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研究生:顏秀航
研究生(外文):Hsiu-Hang Yen
論文名稱:掌性1,1′-雙薁化合物之合成應用
論文名稱(外文):Synthetic Application of Chiral 1,1′-bi-2-azulene Compounds
指導教授:陳阿煌彭金恢
指導教授(外文):Arh-Hwang Chen
學位類別:碩士
校院名稱:國立高雄師範大學
系所名稱: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:2006
畢業學年度:94
語文別:中文
中文關鍵詞:雙薁
外文關鍵詞:azulene
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掌性輔助劑在有機不對稱合成中,一直被廣泛的研究;掌性輔助劑除了本身的應用外,更可以由此製備具有效力、且更經濟的掌性輔助劑;BINOL(1,1'-bi-2-naphthol)是目前化學界最著名的掌性輔助劑之ㄧ,且在合成上應用範圍非常廣泛。
本實驗在研究掌性1,1'-雙薁化合物之合成、應用和研究;首先以2-胺基薁-1,3-二羧酸乙酯(53)為起始物,與格林鈉試劑進行親核性取代反應獲得2-乙醯胺-4-苯基薁-1-羧酸乙酯(106)後,進一步合成2-胺基-4-苯基薁-1-羧酸乙酯(98),利用氯化鐵和掌性試劑進行偶合得到具有光學活性的1,1’-二(2-胺基-4-苯基薁-1-羧酸乙酯) (107)。
本實驗之另一部分,是以2-氯基薁-1,3-二羧酸乙酯(50)為起始物,與四種不同鋰試劑進行親核性取代反應得到4位置分別接上甲基、乙基、丙基、丁基的化合物(101),進一步將2位上的氯基轉換成甲氧基,再將甲氧基以置換成羥基,最後利用氯化鐵進行偶合反應得到化合物(104)。
目錄
中文摘要.....................................................I
英文摘要.....................................................II
目錄.........................................................III
圖目錄........................................................V
第一章 緒論
1-1 前言......................................................1
1-1-1 掌性純物質..........................................3
1-1-2 不對稱合成..........................................6
1-2 BINOL....................................................8
1-2-1 BINOL的合成 .......................................8
1-2-2 BINOL的光學離析...................................10
1-3 薁........................................................15
1-3-1 薁的性質及介紹......................................15
1-3-2 薁的合成............................................17
1-3-2 薁的化學反應........................................21
1-3-2 薁的應用............................................28
1-3-2 雙薁化學............................................31
第二章 合成構想.............................................34
第三章 實驗方法
3-1 ㄧ般敘述..................................................37
3-2 實驗步驟..................................................40
第四章 結果與討論...........................................75
第五章 結論.. ..............................................101
第六章 參考文獻............................................103
第七章 附錄.. ..............................................110
1.陳焜銘, Chemisty,1996, 54, 117.
2.Jiang, Peng.; Lu, Shijie ;Synthesis of (±) Binaphthols via Oxidative Coupling of Naphthols by Cerium Ammonium Nitrate(CAN),Synth. Commun. 2001, 31(1), 131.
3.Ding, K.; Wang, Y.; Zhang, L.; Wu, Y.; Matsuura, T. ;A Novel Two-Phase Oxidative Coupling of 2-Naphthols Suspended in Aqueous Fe3+ Solutions ,Tetrahedron 1996, 52, 1005-1010.
4.Nakajima, M.; Miyoshi, I.; Kanayama, K.; Hashimoto, S. ;Enantioselective Synthesis of Binaphthol Derivatives by Oxidative Coupling of Naphthol Derivatives Catalyzed by Chiral Diamine·Copper Complexes ,J. Org Chem. 1999, 64, 2264-2271.
5.S.W. Hon ; C.H. Li ; J.H. Kuo ; N.B. Barhate;Y.H. Liu;Yu Wang;C.T.Chen.; Catalytic Asymmetric Coupling of 2-Naphthols by Chiral Tridentate Oxovanadium(IV) Complexes ,Org. Lett. 2001, 3, 869-872.
6.Kazlauskas, R. J. ;Resolution of binaphthols and spirobiindanols using cholesterol esterase,J. Am. Chem. Soc. 1989, 111, 4953-4959.
