SU745904A1 - Method of preparing o-silylurethans - Google Patents

Description

(54) METHOD FOR OBTAINING 0-SILURURETHANES

-. -; I Otoosit invention to the method of obtaining O-oshiluretanov General formula G "t BL (o) (1) To where R is alkyl, aryl, alkynyl R, YH, alkyl Cj-Cj ,, alkoyl, SiMej, OSiMej, CHjCHjOSiMea. CHjC (0) OSiMe3, (CHj) 6NHC (O), CH2C6H4CH2NHG (O) OSiMej; fiV NG CHj) m-CHj CHj N C (0) OS i Meuse J CH, CHj -; n is 1-3; m - 4-5, which can be used as catalysts for the vulcanization of silicone and epoxy resins. A known method for the preparation of O-silane urethanes by the reaction of carboxylation of a i oc ιocylano 6 in carbon dioxide, which provides for the pre-launch protection of amines with chlorosilanes, hexamethyldisilazane (HMDS) or other strong agents 1. Its disadvantages are multistage, duration in time. (approximately 40-45 hours). The need to use solvents and acceptors of hydrogen chloride. The closest to the technical essence of the invention is a method for producing 0-silylurethanes by reacting COj with a mixture of an amine and an organosilicon compound, namely hexamethyldisilazane, at a temperature of 80-200 ° C. The disadvantage of this method is the need to strictly control the process temperature, since insignificant temperature deviation from the optimum in the reactor leads to intensive formation of substituted ammonium carbamate, which turns into the target 0-silylure1; en slowly and in a cut) d) um to reactor it is plugging and collecting system. Increasing the temperature of 1ive6dit to decarboxylation. In addition, the N-CrIOxcn-barbeniline lutod is not applicable to diamines, due to the formation of polycarbamates that do not form diurethanes with hexamethyldisilazane and some of the compounds of formula 1 cannot be obtained. Since the reaction proceeds better in the presence of mineral acids. This complicates the process. - i @ te # fc; «-Iv 4, ii- -h The purpose of the invention is to simplify the process and expand the scope of its application. This goal is achieved due to the fact that the organosilicon compound, namely, the silyl ester of the carbamic acid of the general formula D, is reacted with the general formula G Rl oc {o) X I 0 ": where R is alkyl Cj-Cg; Ari, alkenyl Cj-C R, R H, Me, Et, .n .. ,, ..... , .., .., -,, With amine at elevated temperatures, preferably at 55-200C. A distinctive feature of the method is the use of silicon as an organosilicon compound; silyl zirfira carbamic acid of the formula y. Example I. In a flask equipped with a thermometer and a head from a distillation head, 27 g of trimethylsilyl ether diethylcarbamic acid are placed with 28.4 tons of dihexylamine, heated to 1 and taken away with diethylamine (the temperature in a cube r: about 18 increases from 0.1 to 200 ° C ). 9.42 g (90.7%) of diethylamine and 38.9 g (90.7%) of urethane are obtained with a bale. 102 / 1.0 1.4378. . Found,%: C 64.00; H 11.89; Si 9, 19 CieHjsNOjSi ..,, Calculated,%: C 63.70; H 11.69; Si 9.31. IR spectrum:) 1690 cm HMR spectrum: singlet 0.23 ppm OSiMss two multiplets 0.9 and 1.31 ppm and a triplet of 3.13 ppm, corresponding to the protons of the Dagexy residue. Example 2. Under the same conditions, out of 23.1 g of diethylcarbamic acid trimethylsilyl zofira and 24.5 g of piperidine gphy, 7.82 g (89%) of ditylamine and 22.0 g (89.9 %) trimethylsilyl ester of piperidinecarbamic acid with so kip. 61 ° C / 1.5 and pho U453 (Literary data: m.p. 74.5 / 2.5 and nf} 1.4501). Example 3. Under the same conditions, 5.6 g (99.3%) of diethylamine and 15.1 g (96 g) of 14.9 g of pentylamine and 14.6 g of dimethylcarbamic acid trimethylsilyl ester are obtained in a cube of 65-95 ° C. , 8%) of trimethylsilyl ester of pentylcarbamic acid with m.p..84.5 ° C / 1.5 and p 1.4348. Found,%: C 52.98; H 10.31; Si 13.51 CeHziNpaSi. " Calculated,%: C 53.10; H 10.41; Si 13.81. . HK-cneKTpi-O J690 cm and O 3345 cm-. PMR spectrum: 0.26 ppm singlet (OSiMes) and proton signals corresponding to Me (CHj) 4 N. Example 3. Under similar conditions, from 19.8 g of hexamethylenediamine, 68.6 g of trimethylsilyl dystilcarbamic acid ester at a temperature of 65–85 ° C in cubes 11.2 g (91.6%) of daethylamine and 56.6 g (95.5%) of 1,6-bistrimethylsiloxycarbonylaminohexane with mp. 76 ° C Found,%: C 47.98; H 9.30; 81 16.22; Ci4H32N2 O4Si2 Calculated: C, 48.25; H 9.27; Si 16.14. IR: 5 1675 cm, 3375. HMR spectrum: 0.28 ppm (OSIMeg / 1.37 ppm / C-CHg / and 3.08 MD. Example 5. Under similar conditions, out of 59, 4 g of dimethylsilyl zyfir dystilcarbamic acid and 19.4 g of xylylenediamine (75% m- isomer and 25% p-isomer) at a temperature in a cube of 55-85 ° C, 44.2 g (84.4%) of 1.3 and 1,4-bistrimethylc10xixycarbonylaminomethyl benzene are obtained with a melting point of 119-128 ° C. IR -spectrum: (1680-1695 cm and NH 3305-3325 cm. Paideno,%: C 51.98; H 7.80; Si 15.00. C1bH28M204 Sij. Calculated,%: C 52.10; H 7.65 ; Si 15.24. The table shows other 0-silylurethanes synthesized by the described method.

