JPH06321892A - Cystamine carbonate compounds and their production - Google Patents

Abstract

PURPOSE:To simply obtain the subject compound, useful as an intermediate for the production of agrochemicals and medicines in a high yield and in a high purity, without by-producing salts by treating a specific cystamine solution with a carbonic acid. CONSTITUTION:The solution of cystamine of formula I u=is treated with carbonic acid to obtain the objective compound of formula II (X is 1, 2). For example, methanol, etc., is used as a solvent in the reaction.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to cystamine carbonates and a method for producing the same. The cystamine carbonate of the present invention is useful as a raw material for agricultural and pharmaceutical products or various synthetic intermediates.

[0002]

2. Description of the Related Art Hitherto, as cystamine salts, cystamine hydrochloride and sulfate have been widely known.
These cystamine salts are often used as various synthetic intermediates, in which case cystamine is released,
Very often used. Here, in the conventionally known cystamine salts, when liberating as cystamine, it is necessary to neutralize hydrochloric acid or sulfuric acid with an alkali, and thus it is possible to avoid producing a by-product salt such as sodium chloride or sodium sulfate. Absent. In addition, when producing the above-mentioned hydrochlorides and sulfates, strong corrosive acids such as hydrochloric acid and sulfuric acid are used, so there is a high degree of danger in handling them, and there is also a special device with strong acid resistance. Operation is required.

Further, in order to obtain high-purity cystamine hydrochloride and sulfate, complicated operations were required. That is,
If sulfuric acid is simply added to the cystamine alcohol solution, the dehydration reaction of alcohol due to the use of high-concentration sulfuric acid also occurs, and impurities are also generated, or crystals precipitate (paste) during the reaction. As a result, there is a problem that it is difficult to carry out a further neutralization reaction uniformly.
Therefore, as a method for avoiding these problems, Japanese Patent Laid-Open No.
JP-A-110667 and JP-A-59-108761 propose a method in which water and an organic solvent are used in combination, and further, the cystamine concentration and the water / organic solvent ratio in these mixed solvents are specified, and crystallization is performed. In addition, JP-A-60-51165 proposes a method of concentrating an aqueous cystamine sulfate solution to remove water and then crystallizing it with an organic solvent.

However, in any of the conventional methods for producing cystamine salts, water is used as a solvent in any case, so that the ratio of water to an organic solvent is specified, or crystallization is performed after removing water. I had to take a complicated approach.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel cystamine salt and a method for producing the same, which replaces the conventional cystamine hydrochloride and sulfate.

[0006]

[Means for Solving the Problems] The present inventors diligently searched for new cystamine salts in order to solve the above problems. As a result, they have found that cystamine can be simply and highly purified to give cystamine carbonate in high yield by carbonation, and the present invention has been completed.

That is, the present invention is based on the general formula (1)

[Chemical 4] (Wherein, X represents 1 or 2), and a cystamine carbonate represented by the general formula (2)

[Chemical 5] Carbonic acid is allowed to act on a solution of cystamine represented by

[Chemical 6] (In the formula, X represents 1 or 2) and is a method for producing a cystamine carbonate.

[0008] The cystamine carbonate of the present invention is a novel substance useful as an intermediate for agricultural and pharmaceutical products, and it is possible to easily generate carbonic acid and liberate cystamine by heating in a solution. Therefore, when used as various synthetic intermediates, not only does the alkali for neutralization, which was essential in conventional cystamine salts, unnecessary, but it also produces by-product salts such as sodium chloride and sodium sulfate. Nothing.

Further, since there is no fear of side reaction due to high-concentration sulfuric acid, which has been a problem at the time of producing cystamine sulfate, in the production of cystamine carbonate of the present invention,
It is not necessary to use water as a solvent together, it can be produced and precipitated in an organic solvent, and furthermore, cystamine carbonate can be easily obtained in high purity and high yield.

Further, unlike the case where the amount of sulfuric acid had to be strictly regulated when producing cystamine sulfate, it was necessary to strictly regulate the amount of carbonic acid when producing the cystamine carbonates of the present invention. Nonetheless, even if an excessive amount of carbonic acid is used, there is no risk of the side reaction as described above, so it is not necessary to remove the excessive amount of carbonic acid unless there is a special reason. In addition, since it is not necessary to use water as a solvent together during crystallization, the mother liquor after crystallization can be easily repeatedly used as a crystallization solvent. Therefore, it is not necessary to keep the ratio of water and solvent constant, and the operation of recovering the solvent by distillation is unnecessary, and it is not necessary to remove water.