7.Cavazza, M.; Festa, C.; Lenzi, A.; Levi-Minzi, N.; Veracini, C.A.; Zandomeneghi, M. Gazz. Chim. Ital. 1994, 124, 525.
8.Cavazza, M.; Zandomeneghi, M. Gazz. Chim. Ital. 1993, 123,723.
9.Jacques, J.; Fouquey, C. ;Enantiomeric cyclic binaphthyl phosphoric acids as resolving agents ,Tetrahedron Lett. 1971, 12, 4617-4620.
10.Wang, M.; Liu, S. Z.; Liu, J.; Hu, B. F. ;Diastereoselective Synthesis of 1,1'-Binaphthyl-2,2'-diol ,J. Org. Chem. 1995, 60,7364-7365.
11.Gong, B.; Chen, W.; Hu, B. ;A new and efficient method for the resolution of 2,2'-dihydroxy-1,1'-binaphthyl ,J. Org. Chem. 1991, 56, 423-425.
12.Fabbri, D.; Delogu, G.; De Lucchi, O.; Preparation of enantiomerically pure 1,1'-binaphthalene-2,2'-diol and 1,1'-binaphthalene-2,2'-dithiol, J. Org. Chem. 1993, 58,1748-1750.
13.Fabbri, D.; Delogu, G.; De Lucchi, O. ;A Widely Applicable Method of Resolution of Binaphthyls: Preparation of Enantiomerically Pure 1,1'- Binaphthalene-2,2'-diol, 1,1'-Binaphthalene-2,2'-dithiol, 2'-Mercapto-1,1'-binaphthalen-2-ol, and 1,1'-Binaphthalene-8,8'-diol , J. Org. Chem. 1995, 60,6599-6601.
14.Chow, H. F.; Wan, C. W.; Ng, M. K. ;A Versatile Method for the Resolution and Absolute Configuration Assignment of Substituted 1,1'-Bi-2-naphthols, J. Org. Chem. 1996, 61,8712-8714.
15.Toda, F.; Tanaka, K.; Mak, T. C. W.;Mutual optical resolution of bis-β-naphthol and sulfoxides. Absolute configuration and crystal structure of a 1:1 molecular complex, Chem. Lett. 1984, 2085-2088.
16.Toda, F.; Tanaka, K.; Nagamatsu, S. Mutual optical resolution of 2,2′-dihydroxy-1,1′-binaphthyl and alkyl aryl or dialkyl sulfoxides by complex formation, Tetrahedron Lett. 1984,25, 4929-4932.
17. Toda, F.; Tanaka, K. ;Efficient optical resolution of 2,2'-dihydroxy-1,1'-binaphthyl and related compounds by complex formation from tartaric acid ,J. Org. Chem. 1988, 53, 3607-3609.
18.Toda, F.; Tanaka, K.; Nasssimbeni, L.; Niven, M.;Efficient Optical Resolution of 2,2′-Dihydroxy-1,1′-binaphthyl and 10,10′-Dihydroxy-9,9′-biphenanthryl by Complex Formation with Novel Chiral Host Compounds Derived from Tartaric Acid, Chem. Lett.
1988, 1371.
19.Kawashima, M.; Hirata, R. Bull. Chem. Soc. Jpn. 1993, 66, 2002.
20.Kawashima, M.; Hirayame, A.;Direct Optical Resolution of 2,2′-Dihydroxy-1,1′-binaphthy, Chem. Lett. 1990,19, 2299.
21.Schanz, H. J.; Linseis, M. A.; Gilheany, D. G. Improved resolution methods for (R,R)- and (S,S)-cyclohexane-1,2-diamine and (R)- and (S)-BINOL ,Tetrahedron:Asymmetry 2003, 14, 2763-2769.
22.Periasamy, M. Spec. Publ. - R. Soc. Chem. 1997, 205.
23.Periasamy, M.; Bhanu Prasad, A. S.; Bhaskar Kanth, J. V.;Reddy, C.
K. ;A Simple Convenient Method for the Resolution of Racemic
2,2′-Dihydroxy-1,1′-Binaphthyl Using (S)-Proline ,Tetrahedron:
Asymmetry 1995, 6, 341-344.
