臺灣博碩士論文加值系統

第一部份、合成三個新的感測劑9-11來偵測一系列的金屬離子。感測劑9-11可以在含有20％ H2O的DMSO溶液中藉由肉眼來辨識Hg2+，顏色變化會由淡黃變成棕色。尤其是感測劑9亦能以螢光顏色變化及螢光放射強度的增強來辨識Hg2+，另外，感測劑9具有很高的pH適用範圍(4-10)，因此感測劑9是同時能利用肉眼辨識及螢光顏色變化來偵測Hg2+的新感測劑，同時也成功報導應用在試紙來偵測Hg2+。
第二部分、本實驗室設計出兩個同時能偵測陰、陽離子的新化學感測劑，N-benzo-15-crown-5-N''-(4-nitronaphthyl) thiourea (7) 及N-phenyl- N''-(4-nitronaphthyl) thiourea (8)，並利用1H NMR及紫外光光譜儀來探討上述化合物與陰、陽離子鍵結後之圖譜變化和結合常數。
其新化學感測劑7和8分別與陰離子結合時，uv-vis最大吸收峰會往長波長移動，而有明顯的紅移 (red shift) 現象，顏色由黃變紅。另外，以化合物7作為感測劑時，若有陽離子的存在(如Na+，Li+) ，顏色會減弱 (quench)，其強度甚至減弱成無色。而化合物8在陽離子存在的情況下，則不具有減弱的情形。
第三部分、豆莢螟 (Maruca vitrata) 為豆類之重要害蟲1，其為害之作物包括豆科、胡麻科、含羞草科、蘇木科及錦葵科等5科20屬35種作物2-5。在台灣，豆莢螟全年皆會發生，主要為害菜豆、豇豆及毛豆等作物。幼蟲在豆莢內蛀食，嚴重時蛀空子粒。由於文獻上合成雌性豆莢螟性費洛蒙的方法相當繁複且產率不高，又不易控制立體異構，因此本研究乃以HBBr2．SMe2來取代傳統的catecholborane solution，在vinylhalide改以Cp2Zr(H)Cl當作催化來形成。分別以(E)-2-(11-iodoundec-10-enyloxy)tetrahydro-2H-pyran、Potassium (E)-1-Pen-1-enyl trifluoroborate與(E)-2-(9-iodonon-8-enyloxy)-tetrahydro-2H-pyran 、Potassium (E)-1-propenyl trifluoroborate進行Suzuki cross-coupling反應形成diene產物，此方法不但步驟簡便，產率高，且不用擔心立體異構物的問題。

Part I:
Three new chemodosimeters 9-11 were prepared, and their chromogenic and fluorogenic chemodosimetric behaviors toward various metal cations were investigated. Receptor 9-11 show exclusively response toward Hg2+ ions and also distinguish Hg2+ from other metal cations by color changes. Among them, receptor 9 also exhibited a pronounced Hg2+ -induced fluorescence enhancement and wide pH span (4-10). In addition, the test strip of receptor 9 can also be applied for sensing Hg2+ ion in aqueous DMSO. Successfully, therefore, the receptor 9 can be used as a colorimetric and fluorescent chemodosimeter for determination of Hg2+ ion. The use of the test strip of the receptor 9 to detect Hg2+ ion was also reported.

Part II:
A new colorimetric ditopic receptor (7) was synthesized and characterized. Upon investigation of a series of anions, the appearance of the solution of receptor 7 with F- showed a colour change from light-yellowish to orange-red which can be detected by the naked eye. Upon subsequent addition of Na+ or Li+ to the solution, the orange-red colour was no longer observable. The remarkable colour switching (ON and OFF) is thus controlled by the anion and cation recognition.

Part III:
The pheromone components of legume pod borer, (E, E)-10, 12-hexadecadienal, and the soybean pod borer, (E, E)-8-10-dodecadienyl acetate, were synthesized in good yields via Suzuki-Miyaura cross-coupling reactions.

