DE1211633B - Process for the preparation of monocarboxylic acids of the cyclododecane series or their esters - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

C07c

German class: 12 ο - 25

Number: 1211633

File number: O9354IVb / 12o

Filing date: April 18, 1963

Opening day: March 3, 1966

The invention relates to a process for the production of free or esterified monocarboxylic acids, one ring of 12 carbon atoms and one bonded directly to a carbon atom of the ring Have carboxyl group. In particular, the process is used to prepare the cyclododecanecarboxylic acid, the cyclododecenecarboxylic acid, the cyclododecadienecarboxylic acid, their esters and mixtures from the acids or esters.

The process consists in that carbon oxide is added under pressure to a mixture of cyclododecatriene- (l, 5,9) and water or an alcohol at 100 to 200 ° C in the presence of a carbonylation catalyst known nickel or cobalt catalyst can act, the metals either finely divided in the metallic state or as salts or carbonyls. The procedure is in the same way on the different isomers of cyclododecatriene, namely on the cis-trans-trans isomer or the trans-trans-trans isomer, applicable.

The cyclododecane monocarboxylic acid saturated in the cyclododecyl nucleus is prepared after a known process (French patent specification 1286 803) from cyclododecene, which with carbon oxide and hydrogen (OXO reaction) is converted into cyclododecylmethanol, whereupon this Aldehyde is oxidized to the corresponding acid. Since the cyclododecene only comes either from the starting material for the cyclic compounds with 12 carbon atoms generally used triene or from the cyclododecane must be obtained via the cyclododecanol and then the implementation Still in two stages, via the aldehyde, the known process appears rather complicated and cannot compete with the present, much simpler process.

It has already been possible to convert cyclododecatriene into cyclic acids: K. E. Möller and G. Wille have described a process after which the carbon oxide in the presence of acidic catalysts on cyclododecatriene- (l, 5,9) allowed to act, whereupon water or an alcohol is added to the reaction products. This process gives a mixture of isomeric polycyclolic acids with 13C atoms. According to "Angewandte Chemie", Vol. 73, 1961, p. 240, H.Koch and K.E.Möller found that the products obtained are perhydroacenaphthenecarboxylic acids in which the Carboxyl group is bonded to a tertiary carbon atom. They are therefore acids,

Process for the production of
Monocarboxylic acids of the cyclododecane series
or their esters

Applicant:
ORGANICO, Paris

Representative:

Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse and
Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Bad luck man,
Patent Attorneys, Munich 9, Schweigerstr. 2

Named as inventor:
Michel Genas,
Thomas RuIl, Paris

Claimed priority:

France of April 18, 1962 (894 861)

the structure of which is completely different from that of the acids obtainable by the present process. The structure of the acids obtained by the present method has been determined with certainty by determining the acid number, the molecular weight, the infrared spectrum, the spectrum of the nuclear magnetic resonance and the hydrogen and bromine numbers. In the case of free acid is after complete hydrogenation, no lowering of the melting point when mixed with the pure cyclododecanecarboxylic acid ascertain.

The reaction of carbon monoxide to a mixture of water or an alcohol and an ethylene hydrocarbon in the presence of metal carbonyls for the production of carboxylic acids has already been described in German Patent 842 341, but not yet used for the production of monocarboxylic acids from polyolefins. It is surprising that, according to the invention, when reacting cyclododecatrienes, 5.9) with Carbon dioxide and water or an alcohol instead of di- or tricarboxylic acids or theirs Esters which would normally be expected contain essentially monocarboxylic acids. Indeed if the reaction extends selectively to a single one of the double bonds of the cyclododecatriene, without ring formation taking place in the molecule

609 510/434

Find. At the same time, hydrogenation occurs, which results in partial or total saturation of the double bonds in the C ₁₂ ring. This hydrogenation is probably due to the presence of hydrogen in the reaction mixture in the status nascendi, which was formed by the reaction of the carbon dioxide with the water or by the dehydrogenation of the alcohol; it can take place before, during or after the carboxylation. So the end product is a mixture of acids, namely of cyclododecane, cyclododecenecarboxylic acid and cyclododecanedienecarboxylic acid or the corresponding esters and, if the carboxylation was not complete, hydrocarbons, in which, among the latter, the cyclododecene in addition to lower proportions of cyclododecatriene- (1, 5.9) and cyclododecane predominate.

The hydrogen also comes from the formation of aldehydic and alcoholic by-products due to a hydroformylation reaction, the latter, known as the OXO reaction, _{leading to aldehydes due to the action of CO φ H 2} on ethylene hydrocarbons. The alcohols are then created by reducing the aldehydes. This side reaction is all the more important as work is carried out at an elevated temperature.

