气相中Sc+和Ti+与CS2反应的计算研究

以Sc⁺和Ti⁺与CS₂反应作为第一前过渡金属离子与CS₂反应的范例体系. 采用密度泛函(UB3LYP/6-311+G*)方法计算研究了Sc⁺和Ti⁺在基态和激发态与CS₂反应的反应机理. 全参数优化了反应势能面上各驻点的几何构型, 用频率分析方法和内禀反应坐标(IRC)方法对过渡态进行了验证. 计算了不同多重度下的反应交叉势能面. 确定了Sc⁺和Ti⁺与CS₂的反应为插入-消去反应, 找到了基态和激发态金属离子与CS₂反应的主要通道.     

Synthesis and Crystal Structure of (9S,13R,14S)-7,8-Dehydro-4-(4'-bromobenzyloxy)-3,7-dimethoxy-17-methyl-morphinan-6-one Monohydrate

The title compound (9S,13R,14S)-7,8-dehydro-4-(4'-bromo-benzyloxy)-3,7-dime- thoxy-17-methyl-morphinan-6-one monohydrate (O-4-bromobenzylsinomenine) was synthesized by the reaction of (9S, 13R, 14S)-7,8-dehydro-4-hydroxy-3,7-dimethoxy- 17-methyl-morphinan-6-one with 4-bromobenzyl alcohol.Its chemical structure was determined by X-ray single-crystal diffraction.The crystal belongs to the monoclinic system, space group P2<,1> with a = 8.890(2), b = 14.757(4), c = 9.205(2) (A), β = 91.577(4)°, C<,26>H<,30>BrNO<,5>, M<,r> = 516.42,μ = 1.740 mm<'-1>, V = 1207.2(5) (A)<'3>, Z = 2, D<,c> = 1.421 mg/m<'3>, F(000) = 536, R = 0.0785 and wR = 0.1889.