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第五章、利用 α,β- 不飽和酮製備 3,5- 雙 取代衍生物

第五章、利用 α,β- 不飽和酮製備 3,5- 雙 取代衍生物. α,β- 不飽和酮的應用. α,β- 不飽和酮之文獻報導. Nafion-TMS mediated Mukaiyama aldol reaction of silyl enol ethers with aldehydes, obtained from mild oxidation of alcohols with polymer supported perruthenate (PSP), yielded α , β -unsaturated ketones. .

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第五章、利用 α,β- 不飽和酮製備 3,5- 雙 取代衍生物

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  1. 第五章、利用α,β-不飽和酮製備3,5-雙 取代衍生物

  2. α,β-不飽和酮的應用

  3. α,β-不飽和酮之文獻報導 Nafion-TMS mediated Mukaiyama aldol reaction of silyl enol ethers with aldehydes, obtained from mild oxidation of alcohols with polymer supported perruthenate (PSP), yielded α,β-unsaturated ketones.

  4. Haunert, F.; Bolli, M. H.; Hinzen, B.; Ley, S. V. J. Chem. Soc. Perkin Trans. I.1998, 15, 2235.

  5. α, β-unsaturated ketones obtained by base-catalysed condensation of aromatic aldehydes with substituted acetophenone

  6. α, β-unsaturated ketones obtained by base-catalysed condensation of aromatic aldehydes with substituted acetophenone ★ Holla, B. S.; Akberali, P. M.; Shivananda, M. K. IL Farmaco.2000, 55, 256. ★ Pathak, V. N.; Pathak, R.; Gupta, R.; Oza, C. K. Synth. commun.1997, 27, 1811. ★Powers, D. G.; Casebier, D. S.; Fokas, D.; Ryan, W. J. Troth, J. R.; Coffen, D. L. Tetrahedron, 1998, 54, 4085. ★Vishnu Vardhan Reddy, K.; Sampath Rao, P.; Ashok, D. Synth. Commun.1998, 29, 2365. ★Pinto, D. C. G. A.; Silva, A. M. S.; Cavaleiro, J. A. S. Tetrahedron.1999,55, 10187.

  7. Preparation of starting materials 1a,2a : Ar = C6H51c,2c : Ar =p-CH3OC6H4 1b,2b : Ar =p-CH3C6H41d,2d : Ar =p-CH3CH2OC6H4

  8. 雪梨酮環取代的α,β-不飽和酮之合成 1. 以3-芳香基-4-甲醯雪梨酮進行Claisen－Schmidt 縮合反應。 3a: Ar = p-CH3CH2OC6H4 , R' = CH3 , Yield: 52% 3b: Ar = p-CH3CH2OC6H4 , R' = C6H5, Yield: 60%

  9. Syntheses of 5-Sydnonyl-4,5-dihydro-1H- pyrazoles

  10. 2.以3-芳香基-4-甲醯雪梨酮與各種活性亞甲基 化合物進行Knoevenagel縮合反應。 4a: X = CH3 Y = CH34c: X = CH3 Y = OC2H5 4b: X = CH3 Y = C6H54d: X = OC2H5 Y = OC2H5

  11. 起始物亞甲基化合物產物收率*(%) 起始物亞甲基化合物產物收率*(%) 1a ( Ar = C6H5 ) 1a ( Ar = C6H5 ) 4c 4a 5ac 5aa 74 78 1b ( Ar =p-CH3C6H4 ) 1b ( Ar =p-CH3C6H4 ) 4c 4a 5ba 5bc 66 78 1c ( Ar =p-CH3OC6H4 ) 1c ( Ar =p-CH3OC6H4 ) 4a 4c 5cc 5ca 84 76 1d ( Ar =p-CH3CH2OC6H4 ) 1d ( Ar =p-CH3CH2OC6H4 ) 4a 4c 5da 5dc 63 80 1a ( Ar = C6H5 ) 1a ( Ar = C6H5 ) 4d 4b 5ab 5ad 65 78 1b ( Ar =p-CH3C6H4 ) 1b ( Ar =p-CH3C6H4 ) 4b 4d 5bd 5bb 76 77 1c ( Ar =p-CH3OC6H4 ) 1c ( Ar =p-CH3OC6H4 ) 4b 4d 5cb 5cd 74 70 1d ( Ar =p-CH3CH2OC6H4 ) 1d ( Ar =p-CH3CH2OC6H4 ) 4b 4d 5dd 5db 68 80 表1. Knoevenagel 縮合產物(5aa~5dd)之收率 *再結晶收率

