雪梨酮化合物由於具有特殊的電子雲分佈，造成雪梨酮環在酸性或鹼性下均不安定，易發生裂解反應。此外雪梨酮及一些雜環化合物可能會具有生理活性及藥理作用，如果在雪梨酮環的第四位置接上一些官能基團，形成雜環取代基之前驅物，進行環化反應後即可獲得一些可能具有藥理活性作用之3-芳香基-4-雜環取代基雪梨酮化合物。
本研究利用3-芳香基-4-甲醯基雪梨酮與芳香甲醯來進行縮合反應以製備3-芳香基-4-甲醯基雪梨酮芳香甲醯化合物，作為合成3-芳香基-4-雜環取代基雪梨酮化合物的前驅物，再經由環化反應生成3-芳香基-4-雜環基雪梨酮，經過嘗試，利用二氧化鉛當作環化試劑，順利合成出3-芳香基-4-雜環取代基雪梨酮化合物。
本研究也利用芳香氯化氫與2,4-戊二酮及環己酮進行環化反應，順利合成出2-[4-(3,5-二甲基-1-基)苯基]-5-芳香基-[1,3,4]二唑及3-(5-苯基-[1,3,4]二唑基-2-基)-5,6,7,8-四氫-9氫-卡。
本研究內容主要包括如下：
1. 3-芳香基-4-甲醯基雪梨酮與芳香甲醯化合物之縮合反應
2. 3-芳香基-4-甲醯基雪梨酮芳香甲醯類衍生物之環化反應
3. 4-(5-芳香基-1,3,4-二唑-2-基)]苯氯化氫衍生物與2,4-戊二酮之環化反應
4. 4-乙氧醯基苯氯化氫與環己酮之環化反應

Abstract

For sydnone compound , the electron density unnormally distributes on the sydnone ring . This compound is very unstable in the medium condition of acid or base . Furthermore , sydnones and some heterocyclic compounds may possess biological and pharmacological activities . If some functional group were introduced to fourth position of sydnone ring to form the the precursors of heterocyclic substituents , via cyclization , 3-aryl-4-( heterocycle-substituted ) sydnones . It is possible that some biological and pharmacological activities could be obtained .
In this study , 3-aryl-4-formylsydnone benzoylhydrazones which are precursors of 3-aryl-4-heterocyclic sydnones , are prepared by taking adv- antage of condensation reactions of 3-aryl-4-formylsydnones and benzo-ylhydrazine . It is expected that 3-aryl-4-heterocyclic sydnones can be producedby a variety of cyclization reactions. Among the precursors , 3-aryl-4-formylsydnone benzoylhydrazones were found to react with lead oxide to give 3-aryl-4-heterocyclic sydnones successfully .
In this study , 2-[4-(3,5-dimethylpyrazol-1-yl)pheny- l]-5-aryl- [1,3,4]-oxadiazole and 3-(5-aryl-[1,3,4] oxadiazol-2-yl)-5,6,7,8- tetra-hydro- 9H-carbazole are prepared by taking advantage of the cyclic reaction of arylhydrazine hydrochlolorides with 2,4-pentandione and cyclohexanone , respectively .
The four major parts in this research are summarized as follows：
1. The condensation reactions of 3-aryl-4-formylsydnones with compounds with hydrazine groups .
2. The cyclic reactions of 3-aryl-4-formylsydnone benzoylhydrazones with lead oxide .
3. The cyclic reactions of 4-(5-aryl-1,3,4-oxadiazol-2-yl) phenylhydrazine hydrochlorides with 2,4-pentandione .
4. The cyclic reactions of 4-ethoxycarbonylphenylhydrazine hydrochlo-Ride with cyclohexanone .

參考文獻:
