Patent GB-671563-A (GB)
Title: Improvements in or relating to the fractionation of stereoisomers
IPC: C11C1/00
Filed: 1950-01-25
Abstract: A liquid mixture of geometrical cis and trans stereoisomers of straight-chain compounds derivable from unbranched olefins having an unbranched hydrocarbon chain of at least 4 carbon atoms and at least one olefinic C to C double bond, and having only hydrogen p substituents except for a terminal group which may be a hydrocarbon or other group such as carboxyl, ester, hydroxyl, amino, amido or nitrile, is fractionated by treating with urea at 0-75 DEG  C. to form crystalline complexes with part of said mixture in which the trans isomers are concentrated, the cis isomers being concentrated in the separated liquid residue.  Fatty acid stereo-isomers such as oleic and elaidic or linolenic and elaidolinolenic acids, their esters with monohydric alcohols, preferably of 1-10 carbon atoms, e.g. methyl oleate and elaidate, amides such as linoleyl and linolelaidyl, unsaturated nitriles, e.g. those having a C18 hydrocarbon chain, fatty alcohols such as oleyl and elaidyl alcohols, amines, olefins such as octene-2 or hexadecadiene, and mixtures obtained by hydrolysis of vegetable oils or by the Fischer-Tropsch synthesis may be separated.  Preferred mixtures contain 10 or 90 parts of one stereo-isomer and 90 or 10 of the other.  A saturated aqueous solution of urea is preferred.  Selective extraction of particular compounds, e.g. according to molecular weight, may be effected by varying the concentration of the solution and the temperature. The mixture treated is preferably dissolved, for example in low molecular weight ketones or alcohols.  The amount of urea and time of treatment is limited so that only a part of the mixture forms complexes.  The separated fractions may be further treated with urea. The complexes are decomposed by treating with a solvent for urea or for the compound combined therewith, e.g. water or dilute urea solution.  A temperature of 75-100 DEG  C. is generally used. In examples: (1) 75 parts of a 2 : 1 mixture of oleic and elaidic acids are shaken with 600 parts of methyl alcoholic urea, originally saturated at 80 DEG  F., and the complexes separated and decomposed with water at 80 DEG  C. to give a fatty acid mixture which is 51 per cent elaidic; (2) the raffinate acids of (1) are again treated with urea giving a 51 per cent elaidic acid product; (3) 55 parts of a mixture of 19 per cent elaidic, 81 per cent oleic acids is dissolved in 60 parts methyl isobutyl ketone, and shaken with 300 parts aqueous urea, originally saturated at 90 DEG  F., with step-wise reduction of temperature to 70 DEG  F.  The extracted acids are 28 per cent elaidic.ALSO:A mixture in liquid form of geometrical cis and trans stereoisomers of fatty acids is separated by treating with urea at 0-75 DEG C. to form crystalline complexes with part of said mixture in which the trans isomers are concentrated, the cis isomers being concentrated in the separated liquid residue.  Oleic and elaidic or linolenic and elaidolinolenic acids may be separated. Preferred mixtures contain 10 or 90 parts of one stereoisomer and 90 or 10 of the other.  A saturated aqueous solution of urea is preferred. Selective extraction of particular compounds, e.g. according to molecular weight, may be effected by varying the concentration of the solution and the temperature.  The mixture treated is preferably dissolved, for example in low molecular weight ketones or alcohols. The amount of urea and time of treatment is limited so that only a part of the mixture forms complexes.  The separated fractions may be further treated with urea.  The complexes are decomposed by treating with a solvent for urea or for the acid combined therewith, e.g. water or dilute urea solution.  A temperature of 75-100 DEG C. is generally used.  In examples: (1) 75 parts of a 2:1 mixture of oleic and elaidic acids are shaken with 600 parts of methyl alcoholic urea, originally saturated at 80 DEG F., and the complexes separated and decomposed with water at 80 DEG C. to give a fatty acid mixture which is 51 per cent elaidic; (2) the raffinate acids of (1) are again treated with urea giving a 51 per cent elaidic acid product; (3) 55 parts of a mixture of 19 per cent elaidic, 81 per cent oleic acids is dissolved in 60 parts methyl isobutyl ketone, and shaken with 300 parts aqueous urea, originally saturated at 90 DEG F. with step-wise reduction of temperature to 70 DEG F.  The extracted acids are 28 per cent. elaidic.