SU740784A1 - Method of preparing 2-halogenvinyloxyorganosilanes - Google Patents

Description

The invention relates to a new method for producing new 2-halovinyloxyorganosilanes of the general formula I

XCH-CHOS-i R _n (OB ' _at (1) 5 where B and R' are lower alkyl,

X - halogen, η - 2 or 3, 2-Halo vinylvinyloxyorganosilanes of formula 1 are highly active, 10 polyreaction compounds and can be used as intermediates for the multipurpose use in the synthesis of various substances and materials with .15 given practically valuable properties (plasticizers, coatings, special oils , rubber modifiers, biologically active agents, etc.), as well as in the chemical, oil, rubber, electrical, and pharmaceutical industries.

There is a method of obtaining énilOK-25 sisilanes by the interaction of organochlorosilanes with mercurbisacetaldehyde, BUT because of the high toxicity of the latter, it has not been widely used in practice and is not acceptable for the preparation of 2-halogenvinyloxyorganosilane [1].

A known method of producing vinyloxytrialkylsilanes by the interaction of trialkylsilanols with acetylene [2].

A known method based on the interaction of organochlorosilanes with vinyl acetate, but it is applicable to obtain vinyloxyorganosilanes [3]

There is also known a method consisting in the implementation of bistrialkylsilyl mercury with trichloroacetaldehyde _t and allowing to obtain only 2,2-dichlorovinyloxytrialkylsilanes [43. In addition, due to the use of unstable, inaccessible and highly toxic trialkylsilyl derivatives of mercury, it has very limited capabilities and is not promising for practice.

The aim of the invention is to develop a method for producing previously unknown 2-halogenvinyloxyorganosilanes of the formula I, suitable for the targeted synthesis of various practically valuable organic and organosilicon substances and polymeric materials.

This goal is achieved by the fact that 1,2-dihaloethoxyorganosilane is reacted with a tertiary amine in an aprotic organic solvent at a temperature from room temperature to the boiling point of the reaction mixture.

As tertiary amines use triethylamine, pyridine, dimethyl. Nilin ^ quinoline, diethylaniline. However, in practice it is very convenient to use triethylamine as a dehydrohalogenating agent.

Dehydrohalogenation of 1,2-dihaloethoxyorganosilanes with a tertiary amine proceeds easily with an equimolecular reagent ratio or with a slight excess ’(5-10%) of the tertiary amine. The reaction is exothermic and is accompanied by the grinding of products. Therefore, the interaction is best carried out when cooling with ice water in an environment of aprotic organic solvents (ether, benzene, etc.). With a significant amount of solvent, the thermal effect of the reaction is small, and to complete the reaction, additional stirring of the reaction mass at room temperature for 10-12 hours or when heating the reaction mixture for 3-5 hours at 35-40 ° C is required,

The yield of 2-halo-vinyloxyorganosilanes is from 60 to 90%.

'2-Chlorvininyl oxy and 2-bromovinyl ox 1 (silanes are colorless, easily mobile, volatile liquids which are not miscible with water, well soluble in organic solvents,

The individuality, composition and structure of the obtained 2-gridvinyloxyorganosilanes are confirmed by elemental analysis, physicochemical methods (GLC, IKS) and chemical transformations,

According to GLC (LHM-7A instrument, detector-katharometer, column thermostat temperature is 50-70 ° C lower than the boiling point of the studied compounds, the carrier gas is helium, the column length is 3 m, the inner diameter of the column is 4 mm, the stationary phase is Apieson L ( 5%) on an N-AWHMDS chromaton silanized with hexamethyldisiloxane / 98–99.5% purity. IR spectra (IR spectra of the compounds were recorded on a spektromom-2000 instrument in a thin layer between sodium chloride plates) 2-halo-vinyloxyorganosilanes there is absorption of strong intensity in the region (see j 1645-1635 ( Si-O-CH-CH-), 1250, 850, 760 '> ((СНа) Si), 1260 ((СНо>) ₂ Si), 10901020 (Si-OC).

