DE1133720B - Process for the preparation of non-conjugated polyenecarboxylic acids or their esters - Google Patents

Description

The invention relates to a method of manufacture of polyenecarboxylic acids with non-conjugated double bonds or their esters of the general Formula:

R- (CH = CH-CH ₂ -CH = CH-COOR ') »

In this formula, R, if η = 1, denotes hydrogen or an alkyl radical having 1 to 20 carbon atoms optionally substituted by a carbalkoxy, acyloxy or nitrile radical, if η = 2, an optionally substituted alkylene radical as above, R 'is hydrogen , an alkyl, cycloalkyl or aralkyl radical having 1 to 20 carbon atoms and η the number 1 or 2. The process according to the invention consists in that a compound of the general formula

R - (CH = CH - CH ₂ C1) "

have R and η are as defined above, at temperatures from 0 to 75 ° C, preferably between 25 and 6O ⁰ C, at ordinary pressure with an excess mixture of acetylene and carbon monoxide, which comprises from 50 to 75 ° / o acetylene, with nickel carbonyl in a ratio of 0.1 to about 1 mol per 1 mol of total carbon monoxide bound in the resulting polyenecarboxylic acid and with an excess aliphatic, cycloaliphatic or araliphatic alcohol with 1 to 20 carbon

of non-conjugated polyenecarboxylic acids

or their esters

Applicant:

Montecatini Societä Generale per l'Industria Mineraria e Chimica, Milan (Italy)

Representative: Dipl.-Ing. Dipl.-Chem. Dr. phil. Dr. techn.

J. Reitstötter, patent attorney,

Munich 15, Haydnstr. 5

Claimed priority:

Italy of October 10, 1957 (No. 14 486),

January 8, 1958 (No. 164) and April 24, 1958 (No. 6417)

Gian Paolo Chiusoli, Milan (Italy),
has been named as the inventor

Produce pressure in a single step. The polyenoic acids and their esters are therefore easily accessible.

atoms or with water, optionally in counter-30 They can easily be converted into saturated carboxylic acids convert from an organic solvent and / or by conventional hydrogenation processes, of a hydrogen chloride binding agent. It is already known that acetylene with carbon

The method according to the invention allows monoxide in the presence of compounds that are active to produce straight-chain compounds that contain 3 carbons and hydrogen, and catalysts in unstoffatome contain more than 35 saturated acids can be converted as starting materials. It is used chlorine compounds. also known that this carbonylation occurs in

The method according to the invention leads to low or normal or elevated pressure polyene carboxylic acids or their esters, which can be carried out on others.

Way so far not or only cumbersome or difficult. Furthermore, it is known that vinyl chloride, its

was able to produce. For such a production 40 homologues and substitution products with metal one would have to e.g. B. aliphatic or olefinic carbonyls in the presence of carbon monoxide «, / 9-bonds that contain 1 carbon atom less than the desired polyenecarboxylic acids (if included
other isomers could be formed), chlorinate,
then split off hydrogen chloride, then water cyanide 45
add substance and then the nitrile formed
saponify.

In contrast, according to the invention, a large number of polyenecarboxylic acids or their Esters under very simple conditions, namely at moderate temperatures, preferably at room temperature or above, below atmospheric supply saturated carboxylic acids or their esters.

Finally, it is known to produce diene and polyenoic acids by the so-called "ylid process".

As an experiment has shown, vinyl chloride, which is already used for the production of unsaturated, behaves Carboxylic acids has been used, unlike the allyl chlorides used in the invention. That The result of this experiment is given below.

The previously known processes for the preparation of unsaturated carboxylic acids are not general Application capable as the method of the invention.

209 627/339

A known method for producing polyenecarboxylic acid ester ^ in which one acetylene in the liquid state with acrylic acid ester »in the presence of Reacts catalysts, must be carried out under increased pressure, which is a considerable disadvantage has to apply to the method of the invention.

Furthermore, this process only leads to esters of hepta-2,4,6-trien-l-acid, i.e. a single carboxylic acid, while a variety of the carboxylic acids can be prepared by the process of the invention.

The method of the invention is shown schematically by the following equation:

Ni (CO) ₄

R- (CH = CH-CH ₂ Cl) _n + (CO + C ₂ H ₂ + ROH) _n R- (CH = CH-CH ₂ -CH = CH-COOR ') »+ (HCl) _n

R, R 'and η have the meanings mentioned above.

