JPS604156A - Production of serine - Google Patents

Abstract

PURPOSE:To produce the titled compound which is a kind of amino acid, suppressing the production of by-products, by reacting glycine with formaldehyde in the presence of a basic catalyst and cadmium ion, zinc ion or nickel ion. CONSTITUTION:Serine is produced by reacting glycine with formaldehyde in the presence of a basic catalyst (e.g. caustic alkali, alkali carbonate, pyridine, etc.) and in the copresence of cadmium ion, zinc ion or nickel ion. The copresence of the cadmium ion, etc. means the addition of cadmium ion, zinc ion or nickel ion in the form of cadmium salt, zinc salt, nickel salt or their hydroxide (e.g. cadmium sulfate, zinc sulfate, etc.) to the reaction liquid. The concentration of the ion is preferably 0.01-10%.

Description

[Detailed description of the invention] The present invention utilizes glycine and formaldehyde.

This invention relates to improvements in methods for producing phosphorus. For more details,
When producing serine by reacting glycine and formaldehyde, the reaction is carried out using cadmium ions and zinc ions.
Alternatively, the present invention relates to a method for producing serine, which is carried out in the presence of nickel ions.

Serine is a type of amino acid, and many methods have been known for synthesizing serine, including a method in which glycine and formaldehyde are reacted in a basic aqueous solution in the presence of copper ions (Archive
s of Biochemistry and Bio,
pbysics rib, 1 (1959,)). However, in the method using copper ions, the by-product α-
It produces a large amount of hydroxymethylserine and the yield of serine is low, so it has not been put to practical use yet.

The present inventors conducted extensive research with the aim of suppressing the by-product of α-hydroxymethylserine regarding this reaction. As a result, the present inventors discovered that this reaction can be performed using cadmium ions, zinc ions, or nickel ions instead of copper ions. It has been found that by-production of α-hydroxymethylserine can be suppressed when the reaction is carried out in the presence of .

In the method of the invention, the reaction is carried out in the presence of cadmium ions, zinc ions or nickel ions. The presence of cadmium ions, zinc ions, or nickel ions means that cadmium ions, zinc ions, and nickel ions are present in the reaction solution during the reaction.Cadmium ions, zinc ions, or nickel ions are cadmium salts, zinc salts, Alternatively, nickel salts, nickel salts, or hydroxides of these metals may be added to the reaction solution. The concentration of cadmium salt, zinc salt, nickel salt, or hydroxide of these metals in the reaction solution is not particularly limited, but is preferably 0.01 to 10%. The cadmium, zinc or nickel salts or hydroxides of these metals used are, for example, cadmium sulfate, zinc sulfate, nickel sulfate, cadmium chloride, zinc chloride, nickel chloride, cadmium nitrate, zinc nitrate, nickel nitrate. , cadmium carbonate, zinc carbonate, cadmium carbonate, cadmium hydroxide, zinc hydroxide, nickel hydroxide, etc.

Furthermore, the cadmium ions, zinc ions, and nickel ions used in the present invention may be used alone in the reaction solution, or two or more of them may be used as a mixture.

In the method of the present invention, as the basic catalyst used in the reaction, inorganic bases such as caustic alkali and alkali carbonate, organic bases such as pyridine, etc. can be used. Although there is no particular limit to the amount of formaldehyde relative to glycine, it can be used 0.1 to 10 times as much as the glycine. Moreover, water, methanol, etc. are used as this reaction solvent. Reaction temperature 1l-1,60~200℃
And the reaction time is 0.5-5 hours. Nitrogen, air, oxygen, etc. can be used as the reaction atmosphere. Among these, when an oxygen atmosphere is used, it has a good effect on the yield of serine.

After the reaction, cadmium ions, zinc ions, or nickel ions in the reaction solution are removed using hydrogen sulfide or ion exchange resin in the usual manner, and these metal ion removal solutions are added to a concentrated solution with alcohol to remove serine. It can be divided into 1ζ11 as a crystal.