When boiling 2-chlorovinyloxytrimethylsilane with a 2% aqueous solution of sulfuric acid, it hydrolyzes to form chloroacetaldehyde and hexamethyldisiloxane, which confirms the structure of the starting compound.

EXAMPLE e ^- p 1 2-Hlorviniloksitrimetilsilan.

11.1 g (0.059 g · mol) of 1.2 dichloroethoxytrimethylsilane, 30 ml of benzene are added to a synthesis apparatus equipped with a stirrer _f thermometer, reflux condenser and dropping funnel, and 6.1 g (0.06 g mol) are added with constant stirring. ) triethylamine. The reaction mixture is heated to 60 ° C. Cooling the reaction mass with water, stir for 10 hours at room temperature. Then the precipitate is filtered off and washed with benzene. Distillation of the filtrate in vacuo under a stream of nitrogen yields 5.7 g (60%) of 2-chlorovinyloxytrimethylsilane with so on. 40.5 ° C / 21 mm Hg. Art., d? ° 0.9724, _and ² ® 1.4227.

Found,%: C 40.09; H 7.60; Cl 24.03; Si 18.30. '.

C & JS 1 Si ’'

Calculated,%: C 39.85; H 7.32; C1 23.59; Si 18.61.

Example 2. 2-Bromovinyloxytrimethylsilane.

Similarly, to a solution of 17.4 g (0.063 g · mol) of 1,2-dibromethoxytrimethylsilane in 60 ml of dry ether, 6.6 g (0.065 g · mol) of triethylamine are added. The reaction mixture is heated to -36 ° C. Then the reaction mixture is boiled at this temperature for 0.5 hours. After cooling, the precipitate is filtered off and washed with ether. Distillation of the filtrate in vacuo in a stream of nitrogen yields 9 g (74%) of 2-bromovinyloxytrimethylsilane with bp __ 41.5-42 ° С / 11mm Hg, st,, С (d ° 1.2312, '6 ^ 1, 4520,

Found,%: C 31.08; H 5.83; Vg 40.81; Si 14.35 ,,

C ^ H ^ OBrSi

Calculated,%: C 30.80; H 5.64; Wh 41.10; Si 14.36.

Example 3. 2-Chlorvinylside methylethoxysilane.

To a solution of 3.7 g (0.017 g · mol) of 1,2-dichloro-TC5 <sydimethyl, then in 20 ml of benzene 1.17 g (0.017 g · mol) of triethylamine are added. The mixture was heated at 4 ° C for 4 hours. After the usual work-up (example 1), vacuum distillation under a stream of nitrogen yielded 1.9 g (62%) of 2-chlorovinyl oxydimethylethoxysilane with so on. 5b ° C / 10 mmHg, Art. 1.0121, P ^ 1.4236.

. Found,%: C 40.3ί; H, 6.90;

Cl 19.23; Si 15.11.

C ^ O ^ ClSi. Calculated,%: С 39.95; .Н 7.20;

C1 19.67; Si 15.52.

Example 4. 2-Chlorvinyl hydroxymethylpropoxysilane.

To t>, sg (0.02 7 'gmol) of 1,2-dichloroethoxymethylmethoxypropoxysilane. 2.76 g (0.027 gmol) of triethylamine are added to 25 ml of benzene. The mixture is left to stand for -12 h at -room temperature. Then 5 to complete the reaction, heat 1 h at 40 ° C. After the usual processing. By distillation in vacuo under a stream of nitrogen, 3.6 g (68%) of 2-chlorovinyloxymethylpropoxysilane is obtained, bp. 59 ⁶ C / 7 mmHg Art. , 0 ^ 0.9981.13 ^ 1.4280.

Found,%: C 43.81; H, 7.30; Cl, 18.30; Si, 14.80.

C ₇ H _l5 O ₂ ClSi

Calculated,%: C 43.20; H 7.72; , ς

Cl 18.25; -Si ^{14, E}

PRI me R 5. * 2-Bromovinylhydroxymethylpropoxysilane.