The history of cystamine represented by the general formulas (2) and (Chemical Formula 5), which is a raw material for producing the cystamine carbonate of the present invention, is not particularly limited and can be obtained by various known methods. Effective use of cystamine.
For example, J.Gen.Chem.USSR (Engl.Transl) 34 , 3762 (196
4), or by the method described in J. Amer. Chem. Soc., 62 , 1173 (1940) or the like, that is, by oxidizing cysteamine with a suitable oxidizing agent such as hydrogen peroxide in a solution, cystamine Can be obtained.

To produce the cystamine carbonate represented by the general formula (1) (formula 4) of the present invention, first, cystamine is dissolved in a solvent. As a solvent that can be used, any solvent can be used as long as the resulting cystamine carbonate is difficult to dissolve therein. For example, methanol, ethanol, 2
-Alcohols such as propanol and butyl alcohol,
Aprotic polar solvents such as tetrahydrofuran and acetonitrile, esters such as methyl acetate and ethyl acetate, and the like can be mentioned. The amount of the solvent may be such that the precipitated cystamine carbonate can be uniformly stirred, and usually 0.3 to 2 Lit of the solvent is suitable per mol of cystamine. Next, after adding water of equimolar amount of cystamine to the cystamine solution, carbon dioxide is introduced into the solution, and then the precipitated cystamine carbonates are filtered and dried to obtain the object of the present invention. Obtainable. There is no problem if the amount of carbon dioxide introduced is equimolar or more to cystamine.

The temperature and pressure during the production of the above-mentioned cystamine carbonate of the present invention can be carried out at ordinary temperature and normal pressure, and sufficient effects can be obtained.
Further, in the production of cystamine carbonate of the present invention, it is possible to easily reuse the mother liquor after crystallization as a crystallization solvent, and by doing so, the recovery of cystamine can be substantially achieved. It can be 100%.

[0014]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the following, "%" is on a molar basis, unless otherwise specified. The purity of cystamine carbonate was calculated by HPLC.

Example 1 5.0 g (33 mmol) of cystamine and 0.59 g (33 mmol) of water were dissolved in 50 ml of methanol in a reactor (with a stirrer and a carbon dioxide introducing part), and 1.1 Lit of carbon dioxide was added at room temperature. It was introduced over 1 hour. After the introduction is complete, the precipitated crystals are collected by filtration.
After drying, the desired cystamine carbonate 6.6 g (purity 99.4
%, Yield 94%). The melting point was 108-110 ° C.
The analysis results of the obtained cystamine carbonate are as follows.・ Elemental analysis (unit:%, parentheses indicate theoretical values) C: 28.02 (28.11), H: 6.60 (6.41), N: 13.07 (13.2)
3), S: 29.92 (29.88) -infrared absorption spectrum (unit: cm ^-1 ) 3351, 2910, 2173, 1640, 1177, 1148

Example 2 In the same reactor as in Example 1, 5.0 g (33 mmol) cystamine was added.
And 0.59 g (33 mmol) of water were dissolved in 50 ml of 2-propanol, and 1.1 Lit of carbon dioxide was introduced over 1 hour at room temperature. After the completion of the introduction, the precipitated crystals are collected by filtration and dried to give the desired cystamine carbonate (6.7 g, purity 99.5%, yield 95%).
Got The analysis result of the obtained cystamine carbonate was in agreement with that obtained in Example 1.

[0017]

EFFECTS OF THE INVENTION The cystamine carbonates of the present invention are novel cystamine salts that have never existed before and can be easily converted into cystamine. Further, at that time, since a by-product salt is not generated, it can be suitably used as an intermediate for producing agricultural and pharmaceutical products. Further, in the method for producing cystamine carbonate according to the present invention, it is not necessary to handle a highly dangerous strong acid, and a high-purity cystamine carbonate can be easily obtained in a high yield.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenichi Arai 1900, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] 1. General formula (1) (Chemical formula 1) (In the formula, X represents 1 or 2) A cystamine carbonate represented by the formula. 2. General formula (2) (Chemical formula 2) Carbonic acid acts on a solution of cystamine represented by the general formula (1) (Chemical Formula 3) (In the formula, X represents 1 or 2) A method for producing a cystamine carbonate.