臺灣博碩士論文加值系統

將聯胺與苯甲醛(10：1)於95%乙醇中加熱迴流3小時可以得到苯甲醛腙之化合物；而以聯胺與苯甲醛(1：2)於95%乙醇中加熱至50℃1小時便可獲得雙苯亞甲基肼之化合物。苯甲醛腙化合物除硝基外，其餘取代基苯甲醛腙都非常不安定。
苯甲醛腙系列上C α的碳-13化學位移會受苯環上取代基之影響
，依其SCS和Hammett常數(σ)值作圖顯示C α的斜率為-4.01，相關係數為0.939，表示C α受苯環取代基之誘導效應的影響；雙苯亞甲基肼系列C α似乎沒有線性關係。
苯甲醛腙系列之氮-15依化學位移其和常數(σ)值作圖顯示亞胺基與胺基之氮其斜率分別為13.36與3.89，相關係數分別為0.940與0.81
4。

The benzaldehyde hydrazones can be prepared by heating a ethyl alcohol solution containing aryl aldehyde and tenfold hydrazine for three hours. The bis-benzylidene hydrazine can be prepared by heating a ethyl alcohol solution containing isometric aryl aldehyde and hydrazine for an hour. The hydrazone of aryl aldehydes are very unstable except nitro-benzaldehyde hydrazone.
A series of benzaldehyde hydrazones and bis-benzylidene hydrazines for the study on the substituent- induced chemical shifts (SCS) of Cα using the 13C NMR spectral analyses. The correlation between SCS and Hammett constants (σ) shows that the substituent effect via inductive effect for Cα (
slope=-4.01, r2=0.939). No correlation can be made for the bis-benzylidene hydrazine.
A series of benzaldehyde hydrazones for the study on the chemical shifts of N using the 15N NMR spectral analyses, the correlation between chemical shifts and Hammett constants (σ) shows that the substituent effect via inductive effect for the amino N(slope=3.89, r2=0.814。) and the imino N (slope=13.36, r2=0.940)

中文摘．．．．．．．．．．．．．．．．．．．．．I
英文摘要．．．．．．．．．．．．．．．．．．． II
第一章 緒論．．．．．．．．．．．．．．．．． 1
1.1 前言．．．．．．．．．．．．．．．．． 1
1.2 肼與腙．．．．．．．．．．．．．．．． 2
1.3 質譜法(Mass Spectrometry,MS)．．．．． 3
1.4 核磁共振光譜術(NMR)．．．．．．．．．．4
1.5 Hammett方程式．．．．．．．．．．．．．5
第二章 結果與討論．．．．．．．．．．．．．． 7
2.1 苯甲醛腙的製備 ．．．．．．．．．．． 7
2.2 雙苯亞甲基胼的製備．．．．．．．．．．12
2.3 苯甲醛腙與丙酮的縮合反應．．．．．．．16
2.4 4-硝苯甲醛腙與酮的縮合反應．．．．．．20
2.5 硝基苯甲醛與聯胺的長時間．．．．．．．21
第三章 結論．．．．．．．．．．．．．．．．．23
第四章 實驗步驟與數據．．．．．．．．．．．．24
4.1 苯甲醛腙的製備．．．．．．．．．．．．．24
4.1-2 苯甲醛腙之光譜數據．．．．．．．．．． 25
4.2 雙苯亞甲基胼的製備．．．．．．．．．．．32
4.3-1 丙酮與苯甲醛腙的縮合反應．．．．．．． 42
4.3-2 亞異丙基苯亞甲基胼之光譜數據．．．．． 42
第五章 儀器與藥品．．．．．．．．．．．．．．45
5.1 儀器．．．．．．．．．．．．．．．．．．．45
5.2 藥品．．．．．．．．．．．．．．．．． ． 46
第六章 參考文獻．．．．．．．．．．．．．．．50
附圖

