DE1178063C2 - METHOD FOR PRODUCING VINYL COMPOUNDS - Google Patents

Description

The divinylzine had a boiling point of _2i = - 32 ° C.

Example 2 Divinyl mercury

4 moles of vinyl magnesium chloride in tetrahydrofuran solution were placed in a flask with a capacity of 5 liters brought in. It was refluxed

According to the invention a method for
Manufacture of vinyl compounds from vinyl magnesium halides and metal or metalloid 25 filtered. The divinyl zinc was proposed in tetrahydrofuran compounds according to Grignard, kept in a nitrogen atmosphere in solution, which is characterized in that one
Halide or an organohalogen compound one
Element of the IV. Or V main group with a
Ordinal number above 13 or the II. Subgroup of the 3 °
Periodic table with a tetrahydrofuran complex
of the vinyl magnesium chloride, the vinyl group being replaced by aliphatic radicals and in the - «position
can also be substituted by chlorine.

The vinyl magnesium chloride complexes have the following 35 whereupon the addition of 453.6 g (1.671 mol) of mercury

The following formula: silver chloride in 1 l of tetrahydrofuran followed. Outer

\ r \ xr \ r »Warming was during the addition of which

ViMgCl · nQ took 2 hours to complete, not applied.

The reaction mixture was then taking 8 hours

where Vi heated an optionally by aliphatic 40 reflux, followed by the addition of 500 ml of residues and in the α-position also by chlorine substituted water. The hydrolysis led to an aqueous vinyl radical, η denotes an integer from 1 to a layer, an oil phase and a pasty solid-3 and Q stands for tetrahydrofuran. This substance at the bottom of the flask. The solid was treated with vinyl magnesium chloride complexes, solvent treated, and distilled to produce the corresponding ViCl with Magne-45 divinyl mercury (59 ^D / o yield). The sium in the presence of tetrahydrofuran as the reac- theoretical Hg value was 78.77 ⁰ Zo; found tion medium is implemented.

The following equation applies to reactions of a metal salt of subgroup II with vinyl magnesium chlorides:

2ViMgCl · nQ 4- MX ₂ -> 2MgClX f Vi ₂ M + 2nQ where Vi is a vinyl radical of the type specified above,

theoretical Hg value
were 77.3 ⁰ zo.

Example 3 Diphenyl Divinyl Tin

A solution of 196 grams (0.625 moles) of diphenyltin dichloride in 1 1 heptane-octane mixture was entered into a three-necked 3-1 bottle, which with a Stirring device, a dropping funnel and a

X halogen, η a number between 1 and ~ 3 and M a 55 reflux condenser was fitted. A solution from Metal of the II. Subgroup means. 1,344 moles of vinyl magnesium chloride tetrahydrofuran

Metal salts of main group IV with complex in tetrahydrofuran became dropwise to vinylmagnesium chlorides given according to the following equation. The mixture was then refluxed for an additional 3 hours. After cooling down

VIW η η -ι- ώ 'luv ^{6o WUR} ^ ^e poured the reaction mixture in water,

a ■ ViMgU · nU + K _y MA ₄ . acidified _{y something with} s _a i _zsäure. From the

-> Vi _e R _y 'MX _4. (J, _{+ e)} + nQ organic layer were 21 g of phenyltrivinyltin

obtained under a pressure of 1.1 torr at

where Vi, X and η boil the same meanings as about 80 to 85 ° C, and 107 g of diphenyldivinylobene have, M is a metal of main group IV 65 tin with a boiling point of about 139 ° C and R 'is a monovalent organic radical , 1.2 torr. The yields based on tin with an integer from 0 to 3, α an integer 12.1% for phenyltrivinyltin and 52.4% for from 1 to 4, iy + a) is an integer from 1 to 4 . Diphenyl divinyl tin.

Example 4 Tributyl vinyl tin

By reacting 0.8 mol of tributyltin chloride with 1.03 mol of vinylmagnesium chloride-tetiahydrofuran complex in accordance with the procedure of Example 3, tributylvinyltin, boiling point ₆ = 133 ° C., was obtained in 82% yield.

Example 5 Tetravinyltin A solution of vinyl magnesium chloride complex

the 81g divinyltin dichloride, boiling point _x = 46 ° C, obtained. This corresponded to a yield of about 35%.

Example 8

Tetravinyl lead

2 moles of vinyl magnesium chloride complex were slowly added to 1 mole of lead chloride suspended in tetrahydrofuran. After the addition was complete, the mixture was refluxed for 4 hours. It was then cooled and _{filtered off from the MgCl 2} and lead. The solvent was driven off and that consisting of tetravinyl lead

Example 9

Trivinyl Arsenic

In a flask with a capacity of 5 1, 121 g (0.667 moles) of arsenic trichloride in 11 Pentane introduced. For this purpose, at a rate at which mild reflux was maintained.

in tetrahydrofuran, previously obtained by reacting

4g atoms of magnesium with 4Mol vinyl chloride, product distilled under vacuum; Kp. ,, 69 to 70 ° C. Dissolves in tetrahydrofuran, which had been prepared
was placed in a three-necked 5-1 bottle,
which with a stirrer, a dropping funnel
and a reflux condenser cooled with dry ice
was equipped. In the course of 2 ¹ »hours was 20
a solution of 208 g to the contents of this vessel
(0.8 mol) of tin tetrachloride in petroleum ether was added.
Then the mixture was 8 ¹ Z; Stirred under reflux for hours. She was then turned into a mix of

