コバルトカルボニル第三ホスフィン錯体触媒による多不飽和脂肪酸エステルのモノエン体への選択的水素化
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概要
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Homogeneous hydrogenation of soybean oil or methyl ester derived from linseed or cottonseed oil has been studied using complex catalysts [Co (CO) <SUB>3</SUB>PR<SUB>3</SUB>] <SUB>3</SUB> (PR<SUB>3</SUB> is P (n-Bu) <SUB>3</SUB>, P (Cyclohexyl) <SUB>3</SUB> or PPh<SUB>3</SUB>, and the catalysts are abbreviated here (1), (2) or (3) respectively) which are known to hydrogenate cyclododecatriene into cyclododecene with almost complete selectivity in the presence or absence of small amounts of carbon monoxide. In the title reaction, however, addition of ca. 25 atm of carbon monoxide to 4050 atm of hydrogen was essential to secure high selectivity and to prevent catalyst decomposition. Under these pressures the typical figures of reaction time (min) / reaction temperature (°C) were 120/170, 350/145 or 60/185 employing 0.30.8 mol% per ester of (1), (2) or (3) respectively without solvent. Addition of benzene as solvent remarkably accelerates the rate of reaction using (3). Catalyst (3) was appraised as best, because, different from (1) and (2), it does not form saturated products even after unnecessarily delayed reaction and moreover, it can be recovered through timely discontinuance of the reaction. Regardless of the kinds of starting, esters a total amount of ca, 10% of two unidentified peaks was always observed in the gas chromatograms of final products. Remaining ethylenic linkage was widely distributed over monoenoic fatty acid chain on either side of C<SUB>9</SUB> position, and its trans/cis isomer ratio was ca. 1.75. <BR>Formation of small amounts of "Oxo-alcohol" was also observed.
- 日本油化学会の論文