화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Journal of Industrial and Engineering Chemistry, Vol.6, No.2, 125-128, March, 2000
Export Citation
Dehydrogenation Reaction of Cycloalkanones Catalyzed by Palladium Nitrate-Phosphine and -Sulfide Systems
Seong Won Hwang, and Young-ae Whang Park†
  • Department of Chemistry, Sangmyung University, Seoul 110-743, Korea
E-mail:
Activation of the aliphatic carbon-hydrogen bond was investigated in the dehydrogenation reaction of cycloalkanone (1-cyclopentanone, 1-cyclohexanone) using Pd(No3)2-PR3 (PR3=PPh3, P(p-C6H4CH3)3, P(p-C6H4OCH3)3,P(p-C6H4F)3 and Pd(NO3)2-SR2 catalytic systems (SR2=SPh2,S(CH2Ph)2, S(CH2CH2CH3)3, S[C(CH3)3]2, S[CH(CH3)2]2, S[(CH3CH(C2H5)]2). The reaction of cyclic ketones was carried out for 1.5 h in the presence of Pd(NO3)2 with phosphine or sulfide at 75℃. The molar ratio of Pd(NO3)2 to PPh3 providing the highest yield was 1:3 and this ration was maintained for the other phosphines and sulfides used in this work. The yield of 2-cyclohexen-1-one decreased as the basicity of the substituent on the phosphorus decreased; P(p-C6H4CH3)3 > P(p-C6H4OCH3)3 > P(C6H5)3 > P(p-C6H4F)3 > none. For sulfides, a similar trend was observed except for the lower yield than for phosphines with the same substituent; S[C(CH3)2]2 > S[(CH3CH(C2H5)]2 > S[(CH3CH2CH3)2 > S(C6H5)2 > S(CH2C6H5)2 S[C(CH3)3]2. In the case of 2-cyclopenten-1-one, the order of the yield for the phoshine ligand indicated that the reaction proceeded in the same manner as in the case of 2-cyclohexen-1-one; P(p-C6H4CH3)3 > P(C6H5)3 > none > P(p-C6H4F)3. However, the reaction seemed to proceed with a different mechansium for the sulfide ligand considering the different order of the yield; S(C6H5)2 > S(CH2C6H5)2 S[(CH3CH(C2H5)]2 > S[C(CH3)3]2 > S[(CH2CH2CH3)2.
Keywords:C-H activation;dehydrogenation;palladium nitrate;dialkylsulfide;phosphine
  1. Kearby KK, Catalysis, Vol. 3, p. 453, Reinhold, New York (1955)
  2. Tyuryaev Y, Russian Chem. Rev., 35, 1 (1966) 
  3. Carra S, Forni L, Catalysis Rev., Vol. 5, p. 159, Dekker, New York (1971)
  4. Fuchita Y, Harada Y, Inorg. Chem. Acta, 208, 43 (1993) 
  5. Crabtree RH, Chem. Rev., 85 (1985)
  6. Ryabov AD, Chem. Rev., 90 (1990)
  7. Fuchita Y, Hiraki K, Kamogawa Y, Suenaga M, J. Chem. Soc.-Chem. Commun., 941 (1987)
  8. Fuchita Y, Kawakami M, Shimoke K, Polyhedron, 10, 2037 (1991)
  9. Park YW, Hwang SW, Bull. Korean Chem. Soc., 18, 218 (1997)
  10. Park YW, Oh HH, Bull. Korean Chem. Soc., 18, 1123 (1997)
  11. Bennett MA, Robertson GB, Whimp PO, Yoshida TJ, J. Am. Chem. Soc., 95, 3028 (1973)
  12. Ittel SD, Tolman CA, English AD, Jesson JP, J. Am. Chem. Soc., 100, 7577 (1978)
  13. Bianchini C, Perruzini M, Zanobini F, J. Org. Chem., 326, C79 (1987)
  14. Gretz E, Oliver TF, Sen A, J. Am. Chem. Soc., 109, 8109 (1987)
  15. Fujiwara Y, Jintoku T, Uchida Y, New J. Chem., 13, 649 (1989)