Petursson Sigthor
Faculty of Natural Resource Sciences, University of Akureyri, 600 Akureyri, Iceland.
Carbohydr Res. 2003 Apr 22;338(9):963-8. doi: 10.1016/s0008-6215(03)00039-9.
The paper reports the tin(II) chloride catalyzed reactions of diazodiphenylmethane with the cis- and trans-1,2-cyclohexanediols and R,S-1,2-propanediol in 1,2-dimethoxyethane and the identification of the monodiphenylmethyl ethers formed. The catalyst is shown to work for both the cis- and trans-cyclohexanediols, but the catalyst is unstable at high reagent concentrations, especially in the case of the trans-isomer. Conditions where catalyst destruction is negligible show that the rate of the reaction with the trans-isomer is larger than with the cis-isomer. The reactions with 1,2-propanediol show small difference between the selectivity for the primary and secondary hydroxyl groups. This is in contrast with the tin(II) chloride catalyzed reactions of diazomethane and diazophenylmethane in methanol with carbohydrates, glycerol and ribonucleosides, where the primary hydroxyl group does not react.
该论文报道了在1,2 - 二甲氧基乙烷中,氯化亚锡催化重氮二苯甲烷与顺式和反式 - 1,2 - 环己二醇以及R,S - 1,2 - 丙二醇的反应,并对生成的单二苯甲基醚进行了鉴定。结果表明,该催化剂对顺式和反式环己二醇均有效,但在高试剂浓度下不稳定,尤其是对于反式异构体。催化剂破坏可忽略不计的条件表明,与反式异构体的反应速率大于与顺式异构体的反应速率。与1,2 - 丙二醇的反应表明,对伯羟基和仲羟基的选择性差异较小。这与氯化亚锡在甲醇中催化重氮甲烷和重氮苯甲烷与碳水化合物、甘油和核糖核苷的反应形成对比,在后者的反应中伯羟基不发生反应。