DE1274575B - Process for the preparation of esters of non-conjugated polyenecarboxylic acids - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

Whip Kl;

Number:
File number:
Registration date:
Display day:

C07c

BOIj
C09f

12o-21

12 ο-17/03; 12 g-11/00;
22h-2

P 12 74 575.4-42 (M 47421)

December 16, 1960

August 8, 1968

The German patent 1133 720 relates to a process for the preparation of non-conjugated polyenecarboxylic acids or their esters of the general formula

R- (CH = CH-CH ₂ -CH = CH-COO - R% 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, an alkyl, cycloalkyl or aralkyl radical having 1 to 20 carbon atoms and η is the number 1 or 2, which is characterized in that a compound of the general Formula -

R- (CH = CH-CH ₂ Cl) _n

in which R and η have the meaning given above, at temperatures from 0 to 75 ° C., preferably between 25 and 60 ° C., at ordinary pressure with an excess mixture of acetylene and carbon monoxide containing 50 to 75% 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 polycarboxylic 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 one hydrogen chloride binding agent.

In this process, some of the carbon monoxide comes from nickel carbonyl, which is

Process for the production of esters does not
conjugated polyenecarboxylic acids

Addendum to the patent: 1133 720

Applicant:

MONTECATINI Societa Generale per
l'Industria Mineraria e Chimica, Milan (Italy)

Representative:

Dipl.-Ing. Dipl.-Chem. Dr. phil. Dr. techn.
J. Reitstötter and Dr.-Ing. W. Bunte,
Patent Attorneys, 8000 Munich 15, Haydnstr, 5

Named as inventor:

Gian Paolo Chiusoli,

Sergio Merzoni, Milan (Italy)

Claimed priority;
Italy of December 18, 1959 (21112),
dated September 29, 1960 (6978)

right to the implementation of the required amount is added. The implementation is carried out according to the following Formula picture:

R-CH = CH-CH ₈ Cl + CH = CH + CO + ROH

> R-CH = CH- CH ₂ - CH = * = CH - COO - R '+ HCl

in which R is hydrogen or a methyl group and R 'is hydrogen or an alkyl radical. the Implementation also succeeds when R is a phenyl group.

In contrast, the invention relates to a process for the preparation of esters of non-conjugated polyenecarboxylic acids the general formula

R - C (R ₁ ) = C (R ₈ ) - CH ₂ - CH = CH - COO - R ₃ in which R is hydrogen or an alkyl group with 1 to 20 carbon atoms, R ₁ and R ₂ are hydrogen or a methyl group and R ₃ is hydrogen or an alkyl group with 1 to 5 carbon atoms, by reacting a chlorine compound of the general formula

RC (R ₁ ) = C (R ₂ ) -CH ₂ Cl

in which R, R ₁ and R _{2 have} the above meaning, with acetylene, carbon monoxide and an aliphatic alcohol with 1 to 5 carbon atoms, optionally in the presence of an organic solvent and / or a hydrogen chloride-binding agent, according to Patent 1133 720.

The process of the invention is characterized in that the reaction is carried out in the presence of metallic, finely divided nickel and 0.1 to

809 589/479

0.5 moles of thiourea per mole of the chlorine compound in place of nickel carbonyl at one temperature between -10 and + 50 ° C.

It is surprising that the method of the invention leads to this result because of the use of finely divided nickel alone or even in the presence of sulfides, which cause the formation of nickel carbonyls Still favoring during the reaction gives very poor yields. In contrast to through the use of thiourea, which easily corresponds to the allyl chlorides Pseudo-thiuronium salts of the general formula

R-CH = CH- CH ₂ - S-C (NH _{2) 2}

Cl

forms, obtain satisfactory yields.
Comparative experiment

a) A solution of 40 g of metalallyl chloride in methyl alcohol is a mixture of 400 ecm of methyl alcohol, 30 ecm of moist Raney nickel, 20 g of basic magnesium carbonate and 19 g NiS in 6 hours while passing a stream of carbon monoxide and Acetylene with a flow rate of 31 / hour each. added. The reaction temperature is kept between 0 and 5 ° C. The yield of 2,5-hexadienoic acid methyl ester is 8.5%; no methyl acrylate was formed.

b) 20 g of allyl chloride are dissolved in methyl alcohol and added to a suspension of freshly precipitated, finely divided Ni (OH) ₂ in 200 ecm of methyl alcohol in the presence of 0.5 g of Na ₂ S · 2H ₂ O for 3 hours.