The temperature range for carrying out the process of the invention depends on the reactivity of the individual allyl chlorides and alcohols used and is particularly between 25 and 60 ° C.

The carbon monoxide needed for the production is supplied by the nickel carbonyl, and besides Gaseous carbon monoxide is introduced into the reaction chamber at the same time as acetylene.

The nickel carbonyl does not have to be used in stoichiometric amounts in order to make nickel chloride through Implementation with the allyl chloride as the starting material, but it's just renewing those Amounts of nickel carbonyl necessary, which on

other way to be lost by side reaction.

The nickel carbonyl is added in such quantities

set that the reaction with the allyl chloride does not

is disturbed. The converted into nickel chloride

Nickel carbonyl is only part of the total

set carbonyls. One part acts as a catalyst

in the actual reaction. The excess on

Nickel carbonyl about the required for the implementation

Amount is re-generated with the flowing gases

removes which, if necessary, can be reintroduced

can be set.

The following formula shows the effect of nickel carbonyls in the process of the invention:

R-CH = CH-CH ₂ Cl + C ₂ H ₂ + Ni (CO) ₄

RAW

CO CO

I ⁺

CO-CH = CH-CH ₂ -CH = CH-Rj Cl "

CO

-> Ni (CO) ₄ + R'OOC - CH = CH - CH ₂ - CH = CH -

HCl

According to the invention, 1 mole of an allyl chloride reacts with 1 mole of acetylene and 1 mole of carbon monoxide and 1 mole of the monohydric alcohol.

The chlorine of these allyl chlorides reacts easily with nickel carbonyl and gives, for example, dimeric Allyl derivatives and nickel chloride. The consumption of nickel carbonyl therefore varies depending on the reactivity of the allyl chloride, which is why the amount of carbon monoxide supplied in gaseous form Is subject to fluctuations.

Another cause of side reactions is the presence of hydrochloric acid, its effect but can be neutralized either through the use of buffer substances, such as magnesium or calcium carbonate or monosodium phosphate, or from inert solvents such as acetone, glycoJ ether or diethyl ketone.

The use of solvents also serves to prevent the formation of a homogeneous reaction mixture to facilitate this, if this is due to the difficulty in loosening the reactants necessary is.

The same alcohol which is added as a reactant can be used in large excess can be used in order to obtain both a good solubility and thereby the free Hydrochloric acid dilute, causing saponification reactions can be avoided during implementation. ...

This precaution becomes necessary when

the process is carried out at temperatures,

which are more or less above room temperature

lie.

In the presence of water it is beneficial to

tion mixture with inert solvents such as acetone to dilute. Are mixtures of water and If alcohols are used, esters are predominantly formed if the proportion is water is not too high.

An excess of alcohol and water, based on the required stoichiometric amount, is effective favorable to the implementation and yield of the desired polyenecarboxylic acid. A Excess of acetylene, based on the amount of chlorine

of the chlorine present in the allyl chloride used, be useful; it should preferably be over 20% be. But it must be taken into account that in the presence of hydrochloric acid and excess acetylene promote the conversion

is stigt, which leads to the formation of acrylic acid and acrylic acid esters.

The method of the invention is easy to carry out. The allyl chloride and the nickel carbonyl, optionally in solution, are in the reaction

vessel in which the solvent or the alcohol or the water or both by the addition of Carbon monoxide and acetylene are kept in motion, preferably at such a speed

5 6

At the end of the reaction, the free heat of chlorine ion is introduced can be monitored. Neutralized after some hydrochloric acid, then the first Time or almost immediately, if the oxygen is carefully selected alcohol and the solvent and then the polyene had been removed from the reaction vessel, carboxylic acid either immediately or after the solution turns yellow to reddish brown and water is added and the nickel chloride is separated off and after in. green. The rate at which the solution is distilled off.

to which the reactants are to be fed If carboxylic acids are produced, can

are advantageously adjusted so that they are separated off in the form of the alkali salts

Change to green is avoided, namely around and then back in freedom by acidification

an unnecessarily high consumption of nickel carbonyl io can be set.

to avoid. The heat of reaction can also be caused by the resulting nickel chloride solution