  12. Syntheses of 5-sydnonyl-4,5-dihydro-1H- pyrazoles

  13. 3.以4-乙醯-3-芳香基雪梨酮進行Claisen－ Schmidt縮合反應 2a : Ar = p-CH3C6H46a : Ar = C6H5 6c : Ar = p-CH3OC6H4 2b : Ar = p-CH3OC6H4 6b : Ar = p-CH3C6H4 6d : Ar = p-ClC6H4 2c : Ar = p-ClC6H4

  14. 起始物 芳香族醛 產物 收率(%)* 2a ( Ar =p-CH3C6H4 ) 6a ( Ar' = C6H5) 7aa 64 2b ( Ar =p-CH3OC6H4) 6a ( Ar' = C6H5) 7ba 72 2c ( Ar = p-ClC6H4) 6a ( Ar' = C6H5) 7ca 55 2a ( Ar =p-CH3C6H4 ) 6b ( Ar' =p-CH3C6H4) 7ab 52 2b ( Ar =p-CH3OC6H4) 6b ( Ar' =p-CH3C6H4) 7bb 54 2c ( Ar = p-ClC6H4) 6b ( Ar' =p-CH3C6H4) 7cb 50 2a ( Ar =p-CH3C6H4 ) 6c ( Ar' =p-CH3OC6H4) 7ac 42 2b ( Ar =p-CH3OC6H4) 6c ( Ar' =p-CH3OC6H4) 7bc 45 2c ( Ar = p-ClC6H4) 6c ( Ar' =p-CH3OC6H4) 7cc 40 2a ( Ar =p-CH3C6H4 ) 6d ( Ar' =p-ClC6H4) 7ad 65 2b ( Ar =p-CH3OC6H4) 6d ( Ar' =p-ClC6H4) 7bd 79 2c ( Ar = p-ClC6H4) 6d ( Ar' =p-ClC6H4) 7cd 55 表2、1-(3-芳香基雪梨酮-4-基)-3-芳香基- 丙-2-烯-1-酮(7aa~7cd) 之收率 *再結晶收率

  15. 圖一、1-[3-(4-甲苯基)雪梨酮-4-基]-3-(4-甲苯基)-丙圖一、1-[3-(4-甲苯基)雪梨酮-4-基]-3-(4-甲苯基)-丙 -2-烯-1-酮(7ab)之分子結構圖

  16. 1H-pyrazoles化合物的合成 ★ Satyanarayana, K.; Rao, M. N. A. J. Pharm. Sci.1995, 84, 263. ★ Satyanarayana, K.; Rao, M. N. A. Eur J Med Chem.1995, 30, 641. ★ Holla, B. S.; Akberali, P. M.; Shivananda, M. K. IL Farmaco. 2000, 55, 256. 1H- pyrazoles化合物具有抗菌、抗發炎、抗過敏、止痛等特殊藥效，早已成為科學家們所熱衷於研究的對象。而近幾年來無論是其衍生物的合成或新合成方法的開發，甚至其藥理活性的探討研究已在世界各國如火如荼地展開

  17. Syntheses of 3-(3-arylsydnon-4-yl)-5-aryl -4,5-dihydro-1H-pyrazoles Method : 1. Starting material : Hydrazine hydrate = 0.5 mmole : 2 mmole 2. Solvent : 95% EtOH 3 mL 3. Heating 60 ℃ for 4~5 hrs

  18. 化合物 Ar Ar' 收率(%) 8aa p-CH3C6H4 C6H5 80 8ab p-CH3C6H4 p-CH3C6H4 60 8bb p-CH3OC6H4 p-CH3C6H4 55 8cb p-ClC6H4 p-CH3C6H4 54 8ac p-CH3C6H4 p-CH3OC6H4 81 8bc p-CH3OC6H4 p-CH3OC6H4 68 8cc p-ClC6H4 p-CH3OC6H4 62 8ad p-CH3C6H4 p-ClC6H4 72 8bd p-CH3OC6H4 p-ClC6H4 78 表3、 3-(3-芳香基雪梨酮-4-基)-5-芳香基-4,5- 二氫-1H-化合物(8)之收率

  19. Furture Project and Development

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