A continuous gas stream of carbon monoxide and acetylene is then generated at one flow rate of 51 / hour each passed at a temperature of 50 to 60 ° C in the reaction vessel without that only traces of the desired reaction product are formed.

If, on the other hand, the same experiment is carried out in the presence of thiourea instead of NiS, in this way, yields of the 2,5-hexadienoic acid methyl ester of up to 70% are obtained.

It should be noted, however, that the temperature in experiment a) is too low to allow the formation of Ni (CO) ₄ , so that only a small amount of the ester could be formed.

Although the conditions of experiment b) are particularly _{suitable for the formation of Ni (CO) 4} , no ester is nevertheless formed.

It is already known that by reacting allyl halides with carbon monoxide in the presence of nickel carbonyl the ^, ^ - unsaturated carboxylic acids and using molar amounts of acetylene, the «, ^ - unsaturated carboxylic acids are obtained, which contain 2 more carbon atoms than the mentioned / ^ - unsaturated carboxylic acids (cf.La Chimica e L'Industria, Vol. 41, 1959, pp. 503-515, Gazetta Chimica Italiana, Vol. 89, 1959, pp. 1332 bis 1337, and French patent specification 1 212 892).

According to these known processes, nickel carbonyl is required. This not only serves as a catalyst, it is directly involved in the implementation by forming complex connections.

From the information in the cited literature it follows that the implementation of the reaction is not possible without nickel carbonyl.

It is also known that in the production of - unsaturated carboxylic acids, especially of acrylic acid, the carbonylation of the alkyne not only in the presence of nickel carbonyl and Nickel salts can perform, but that carbonyl-forming metals themselves can be used nen (see German patents 854 948, 859 612, 868 149, 881 650 and 944 789).

It also follows that the presence of nickel carbonyl is necessary to realize the reaction according to R ep pe, and that _{only those metals can be used in place of Ni (CO 4} ) which are capable of in the presence of carbon monoxide and suitable accelerators to form nickel carbonyl. The nickel carbonyl cannot therefore be used in the production of acrylic acid esters

ao addition of acetylene, carbon monoxide and alcohols are replaced.

In the German Auslegeschrift 1000 806 is also stated that nickel halides are used as catalysts in the reaction according to R ep pe

as and also through the addition of compounds can be activated which the group

_N — C — S, —N — C — Se, —N — C — Te

contained, whereby the formation of the nickel carbonyl is made possible.

Thiourea is one of these accelerators. But it cannot be deduced from this that compounds with the aforementioned groups only activate the metals alone, especially since even when metals are used, a halogen must be present so that the corresponding Metal halides is made possible.

According to the method of German Auslegeschrift 1 046 030, the reaction is carried out according to R ep pe in the presence carried out by nickel carbonyl as a catalyst, with compounds of the above Groups can be activated. No indication is given that the nickel carbonyl is through finely divided nickel can be replaced and that the activating agent for the nickel carbonyl also can be those for metallic nickel.

The main advantage of the method of the invention lies in comparison with the method mentioned in that the use of nickel carbonyl can be dispensed with.

According to the method of the invention, in addition to Raney nickel, finely divided nickel, which is based on various Way has been manufactured, can be used. The nickel can by decomposition of Nickel formate, by reducing nickel hydroxide with hydrogen or by reducing nickel chloride have been made with finely divided iron. In the latter case, amounts of nickel chloride are sufficient of less than 20%, based on the iron, which is continuously nickel from the nickel formed during the reaction Sets nickel chloride free. The iron used is reduced without any difficulty its oxides or by simply grinding ordinary ferrous metal and the following Sieve obtained on a 16,000-mesh sieve (DIN E130). If this iron powder is used, work under a protective gas, as this iron is pyrophoric. The

amount of nickel or iron needed is less than the stoichiometric amount and depends on the type of the converted chlorine derivative.

