臺灣博碩士論文加值系統

本碩士論文在敘述具取代基的3-methylbenzo[b]oxepine以及benzo [b] oxecine的合成。除此，它們的萘環的同類物也被合成以及報告。
從酚與丙烯溴合成的丙烯苯醚經Claisen轉位得到了鄰位的丙烯基酚，將得到的丙烯基酚分別與氯化丙酮進行SN2反應而得到1-aryloxy -2-propanones.接著與methylene triphenyl phorphine試劑,進行Wittig反應，而得到allyl methylallyloxybenzene作為ring-closing metathesis (RCM)的前驅物，最後將此前驅物以Grubbs’催化劑進行合環反應而分別得到取代的3-methylbenzo[b]oxepines，另一方面當1-aryloxy-2 -propanones與vinyl magnesium bromide反應得allylphenoxy -2-hydr oxy -2-methylallyloxybenzenes為合環置換(RCM)的前驅物，最後經Grubbs’催化劑作用而得到3-hydroxy-3-methylbenzo [b]oxocines.另外以1-naphthol為起始物，經相同的化學反應分別合成9-methyl-7,10 -dihydro-11-oxacyclohepta[a]naphthalene以及10-hydroxy-10-methyl - 10, 11 – dihydro-7H-12- oxacyclocta[a] naphthalene.

In this master thesis, the synthesis of substituted 3-methylbenzo[b]oxepines and benzo[b]oxocines is described. In addition, their naphthalene counterparts are synthesized and reported. Allyl aryl ethers, prepared respectively from phenols and allyl bromide, were subjected to the Claisen rearrangement to give o-allylphenols. The giving phenols were respectively reacted with chloroacetone to undergo SN2 reaction to afford 1-aryloxy-2-propanones. Followed by reactions with methylenetriphenylphosphine to undergo Wittig reaction, the resulting propanones were converted into allyl methylallyloxybenzenes, The resulting precursors were cyclized with the aid of Grubb’s catalyst to undergo ring-closing metathesis reaction to give substituted 3-methylbenzo[b]oxepines, respectively. On the other hand, when 1-aryloxy-2- propanones were respectively reacted with vinyl magnesium bromide,the allylphenoxy-2-hydroxy-2-methylallyloxybenzenes as the precursor of RCM were produced. Finally, the resulting precursors were cyclized with the aid of Grubb’s catalyst to undergo ring-closing metathesis reaction to give substituted 3-hydroxyl-3-methyl benzo[b]oxocines, respectively. Furthermore, using 1-naphthol as starting material and following the same reaction processes for substituted benzo[b]oxepines and benzo[b]oxocines, the naphthalene counterparts, such as 9-methyl-7, 10-dihydro-11-oxacyclohepta[a]naphthalenes and 10-hydroxy-10-methyl - 10, 11 – dihydro-7H-12- oxacyclocta[a] naphthalene were produced, respectively.

目 錄
中文摘要 .......................................................10
英文摘要 .......................................................11
第一章
1-1前言 .......................................................12
1-2研究動機 ....................................................20
第二章
2-1 Substituted 3-methylbenzo[b] oxepines的合成.................22
2-2 Substituted 3-methyl-3-hydroxybenzo[b] oxocines的合成.......23
2-3萘環類似物的新法合成.........................................24
2-4重要反應.....................................................25
三、結果與討論..................................................28
四、結論........................................................43
五、實驗部份
1- 溶煤及處理過程.........................................45
2- 實驗藥品...............................................46
3- 實驗儀器...............................................47
4- 實驗步驟...............................................48
六、參考文獻....................................................83

