SU905228A1 - Method for preparing thiourea - Google Patents

Description

(54) METHOD FOR OBTAINING POLYMOCHEVINA

I

The invention relates to the synthesis of high molecular weight compounds, namely the synthesis of polyurea based on natural diaminocarboxylic acids, which can be used in various fields of medicine as biocompatible polymers.

A known method for producing polyurea by reacting a diisocyanate with. diamines in dimethylformamide t

However, the low melting point and the significant hydrophilicity of these products prevent the use of the resulting polyureas for the production of plastics and fibers.

The closest to the proposed technical essence is the method of producing polyureas by reacting N, N -brystrimethylsilyl derivatives of natural diaminocarboxylic acid tkirov with carbonyl derivatives of organic compounds in an aprotic solvent medium 2.

The disadvantages of the known polyurea synthesis method are; the need to use for their synthesis diisocyanates based on diaminocarboxylic acid esters, which are obtained as a result of a laborious and nontechnological synthesis process, consisting in the use of absolute, highly flammable J1E1Xx solvents (e.g. - diaminocarboxylic acids, the need for multiple high-vacuum distillation of diisocyanates in order to bring them to the required condition; using absolute alcohol (methyl or ethyl) to release silylated amino groups; the need to synthesize a large number of diisocyanatoB for the preparation of polinocevins of various structures, for example, for the synthesis of polyureas based on I.LI D isomers of the natural diamino arbonic acid, it is necessary to synthesize separately for diisocyanate. The purpose of the invention is to obtain limochevins with a wide range of properties with simultaneous simplification of the THRD: -sob. The specified goal is achieved t; . In the preparation of polyurea, the interaction of N, N-bistrymethyl silyl derivatives of natural diaminocarboxylic acid esters with carbonyl derivatives of organic compounds in an aprotic medium; -: g. ../Britel as a carbonyl derivative of organic compounds, bis- (p-nitrophenyl) carbonate or bis- (254-dinitrophenyl.) Can be used and the reaction is carried out at 20-25 ° C and at 80-JOO C. -3 hours, followed by isolation of the polymer-. Iodine by the term activated carbon is meant to carbonate OUH- (o) (j-2. 4o)) —NO2 — blOi NOi. The polychlocenes thus obtained have C 0.3–0.9 dl / g, and for the rest of the parameters (IR -spectra solubility, melting point is identical to polymers 5 obtained by a known method from the corresponding diisodianates, Example I. In a three-necked collar equipped with a stirrer, inlet and outlet for argon, 3.28 g (0.01 mo N, N-bis ethyl ester -trimethylsl1Il- (1) -TMCL-lysine was dissolved in 0 ml of M, N dimethylacetamide (DMAA) and 3.94 g (0.01 mol of bis 254-dinitrophenylcarbo Ata (DNFK has a strong exothermic effect) and turn on the stirrer. After ZG - 40 minutes, the solution quickly thickens and a jelly-like mass is formed to ensure a homogeneous flow of the reaction, the mixture is heated up to 90 seconds and re-stirred for 3 hours, purging all the way; argon. a viscous solution that is poured in hot form into water. The polymer which is precipitated in the form of a powder is filtered off and washed thoroughly with water; dried ii extracted in a Coxlep acetone