第一部份、
一、緒論 １
二、結果與討論 ６
三、結論 ８２
四、實驗儀器 ８３
伍、實驗步驟與數據 ８４
六、參考文獻 １２６ 
第二部份、
一、緒論 １
二、結果與討論 ６
三、結論 ５９
四、實驗儀器 ６０
伍、實驗步驟與數據 ６２
六、參考文獻   ８３ 
第三部份、
一、摘要 １
二、緒論 ２
三、結果與討論 ２２
四、實驗儀器 ２７
伍、實驗步驟與數據 ３０
六、參考文獻 ７４ 

第一部份
2000, 205, 41.
3.
A. P. de Silva, H. Q. N. Gunaratne, T. Gunnlaugsson, A. J. M. Huxley, C. P. McCoy, J. T. Rademacher and T. E. Rice, Chem. Rev., 1997, 97, 1515.
4.
P. B. Tchounwou, W. K. Ayensu, N. Ninashvili and D. Sutton, Environ. Toxicol., 2003, 18, 149.
5.
P. Grandjean, P. Weihe, R. F. White and F. Debes, Environ. Res., 1998, 77. 165.
6.
T. Takeuchi, N. Morikawa, H. Matsumoto and Y. Shiraishi, Acta Neuropathol., 1962, 2, 40.
7.
M. Harada, Crit. Rev. Toxicol., 1995, 25, 1.
8.
A. Coskun, M. D. Yilmaz and E. U. Akkaya, Org. Lett., 2007, 9, 607.
9.
M. H. Lee, J.-S. Wu, J. W. Lee, J. H. Jung and J. S. Kim, Org. Lett., 2007, 9. 2501.
10.
J. Wang and X. Qian, Org. Lett., 2006, 8, 3721.
11.
S. Yoon, A. E. Albers, A. Wong and C. J. Chang, J. Am. Chem. Soc., 2005, 127, 16030.
12.
X. Guo, X. Qian and L. Jia, J. Am. Chem. Soc., 2004, 126, 2272.
13.
E. M. Nolan and S. J. Lippard, J. Am. Chem. Soc., 2003, 125, 14270.
14.
E. M. Nolan and S. Lippard, J. Chem. Rev., 2008, 108, 3443.
15.
J. Manimala and E. V. Anslyn, Eur. J. Org. Chem., 2002, 3909.
16.
K. S. Kim and L. Qian, Tetrahedron Lett., 1993, 34, 7677.
17.
R. A. Batey and D. A. Powell, Org. Lett., 2000, 2, 3237.
18.
D. Boeglin, S. Cantel, A. Heitz, J. Martinez and J. A. Fehrentz, Org. Lett., 2003, 5, 4465.
19.
M. Y. Chae and A. W. Czarnik, J. Am. Chem. Soc., 1992, 114, 9704.
20.
G. Hennrich, W. Walther, U. Resch-Genger and H. Sonnenschein, Inorg. Chem. 2001, 40, 641.
21.
K. C. Song, J. S. Kim, S. M. Park, K. C. Chung, S. Ahn, and S.-K. Chang, Org. Lett., 2006, 8, 3413.
22.
B. Liu and H. Tian, Chem. Commun., 2005, 3156.
23.
Y. K. Yang, K. J. Yook and J. Tae, J. Am. Chem. Soc., 2005, 127, 16760.
24.
S. K. Ko, Y. K. Yang, J. Tae and I. Shin, J. Am. Chem. Soc., 2006, 128, 14150.
25.
J. S. Wu, I. C. Hwang, K. S. Kim and J. S. Kim, Org. Lett., 2007, 9, 907.
26.
J. Ros-Lis, M. D. Marcos, R. Martinez-Manez and J. Soto, Angew. Chem. Int. Ed., 2005, 44, 4405.
27.
M. H. Lee, B. K. Cho, J. Yoon, J. S. Kim, Org. Lett., 2007, 9, 4515.
28.
M.G. Choi, D. H. Ryu, H. L. Jeon, S. Cha, J. Cho, H. H. Joo, K. S. Hong, C. Lee, S. Ahn and S. K. Chang, Org. Lett., 2008, 10, 3717.
29.
F. M. Winnik, Chem. Rev., 1993, 93, 587.
30.
J. S. Kim, K. H. Noh, S. H. Lee, S. K. Kim, J. Yoon, J. Org. Chem., 2003, 68, 597.
31.
H. Yuasa, N. Miyagawa, T. Izumi, M. Nakatani, M. Izumi and H. Hashimoto, Org. Lett., 2004, 6, 1489.
32.
A. Corsaro and V. Pistara, Tetrahedron, 1998, 54, 15027.
33.
Detection limit is defined by 3σ/K. Hereσand K refer to standard deviation of the blank solutions and the slope of linear regression curve observed in Figure 4c, respectively, see : A. Ono and H. Togashi, Angew. Chem., Int. Ed., 2004, 43, 4300.
34.
J. Liu and Y. Lu, Angew. Chem., Int. Ed., 2007, 46, 7587.
35.
R. Martinez-Manez, A. Espinosa, A. Tarraga and P. Molina, Org. Lett. 2005, 7, 5869.
36.
S. H. Kim, J. S. Kim, S. M. Park and S. K. Chang, Org. Lett. 2006, 8, 371.
37.
J. Yoon, N. E. Ohler, D. H. Vance, W. D. Aumiller and A. W. Czarnik, Tetrahedron Lett. 1997, 38, 3845.
38.
K. Feng, F. L. Hsu, K. Bota and X. R. Bu, Microchem. J. 2005, 81, 23.
39.
The fluorescence quantum yields were measured with respect to anthracence as standard (Φ=0.27 ± 0.03). W. R. Dawson and M. W. Windsor, J. Phys. Chem., 1968, 72, 3251. For more information, see the supporting information.
40.
R. Kato, S. Nishizawa, T. Hayashita and N. Teramea, Tetrahedron Lett., 2001, 42, 5053.
41.
N. Gimeno, X. Li, J. R. Durrant and R. Vilar, Chem. Eur. J. 2008, 14, 3006.
42.
T. Gunnlaugsson, A. P. Davis, G. M. Hussey and J. Tierney, Org. Biomol. Chem. 2004, 2, 1856.
43.
M. Zhu, M. Yuan, X. Liu, Org. Lett., 2008, 10 (7), pp 1481–1484.