To 22.5 g (0.07 g-mol) of 1,2-dibromoethoxymethylpropo. Xysilane in 30 ml of ether, 7.12 g (0.071 g; 'mol) of triethylamine are added. There is a warming up of the reaction mixture and a slight boiling of ether. After cooling, the reaction mass was left to stand at room temperature for 12 hours. After normal processing, 13.9 g (83%) of 2-bromovinylhydroxymethylpropoxysilane with a boiling point of 70-71 ^a C / 7 mm Hg were isolated. Art., 2060, Ps§ 1.4462.

Found,%: C 35.40-; H, 6.61; 3Q

VG 33.60; Si 11.58. ‘.

C-jH ^^ BrSi

Calculated,%: C 35.15; H 6.27; Vg 33.47; -Si 11.71.

PRI me R 6. 2-Chlorovinyloxy-35 dimethylbutoxysilane.

Obtained from 7.4 g (0.03 g mol)

1,2-dichloroethoxymethylbutoxysilane and 3.52 g (0.035 g · mol) of triethylamine in 40 mp ether. Yield 3.9 g of 4Q (63%), t. 74 ° C / 7 mm Hg St., J? b, 9775.13 ^ 1.4293.

Found,%: C 46.30; H, 8.10; C1, 17.35; Si 13.30.

CgH ^ ClSi

Calculated,%: C 46.10; H 8.15;

Cl 17.03; Si 13.44.

Example 7, 2-Bromovinyloxymethylbutoxysilane.

Obtained from 16.1 g (0.042 g mol)

1.2-dibromoethoxymethylbutoxysilane and 5.35 ir (0.053 g · 'mol) of triethylamine in 35 ml of ether.' Yield 11.2 g (90%), t. 81 ° C / 7 mmHg. st., 3 ^ 1.1792, hp’1.4473, s Found,%: C 38.15; H 6.93; Br 31.30, SL 10.71.

CgHj-, Ο, ^ Br S1, Calculated,% f C 37.92; H 6.72;

Wh 31.65; Si 11.06,

Claims (1)