To carry out the process according to the invention, the carbon oxide is allowed to act under a pressure of at least 150 kg / cm ² , preferably from 200 to 350 kg / cm ² . You can, however, work without increasing the pressure, but this is not an advantage. The reaction temperature is between 100 and 200 ⁰ C, preferably between 150 and 18O ⁰ C. Above 18O ⁰ C, more hydrogen is formed, thereby increasing the amount of resulting from the hydroformylation products.

The finely divided metals of cobalt and nickel are obtained by reducing their oxides with hydrogen or by decomposing their alloys with aluminum with sodium. You can can also be obtained by decomposing their carbonyls. If you apply them in the form of their salts, so the salts with organic acids show the best results. When applying the finely divided Metals or their salts as catalysts it is advantageous to use a small amount of their sulfides or something Adding sulfur, whereby the formation of the carbonyls is favored. Presumably they actually are the metal carbonyls formed by the reaction of the carbon monoxide with the metals or salts, which ultimately catalyze the reaction.

If you want to get the free acids, you use water as the reactant, and in this water Case, it is advantageous to add a solvent as a solubilizer that contains both the cyclododecatriene (l, 5,9) as well as dissolving the water, and adding a sufficient amount to make a homogeneous solution at the reaction temperature to obtain. The solvent must be inert under the reaction conditions. One can for example Use acetone, dioxane or the ethers of glycols or polyglycols.

If the product you are looking for is an ester of cyclododecanecarboxylic acid, so the water is replaced by an alcohol. In this case the reaction mixture is homogeneous and there is no need for an inert one Add solvent. It is preferred to use saturated aliphatic alcohols, their molecule Contains 1 to 4 carbon atoms.

The carboxylic acids obtainable according to the invention, namely the cyclododecane, cyclododecene and Cyclododecadienoic acid, are useful as pesticides. The esters of these acids can serve as plasticizers. The carboxylic acids or esters obtained can be obtained by hydrogenation ίο convert to cyclododecanecarboxylic acid or its ester at any time.

The examples serve to explain the process according to the invention in more detail.

example 1

90 g of cyclododecatriene (l, 5.9), 300 cm ^{3 of} acetone, 30 cm ^{3 of} water, 5 g of Raney cobalt and 1 g of cobalt sulfide are placed in a 1-1 stainless steel autoclave equipped with a stirrer. After flushing the autoclave with carbon dioxide, it is filled with carbon dioxide under a pressure of 120 kg / cm ² and the autoclave is heated to 175 ° C. while stirring. The pressure initially rises to 220 kg / cm ² and has fallen to 208 kg / cm ^{2 after a few hours.} By reintroducing carbon oxide, the pressure is increased again to 230 kg / cm ² and stirring is continued for 8 hours, the pressure dropping to 220 kg / cm ² . The contents of the autoclave are allowed to cool to 150 ° C. and slowly blown off to atmospheric pressure. During the venting, the acetone is completely distilled out, which can be condensed for reuse. The cobalt carbonyl, which is not stable at 150 ° C. under atmospheric pressure, decomposes and forms finely divided cobalt, which can be used in a further operation in place of the Raney cobalt. In order to make the decomposition of the carbonyl more complete, the autoclave is blown with nitrogen while maintaining the temperature of 150 ° C.

After cooling, the contents of the autoclave are taken up in benzene. The one present in powder form Cobalt is separated off by filtration. The benzene layer is washed with dilute hydrochloric acid, to decompose small amounts of cobalt salts that have gone into solution. Afterward the benzene solution is washed with a 10% soda solution. The aqueous layer is diluted with Acidified hydrochloric acid. The acids precipitate out of the solution and are taken up in petroleum ether.

The petroleum ether solution is then washed with water and dried over sodium sulfate, whereupon the solvent is distilled off under reduced pressure.
~ The residue represents 15.6 g of a viscous liquid. Its acid number is 267.5 (theoretical value for cyclododecanecarboxylic acid: 263.5; for cyclododecadienecarboxylic acid: 268.5). Its bromine number is 58.8 (theoretical value for cyclododecenecarboxylic acid: 76.5, for cyclododecadienoic acid: 154).

For the purpose of identification, the acids were converted into their methyl esters, which were hydrogenated in methanol solution in the presence of Raney nickel at 70 ° C. and 70 kg / cm ² hydrogen pressure. The saturated methyl ester was saponified, the acid obtained was recrystallized from petroleum ether and aqueous methanol to give a white product which melted at 99.5 ° C. and which had already been identified

Sample of cyclododecanecarboxylic acid showed no lowering of the melting point. The infrared spectra of the obtained product and the identified comparative sample coincided. The vapor chromatogram the hydrogenated methyl ester was identical to that of a methyl ester of cyclododecanecarboxylic acid.

