臺灣博碩士論文加值系統

(一)、喃和丙二烯醚基之分子內Diels-Alder反應之研究（七）
學生：嚴嘉蕙指導教授：吳獻仁 博士
國立交通大學應用化學研究所
中文摘要
喃（furan）和丙二烯醚親二烯基（allenyl ether dienophile）進行分子內Diels-Alder反應後，緊接著進行三甲矽烷基（trimethylsilyl group）的重排反應。將化合物73-75，77-81（5-(trimethylsilyl)-2-furfuryl propargyl ethers）和t-BuOK在83℃下迴流10小時可得到三甲矽烷基進行1,2-重排後的產物82-88以及Brook重排後的產物90-96。在化合物130上有兩個喃甲基性氫原子（furfurylic hydrogen atoms），先經由進行分子內Diels-Alder反應後，再進行喃環轉移反應（furan ring transfer reaction）及Brook重排反應後得到化合物131。
為了探討如Scheme 10、11、12及17中的甲基硫代基（methylthio group）、甲亞磺醯基（methylsulfinyl group）、甲磺醯基（methylsulfonyl group）及三甲矽烷基（trimethylsilyl group）在進行重排反應時是經由「分子間」或「分子內」的重排，我們分別製備了furfuryl propargyl ether化合物139、145、151及159，再將化合物139和141、145和147、151和153及159和77的混合物在相同的條件下迴流6~10小時後可得分子內重排後的產物140和142、144和148、152和154及85，93，95，160，並沒有得到分子間交叉重排的產物143和144、149和150、155和156及161和162。
(二)、骨架上含二個氧原子之含氧籠狀化合物之合成及其面向選擇性之研究（一）
利用碘誘導環化反應可合成出3,8-dioxapentacyclo[8.2.2.02,9.04,12.07,11]-5-tridecenes，3,8-dioxapentacyclo[8.2.1.02,9.04,12.07,11]-5-tetradecenes等籠狀化合物232-234，248，249及雙籠狀化合物283、293；亦可利用此法來決定1,4-對苯與環戊二烯及環己二烯之雙加成物的立體化學。
為了探討加成碳中心的s*軌域和化合物骨架上異原子所含的未共用電子間的相互作用可能在進行p面向選擇時扮演了相當重要的角色，我們將上述籠狀化合物做了加成反應。這些加成產物的立體化學是經由2D和NOE實驗來決定。其中化合物255及266的構造則是經由X-ray分析後確定。

(I) Study on the Intramolecular Diels-Alder Reaction of Furans with Allenyl Ethers（VII）
Student : Chia-Hui Yen Advisors : Dr. Hsien-Jen Wu
Department of Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan 30050, R. O. C.
ABSTRACT
The intramolecular Diels-Alder reactions of furan diene with allenyl ether dienophile followed by the trimethylsilyl group rearrangement are reported.
Refluxing the 5-(trimethylsilyl)-2-furfuryl propargyl ethers 73-75, 77-81 with t-BuOK in t-BuOH at 83℃ for 10 h gave the trimethylsilyl group 1,2-rearrangement products 82-88 and Brook rearrangement products 90-96. The reaction mechanisms for these novel intramolecular Diels-Alder reactions were discussed. In the case of 130, which possessed two furfurylic hydrogen atoms, compound 131 was obtained via an intramolecular Diels-Alder reaction followed by the furan ring transfer reaction and Brook rearrangement.
In order to find the methylthio group, the methylsulfinyl group, the methylsulfonyl group and the trimethylsilyl group's rearrangement as shown in Scheme 10; 11; 12 and 17 to be intramolecular or intermolecular rearrangement reaction, the furfuryl ether 139, 145, 151 and 159 were prepared, respectively. Refluxing the mixture of the propargyl ether 139 and 141, 145 and 147, 151 and 153, 77 and 159 with t-BuOK in t-BuOH at 83 oC for 6~10h gave the rearrangement products 140 and 142, 144 and 148, 152 and 154, 85, 93, 95 and 160. No detectable amount of the cross-rearrangement products 143 or 144, 149 or 150, 155 or 156; 161 or 162 was obtained.
(II) Synthesis and Facial Selectivity of Dioxa-Cage Compounds (I)
The syntheses of 3,8-dioxapentacyclo[8.2.2.02,9.04,12.07,11]-5-tridecenes, 3,8-dioxapentacyclo[8.2.1.02,9.04,12.07,11]-5-tetradecenes 232-234, 248,249 and dioxa-cages 283, 293 have been accomplished in a short sequence via iodine-induced cyclization reaction. The synthesis of dioxa-cage compounds can be used as a new method for the determination of the stereochemistry of the bisadducts of p-quinone with cyclopentadiene and cyclohexadiene.