This invention relates to a new process for the preparation of new 2-halo-vinyloxy-organosilanes of a common formula XCH-CnOS-i Well, (0y) s-n where R and R are lower alkyl, X is halogen, and - 2 or 3, 2-Haloidvinyloks, and organo-forces E of formula 1 are highly active polyreaction compounds and can be used as intermediate multi-purpose products in the process of synthesizing various substances and materials with desired properties (plasticizers, coatings, spetsmassel, rubber modifiers, biologically active agents, etc.) in the chemical, petroleum, rubber-engineering, electrical engineering and pharmaceutical industries. The known method is the preparation of zinyl sisilanes by reacting organochlorosilanes with mercurby acetal gol dom, but the CIVIL high toxicity of the latter has not found wide application in practice and is not acceptable for producing 2-halogenvinyloxyorganosilanes 1. There is a known method for the production of vinyloxytrialkylsilanes by reacting trialkylsilane dhislohydrinsolenes. the interaction of organochlorosilanes with vinyl acetate, but it is applicable to the preparation of vinyloxyorganosilanes 3, It is also known that the method consisting in alizatsii bistrialkilsililrtuti with trichloroacetaldehyde., and allowing the receive only 2,2-dihlorviniloksitrialkilsilany 4. Furthermore, due to the use of low stability, and highly .trudnodostupnyh trialkylsilyl derivatives of mercury, it has very limited capacity and is promising for practice. The aim of the invention is to develop a method for producing previously unknown 2-halo-vinyloxy-organosilanes of formula I, suitable for the targeted synthesis of various practically valuable organic and organosilicon substances and polymeric materials. This goal achieves that 1, 2-dihaloethoxy-or-sorcosilane can be reacted with a tertiary amine in an aprotic organic solvent at a temperature from room temperature to the boiling point of the reaction mixture. As tertiary amines, triethylamine, pyridine, dimethylaniline quinoline, diethylanylCH are used. However, in practice it is very convenient to use triethylamine as a dehydrohalide and a cursory agent. The dehydrohalogenation of 1,2-dihaloethoxyorganosilanes with a tertiary amine readily proceeds at an ec / minimal ratio of reagents or with a slight excess (5-10%) of tr amine. The reaction is exothermic and is accompanied by the resinification of the product. Therefore, the interaction is best carried out when cooled with ice water in aprotic organic solvents (ether, benzene, etc.). With a significant amount of solvent, the thermal effect of the reaction is small, and to complete the reaction, additional stirring of the reaction mass is required at room temperature for 10–12 h or when heating the reaction mixture for 3-5 h at 35–40 s, the yield of 2-halogenovyloxyorganosilanes from 60 to 90 % The 2-vinyl vinyloxy- and 2 bromovinyls silans are colorless, highly mobile, volatile, 1H-ge fluids, not miscible with water, highly soluble in organic solvents. The individuality, composition, and structure of the 2-halo-vinyloxyorganosilanes obtained are confirmed by elemental-analysis, physico-physical, 2-halo-vinyloxyorganosilanes, confirmed by elemental-analysis, physico-physical 2 methods mi (GLC, IR) and chemical transformations. According to GLC (LHM-7A device, detector-catarometer, column thermostat temperature 50–70 ° C below the boiling temperature of the compounds &amp; x compounds, carrier gas — helium, dl: And for columns 3 m, internal diameter of the column 4 mm, Apiason L stationary phase (5%) on N-AWHfJDS chromatone silanized with hexamethyldisiloxane / 98-99.5% purity of the substances obtained. In the IR spectra (IR spectra of the compounds were recorded on a spektromom-2000 instrument in a thin layer between chloride plates sodium) 2 - halogenvinyloxyorganosil absorption of strong intensity in the region (with ) 1645-16 (Si-0-CH-CH-), 1250, 850, 760 ((СНа) Si), 12bO (((СНо,) 2 Si) f 10901020 (S1-OC). When boiling 2- chlorvinyloxy-trimethylsilane with a 2% aqueous solution of sulfuric acid is hydrolyzed to form aldehyde chloracet and hexamethyldisiloxane, which confirms the structure of the starting compound. Example 1, 2-Chloroxyloxytrimethylsilane. In a synthesis instrument, remove agitator :, With a thermometer, reflux condenser and addition funnel, 11.1 g (0.059 g-mol) of 1,2 