24.Periasamy, M.; Venkatraman, L.; Thomas, K. R. J. ;New Methods of Resolution and Enrichment of Enantiomeric Excesses of
1,1'-Bi-2-naphthol ,J. Org. Chem. 1997, 62, 4302-4306.
25.Du, H.; Ji, B.; Wang, Y.; Sun, J.; Meng, J.; Ding, K.;A new method
for optical resolution of BINOL by molecular complexation with
(S)-5-oxopyrrolidine-2-carboxanilide ,Tetrahedron Lett. 2002, 43, 5273-5276.
26.Cai, D.; Hughes, D. L.; Verhoeven, T. R.; Reider, P. J. ;Simple and
Efficient Resolution of 1,1′-Bi-2-naphthol ,Tetrahedron Lett. 1995, 36,7991-7994.
27.Cai, D.; Hughes, D. L.; Verhoeven, T. R.; Reider, P. J. Org. Synth.
1999, 76, 1.
28.Hu, Q. S.; Vitharana, D.; Pu, L.;An Efficient and Practical Direct
Resolution of Racemic 1,1′-Bi-2-naphthol to Both of Its Pure
Enantiomers, Tetrahedron: Asymmetry 1995,6, 2123-2126.
29.Tanaka, K.; Okada, T.; Toda, F. Angew. Chem., Int. Ed. Engl.1993, 32, 1147.
30.Toda, F.; Tanaka, K. New chiral ammonium salt hosts derived from amino acids: very efficient optical resolution of 2,2 -dihydroxy-1,1 -binaphthyl by complexation with these host compounds ,Chem. Commun. 1997, 1087-1088.
31.Toda, F.; Tanaka, K.; Sawada, H. J. Chem. Soc., Perkin Trans.
1 1995, 3065.
32.Wang, Y.; Sun, J.; Ding, K. ;Practical Method and Novel
Mechanism for Optical Resolution of BINOL by Molecular Complexation with N-Benzylcinchoninium Chloride ,Tetrahedron 2000, 56, 4447-4451.
33.Periasamy, M.; Venkatraman, L.; Sivakumar, S.; Sampathkumar,N.; Ramanathan, C. R.;A New, Convenient Method of Resolution of
Racemic 1,1'-Bi-2-naphthol Using Boric Acid and (R)-(+)-
-Methylbenzylamine ,J. Org. Chem. 1999, 64, 7643-7645.
34.Periasamy, M.; Ramanathan, C. R.; Kumar, N. S. ;Resolution of
trans-(±)-2-(pyrrolidinyl)cyclohexanol and its methyl ether using
boric acid and chiral 1,1′-bi-2-naphthol ,Tetrahedron:Asymmetry
1999, 10, 2307-2310.
35.Piesse, D. Compt. Rend. 1864, 57, 1016.
36.Hadden, R. C.; Raghavachari, K. ;Planar cis-[10]annulene and
azulene revisited, J. Am. Chem. Soc. 1982, 104, 3516-3518.
37.Tobler, H. J.; Bauder, A.; Günthard, H. H. ;The microwave spectrum and dipole moment of azulene, J. Mol. Spectrcscopy. 1965, 18, 239-246.
38.Clar, E. J. Chem. Soc. 1950, 1823.
39.Loyid, D. Non-Benzenoid Conjugated Corbocyclic Compounds,
Elsevier, 1984, p.351.
40.邱淑卿, 雙薁酚掌性輔助劑:1,1''-二(3-乙氧羰基-4,8-二苯基-2-薁酚)之合成研究,國立高雄師範大學化學研究所碩士論文, 2001。
41.Gupta, Y. N.; Mani, S. R.; Houk, K. N. Tetrahedron Lett. 1981, 495.
42.Dunn, L.C.; Chang Y-M.; Houk, K. N. ;The [6 + 4] Cycloadditions
of Diethylaminobutadiene to Fulvenes. A New Synthesis of Azulenes,J. Am. Chem. Soc. 1976, 98, 7095-7096.
43.(a) Hafner, K. Angew. Chem. 1955, 67, 301.
(b) Hafner, K. Angew. Chem. 1957, 69, 393.