1. Newton, C. G.; Romsden, C. A . Tetrahedron 1982, 38,2965.
2. Earl, J. C. and Mackney, A. W. J. Chem. Soc., 1935, 899.
3. Simpson, J. C. E. J. Chem. Soc., 1946, 94.
4. Baker, W. and Ollis, W. D. Quart. Rew., 1957, 11, 15.
5. Kartritzky AR. Chem. Ind. 1955, 521.
6. Earl. J. C.; Leake, E.W. and LeFevre, R. J. W. Nature, 1947, 160, 366.
7. Baker, W.; Ollis, W. D.; Poole, V. D.Barltrop, J. A.; Hill, R. A. W. and Sutton, L. E. Nature, 1947, 160, 366.
8. Hill, R. A. W. and Sutton, L. E. J. Chim. Phys., 1949, 46, 244.
9. Hill, R. A. W. and Sutton, L. E. J. Chem. Soc., 1949,746.
10. Hill, R. A. W. and Sutton, L. E. J. Chem. Soc., 1953, 1482.
11. Barod’Ko, Yu. G. and Syrkin, Ya. K. Dokl. Akad. Nauk. SSSR., 1960, 134, 1127.; C. A. 1961, 55, 12039.
12. Earl. J. C.; Leake, E.W. and LeFevre, R. J. W. J. Chem. Soc., 1948, 2269.
13. Stewart, F. H. C. Chem. Rew., 1964, 64, 129.
14. Ohta, M. and Kato, H. Nippon Kagaku Zasshi,1965, 86, 661.
15. Ohta, M. and Kato, H., “ Non-benzenoid Aromatics, I”, (Edited by Suyder, J. P.), 117, Academic Press, New York, London (1969).
16. Earl. J. C.; LeFevre, R. J. W. and Wilson, I. R. J. Chem. Soc., 1949,5103.
17. Greco, C. V.; Tobias, J. and Kier, L. B. J. Heterocyclic Chem., 1967, 4, 160.
18. Metz, F. I.; Servoss, W. C. and Welsh, F. E. J. Phys. Chem., 1962, 66, 2446.
19. Lees, W. A. and Buraway, A. Tetrahedron, 1963, 19, 619.
20. Zuman, P. and Voaden, D. J. Tetrahedron, 1961, 16, 130.
21. Stewart, F. H. J. Chem. Soc. 1963, 2009.
22. Matsunage, Y. Bull. Chem. Soc. Japan, 1957, 30, 227.
23. Eley, D. D.; Parfitt, G. D.; Perry, M. J. and Taysum, G. H. Trans Faraday Soc., 1953, 49, 79.
24. Daerike, H. V. and Druey, J. Helv. Chim. Acta, 1962, 45, 2426.
25. Setwart, F. H. C. Chem. Ind. (Londan), 1963, 1926.
26. Lawson, K. D.; Brey, Jr.W. S. and Kier, L. B. J. Am. Chem. Soc., 1964, 86, 463.
27. Kier, L. B. and Roche, E. B. J. Pharm. Sci., 1966, 55, 807.
28. Kier, L. B. Tetrahedron Lett., 1967, 123.
29. Roche, E. B. and Kier, L. B. Tetrahedron, 1968, 24, 1673.
30. Orgel, L. E.; Cottrell, T. L;. Dick, W. and Sutton, L. E. Trans Faraday Soc., 1951, 47, 223.
31. Wen, C. M. and Tien, H. J. J. Chin. Chem. Soc., 1975, 22, 255.
32. Schmiat, G. M. J. Bull. Res. Council Israel, 1951, 1, 123.; C. A. 1952, 46, 2871.
33. Barnighausen, H.; Jellinek, F. and Vos, A. Proc. Chem. Soc., 1961, 120.
34. Barnighausen, H.; Jellinek, F.; Munnik, J. and Vos, A. Acta, Cryst., 1963, 16, 471.; C. A. 1964, 60, 8215.
35. Thiessen, W. E. and Hope, H. J. Am. Chem. Soc., 1967, 89, 5977.
36. Adams, R.; Johnson, J. R. and Wilcox, C. F. J. “ Laboratory Experimental in Organic Chemistry” 6th ed., MacMillan Inc. New York 1970, 314.