Control of the feed rate of the reaction part - the nickel as nickel carbonyl again according to known ones

takers can also be obtained with the help of conventional cooling devices,

services are discharged. Those obtained by the method of the invention

As a result of the low temperature, the minor polyenecarboxylic acids will contain two non-conjugated ones reaction slowed down. The reaction time depends on double bonds, one of which is with the carbonylder Temperature as well as on the type of group used the carboxyl group is conjugated. they are Allyl chloride. You work continuously with im fairly stable connections and have over circulation guided gases, the predominantly cis form is achieved.

part of the fact that one can particularly reduce the losses of the gases produced by the process of the invention

Avoid cracked nickel carbonyls and avoid the important 7-cyano-2,5-heptadiene-1-acid and its

can reduce consumption during implementation. Esters can be prepared from 1-chloro-4-cyano-2-butene.

In addition, the possibility is thereby given, The 7-cyano-2,5-heptadien-l-acid becomes as viscous

carefully monitor the reaction conditions, separate oil. The methyl ester of this acid has the

if one considers the composition of the circuit 25 Kp., = 134 to 138 ° C and the refractive index «?? = 1.4788;

The gas mixture is kept constant and the isopropyl ester has a boiling point of ₁₃ = 160 to 165 ° C; the

Significant amounts of fresh gas in the cyclohexyl ester circuit, bp ₅ = 180 to 183 ⁰ C.

introduces. The yield increases accordingly and the 2,5-hexadiene-1-acid
the consumption of nickel carbonyl decreases.

The 30th containing acetylene and carbon monoxide

The gas mixture that is passed through the liquid is a liquid with a boiling point of ₁₂ = 95 to 105 ° C.

contains a larger amount of acetylene than it contains. Hydrogenation of this acid becomes caproic acid

Formula image reproduced above about the received.

Corresponds to the course of the reaction. The methyl ester of 2,5-hexadiene-l-acid is boiling

see that according to this formula, the 35 at 63 to 66 ⁰ C and 34 mm of mercury; the

Carbon monoxide and acetylene in the ratio of the refractive index n ^s S is 1.4495; the ethyl ester boils

1: 1 are necessary, but that part of the carbon between 50 and 55 ° C and 5 mm and the benzyl ester

monoxyds is consumed by nickel carbonyl. at 150 to 165 ⁰ C and 20 mm mercury column.

The proportion of crotyl chloride made from butadiene and made by the nickel carbonyl

The carbon monoxide required varies depending on the hydrochloric acid, was 2,5-heptadiene-l-acid,
Type of allyl chloride used and the reaction conditions.

When using l-chloro-4-cyano-2-butene as a liquid obtained at 117 to 124 ° C and

the amount of acetylene in the gas mixture should boil 55 to 15 mm of mercury. By hydrogenation

75 ° / o and the amount of carbon monoxide 25 to 45 ° / o 45 from this, enanthic acid is obtained. The enanthic acid

be. methyl ester boils at about 72 to 75 ° C and

The slow and regular supply of the reac- 20 mm mercury column. The refractive index n is ² g

Participants in the diluted mixture favored 1.4567.

the implementation and delivers the best results. From l-chloro-4-acetoxy-2-butene, which is obtained from 1,4-dichloro

Diluted solutions contain more than 50 total 2-butene and sodium acetate has been available

10 parts of solvent per part of allyl chloride. 7-acetoxy-2,5-heptadiene-1-acid methyl ester obtained,

CH ₃ COO-CH = CH-CH ₂ -CH = CH-COOCh ₃

at 122 to 129 ° C and 6 mm mercury From 5-chloro-3-pentene-1-acid methyl ester became the

boils. 2,5-octadiene-1,8-diacid dimethyl ester,

H ₃ COOC-CH = CH-CH ₂ -Ch = CH-CH ₂ -COOCH ₃

obtained with the b.p. ₈ = 133 to 138 ^° C. made by chlorination of the dimeric 1-chloro

Hydrogenation of this ester produces cork-4-acetoxy-2-butene and becomes dimethyl tetradeca-2,5,9,12-tetrate. Obtained from 1,8-dichloro-2,6-octadiene, herene-1,4-diacid dimethyl ester

H ₃ COOC-CH = CH-CH ₂ -CH = CH-CH ₂ -CH ₂ -CH = CH-CH ₂ -CH = CH-COOCh ₃

a liquid with Kp. _lo = about 200 to 210 ° C. 65 crystallized hydrogenation and the melting point by hydrogenation with hydrogen arises from 41 ° C.

in the presence of palladium in methanol the dodeca die prepared by the process of the invention

dicarboxylic acid dimethyl ester, which already during the connections show an absorption in the infrared

7 8

band of 825 cm " ¹ (this band means one containing 400 ecm of methanol, a mixture of

a carboxyl group conjugated cis double bond); 101 acetylene and 101 carbon monoxide per hour

in the absence of ultraviolet, after purging with nitrogen at 35 ^° C.