Mes8S (r) M (Sbn, h) 2

Me3SiOC (0) N- (CH2) 4X

Me3SiOC (O) NHCsHij

lMe3SiOC (O) NH (CH2) 3l2 il, 3- (l, 4) - {Me3SiOC {b) NHCH2

Xx

MeSilOCCONHB J

(O) NHB) (O) NH (CH2) 20SiMe3 OC (O) Me3SiOCH2CH2NHt; (O) OSilVle3X Msz5yS (O) 1 CH2CHNYS (O)) CH MeZ54OM () eCO) O5 | ) C (O) O51MESXX Vin Si OS (O) (O) NHArl 3 x

 Individual substances. ™ Transparent thick non-distilled liquids; the yield is determined by the amount of amine liberated.

 Low melting non-distilled substance that decomposes when heated to 65 C.

(Sbn, h) 2 MI

(SCLT-n

Cshjinhj

NH2 (CH2) 6NH2

(0) NHMe

B.NH2

MeSifOC (0) NEt

2J3 Me3SiOC (0) NEt2МН2СН2СбН4СН2МН2 J (0) Me3SiO (CH2) 2NH2 Me3SiO (CH2) 2NH2 Me3SiOe (O) NEt2, CH, CH NEt2 Me3SiOC (O) CH2NH2 Viri Si OC (O) (O) NMe2l3

25 - 110-120 90.7106 / 1.0

2087-114 89.9 74.5 / 2.5

2040-90, 96.1 84.5 / 1.5 1540-78 94.5 2035-82 97.0 P8-128 IS20-75 94.1 -70 97.1 60-7592.6 60-7590.7 79.5 / 1.0 60-185 89.6-12 12645.30 -. 40-75 64.289 / 2, 76 20-70 96.6

20

20-65 92.7

63.69 11.93 63-70 11.93 1.4379

53.77 9.4353.69 9.51 1.4501

52.98 10.3153.10 10.41 1.4348 76-78 28-31 49.27 45.34 43.30 49.90

Claims (2)

53.60 5.3153.32 5.72 48.70 9.07 48.24 9.27 52.24 7.79 52.10 7.65 49.29 8.39 49.09 8.49 8.40 49.09 8.49 1.4502 8.20 45DO 8.25 1.4469 9.36 4333 9.29 1.4308 8.2, 45.25 8.25 .37 40.90 9.28 1.4280 8.5942.90 8.71 8.1150.60 8.24 974 The method allows to synthesize bis-0-sypyluret 1 of sufficient purity without special purification techniques. Another advantage of the proposed method is the possibility of reusing a byproduct of the synthesis, diztilamine, in the step of preparing diethylcarbamic acid trimethylsilyl ester, which reduces the cost of the process. An advantage of the proposed method is also the possibility of obtaining bis-0-silylurethanes and other unstable 0-silnurethane, which cannot be obtained by known methods. In addition, due to the quantitative process flow, the resulting target product does not require additional purification, which significantly reduces the total process time from 5 to 25 minutes. The invention The method of glorification of cigasturethanes by the interaction of organosilicon compound with an amine at an elevated temperature, about the fact that, in order to simplify the process and to expand the field of application of the method, the silicamide compound using the general formula G: l: Bn iloc (oX I-Tj J4-fl R - alkyl aryl, alkene R, R H; Me; Et; 2. Method no. 1, except that the process is carried out at 55-200 ° C. Sources of information taken into account in the examination 1.H.Breederveld. Rec. Trav.Chim 1% 2, 81,. 276. 2. USSR author's certificate K 486021, l. C 07 F 7/10, 1974 (prototype).