本論文主旨在研究1,3,3-三甲基雙環[2.2.2]辛-5,7-二烯-2-酮
系列化合物35之光化學反應。
我們以已知的合成方法，利用雙烯化合物4-三氟甲磺醯氧基-
2,6,6-三甲基環己-2,4-二烯酮37，與丁炔二酸二甲酯、二苯基乙炔
、苯基乙炔、丙炔酸乙酯以及苯基乙烯基亞□進行[4+2]環加成反應
，得到產物38a-f，產率介於67~96%之間，其中與苯基乙烯基亞□
反應所得之38f是先進行環加成反應再經由消去反應而得。再將38a-f
於鈀錯合物的催化下進行還原反應，得到雙環[2.2.2]辛二烯酮化合物35a-f，產率在36~97%之間。以雙環[2.2.2]辛二烯酮化合物35af，在添加光敏化劑與沒有光敏化劑的不同條件下，探討雙-π-甲烷(di-π-methane，DPM)和氧-雙-π-甲烷(oxa-di-π-methane，ODPM)競爭重排反應。從實驗結果可知，在加入光敏化劑的條件下，只有35a、35b與35e才有重排反應產生，並且是由較具優勢的DPM重排反應所得，具位向選擇性，而35c、35d與35f則不得到重排產物。可由反應機構中推知取代基R具有穩定自由基中間體的電子效應。
在未添加光敏化劑的條件下，只有35b才有單離到15~18%的DPM重排產物，產生了系統間跨越與α-斷裂相競爭；其他皆只單離到雙環[2.2.2]系統經由α-斷裂而來的產物40a-f。

This thesis describes the studies on the photochemical reactions of 1,3,3-trimethylbicyclo[2.2.2]octa-5,7-dien-2-ones (35) which were synthesized by making use of the methodology developed in our laboratory. Cycloadducts 38a-e were obtained via the Diels-Alder reaction of 4-trifluoromethanesulfonyloxy-2,6,6-trimethylcyclohexa-2,4-dienone (37) with dimethyl acetylenedicarboxylate, diphenylacetylene, phenylacetylene, and ethyl propiolate in the yields of 73-96%. The cycloadduct 38f was derived from the Diels-Alder reaction of 37 and phenyl vinyl sulfoxide followed by elimination reaction. The palladium catalyzed reduction of cycloadducts 38a-f furnished dienones 35a-f in
36-97% yields. The photochemical reactions of 35a-f were examined under the condition with or without a photosensitizer to find out the modes of reactions including the competitivity of di-π-methane(DPM)
rearrangement and oxa-di-π-methane(ODPM) rearrangement. The
reactions of 35a, 35b, and 35e under the sensitized condition underwent DPM rearrangement, but in contrast, 35c, 35d, and 35f did not undergo DPM rearrangement under the similar condition. The proposed mechanism suggests that substituents R of the bicyclo[2.2.2] adducts that stabilize the radical intermediates favor the pathway leading to the DPM products.
Under the conditions of direct irradiation in various solvents, the products 40a-f were obtained from 35a-f via the α-cleavage of bicyclo[2.2.2] system. In the case of 35b, DPM rearrangement products was generated in 15 to 18% yields, this may be due to the reason that the first excited singlet state of 35b undergoes the intersystem crossing at a rate competitive to that of the Norrish type Ι cleavage for the excited singlet state of 35b.

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