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研究生:林威帆
研究生(外文):Lin, Weifan
論文名稱:1,2,9-三羥甲基-5,5-二甲基[4.4.0]雙環癸烷化合物之合成研究
論文名稱(外文):Study On The Synthesis Of Enantiomerically Pure 1,2,9-Trihydroxymethyl-5,5-Dimethyl Bicyclo[4.4.0]Decane
指導教授:楊德芳楊德芳引用關係
指導教授(外文):Yang, Tefang
口試委員:賴榮豊陳焜銘
口試委員(外文):Lai, LongliChen, Kwunmin
口試日期:2012-06-22
學位類別:碩士
校院名稱:國立暨南國際大學
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:2012
畢業學年度:100
語文別:中文
論文頁數:132
中文關鍵詞:狄爾斯–阿爾德反應消旋混合物化學切割
外文關鍵詞:Diels-Alder reactionracemic mixturechemical cutting
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本篇論文主要是利用不同的路徑來合成出1,2,9-三羥甲基-5,5-二甲基[4.4.0]雙環癸烷的過程,首先在路徑一中我們有得到benzyloxydiene 29但進行Diels–Alder反應卻只得到少許產物,在路徑二當中無法順利將化合物40進行合環反應,於是我們在路徑三和路徑四中以2-methylcyclohexanone 44為起始物來進行反應可合出vinylcyclohexene,再與DMAD進行Diels–Alder反應,得到消旋混合物,然後再進一步進行還原反應可得到消旋雙醇混合物。在路徑三當中,我們使用不同掌性試劑來進行化學切割,但都沒有達到分離效果,所以改用路徑四的條件,發現消旋雙醇混合物61與(S)–(+)–ketopinic acid反應可做化學切割,得到化合物63、化合物64和二羥甲基[4.4.0]雙環癸二烯65,再將化合物63進行還原反應得到二羥甲基[4.4.0]雙環癸二烯66。我們最後分別將兩個鏡像異構物二羥甲基[4.4.0]雙環癸二烯 65和二羥甲基[4.4.0]雙環癸二烯 66再進行氫化反應和去保護,就能得到三羥甲基[4.4.0]雙環癸烷68和三羥甲基[4.4.0]雙環癸烷70。
The purpose of this assignment is use different paths to synthesize 1,2,9-trihydroxymethyl-5,5-dimethyl bicyclo[4.4.0]decane. Through the fist path we got benzyloxydiene 29, however, there was only small product during the Diels-Alder reaction, therefore, in the second path we could not carry on successfully by with the Compound 40 in the ring closing reaction. Consequently, in path 3 and 4 we used 2-methylcyclohexanone 44 as the starting material to do the reaction and the result came out with vinylcyclohexen, and we got racemic mixture by using the DMAD in the Diels-Alder reaction. Further, we used the reduction again and we got racemic diol mixture. In path 3, we using different chriral reagent to do the chemical cutting but the result what we got was not separate. Therefore, so switch to path four of the conditions and found out that the racemic diol mixture 61 and(S)–(+)–ketopinic acid could do the reaction in the chemical cutting and we got Compound 63, Compound 64 as well as the dihydroxymethylbicyclo[4.4.0]decadiene 65. Moreover, by using the reduction with Compounds 63 we got dihydroxymethylbicyclo[4.4.0]decadiene 66. Last, we respectively the two enantiomer which were dihydroxymethyl bicyclo[4.4.0]decadiene 65 and dihydroxymethylbicyclo[4.4.0]decadiene 66 in the hydrogenation and deprotection were trihydroxymethylbicyclo[4.4.0]decane 68 and trihydroxymethyl bicyclo[4.4.0]decane 70.
目錄
謝誌..........................................................................................................I
中文摘要................................................................................................II
英文摘要...............................................................................................III
目錄........................................................................................................IV
圖目錄.....................................................................................................V
表目錄.....................................................................................................V
反應流程目錄.......................................................................................V
第一章 緒論
一、 前言.............................................................................................1
二、 萜類(Terpenoid)的種類介紹.................................................5
三、 文獻回顧.....................................................................................6
第二章 結果與討論...........................................................................12
第三章 結論.........................................................................................27
本實驗所使用之藥品與儀器...........................................................28
實驗步驟及化合物光譜數據...........................................................29
參考文獻................................................................................................68
1H光譜圖...............................................................................................70
13C光譜圖............................................................................................102