Sorption maxima between 220 and 350 ιημ (which led. It will be the same within 6 hours

Double bonds are not conjugated). 5 parts by volume of the two methanol solutions, each

Both the unsaturated and the saturated in 100 ecm 30 g nickel carbonyl and 40 g 1-chlorine

Compounds can be contained, for example, as soft 4-cyano-2-butene, added dropwise. According to the im

Makers and solvents and the procedure described as an intermediate example 1 are obtained

products for the production of other organic 45 g of 7-cyano-2,5-heptadiene-1-acid methyl ester with the

Use connections. io bp ₁₃ = 40 to 160 ⁰ C; n ™ = 1.4788; the yield

Behavior of vinyl chloride in the process of ^ uf dim nickel content of the aqueous solution gives brnndung _is ^ _that nickel carbonyl _6g were decomposed, the

Into a 300 ecm flask which corresponds to 200 ecm 0.035 moles. Based on 45 g of the methyl methyl alcohol and with a stirrer, reflux ester, molecular weight 165, 0.13 mol cooler, thermometer, gas inlet tube and two Ni (CO) ₄ per mol of bound carbon monoxide were dripped, which funnels to a common Pipe needs.

are connected, is provided, a mixture Example 3

from each 51 acetylene and 51 carbon monoxide per hour

introduced. At the same time letting 25 g Vinyl chloride 20 In a flask, which is located in a water bath and 20 g of nickel carbonyl within 3 hours at 30 ⁰ C of 35 ° C, 250 cc of acetone and added dropwise. Introduced 20 ecm of water. The mix will

After this time it was impossible to stir the air through an oxygen-free sticktion by distillation any compound is removed from the reactant stream and this becomes a gas stream to separate the mixture. 25 each from 101 carbon monoxide and 101 acetylene per hour

The following examples illustrate the invention. initiated. Then leave two acetone solutions that _ ... contain 25 g allyl chloride or 30 g nickel carbonyl,

Example 1 add dropwise. The solution gradually takes one

In a 500 ecm flask, which is brown-yellow in color. The addition of the reaction stirrer, The reflux condenser, thermometer, gas inlet 3 ° participant takes 6 hours.

tube and two dropping funnels that make up a nickel chloride crystals from this solution

common pipe are connected, provided, disconnected. The mixture is based on the aforementioned After purging with nitrogen, a mixture is kept at temperature for 1 hour. This is done again of 101 carbon monoxide and 101 acetylene per hour nitrogen passed through, and the volatile compounds 45 ° C introduced. The gas is allowed to fertilize through the 35 distilled off under a slight vacuum. Inlet tube which is dissolved in 200 ecm of methanol. The residue is taken up in water and dives, pearls. This is extracted from the two dropping funnels with ether.

equal volume of two solutions containing 50 g of nickel. The remaining solution contains 3.9 g of nickel carbonyl and 40 g of 1-chloro-4-cyano-2-butene in each chloride, which means a consumption of 11.3 g or 100 ecm of methanol , corresponds to 40 0.06 mol of nickel carbonyl within 3 hours. Added dropwise through distillery; 13 g of nickel carbonyl were removed from the solution with 17 g of 2,5-hexadiene-1-acid, molecular weight 112, from the gas flowing through the ether extract. The supply of gases is continued, bp ₁₂ = 95 to 105 ^° C., is maintained. The acid number until the solution turns a greenish color. It is 114; the yield 45%. Based on 17 g, the mixture is then cooled, nitrogen is passed through and 45 2,5-hexadiene-1-acid, i.e. 0.4 mol Ni (CO) ₄ , the methyl alcohol is consumed at the same time as something per mol of bound carbon monoxide. Nickel carbonyl distilled off. The residue is in By hydrogenating this acid in the presence of

Added water and the organic layer of palladium at room temperature forms caproic acid. severed.