The present invention will be explained below using examples.

Example 1 1.57.65q6 of glycine, 262 of formalin, 127 of sodium hydroxide, 1 g of water filter O, and 0.05'j of cadmium sulfate Cd5o, -XH2O were added to a Hastelloy C autoclave with contents of 50 l, and 50 Kq/art of oxygen was added. After sealing, the mixture was stirred at 120° C. 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 cadmium ions as cadmium sulfide, which was separated by f. As a result of measuring the liquid chromatography, it was 0.7
2? of serine was obtained. The yield of serine was 644. There was almost no by-product of α-hydroxymethylserine, and almost no other by-products were observed.

Example 2 In the method of Example 1, zinc chloride ZNCZ20.05 Y was used as a substitute for cadmium sulfate, and the other procedures were as in Example 1.
As a result of conducting the same experiment as above, 0.62 ft of serine was obtained. The yield of serine was 306%. There was almost no by-product of α-hydroxymethylserine, and almost no other by-products were observed.

Example 6 In the method of Example 1, nickel nitrate Nr (NO3) 2.6H200,051i was used instead of cadmium sulfate.
As a result of carrying out an experiment in the same manner as in Example 1 except using ', serine of 0.5717' was obtained. The yield of serine is 27
It was 3%. Approximately 4 α-hydroxymethylserine was observed to be produced as a by-product. Almost no other by-products were observed.

Example 4 The method of Example 1, except that 50 Kg/oA of nitrogen was used instead of oxygen as the reaction atmosphere, and the other conditions were as in Example 1.
As a result of conducting the same experiment as above, 0.11 g of serine was obtained. The yield of serine was 5.5%. Almost no formation of α-hydroxymethylserine and other by-products was observed.

Reference Example 1 An experiment was carried out in the same manner as in Example 1 except that copper sulfate CuSO4.5H200,057 was used in place of cadmium sulfate, and as a result, 062 g of serine was obtained. The yield of serine was 294%.

050 α-hydroxymethylserine was obtained as a by-product, and the yield was 185%. Almost no other by-products were observed.

Patent applicant: Mitsui Toatsu Kagaku Co., Ltd. Procedural amendment (spontaneous) 9 Judgment of July 1, 1981 Kazuo Wakasugi, Commissioner of the Patent Office 2 Name of the invention Process for producing serine 3 Person making the amendment 1) In the specification, page 3, line 3, ``Nickel ion is a cadmium salt,'' 1 is corrected to ``Nickel ion is an inorganic or organic cadmium salt.''

2) Similarly, on page 3, line 14, “nickel carbonate,”
and "cadmium hydroxide", "cadmium acetate, zinc acetate, nickel acetate, cadmium formate, zinc formate, nickel formate, cadmium oxalate, zinc oxalate, nickel oxalate"
Add a sentence.

3) Similarly, add the following example after the 14th line on page 6.

"Example 5 In the method of Example 1, cadmium formate Cd (HCOO), .
75 ri of serine was obtained. The yield of serine was 35.9%. There was almost no by-product of α-hydroxymethylserine, and almost no other by-products were observed.

Example 6 In the method of Example 1, cadmium oxalate Cd (COO), 0.059 was used instead of cadmium sulfate, and as a result of conducting an experiment in the same manner as in Example 1, 0.73 g was obtained.
− of serine was obtained. The yield of serine was 34.6%. There was almost no by-product of α-hydroxymethylserine, and almost no other by-products were observed. 1 to 7

Claims (1)

[Claims] 1) Production of serine by reacting glycine and formaldehyde in the presence of a basic catalyst to produce serine, which is characterized in that the reaction is carried out in the coexistence of cadmium ions, zinc ions, or nickel ions. Law. 2) The method according to claim 1, in which oxygen is used as the reaction atmosphere.