Nishiwaki Yoshiki, Sakaguchi Satoshi, Ishii Yasutaka
Department of Applied Chemistry, Faculty of Engineering, Kansai University, Suita, Osaka 564-8680, Japan.
J Org Chem. 2002 Aug 9;67(16):5663-8. doi: 10.1021/jo025632d.
Nitration of light alkanes and the alkyl side-chain of aromatic compounds with NO(2) and HNO(3) was successfully achieved by the use of N-hydroxyphthalimide (NHPI) as a catalyst under relatively mild conditions. For example, the nitration of propane with NO(2) catalyzed by NHPI at 100 degrees C for 14 h gave 2-nitropropane in good yield without formation of 1-nitropropane and cleaved products such as nitroethane and nitromethane. Various aliphatic nitroalkanes, which are difficult to prepare by conventional methods, could be selectively obtained by means of the present methodology by using NHPI as the key catalyst. In addition, the side-chain nitration of alkylbenzenes such as toluene was selectively carried out to lead to alpha-nitrotoluene without the ring nitration. The present reaction provides an efficient selective method for the nitration of light alkanes and alkylbenzenes, which has been very difficult to carry out so far.
在相对温和的条件下，通过使用N-羟基邻苯二甲酰亚胺（NHPI）作为催化剂，成功实现了用NO(2)和HNO(3)对轻质烷烃和芳香族化合物的烷基侧链进行硝化。例如，在100℃下，NHPI催化NO(2)对丙烷进行硝化反应14小时，得到了高产率的2-硝基丙烷，且没有生成1-硝基丙烷以及裂解产物如硝基乙烷和硝基甲烷。通过使用NHPI作为关键催化剂，借助本方法可以选择性地获得各种难以通过传统方法制备的脂肪族硝基烷烃。此外，烷基苯如甲苯的侧链硝化反应能够选择性地进行，生成α-硝基甲苯而不会发生环硝化。本反应为轻质烷烃和烷基苯的硝化提供了一种高效的选择性方法，而这在迄今为止一直是非常难以实现的。