After drying this layer over sodium 50 Example 4

sulfate and distilling at 140 to 160 ⁰ C and 13 mm in a flask equipped with a stirrer and

Mercury, 40 g of 7-cyano-2,5-heptadiene reflux condenser containing 400 ecm of methyl alcohol are obtained 1-acid methyl ester, a liquid which is heated to 35 ° C. and in each of which 101 quickly turns yellow; ni ° = 1.4788; the yield being carbon monoxide and 101 acetylene passed per hour carries 70%, 25 g of allyl chloride are added dropwise at the same time

The nickel content of the aqueous solution gives 30 g of nickel carbonyl within 6 hours. The fact that 15 g of nickel carbonyl have been decomposed, the solution first takes a yellow and then corresponds to a 0.087MoI. In 40 g of the methyl ester, brown-red color. During the color change, molecular weight 165, 0.24MoI are carbon mon- ite, the temperature rises, and it is necessary to bind the oxide. According to the equation 0.24: 0.087 60 to cool the reaction mixture and the reaction = 1: x are therefore 0.36 mol of participants per mole of carbon monoxide to be gradually added to the reac-Ni (CO) _{4 has been} consumed. to control thermal heat.

. ₁₉ After one hour, the mixture causes stick

ßeispiel I _{material ge} i _{eitet and the} Wing _c h _t i _ge portion which to

Into a flask with a capacity of 1000 ecm, which ^{boils at 65 8O 0} C under atmospheric pressure, in the light

Stirrer, reflux condenser, thermometer, gas inlet vacuum distilled off.

inlet pipe and two into a single inlet pipe The residue is taken up in water,

connected dropping funnels is provided and the nickel content of the aqueous solution is 7.7 g,

corresponding to a consumption of nickel carbonyl and 101 acetylene per hour for a total of 6 hours

from 21 g. _ be initiated.

The aqueous solution is extracted with ether, resulting nickel chloride crystals are from the

the ether extract was dried over sodium sulfate and the solution was separated off. The work-up takes place after

filtered. Finally the ether is removed and the 5 to Example 7. 19 g are obtained by distillation

Distilled residue. Obtained at 35 to 4O ⁰ C 2,5-heptadiene-l-oic acid with Kp. = ₁₅ 117-124 ⁰ C.

and 12 mm mercury column 16 g 2,5-hexadiene- The acidimetrically determined acid number is 126;

1-acid methyl ester; the yield is 38%; which the yield 54%

B.p. ₂₈ = 62 to 63 ° C; n% ° = 1.4481; D ™ = 0.9435. 14.8 g of nickel carbonyl are consumed,

Based on 16 g of the 2,5-hexadiene-l-acid methyl io speaking 0.086 mol. Based on 19 g of the 2,5-hepta-

esters, molecular weight 126, became 1 mole of dien-1-acid, molecular weight 127, were thus

Ni (CO) ₄ per mole of bound carbon monoxide reduces 0.61 mole of Ni (CO) ₄ per mole of bound carbon monoxide

needs. This ester results in the hydrogenation consumed in oxide. From the heptadienoic acid arises

Presence of palladium at room temperature by hydrogenation in the presence of palladium

Caproic acid methyl ester. 15 Room temperature enanthic acid.

Example 5 Example 9

In a flask containing 300 ecm of ethyl alcohol, 25 g of crotyl chloride and 25 g of nickel carbonyl

and in each of 101 carbon monoxide and 101 carbon monoxide are passed ^{into a flask at 3O 0} C within 6 hours, 25 g of 20 containing 400 ecm of methyl alcohol and allyl chloride and 30 g of nickel carbonyl as ethanolic the 101 Carbon monoxide and 101 acetylene per solution at 45 ⁰ C given within 3 hours. Hour.

Following the procedure of Example 4, 14 g are obtained in the manner described in Example 8

2,5-hexadiene-1-acid ethyl ester with b.p. _lo = 50 to 28 g of a crude acid obtained which obtained 55 ° C. on distillation; the yield is 31%. 25 g of nickel carbonyl are consumed in a vacuum of 10 mm mercury column at 58 to 18 g of nickel carbonyl during the reaction, 62 ° C. 20 g of 2,5-heptadiene-1-acid methyl ester with KP. _{1 ()} corresponds to 0.105 mol. Based on 14 g of 2,5-hexa- = 58 to 62 ^° C .; the yield is 51%; dien-1-acid ethyl ester thus 1 mole of Ni (CO) ₄ was ₁₅ bp = 67-68 ⁰ C. nf = 1.4560; D.? = 0.9358. consumed per mole of bound carbon monoxide. 14.5 g of nickel carbonyl are consumed,

30 meaning 0.084 mol. Based on 20 g of the methyl

Example 6 esters were thus bound 0.6 mol of Ni (CO) ₄ per mol

denem carbon monoxide consumed.

