Hydrosilylation of long chain unsaturated fatty acid esters

Abstract

The addition of a series of silicon hydrides: trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyl dichlorosilane, and methyl phenyt chlorosilane to esters of long chain unsaturated fatty acids, such as oleic, linoleic acids, and 10-undecenoic acid, was studied with respect to catalysts, temperature, and solvents. Higher yields were obtained on carrying out the hydrosilylation reactions in the presence of chloroplatinic acid or Pt on C catalysts in bulk without solvent, as compared with peroxide catalysts. The addition reaction with methyl 10-undecenoate, which has a terminal double bond, gave a higher yield than that with methyl oleate. NMR data of the products from methyl 10-undecenoate and methyl oleate, as well as their reduction products with lithium aluminum hydride, have shown that, with the former ester, the silyl moiety added exclusively to the terminal carbon atom, while, with the latter, no migration of the silyl moiety to the terminal carbon atom was observed.

Toward new biosilicones: hydrosilylation of fish oil unsaturated fatty acid esters

“…In a spectroscopic study of the hydrosilylated undecanoic acid methyl ester synthesized previously by Saghian and Gertner, 16 the 13 C NMR analysis confirmed the silylation of C11. Mass spectra (EI) of all the adducts showed the molecular ion and the two fragmentation pathways characteristic of saturated FAMEs, 18 i.e.…”

“…Nuclear magnetic resonance (NMR) spectra were recorded on Bruker AC 80 ( With the purpose of comparing the regioselectivity of these radical-initiated and Platinumcatalyzed hydrosilylations, we reproduced the Speier-catalyzed hydrosilylation of methyloleate as described by Saghian and Gertner. 16 We observed by mass analyses of the reaction product that the carbon chain fragmentation process led to two different silylated last fragments (m/z: 281 and 267 corresponding respectively to the C10 and C9 silylated compounds), thus confirming their hypothesis of two isomeric adducts (C9, C10). .…”

“…16 Molecular modeling (see Section 2) of the two isomeric reaction intermediates according to the published structure 19 showed that they have almost the same stability (Fig. 1), accounting for the low regioselectivity.…”

Hydrosilylation of unsaturated fatty acid N‐phenyl amides

“…2 Moreover, transition metal-catalyzed hydrosilylation of olefins, which has been the methodology of choice to attach organic group on a chain, 3,4 has also been explored in the case of fatty compounds. 5,6 In this context, we recently reported the syntheses of organohalosilyl fatty acid methyl esters (FAME) by hydrosilylation of unsaturated FAME (methylundecenoate and 9-methyloleate) for the preparation of ambiphilic polysiloxanes. 7 In contrast, to the best of our knowledge, the hydrosilylation of fatty acid amides has never been developed and remains a stimulating challenge as the fatty acid amides represent an important class of bioactive lipids in human and other mammals.…”

Highly Selective C‐Silylation of Fatty Acid Methyl Esters

“…[10] In this context, we recently reported the syntheses of organohalosilyl FAMEs by hydrosilylation of unsaturated FAMEs (methyl undecenoate and 9-methyl oleate) for the preparation of ambiphilic polysiloxanes. [11] This study has allowed silylation both at the terminal and at various internal positions of the FAMEs.…”