In order to test for the hypothesis that the orbital interactions between the s* orbital of the addition carbon center and the nonbonding electrons on the heteroatoms in the skeleton of substrates may play a profound effect on the p-facial selectivity, we have studied some addition reactions on the dioxa-cage compounds 232-234 and 283, 248,249 and 293. The stereochemistry of these addition products was determined on the basis of 2D and NOE experiments. The structures of compounds 255, 266, were proven by X-ray analysis.

目 錄
中文摘要……………………………………………………...i
英文摘要…………………………………………………….iii
謝誌…………………………………………………………….v
目錄…………………………………………………………..vi
表目錄………….…………………………………………..vii
圖目錄……………………………………………………….vii
第一部分喃和丙二烯醚基之分子內Diels-Alder反應之研究（七）
第一章 緒論………………………………………………..….2
1.1 文獻回顧…………………………………..….2
1.2 研究構想……………………………………...9
第二章 結果與討論…………………………………………10
2.1 在喃環第二個碳的位置上引進三甲矽烷基後進行分子內Diels-Alder反應之研究…………………………………...……10
2.2經由交叉重排反應來探討此類反應是經由分子間或分子內重排反應而得……………………………………………………...….17
第三章結論………………………………………………..…23
第四章實驗…………………………………………..….….25
4.1 一般敘述……………………………..……..25
4.2 合成步驟及光譜數據………………..…..26
第二部分骨架上含二個氧原子之含氧籠狀化合物之合成及其面向選擇性之研究（一）
第五章緒論…………………………………………………..53
5.1 文獻回顧………………………………….….53
5.2 研究構想……………………………………..66
第六章結果與討論…………………………………………67
6.1由1,4-對苯（p-benzoquinone）衍生物合成雜環籠狀化合物……………………………………………………………….67
6.2將由1,4-對苯（p-benzoquinone）衍生物合成的雜環籠狀化合物進行p 面向選擇性加成的研究………………………….70
6.3利用合成雙氧籠狀化合物來決定環戊二烯及環己二烯和對苯雙加成產物的立體化學………………………………………..84
第七章結論…………………………………………….…….98
第八章實驗……………………………………………..….100
8.1 一般敘述……………………………….…..100
8.2 合成步驟及光譜數據……………………101
第九章參考文獻……………………………………………135
附錄一：1H, DEPT, 2D, NOE等NMR光譜圖……..…142
附綠二：X-ray單晶繞射數據資料………………….…283
附錄三：Publication List……………………………….300
簡歷……………………………………………………………301
表目錄
表一：化合物64-72之產率…………………………………………………………10
表二：化合物73-81之產率…………………………………………………………11
表三：化合物82-89及化合物90-97之產率………………………………………12
圖目錄
圖一：(CH)2n多碳環籠狀化合物結構圖……………………………...…………......53
圖二：其他多碳環籠狀化合物結構圖……………………………………………..54
圖三：Cram's rule…………………...………………………………………………..61
圖四：環己酮還原反應選擇性圖……………………………….………………...…61
圖五：扭張力對環己酮進行親和劑加成反應的面向選擇性圖…………………....62
圖六：Kinetic anomeric effect及kinetic a effect……………………………………62
圖七：Cieplak理論解釋環己酮的還原反應……………………………………...…63
圖八：Cieplak理論解釋C5取代基金剛酮213的加成方向…………………...…....64
圖九：Adocock解釋C5取代基金剛酮213進行還原反應的模型………………….66
圖十：化合物254之H,H-COSY光譜圖……………………………………..…...72
圖十一：化合物254之NOE光譜圖………………………………………………....73
圖十二：化合物255之X-ray單晶體繞射結構圖………………………………...…74
圖十三：化合物260之H,H-COSY光譜圖………………………………….………76
圖十四：化合物260之NOE光譜圖……………………………………………..…..77
圖十五：化合物266之X-ray單晶體繞射結構圖………………………………..….79
圖十六：化合物270之H,H-COSY光譜圖……………………………………...…80
圖十七：化合物270之NOE光譜圖………………………………………………..81
圖十八：化合物274之H,H-COSY光譜圖……………………………………..….82
圖十九：化合物274之NOE光譜圖…………………………………………………83
圖二十：化合物284之H,H-COSY光譜圖……………………………………….....87