In a flask, which 400 ecm isopropyl alcohol is produced from the methyl heptadienoate through

contains and in each of which 101 carbon monoxide and hydrogenation in the presence of palladium at room 101 Acetylene are passed per hour, two 35 temperature enanthic acid methyl esters. Solutions of 25 g of allyl chloride or 30 g of nickel.

carbonyl in 100 ecm isopropyl alcohol in each case in Example 10

40 ⁰ C given within 4 hours. 18 g of 5-chloro-3-penten-1-acid methyl ester and 10 g

According to the nickel carbonyl procedure described in Example 5, 16 g of 2,5-hexadiene-1-isopropyl ester with 40% of 5 g of MgCO ₃ with 5 l of carbon monoxide each and a _{b.p. 5} = 36 to 42 are added for 6 hours at 30 ° C ° C obtained; the yield 51 acetylene treated per hour. It will be 2.7 g of 31% - ^In the reaction, 22 g of nickel carbonyl nickel are consumed. By vacuum distillation carbonyl consumed, corresponding to 0.12 mol. Based be 13 g of 2,5-octadiene-l, 8-disäuredimethylester with 16 g of the ester, molecular weight 154, bp were. Get ₈ = 133-138 ⁰ C, with 1 .2MoI Ni (CO) ₄ per mole of bound carbon- 45 2.7 g of Ni (CO) ₄ consumed correspond to 0.15 moles of monoxide consumed. Based on 13 g of the dimethyl ester, molecular

. . weight 198, i.e. 1.1 moles Ni (CO) ₄ per mole

^Eis P ^le bound carbon monoxide consumed.

In a flask which gives 130 g of benzyl alcohol and this ester by hydrogenation in the presence

250 ecm of acetone and in each of which 101 carbons 50 of palladium-suberic acid dimethyl ester. monoxide and 101 acetylene passed per hour

are 25 g of allyl chloride and 30 g of nickel Example 11

carbonyl as acetone solution within 4 hours
40 ⁰ C given. 30 g of 1-chloro-4-acetoxy-2-butene in methyl alcohol

Following the procedure described in Example 6, operation of 55 and 20 g nickel carbonyl also in methyl alcohol after distilling off the benzyl alcohol are introduced with stirring into a flask containing 20 g of 2,5-hexadiene-l-säurebenzylester with Kp. _2O the 300 cc of methyl alcohol and 8 g of magnesium = 150 to 162 ⁰ C obtained; the yield is carbonate contains. Thereupon 101 charcoals-27% · 17 g nickel carbonyl are consumed, monoxide and 101 acetylene per hour corresponding to 0.1 mol. Based on 20 g of benzyl-60 are passed into the flask. The temperature is measured using a Wasseresters, with 1 mol of Ni (CO) ₄ was maintained per mole of bound bath at 4O ⁰ C. The addition of the reaction consumes carbon monoxide. participant lasts 4 hours. The implementation is

-ίο finished ^after another hour. It will be 10 g

Example 8 Nickel carbonyl consumed. In the end, 21 g

Two acetone solutions of 25 g crotyl 65 obtained a crude ester from which by vacuum and 25 g of nickel carbonyl to be at 3O ⁰ C in a distillation gave 14 g of 7-acetoxy-2,5-heptadien-l-oic acid flask containing 300 cc acetone and 30 g methylester with Kp _e = gained 120 to 130 ⁰ C contains water and in the per 101 carbon monoxide. the yield is 35% · 10 g consumed

11 12

Ni (CO) ₄ correspond to 0.058 mol. Based on 14 g After 2.2 g of the first runnings, the unreacted chlorine

Methylesters of, molecular weight 184 were contains cyanobutene go in Kp. _n = 140 to 155 ⁰ C so 0,7MoI Ni (CO) ₄ bound per mole of carbon 49 g of 7-cyano-2,5-heptadien-l-säuremethylester above;

monoxide consumed. the yield is 85%. The nickel content found in

_R. . , ₁₀ 5 of the aqueous solution is present as nickel chloride,

Example U is 2.07 g. 1.89 g Ni (CO) ₄ corresponds to 0.01 mol.

