黃鳴龍反應(yīng)化學(xué)知識

黃鳴龍反應(yīng)醛酮在堿性條件下與肼作用生腙，加熱分解，將羰基還原為亞甲基的反應(yīng)。原來Wolff-Kishner的方法是將醛或酮與肼和金屬鈉或鉀在高溫(約200°C)下加熱反應(yīng)，需要在封管或高壓釜中進(jìn)行，操作不方便。黃鳴龍改進(jìn)了此反應(yīng)，不用封管而在高沸點(diǎn)溶劑如一縮二乙二醇(二甘醇，b.p.245°C)中反應(yīng)，用氫氧化鈉或氫氧化鉀代替金屬鈉作堿。黃鳴龍改進(jìn)法只需將酮類和醛類與氫氧化鉀和氫氧化鈉(代替金屬鈉)，85%(有時可用50%)水合肼(代替無水肼)及雙縮乙二醇或三縮乙二醇(代替封管或高壓釜)，同置于圓底燒瓶內(nèi)，回流1小時生成腙，移去冷凝管，繼續(xù)加熱，除去水和過量的肼，直到溶液溫度上升至190-200oC時，再插上冷凝管，保持此溫度23小時，然后按常規(guī)方法處理即得。若被還原的物質(zhì)還原后的生成物沸點(diǎn)低于190-200oC，則在蒸去水分時，物質(zhì)亦隨之逸去，故必須在冷凝管與燒瓶間裝一分液管，借以除去水分。后來發(fā)展出了利用TsNH2NH2和酮反應(yīng)生成Ts腙，再還原為亞甲基的Caglioti還原反應(yīng)條件更加溫和，而且不用加堿。反應(yīng)機(jī)理反應(yīng)實(shí)例黃鳴龍改進(jìn)法，此反應(yīng)會消除一分子乙烯?！綯etrahedronLett.

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