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Allyl Chloride의 Epoxidation 반응 연구-I. 균일상 몰리브덴촉매의 반응활성 및 반응메카니즘
Study on the Epoxidation of Allyl Chloride-I. Catalytic Activity and Reaction Mechanism of Homogeneous Molybdenum Catalysts
HWAHAK KONGHAK, December 1991, 29(6), 687-692(6), NONE
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Abstract
여러 가지 Mo 촉매 존재하에서 allyl chloride를 tert-butyl hydroperoxide로 액상 epoxidation시키는 연구가 회분식반응기를 이용하여 이루어졌다. 반응은 1,1,2,2-tetrachloroethane 용액중에서 반응온도 53-76℃, 상압, 촉매농도 1.5×10-3몰의 조건에서 수행하였으며, MoO2(acetylacetone)2와 MoCl5가 활성 및 선택성면에서 가장 좋은 촉매로 나타났다. Epoxidation은 부반응 생성물인 tert-butyl alcohol, 피리딘 등과 같은 Lewis 염기에 의하여 매우 심하게 활성이 저하되었다. MoO2(acetylacetonate)2 촉매계에 대한 반응속도 자료를 얻었으며, Michaelis-Menten 속도론으로 나타낼 수 있었다.
Homogeneous liquid phase epoxidation of allyl chloride with tert-butyl hydroperoxide was carried out in the presence of various Mo catalysts in a batch reactor. The reaction has been carried out at 53-76℃ and 1atm with 1.5×103mol/liter of catalyst in 1,1,2,2-tetrachloroethane solution. MoO2(acetylacetonate)2 and MoCl5 were found to be the most active and selective catalyst. The epoxidation was strogly inhibited by Lewis base such as tert-butyl alcohol, pyridine and water. Kinetic data were obtained for the MoO2(acetyl-acetonate)2 catalyst system and could be represented by Michaelis-Menten kinetics.
References
Hatch LF, Sami M, "From Hydrocarbons to Petrochemicals," Gulf Publishing Co., Houston (1981)
Wiseman P, "An Introduction to Industrial Organic Chemistry," Applied Science Publishers (1979)
Chemical Week, April 5, 33 (1978)
Simmrock KH, Hydrocarb. Process., 106 (1978)
Indictor N, Brill WF, J. Org. Chem., 2074 (1965)
Su CC, Ph.D. Dissertation, Kent State University, USA (1972)
Gould ES, Hiatt RR, Irwin KC, J. Am. Chem. Soc., 90, 4573 (1968)
Sheldon RA, Doorn JA, Schram CWA, J. Catal., 31, 438 (1973)
Sharpless KB, Townsend JM, Wiliams DR, J. Am. Chem. Soc., 94, 295 (1972)
Sheldon RA, Rec. Trav. Chim., 92, 253 (1973)
Bailar JC, Emelus HJ, Nyholm R, Trotman D, "Comprehensive Inorganic Chemistry," Pergamon Press (1975)
Mimoun H, "The Chemistry of Peroxides," John Wiley and Sons, Chichester (1983)
Avery HE, "Basic Reaction Kinetics and Mechanism," The McMillan Press Ltd. (1981)
Wiseman P, "An Introduction to Industrial Organic Chemistry," Applied Science Publishers (1979)
Chemical Week, April 5, 33 (1978)
Simmrock KH, Hydrocarb. Process., 106 (1978)
Indictor N, Brill WF, J. Org. Chem., 2074 (1965)
Su CC, Ph.D. Dissertation, Kent State University, USA (1972)
Gould ES, Hiatt RR, Irwin KC, J. Am. Chem. Soc., 90, 4573 (1968)
Sheldon RA, Doorn JA, Schram CWA, J. Catal., 31, 438 (1973)
Sharpless KB, Townsend JM, Wiliams DR, J. Am. Chem. Soc., 94, 295 (1972)
Sheldon RA, Rec. Trav. Chim., 92, 253 (1973)
Bailar JC, Emelus HJ, Nyholm R, Trotman D, "Comprehensive Inorganic Chemistry," Pergamon Press (1975)
Mimoun H, "The Chemistry of Peroxides," John Wiley and Sons, Chichester (1983)
Avery HE, "Basic Reaction Kinetics and Mechanism," The McMillan Press Ltd. (1981)
