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題名 | Chemistry of Isodrin Derivatives. Solvolysis of Two Benzo-Fused Laticyclic Systems=緯環結構對於水解反應速率之效應 |
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作者姓名(中文) | 周大新; | 書刊名 | 中央研究院化學研究所集刊 |
卷期 | 44 1997.03[民86.03] |
頁次 | 頁25-33 |
分類號 | 346.225 |
關鍵詞 | 緯環結構; 水解反應; 速率; |
語文 | 英文(English) |
英文摘要 | 本報告測量化合物 2、3、4、5 的水解速率常數,並以理論模型解釋其相對值之 差異。化合物 1 至 6 之水解速率與理論計算所得之反應熱有相當良好的對應性。化合物 1 、3、4 結構上的第二個雙鍵提供碳陽離子額外之穩定性,使它們的水解速率比化合物2、5 稍快。化合物 6 之轡構上雖然僅有一個雙鍵,但其水解速率亦較化物 2 為快;此乃因為它 的飽和碳鍵絅構也能十分有效的穩定碳陽離子上的正電荷。理論計算顯示,對於此一系列的 氣態的分子而言,飽和碳鍵穩定離子的能力並不亞於雙鍵。 ingle norbornene systems of 2 and 5. For the partial saturated system 6, a rate enhancement comparable to that of 1 and 3 has also been reported although its structure is more similar to those of 2 and 5. The stability of cation 6 is ascribed to a large degree of a-bond participation in the high lying molecular orbitals. Examination on charge distributions on the cations of 1,2, and 6 indicaated that a-bonds contribute more than π -orbitals in stabilizing the positive charge. |
本系統之摘要資訊系依該期刊論文摘要之資訊為主。