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The effect of sulfur and some of its compounds on the oxo synthesis

V. Macho

Research Institute for Petrochemistry, 972 71 Nov√°ky


Abstract: Elementary S had a retarding effect on the oxo synthesis and decreased the conversion of olefins on aldehydes. By applying 0.2% Co (wt.), calcd. on the wt. of C6-C7 olefins, at 0.1% wt. of S, the conversion is approx. 42% and at 0.2% wt. of S only 12.0%. By applying an equimolar amt. of S, based on the amt. of Co present in the reaction medium, the conversion of olefins was approx. 45.0% and the finished product did not contain sol. carbonyls of Co. By increasing the amt. of Co, the reaction speed and the conversion linearly increased. Because of the fact that S limited the formation of Co carbonyls, the optimum amt. of catalyst was detd. by the purity of raw materials. Analogously, CS2 had an effect similar to that of S, considerably less than that of EtSH. Quant. the detrimental effect of S, CS2, and EtSH (calcd. from M effect) on the oxo synthesis was expressed in this relation: S-CS2EtSH = 100:71:1.6. Thiophenes and tetrahydrothiophenes in amts. of 5-7% (based on the wt. of olefins) did not retard or inhibit oxo synthesis and did not decrease the conversion, so that thio-S can be regarded as harmless. Only S and S compds., capable under conditions of the oxo synthesis of attacking Co carbonyls, were harmful.

Full paper in Portable Document Format: 153a181.pdf (in Slovak)


Chemical Papers 15 (3) 181–190 (1961)

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