44.Nozoe, T.; Matsumura, S.; Murase, Y. ;Seto, S. Chem. Ind. London 1955, 1257.
45.Nozoe, T.; Seto, S.; Matsumura, S.; Murase, Y. Bull. Chem. Soc. Jpn
1962, 35, 1179.
46.Yang,P.W.; Yasunami, M.; Takase, K.. The formation of azulene derivatives by the reaction of 2H-cyclohepta[b]furan-2-ones with enamines ,Tetrahedron Lett 1971, 12,4275-4278.
47.Pfau A. St.;Plattner P. A. HeIv. Chim. Acta.1936, 19, 858.
48.Plattner P. A.;Pfau A. St. Helv. Chim. Acta. 1937, 20, 224.
49.Anderson A. G.;Nelson J. A. ;Azulene. I. An Improved Synthesis,
J. Am. Chem. Soc. 1951, 73, 232-235.
50.Nozoe T.;Seto S.;Matsumura S. Bull. Chem. Soc. Jpn. 1962, 35, 1190 .
51.A. H. Chen;Nozoe Tetsuo;Electromethoxylation of Diethyl
2-Hydroxyazulene 1,3-Dicarboxylate and 2-Amino-1,3- Dicyanoazulene ,Tetrahedron Lett. 1998, 39, 7511-7512.
52.Abe N.;Morita T.;Takase K. Cobalt-catalyzed synthesis of pyridines from acetylenes and nitriles ,Tetrahedron Lett. 1973, 14, 3383-3384.
53.A. H. Chen;S.C. Chiu;Y.C. Kuo;Arylation of Diethyl
2-Chloroazulene-1,3-Dicarboxylate with Grignard Reagent, Synthetic Commun. 2003, 33, 2701-2707.
54.Morita T.;Fujita T.;Takase K. Bull. Chem. Soc. Jpn. 1980, 53, 1647.
55.Anderson A. G.; Nelson J. A. ;Electrophilic Substitution of Azulene ,
J. Am. Chem. Soc. 1950, 72, 3824-3825.
56.Anderson A. G.;Nelson J. A.;Tazuma J. J.;Azulene. III.
Electrophilic Substitution, J. Am. Chem. Soc.1953, 75, 4980-4989.
57.Anderson A. G.;Replogle L. L. ;Communications- Electrophilic
Substitution of 1,3-Dichloroazulene ,J. Org. Chem. 1960, 25, 1275-1275.
58.Hafner K.;Moritz K. L. Ann. 1962, 656, 40.
59.Nozoe T;Seto S.;Matsumura S.;Murase Y. Bull. Chem. Soc. Jpn.,
1962, 35,1179.
60.Nozoe T.;Seto S.;Matsumura S. Bull. Chem. Soc. Jpn. 1962, 35,
1190 .
61.Takase K.;Yasunami M. U. S.Patent 4 1986, 595, 684.
62.Takase K.;Yasunami M. U. S.Patent 4 1987, 656,194.
63.Yokota M.; Uchibori S.; Hayashi H.; Koyama R.; Kosakai K.;
Wakabayashi S.; Tomiyama T. Azulene Derivatives as Receptor Antagonists -- II. Synthesis and Biological Activity of 6-Mono- and 6-Dihydroxylated-isopropylazulenes ,Bioorg. Med. Chem. 1996, 4, 575-591.
64.Estdale, S. E.; Brette, R.; Dunmur, D. A.; Marson, C. M. ;The
azulene ring as a structural element in liquid crystals ,J. Mater. Chem.
1997, 7(3), 391-401.
65.Morita T.; Takse K.; Kaneko M. Jap.Pat. 1990, 0269438.
66.Morita T.;Tahare K. Bull. Chem. Soc. Jpn. 1982, 55, 1144.
67.A. H. Chen;Yang C. H.;Moritia T. Chemistry(Chin. Chem. Soc.)
1995, 52, 115.
68.洪志熙, 1, 1′-雙薁烷基取代掌性輔助劑之合成、性質及應用研究,國立高雄師範大學化學研究所碩士論文, 2003。
69.郭育成, 1,1′-雙薁苯基取代掌性輔助劑之合成、性質及應用研究,國立高雄師範大學化學研究所碩士論文, 2003。
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