The presence of quaternary ammonium ions means that quaternary ammonium ions are present in the reaction solution during the reaction, and quaternary ammonium ions react with quaternary ammonium salts or quaternary ammonium hydroxides. This can be done by adding it to the liquid. There is no particular restriction on the concentration of quaternary ammonium salt or quaternary ammonium hydroxide in the reaction solution, but it is preferably 0.
01-1%. The quaternary ammonium ion used preferably contains an alkyl group and a lower argyl group such as methyl, ethyl, n-propyl and/or n-butyl. For example, tetramethylammonium ion, tetraethylammonium ion, Tetra n-propylammonium ion, 2tetra n-butylammonium ion, trimethylethylammonium ion,
These include dimethyldiethylammonium ion, methyltriethylammonium ion, trimethyl n-propylammonium ion, trimethyl n-butylammonium ion, triethyl n-propylammonium ion, triethyl n-butylammonium ion, and the like.

The reaction conditions in the method of the present invention are similar to the conventional reaction between glycine steel and formaldehyde, except that quaternary ammonium ions are added to the reaction solution. For example, the catalysts used for this reaction include caustic alkali,
Inorganic bases such as alkali carbonate and organic bases such as pyridine can be used. Further, for glycine steel, the amount of formaldehyde is not particularly limited, but preferably 0.1
~10 times more can be used. Furthermore, when preparing the reaction solution, glycine steel made from glycine and copper salt may be used in advance;
Copper salts such as copper carbonate and basic copper carbonate may be added separately. Moreover, water, methanol, etc. are used as this reaction solvent. The reaction temperature was 60-150℃, and the reaction time was 0.
．． 5 to 5 hours. Additionally, oxygen can be supplied to the reaction solution to prevent reduction of pot ions during the reaction.

After the reaction, copper ions in the reaction solution are removed using hydrogen sulfide or ion exchange resin as usual, the copper ion removal solution is concentrated, and alcohol is added to the concentrated solution to crystallize serine. It can be separated as The present invention will be explained below using examples.

Example 1 Glycine steel 267.65% formalin 172? , 112 g of potassium hydroxide, 60 g of water and 1.01 g of a 10% tetramethylammonium hydroxide aqueous solution were added, and after sealing in 50 Kg/cni of oxygen, the temperature was 70°C.
The mixture was stirred for 1 hour. After cooling, concentrated hydrochloric acid was added to the reaction solution to make it acidic, and then sodium sulfide was added to precipitate copper ions as copper sulfide, which was then distributed from house to house. Table 1 shows the results of measuring the r liquid by liquid chromatography.

Examples 2 to 8 In the method of Example 1, various quaternary ammonium ion-containing compounds were used instead of the 10% tetramethylammonium hydroxide aqueous solution 1,0, and the experiment was carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 The results of the method of Example 1 without using 10% tetramethylammonium hydroxide aqueous solution 1D2 are shown in Table 1.
Shown below.

Claims (1)

[Claims] 1) A method for producing serine, which comprises reacting green steel and formaldehyde in the presence of a salt catalyst to produce serine in the presence of quaternary ammonium ions. . 2) The method according to claim 1, wherein the quaternary ammonium ion is a quaternary lower alkyl ammonium ion.