DE1046031B - Process for the production of vinyl compounds - Google Patents

Description

GERMAN

It has been found that vinyl compounds of the general formula

Method of manufacture
of vinyl compounds

CH ₂ C =
ι CH R - J
R. R.

in which X ₁ and X _{2 are} acyl, carboxyalkyl, carboxyaryl, carboxamide or nitrile groups and R is hydrogen or any aliphatic, cycloaliphatic, aromatic or heterocyclic radical is obtained when acetylene is used in the presence of compounds of subgroup II of the periodic system, especially of salts of these compounds with organic acids, with compounds of the general formula

^R \ / ^X1

CH-C = C '
/ I

^R R

in which X ₁ , X ₂ and R are as defined above.

From the book by W. R ep pe, »New developments in the field of the chemistry of acetylene and Carbon oxides, 1949, vinylation is more diverse of organic compounds known. The explanations open up "the possibility of all connections to vinylate whose active hydrogen is bonded to oxygen; especially the carboxylic acids and even the weaker acidic phenols only give in vinylation under the same conditions resinous compounds. R. C. Fuson refers to such in Advanced Organic Chemistry, 1950 Compounds with active hydrogen, which can form stable sodium or potassium salts, as vinylable. The starting materials used in the process of the invention are not included in any of these connection types mentioned. So it can be described as surprising that the invention Reaction on quaternary carbon atoms, i.e. on those that have no hydrogen atom at all and after the reaction with acetylene carry the vinyl group.

Applicant:

Aniline & Soda Factory in Baden
Aktiengesellschaft, Ludwigshafen / Rhem

Dr. Walter Reppe, Heidelberg,

and Dr. Matthias Seefelder,

Ludwigshafen / Rhine-Oppau,

have been named as inventors

only through a simultaneous or rather preceding, but not foreseeable, shift of the Double bond has become possible. So far there has been no method of making connections which have two unsaturated substituents on such a quaternary carbon atom.

As is known, the starting compounds are obtained by condensation of aliphatic, cycloaliphatic or araliphatic aldehydes or ketones, which contain at least 2 carbon atoms and which have at least 1 hydrogen atom on the carbon atom adjacent to the carbonyl group, with the reactive methylene groups of /? - diketanes, jß-keto acids and ^ -Dicarboxylic acids or their functional derivatives, such as esters, amides or nitriles. Heterocyclic derivatives of these compounds, e.g. B. barbituric acids "dder. Pyrazolones come into consideration. ..---. , .... _:

Examples of these starting materials may be mentioned Ethylidene malonic acid ester, cyclohexylidene malonic acid ester, Isobutylidenecenoacetic acid ester, 5-isopropyl- ~ idenbarbituric acid, isopropylideneacetoacetate, l-phenyl-3-methyl-4-isobutylidene-pyrazolone- (5), isopentylidene acetylacetone, 2 - (phenylethylidene) - cyclo-

hexanedione- (1,3). = " ^: ". - - - - -.

The implementation that z. B. in the case of isopropylidenemalonic acid diethyl ester with Acelon is formulated as follows: ■

CH ₃

CH,

COOC ₂ H ₅

COOC ₂ H ₅

H ₉ C

H ₃ C

/ COOC ₃ H ₅
ru ρ Tj 809 698/539 / \ - -
COOC ₂ H ₅

is carried out in such a way that acetylene in the presence of catalysts on the above Allow starting materials to act.

Suitable catalysts are the compounds of the metals of subgroup II of the periodic Systems; Particularly suitable compounds are those which are soluble in the reaction mixture when working in the liquid state, e.g. B. the salts of these metals with organic acids. Examples are zinc acetate, zinc butyrate, zinc stearate, and cadmium naphthenate and mercury acetate.

The reaction is ⁰ to 200 C, carried out at temperatures of 120 to 300 ° C, preferably from 150 '. It is advantageous to work in the liquid state, the starting materials being used alone or in a mixture with solvents or diluents. Suitable solvents or diluents of this type are in principle all compounds which are heat-resistant under the reaction conditions and are not attacked by the reactants, e.g. B. hydrocarbons or ethers. When working in the liquid state, the acetylene is advantageously used under increased pressure, it being expedient to dilute it with an inert gas or steam. - "" 25

However, the process can also be carried out in such a way that the reactants are brought together passes in vapor form over the fixed catalyst. To obtain the reaction products in its pure form, a simple distillation is usually sufficient. The obtained by this procedure Vinyl compounds can be used to produce polymers in the presence of free radical catalysts be used.