第二部份
Olsher, U.; Frolow, F.; Dalley, N. K.; Weiming, J.; Yu, Z-Y.;
Knobeloch, J. M.; Bartsch, R., J. Am. Chem. Soc.,1991, 113, 6570.
5. Mahoney, J. M.; Beatty, A. M.; Smith, B. D. J. Am. Chem. Soc., 2001, 123, 5847
6. de Silva, A. P.; Gunaratne, H. Q. N.; McCoy, C. P.; Nature,1993,364,42.
7. Shukla, R.; Kida, T.; Smith, B. D. Org. Lett., 2000, 2, 3099.
8. Miyaji, H.; Collinson, S. R.; Prokes, I.; Tucker, J. H., Chem. Commun., 2003, 1 ,64.
9. de Silva, A. P.; Dixon, I. M.; Gunaratne, H. Q. N.; Gunnlaugsson, T.; Maxwell, P. R.S. ; Rice, T. E. J. Am. Chem. Soc., 1999, 121, 1393.
10. Gunnlaugsson, T.; MacDonail, D. A.; Parker, D. Chem. Commum., 2000, 93.
11. Outt, P. E.; Ares, J. J.; Roberts, G. E.; Wang, X.; Cupps, T. L.;
Wireko, F. C., J. Org. Chem., 1998, 63, 5762.
12. Lee, K. H.; Lee, H. Y.; Lee, D. H.; Hong, J. I., Tetrahedron lett., 2001, 5447.
13. Nishizawa, S.; Kato, R.; Hayashi, T.; Teramae, E., Anal. Sci., 1998, 14, 595.
14. Miyaji, H.; Collinson, S. R.; Prokes, I.; Tucker, J. H., Chem. Commun., 2003, 1 ,64.
15. Uppadine, L. H.; Redman, J. E.; Dent, S. W.; Drew, M. G. B.; Beer, P. D., Inorg. Chem., 2001, 40 , 2860.
16. Mahoney, J. M.; Beatty, A. M.; Smith, B. D., J. Am. Chem. Soc., 2001, 123 , 5847.