The amount of required by the process of the invention for the reaction with Raney nickel Thiourea is larger than that when using nickel, made from iron and nickel chloride, because the Raney nickel contains active hydrogen, which is removed when reacted with thiourea.

The use of thiourea and metals can be kept low if the during hydrochloric acid formed from the reaction is continuously neutralized. As a neutralizing Agents can be sodium, potassium, calcium and magnesium hydroxides and carbonates will. However, it must be ensured that the pH of the reaction mixture is below 7, in order to avoid reactions of the alkali used with the allyl chloride, iron and nickel chlorides.

The process of the invention makes it possible to produce esters of primary ones containing up to 20 carbon atoms Allyl chlorides of the general formula

R ₁
R.

C = C (R ₂ ) -CH ₂ -Cl

produce, in which R, R ₁ and R _{2 have} the meaning given above.

It should also be noted that the increase in the amount of thiourea in the reaction mixture Reason for the isomerizing effect of the thiourea, depending on the nature of each one used Chlorine compound, the reaction conditions and the treatment depends on the work-up, not only to compounds with conjugated double bonds in the cis form, but also to minor ones Quantities of the trans compound and isomers with conjugated double bonds can lead to the tautomeric behavior is a distinctive property of this compound; z. B. contains the 2,5-heptadienoic acid ester 10-15% of the 3,5-tautomer. This is generally not a disadvantage the use is associated with their conversion into conjugated compounds; that is how they are suitable as drying oils. Hydrogenation also gives rise to saturated esters from the tautomers, the serve as plasticizers.

The procedure can be carried out in the following way:

The alcohol and the finely divided Raney nickel or that by reacting with nickel chloride Finely divided nickel obtained from iron is introduced into the reaction vessel.

While stirring the mixture, the reaction vessel is flushed with nitrogen. The Raney nickel or the nickel chloride and the iron are added to the reaction mixture in a stoichiometric excess added, and the unused is filtered off after the reaction has ended.

A gas stream of carbon monoxide and acetylene is then passed through the solution and this is kept at the desired reaction temperature by heating or by cooling.

The ratio of acetylene to carbon monoxide depends on the reactivity of the chlorine compound from and is changeable. The amount added depends on the consumption in the cycle.

Examples 1 to 7 below are carried out without recirculation of the gases, but is the ratio of the amount of gas supplied of 11 / hour in each case. retained because this makes both an undesirable Reaction termination due to a lack of acetylene and an excessive formation of by-products due to an excess of acetylene

ίο is avoided. As in Example 9, however, the process can be carried out with recirculation of the gases by maintaining an amount of gas corresponding to the conversion.
The mixture of the allyl chloride and thiourea in alcohol is slowly introduced into the reaction vessel under temperature control. The duration of the addition depends on the reactivity of the allyl chloride used in each case.
The reaction is complete within a few hours.

ao ends. Then the gas mixture still present is removed by a stream of nitrogen, the nickel and Excess iron is filtered off and the alcohol together with the unreacted starting materials, which distill off with any water present in the alcohol. The extraction the ester is carried out by salting out the distillate with a saturated aqueous calcium chloride solution. The oily layer is reabsorbed in a little water, poured off or extracted with ether, washed with water, dried and distilled. The distillation is carried out in vacuo.

The examples illustrate the invention.

example 1

In a five-necked flask with a capacity of 11, which is equipped with a thermometer, stirrer, gas inlet tube, A reflux condenser and separating funnel are provided, 400 ml of methanol and 30 ml of moist Raney nickel are added introduced. The device is purged with nitrogen, the slurry stirred, and the Carbon monoxide and acetylene at a flow rate of 3 1 / hour each. initiated; the The temperature of the slurry is brought to -10 ° C. by cooling during the entire reaction time held.

As soon as the temperature of -10 ° C is reached, with the dropwise addition of a solution of 40 g (0.522 mol) of allyl chloride and 8 g (0.105 mol) Thiourea started in 180 ml of methanol. The feed is regulated in such a way that the addition of the Solution completes in about 6 hours. The supply of carbon monoxide and acetylene is still going on continued for about 30 minutes and then the gases are removed by a stream of nitrogen.