In a small glass column with 11 capacity based on 49 g of the methyl ester, molecular

A diameter of 50 mm is given a weight of 500 ecm, i.e. 0.03 mol Ni (CO) ₄ per mol of methanol and a gas-bound carbon monoxide circulated through a circuit are consumed.

mixture of 65% acetylene and 35% carbon monio

a oxide at 40 ⁰ C. In the cycle is a supply example 14

container with 101 contents switched on.

A solution of 300 ecm of methanol will then be mixed with 30 g of water of crystallization within 7 hours.

of 200 ecm of 1-chloro-4-cyano-2-butene in 500 ecm-containing nickel acetate under the conditions described in Example 13 methanol and a solution of 45 ecm nickel-15; the mixture carbonyl in 500 ecm of methanol was added. After 45 minutes with carbon monoxide, acetylene, 6 ecm of nickel, the uptake of the gas mixture is so tetracarbonyl and 40 g of 1-chloro-4-cyano-2-butene that the addition of further acetylene acts. This gives 37 g of 7-cyano-2,5-heptadien-l-oic acid-carbon monoxide is necessary, the _lo = obtain controlled so methylester with Kp 140 to 16O ⁰ C. it is found that the acetylene content is approximately 60%. The yield is 64%.

The temperature is determined by a stream of air in the that corresponds to the ingested carbon monoxide

Jacket of the column kept at the same height. 5.141. The amount of nickel found in the solution, the liquid from which the initial amount of nickel exceeds, is removed through an overflow column and placed in a suitable vessel Ig. 5.141 carbon monoxide corresponds to 0.22 mol. collected. At the end of the reaction, nitrogen is added as 5 g of Ni (CO) ₄ consumed corresponds to 0.02 mol. It is passed through the column and the mixture is thus 0.17 mol of Ni (CO) ₄ per mol of bound content. The total consumption of nickel carbonyl, carbon monoxide consumed, found as nickel chloride, corresponds to 20 g. .

The methyl alcohol of the mixture is distilled off. Example 15

and the nickel chloride is separated off as an aqueous solution. 30 25 g of allyl chloride in 200 cc methanol, 13 cc The residue g lead are on distillation 9 carbonyl nickel in 100 cc of methanol are innerbei Kp. _Lo to 14O ⁰ C, 184 g of a fraction having a bp., Where 3 hours in the column half _14, which = 140 to 168 ° C, the 135 g of 7-cyano-2,5-heptadiene already contains 300 ecm of methanol and through which 1-acid methyl ester, yield 47% and 2,5-octadiene acetylene and carbon monoxide are passed. The dimethyl diacid and 11g tailings with a boiling point of ₁₄ 35 temperature are 40.degree.

up to 178 ° C. After 3 hours of reaction one passes through the

39.4 g of consumed Ni (CO) ₄ correspond to 0.23 mol. Reaction mixture nitrogen. From the received

Based on 135 g of 7-cyano-2,5-heptadien-l-acid solution is a lead up to 8O ⁰ C distilled off

methyl ester, molecular weight 165, and the residue were taken up in ether. The methanol distilled off is obtained from 0.28 mole of Ni (CO) ₄ per mole of bound carbon mono- 40

oxide consumed. Addition of a saturated calcium chloride solution

Example 13 additional amount of reaction product.

The ether solution is removed by vacuum distillation

300 ecm of methyl alcohol are added to the column described in the two batches, 28 g of 2,5-hexadiene-1-acid play 12, and a mixture of 65% acetylene and circulating _{in the 45 methyl ester, molecular weight 126, with the bp S4 is passed} = 63 to 66 ⁰ C obtained; the yield is 34%. 35% carbon monoxide at a rate of 8 g of nickel is found in the solution as chloride, of about 1001 per hour. Thereupon, 6.56 g of spent Ni (CO) ₄ corresponding to 0.038 mol. Over 3 hours two solutions, each Based on 26 g of Methylesters were therefore 100 cc methanol, a 20 g of 1-chloro- which 50 mol 0.17 Ni (CO) ₄ per mole of bound carbon mon-4-cyano-2-butene and the other 3 ecm nickel carbonyl oxide consumed, contains, added. After 45 minutes the Beisniell6