圖二十一：化合物284之NOE光譜圖………………………………………………88
圖二十二：化合物293之H,H-COSY光譜圖…………………………………….…91
圖二十三：化合物293之NOE光譜圖……………………………………………..92
圖二十四：化合物298之H,H-COSY光譜圖……………………………………...93
圖二十五：化合物298之NOE光譜圖……………………………………………94
圖二十六：化合物302之H,H-COSY光譜圖……………………………………...96
圖二十七：化合物302之NOE光譜圖…………………………………………..…97
附圖1：化合物63之1H NMR光譜圖……………………………………….……..143
附圖2：化合物64之1H NMR光譜圖……………………………………...………144
附圖3：化合物65之1H NMR光譜圖……………………………………...………145
附圖4：化合物66之1H NMR光譜圖……………………………………...………146
附圖5：化合物67之1H NMR光譜圖……………………………………...………147
附圖6：化合物68之1H NMR光譜圖……………………………..………...…..…148
附圖7：化合物69之1H NMR光譜圖……………………………………………...149
附圖8：化合物70之1H NMR光譜圖……………………………………...………150
附圖9：化合物71之1H NMR光譜圖………………………………………...……151
附圖10：化合物72之1H NMR光譜圖………...…………………………...……...152
附圖11：化合物73之1H NMR光譜圖……………………………………...……..153
附圖12：化合物74之1H NMR光譜圖……………………………………...……..154
附圖13：化合物75之1H NMR光譜圖………………...….……………………….155
附圖14：化合物77之1H NMR光譜圖…………….….....………………………...156
附圖15：化合物78之1H NMR光譜圖………...……...…………………………...157
附圖16：化合物79之1H NMR光譜圖………………...…………………………..158
附圖17：化合物80之1H NMR光譜圖………………...………………………..…159
附圖18：化合物81之1H NMR光譜圖………...………...………………………...160
附圖19：化合物82之1H NMR光譜圖………….……...………………………….161
附圖20：化合物83之1H NMR光譜圖………….……...………………………….162
附圖21：化合物84之1H NMR光譜圖…………………...………………………..163
附圖22：化合物85之1H NMR光譜圖………….…..……...…………………..….164
附圖23：化合物86之1H NMR光譜圖…………....…..……...………….….…..…165
附圖24：化合物87之1H NMR光譜圖………….…..………...………………..….166
附圖25：化合物88之1H NMR光譜圖………….…..…….…...…………...…..….167
附圖26：化合物90之1H NMR光譜圖………….…..………...………………..….168
附圖27：化合物91之1H NMR光譜圖………….…..………...………………..….169
附圖28：化合物92之1H NMR光譜圖………….……………...…..…………..….170
附圖29：化合物93之1H NMR光譜圖………….……………...…….………...….171
附圖30：化合物94之1H NMR光譜圖…………..……………….……………..…172
附圖31：化合物95之1H NMR光譜圖………..….…………….……….……...….173
附圖32：化合物96之1H NMR光譜圖………….…………..…….…..…………...174
附圖33：化合物98之1H NMR光譜圖………….….…………….……...………...175
附圖34：化合物128之1H NMR光譜圖………….…….…….………………...….176
附圖35：化合物129之1H NMR光譜圖………….……...………...………….…...177
附圖36：化合物130之1H NMR光譜圖………………..…………...………….….178
附圖37：化合物131之1H NMR光譜圖………….……..…...…………..……..….179
附圖38：化合物137之1H NMR光譜圖………….……...…...………………...….180
附圖39：化合物138之1H NMR光譜圖………….……...…...………………...….181
附圖40：化合物139之1H NMR光譜圖………….…….…...………………….….182
附圖41：化合物140之1H NMR光譜圖………….……...…...….………………...183
附圖42：化合物141之1H NMR光譜圖………….………..…….….……………..184
附圖43：化合物142之1H NMR光譜圖………………......……..………………...185
附圖44：化合物145之1H NMR光譜圖………….……......……...…………….....186
附圖45：化合物146之1H NMR光譜圖………….……....……..………………....187
附圖46：化合物147之1H NMR光譜圖………….……......………………….…...188
附圖47：化合物148之1H NMR光譜圖………….…….....…………………….....189
附圖48：化合物151之1H NMR光譜圖………….……....……………………......190
附圖49：化合物152之1H NMR光譜圖………….…….....…………………..…...191
附圖50：化合物153之1H NMR光譜圖………….…….....…………………….....192
附圖51：化合物154之1H NMR光譜圖………….……......……………….……...193
