Reactions of halo- and dihaloadamantanes with nitromethane anions by theSRN1 mechanism
作者:Ana N. Santiago、Carlos A. Toledo、Roberto A. Rossi
DOI:10.1002/poc.603
日期:2003.8
1-bromo-, 2-bromo-, 1,3-dibromo- and 1,4-dibromoadamantane with −CH2NO2 anions were studied in DMSO and in liquid ammonia. The photostimulated reaction of 1-haloadamantane (1-AdX, X = Br, I) or 2-AdBr with −CH2NO2 anions gave good yields of the substitution product 1-AdCH2NO2 and 2-AdCH2NO2, respectively, in the presence of the enolate anions of acetone (entrainment conditions). On the other hand, 1-adamantanol
1-溴,2-溴,1,3-二溴和1,4-二溴金刚烷用的反应- CH 2 NO 2的阴离子在DMSO中并在液氨进行了研究。1-haloadamantane的光刺激反应(1-的AdX,X = Br的,I)或2- AdBr与- CH 2 NO 2周的阴离子,得到取代产物的良好的产率1-ADCH 2 NO 2和2- ADCH 2 NO 2,分别在丙酮的烯醇阴离子存在下(夹带条件)。另一方面,1-金刚烷醇是在没有辐射的DMSO中而不是在液氨中进行的反应的主要产物。1,3-二溴和1,4-二溴金刚烷与-在丙酮的烯醇盐阴离子存在下于辐射下的CH 2 NO 2阴离子。第一种化合物给出了破坏性产物11,而第二种化合物给出了单溴代产物15和16,以及破坏性产物17。化合物15和16被证明是17的中间体。版权所有©2003 John Wiley&Sons,Ltd.