A Study Of Double Bond Isomerization In Alkene Catalyzed By Ru-H Complex

Double bound isomerization was for the development a chemical reaction which developed using the oil resource, until now still held the extremely important status in the petroleum chemical industry and expands to the organic synthesis domain. In this thesis, two Ru-H complexes were designed and synthesized. Their catalytic activity for 1-hexene double bound isomerization was investigated and their catalytic reaction conditions were optimized for double bound isomerization. It was demonstrated that the Ru-H complexes are good catalysts for double bound isomerization featured by mild reaction conditions, high catalytic activity, good selectivity. The details are as follows:1.An Oil-solule Ru-H complex RuHCl(PPh₃)₃ and water-solule Ru-H complexRuHCl(TPPTS)₃ were synthesized, [TPPTS:P(m-C₆H₄SO₃Na)₃] .The prepared method of RuHCl(PPh₃)₃ was modified, which can carried out in milder reaction conditions , easier operations with a good yield and purity.2.The double bound isomerization reaction of 1-hexene catalyzed by RuHCl(PPh₃)₃ was investigated . The conversion of 1-hexene was 97.5% and the selectivities of 2-hexene and 3-hexene were 21.6% and 78.4% respectively at optimum conditions 100℃, 0.3MPa, RuHCl(PPh₃)₃ 4mmol/L, 0.5h. The reaction kinetics was studied and the activation energy Ea₁was 71.8KJ/mol and Ea₂ was 67.9KJ/mol shown a good catalytic characterization.3.RuHCl(PPh₃)₃ was synthesized in situ in order to catalyze the double bound isomerization reaction of 1-hexene. The conversion of 1-hexene was 97.0% and the selectivities of 2-hexene and 3-hexene were 32.8% and 67.2% respectively at optimum conditions 100℃, 0.5h,l-Hexene / RuCl₂(PPh₃)₃ 2000(mol).4.The double bound isomerization reaction of 1-hexene catalyzed by RuHCl(TPPTS)3 was studied.The effects of reaction temperature ,concentrations of CTAB,TPPTS and catalyst on the conversion and selectivity were investigated. The conversion of 1-hexene was 82.4% and the selectivities of 2-hexene and 3-hexene were32.8% and 67.2% respectively at 160℃, 1.0MPa,RuHCl(TPPTS)₃ 3.2mmol/L,CTAB 7mmol/L ,TPPTS 3.2mmol/L,6h. The skeletal isomerization of 1-hexene was not found. The catalyst can be repeated for 5 times.5. The isomerization reaction of different olefins was investigated by RuHCl(TPPTS)3. The results showed that the conversion decreased along with increased carbon number.