The parts mentioned in the examples are parts by weight.

example 1

520 parts of diethyl isopropylidene malonate are treated together with 16 parts of zinc stearate in a pressure vessel at 180 ° C. with an acetylene-nitrogen mixture in a ratio of 2: 1 under 25 atm. Pressure. The used acetylene is replaced from time to time by pressing in fresh. When the acetylene is no longer absorbed, the pressure vessel is cooled and let down. The liquid reaction product is fractionally distilled, whereby 430 parts of vinylisopropenylmalonic acid diethyl ester of bp ·. ₁₈ = 128 ° C can be obtained, corresponding to a yield of 76% of theory.

Example 2

As in Example 1, 780 parts of isobutylidenemalonic acid diethyl ester together with 25 parts of cadmium naphthenate are treated with acetylene at 180 ° C. under pressure until no more absorption takes place. The fractional distillation of the reaction mixture gives 420 parts of vinyl isobutenylmalonic acid diethyl ester with a b.p. ₁₈ = 138 to 140 ° C., corresponding to a yield of 48% of theory,

Example 3

300 parts Äthylidenmalonsäurediäthylester are mixed with 10 parts of zinc stearate, and in a pressure vessel at 180 ⁰ C with an acetylene-nitrogen mixture 2: 1 under 25 atm pressure treated, longer takes place until no Acetylenaufnahme. The cooled reaction mixture is distilled. 155 parts of diethyl divinylmalonate with a boiling point of ₁₈ = 121 to 126 ° C. are obtained, corresponding to a yield of 34% of theory.

Example 4

260 parts of cyclohexylidenemalonic acid diethyl ester and 8 parts of zinc stearate are treated with acetylene under pressure as in Example 1 at 180 ° C. until no more absorption takes place. The fractional distillation of the mixture gives 200 parts of vinylcyclohexenylmalonic acid diethyl ester with a boiling point of ₀₄ = 116 ° to 118 ° C., corresponding to a yield of 70% of theory.

Example 5

450 parts of ethyl isobutylidenecyanoacetate and 15 parts of zinc naphthenate are treated in the manner described in Example 1 at 180 ° C. with acetylene under pressure until no more absorption takes place. In the fractional distillation of the reaction mixture, 220 parts of vinyl isobutylene cyanoacetic acid ethyl ester with a b.p. ₂₀ = 133 to 138 ° C., corresponding to a yield of 42% of theory.

Example 6

In a pressure vessel, a solution of 240 parts of 1-phenyl-3-meth.yl-4-isopropylidenepyrazolone (5) and 20 parts of zinc stearate in 1000 parts of N-methylpyrrolidone is ^{treated with acetylene at 200 °} C. until no more acetylene is absorbed he follows. Fractional distillation of the mixture gives 70 parts of 1-phenyl-S-methyl ^ -vinyl ^ -isopropenyl-pyrazolone- (5), which pass under a pressure of mm Hg between 155 and 165 ° C.

Claims (1)

Claim: Process for the preparation of vinyl compounds of the general formula = CH X ₁ RC = CX ₂ I I R R characterized in that acetylene is used in the presence of compounds of the IL subgroup of the periodic table, especially the salts of these metals with organic acids, with Compounds of the general formula R_CH-C = C R R in which X ₁ and X ^ are an acyl, carboxyalkyl, carboxyaryl, carboxamide or nitrile group and R is hydrogen or an aliphatic, cycloaliphatic, aromatic or heterocyclic radical, at 120 to 300 ° C in liquid or in vapor form .stand, optionally in the presence of solvents or diluents, reacted. Considered publications:
W. Repp> e, New Developments in the Field the chemistry of acetylene and carbon dioxide, 1949, P. 3 and following sections; R. C. Fuson, Advanced Organic Chemistry, 1950, Pp. 74 to 76. © 809 698/539 12.58