Olefins rhodium-catalyzed biphasic

Rhodium-catalyzed biphasic hydroformylation of olefins. The Ruhrchemie-Rhone Poulenc process for manufacturing... 

Epoxidation of oleic and linoleic acid was readily achieved by treatment with the acetonitrile complex of hypofluorous acid (55). Phase-transfer-catalyzed biphasic epoxidation of unsaturated triglycerides was accomplished with ethylmethyldioxirane in 2-butanone (56). The enantioselective formation of an a,P-epoxy alcohol by reaction of methyl 13()S)-hydroperoxy-18 2(9Z,llfi) with titanium isopropoxide has been reported (57). An immobilized form of Candida antartica on acrylic resin (Novozyme 435) was used to catalyze the perhydrolysis and the interesterification of esters. Unsaturated alcohols were converted with an ester in the presence of hydrogen peroxide to esters of epoxidized alcohols (e.g., epoxystearylbutyrate) directly (58). Homoallyl ethers were obtained from olefinic fatty esters by the ethylaluminium-in-duced reactions with dimethyl acetals of formaldehyde, acetaldehyde, isobutyralde-hyde, and pivaldehyde (59). Reaction of 18 2(9Z, 12Z) with 50% BF3-methanol gave monomethoxy and dimethoxy derivatives (60). A bulky phosphite-modified rhodium catalyst was developed for the hydroformylation of methyl 18 1 (9Z)and 18 1(9 ), which furnished mixtures of formylstearate and diformylstearate (61). 

Hydroformylation of Aliphatic Olefins In 1997, Herrmann and coworkers [25] were the first to use NHCs and imidazohum salts, respectively, as hgands or preligands in rhodium-catalyzed hydroformylation. The isolated NHC-rhodium complexes 1 and 2 (Figure 2.55) and the complexes prepared in situ from the water-soluble imidazolium salts 3a-c and rhodium(lll)acetate were tested in the homogeneous and biphasic hydroformylation of propene. The catalyst derived from 1 produced >99% yield of isomeric butanals (CO/H2 = 1 1,10 MPa S/C = 100 000 1, toluene, 60 h). In the biphasic system, after 20 h of reaction time and S/C = 10000 1 in water, rhodium catalysts derived from 2 or based on hgands 3a-c allowed up... 

The rhodium/TPPTS-catalyzed hydroformylation of 1-octene and other higher olefins in an aqueous biphasic system was studied at pressures from 40 to 90 bar and temperatures of up to 120 °C. Nonionic amphiphiles of the alkoxyethylene type were applied to promote the contact between the reacting species by enlargement of the interfacial area. The highest reaction rates were obtained at a surfactant concentration of about 1 wt% [109]. 

The rhodium/TPPTS-catalyzed hydroformylation of higher olefins in organic/ aqueous biphasic system in the presence of double long-chain cationic surfactants (37) was studied at 100 °C and 20 bar CO H2 = 1 1 pressure. The reaction rate was comparable with that in homogeneous catalysis system [111]. 

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