Method for preparing bis-(1-vinylimidazole)zinc diacetate

FIELD: chemistry of organometallic compounds, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing the chelate compound bis-(1-vinylimidazole)zinc diacetate (I) representing the medicinal preparation of acizol that is the effective antidote and antioxidant. Method for preparing the compound (I) is carried out in the absence of organic solvents at temperature 20-35°C in the mole ratio 1-vinylimidazole : zinc diacetate in the range from 10:1 to 3:1. Method provides exclusion fire hazard and explosion hazard solvent from the technological process and enhancement of the yield of highly pure acizol satisfied for Pharmacopoeia requirements.

EFFECT: improved method for preparing.

2 cl, 4 ex

 

The invention relates to an improved method for the production of complex compounds - substituted azoles, specifically obtain bis-(1-vinylimidazole)zincdiacetate - medicine alzola, which is an effective antidote and antihypoxic drug. Describes how to obtain a complex compound of 1-vinylimidazole with cindicates composition 2:1, wherein the reaction is carried out in the absence of organic solvents in the solution of an excess of reagent - 1-vinylimidazole, at a temperature of 20-35°and a molar ratio of ligand : salt in the range from 10:1 to 3:1. The advantage of this method is that it allows you to exclude from the process fire and explosion solvents, phase dissolution in original compounds, to reduce production costs and increases output to 99.8% high purity Pharmacopoeia alzola.

The invention relates to the field of organic chemistry, in particular to improvements in the method of producing metal complexes based on substituted azoles and can be used for the synthesis of bis-(1-vinylimidazole)zincdiacetate ("Aziza"®that trademark No. 198457, "acizolum"®that trademark No. 199574) is a highly effective antidote for carbon monoxide (RF Patents №№2070201, 2038079). Azizol permitted as an antidote to protect p and poisoning by carbon monoxide and other combustion products for medical use and industrial production (registration certificate R No. 001936/01-2002, 02.12.2002). Showing high antihypoxant activity (Patent RF №2115653), azizol also effective in the treatment and prevention of psoriasis (RF Patent No. 2204392).

A method of obtaining antidote carbon monoxide, namely the complex of bis-(1-vinylimidazole)zincchloride based on the interaction of the ligand and salt in absolute ethyl alcohol, which allows you to get the antidote with the release of 92% (Ed. mon. The USSR №1822155). The disadvantage of this method are significant costs on the selection of the target product (repeated washing with alcohol formed complex and drying it in a vacuum).

Also known is an example of the synthesis of the complex bis-(1-vinylimidazole)zincdiacetate by the reaction of 1-vinylimidazole with crystalline diacetate zinc (Zn(OCOCH3)2·2H2About acetone-ether mixture (1:3). The output of alzola using this method is equal to 90% (RF Patent No. 2070201). The method of producing alzola exit 85% described in the patent of the Russian Federation No. 2115653 and based on the interaction of anhydrous zinc diacetate with 1-vinylimidazole in a mixture of acetone : ether (1:1). However, for the full bicrystalline complex from the mother liquor and their separation requires cooling the reaction mixture to 0-5°C.

Known RF Patent №2118960 on a production line obtain bis-(1-vinylimidazole)zincdiacetate (output 89-93%), which, by providing a who's who of agnosti preliminary dissolution of 1-vinylimidazole in acetone-ether mixture and dehydration zinc diacetate is achieved by preventing the dissolution of the formed metal complex in the mother solution in the process synthesis.

The disadvantages of all the above methods are used in the process of obtaining alzola fire and explosive solvents, the complexity of its secretion, which leads to high production costs, and not a high yield of finished product.

We propose an improved method for producing high-purity alzola with a quantitative yield of 99.8 per cent. The technical objective of the invention is simpler and cheaper way to get alzola by changing the process conditions, eliminating the preparatory stages, as well as complicated isolation and purification of the target product.

This object is achieved in that it is proposed to carry out the process of complexation of zincdiacetate directly in the excess of reagent - 1-vinylimidazole (in the interval ratio of initial connection - 1-vinylimidazole : anhydrous zinc diacetate from 10:1 to 3:1) without using any organic solvents at room temperature (20-25° (C) and stirring. Without additional cooling is provided by full crystallization target zinc complex in the reaction mixture. After separation of alzola filtering unreacted 1-vinylimidazole can be re-directed to the synthesis of the desired metal complex.

This method is you can get arizol high purity (99.5%pure). Physico-chemical parameters of selected samples of the preparation meet these specifications by the Fund on the substance of alzola (No. 42-0409-2691-02).

The following examples illustrate the present invention.

Example 1. To 19,76 g (0.21 mol) of 1-vinylimidazole at 20-25°and With stirring, gradually add of 3.85 g (0,021 mol) Zn(OCOCH3)2(reagent ratio 10:1). Loose white fine precipitate is sucked off over a SCHOTT, washed with toluene, dried in the air, get 6,94 g (89%) complex of bis-(1-vinylimidazole) zincdiacetate with so pl. 104-106°C.