附圖52：化合物157之1H NMR光譜圖………….…….....……………..….……..194
附圖53：化合物158之1H NMR光譜圖………….…...…..……………..………...195
附圖54：化合物159之1H NMR光譜圖………….…...…..…………...……...…...196
附圖55：化合物160之1H NMR光譜圖………….…...…...……………….……...197
附圖56：化合物165之1H NMR光譜圖………….…...…...……………..…...…...198
附圖57：化合物221之1H NMR光譜圖………….…...….…………………...…...199
附圖58：化合物222之1H NMR光譜圖………….…...….………………………..200
附圖59：化合物223之1H NMR光譜圖………………….…….……………….....201
附圖60：化合物224之1H NMR光譜圖………………….………………..….…...202
附圖61：化合物225之1H NMR光譜圖…………………………………………...203
附圖62：化合物226之1H NMR光譜圖………….…...…………………………...204
附圖63：化合物227之1H NMR光譜圖………………………………...…….…...205
附圖64：化合物228之1H NMR光譜圖…………………………………………...206
附圖65：化合物229之1H NMR光譜圖………………………………...………....207
附圖66：化合物232之1H NMR光譜圖………………….………………..……....208
附圖67：化合物233之1H NMR光譜圖…………....……………………………...209
附圖68：化合物233之H-H COSY光譜圖……….….……..…………………......210
附圖69：化合物233之H-C COSY光譜圖…………………...………………...….210
附圖70：化合物234之1H NMR光譜圖…………....…………….………………..211
附圖71：化合物235之1H NMR光譜圖………………….………………………..212
附圖72：化合物236之1H NMR光譜圖………….…...….……...…………….....213
附圖73：化合物237之1H NMR光譜圖………….…...….………………………..214
附圖74：化合物238之1H NMR光譜圖………….…...……….…………………..215
附圖75：化合物239之1H NMR光譜圖………….…...….…….………………...216
附圖76：化合物240之1H NMR光譜圖………….…...……………………..…...217
附圖77：化合物241之1H NMR光譜圖………….…...….…….………………….218
附圖78：化合物242之1H NMR光譜圖………….…...…………………....……...219
附圖79：化合物243之1H NMR光譜圖………….……….…………………..…...220
附圖80：化合物244之1H NMR光譜圖………….……...……………...…….…...221
附圖81：化合物245之1H NMR光譜圖………….……...…………………….…..222
附圖82：化合物246之1H NMR光譜圖………….……....………………..….…...223
附圖83：化合物247之1H NMR光譜圖………….……....………………...……...224
附圖84：化合物248之1H NMR光譜圖………….……....…………………...…...225
附圖85：化合物249之1H NMR光譜圖………….……....…………………...…...226
附圖86：化合物250之1H NMR光譜圖………….…………………………........227
附圖87：化合物251之1H NMR光譜圖………….…………………………........228
附圖88：化合物252之1H NMR光譜圖………….……...…....……………..…...229
附圖89：化合物253之1H NMR光譜圖………….……...…………………….....230
附圖90：化合物254之1H NMR光譜圖………….…………………………...…...231
附圖92：化合物254之H-C COSY光譜圖……….………………………...……...232
附圖93：化合物254之NOE光譜圖………………………………………..…..….233
附圖94：化合物254之NOE光譜圖…………………………………..………..….233
附圖95：化合物255之1H NMR光譜圖…………….…...……………...….……...234
附圖96：化合物255之H-H COSY光譜圖………….…………………...……...235
附圖97：化合物255之H-C COSY光譜圖…………………………………......….235
附圖98：化合物255之NOE光譜圖……….…………………………………...….236
附圖99：化合物255之NOE光譜圖…………………………………………..….236
附圖100：化合物255之NOE光譜圖……………………………………….….….237
附圖101：化合物256之1H NMR光譜圖………...….……………………..……...238
附圖102：化合物256之H-H COSY光譜圖………...….…………………..……...239
附圖103：化合物256之H-C COSY光譜圖……………………..……………..….239
附圖104：化合物256之NOE光譜圖…………………………………………..….240
附圖105：化合物256之NOE光譜圖……………………..……...………………..240
附圖106：化合物256之NOE光譜圖………………………….….……………….241
附圖107：化合物260之1H NMR光譜圖……………..…….……….…………….242
附圖108：化合物260之H-H COSY光譜圖…………....…….…………………....243
附圖109：化合物260之H-C COSY光譜圖……………………...………………..243