(1)K. J. Hale, V. M. Delisser, L. K. Yeh, A. Peak, S. Manaviazar, G. S. Bhatia, Tetrahedron Lett. 1994, 35, 7685.
(2)S. Shibahara, S. Kondo, K. Maeda, H. Umezawa, M. Ohno, S. Shibahara, J. Am. Chem. Soc. 1972, 94, 4353.
(3)M. A. Avery, S. Mehrotra, J. D. Bonk, J. A. Vroman, D. K. Goins, J. Millar, J. Med. Chem. 1996, 39, 2900.
(4)H. Sun, K. M. Millar, J. Yang, K. Abboud, B. A. Horenstein, Tetrahedron Lett. 2000, 41, 2801.
(5)R. Tamian, C. Mineur, L. Ghosez, Tetrahedron Lett. 1995, 36, 8977.
(6)G. Wittig, U. Schöllkopf, Chem. Ber. 1954, 87, 1318.
(7)E. Vedejs, G. P. Meier, K. A. J. Snoble, J. Am. Chem. Soc. 1981, 103, 2823.
(8)A. V. Shastin, V. N. Korotchenko, V. G. Nenajdenko, E. S. Balenkova, Tetrahedron, 2000, 56, 6557.
(9)A. V. Shastin, V. N. Korotchenko, V. G. Nenajdenko, E. S. Balenkova, Synthesis, 2001, 14, 2081.
(10)D. A. Skoog, in ”Principles of Instrumental Analysis”, 3rd ed., Saunders College Publishing, New York, 1985.
(11)S. Datta, A. De, S. P. Bhattacharyya, C. Medhi, J. S. A. Brunskill, S. Fadoujou, S. Fish, J. Chem. Soc. Perkin Trans. 2, 1988, 1599.
(12)G. F. Godfrey, M. Godfrey, J. Chem. Soc. Perkin Trans. 2, 1988, 133.
(13)P. L. Hammett, J. Am. Chem. Soc. 1937, 59, 96.
(14)S. T. Lin, M. L. Lin, J. Chem. Soc. Perkin Trans. 2, 1990, 91.
(15)S. T. Lin, S. H. Leu, C. Y. Chen, J. Chem. Res. 1996, 130-131(S), 716-734(M).
(16)S. T. Lin, Y. F. Yao, J. Chin. Chem. Soc., 1992, 39, 415.
(17)G. C. Levy, R. L. Lichter, in “Nitrogen-15 Nuclear Magnetic Resonance Spectroscopy”, Wiley: New York, 1979, 92.
(18)M. Giurg, S. B. Said, S. Ludwik, J. Mlochowski, Synth. Commun. 2001, 31, 3151.
(19)K. Anna, T. Krzysztof, Z. Andrzej, Synthesis, 1986, 4, 298.
(20)G. R. Newkome, D. L. Fishel, J. Org. Chem. 1966, 31, 677.
(21)B. Y. Dakova, M. J. Evers, L. R. Christinane, M. R. Guillaume, Bull. Soc. Chim. Belg. 1987, 96, 219.
(22)E. Franzen, , J. Prakt. Chem. 1910, 82, 248.
(23)M. Giurg, S. B. Said, S. Ludwik, J. Mlochowski, Synth. Commun. 2001, 31, 3151..
(24)M. Giurg, J. Mlochowski, Pol. J. Chem. 1994, 68, 2333.
(25)J. Bogoslowski, , J. Gen. Chem. USSR (Engl.Transl.), 1957, 27, 177.
(26)L. N. Ferguson, T. C. Goodwin, J. Am. Chem. Soc. 1949, 71, 633.
(27)A. F. Hegarty, J. A. Kearney, P. A. Cashell, F. L. Scott, J. Chem. Soc. Perkin Trans. 2, 1976, 242.
(28)R. F. Smith, J. A. Albright, A. M. Waring, J. Org. Chem. 1966, 31, 4100.
(29)H. J. Barber, R. Slack, J. Am. Chem. Soc. 1943,65, 1776.
(30)H. E. Zimmerman, S. Somasekhara, J. Am. Chem. Soc. 1960, 82, 5865.
(31)J. C. Petitpierre, Chem. Abstr. 1977, 87, 93582.
(32)E. R. Blout, R. M. Gofstein, J. Am. Chem. Soc. 1945, 67, 13.