SU1203088A1 - Method of producing lakylvinyltellurides - Google Patents

Description

one

The invention relates to the field of organometallic synthesis, and to a method for producing previously unknown alkyl vinyl tellurides of the general formula CHi CHTeR, where., DH /, iso-CjHy, CiH., Which are promising monomers, co-numbers and intermediates for organo-synthetic synthesis.

The aim of the invention is to develop a method for producing new alkyl vinyl tellurides.

Example, Heated to 105-115 ° C 12.76 g (0.1 mol) of elemental tellurium, 48.5 g (0.87 mol) KOH 24.6 g (0.3 mol) of tin chloride, 1.37 g ( 0.01 mol) butyl bromide and 150 ml of water in a one-liter rotating autoclave under acetylene pressure (initial pressure 12 atm, residual 7 atm) for 5 h. The organic mixture is separated from the reaction mixture, dried in potash and fractionated in vacuo. 1.49 g (70%) of butyl vinyl telluride are obtained, bp. 53 C / 3 mmHg; Ex 1.5503. Spectrum of the NDP (B, MD, JHH, Hz)): 7.01 k, 6.21 d, 5.74 d, 2.70 t, 1.75 m, 1.38 m, 0.94 t ; 10.2,

..TR "NS .y. Mr. Jl / u1, j.

IR spectrum, cm-M3060 / U (CH2), ZOU / 1 (CH) /; 2980, 2950, 2925, 2865, 2855 (U (C – H)) /; 1573 / K () /; 1460 / (- GSNg) /; 1370 / e (CEj) /; 1230; 1180; 1160 / (CH, CH) /; 960 / g (CH,

885 / aJ (Cl4) /; 510 / V (C-Te) /.

Molecular ion in the mass spectrum of M 214.

Found,%: C 34.30; H 5.90; Te 60.40

.gte

Calculated,%: C 34.03; H 5.70, Te 60.27.

Along with butylvinyltelluride, in the reaction mixture, there are di-vinyltelluride and dibutyltelluride.

PRI mme R 2. Heated at 105-1 12.76 g (0.1 mol); elemental tellurium, 48.5 g (0.87 mol) of KOH, 24.6 g (0.13 mol) of tin chloride, 1.23 g (0.01 mol) of propyl bromide and 150 ml of water in a one-liter rotating autoclave. pressure of acetylene (initial pressure 13 atm, residual 9 atm), for 5 hours. The lower organic layer is separated and distilled in vacuum. 1.35 g (68%) of vinylpro030882 are obtained

piltelluride, t.kip. 83-84 C / / 40 mmHg; , 5701.

PMR spectrum (, MD, Hz |:

7.03k, 6.24 d, 5.75 d, 2.70 t,

S 1.72 m, 1.39 t; 10.2,

Molecular ion in M 200 mass spectrum.

Found,%: C 30.58; H 5,

10 Te 64.83;

Calculated,%: C 30.37; H 5.09; Te 64,54

Along with vinyl propylenetelluride

15 in the reaction, divinyltels reed and dipropyl telluride are formed.

PRI me R 3. Heated at 105-115 C 12.76 g; (0.1 mol) Those 48.5 g (0.87 mol) KOH, 24.6 g (0.13 mol)

20 tin chloride, 13.7 g (O mol) butyl bromide and 150 MP of water in one. liter rotating autoclave under acetylene pressure (initial pressure 13 atm, residual pressure - 6

25 for 5 hours. The lower organic layer is separated and fractionated under vacuum. 8.2 g of butylvinyltelluride are obtained (yield 58%, hereinafter calculated to form

30. Scheme: ЗТе + СНО 2Те + ТеО + ЗН2.0)

Example 4. Heated at 105-1154 12.76 gG (0, Gmol) Those, 48.5 g (0.87 mol) KOH, 24.6 g (0.13 mol) tin chloride, 10.1 g (0 , 1 mole)

22 ethyl bromide and 150 ml of water in a one-liter rotating autoclave under acetylene pressure (initial pressure 13 atm, residual 8 atm | for 5 hours. Lower organic

The d0 layer is separated and distilled at atmospheric pressure. Obtain 12.2 g of the fraction with so Kip. containing, according to this PC, 6.2 g (J output 50% j of vinyl ethyl teluride, 4 g of divinyltel45 luride and 2 g of diethyltelluride.