dichloroethoxytrimethylsilane, 30 benzene are placed and, with constant mixing, 6.1 g (0.06 g-m) are added. l) of triethylamine. The reaction mass is heated to 60 ° C. Cooling the reaction mass with water is stirred for 10 hours at room temperature. Then the precipitate is filtered and washed with benzene. By distillation of the filtrate under vacuum in a stream of nitrogen, 5.7 g (60%) of 2-chlorovinyloxytrimethylsilane are obtained with a bale. 40.5С721 t.iM рт. st, d4 ° 0.9724,, 4227. Found,%: C 40.09; H 7.60; C1 24.03, Si 18.30 ,, C H .OClSi Calculated,%: C 39.85. H 7.32 C1 23.59 Si 18.61. Example 2, 2-Bromovinyloxytrimethylsilane. Similarly, to a solution of 17.4 g (0.063 g-mol) of 1,2-dibromoethoxytrimethylsilane in 60 ml of dry ether was added 6.6 I (0.065 g "mol) of triethylshna. The reaction mass is heated to 36 ° C. The reaction mixture is then boiled at a temperature of 0.5 hours. After cooling, the precipitate is filtered off and washed with ether. By distillation of the filtrate under vacuum in a stream of nitrogen, 9 g of (741) 2-bromovinyloxytrimethylsilane were obtained with a bale. 41, 5-42 ° s / 11mm Hg. cT ,, dl ° 1.2312, 1.4520. Found, -%: C 31.08; H 5.83; Br 40.81, - Si 14.35 ,, CgH OBrSi Calculated: С 30.80; H 5.64; VG 41.10; Si 14.36. Example 3. 2-Chlorovinyl xydimethyl ztoxruilane. To a solution of 3.7 g (0.017 g-mol) of 1,2-dichloro-5-sidymethylethoxysilane. In a 20 g-t of benzene, 1.17 g (0.017 Gmol) of tris ylamine was added. The mixture is heated at 40 ° C for 4 hours. After the usual treatment (example 1) by distillation in a vacuum in a stream of nitrogen, 1.9 g (62%) of 2-chlorovinyl oxydimethyl ethoxysilac are obtained with a boil. mm Hg, st. ,, 0121,, П5 °. , 4236,. Found,%; C 40.31; H 6.90; Cll9.23, Si 15.11. Calculated,%: C 39.95; H 7.20; C1 19.67; Si 15.52. Example 4. 2-Chlorovinyl-oxydimethylpropoxysilane. K b, J g (O, 027 t-mol) of 1,2-dichloroethoxyd and 4-ethylpropoxysilane. 2.76 g {0.027 g-mol) of trinethylamine is added to 25 ml of benzene. The mixture is left to stand for -12 hours at-room temperature. Then, to complete the reaction, it is heated for 1 hour at 40 ° C. After usual treatment by distillation in vacuum in a stream of nitrogen, 3.6 g (68%) of 2-chloroium and oxymethyl propoxy silane are obtained. Art. ,, 9981, p, 42 Found,%: 43.81; H 7.30; C1 18.30, Si 14.80. Calculated,%: C 43.20; H 7.72; C1 18.25; -Si 14.4X Pr m and m p 5, Bromovinyloxide methylpropoxysilane, K 22.5 g (0.07 gmol) 1,2-dibro ethoxydimethylproxysilane in 30 m of ether, add 7.12 g (0.071 The reaction mixture and the weakening of ether take place. After cooling, the reaction mass is left to stand at room temperature for 12. After the usual treatment, 13.9 g (83%) of 2-bromovinyl oxydimethyl propoxy sulphate are separated. t, kip, 70-71 mm Hg, cent., d4 1/2060, 4462. Found: C 35.40; H 6.61; Br 33.60; Si 11.58. Calculated,% : C 35.15; H 6.27; Br 33.47; -Si 11.71. Example 6, 2-chlorovinyl-oxydimethylbutoxysilane. learn from 7.4 g (0.03 g-mol) of 1,2-dichloroethoxydimethylbutoxysi-Lane and 3.52 g (0.035 g-mol) of triethyl amine in 40 ml of ether. Yield 3.9 g (63%), t.kip, 74 ° С / 7 mm Hg, cent., Dfb, 9775, 4293. Found: C, 46.30; H 8.10; C1 17.35; Si 13.30. Calculated,%: C 46.10 ; H 8.15; C1 17.03, Si 13.44. Example 7. 2-Bromovinyl oxydimethylbutoxysilane. Prepared from 16.1 g (0.042 g-mol) 1.2 dibrmethyl6 dimethylbutoxysilane and 5.35ir (0.053 g-mol) triethylamine in 35 ml of ether / Yield 11.2 g (90%), t, kip, 81 ° С / 7 mm Hg, cent.,, 1792,, 4473. S Found,%: C 38.15; H 6.93f Br 31.30, Si 10.71. , 2, BrSi, Calculated,% g C 37.92; H 6.72; Br 31.65; Si 11.06, Claim 1, Method for producing 2-halo-vinylsio-organosilanes of the general formula CHF -CHOSiR (OR), where R and R are lower alkyl, X is halogen, P g; 2 or 3, 3 included in the fact that 1,2-dihaloethoxyorgansilane is reacted with a tertiary amine in an aprotic organic solvent at a temperature ranging from KONAT to boiling point of the reaction mixture. Sources of information taken into account during examination 1, Nesmenov A , N, Lutsenko, I, F, Vrattsev.V.A. Vinyloxysilanes, DAN SSSR, 1959, 128, p. 551, 2, USSR Copyright Certificate No. 132223, cl. C 07 F 7/18, i960. 3, USSR Author's Certificate No. 570614, cl. C 07 F 7/18, 1977, 4.,. LJaeshiepp G. Nemnann W.P. Preparation of 2,2-dichlorovinyloxytriapkililanes -.Organometal. Chem 972, 41, 277.