Hydroformylation Of Olefin Catalyzed By Rhodium-Phosphine Complexes

Hydrofrmyaltion is a typical atomic economical reaction, to which great attention has been attached, most of investigations in this field focus on the synthesis of new effective phosphines, to find a catalyst with better catalytic performance. In this paper, two phosphines were synthesized, and their catalytic properties in the hydroformylation of higher olefm were investigated systematically. The main works include:1. Two phosphine ligands. 4-octyllphenyl-diphenylphosphine(l), 4-dodecylphenyl-diphenylphosphine(2) were synthesized and were characterized by FTIR, MS, 1H and 31PNMR.2. Catalytic properties of two kinds of catalyst systems Rh(acac)(CO)2+1 Rh(acac)(CO)2 +2 were investigated in the hydroformylation of 1-dodecene . The results indicated that the catalytic activity is high, and the mechanism can be explained by the Wilkinson's mechanism.Two-phase catalytic system with water-soluble organometallic complexes as catalysts is one of the frontier fields in the "Green Chemistry" that is progressing quickly recently . Water-soluble rhodium-phosphine complexes have been successfully applied in lower olefin hydroformylation. However, for higher olefin, the reaction rate is too slow due to low solubility of the substrate in water. One way to increase the solubility of the substrates in water is to add surfactant to the system. This strategy has been used in the hydroformylation of alkenes with rhodium-TPPTS(Rh-TPPTS) systems. In this paper , The eleven cationic surfactants, C16H33N (C2H5) 3Br (1) C16H33N (CH3)2C12H25Br (2) C22H45N (CH3)2C16H33Br (3) C22H45N (CH3) 3I (4)C22H45N (CH3) 2C2H5Br (5) C22H45N (CH3)2C4H9Br (6) C22H45N (CH3) 2C8H17Br (7)C22H45N(CH3)2C12H25Br(8) C12H25N (CH3)3I(9) (C12H25)2N(CH3)2I(10)(C16H33)2NCH3)2Br(11) were synthezed. and characterized by 1H NMR. Their effects on 1-dodecene hydroformylation catalyzed by Rh-TPPTS were investigated in aqueous two-phase catalytic system. The results indicated that longer lipophilic chain and smaller cationic group of surfactant were favored to accelerate the reaction rate of the hydroformylation, but the role of lipophilic chain was more significant.