SU556135A1 - The method of obtaining aliphatic carboxylic acids - Google Patents

Description

gas, load 5.5 g (O 05 g-mol) of cyclooctane, ShOml dioxane and 4 ml of methanol. At a temperature of about 0 ° C, an ozone-oxygen mixture (5.5% by weight of ozone) is passed through the solution at a rate of 25 l / h until 0.05 gmol of ozone is absorbed. The reaction mixture is purged with argon, 0.1 g of Lindlar catalyst is added (palladium coated on calcium carbonate with an admixture of lead oxide Pd: CaCO3: PbO: 4: 90: 6 wt.% And stirred in a hydrogen atmosphere at room temperature and normal pressure until the peroxide test with potassium iodide is negative (10-15 hours). The catalyst is filtered off and the solvent is distilled off under reduced pressure. White crystals of corky acid are obtained in the residue. Yield 7.6 g (87.5%), sample on aldehydes with phosphoric acid solution 2,4-dinitrophenylhydrin zine negative;.. m.p. 134-136 ° C after recrystallization from ethyl acetate: mp 140 ° C 139,5- sample mixed media audio-product clearly shows no melting point depression, IR spectrum identical notorious compounds.....

Example 2. 5.5 g of cycloocten are ozonated as described in Example 1, 0.1 g of Lindlar catalyst, isolated from the previous test, is added and hydrogenated for 10-15 hours, as described in Example 1. The yield of cork acid is 7.6 g (87.5%); m.p. 134-136 ° C.

Example 3. 5.5 g of cycloocten are ozonated as described in Example 1, 0.1 g of catalyst (10% Pd on coal) is added and hydrogenated as in Example 1. 2 g of viscous liquid containing corky acid crystals are recovered. . After treatment with ether, filter 0.1 g (1.2%) of cork acid; m.p. 130-133 ° C; m.p. 139-140 ° C (from ethyl acetate).

From the filtrate, after evaporation, 1.9 g of a mixture of aldehyde and acid is obtained, which gives a hydrazone precipitate upon reaction with a phosphoric acid solution of 2,4-dinitrophenylhydrazine.

Example 4. 5.5 g (0.05 g-mol) of cyclooctane are ozonated in 100 ml of dioxane containing 4 ml of water at a temperature, then hydrogenated, as described in example 1, to a negative reaction to peroxides (10-15 hours) , and 6.9 g (79.5%) of cork acid are recovered; m.p. 135-137C.

Example 5. 5.5 g of cycloocten are ozonated in 100 ml of dioisane at a temperature of 5-10 ° C, then hydrogenated as described in example 1 to a negative reaction to peroxides (10-15 hours) and 7.2 g (83 %) cork acid; m.p. 129-131 ° C; 139-140 ° C (from ethyl acetate).

Example 6. 5.5 g of cycloocten are ozonated in 100 ml of tetrahydrofuran containing 4 ml of methanol at a temperature of from -50 to -30 ° C and then hydrogenated, as described in example 1, for 1.5-2 days. The catalyst is filtered off and after evaporation of the solvent.

7.2 g (83%) of cork acid are obtained; m.p. 128-130 ° C, after recrystallization from ethyl acetate so pl. 139-140 ° C.

Example 7. 5.5 g of cycloocten are ozonated in 100 ml of tetrahydrofuran containing 4 ml of methanol at a temperature of from -50 to -30 ° C, then 100 ml of methanol is added and hydrogenated as described in example 1, to a negative reaction on peroxide (20 hours). The catalyst is filtered off and the solvent is distilled off. The output of cork acid 7.5 g (86%); m.p. 128-130 ° C.

Example 8. 5.5 g of cyclooctene are ozonated in 100 ml of tetrahydrofuran and 4 ml of methanol at a temperature of 5-10 ° C, 100 ml of methanol are added and hydrogenated, as described in Example 1, to a negative reaction to peroxides (4 hours). 8.6 g (99%) of cork acid was recovered; m.p. 129-13GS; 133-140 ° C (from ethyl acetate).

Example 9. 5.5 g of cycloocten are ozonated in 100 ml of ether containing 8 ml of methanol at a temperature of -75 ° C and then hydrogenated as described in Example 1. 7.0 g (80%) of corky acid was isolated; m.p. 130-132 ° C; 139-140 ° C (from ethyl acetate).

Example 10 5.5 g of cyclooctene are ozonated in 100 ml of ethyl acetate containing 4 ml of methanol at a temperature of 5-10 ° C and then hydrogenated as described in Example 1. 7.6 g (87.5%) of cork acid are recovered. ; m.p. 128-130 ° C; 139-140 ° C (from ethyl acetate).

Example II Ozonate 4.1 g

(0.05 g-mol) of cyclohexene in 100 ml of tetrahydrofuran containing 4 ml of methanol at a temperature of 5-10 ° C and hydrogenated as described in Example 1. After evaporation of the solvent, 7.15 g (98%) of adipic acid is obtained; m.p. 141 -143 ° C; 152-153 ° C (from ethyl acetate).

The displacement test with the notorious compound does not show a melting point depression.

The IR spectra of both products are identical.

Example 12. 8.25 g (0.05 g-mol) of cyclododecene are ozonated in 100 ml of dioxane containing 4 ml of methanol at a temperature of about 0 ° C and then hydrogenated as described in Example 1. 9.0 g ( 78%) 1.10 decanedicarboxylic acid; m.p. 124-126 ° C; 128-129 ° C (from ethyl acetate).

The displacement test with the notorious sample does not show a decrease in the melting temperature.

The IR spectra of the obtained product and the known sample are identical.

Claims (2)

Invention Formula A method of producing aliphatic carboxylic acids by ozonizing cycloolefins in an organic solvent medium, followed by decomposition of the ozonolysis products in a gas atmosphere and in the presence of a catalyst. 5 exc and cha yush.iy so. that, in order to simplify the process, an ether or ester is used as an organic solvent, hydrogen is used as a gas, and a palladium catalyst is used as a catalyst.5 6 Sources of information taken during the examination: 1. Auth. St. No. 184830, class C 07C 51/18, 1964. 2. Auth. sv Л 390066, кл. C 07C 51/18, 1970 (prototype).