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研究生:陳世峰
研究生(外文):Shih Feng Chen
論文名稱:Dimethyl-3,3-cyclopentyl-3H-pyrazole-4,5-dicarboxylate之熱化學反應及反應機構探討
論文名稱(外文):Thermolysis of dimethyl-3,3-cyclopentyl-3H-pyrazole-4,5-dicarboxylate
指導教授:顏耀平
學位類別:碩士
校院名稱:靜宜大學
系所名稱:應用化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2000
畢業學年度:89
語文別:英文
論文頁數:82
中文關鍵詞:熱化學反應重排反應
外文關鍵詞:diazovan Alphen-Huttle rearrangement reaction15-shifts15-sigmatropic migration3H-pyrazoleArrhenius Theory
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Dimethyl 3,3-cyclopentyl-3H-pyrazole-4,5-dicarboxylate(18)受熱後會進行兩種熱重排反應,即C-3位的cyclopentyl group 會進行[1,5]-sigmatropic rearrangement擴環至C-4位而生成dimethyl-4,5,6,7-
tetrahydro-3aH-indazole-3,3a-dicarboxylate (21)和擴環至N-2位上生成dimethyl-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2,3-
dicarboxylate(22)。
另外,化合物21在較高的溫度下加熱,其methoxycarbonyl group會進行兩次[1,5]-sigmatropic migration而生成中間體dimethyl-4,5,6,7-tetrahydroindazole-2,3-dicarboxylate(23)最後N-1位經[1,5]-sigmatropic migration 至N-2生成最終產物dimethyl-4,5,6,7-
tetrahydroindazole-1,3-dicarboxylate(24)。
根據Arrhenius Theory 求得化合物18之消失活化能Ea=26.30±0.1
kcal/mol及logA=12.8±0.1其值表示是進行典型的分子內環化過程( intramolecular cyclic process)。

Thermal rearrangement of dimethyl-3,3-cyclopentyl-3H-pyrazole-
4,5-dicarboxylate (18) lead to formation of dimethyl-4,5,6,7-tetrahydro-3aH-indazole-3,3a-dicarboxylate (21)and dimethyl-4,5,6,7- tetrahydropyrazolo[1,5-a]pyridine-2,3-dicarboxylate (22).
In the 21 case, the latter rearrangement is follow by two successive [1,5]-sigmatropic migration of a methoxycarboxylate group and gives the intermediate, dimethyl-4,5,6,7-tetrahydroindazole-2,3-dicarboxylate(23).The final product,dimethyl-4,5,6,7-tetrahydroindazole-1,3-dicarboxylate(24)results from the methoxycarbonyl group migration initially at N-1,followed by sequential migration to N-2.
The arrhenius parameter for the rearrangement of dimethyl-3,3-cyclopentyl-3H-pyrazole-4,5-dicarboxylate(18) were
determined. The activation energy Ea=26.3±0.1kcal/mol and logA=12.8±0.1 is typical for intramolecular cyclic process 。

目 錄
摘要 ---------------------------------------------1-2
壹、緒論----------------------------------------- 3-9
貳、結果與討論-----------------------------------10-40
參、實驗儀器與藥品-------------------------------41-43
肆、實驗步驟與數據-------------------------------44-79
伍、附錄-----------------------------------------80-81
陸、參考文獻-------------------------------------82

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