Found, %: C 45,27; N To 4.73; N Of 14.90; Zn 17,62. C14H18N4About4Zn. Calculated, %: C 45,21; N 4,84; N 15,07; Zn 17,61. UV λmax225 nm.

Example 2. To 19,76 g (0.21 mol) of 1-vinylimidazole at 20-25°and With stirring, gradually add 5.50 g (0.03 mol) of Zn(ASON3)2(reagent ratio 7:1). Loose white fine precipitate is sucked off over a SCHOTT, washed with toluene, dried in the air, getting there is a 10.03 g (90%) of the complex bis-(1-vinylimidazole)zincdiacetate with so pl. 103-105°C.

Found, %: 45,07; N 4,82; N 14,99; Zn 17,47. C14H18N4About4Zn. Calculated, %: C 45,21; N 4,84; N 15,07; Zn 17,61. UV λmax224 nm.

Example 3. To 18,82 g (0.20 mol) of 1-vinylimidazole at 20-25°and With stirring, gradually add 9,17 g (0.05 mol) of Zn(ASON3)2(the ratio of Reagan the s 4:1). Loose white fine precipitate is sucked off over a SCHOTT, washed with toluene, dried in the air, get 18,54 g (99.8 per cent) complex of bis-(1-vinylimidazole) zincdiacetate with so pl. 104-105°C.

Found, %: C 45,37; N A 4.86; N 14,89; Zn 17,63. C14H18N4About4Zn. Calculated, %: C 45,21; N 4,84; N 15,07; Zn 17,61. UV λmax225 nm.

Example 4. To 19,76 g (0.21 mol) of 1-vinylimidazole at 20-25°and With stirring, gradually add 12,84 g (0.07 mol) of Zn(ASON3)2(reagent ratio 3:1). After making full salt in the reaction mixture to the resulting viscous white precipitate add 20 ml of toluene, stirred, fine precipitate is sucked off over a SCHOTT, washed with toluene, dried in the air, get 25,81 g (99,23%) complex of bis-(1-vinylimidazole)zincdiacetate with so pl. 105-107°C.

Found, %: C 45,29; N Is 4.85; N 14,99; Zn 17,59. C14H18N4About4Zn. Calculated, %: C 45,21; N 4,84; N 15,07; Zn 17,61. UV λmax223 nm.

Infrared spectra obtained by this technique the sample alzola have a full match of the absorption bands with the bands of the spectrum of the control sample for the position and intensities of the bands.

Thus, it is shown that high-purity bis-(1-vinylimidazole)cindicates (azizul) can be obtained in a much simpler way than with previously known methods. R the realizations of the proposed method on an industrial scale on a standard equipment will allow to avoid fire and explosion solvents (acetone, ether), the high costs of removing a target product and increase, almost to the quantity of his output, and a significant reduction of the process time and energy costs will not affect the Pharmacopoeia purity alzola.

Literature used

1. RF patent №2070201. Bis-(1-vinylimidazole)cindicates as an antidote carbon monoxide. Domnina Y.S., Skvortsova GG, Nikolaev, V.N., Urumov O.Y, V.V. Maslov // BI 1996, no.34.

2. RF patent №2038079. The antidote carbon monoxide. Domnina Y.S., Soshnikova A.I., M.G. Voronkov, Urumov O.Y, Tiunov L.A., Ryazanov AG, Chumakov CENTURIES, Harutyunyan, S., Sokolovskiy T.M., V.A. Serov, Iliev V.T.//BI 1995. No. 18.

3. RF patent №2115653. Complex compounds of imidazoles, showing antidote and antihypoxant activity. Soshnikova A.I., Domnina Y.S., Tiunov L.A., Chumakov CENTURIES, V.A. Barinov, the Wart VK//BI 1998. No. 20.

4. RF patent №2204392. For the treatment of psoriasis. Babadjanov HH, Babadjanova SH, Trofimov B.A., Stankevich VK, Bakalova L.V., Nechiporenko S. p., Grisak SHOSTAKOVICH, Shilov, V.N., Barinov VA // BI 2003. No. 14.

5. Auth. mon. The USSR №1822155 (31.03.1976). Bis-(1-vinylimidazole)zincchloride as an antidote carbon monoxide. Domnina Y.S., Skvortsova GG, Ivlev, Y., Urumov O.Y, V.M. Vinogradov // BI 1995. No. 4.

6. RF patent №2118960. Line obtain bis-(1-vinylimidazole)zincdiacetate. Domnina Y.S., Soshnikova AI // BI 1998. No. 26.

SPO is about getting bis-(1-vinylimidazole)zincdiacetate (alzola) interaction of zinc diacetate with 1-vinylimidazole, characterized in that the process is carried out at a molar ratio of 1-vinylimidazole: cindicates in the range from 10:1 to 3:1.



 

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