CS200754B1 - Polythioglycoloyloxyethylmethacrylate and process for preparing thereof - Google Patents

Description

The preparation of structural units of general vaoroa 1 represents a novel type of dopoeial non-described macromolecular carrier of the polyacrylate type.

The essence of the preparation of polytioglycoloyloxyethyl methacrylate and the repeating aa structural units of the general vaorea I according to the invention is that aa polyhydroxyethylaetacrylate and the repeating aa structural units of vaoroa II

0 - 1 what AND 0 CHg - σκι * C - CH 2 WHAT 1 0 AND C - CHg - WHAT 1 0 1 CH- P no. 1 what 1 0 AND | r ² CHg 1 CHg | 0¾ CHg-OH CHg-OH ®2 1 0 AND 0 | 1 what AND CH1 * CH- j ' 1 what AND 1 C 1 CHg C CHg C CH- 1 1 no. 1 1 CHj WHAT l WHAT l CHj 0 | 0 | CHg 1 CHg CHg-OH | CHg-OH

(11) undergoes the transesterification and thioglycolic acid ethers in an organic roepulant and mineral acid medium and at reflux, at a temperature of 60 to 70 ° C, and optionally for the preparation of a structural compound of the general formula I, where

R is - CHg - CHg - O - CO - CHg - S - S - COOB, to the polytioglycoloyloxyethyl methacrylate, and to Structural units of general vaorea I, where

R is -CHg-CHg-O-CO-CHg-SH, is treated with 6,6'-dithiodinicotinic acid at room temperature.

The simple and time-consuming process of transesterification and activation makes it possible to prepare a chromatographic carrier of high purity.

In general, the synthesis of macromolecular polythiols is carried out by polyhydroxyethylmata3

200,754 crystals were re-etherified with thioglycolic acid ester. The reaction takes place in an environment of an organic solvent and a mineral acid at reflux. The material is dried at 70 to 90 ° C after sieving. Its structure, in particular as regards the presence of sulfur, is capable of elemntary analysis.

Example 1

Preparation of a Polymer with Structural Units of Formula 1 wherein R is -O-CH-O-CO-OL-SH

Weigh 35.2 g of Spheron P 100 (polyhydroxyethyl methacrylate) into flask e, add 46.3 g of thioglycolic acid methyl ester, 130 ml of tetrahydrofuran and 10 ml of conc. i ^ SO ^.

The mixture was refluxed for 2 h, filtered, washed with tetrahydrofuran and dried at 80 ° C. The presence of SH-groups in the polymer of formula I was confirmed by elemental analysis (% C 55.55,% H 7.19,

5,56). In a similar manner, a polymer of formula (I) may be prepared except that dioxane is used instead of tetrahydrofuran and hydrogen chloride gas is used instead.

Example 2

Preparation of a Polymer with Structural Units of Formula I wherein R is

- ^ C - _CH2 - O - CO - CEG - S - S

The COOH g of the polymer of formula I exemplified was washed with 50 ml of acetone-0.05 N sodium carbonate (6: 4). 10 ml of a solution of 6,6'-dithiodinicotinic acid / mg of acid in 10 ml of acetone-sodium carbonate (6: 4) is added to the washed carriers and stirred for 1 hour at room temperature. Mosic is passed through 60% acetone in distilled water. The binding ability of the activated carrier was gilded with labeled J human albumin.

125 The amount of bound J albumin per polymer in a concentration-dependent relationship 125 J albumin / g polymer // µg / 125 Conc. J albumin // Ug per ml / 55.62 2.49 129.38 4.91 175.84 9.90 379.85 24.39 482.42 41.61 840.46 90.90 1,053.41 166.66 1,324.87 285.71 1 387,24 414.95

Determined by radioactivity of the polymer after incubation with labeled human

200 754 albumin in Tria-HCl buffer, pH 8.0 / 30 min, 25 ° C, albumin by perfect residence.

Prepared derivatives and structural units

- CHg - CHg - O - CO - CHg - SH

- CHg - CHg - 0 - CO - CH - S - Sulfate and / or removal of unreacted formula I, where R is

and of formula II have physically and hydrodynamic properties practically identical to those of the starting carrier. The activated derivative reacts quantitatively with the structural units of formula II and with SH-groups of low-molecular-weight thiols and proteins. This derivative may be used in the separation of thiol from aethiol peptides and proteins, in the separation of SH enzymes from denatured enzymes and in the protection of SH groups of proteins. In comparison, and similar dextran and polyacrylamide type aa bearers, the prepared derivative exhibits abaolute resistance to microorganisms and stellate to agents used in protein hydrolysis, ultimately resulting from its structure.

OBJECT OF THE INVENTION

Claims (2)

OBJECT OF THE INVENTION / 1 /, C - CH, I CH, CH. I ² c I co I o CH, CH, I ³ c - ch ₂ I co AND 0 - R CH, CH, AND I co I c I cu. where R is - CH 8 CH 8 O CO CH 8 SH or - CHg-CHg-0-CO-CHg-S-S- COOH 200 754 1. Polytioglycoloyloxyeryl methacrylate and repeating aa Structural units of the general formula I CH, ¹³ CO i O AND CH, I <* 2 I co CH, ¹³ CH, | ³ CH, | ³ c - AND CHg - C-CHg- c - l what AND what AND what AND 1 0 - R 1 0 - R 1 0 2. A process for the preparation of polytioglycoloyloxyethyl methacrylate according to claim 1, characterized in that the polyhydroxyethylipetacrylate β is repeated by structural units of the formula II. CH, | ** CH, ¹³ CH, ¹³ CH, 1 ^J -Ο- Ι CHg - c - ch ₂ - C - CH ₂ - and C - WHAT 1 what AND WHAT | what 1 1 0 1 0 1 0 1 0 1 1 AND AND CH, | * CH, | * ®2 TARGET, TARGET, CHg-OH 1 0¾ - OH TARGET, t 0 1 0 1 WHAT | CH, | ^J CH, | ^J 1 WHAT | 1 -ο- Ι cb ₂ - 1 C - CH, I ^{et al} 1 C - CH3 | ‘ 1 c 1 CH ₃ CH ₃ WHAT AND WHAT AND 1 0 | 1 0 1 CH, | * | 0¾ CH ₂ - OH CH ₂ - OH subjected to a pre-esterification with a thioglycolic acid ester in an organic solvent and mineral acid medium at reflux at 60 to 70 ° C, optionally for the preparation of a compound having Structural Units of Formula 1 wherein R is R 2; COOH - CH, O - CO - CH for the resulting polytioglycoloyloxyethyl methacrylate with Structural Units of Formula I wherein R is - CBg C ^ WHAT CH-SH impregnated with 6,6'-dithiodinicotinic acid at room temperature.