DE1272918B - Process for the large-scale production of di- or tribasic cyclohexenecarboxylic acids or their functional derivatives - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CI .:

C07c

BOIj
C08g

German class: 12 ο - 25

12 g-1/03; 39 c-16;
39C-30

Number: 1272918

File number: P 12 72 918.9-42 (B 73541)

Filing date: September 17, 1963

Opening day: July 18, 1968

With the invention, di- or tribasic cyclohexenecarboxylic acids or their functional components Derivatives in comparison with known methods as described in J. Amer. Oil Chemist's Soc., Vol. 34, 1957, pp. 136 to 138, and Vol. 35, 1958, pp. 238 to 240 (reported in Chem. Zentralblatt 1959, P. 13 759 and 13 760), are described in a simpler manner and in almost theoretical yield getting produced.

The present invention is directed to a method for the large-scale production of di- or tribasic cyclohexenecarboxylic acids or their functional derivatives by addition of suitable dienophilic carboxylic acids or of their functional derivatives of conjugated unsaturated fatty acids with cis-trans conjugated double bonds, such as maleic anhydride, in the presence of iodine at an elevated temperature in the presence of ultraviolet Light, and is characterized in that in the presence of only 0.01 to 0.2 percent by weight Iodine works and uses the reactants in practically equimolecular amounts.

The present invention is based on the discovery that isomerization of the cis-trans starting compound into the trans-trans isomer and formation of the Diels-Alder adduction product can be carried out. By adhering to the reaction conditions according to the invention the formation of higher molecular weight by-products is reduced.

As functional acid derivatives, for. B. serve anhydrides, esters, amides or nitriles.

Suitable dienophilic compounds are e.g. B. maleic acid or maleic anhydride, acrylonitrile, Acrylic acid or methyl acrylate. Suitable conjugated starting materials are mixtures of fatty acid or esters which isomers of polyunsaturated acids or esters conjugated with Contain double bonds. Typical examples are dehydrated castor oil fatty acids, which im essentially from a mixture of isomers of conjugated and non-conjugated linolenic acid or isomerized unsaturated fat products and z. B. by catalytic isomerization of multiple unsaturated oils are obtained, as well as the products that are produced by an alkali isomerization or by an isomerization process of polyunsaturated Esters are formed.

The catalytic amounts of iodine are 0.01 to 0.2 percent by weight of the material used. Larger amounts lead to a progressive discoloration of the products. Quantities from 0.05 to 0.2 Large-scale manufacturing processes
of two- or three-basic
Cyclohexenecarboxylic acids or their
functional derivatives

Annielder:

J. Ribby & SdHirfcirnited, Liverpool,

Lancashire (UK)

Representative:

Dr. rer. nat. J. D. Frhr. v. Uexküll, patent attorney,

2000 Hamburg 52, Königgrätzstr. 8th

Named as inventor:

Raymond Vincent Crawford,

Greasby, Wirral, Cheshire;

Patrick Arthur Toseland, Woolton, Liverpool,

Lancashire (UK)

Claimed priority:

Great Britain 19 September 1962 (35 592)

Weight percent is therefore preferred. The reaction conditions depend on the dienophiles used Connections. The temperature is between 60 and 250 ° C.

To achieve the best working conditions and the formation of polybasic acids as a by-product To suppress the temperature, the temperature should be kept below 110 ° C.

The process can be carried out with or without a solvent, e.g. B. petroleum hydrocarbons, and at normal pressure or can also be carried out at elevated pressure, which is preferred when using volatile dienophiles will. When vinyl monomers such as an acrylic acid ester are used, hydroquinone or other radical polymerization inhibitors are added.

You can work in detail as follows:

a) Iodine, the dienophilic compound and the conjugated material are mixed together and warmed;

b) the iodine is added to the conjugated material and the mixture is brought to the equilibrium point the cis-trans, trans-trans iso-

809 570/595

3 4

merization brought before the dienophile Ver with a yield of 94% of the theoretical advertising binding is added; tes was isolated by filtration. The end product

c) The dienophilic compound is added to the conjugated product ^{, a white powder with a content of 3} % of the material, and the iodine is converted into unreacted fatty acid.

several servings added, for example ⁵ Example2

wise one to the content of trans- at the beginning. . . .

trans compound equivalent amount and 296 g conjugated TaU oil methyl ester with a mixture

When the main part of the trans-trans ^{content of 46} % conjugated dienes has reacted with 34 g of the compound, the remaining amount of the ice-shaped acrylic acid, 0.3 g of hydroquinone, is added as an inhibiting dienophile compound; ^{10 substance for} radical polymerization and with

,.,, Tj-jj ι · · .. λ / γ 0.3 g of iodine heated under nitrogen and 2 hours

d) all the iodine is the conjugated ma- _{bd 2QQ to 21QO c under reflux} treated. The tenal was added, and the dienophilic compound _{content of conjugated} A _n ^ _{6n fell to 3} o _{/ o} . is at the beginning of the reaction or in several _{times unconverted} acrylic acid was added by dividing during the reaction. _{lg WaS (} £ _{Qn with w} * _{sssr removed} ^J. p _{as product remained}

The iodine catalyst used in the reaction is returned as a residue after the unreacted may have been removed from the reaction product on various esters by vacuum distillation. That Way to be removed. For example, the product had an acid number of 147, and the off-reaction product 2 hours at 100 ° C with 0.2 loot was 96% of the theoretical value,

weight percent zinc dust and 20 weight percent 20.

