SU1118638A1 - Ethylenediamine derivatives as stabilizer for unsaturated hydrocarbons or their chlorine derivatives - Google Patents

Description

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11186382

This invention relates to new derivatives of ethylene diamine of a common forchemical compound, namely, mules.

,)

but CHO) (dH /), - If- s1Ng (Ng-5- (H «), dH g - (oS-OH

cJ (cJH, -,) 3

, -C NgCHOOWN These compounds can be used as a stabilizer for unsaturated hydrocarbons or their chlorine derivatives. Known use of N, N, P-tri- (2-methyl-propen-2) -y, M-bis- (2,3-zpoxypropane) -diethylenetriamine CO and N, N-bis- (2-methylpropen-2) -Y, K, n-tri- (2,3-epoxypropane) -diethylenetriamine 2 3 as a stabilizer for halogenated hydrocarbons. c1 () h. as a stabilizer for unsaturated and chlorine-containing x C 3 rubbers. However, the use of the compound of formula II for the stabilization of unsaturated hydrocarbons or their chlorine derivatives is not known-. The chain of the invention is the synthesis of compounds of the general formula I, which have an improved stabilizing activity for unsaturated hydrocarbons or their chlorine derivatives. This goal is achieved by new derivatives of ethylenediamine of general formula I, which can be used as a stabilizer of unsaturated hydrocarbons and their chlorine derivatives. The compounds of formula I are obtained in a known manner in two stages: by the action of H, / 3-ethylpiperazine with dichloroethane in isopropyl alcohol with heating and subsequent condensation of N, N-bis-piperazinoethylethylenediamine intermediate with 3,5-di-tert-butyl-4-hydroxy -K, N-dimesh1benzylamine (Maynich base) or with formaldehyde and 2,6-ditertbutylphenol when heated.

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C (CH3) C Disadvantages of using these stabilizers are the difficulty of obtaining the required individual alkyl derivatives of diethylene triamine, since this alkylation process is non-selective, therefore not shown, the characteristic data of these stabilizers, these stabilizers are poorly compatible with organochlorine products (poorly soluble in them). The use of a piperazine derivative of the formula is known. (-D) s The structure of the compounds of formula I by the evidence of elemental analysis, IR spectra and chemically counter-synthesis. EXAMPLE 1 Preparation of N, N-bis-fN- (4-hydroxy-351 5-di-tert-butyl) benzyl-piperazino-ethyl-ethylenediamine (1a). In a 3-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, 12.9, g (0.1 M) N, -aminoethylpiperazine are loaded, 5 g (0.05 M) dichloroethane is added dropwise at this temperature. The reaction mixture is heated for 2 hours, then 5.6 g (O, 1M) KOH in 50 MP of isopropyl alcohol is added and heating is continued at 90 ° C for 3 hours. The reaction mixture is cooled. Then, the resulting filtrate (solution of bis-piperazinoethyl-ethylenediamine in isopropyl alcohol), 26.3 g (0.1 M) of 3,5-di-tert-butyl-4-hydroxy-N, K-dimethylbenzylamine (Mannich base ) and heated for 4 h at. The alcohol and the dimethylamine that is removed are then removed and the residue is recrystallized from a mixture of ether and petroleum ether (1: 1). Obtain 28 g (78%) of compound 1A, So pl. 260 {262 С, -YK-spectrum,) cm: 1565 tNH) 3575 (ОН), Found,%: C 73.71, H 10.92, N 11.02. C U-igNfP Calculated,%: C 73.33, H 10.55, N 11.66. Example 2i Preparation of N, N, N7 N j-TeTpa- (4-OKCH-3,5-AH-TpeT-6yTHn) benzyl-N, n-bis-piperazinoethyl-ethylenediamine (16). Under the conditions of Example 1, 12.9 g (0.1 M M, p-aminoethyl piperazine is heated to 120 C; 5 g (0.05 M) of dichloroethane are added dropwise at this temperature, heated for 2.5 h, then 5.6 g are added KOH in 75.0 MP of isopropyl alcohol and heated for 3 h at t. The reaction mixture is cooled, washed with 25 ml of isopropyl alcohol, and the filtrate is again loaded into the reaction flask, and 52.6 g (0.2 M) of the base are loaded into the same. Mannika. The reaction mixture is first heated for 2 hours at a boiling point temperature of isopropyl alcohol, then the temperature of the reaction mixture is raised alcohol and dimethyl amine are distilled off at the same time for 1.5 hours. The product is crystallized from ether and petroleum ether. 49.4 g (86%) of compound 16 are obtained, mp 157-159 ° C, IR -spectrum),). cm-: 3570 (OH). Found,%: C 77.18, H 10.56, N 6.96. C74Hl2oNt04. Calculated,%: C, 76.81; H tO, 38, N, 7.26. Under the conditions of Example 1, the N, N bis-piperazinoethyl-ethylenediamine intermediate was isolated and distilled under vacuum. Obtain 13 g (92%) of the product. Bp 258-260 C (10-12), m.p. , p 1.5140. IR spectrum, CM-i: 1570 (NH), UV spectrum, nm, (e): 205 (4130), PMR Spectrum (CFjCOOH) MD, 2.47, 2.77 and 3.45. . 2.84 g (0, p1M) of an intermediate product, 8 ml of 36% aqueous formaldehyde, 8.24 g of 2,6-di-tert-butylphenol are loaded into the reaction flask and the contents of the flask are heated to 100 ° C for 6 hours. is isolated by crystallization from ether and petroleum ether. 8.3 g (72%) of compound 16 are obtained, mp 256-157 ° C. Found,%: C 77.23, H10.64 ,. N 6.84 .. Calculated,%: C, 76.81; H, 10.38;, N, 7.26. Compounds 1a and 16 are tested as stabilizers of unsaturated hydrocarbons and their derivatives according to the following procedure. 100 g of the unsaturated compound is charged to the distillation flask, the stabilizer is introduced and distilled at atmospheric pressure. The resinification of the product is determined by the ratio of the resin formed during the distillation, minus the amount of stabilizer to the weight of the non-unsaturated unsaturated compound. Test results with application-. the proposed and known stabilizers are given in the table. To compare the effectiveness of stabilization, the results of tests of the blank run are also given - without the use of a stabilizer. As can be seen from the table, compounds of the general formula I reduce the percentage of tarred unsaturated hydrocarbons and their chlorine derivatives and are superior in their effect to the known stabilizer N, N-bis- (2-mi-ippene-2) -N, N, N.-three (2 , 3-e poksipropan) -diethylenetriamine 2,

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1,1,2,3-Tet