菜单
  

        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.
    [5].O I Yarovaya,D V Korchagina,O V Salomatina,et al.Synthesis of heterocyclic compounds in acid-catalysed reactions of citral epoxides[J].Mendeleev Commun.,2003,13(1):27-28.
    [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
    [8] L M Bradley,J W Springer,G M Delate et al.Epoxidation of geraniol:an advanced organic experiment that illustrates asymmetric synthesis[J]Journal of Chemical Education,1997,74(11):1336-1338
    [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.
    [12] D Mohajer, R Tayebee, H Goudarziafshar. Sodium periodate epoxidation of alkenes catalyzed by manganese porphyrins[J]. J Chem Res Synop, 1999, 1: 168-169.
    [13] S Sakaguchi,Y Nishiyama,Y Ishii. Selective oxidation of moneterpenes with hydrogen peroxide catalyzed by peroxotungstophosphate(PCWP)[J]. J Org Chem, 1996,61(16): 5307-5311.
    [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.
    [15] G Majetich, J Shimkus, Yang Li. Epoxidation of olefins by
       β-bromoalkoxydimethyl-sulfonium ylides[J].Tetrahedron Letters, 2010, 51(52):6830–6834.
    [16] A Kumar, V Bhakuni. Enantioselective epoxidation using liposomised m- chloro- perbenzoic acid [J].
    Tetrahedron Letters, 1996,37(27): 4751-4754.
    [17] A S Rao. Addition reactions with formation of carbon-oxygen bonds: general methods of epoxidation[J]. Comp Org Synth,1991, 7: 357-387
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