37. Baker, W.; Ollis, W. D. and Poole, V. D. J. Chem. Soc. 1949, 307.
38. Tien, H. J.; Yeh, M. Y. and Tien, J. M. J. Chin. Chem. Soc. 1977, 24,115.
39. Tien, J. M. and Hunsberger, I. M. J. Am. Chem. Soc. 1955, 77, 6604.
40. Thoman, C. J. and Voaden, D. J. Org. Synth. 1965, 45, 96.
41. Weintraub, P. M. and Bambury, R. E. Tetrahedron Lett., 1969, 579.
42. Tien, H. J.; Nonaka, T.; FuChigami, T.; Sekine, T. and Ohta, M. Nippon Kagaku, Kaishi, 1978, 1310.
43. Tien, J. M. and Hungsberger, I. M. J. Am. Chem. Soc. 1961, 83, 178.
44. Gotthardt, H. and Reiter, F. Chem. Ber. 1979, 112, 1193; C. A. 91,5155t.
45. Maerky, M.; Hansen, H. J. and Schmid, H. Helv. Chim. Acta 1971,54,1275.
46. Huseya, Y.; Chinone, A. and Ohta, M. Bull. Chem. Soc. Jpn. 1972,45,3202.
47. Bhat, V.; Dixit, V. M.; Ugarker, B. G.; Trozzolo, A. M. and George, M. V. J. Org. Chem. 1979, 44, 2957.
48. Huisgen, R.; Gotthardt, H. and Grashey, R. Angew. Chem. 1962, 74,30.
49. Gotthardt, H. and Huisgen, R. Chem. Ber. 1968, 101, 552.
50. Gotthardt, H. and Tieter, F. Chem. Ber. 1979, 112, 1193.
51. Huisgen, R.; Grashey, R.; Gotthardt, H. and Schjmidt, R. Angew. Chem. 1962, 74, 29.
52. Gotthardt, H. and Tieter, F. Chem. Ber. 1979, 112, 1635.
53. Kato, H.; Sato, S. and Ohta, M. Tetrahedron Lett. 1967, 4261.
54. Kenner, J. and Mackay, K. Nature 1946, 158, 909.
55. Tien, H. J.; Yeh, M. Y. and Huang, C. Y. J. Chin. Chem. Soc. 1985,32, 461.
56. Kuo, C. N.; Wu, M. H.; Chen, S. P.; Li, T. P.; Hwang, C. Y. and Yeh, M. Y. J. Chin. Chem. Soc. 1994, 41, 849.
57. Tien, H. J. and Ohta, M. Bull. Chem. Soc. Japan 1972, 45, 2924.
58. Thoman, C. J.; Voaden, D. J. and Hunsberger, I. M. J. Org. Chem.1964, 29, 2044.
59. Tien, H. J. and Ohta, M. Bull. Chem. Soc. Japan 1972, 45, 2924.
60. Thoman, C. J.; Voaden, D. J. and Hunsberger, I. M. J. Org. Chem.1964, 29, 2044.
61. Tien, H. J.; Yeh, M. Y. and Huang, C. Y. J. Chin. Chem. Soc. 1985,32, 461.
62. Tien, J. M. and Hunsberger, I. M. J. Am. Chem. Soc. 1961, 83, 178.
63. Kier, C. B. and Roche, E. B. J. Pharm. Soc. 1967, 56, 149.
64. Imashiro, Y. and Masuda, K. Japa. 1969, 69, 411; C. A. 72,111482q.
65. Mashkovakii, M. D.; Yashunskii, V. C. and Al’ tshuler, R. Fr. 1970,1, 589, 783; C. A. 74,13131w.
66. Vitolo, M. L.; Webb, J. Biochim. Pharmacol. 1985, 34, 3011.