1. Wang. M.; Heinstein, P.; Zhou, J. Y.; Liu, Y. C; Chen, X. Y.; Chen, D. ; Chang, C. J. J. Chem. Soc. Perkin. Trans. I, 1996, 845-851.
2.(a)Nakal, K; Yoshimoto, Y; Sawa, T,; Homma, Y.; Hamada, M,; Takeuchi, T.; Imoto. M. J. Antibiot, 2000, 53, 1130~1136.
(b)Gaul, C.; Danishefsky, S, J. Tertrahedrom Lett. 2002, 43, 9038~9042.
3.Tsuji, J.; Hashiguchi, S. Tetrahedron Lett. 1980, 2955~2958.
4.Tsuji, J.; Hashiguchi, S. Tertrahedrom Lett. 1980,2955~2958.
5.Schrocj, R. R; Feldman, J.; Cannizzo, L. F.; Grubbs, R. H. Macromolecules, 1987, 20, 1169~1172.
6.Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem.Int.Ed.Engl, 1995, 34, 2039-2041
7.(b) Furstner, A.; Angew. Chem. Int. Ed. Engl. 2000, 38, 3012-3043.
8.(a)Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H. J. Am. Chem. SOC. 1992, 114, 3974.
(b) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem.Int.Ed.Engl, 1995, 34, 2039-2041
9. De Clercg, B,; Verpoort, F. J. Tertrahedrom Lett. 2002, 43, 9101~9104.
10.Chang, S.; Jones, L., Ⅱ ; Wang. C.; Henling, L. M. ; Grubbs, R. H. Organometalbics, 1998, 17, 3460-3465
11. De Clercg, B,; Verpoort, F. J. Organometalbics, 2003,
12.Scholl, M. Tranka, T. M.; Morgom, J. P; Grubbs, R. H. Tertrahedron Lett. 1999, 40, 2247~2250.
13. Wang, E.-C.; Huang, K.-S.; Lin, J.-R.; Hsu, M.-K.; J. Chin. Chem. Soc. 2001, 48, 83-90.
14. Huang, K. S.; Wang, E. C. Tetrahedron Lett. 2001, 42, 6155-6157.
15. Huang, K. C.；Wang, E. C.; J. Chin Chem. Soc. 2004, 51, 383-391.
16. Huang, K. C.；Wang, E. C.; Chen H, M. J. Chin. Chem. Soc. 2004, 51, 807-816.
17. Wang, E. C.; Hsu, M. K.; Lin, Y. L.; Huang, K. S. Heterocycles. 2002, 57, 1997-2010.
18. Wang, E. C.; Wang, C. C.; Hsu, M. K.; Huang, K. S. Heterocycles. 2002, 57, 2021-2034.
19. Tsai, T. W.; Wang, E. C.; Huang, K. C.; Li, S. R.; Wang, Y. F.; Lin, Y. L.; Chen, Y. H. Heterocycles. 2004, 63, 1771-1781.
20. Lin, Y. L. Master thesis, Kaohsiung Medical University, 2004.
21. Macias, F. A; Molinillo, J. M. G,; Varela, R. M.; Torres, V. A.; Fronczek, F, R. J. Org. Chem. 1994, 59, 8261-8266.
22. Takabatake, K.; Nishi, I,; Shindo, M.; Shishido, K. J. Chem. Soc, Perkin Trans. 2000, 1807.
23. Asakawa, Y.; Hashimoto, T.; Takikawa, K.; Tori, M,; Ogawa, S. Phytochemistry, 1991, 30, 235.
24. Yamaguchi, S.; Furihata, K,; Miyazawa, M; YoKoyama, H.; Hirai, Y. Tertrahedrom Lett, 2000, 41, 4787-4790
25. (a) Shimizu, Y.; Chou, H. N.; Bando, H.; Van Duyne, G.; Clardy, J. C. J. Am. Chem. Soc, 1986, 108, 514-515
(b) Yasumoto, T.; Murata, M. Chem. Rev. 1993, 93, 1897-1909
26. Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18-29.
27. Chang. S. K. Master thesis, Kaohsiung Medical University, 2003.
28.Ding, W.; Pu, J.; Zhang, C. Synthesis, 1992, 635-637
29. Huang, K. S.; Wang, E. C. Tetrahedron Lett. 2001, 42, 6155-6157.
30. Wang, E. C.; Hsu, M. K.; Lin, Y. L.; Huang, K. S. Heterocycles. 2002, 57, 1997-2010.
31.Tina M.Trnka.；Grubbs, R. H.; Acc. Chem. Res. 2001, 34, 18-29
32. James, R.V.; Ryan, E. L. Tetrahedron Lett. 2000, 41, 1151-1154.