apparatus ;-), You yield 96% Ifip 0.95 dl / g in dimethyl oxide, g / dl -fc 25c. Example 2. In a three-necked column, equipped with a stirrer, inlet and outlet s for argon, 3, 18 g (0.0 mol) of N, N-bis-trimethacryl-L-lysine ethyl ester is dissolved in 10 ml of dimethylethamide, at 25 ° C add 3 „04 g (OjO monk) bis .: li-nitrophenyl carbonate (human diet & exothermic effect) turn on the stirrer and stir for 2 hours. The viscosity of the solution at room temperature for this period of time increases slightly, therefore, include heating and the reaction mixture is maintained at 6 h, all the time blowing the flask with argon. The solution is cooled to room temperature (the formation of a gel-like mass was not observed) and poured into water. The polymer (in combination with I-NITROPHENOL) drops out in the form of a liquid resin, which solidifies as L-nitrofg removes: la Water thoroughly poly. . dried in vacuum and extracted in Soxhlett’s apparatus with acetone. Polymer yield 97%, Inp — DL / g in dimethyl sulfo. e 5 C 0 5 g / dl., Example 3 Synthesis of the polymer is carried out in accordance with the procedure given in example j with the difference that instead of dimethyl acetate,; : ipa i:;: user N-MeTmylirrolidone (N-Mn) o Polymer yield 95%, dl / g in dimethyl sulfoxide. Example 4 Synthesis of the polymer is carried out in accordance with the procedure given in Example 1, with the difference that instead of N, K-bis trimethylsilyl-1-lysine ethyl ester, N, N-bis-trimethylsil-1-01-lysine ethyl ester is taken (Db ) TMCL. The polymer yield is 97%, 76 dl / g in dimethyl sulfoxide, 5 g / dl, t-Example 5, Synthesis of a polymer is of an essence 5 sweat in accordance with example f with the difference that instead of ethyl ester N, N-bis-trimethc silyl-1- The substance used is N, M-bis-trimethyl-silyl-1-ornitol 90% yield of ethyl ester,) p 0, 32 dl / g in dimethyl sulfoxide, 5 g / dl, C, Example 6, Synthesis of the polymer is carried out in accordance with the method shown in example 1, with the difference that instead of ethyl ester N, N-bis-trimethylsilyl-L-lys on the use of diethyl ester N, N-bis-trimethylsilyl-L-cystine. Polymer yield 96%, 0.85 dl / g in dimethyl sulfoxide, 5 g / dl,. Example 7. In a three-necked co with a stirrer, inlet and outlet for argon, 1.59 g (0.005 mol) of N, N-bis-methyl-C-lysine ethyl ester is dissolved in 10 ml of N, N-dimethyl acetamide, added 3.94 g (0.01 mol) of bis-2,4-dinitrophenyl carbonate are added, the stirrer is turned on and the mixture is stirred at room temperature for 2 hours. To the reaction solution is then added 2.20 g (0.005 mol) of diethyl ether N, N -bis-trimethylsilyl-L-cystine (the ratio of two diaminocarboxylic acid derivatives is 1: 1) include heating and the mixture is heated to 90 ° C for 3 hours. The reaction solution is poured into water. The precipitated polymer is filtered off, rinsed thoroughly with an Egrda, dried and extracted with ethyl acetate in a Soxhlett apparatus. The polymer yield is 97%) 0.68 dl / g in dimethyl sulfoxide, 5 g / dl, Example 8. The synthesis of the polymer is carried out in accordance with the procedure described in example 7, with the difference that instead of ethyl N, N - Bis-trimethylsilyl-1-lysine is used with N, N-bis-trimethyl-spm-L-cystine diethyl ether, and then N, N (L) TMSL (O) is added to the registration solution.