The filtrate freed from the excess Raney nickel is heated on a water bath, whereby the Distill off alcohol and a small amount of the crude ester.

The distillation residue is taken up in water and the separated oily layer in ether.

The resulting solution contains nickel chloride, which corresponds to 7.7 g of metallic nickel.

After salting out the distillate with the same amount of a saturated aqueous calcium chloride solution the upper layer is taken up in ethyl ether and the solution is combined with the previous ether extract.

7 8

The two ether extracts are in the oil bath monoxide and acetylene were distilled with a flow ^ ·, whereby first up to 100 ° C of the flow rate of 3 1 / hour each. initiated. And then at 63 to 66 ° C and a pressure of a temperature of about 10 ^Q C is in the Au £ - 34 mm Hg 25 g of 2,5-Hexadiensäure- slurry a solution of 40 g (0.442 mol) of methylester distill over, this corresponds to one am- 5 crotyl chloride in 180 ml of methanol added dropwise for 5 hours,

booty of 37 percent by weight .. After working up the reaction mixture

. "As in Example 1, 40 g of 2,5-heptadiene

B ei s ρ ι el 2 acid methyl ester, boiling point _2O = 72 to 75 ° C, which is approximately

In a 1000 ml glass flask containing 2 to 3% of the 3.5t and 2.4 isomers. the

Thermometer, stirrer, gas inlet pipe, return ^ q yield is 64 percent by weight,

If the flow cooler and separatory funnel are provided, 5.6 g of nickel were converted into the chloride.

400 ml of methanol and 30 ml of fenced Raney-Niekel _R. -ic

introduced. The device is operated with nitrogen

Rinse, stir the slurry, and add the charcoal to a flask as in the previous example

400 ml of methanol and 15 g of finely divided iron are used for monoxide and acetylene with a flow screw

speed of 31 / hour each. initiated. (Particle size of a sieve with 16,000 meshes / em ²

As soon as the temperature of the slurry has reached 20 ° C. = DIN E 130) and 5 g of nickel chloride, NiCl ₂ · 6H ₂ O, a solution is introduced with the dropwise addition. After flushing the flask with 40 g (0.424 mol) of 96% methallyl chloride and nitrogen, the slurry is passed and the 24 g (0.313 mol) of thiourea in 150 ml of methanol ap carbon monoxide is started at a flow rate. The feed is adjusted so that the of 2 1 / hour. and acetylene is completed with one flow addition in 6 hours. speed of 3 l / h initiated. In the up-

Passing carbon monoxide and acetyl slurry through it becomes a solution of 40 g at 20 ° C

len is continued for another 30 minutes and the not (0.442 mol) crotyl chloride and 16 g (0.182 mol)

Used gases are replaced by nitrogen as thiourea in 180 ml of methanol in 5 hours

electricity removed, dripped.

By working up the reaction mixture as after 6 hours, the gases are through a

in example 1 34 g of 5-methyl-2, S-hexadiene nitrogen stream are removed. The implementation mix

acid methyl ester with b.p. ₁₈ = 65 to 69 ° C, the 2 bis is worked up as in Example 1. You get

Contains 3% of the 3,5- and 2,4-isomers. 30 31 g of 2,5-heptadienoic acid methyl ester, boiling point _2O = 72 bis

3 g of nickel were converted to the chloride. 75 ° C, which is about 2 to 3% of the 3.5 and

The yield is 57%. Contains 2,4 isomers. The yield is 50 ge

_. ,, _ weight percent.
Example 3

In a 1000 ml glass flask, which is filled with gg

Thermometer, stirrer, reflux condenser and Seheide- In a flask as in the example above = -

funnel is provided, 400 ml of methanol, 15 g len, 400 ml of methanol and 30 ml of moist

finely divided iron (particle size of a sieve with nickel, obtained by reducing nickel

16,000 mesh / cm ² ; DIN E 130) and 5 g nickel hydroxide with hydrogen in water at 100 to

Chloride, NiCl ₂ Ή _? Ο, introduced. After passing through 40 120 ° C and 50 at, introduced. After flushing

the vessel is flushed with nitrogen, the flask is rinsed with nitrogen, the slurry is

