SU538000A1 - Method for preparing organocyclothythiazans - Google Patents

Description

The invention relates to the chemistry of organosilicon compounds, in particular to a method for producing organocyclostiltiazans containing both silthian (Si-S-Si) and silazane (Si-N-Si) structural units that can be used in the synthesis of polymers.

A known method for producing organocyclostiltiazanes by thiolysis of 1 organocyclosilazanes or rearranging 2 organosiltianes with organosilazanes when heated for a day.

There is also known a method for producing organocyclostiltiazans by thiolysis of a, d) dichlorosilazane with hydrogen sulfide 3.

However, this method is accompanied by the formation of a mixture of products of silthian and silazane structures, which leads to a decrease in the yield of the target product; It does not allow synthesizing products with an adjustable combination of Si-S-Si and Si-N-Si units and requires the use of hydrogen sulfide gas.

The purpose of the invention is to increase the yield of the target product and simplify the process - is achieved by treating a mixture of hexa-organo-disilicane and hexa-organo-disilazane with diorganodichlorosilane at 120-200 ° C in the presence of a nitrogenous base, preferably 0.2-0.4 mol per 1 mol of diorganodichlorosilane, with simultaneous removal of the triorganochlorosilane. Hexa-organodisylthiane, hexa-organodisilazane and diorganodichlorosilane are usually taken in a molar depletion of 1: 2: 3 - 2: 1: 3, respectively.

Example 1. In a flask equipped with a reflux condenser, 5 g (0.028 g-mol) of hexamethyldisiltiane (HMDST), 9.05 g (0.056 g-mol) of hexamethyldisilazane (HMDS) and

16.09 g (0.084 g-mol) of methylphenyldichlorosilane (MFDS), 1.45 g (0.0106 gmol) of pyridine was added and heated, and the release of trimethylchlorosilane (TMC) was observed at 120 ° C. The process is carried out for 4 hours with continuous distillation of volatile TMHS, the yield of which, after termination of the reaction at 130 ° C, reaches 17.5 g (92.2%). The cubic liquid is distilled, the residue is recrystallized from benzene and 9.2 g is recovered.

(77.5%) trimethyltriphenylcyclotrisylthiadiazan, t. Kip. 172 ° C / 2 mm; m.p. 87-88 ° C.

11, / SbN5

PC -KN

-one.

/

BH5

Found,%: Si 19,10; S 7.81; N 5.71; a pier weight 431.

Calculated,%: Si 19.89; S 7.57; N 6.63; a pier weight 422.

IR spectrum, CM-I: 928-932, 1170 (Si — NH — Si), 470-485 (Si — S — Si), 3330 (N — H), 1110, 1425, 1592 (Si — CfiHs).

Example 2. Analogously to example 1 of 7 g (0.0392 g-mol) HMDST, 3.16 g (0.019 g-mol) of HMDS and 11.25 g (0.059 g-mol) of MFDC in the presence of 1.95 g (0.022 g-mol) iiridine at 120-180 ° C get 7.95 g (92%) of trimethyltriphenylcyclotrisyldithiazan, t. Kip. 210-212 ° C / 3 mm; m.p. 99 / 10GS.

Sy bn5 5

s-SNZ I I / CH St ST / Cht1 /

Sat%

Kh

Found,%: Si 17.92; S 14.14; N 2.99; a pier weight 436.

Calculated,%: Si 18.63; S 14.55; N 3.19.

IR spectrum, cM-i; 932, 1175 (Si-NH-Si), 415, 480-485 (Si-S-Si), 3375 (N-H), 1110, 1425, 1590 (Si-CeHs).

Example 3. 5 g (0,026 g-mol) HMDST, 9.05 g (0.056 g-mol) HMDS, 21.3 g (0.0345 g-mol) of diphenyldichlorosilane and 1.45 g (0.016 g-mol) of pyridine heat 4 hours.

The release of volatile TMHS starts and ends at 200 ° C. The output TMHS 13.1 g (94,5%).

The bottom residue is evacuated, the residue is recrystallized from benzene and 14.5 g (83%) of hexaphenylcyclotrisylthiadiazan are obtained, m.p. 197 ° C.

Found,%: Si 12.95; S 4.85; N 5.55; a pier weight 597.

Calculated,%: Si 13.81; S 5.26; N 4.60; a pier weight 608.

IR spectrum, CM-I: 930, 1175 (Si — NH — Si), 411, 470–485, 535 (Si – S – Si), 3360, 3370 (NH), 1120, 1428, 1590 (Si – CsHs ).

Claims (3)

1. A method of producing organocyclostiltiazanes based on organosilazanes, characterized in that, in order to increase the yield of the target product and simplify the process, a mixture of hexaorganodisylthiane and hexaorganodisilazane is reacted with diorganodichlorosilane at 120-200 ° C in the presence of a nitrogenous base with a sample of a sample in a sample of a sample of a sample in a sample of a sample of a sample in a sample of a sample of a sample of a sample of a sample of a sample of a sample of a sample in a sample of a sample of a sample of a sample of a sample of a sample of a sample of a sample of a sample of a sample in a sample of a sample of a sample of a sample in a sample of a sample of a sample of a sample of a sample of a sample of a sample of a sample of a sample. 2. A method according to claim 1, characterized in that the hexa-organoanodisylthian, hexa-organo-disisilazane and dioorganodichlorosilane are taken in a molar ratio of 1: 2: 3 to 2: 1: 3, respectively. 3. Method according to paragraphs. 1 and 2, characterized in that the nitrogen base is taken in an amount of 0.2-0.4 mol per 1 mol of diorganodichlorosilane. Sources of information taken into account in the examination: 1. JOH, 43, 683, 1973. 2.Chem. Zent., 39, 645, 1968. 3.Pure, and Appl. Chem., 13, 263, 1966.