DNFK

(L) TML (O

PFC

DMMA 25 / 0.5 96 0.95 90/3

97 0.4

DMAA-25/2 100/6 -bis-trimethylsil-1-lysine. The polymer yield is 98%, 0.71 dl / l in dimethyl sulfoxide, 5 g / dl, t 25C. Example 9. Synthesis of the polymer was carried out in accordance with the procedure described in Example 7, with the difference that 0.002 mol of N, N-bis-trimethylsilyl-1-lysine ethyl ester was taken instead of 0.005, and 0.008 mol of diethyl ether was taken instead of 0.005 mol N, N -bis-trimethylsilyl-1-cystine. The polymer yield 96%, 70 DL / g in dimethyl sulfoxide, 5 g / dL,. Example 10. Synthesis of the polymer was carried out in accordance with the procedure described in Example 7, with the difference that 0.008 mol of N, N-bis-trimethyl-1-silyl-1-lysine ethyl ester and 0.002 mol of L-cystine diethyl ether were taken. Yield 97%, lfip 0.68 dl / g in dimethyl sulfoxide, 5 g / dl,. Example P. Synthesis of the polymer is carried out in accordance with the procedure described in example 7, with the difference that instead of ethyl ester of N, N-bis-trimethylsilyl-L-lysine, take ethyl ester of N, N-bis-trimethylsilyl-D1-lysine . The polymer yield is 95%, K) pp 0.52 dl / g in dimethyl sulfoxide, 5 g / dl,. Example 12. Synthesis of the polymer is carried out in accordance with the procedure given in Example 7, with the difference that instead of N, N-bis-trimethylsilyl-L-lysine ethyl ester, N, N-bis-trimethylsilyl-L- ethyl ester is taken opnitine. The polymer yield is 89%, 0.28 dl / g in imethyl sulfoxide, 5 g / dl, t 25C. The main characteristics of semi-polymers are given in table.

(L) -shap (1)

DNFK

(D1) walking (1)

DNFK

(L) taso (1)

DIFK

(L) TMSC (1)

DNFK

{L) TML (0.5)

 (L) TMSC (0.5)

DNFK (L) TMSC (0.5)

+

(L) TML (0.5)

Note: TMSO is N, N-bis-trimethylsilyl-ornithine ethyl ester; TMHL is ethyl ester of N, N-bis-trimethylsilyl lysine; TMSC - N, N-bis-trimethylsilylcystine diethyl ether; DNFC-bis-2,4-dinitrophenylcaronate, PNFC-bis p-nitrophenylcarbonate; DMAA - N, N-dimethylacetamide; N-MII-N-methylpyrrolidone. Viscosity is determined in dimethyl sulfoxide at, 5 g / dL.

The use of the proposed method for the preparation of polyurea based on natural dinocarboxylic acids provides the following advantages compared with the known methods: ease of preparation of high molecular weight glymethyl urea based on 905228

8 Continuation of the table

NMP 25 / 0.5 95 0.95 90/3

DMAA 25 / 0.5 97 0.76 90/3

DMAA25 / 0.5 900.32

90/3

DMAA 25 / 0.5 96 0.85 90/3

D11AA 25/2

970.68 90/3

25/2

98

0.71

DMAA

Claims (2)

Native diaminocarboxylic acids using only their trimethylsilyl derivatives and one activated carbonate, for example bis-2,4-dinitrophenylcarbonate, did not use hard-to-reach diiso-anats, no need to remove 9 tons of trin-methyls of protective protective groups from amino groups, there is a wide possibility of synthesis. the basis of two or more diaminocarboxylic acids (including or DL), using for this purpose only N, N-bis-trimethylsilyl derivatives of their esters and one activated carbon , For example bis-2, 4-dinitrofenilkarbonat; ease of handling and ease of purification of activated carbonates are reduced with crystalline compounds. The invention method for producing polyurea by reacting N, N-bic-trimethylsilyl derivatives of esters of natural diaminocarboxylic acids with carbonyl derivatives of organic compounds in an aprotic solvent medium, in order to obtain a polyurea with a wide range of properties while simplifying the process carbonyl derivatives of organic compounds use bis- (p-nitrophenip) carbonate or bis- (2,4-dinitrophenyl) carbonate and the reaction is carried out at 20-25 ° C for 0.5-2 hours and at 80-10 0 ° C followed by the release of poly. Sources of information taken into account in the examination 1. Saunders J.H., Frish K.K. Polyurethane Chemistry. M., Himi, 1968, p. 13-14. 2.Sentsova T.I., Butaeva V.I. “Davidovich Yu.A., Rogozhin S.V., Korshak V.V. Synthesis of synthetic active polyureas on the basis of natural diaminocarboxylic acids. Report of the Academy of Sciences of the USSR 232, 225, 1977 (prototype).