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化学学报
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化学学报 ›› 1998, Vol. 56 ›› Issue (9): 840-847. 上一篇    下一篇

研究论文

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

王义贵;孙昌俊;邓从豪   

  1. 山东大学理论化学研究室.济南(250100)
  • 发布日期:1998-09-15

Theoretical studies of acyl reagents with umploung central carbonⅡ: A theoretical study of CH~2=C(OH)Na

Wang Yigui;Sun Changjun;Deng Conghao   

  1. Shandong Univ, Theoret Chem Lab.Jinan(250100)
  • Published:1998-09-15

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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。

关键词: 酰基, 阴离子, 等效物, 类卡宾, 从头计算法, 异构化, 构型, 反转, 极性, 亲核反应

Analytical gradient optimizations were carried out using Gaussian 92 program at MP2/6-31+G^* level for equilibrium structures and transition states of CH~2=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 H~2C=C(OH)Na to serve as acyl anion equivalent. When H~2C=C(OH)Na reacts as a carbenoid, it will have a transition state like structure 2. Compared with CH~2=C(OH)Li, CH~2=C(OH)Na is easier to serve as acyl anion equivalent, but more difficult to react as carbenoid.

Key words: ACYL GROUP, ANION, CARBENOID, AB INITIO CALCULATION, ISOMERIZATION, CONFIGURATION, REVERSE, POLARITY, NUCLEOPHILIC REACTION

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