Vinyl ethyltelluride is purified by the method of preparative GLC, t, kip. 138-139 C, 1, 5865. 50 PMR spectrum (S, ppm; Jmi ,,

7.04k; 6.26 d; 5.76 d; 2.69 to;

1 67 t- 10 2- t IT g

Jjo / t, 1U, /, J (1 /, J.

Nuclear Magnetic Resonance Spectrum (E, M.D.): 126.78; 107.86; 17.79; 1.92.

55 IR spectrum: 3060, / (Cllj) / ZOU / (CH) /; 2980; 2950, 2920, 2860) /; 1572 / (C-C) /; 1440/5 (SNg) /; 1370 / (CEZ) /; 1230;

1185; (I (CH, CH) /: 960 / PSN) /; - 860 (C%) /; 5.15 (i) (C-Te) /.

Molecular ion in the mass spectrum of M 186.

Found,%: p. 26.35; H 4.55; Te 69,76

TSNDTe,

Calculated,%: C 26, .15; H 4.39; Te 69,46

Example5. 12.76 g (0.1 mol) of Te, 48.5 g (0.87 mol) of KOH, 24.6 g (0.13 mol) of tin chloride, 12.3 g (0 , 1 mol) isopropyl bromide and 150 ml of water in a one-liter rotating autoclave under acetylene pressure (initial pressure 14 atm, relative - 9 atm / for 5 h. The lower organic layer is separated and distilled in vacuo. Get 6.55 g (50%) of vinyl isopropyl telluride, t, bale 72 C / / 3.7 mm Hg; nj 1.5622.

PMR spectrum (§, MD;, Hz): 7.09 q, 6.35 d; 5.84 d; 3.40 m; 1 yL p-t-Sh 9 TTpOkH-t 17 S

IjDt d, J ltl, C, J J f

Spectrum C (g, MD.I 128.93; .107.87; 26.80; 13.30.

IR CM: 3060 / (SNd) / 3010 / V (CH) /; 2965, 2940, 2915.: -2885 (v-C); 1575 /) (1460 / “CH.2) /; 1378.1365 / (CHj) /; 1235; I195; 1145, C-H5 /; 965 / f (CH) /; 900 / W (CH); 520 /) / (C-Te) /.

Molecular ion in M 200 mass spectrum

 Found,%: C 30.60; H 5.24; Te 64.90

Calculated,%: t 30.37; H 5.09; Those 64.54.

PRI me R 6. Heat at 90-100 ° C in a one-liter rotating autoclave for 5 hours under acetylene pressure. (Initial pressure 13 atm, residual 9 atm) 12.76 g (0.1 mol) Te, 48 , 5 g (0.87 mol KOH, 24.6 g (0.13 mol tin chloride, 13.7 g (0.1 mol) / butyl bromide and 150 ml of water. The lower organic layer is separated and fractionated in vacuo 7.1 g (50% // butyl vinyl telluride) are obtained.

PRI me R 7. Heated at 120-130 ° C 12.76 g (0.1 mol) Te, 48.5 g (0.87 mol) KOH, 24.6 g (0.13 mol) chloride tin, 13.7 (0.1 mol) of butyl bromide and 150 ml of water in a one-liter rotating AB203088

toquelav under pressure of acetylene (initial pressure 13 atm, residual - 8 atm for 5 h. The lower organic layer is separated and fractionated in vacuo. 6.5 g (46%) of butylvinyltelluride are obtained.

PRI me R 8. Heated at 105-1 12.76 g (0.1 mol); Te, 48.5 (0.87 mol.), 24.6 (0.13 mol /

Q of tin chloride, 18.4 g (0.1 mol) of butyl iodide and 150 ml of water in a one-liter rotating autoclave under acetylene pressure (initial pressure 13 atm, residual pressure - 9 atm)

, within 5 hours. The lower organic layer is separated and fractionated in vacuo. 3.2 g of f23% j butylvillintelluride are obtained.

PRI me R 9, Heated at

2Q 105-115 C 12.76 g (0.1 mol) Those

48.5 g (0.87 mol) KOH, 24.6 g (0.13 mol) of tin chloride, 9.6 g (0.1 mol) of butyl chloride and 150 ml of water in a single-liter rotating autoclave under acetylene pressure

(the initial pressure is 14 atm, the residual pressure is 9 atm for 5 h. The lower organic layer is separated and fractionated in vacuo. 1.2 g (8%) of butylvinyltelluride are obtained.

