薁衍生物與α.β–不飽和酮之Michael Addition反應及其應用之研究

薁核的主要特性為在5員環1.3-位置傾向容易帶負電荷，主要進行的反應以親電性反應為主。本篇研究主要是利用此一特性，當薁核在3-位置無取代基時，於酸催化下，可與3–丁烯–2–酮進行Michael Addition，而合成3–（2–乙醯基乙基）薁衍生物。當薁核在3-位無取代基且2-位為胺基時，於酸催化下，與3–丁烯–2–酮進行Michael Addition，則可以直接環化得到薁併﹝2,1–b﹞吡啶衍生物。當薁核在3-位無取代基且2-位為甲氧羰基時，於上述條件下可生成2–甲氧羰基甲基–3–（2–乙醯基乙基）薁衍生物，此化合物在鹼性條件下可環化形成二氫苯併﹝a﹞薁衍生物，之後再與2.3–二氯–5.6–二氰基苯醌脫氫，則可順利地合成出苯併﹝a﹞薁衍生物。若薁核在3-位無取代基且4-位為乙氧基時，於上述條件下可生成3–（2–乙醯基乙基）–4–乙氧基薁衍生物，此化合物與2.3–二氯–5.6–二氰基苯醌作用，之後再與聯胺（N2H4）作用，則可合成出薁併﹝1,8a,8–c,d﹞噠嗪衍生物。

關鍵字

薁衍生物； α.β–不飽和酮

並列摘要

The five member of azulene which was tend to be negative chage was his main property. Electrophile reaction was the main proceeding reaction used in this paper survey. When the 3–position of azulene can not be substituted, azulene and methyl vinyl ketone process Michael Addition under acidic catalyzation thus synthesis 3–（2–acetylethyl）azulene derivatives. When the 2–aminoazulene derivatives and methyl vinyl ketone process Michael Addition under acidic catalyzation thus cyclization and achieve azuleno[2,1–b]pyridine derivatives. 2–methoxycarbonylmethyl–3–（2–acetylethyl）azulene derivatives can be cyclized to be dihydrobenz[a]azulene derivative under basic condition then 2,3–dichloro–5,6–dicyano–p–benzochinony dehydrogenation to be benz[a]azulene derivative. Besides, 3–（2–acetylethyl）–4–ethoxyazulene derivatives react with DDQ, then react with N2H4 to be azuleno[1,8a,8–c,d]pyridazine.

並列關鍵字

Michael Addition ； azulenes ； α.β–unsaturated ketone

參考文獻

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薁衍生物與α.β–不飽和酮之Michael Addition反應及其應用之研究

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