Saturated branched fatty acids containing 21 to 28 carbon atoms

Organic compounds -- part of the class 532-570 series – Organic compounds – Fatty compounds having an acid moiety which contains the...

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554142, C07C 5136

Patent

active

054018650

DESCRIPTION:

BRIEF SUMMARY
BACKGROUND OF THE INVENTION

1. Field of the Invention
This invention relates to saturated branched fatty acids or esters thereof with C.sub.1-36 alkanols obtainable by hydrogenation of olefinically unsaturated adducts of propylene with polyunsaturated C.sub.18-22 fatty acids or esters thereof with C.sub.1-36 alkanols in molar ratios of propylene to fatty acids or fatty acid esters of 1:1 to 2:1.
2. Statement of Related Art
Fatty acids branched in the alkyl chain of the Guerbet acid type, obtainable by "guerbetization" of the corresponding fatty alcohols and oxidation of the Guerbet alcohols to the corresponding acids, are technologically interesting intermediate products because they, or their alkyl esters, have distinctly reduced pour points by comparison with the corresponding unbranched isomers. However, the production of Guerbet acids is technologically complicated and can only be carried out with unsatisfactory yields. Accordingly, there has been no shortage of attempts to produce corresponding fatty acid derivatives branched in the alkyl chain from fatty acids or esters thereof. A typical example of this is the layer-silicate-catalyzed dimerization of fatty acids. Unfortunately, considerable quantities of trimeric fatty acids and methyl-branched fatty acids, so-called isofatty acids, are also formed in this reaction. Another, albeit complicated, process gives branched fatty acid derivatives from conjuene fatty acids in the trans-trans form with activated dienophiles under the conditions of a Dieis-Alder reaction; for example, a branched C.sub.21 dicarboxylic acid can be obtained in this way from linoleic acid and acrylic acid, of. U.S. Pat. Nos. 3,734,859, 3,753,968, DE-B 2 253 930. Other branched fatty acid derivatives have been obtained by thermal or acid-catalyzed addition of activated enophiles onto unsaturated fatty acid derivatives. For example, maleic anhydride can be added onto oleic acid in the presence of an acid as catalyst in yields of up to 70%, cf. Fat. Sci. Technol., 1, 1 (1988). However, the presence of more than one carboxyl group in the reaction products mentioned above has often proved to be troublesome.
Finally, attempts have also been made to add saturated hydrocarbons onto fatty acids by heat-initiated radical addition of saturated hydrocarbons onto fatty acids. The addition of cyclohexane onto oleic acid methyl ester at 340.degree. C./200 bar gives alkyl-branched fatty acids with 70% selectivity, but in a yield of only 2.8%, of. J. O. Metzger et al., Fat. Sci. Technol. 1 (1989), 18.


DESCRIPTION OF THE INVENTION

The present invention is directed to the provision of saturated branched fatty acids or esters of the type mentioned at the beginning which can be readily obtained in high yields. The compounds provided in accordance with the invention are new products which, for example, differ in their chain length alone from the naturally occurring ethyl-branched fatty acids containing a total of 12 to 18 carbon atoms described in A. Smith et al. Biomed. Mass Spectrom., 6 (8), 347-349.
The saturated branched fatty acids according to the invention or esters thereof may be obtained by hydrogenation of olefinically unsaturated adducts of propylene with polyunsaturated C.sub.18-22 fatty acids or esters thereof with C.sub.1-36 alkanols in molar ratios of propylene to fatty acids or fatty acid esters of 1:1 to 2:1.
These propylene adducts are the subject of Applicants' patent application Ser. No. 07/915,844 (D 9010 PCT/US) filed at the same time as the present application to which reference is hereby specifically made and of which the essential disclosure is summarized in the following.
Suitable starting products for the production of the olefinically unsaturated adducts according to the cited patent application are unsaturated fatty acids containing 18 to 22 carbon atoms and more than one olefinic double bond, such as linoleic acid, isomerized linoleic acid containing conjugated double bonds (so-called C.sub.18 : 2-conjuene fatty acid), linolenic acid, arachidonic acid, docosadienoic a

REFERENCES:
patent: 3636122 (1972-01-01), Cramer et al.
patent: 3734859 (1973-05-01), Ward
patent: 3753968 (1973-08-01), Ward
patent: 4371469 (1983-02-01), Foglia et al.
patent: 4973431 (1990-11-01), Struve et al.
Biomed. Mass Spectrom, 6(8), A. Smith et al., pp. 347-349 1979.
Journal of Molecular Catalysis, M. Bochman et al., 22(1984), pp. 363-365.
Comprehensive Organometallic Chem., G. Wilkinson(Ed.), 1982, pp. 414-429 1982.
Radical Addition of Methyl Acetoxy Acetate to Olefins and Pyrolysis of the Adducts Yu. N. Oglbin, G. I. Nikishin and L. M. Ilina Feb. 1967.
CA 66: 10623 [1966].

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