Stir water. The reaction pro-Example 3

duct z. B. with an aqueous thiosulfate-potassium 150 g of methyl ester conjugated fatty acids

treat iodide mixture. , -__ soybean oil with a content of 47% conjugated die-

The reaction product can be based on different ne and 5% conjugated trienes were

Way to be separated. When conjugated fats- 25 men with 0.15 g iodine, 0.3 g hydroquinone and 22 g

acids or volatile conjugated fatty acid esters than acrylic heated. The reaction was taking 1 hour

conjugated reaction component is used nitrogen in a shaking autoclave at 180 to 200 ° C

the, so the reaction product of the non-carried out. The unreacted fatty acid esters

reacted material (mainly palmitin or were removed by distillation. The adduct

Oleic acid or its ester) by distillation at 30 was then distilled under high vacuum. That

be separated under reduced pressure. The more volatile product had a saponification equivalent of 178

Adducts such as the adducts of methyl esters and and fell in a yield of 90% of the theoretical

Acrylic acid methyl ester, can with a further yield of.

Purification under reduced pressure distilled example 4

will. 35

The addition product of conjugated fatty acids 500 g of dehydrated castor oil fatty acids with a

and maleic anhydride can thereby be isolated.Content of 44% conjugated dienes were 20 Mi-

be that the reaction mixture is heated in large grooves with 0.025 g of iodine at 90 to 100.degree.

Amounts of hexane or heptane dissolves and room- Then 40 g of maleic anhydride were added

temperature cools, with a lower one added to the 40 stirring. The temperature was 3 hours

Leave the main part of the adduct-containing layer deposited at 90 to 100 ° C., whereupon a further 0.025 g

det and can be withdrawn. For stronger iodine and then add 40 g of maleic anhydride

Cooling to about 5 ° C, the adduct can have been put into white. The mixture was taking 3 hours

solid crystals are obtained, which are then filtered off and heated with gentle stirring until the content of conju-

will. 45 yaw shares had dropped to 4%. One

The addition product of methyl esters and distillation analysis of the product indicated the presence of maleic anhydride can be obtained by having 264 g of the adduct, which is · 85% of the theoman the reaction mixture at room temperature corresponded to the retic yield. All of the reac crystallizes and the tribasic product abation product, which consists of tribasic acid and 48% filtered. 50 linoleic acid had to be converted into water

In the following, the invention is to play on the basis of insoluble alkyd resins with air-drying properties are explained in more detail. th suitable.

Example 1 Example 5

296 g of conjugated soy fatty acids with a content of 55 1500 g of methyl esters isomerized with alkali

of 47% conjugated dienes and 5% conjugated sunflower oil with a content of 55% conjugate

Trienes were 20 minutes with 0.15 g of iodine at 90 gated dienes were heated to 95 ° C and with

heated to 100 ° C. Then 0.1 g of iodine were added with stirring. The temperature was 1 hour

25.5 g of maleic anhydride were added. Maintain the tempera- ture; then were slowly taking

door was left at 90 to 100 ° C. for 3 hours. 60 stirring 135 g of maleic anhydride added. the

Then 0.15 g of iodine and then the temperature was kept below 110 ° C. for 3 hours.

25.5 g of maleic anhydride were added, the whole of which was added 0.2 g of iodine and then another

The mass was heated and added under 135 g of maleic anhydride for a further 3 hours. The reaction

Treated with moderate stirring. After- the content was continued for 4 hours. A thereafter

conjugated fractions of the total mass decreased to 3 %- 65 performed ultraviolet spectrophotometric analysis

When the product had decreased, it was cooled and found to contain 3% conjugated dienes.

700 ml of heptane poured and 48 hours at 5 ° C. 15 g of dicyclopentadiene were added, which are

leave, whereupon the adduct crystallized out and reacted with the unreacted maleic anhydride

should set, and the iodine was obtained by adding 15 g of zinc dust and 200 ml of water, heating for 2 hours removed at 100 ° C and filtering. Distillation of the product gave a residue of 1025 g of an addition product with a content of 4% monobasic methyl esters.

The cyclohexenecarboxylic acids prepared according to the invention can be used, for example, as plasticizers and as intermediate products in the manufacture of plasticizers for hardening epoxy resins, for the production of polyesters in the manufacture of alkyd resins and as a substitute for other two- and tribasic acids and esters can be used.

Claims (1)

Claim: Process for the large-scale production of di- or tribasic cyclohexenecarboxylic acids or their functional derivatives by addition of suitable dienophilic carboxylic acids or from their functional derivatives to conjugated unsaturated fatty acids with cis-trans conjugated Double bonds, such as maleic anhydride, in the presence of iodine at an elevated temperature in the presence of ultraviolet Light, characterized in that in the presence of only 0.01 to 0.2 percent by weight Iodine works and uses the reactants in practically equimolecular amounts. Considered publications:
German Auslegeschrift No. 1048 272;
U.S. Patents Nos. 2374,381, 2342113, 2444328;
J. Amer. Oil Chemist's Soc, Vol. 35, 1958, p. 238 to 240 (reported in Chem. Zentralblatt 1959, S. 13760), Vol. 34, 1957, pp. 136 to 138 (referenced in Chem. Zentralblatt 1959, p. 13759).