黄鸣龙反应化学知识

黄鸣龙反应醛酮在碱性条件下与肼作用生腙，加热分解，将羰基还原为亚甲基的反应。原来Wolff-Kishner的方法是将醛或酮与肼和金属钠或钾在高温(约200°C)下加热反应，需要在封管或高压釜中进行，操作不方便。黄鸣龙改进了此反应，不用封管而在高沸点溶剂如一缩二乙二醇(二甘醇，b.p.245°C)中反应，用氢氧化钠或氢氧化钾代替金属钠作碱。黄鸣龙改进法只需将酮类和醛类与氢氧化钾和氢氧化钠(代替金属钠)，85%(有时可用50%)水合肼(代替无水肼)及双缩乙二醇或三缩乙二醇(代替封管或高压釜)，同置于圆底烧瓶内，回流1小时生成腙，移去冷凝管，继续加热，除去水和过量的肼，直到溶液温度上升至190-200oC时，再插上冷凝管，保持此温度23小时，然后按常规方法处理即得。若被还原的物质还原后的生成物沸点低于190-200oC，则在蒸去水分时，物质亦随之逸去，故必须在冷凝管与烧瓶间装一分液管，借以除去水分。后来发展出了利用TsNH2NH2和酮反应生成Ts腙，再还原为亚甲基的Caglioti还原反应条件更加温和，而且不用加碱。反应机理反应实例黄鸣龙改进法，此反应会消除一分子乙烯。【TetrahedronLett.

1989,30,1353-1356】【Synlett

1999,1573-1592】【J.Org.Chem.,

1999,64,3398】【Steroids

2002,67,

31-38】【J.Am.Chem.Soc.,

2004,126,5436】【Synth.Commun.

2006,36,2183-2187】【Org.ProcessRes.Dev.

2009,13,576–580】【GreenChem.,

2014,16,176-180】Amixtureof18.2gofbenzophenone,7gofsodiumhydroxide,100mLoftriethyleneglycol

and10mLof85%hydrazinehydratewasrefluxedfor1h.Thenthecondenserwas

removeduntilthetemperatureofthesolutionwashadreached195~200oC,whenrefluxing

wascontinuedforaboutthreehours.Themixturewascooledandextractedwithether.

Theetherresidueondistillationoversodiumgave14.0g(83.3%)ofpurehydrocarbon,b.p.

149oCat29mmg.Areactionwith14.2g(0.1mol)oftheketone,9mL(0.18mol)ofhydrazinehydrate,20gof

sodiumand400mLofdithethleneglycolwascarriedoutat170-190oforsixty-eighthours.

Afterdilutionwithwater,extractionwithether.Theorganiclayerwaswashedinturnwith

water,dilutehydrochloricacid,andagainwithwater.Theextractwasdriedoveranhydrous

magnesiumsulfate.Removalofsolventleftthecrudehydrocarbon,whichwasredistilled

oversodiumtogive8.95g(70%)of2,6-dimethylheptane,bp131-133oC。相关文献1.(a)Kishner,N.J.Russ.Phys.Chem.Soc.1911,43,582-595.

(b)Wolff,L.Ann.1912,394,86.(c)Huang,MinlonJ.Am.Chem.

Soc.1946,68,2487-2488.(d)Huang,MinlonJ.Am.Chem.Soc.1949,71,

3301-3303.(TheHuangMinlonmodification).2.Todd,D.Org.React.1948,4,378-422.(Review).3.Cram,D.J.;Sahyun,M.R.V.;Knox,G.R.J.Am.Chem.Soc.1962,84,1734-1735.4.Murray,R.K.,Jr.;Babiak,K.A.J.Org.Chem.1973,38,2556-2557.5.Lemieux,R.P.;Beak,P.TetrahedronLett.1989,30,1353-1356.6.Taber,D.F.;Stachel,S.J.TetrahedronLett.1992,33,903-906.7.Gadhwal,S.;Baruah,M.;Sandhu,J.S.Synlett1999,1573-1592.8.Szendi,Z.;Forgó,P.;Tasi,G.;Böcskei,Z.;Nyerges,L.;Sweet,F.Steroids2002,67,

31-38.9.Bashore,C.G.;Samardjiev,I.J.;Bordner,J.;Coe,J.W.J.Am.Chem.Soc.2003,125,

3268-3272.10.Pasha,M.A.Synth.Commun.2006,36,2183-2187.11.Song,Y.-H.;Seo,J.J.Heterocycl.Chem.2007,44,1439-1443.12.Shibahara,M.;Watanabe,M.;Aso,K.;Shinmyozu,T.Synthesis2008,3749-3754.13.Kuethe,J.T.;Childers,K.G.;Peng,Z.;Journet,M.;Humphrey,G.R.;Vickery,T.;

Bachert,D.;Lam,T.T.Org.ProcessRes.Dev.2009,13,576–580.参考资料：一、J.J.Li,Name