Solution darker and finally takes a brown-

red color. There is further carbon monoxide and 80 g of allyl chloride, diluted with 1200 ecm of methanol

Acetylene introduced and the pressure within the 55 and 36 ecm nickel carbonyl in 400 ecm methanol circuit with 20 cm water column on the suction side are added within 8 hours at 40 to 45 ⁰ C in the pump and the acetylene content at about 65% reaction vessel. The circulated kept. The temperature is 40 ^° C. At the end of the mixture of carbon monoxide and acetylene, the reaction is discolored. The solution is about 1001 per hour. By distilling the reaction mixture from the lower part of the column and treating the methanol, the process is repeated with the same amounts as 50 g of 2,5-hexa reactants with a calcium chloride solution. diene-1-acid methyl ester, molecular weight 126, obtained

Th from the total reaction mixture obtained; the yield is 37%. 17 g of nickel are distilled off the methanol. The residue is found in the solution as chloride, water is added, the nickel chloride solution is removed. 26.5 g of consumed Ni (CO) ₄ correspond to 0.15 mol. Is separated and extracted with ethyl ether. The ether solution, based on 50 g of the methyl ester, is dried over sodium sulfate and then 0.3 mol of Ni (CO) ₄ per mol of bound carbon monoxide is consumed.

Example 17

Two solutions of 20 g of crotyl chloride and 9 ecm nickel carbonyl in 100 ecm methanol each are in the Given column, which contains 200 ecm of methanol and through which carbon monoxide and acetylene how in the previous examples are circulated.

The temperature during the reaction is maintained at 30 ⁰ C. The reaction time is 3 hours. By distillation of the reaction liquid g of _{2,5-heptadiene-l-2O} säuremethylester be obtained == ⁰ to 75 C with the Kp. the yield is 42%. 3.2 g of nickel are consumed. 4.2 g of Ni (CO) ₁ consumed correspond to 0.04 moles. Based on 13 g of the ester, 0.4 moles of Ni (CO) _{4 were} consumed per mole of bound carbon monoxide.

Claims (3)

PATENT CLAIMS: 1. Process for the preparation of non-conjugated polyenecarboxylic acids or their esters of general formula R- (CH = CH- CH ₂ - CH = CH- COOR ') » in which R, if η = 1, is hydrogen or an alkyl radical with 1 to 20 carbon atoms optionally substituted by a carbalkoxy, acyloxy or nitrile radical, if η = 2, an optionally substituted alkylene radical, R 'is hydrogen Alkyl, cycloalkyl or aralkyl radical with 1 to 20 carbon atoms and η denotes the number 1 or 2, characterized in that a compound of the general formula R - (CH = CH - CH ₂ C1) _W have R and η are as defined above, at temperatures from 0 to 75 ° C, preferably between 25 and 6O ⁰ C, at ordinary pressure with an excess mixture of acetylene and carbon monoxide, which comprises from 50 to 75 ° / ₀ acetylene, with nickel carbonyl in a ratio of 0.1 to about 1 mol per 1 mol of total carbon monoxide bound in the resulting polyene carboxylic acid and with an excess aliphatic, cycloaliphatic or araliphatic alcohol having 1 to 20 carbon atoms or with water, optionally in the presence of an organic solvent and or or a hydrogen chloride-binding agent. 2. The method according to claim 1, characterized in that the reaction in acetone, Cyclohexanone, ethylene glycol dimethyl ether or in the alcohols used for the reaction as Solvent carries out. 3. The method according to claim 1 and 2, characterized in that the reaction is carried out in Presence of magnesium carbonate, calcium carbonate or sodium hydrogen phosphate as binding agents for hydrogen chloride Agent carries out. Considered publications: German Patent Nos. 895 767, 805 641;
German Auslegeschrift No. 1 005 954;
Austrian Patent No. 164 026;
U.S. Patent Nos. 2,582,911, 2,613,222, 2,778,848; W. Reppe, New Developments in the Field der Chemie des Acetylene und Kohlenoxyds, 1949, p. 95 and following; Liebigs Annalen der Chemie, Vol. 582, 1953, pp. 1 to 71; JW Copenhaver and M.H. Bigelοw, Acetylene and Carbon Monoxyde Chemistry, 1949, p. 251;
Angewandte Chemie, Vol. 68, 1956, pp. 505 to 508. © 20 »627/339 7.62