Homogenous catalysis in the reactions of olefinic substances. V. Hydrogenation of soybean oil methyl ester with triphenylphosphine and triphenylarsine palladium catalysts

Abstract

Some palladium complexes containing coordinated triphenylphosphine or arsine have been found to be effective and selective catalysts in the homogeneous hydrogenation of soybean oil methyl ester. The characteristic features of the catalysis are 1) isomerization ofcis double bonds totrans double bonds, 2) migration of isolated double bonds to form conjugated dienes, 3) selective hydrogenation of poly olefines to mono olefines without hydrogenation of mono olefine, 4) ester exchange of methyl ester to butyl ester, 5) effective hydrogenation and isomerization by methanol in the absence of elemental hydrogen. The catalytic activity of a variety of palladium complexes decreases in the following order: (ϕ3P)2PdCl2+SnCl2ƃ2H2O>(ϕ3P)2PdCl2+GeCl2>(ϕ3P)2Pd(CN)2> (ϕ3As)2Pd(CN)2>(ϕ3P)2PdCl2 » (ϕ3As)2PdCl2. However, neither K2PdCl4 with SnCl2ƃ2H2O nor (ϕ3P)2Pd(SCN)2 was effective for hydrogenation. The hydrogenation and isomerization of soybean oil methyl ester have been examined under various conditions using a mixture of (ϕ3P)2PdCl2 and SnCl2ƃ2H2O. Under nitrogen pressure, in benzene and methanol as a solvent, both isomerization and hydrogenation of soybean oil methyl ester proceeded less effectively than under hydrogen pressure.

Study of homo- and cross-coupling competition in the reaction of triarylbismuth(V) dicarboxylates with methyl acrylate in the presence of a palladium catalyst

“…All solvents were distilled prior to use. Pd(OAc) 2 [28], Pd 2 (dba) 3 [29], Pd(Ph 3 P) 2 Cl 2 [30] were prepared by the reported methods, and PdCl 2 , dppm, dppe, dppp, dppb, BINAP, xantphos were commercially available. Ph 2 BiCl was prepared by a treatment of Ph 3 Bi and BiCl 3 in a 2:1 ratio in dry ether [31].…”

Highly Conjugated Poly(thiophene)s − Synthesis of Regioregular 3-Alkylthiophene Polymers and 3-Alkylthiophene/Thiophene Copolymers

“…Ni(dppp)Cl 2 and n-butyllithium (2.5  solution in hexanes) were purchased from Aldrich. The palladium complexes were prepared according to literature procedures: Pd(PPh 3 ) 4 , [55] Pd(PPh 3 ) 2 Cl 2 , [56] Pd 2 (dba) 3 (CHCl 3 ). [57] UV/Vis spectra were recorded on an MC 2 Safas spectrometer and emission spectra on an SLM-Aminco MC 200 spectrometer.…”

Pd(II)‐Catalyzed Synthesis of Unsymmetrical Biaryls from Tetraphenylborate and Aryl Halides Under Microwave Activation

“…1 H NMR spectra were recorded at [9] General Procedure for the Preparation of Compounds 3a-j A mixture of sodium tetraphenylborate (1 mmol), aryl halide (1.7 mmol), [PdCl 2 (PPh 3 ) 2 ] (0.05 mmol), KF/Al 2 O 3 (3.2 mmol), and DMF (15 mL) was irradiated at 675 W for 10 min by microwaves under a nitrogen atmosphere. The precipitate was filtrated, and the filtrate was poured into a saturated aqueous sodium chloride (50 mL) and extracted with diethyl ether (3 Â 20 mL).…”