PRI me R 10. Heated at 105-P5 With 12.76 g (0.1 mol): Those. 34.8 g (0.87 mol) of caustic soda,

24.6 g (0.13 mol) tin chloride,

13.7 (0.1 mol) butyl bromide and

35 150 ml of water in a one-liter rotating autoclave under acetylene pressure ((initial pressure 13 atm, residual pressure - 9 atm / for 5 h. The lower organic layer is separated

 and fractionated in vacuo. 2.8 g (20%) of butyl vinyl telluride are obtained. Example 11. Heated at 105-115 With 12.76 g (0.1 mol) Those, 33.6 g (0.6 mol) KOH, 24.6 g

5 (0.13 mole of tin chloride, 13.7 g (0.1 mole of butyl bromide and 150 ml of water in a one-liter rotating autoclave under acetylene pressure

 (the initial pressure is 13 atm, the residual pressure is 9 atm | for 5 hours. The lower organic layer is separated and fractionated in vacuo. 1.4 are obtained (07 a f butyl vinyl teluride).

Example 12. Heated at-10555 12.76 g (0.1 mol) Those, 56 g f, 0 mol / KOH, 24.6 g (0.13 mol) of tin chloride, 13.7 g (0.1 mol butyl bromide and 1.50 ml of water in one 30

51

liter of rotating autoclave under acetylene pressure (initial pressure 14 atm, residual pressure 9 atm) for 5 hours. The lower organic layer is separated and fractionated in vacuo. 7.8 g (.55% jl butyl tinyltelluride) are obtained.

PRI me R 13. Heated at 105-1 12.76 g (0.1 mol), Te, 48.5 g (0.87 mol) KOH, 8.5 g (0.13 mol) zinc, 13 , 7 g (0.1 mol) of butyl bromide and 150 ml of water in a one-liter rotating autoclave under acetylene pressure (initial pressure 13 atm, residual 9 atm) for 5 hours. The lower organic layer is separated and fractionated in vacuo. 4.6 g (32%) butyl vinyl telluridar are obtained.

PRI me R 14. Heated at 105-115 C 12.76 g (0.1 mol) Those, 48.5 g (0.87 mol) KOH, 19.0 g (o., 1 mol) chloride tin, 13.7 g (0.1 mol) of butyl bromide and 150 ml of water in a one-liter rotating autoclave under acetylene pressure (initial pressure 13 atm, residual 8 atm) for 5 hours.

030886

the organic slurry is separated and fractionated in vacuo. 6.8 i (48%) of butyl vinyl telluride are obtained.

PRI me R 15. Heated at 5 105-1 15 with 12.76 g (0.1 mol) Te, 48.3 g (0.87 mol) KOH, 30.4 g (0.16 mol) chloride, tin, 13.7 g (0.1 mol) of butyl bromide and 150 ml of water in a one-liter rotating autoclave under acetylene pressure | (initial pressure 14 atm, residual - 9 atm) for 5 h. The lower organic layer is separated and fractionated in vacuo. Get

15 7.4 (52%) butyl vinyl telluride.

EXAMPLE 16: 12.7-6 g (0.1 mol) of elemental tellurium, 48.5 g are heated at 105-115 ° C in a one-liter rotating autoclave.

20 (0.87 mol) KOH, 24.6 g (0.13 mol) of tin chloride, 13.7 g of 0.1 mol of butyl bromide and 150 ml of water under acetylene pressure / (initial pressure 10 atm, residual 5 atm) in

25 for 5 hours The lower organic layer is separated and fractionated in vacuo. 7.4 g (52%) of butyl vinyl telluride are obtained.

Claims (1)

METHOD FOR PRODUCING ALKYL VINYL TELLURIDES of the general formula CHi = CHTeR, where R-CtHjf, CjH _t , »SO-CjH _? , C (, H _e , characterized in that the acetylene is reacted with tellurium and the corresponding alkyl halide at 90-130 ° C and pressure 10-14 atm in an aqueous alkaline medium in the presence of zinc or tin chloride as a reducing agent in a molar ratio of tellurium, alkyl halide, alkali and reducing agent 1: (0.1-1.0) :( 6-10) :( 1-1, 6). Not*