中心碳极性反转的酰基化试剂的理论研究——Ⅱ.H_2C=C(OH)Na的理论研究  

Theoretical Studies of Acyl Reagents with Umploung Central Carbon Ⅱ.A Theoretical Study of CH_2 =C(OH)Na

作　　者：王义贵[1] 孙昌俊[1] 邓从豪[1] 

机构地区：[1]山东大学理论化学研究室,济南250100

出　　处：《化学学报》1998年第9期840-847,共8页Acta Chimica Sinica

基　　金：国家自然科学基金资助(29773025)

摘　　要：用MP2/6-31+G解析梯度方法,研究乙酰基负离子等效物CH_2=C(OH)Na的结构,得到了四个平衡构型.偏位取代的三元环结构1最稳定,将是最易存在的结构.H_2C=C(OH)Na具有双重反应性,结构4是发生亲核反应的中间体,发生类卡宾反应时经过类似构型2的中间状态.同H_2C=C(OH)Li相比较,H_2C=C(OH)Na碳负离子反应将更突出,发生类卡宾反应则更加困难.Analytical gradient optimizations were carried out using Gaussian 92 program at MP2/ 6-31 + G* level for equilibrium structures and transition states of CH2 == C(OH)Na. Four structures were reported. Structure 1 with a deflection three- member ring is the most stable one, and will be dominant in existence. Structure 4 is the reaction intermediate for H2C=C(OH)Na to serve as acyl anion equivalent. When H2C= C(OH)Na reacts as a carbenoid, it will have a transition state like structure 2. Compared with CH2 == C(OH)Li,CH2 = C(OH)Na is easier to serve as acyl anion equivalent,but more difficult to react as carbenoid.

关 键 词：酰基负离子 类卡宾 极性反转 乙酰基 等效物 

分 类 号：O627.11[理学—有机化学] O621.3[理学—化学]