150 ecm of concentrated hydrochloric acid and 4 l of water was obtained, 2.4 mol of vinyl magnesium chloride in poured. Two liquid layers formed. 864 ml of tetrahydrofuran added. The reflux The organic layer continued on its own over sodium sulfate until 2.2 moles of vinyl dried and then distilled. After the magnesium chloride has been added. According to solvent The reaction was terminated at atmospheric pressure (4 hours) 100 g of crude tetravinylation mixture were refluxed for a further 2 hours tin distilled off under vacuum. This compound is heated and then left to stand overnight. the contained 48.7% tin (theoretical 52.3%). The solution was removed from the saline under nitrogen prey was thus around 50%. The reaction mixture is filtered off. To which salt became

In another attempt in which water was attempted to be added; a was, the distillation under atmospheric pressure 35 organic layer and an aqueous layer which to terminate, polymerization suddenly occurred containing a dispersed solid phase. The organic

Layers were separated, dried and decanted. The aqueous layer was acidified, causing the solid phase to dissolve; an organic layer and an aqueous layer remained. The organic phases were combined and fractionally distilled. The yield of trivinyl arsenic was 39.6%; Κρ. _7β0 = 122 to 124 ° C. The theoretical As value is 48.0%;

hydrofuran complex (0.7 mol) "found in tetrahydrofuran 45 was 47.76%. was added dropwise to a mixture of 522 g
(2 mol) tin tetrachloride and 1 1 heptane-octane mixture added in a three-necked 3-1 bottle,
those with a stirrer, a dropping funnel
and reflux condenser. After the 5 °
The reaction mixture was added for 30 minutes
heated to reflux. She was then overnight
left standing, and the solid matter, which is
deposited were from the solution

filtered off. The filtrate was from the solvents 55 vinyl magnesium chloride. During the first part freed, with a black liquid residue before the addition, the heat of reaction was sufficient, stayed. Distillation was used to vigorously reflux the residue. As about Vinyl tin trichloride with a boiling point of 168 2.5 equivalents of vinyl magnesium chloride (1.67MoI) until 170 ° C obtained at atmospheric pressure had been added (2 hours addition until (28 ° C at 1.2 torr). The yield was about 45% 60 at this point) the reflux stopped. The addition the theory. was adjusted and the reaction mixture became

Heated under reflux for 2 hours. The remaining vinyl magnesium chloride was then added. The reaction mixture was left to stand overnight and then hydrolyzed to give an aqueous phase and a solid phase. The solid phase contained trivinyl phosphorus, 86.9% yield; Κρ .. _β0 = 116.6 ^ο α

the crowd. By analysis it was found that the product in this case consists essentially of polytetravinyltin duration.

Example 6 vinyl tin trichloride A solution of vinyl magnesium chloride tetra

Example 10 Trivinyl Phosphorus

In a flask with a capacity of 5 l was 91.6 g (0.667 mol) of phosphorus trichloride and 1 1 pentane introduced. To this, 800 ml of vinyl magnesium chloride in tetrahydrofuran was added. The tetrahydrofuran solution contained 2.2 moles

Example 7

Vinyl tin dichloride

Following the procedure of Example 6, 2.06 moles of vinyl magnesium chloride tetrahydrofuran were obtained implemented with 2 mol tin tetrachloride. This was

Example 11

Trivinyl antimony

228 g (1 mol) of anionic trichloride were dissolved in 1.5 l of tetrahydrofuran in a flask with a capacity of 5 l. 1.5 l of a solution of vinyl magnesium chloride in tetrahydrofuran (3.0 normal) were added dropwise with stirring over the course of one hour. The vessel temperature rose to 60 ° C. during the addition. The solution was stirred for 2 hours without cooling. There were added 700 cc of water is added slowly, and the mixture was cooled so that the temperature did not exceed 30 ⁰ C. The mixture separated into aqueous and organic layers. The organic layer was separated and filtered to give a clear orange fitrate. The filtrate was fractionally distilled under vacuum and the sample which passed at 62-64 ° C and 46 torr was collected. This sample weighed 43 g (21.5% yield) and upon analysis showed 58.58% Sb (theoretical value 60.01%).

Claims (2)

Patent claims: 1. Process for the production of vinyl compounds of vinyl magnesium halides and metal or metalloid compounds according to Grignard, characterized in that one is a halide or an organohalogen compound of an element of main group IV or V with an ordinal number above 13 or the II. subgroup of the periodic table with a Tetrahydrofuran complex of vinyl magnesium chloride converts, with the vinyl group through aliphatic radicals and can also be substituted in a position by chlorine. 2. The method according to claim 1, characterized in that that one works in tetrahydrofuran as a solvent. Metal or metalloid derivatives of main group V are followed by vinyl magnesium chloride the following equation: a -ViMgCl · nQ -r MX ₃ -> - Vi ₀ MX ₃ . _a + nQ wherein Vr, X and η have the same meanings as above, α represents an integer from 1 to 3 and M denotes an element of main group V. The invention is explained in more detail in the following examples. All examples were carried out under an oxygen-free, dry nitrogen atmosphere. Example 1 Divinyl Zinc 1 mole of vinyl tetrahydrofuran complex in an excess of tetrahydrofuran became slow added to a stirred slurry of 0.5 moles of anhydrous zinc chloride in tetrahydrofuran. After the addition was complete, the mixture was refluxed for 4 to 5 hours warmed up. The mixture was then cooled and