第三部份
1.
易希陶,經濟昆蟲學, 1963, 464頁.
2.
柯禮道;方菊蓮;李志強,豆野螟的生物學特性及防治,昆蟲學報, 1985, 28, 51-59.
3.
Liao, C. T.; Chen, C. C. Bull. Taichung, 1998, 59, 47-52.
4.
Shama, H. C. Crop prot. 1998, 17, 373-386.
5.
Ecology and Control, Taylor, T. A. Maruca testulalis: an important pest of tropical grain legumes. Taylor, T. A.: New York, 1978.
6.
黃啟鐘, 彭武康,溫度對豆莢螟(Maruca vitrata)在田菁上發育之影響,植物保護學會會刊, 2002, 44, 245-248.
7.
黃啟鐘, 彭武康,豆莢螟(Maruca vitrata)(鱗翅目：螟蛾科)之羽化、交尾與產卵行為,台灣昆蟲, 2001, 21, 37-45.
8.
Okeyo-Owuor, J. B.; Ochieny R. S. Insect. Sci. Appl.1981, 263-268
9.
Downham, M. C. A.; Tamo, M.; Hall, D. R.; Datinon, B.; Adetonah, S.; Farman D. I. Entomol. Exp. Appl. 2004, 110, 151-158
10.
Vang, L. V.; Ishitani, M.; Komai, F.; Yamamoto, M.; Ando, T. Appl. Entomol. Zool. 2006, 41, 507-513.
11.
Bestmann, H.J.; Suess, J.; Vostrowsky, O. Tetrahedron Lett. 1978, 36, 3329-3332.
12.
Miyarua, N.; Suginome, H. Tetrahedron Lett. 1983, 24, 1527-1530.
13.
Yadav, J. S.; Balakrishnan, K.; Sivadasan, L. Indian J. Chem. 1989, 28, 297-302.
14.
Yadav, J. S.; Deshpande, P. K.; Reddy, E. R. Synth. Commun. 1989, 19, 125-134.
15.
Vig, O. P.; Sharma, M. L.; Gupta, R. J. Indian Chem. Soc. 1990, 67, 37-38
16.
Yamada S.; Ohsawa, H.; Suzuki, T.; Takayama, H. J. Org. Chem. 1986, 51, 4934-4940.
17.
Larock, R. C.; Han, X. J. Org. Chem. 1999, 64, 1875-1887.
18.
Darses, S.; Gent, J. P. Tetrahedron Lett.1997, 25, 4393-4396.
19.
Molander,G. A.; Ito, T. Organic Lett. 2001, 3, 393-396.
20.
Molander, G. A.; Biolatto, B. Organic Lett. 2002, 4, 1867-1870.
21.
Molander, G. A.; Carmem, R. B. J. Org. Chem. 2002, 67, 8424-8429.
22.
Molander, G. A.; Rivero, M. R. Org. Lett. 2002, 4, 107-109.
23.
Molander, G. A.; Felix, L. A. J. Org. Chem. 2005, 70, 3950-3956.
24.
Molander, G. A.; Brown, A. R. J. Org. Chem. 2006, 71, 9681-9686.
25.
Molander, G. A.; Yokoyama, Y. J. Org. Chem. 2006, 71, 2493-2498.
26.
Batey, R. A.; Quach, T. D. Tetrahedron Lett. 2001, 42, 9099-9103.
27.
Vedejs, E. R.; Chapman, W.; Fields, S. C.; Lin, S.; Schrimpf, M. R. J. Org. Chem. 1995, 60, 3020-3027.
28.
Vedejs, E.; Fields, S. C.; Hayashi, R. S.; Hitchcock, R.; Powell, D. R.; Schrimpf, M. R. J. Am. Chem. Soc. 1999, 121, 2460-2470.
29.
Kabalka, G. W.; Al-Masum, M. Org. Lett. 2006, 8, 11-13.
30.
Pucheault, M.; Darses, S.; Genet, J. P. Eur. J. Org. Chem. 2002, 3552-3557.
31.
Al-Masum, M.; Kabalka, G. W. Tetrahedron Lett. 2005, 46, 6329-6331.
32.
Denmark, S. E.; Yang, S. M. J. A. C. S. 2002, 124, 2102-2103.
33.
Ravindranath, N.; Ramesh, C.; Das, B. Synlett. 2001, 11, 1777-1779.
34.
Stille, J.; James, K.; Simpson, H. J. Am. Chem. Soc. 1987, 109, 2138-2152.
35.
Molander, G. A.; Ham, J.; Seapy, D. G. Tetrahedron, 2007, 63, 768-775.