摘要
本文用 RHF/STO-3G 解析梯度方法研究了亚烷基卡宾 XYC=C:(X,Y=Cl,H,Me 和 F)的重排反应,给出了平衡态与过渡态构型.对该组体系的计算发现:基团的迁移活性顺序为 Cl>H>Me>F;迁移性小的基团增大迁移基团的迁移活性:取代基不同一般比取代基相同的卡宾稳定性低;基团的迁移活性顺序与电负性顺序不一致;中心原子与 C=C 双键夹角小的基团优先迁移.
The 1,2-rearrangements of alkylidenecarbenes XYC=C:(X,Y=Cl,H,Me andF)have been studied by RHF/STO-3G gradient method.The equilibrium andtransition structures are fully optimized.For these systems at the STO-3G level,theshift reactivities are in the order of Cl>H>Me>F,which is different to that of theirelectronegativities;the fixed group with lower shift reactivity enhances that of theshift group;the carbenes with the same substituent groups are generally more stablethan that with different substituent groups;the shift rule is that the group withsmaller angle formed by its central atom with C=C bond migrates prior to the other.
出处
《化学学报》
SCIE
CAS
1988年第12期1155-1160,共6页
Acta Chimica Sinica