圖目錄:
Figure 1………..……………...………………………………………………………3
Figure 2………..……………...………………………………………………………4
Figure 3………..……………...………………………………………………………6
Figure 4………..……………...………………………………………………………7
Figure 5………..……………...………………………………………………………8
Figure 6………..……………...………………………………………………………8
Figure 7………..……………...………………………………………………………9
Figure 8………..……………...……………………………………………...………10
Figure 9………..……………...……………………………………………………...11

表目錄:
表 1………..……………...…………………………………………………..……...14

反應流程目錄:
Scheme 1……....……………...……………………………………………………...13
Scheme 2……....……………...……………………………………………………...13
Scheme 3……....……………...……………………………………………………...14
Scheme 4……....……………...……………………………………………………...15
Scheme 5……....……………...……………………………………………………...17
Scheme 6……....……………...……………………………………………………...19
Scheme 7……....……………...……………………………………………………...21
Scheme 8……....……………...……………………………………………………...23
Scheme 9……....……………...……………………………………………………...24
Scheme 10……....…………...…………………………………………………..…...26
Scheme 11……....……………...………………………………………………….....26


參考文獻:
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2 Barrero, A. F.; Corte´s, M.; Manzaneda, E. A.; Cabrera, E.; Chahboun, R.; Lara, M. and Rivas, A. R. J. Nat. Prod. 1999, 62, 1488-1491.
3 Toshima, H.; Oikawa, H.; Toyomasu, T.; Sassa, T. Tetrahedron 2000, 56, 8443–8450.
4 Abad, A.; Agullo, C.; Castelblanque, L.; Cunat, A. C.; Navarro, I.; Arellano, M. C. R. J. Org. Chem. 2000, 65, 4189-4192.
5 Toshima, H.; Oikawa, H., Toyomasu, T.; Sassa, T. Biosci. Biotechnol. Biochem. 2001, 65, 1244–1247.
6 Cortes, M.; Valderrama, J. A.; Cuellar, M.; Armstrong, V.; Preite, M. J. Nat. Prod. 2001, 64, 348-349.
7 Monica, C. D.; Sala, G. D.; Izzo, I.; Petrocellis, L. D.; Marzo, V.; Spinella, A. Tetrahedron 2007, 63, 6866–6873.
8 Colombi, L.; Bosshard, A.; Schinz, H. and Seidel, C. F. Volumen XXXIV, Fasciculus I 1951–No. 28.
9 Wittig, G.; Geissler, G.. Justus Liebigs Ann. Chem. 1953, 44, 580.
10 (a)Herbert, C. B.; Ulhas, P. D. J. Org. Chem. 1994, 59, 2025-2032. (b)Dvornikova, I. A.; Frolova, L. L.; Kuchin, A. V.; Beletskaya, I. P. R. J. Org. Chem. 2007, 43, 352-358.
11 Miller, D. J.; Yu, F.; Knight, D. W.; Allemann, R. K. Org. Biomol. Chem. 2009, 7, 962–975.
12 Alison M. R.; Patrick G. S. J. Chem. Soc., Perkin Trans. 1998, 1, 2795–2801.

13 Heathcock, C. H.; Steafford, J. A.; Clark, D. L. J. Org. Chem. 1992, 57, 2575–2585.
14 (a)Huang, S. L.; Omura, K.; Swern, D. J. Org. Chem. 1976, 41,3329.
(b)Mancuso, A. J.; Swern, D. Synthesis 1981, 165.
15 Bourdron, J.; Commeiras, L.; Audran, G.; Vanthuyne, N.; Hubaud, J. C.; Parrain, J. L. J. Org. Chem. 2007, 72, 3770–3775.
16 Liu, H. J.; Yeh, W. L.; Browne, E. N.C. Can. J. Chem. 1995, 73, 1135-1 147.
17 Delogu, G.; Fabbri, D.; Dettori, M. A.; Forni, A.; Casalone, G. Tetrahedron: Asymmetry 2004, 15, 275–282.
18 Sophie, F.; Sylvie, P. L. B.; Cyrille, B.; Pete, J. P.; Rene, F.; Olivier, P. J. Org. Chem. 2002, 67, 1061-1070.
19 Aikawa, H.; Takahira, Y.; Yamaguchi, M. Chem. Commun. 2011, 47, 1479–1481.
20 Benites, J.; Preite, M. D.; Cortes, M. SYNTHETIC COMMUNICATIONS, 2001, 31, 1347–1354.
21 Yang, T. F.; Tseng, C. H.; Shen, C. H.; Chen, L. H.; Kao, L. T. Tetrahedron 2009, 65, 9854–9861.

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