反应机理金属复氢化物具有四氢铝离子(AlH4-)或四氢硼离子(BH4-)的复盐结构,具有亲核性,可向羰基中带正电的碳原子进攻,继而发生氢负离子转移而进行还原。
特点:
A. 反应时分子中存在的硝基、氰基、亚氨基、双键、卤素等可不受影响
B. 对α,β-不饱和醛酮的还原,可使用氰基硼氢化钠或氢化二异丁基铝,
如:9-硼双环-壬烷。
本实验即选用硼氢化钠(NaBH4)作反应剂对醛基进行还原,产物为醇。
醛、酮的羰基都能被还原成醇羟基,也可以被彻底还原为亚甲基。反应条件不同,还原产物也不同。不同的醛、酮可根据实际情况采用不同的还原剂进行还原反应。
硼氢化钠或硼氢化钾(NaBH4,KBH4)是较缓和的负氢还原剂,它可以还原醛、酮,而且有较好的反应活性和较高的选择性,控制反应条件可以只还原醛、酮的羰基而不影响其它官能团[24]。LiAlH4和NaBH4或KBH4虽然都是高活性的负氢型还原剂,但对于有空间位阻的酮的还原,有立体选择性。
参考文献
[1] Ethers, by Lawrence Karas and W. J. Piel//Kirk Othmer Encyclopedia of Chemical Technology. John Wiley & Sons, Inc. 2004.
[2] Merck Index of Chemicals and Drugs, 9th ed.
[3] Morrison, Robert Thornton; Boyd, Robert Neilson: Organic Chemistry, 2nd ed., Allyn and Bacon 1972, p. 569
[4] Donald Starr and R. M. Hixon (1943). "Tetrahydrofuran". Org. Synth.; Coll. Vol. 2: 566.
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[6] O I Yarovaya, O V Salomatina, D V Korchagina,et al.Transformations of 6,7-epoxy derivatives of citral and citronellal in various acidic media[J],Russian of journal of organic chemistry,2002,38(11):1594-1605
[7]. K P Volcho,O I Yarovaya, S Y Kurbakova,et al.Synthesis of epoxy dinitriles from citral and their acid catalyzed transformations[J], Russian of journal of organic chemistry,2007,43(4):511-517
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[9] O I Yarovaya, O V Salomatina, D V Korchagina,et al.Transformations of 6,7-epoxy derivatives of citral and citronellal in various acidic media[J].Russian of journal of organic chemistry,2002,38(11):1594-1605.
[10] D V Korchagina,O I Yarovaya ,O V Salomatina,et al.Synthesis of heterocyclic compounds in acid-catalysed reactions of citral epoxides[J].Mendeleev Commun.,2003,13(1):27-28.
[11] K P Volcho,O I Yarovaya, S Y Kurbakova,et al.Synthesis of epoxy dinitriles from citral and their acid catalyzed transformations[J].Russian of journal of organic chemistry,2007,43(4):511-517.
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[14] Xue Li Geng, Zhi Wang,X Q Li et al. A simple method for epoxidation of olefins using sodium chlorite as an oxidant without a catalyst[J]. Journal of Organic Chemistry, 2005,70(23): 9610-9613.
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β-bromoalkoxydimethyl-sulfonium ylides[J].Tetrahedron Letters, 2010, 51(52):6830–6834.
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