Melting stirred and the carbon monoxide and mung and passed the carbon monoxide and Acety ^

Acetylene with a flow rate of len with a flow rate of each

each 3 1 / hour initiated, the temperature is 31 / hour. a.

the slurry becomes 30 ° C, it becomes a solution of 45. At the temperature of 30 ° C it becomes a solution

40 grams (0.424 moles) of methallyl chloride and 24 grams of 30 grams (0.331 moles) of crotyl chloride and 10 grams

(0.313 mol) thiourea in 150 ml of methanol (0.130 mol) thiourea in 180 ml of methanol in

Added dropwise for 5 hours, dripped in from the dropping funnel for 5 hours.

After 6 hours the gases will pass through. After a total of 6 hours the gases will pass through

Nitrogen stream removed. The 5p nitrogen was removed by working up. The conversion mixture is

Reaction mixture as in Example 1, 35 g as in Example 1 are worked up. 16 g are obtained

5-methyl-2 ₃ 5-hexadienoic acid methyl ester with the 2,5-heptadienoic _{acid methyl ester, b.p. 2o} = 72 to 75 ° C,

B.p. ₁₈ ⁼ 65 to 69 ° C, which is about 2 to 3% of the about 2 to 3% of the 3,5- and 2,4-isomers

Contains 3,5- and 2,4-isomers. The contents. The yield is 34 percent by weight,

booty is 59 percent by weight. 55 4 g of nickel were converted to the chloride.

3.5 g iron and 0.75 g nickel are converted into chlorides _, .., "

convicted. "Example 7

Example 4 - ^ ^{1 a 500} ml flask with a

Thermometer, stirrer, gas inlet pipe, back

In a 1000 ml flask, which is provided with a ßo flow cooler and separating funnel, are

Thermometer, stirrer, gas inlet tube, Rüek 100 ml of methanol and 7 ml of moist Raney nickel

Flow cooler and dropping funnel is provided and the introduced.

Containing 400 ml of methyl alcohol, 14 g are added after purging the flask with nitrogen (0.182 mol) thiourea and 30 ml of moist Raney- the slurry is stirred and the carbon-nickel introduced; the rise in temperature is monoxide and the acetylene carries a current 10 ° C. speed of 2 l / hour each. initiated. Of the

After flushing the flask with nitrogen slurry is at 20 C, a solution of ^p

when the slurry is stirred, the carbon becomes 13.5 g (0.092 mole) of 5.5 "dimethyl-2-hexenyl chloride

and 4.0 g (0.052 mol) of thiourea in 100.0 g of methanol were added dropwise in 5 hours. After total The gases are removed with nitrogen for 6 hours. The reaction mixture is worked up as in Example 1.

10 g of 8,8-dimethyl-2,5-nonadienoic acid methyl ester are obtained, b.p. ₈ = 97 to 100 ° C. The yield is 55 percent by weight.

2.5 grams of nickel were converted to the chloride.

Example 8

800 ml of methanol, nickel chloride hexahydrate, 4 g (0.052 mol) of thiourea and 21 g of basic magnesium carbonate, (MgCO ₃ ) ₄ · Mg (OH) ₂ · 5 H ₂ O, introduced. Carbon monoxide is generated within 6 hours at 30 ° C

S and acetylene at a flow rate of 4 liters per hour each. initiated and added dropwise 40 g (0.442 mol) of crotyl chloride in 100 ml of methanol in 5 hours.
After filtering the reaction mixture

ο the alcohol is distilled off and the distillation residue absorbed in sulfuric acid water and the oily layer in ether; the ethereal solution becomes dried over calcium chloride and distilled. 43.7 g of methyl 2,5-heptadienoic acid are obtained

10 g nickel chloride, NiCl ₂ 6H ₂ O, 7 g powdered 15 ester, b.p. _2O = 72 to 77 ° C, which is about 2 to 3% and under carbon dioxide on a sieve with the 3.5 and 2.4 Contains isomers. The yield 16,000 meshes (DIN E 130) sieved iron, 4 g is 70 percent by weight, the distillation residue (0.052 mol) thiourea and 15 g basic was 2.1 g.
Magnesium carbonate, (MgCO ₃ ) ₄ Mg (OH) ₂ 5 H ₂ O,
introduced. 20th

After purging the flask with nitrogen, stir the slurry and add carbon monoxide and the acetylene at a flow rate of 4 liters per hour each. 6 hours at 30 ° C initiated. At the same time, 40 g (0.433 mol) of 98% commercial methallyl chloride are obtained added dropwise into 100 ml of methanol in 5 hours.

