JPS5931759A - Carboxymethyldithiocarbamic acid benzyl ester and its preparation - Google Patents

Abstract

NEW MATERIAL:Carboxymethyldithiocarbamic acid benzyl ester of formula. USE:Useful as a raw material for the preparation of 5-mercaptotetrazolyl-1-acetic acid. It can be prepared economically, in high yield by simple process. PROCESS:An alkali metal salt of glycine obtained by the alkali neutralization of glycine in an aqueous system, is added with a surface active agent (preferably, Nissan Disfoam CK-140, product of Nippon Yushi Co.) and/or a phase-transfer catalyst (preferably TOMAC, product of Koei Kagaku Kogyo Co.). CS2 is added dropwise to the mixture at 0-50 deg.C, preferably 25-35 deg.C to obtain M(1)OOCCH2 NHCS2M(1) [M(1) is alkali metal]. The product is added with benzyl halide and neutralized with a mineral acid to about 2.5pH to obtain the objective compound of formula.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound named benzyl carboxymethyldithiocarbamate, which is very useful in 5-mercaptotetrazolyl-l-acetic acid, and to a process for its preparation.

The method for producing the novel compound of the present invention is shown in the following reaction formula.

HOOC! OH2NH2+machine■):lH→M(■)00
0CR2NH2+ H2O (11 (M engineering=alkali metal) M(1)00 00H2NH2+OS2+ M(1)O
H-+'M(1)OOC! OH2NHCS2M(1)
10H20 f21M(I)OOC C! H2NH
OS2M(1)+C6H5CH2X-+M(I)OOc
CH2NH2Cs2cH2c6H50M(1)X
(3) (X halogen atom) M(I)OOcCH2NHCS,,OH. , C! 6 Hg
-1-L Hoo CCH2NHCs2aH2(' C
6H, 50M (I? ” '(+) First, as shown in the reaction formula (1+), glycine is neutralized with an alkali in an aqueous system to generate an alkali metal salt.

Next, as shown in the reaction formula (2), in order to promote the reaction of vcC82, a surfactant (in this case, use of Nira Sandis Home CK-140 manufactured by NOF Corporation) or/and a phase transfer catalyst is used. IJ-n-octylamine methyl chloride (manufactured by Koei Chemical Industry Co., Ltd., trade name, T O
MAC).

Addition of this surfactant and/or phase transfer catalyst is one of the characteristics of the method for producing the substance of the present invention.

That is, glycine alkali metal salt (1 part by weight), alkali (
Add an equimolar amount of C82 to glycine in an aqueous solution containing 1 part by weight) and the above additives at 0 to 50°C, preferably 25 to 35°C.
After adding 0 drops, ripen at the same temperature for 30 minutes or more. O
It is difficult to use C82 at temperatures below 50°C because the reaction is slow and C82 boils at temperatures above 50°C.

Next, as shown in reaction formula (3), before the benzyl halide is added dropwise, the benzyl halide is dissolved, such as alcohol, and a stable polar solvent is added. As the polar solvent, one having a boiling point of 50 to 100''c/76omHy is preferable.

Note that this polar solvent may be added at the stage of reaction formula (1) or (2).

Benzyl chloride is preferred as the benzyl halide, and the amount used is preferably 0.8 to 1.2 times the mole of glycine, and the temperature is 0 to 80°C, preferably 10 to 3°C. It is preferable to ripen for 30 minutes or more after dropping.

Then add water if necessary. If the amount of water added is too small, the reaction solution may foam violently in the latter stage of elution of the polar solvent and may overflow from the container. Then, the polar solvent is eluted under reduced pressure at 70° C. or lower (the lower the temperature, the better).

However, in the case of a polar solvent in which benzyl carboxymethyldithiocarbamate is insoluble, it is not necessary to elute it.

Furthermore, in reaction (4), water or an organic solvent is first added as necessary. In this case, if the amount of organic solvent is small, stirring becomes difficult when the mineral acid is added dropwise.

Next, use mineral acid to bring the pH to around 5. Crystals were separated from the reaction mother liquor and dried to obtain crystals of benzyl carboxymethyldithiocarbamate. The yield is over 80%. The crystals are purified if necessary.

Regarding the purified sample of the present invention, (a) The melting point of the new substance of the present invention is 162.5 as a result of measurement.
~1666, 6°C.

(Note) The results of elemental analysis are shown in Table 1.
The table theoretical value was calculated as 〇-CH2CS2NHCS2COOH.

It can be seen from Table 1 that the measured values are in good agreement with the theory.

e'1 Next, the NMR spectrum is shown in FIG.