67. Dubois, J. E., Fakhrayan, H., Doucent, J. P. and EI Hage Chahine, J. M., Inorg. Chem., 1992, 31, 853.
68. Thoman, C.J.; Voaden, D.J. ; Hunsberger, I. M. , J. Org. Chem. Soc., 1964, 29, 2044.
69. Tien, H. J.; Yeh, M. Y. ; Wu, C.H. and Chen. H. T. , J. Chin. Chem. Soc. 1984, 31, 191.
70. Tien, H. J.; Yeh, M. Y. and H.J. , J. Chin. Chem. Soc. 1985, 33, 83.
71. Tien, H. J.; Yeh, M. Y. and H.J. , C. Y., and Chen, M. H. , J. Chin. Chem. Soc. 1985, 32, 461.
72. 游憲政 國立成功大學化學研究所碩士論文 1991
73. 洪偉章 國立成功大學化學研究所碩士論文 1988
74. Jugie G. , Smith J. A. S. Martin G. J. ,Chem. Soc., Perkin Trans. 1 ,1975, 2 , 925.
75. 盧麗慧 國立成功大學化學研究所碩士論文 1991
76. Masuda K., Kikuchi K., Imajo Y., Japan Patent, 1972, 29, 511.
77. Pattanashetti, P.P.; Tikare, R. K.; Dambal, D. B.; Badami, B. V. and Puranik, G. S. Arch. Pharm. 1984, 317, 1, 59.
78. R. G. Dubenko, P. S. Pelkis. Khimiya Getersiklicheskikh Soedinenii. 1967, 3, 1.
79. R. G. Dubenko, E. F. Gorbenko. Chem. Heterocyclic compd. 1967, 3, 1.
80. Thomas, J. (Delalande S. A. ) Chem. Abstr. 1974, 81, 136153g.
81. Grigat, E . ; Puetter, R. ( Farbenfabriken Bayer A.-G ) Chem. Abstr. 1971, 75, 36042c.
82. Yale, H. L. ; Losee, K. J. Med. Chem. 1966, 9, 478.
83. Adelstein, G. W. ; Yen, C. H.; Dajani, E. Z. ; Bianchi, R. G. J. Med. Chem. 1976, 19, 1221.
84. C. Adachi, T. Tsutsui and S. Saito, Appl. Phis. Lett. 1989, 55, 1489.
85. Nguyen, T. H.; Milcent, R. and Barbier, G. J. Heterocycl. Chem. 1985, 22, 1383.
86. P. S. N. Reddy, Indian J. Chem. Sect. B, 1987, 26B, 890.
87. El-Bakoush, M. M. and Parrick, J. J. Heterocycl. Chem. 1988, 25,1055.
88. Gelvin, C. R. and Turnbull, K. Helv. Chim. Acta. 1992, 75, 6, 1931.
89. Parlok, J. J. J. Heterocycl. Chem. 1998, 35, 1493.
90. Frinkelstein, B. L.; Strok, C. J. Pesticide Sci. 1997, 50, 324.
91. Valberkel, P. M. ; Sherrington, D. C. Polymer 1996, 37, 1431.
92. Gajare, A. S. ; Bhawasar, S. B. ; Shingare, M. S. Ind. J. Chem,1997, 6, 321.
93. Keasling, H. H. ; Willette, R. E.; Szmuskovicz, J. Med. Chem. Chem. 1964, 7, 94.
94. Goddard, C. J. ; Schulte, Chem. Abstr. 1992, 116, 83669 .
95. Tatsugi, J.; Ikuma, K. ; Izawa, Y. Tetrahedron Lett. 1995, 36, 8611.
96. Labroo, R. B. ; Cohen, L. A. J. Org. Chem. 1990, 55, 4901.
97. 郭文發 國立成功大學化學研究所博士論文 2000
98. Pattanashetti, P.P.; Tikare, R. K.; Dambal, D. B.; Badami, B. V. and Puranik, G. S. Arch. Pharm. 1984, 317, 1, 59.