附圖110：化合物260之NOE光譜圖…………………………………………..….244
附圖111：化合物260之NOE光譜圖…………………………………………..….244
附圖112：化合物261之1H NMR光譜圖………………….……………………....245
附圖113：化合物261之H-H COSY光譜圖………...….…….…………………...246
附圖114：化合物261之H-C COSY光譜圖…………………………………....….246
附圖115：化合物261之NOE光譜圖…………………………………………..….247
附圖116：化合物261之NOE光譜圖…………………………………………..….247
附圖117：化合物266之1H NMR光譜圖………….…...….……………………....248
附圖118：化合物266之H-H COSY光譜圖………………….…………………....249
附圖119：化合物266之H-C COSY光譜圖………………….………………...….249
附圖120：化合物266之NOE光譜圖…………………………………………..….250
附圖121：化合物266之NOE光譜圖…………………………………………..….250
附圖122：化合物270之1H NMR光譜圖………….…...….……………………....251
附圖123：化合物270之H-H COSY光譜圖……...…….…….…………………....252
附圖124：化合物270之H-C COSY光譜圖………………….………………...….252
附圖125：化合物270之NOE光譜圖…………………………………………..….253
附圖126：化合物270之NOE光譜圖…………………………………………..….253
附圖127：化合物271之1H NMR光譜圖………………….………………….…...254
附圖128：化合物271之H-H COSY光譜圖………...….………………….……...255
附圖129：化合物271之NOE光圖…………………………………………...……256
附圖130：化合物271之NOE光譜圖………….…….………………………..…...256
附圖131：化合物274之1H NMR光譜圖………….…...….…...………………...257
附圖132：化合物274之H-H COSY光譜圖…………...…….……………....…...258
附圖133：化合物274之H-C COSY光譜圖………………….…………………..258
附圖134：化合物274之NOE光譜圖…………………………………………….259
附圖135：化合物274之NOE光譜圖…………………………………………….259
附圖136：化合物280之1H NMR光譜圖………….…………...…….…………..260
附圖137：化合物281之1H NMR光譜圖………….…………..…….…………..261
附圖138：化合物282之1H NMR光譜圖………….……………...…….…….....262
附圖139：化合物283之1H NMR光譜圖………….…….……...………………..263
附圖140：化合物284之1H NMR光譜圖………….…………..………………...264
附圖141：化合物284之H-H COSY光譜圖………..…….…….………………..265
附圖142：化合物284之H-C COSY光譜圖………………….…..……………....265
附圖143：化合物284之NOE光譜圖……………………………………….…....266
附圖144：化合物284之NOE光譜圖……………………………………….…....266
附圖145：化合物285之1H NMR光譜圖………….…….……………...……......267
附圖146：化合物289之1H NMR光譜圖………….…….…………...…………..268
附圖147：化合物290之1H NMR光譜圖………….…….………...…………......269
附圖148：化合物292之1H NMR光譜圖………….……………...……………...270
附圖149：化合物293之1H NMR光譜圖………….…….……………………....271
附圖150：化合物293之H-H COSY光譜圖…...……….…….……………….…...272
附圖151：化合物293之H-C COSY光譜圖………………….……………...…….272
附圖152：化合物293之NOE光譜圖…………………………………………..….273
附圖153：化合物293之NOE光譜圖…………………………………………..….273
附圖154：化合物294之1H NMR光譜圖………….……....……………………....274
附圖155：化合物298之1H NMR光譜圖………….………..……………………..275
附圖156：化合物298之H-H COSY光譜圖………….…….……………….…...276
附圖157：化合物298之H-C COSY光譜圖………………….………………….276
附圖158：化合物298之NOE光譜圖……………………………………….….….277
附圖159：化合物298之NOE光譜圖…………………………………………..….277
附圖160：化合物300之1H NMR光譜圖...………….…………………………….278
附圖161：化合物300之H-H COSY光譜圖………….…….……………………...279
附圖162：化合物300之H-C COSY光譜圖………………….……………...…….279
附圖163：化合物302之1H NMR光譜圖………...….…….………………………280
附圖164：化合物302之H-H COSY光譜圖……...…….…………………..……...281
附圖165：化合物302之H-C COSY光譜圖………………………………....…….281
附圖166：化合物302之NOE光譜圖……………………………………….….….282
附圖167：化合物302之NOE光譜圖……………………………………….….….282

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