The reaction mixture is then nitrated, the filtrate is distilled, the residue is treated with 10% aqueous sulfuric acid and taken up in ether. After drying the solution over sodium sulfate and subsequent distillation, 39.2 g of 5-methyl-2,5-hexadienoic acid methyl ester, b.p. ₁₈ = 65 to 69 ° C, are obtained, which is about 2 to 3% of the 3,5- and 2 , 4-isomers contain. The yield is 65 percent by weight, the residue 3.2 g.

Example 9

In the flask of the above example, 800 ml of methanol, 10 g of nickel chloride, NiCl ₂ -6 H ₂ O, 7 g of powdered iron sieved on a 10,000 mesh sieve (DIN E 130), 4 g (0.052 mol) of thiourea and 6.5 g of magnesium oxide, MgO, introduced. 30 g (0.331 mol) of metalallyl chloride are added to this mixture at 30.degree. C. and the gases are returned to the circuit by means of a pump. The circuit is kept at a pressure of 20 mm of water above atmospheric pressure. After carefully purging the flask with nitrogen, carbon monoxide and then acetylene are introduced. The amount of acetylene is gradually from an initial 2 1 / hour. after 6 hours increased to 3.6 liters.

The reaction mixture is filtered and the distillation residue is taken up in sulfuric acid water and then in ether. After drying the ethereal solution over sodium sulfate and subsequent distillation, 32 g of 5-methyl-2,5-hexadienoic acid methyl ester, b.p. ₁₈ = 65 to 69 ° C, are obtained, which is about 2 to 3% of the 3.5 and 2.4 Isomers. This corresponds to a yield of 70 percent by weight. The residue is 2.7 g.

65

Example 10

In the flask as in Example 8 are 800 ml of methanol, 7 g of powdered and on a sieve with 16,000 mesh (DIN E 130) sieved iron, 10 g

809 589/479 7.68 © Bundesdruckerei Berlin

Claims (2)

Patent claims: 1. Process for the preparation of esters of non-conjugated polyenecarboxylic acids of the general formula RC (R ₁ ) ^ = C (R ₂ ) CH ₂ CH = CH COO R ₃ in which R is hydrogen or an alkyl group having 1 to 20 carbon atoms, R ₁ and R ₂ are hydrogen or a methyl group and R ₃ is hydrogen or an alkyl group having 1 to 5 carbon atoms, by reacting a chlorine compound of the general formula R - C (R ₁ ) = C (R ₂ ) - CH ₂ Cl in which R, R ₁ and R _{2 have} the above meaning, with acetylene, carbon monoxide and an aliphatic alcohol having 1 to 5 carbon atoms, optionally in the presence of an organic solvent and / or a hydrogen chloride-binding agent, according to Patent 1133720, characterized in that the reaction is carried out in the presence of metallic, finely divided nickel and 0.1 to 0.5 mol of thiourea per mol of the chlorine compound instead of nickel carbonyl at a temperature between -10 and + 50.degree. 2. The method according to claim 1, characterized in that the reaction is carried out in the presence of Raney nickel or a finely divided nickel, which in the reaction mixture by reacting nickel chloride with the by grinding of metallic iron and subsequent sieving with a sieve with 16,000 Mesh (DIN E 130) obtained iron dust is obtained. Considered publications: German Patent Nos. 854 948, 859 617, 868149, 881650,944789; German Auslegeschriften No. 1000 806, 1046 030; French Patent Nos. 1229161,892; Journal of Organic Chemistry, Vol. 24, 1959, pp. 836-839; La Chimica e L'Industria, Vol. 41, 1959, pp. 503-515; Gazetta Chimica Italiana, Vol. 89, 1959, pp. 1332-1337.