The results of the comparison samples and other methods of determination show that the Acidic products obtained from a mixture of cyclododecanecarboxylic acid with the reaction analogous unsaturated acids.

The acid mixture consists of about 35% cyclododecanecarboxylic acid and about 47% of cyclododecenecarboxylic acid and about 18% cyclododecadiene carboxylic acid. The ones that make up about 78% neutral reaction products are distilled off from the benzene solution in vacuo. You get 70 g of distillate, which is a mixture of cyclododecatriene, -diene, -decene and -decane, of which the unsaturated cyclic hydrocarbons make up 90% (63 g). Under consideration of Cycloolefins which can be recycled to the process are calculated to have a yield of acids of 44.5%.

Example 2

The apparatus used in Example 1 is filled with 90 g of cyclododecatriene (1,5,9), 300 cm ^{3 of} methanol, 4.9 g of finely divided cobalt from the experiment according to Example 1 and 1 g of cobalt sulfide, after which the autoclave is flushed with carbon oxide . Carbon oxide is then pressed in up to a pressure of 160 kg and the mixture is heated to 175 ° C., as a result of which the pressure rises ^{to 275 kg / cm 2.} The autoclave is stirred for 12 hours, both the temperature of 175 ° C. and the pressure of 275 kg / cm ^{2 being} maintained by repeatedly introducing carbon oxide - which compensates for the pressure drop resulting from the CO consumption. After 12 hours, the internal pressure of the autoclave is released to atmospheric pressure. The contents of the autoclave are allowed to cool and are taken up in benzene. The benzene solution is freed from the deposited cobalt by filtration and washed with dilute hydrochloric acid to destroy the cobalt traces and then with water. The benzene is removed by distillation under reduced pressure. The residue is distilled at a pressure of 1 mm Hg.

The top product obtained in the distillation is a hydrocarbon fraction in which through Gas chromatography shows the presence of 13.8 g of cyclododecene and cyclododecadiene, that can be used again for a subsequent operation. Starts between 115 and 125 ° C one 67 g of an ester fraction, which consists of 88% ester (58.8 g pure product) and 8% cyclododecylcarbinol composed.

Taking into account the cyclododecene and cyclododecadiene obtained, the yield is 56.7% of theory.

Example 3

The procedure is analogous to Example 2, but with the difference that instead of an initial pressure of 160 kg / cm ² for the carbon oxide, one

S uses those of 140 kg / cm ² . The proportion of higher-boiling products formed in the reaction decreases in this case, and the yield of methyl ester of cyclododecanecarboxylic acid is 62.5% of theory, although the reusable unsaturated hydrocarbons are taken into account.

Example 4

A 1-1 autoclave with a stirrer is charged with 90 g of cyclododecatriene (1,5,9), 250 ml of methanol, 5 g of Raney nickel and 1 g of nickel sulfide. After purging with carbon dioxide, the autoclave is filled with carbon dioxide up to a pressure of 120 kg / m ² and heated to 200 ° C, the pressure being increased to 200 kg / m 2.

ao cm ² increases. 200 ° C. and kg / cm ^{2 are maintained for} 30 hours with stirring.

The reaction products are obtained as in Example 2. 18 g of a mixture are obtained from cyclododecadiene and cyclododecadecene and 62.3 g of mixed methyl esters of cyclododecane, Cyclododecene and cyclododecadiene monocarboxylic acids. Taking into account, the yield of esters is that in the process for recyclable hydrocarbons 59%. In addition, 6 g of cyclododecyl carbinol were formed.

Claims (3)

Patent claims: 1. Process for the preparation of monocarboxylic acids of the cyclododecane series or their esters by treating Cyclododecatrien- (1,5,9) with carbon oxide and water or an alcohol at pressures of 150 to 350 kg / cm ² and elevated temperatures in the presence of a Catalyst, characterized in that the carbonylation is carried out in the presence of a nickel or cobalt catalyst known as a carbonylation catalyst in the form of a finely divided metal, salt or carbonyl at 100 to 200 ° C, advantageously at 150 to 180 ° C. 2. The method according to claim 1, characterized in that the catalyst used is nickel or cobalt used in the form of a salt with an organic acid and that one Add a small amount of nickel or cobalt sulfide. 3. The method according to claim 1, characterized in that the reaction is carried out in the presence of water and an inert solvent such as acetone, dioxane, glycol or polyglycol ether carried out in an amount sufficient to simultaneously dissolve the water and the cyclododecatriene- (1,5,9). Considered publications:
German Auslegeschrift No. 1068 255;
French patent specification No. 1286 803.