金属催化的计量硝化反应

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近年来由于对环境保护越来越重视,一类新的硝化方法发展了起来。这种方法用镧系金属 lanthanide(III) IV 族金属的三氟磺酸盐 [Ln(OTf)3, Ln=La-Lu; M(OTf) 4, M= Hf, Zr] 以及 tris(trifluoromethanesulphonyl)methides("triflides") [M(CTf3) 3; M=Yb, Sc] 作催化剂【a. Waller, F. J.;Barrett, A. G. M.; Braddock, D. C.; Ramprasad, D. Chem. Commun. 1997,613. b. For an interesting report utilizing La(NO3)3/HCl/NaNO3 for thenitration of phenols see: Ouertani, M.; Girard, P.; Kagan, H. B. TetrahedronLett. 1982, 23, 4315. c. Waller, F. J.; Barrett, A. G. M.;Braddock, D. C.; Ramprasad, D. Tetrahedron Lett. 1998, 39,1641.】,催化等当量的硝酸(69%)硝化苯环,这种方法对一般的苯环及一些钝化的苯环都能得到高产率。由于只用等当量的硝酸,所以副产物仅仅是水,没有废酸产生,而且催化剂可以回收,并经过简单处理后反复使用。因此这种方法是较为环保的一种方法。


Nitric acid (69%; 274 mg, 3.0 mmol) was added to a stirredsuspension of ytterbium(III) triflate (186 mg, 0.30 mmol) in 1,2-dichloroethane(5 mL). The suspension dissolved to give a two phase system in which theaqueous phase was the more dense.  Toluene(270 mg, 3.0 mmol) was added and the stirredmixture was heated at reflux for 12 h.  Duringthe reaction a white solid precipitated and the organic phase became yellow,and after 12 h no phase boundary was apparent.  The solution was allowed to cool and dilutedwith water. The yellow organic phase was dried (MgSO4) and evaporated to give nitrotoluene (390 mg, 95%). Thecolourless aqueous phase was evaporated to give ytterbium(III) triflate as a whitefree-flowing solid (183 mg, 98%).


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