From Figure 1, ppm(r) 10,3 NH (c)7,3
p (a) 4,5CH2 (b) 4.2 CH2 (d) Note that the NMR spectrum in Figure 1 shows a slightly higher chemical shift of the carboxyl group 10H, which is not shown in Figure 1. ” No other peaks were observed.

From the results of (a) to ←, it can be seen that the compound of the present invention is $cH2c S2NHan,,c OOH as described above. (a) (b) (cXd) The compound obtained by the present invention is a new compound. , the yield is high,
It has the advantage of easy manufacturing operations and low manufacturing costs.

Example 1 40 g (1.0 mol) of caustic soda was dissolved in 90 y of water,
Dissolve 37.5y (0.5 mol) of glycine at room temperature.

Next, 1 y of a surfactant (Ninsandice Home 0K-140 manufactured by NOF Corporation) is added.

Carbon disulfide 38y (0.5 mol) at 30-35 °C
Add over 0 minutes and stir at the same temperature for 3 hours.

After adding 25 ml of Meknol, benzyl chloride 63.3y (0.5 mol) was added at 15-20°C for 30 minutes, and the mixture was stirred at the same temperature for 3 hours.

Next, 100 y of water is added, Mek/-L is eluted under reduced pressure, and then 509 y of water is added. While cooling, add concentrated hydrochloric acid to adjust the pH to 2.
,5 acidic. It was centrifuged and dried under vacuum to obtain crystals 110p of benzyl carboxymethyldithiocarbamate.

The purity of the crystals determined by alkaline titration was 92.8%, and the yield was 84.3%.

Comparative Example 1 The yield of carboxymethyl dithiocal/(benzyl mate) was 55.0%, which was extremely low when the surfactant Nirasandisform 0K-140 was not added using the same method as in Example 1.

Example 2 In the same manner as in Example 1, in the same reaction as a phase transfer catalyst instead of a surfactant) IJ-n-ocdylmedyl chloride (manufactured by Koei Chemical Industry Co., Ltd., trade name: TOMA)
The test was carried out by adding 1y of C).

The purity of the resulting benzyl carboxymethyldithiocarbamate was 92.0% and the yield was 85.0%.

From the above, it has been found that in the present invention, carboxymethyldithiocarno(benzyl mate) can be obtained with similar purity and yield when a surfactant or a phase transfer catalyst is added.

Example 3 In the same manner as in Example 1, a similar reaction was carried out using a combination of the surfactants o and sy used in Example 1 and the phase transfer catalyst 0°5y used in Example 2 instead of the surfactant. I made him do it.

The purity of the resulting benzyl carboxymethyldithiocarbamate was 94.3% and the yield was 82.5%.

[Brief explanation of drawings]

FIG. 1 shows the NMR spectrum of the novel substance of the present invention. *, G 1CH3 c, CH2 bonded to NH3 alN, are NMR spectra of dogs. Patent applicant Kazuo Wakasugi, Commissioner of the Patent Office, Toyo Kasei Kogyo Co., Ltd. Description of the case 1982 Patent Application No. 141540 2 Name of the invention Carboxymethyl dithiocarno (benzyl mate and its manufacturing process 3) Related Patent Applicant Address 1-2-6 Dojimahama, Kita-ku, Osaka Name Toyo Kasei Kogyo Co., Ltd. President and CEO Eie Kobayashi 4 Agent 550 Description (1) Page 1, line 5 to line 1 from the bottom Scope of Claims As attached Correction (4)
Page 5, line 3 from the bottom (5) Page 7, line 11, “pE2.sJ corrected to [PH2,5J” (6) Page 9, line 6, “CH3” corrected to “CH2” (7) Page 9, line 7 ``NH3'' is corrected to ``NHJ'' Claim 1 Benzyl carboxymethyl dithiocarbamate HHH 2 glycine represented by the following chemical formula is dissolved in an alkali to add a surfactant or/and a phase transfer catalyst, and then C82 is added. In addition, orchid (■)
00CCH2NHC82M(■) [Here, MCI) is alkali modern] is generated, and then benzyl halide is added to produce M(■)00 CCH2N HCB20H2C6H
A method for producing benzyl carboxymethyldithiocarbamate by producing 5 and further neutralizing it with a mineral acid. 607-

Claims (1)

[Scope of Claims] l Benzyl carboxymethyldithiocarlebatriphosphate represented by the following chemical formula. 2. Glycine is dissolved in alkali, a surfactant or/and a phase transfer catalyst is added, and then CS2 is placed on the right side and M(I
) OoccH2NHCS,, McD (MCI here)
is an alkali metal], and then the benzyl halide is rounded to form M(I)OOCOH2NHCS20H2C6H,
A method for producing carboxymethyl dithiocal/(benzyl mate) by producing and further neutralizing with mineral acid.