1-硝基环己烯的合成方法改进  

An improvement of the synthesis for 1-nitro-cyclohexene

作　　者：徐海云[1] 冯翠兰[1] 

机构地区：[1]商丘师范学院化学系,河南商丘476000

出　　处：《化学试剂》2011年第10期951-954,共4页Chemical Reagents

基　　金：河南省科技厅科技攻关项目(082102210050);河南省教育厅自然科学研究计划项目(2008B150018);河南省教育厅自然科学研究资助计划项目(2011A150023);商丘师院重大项目培育计划立项项目(2011ZDPY02);安徽省高校自然科学基金项目(KJ2007B093)

摘　　要：环己醇在以浓硫酸和磷酸组成的混合酸催化作用下,脱水得到环己烯,且当混合酸中浓硫酸和磷酸的体积比为1∶2时,环己烯的收率最高;在乙二醇(EG)作用下,亚硝酸钠和碘在乙酸乙酯和水中硝化环己烯得到标题化合物,其结构经1HNMRI、R和元素分析表征。该"一锅"合成法采用碘-乙二醇/亚硝酸钠替代氯化汞/亚硝酸钠硝化环己烯制备标题化合物,不涉及用碱液对中间产物的处理,也避免了高毒性有机试剂的使用且反应为均相体系,预处理简单方便,产率较高。Cyclohexene was obtained by dehydration of cyclohexanol using mixed acid composed of concentrated sulfuric acid and phosphoric acid as catalyst,and when the volume ratio of concentrated sulfuric acid to phosphoric acid in the mixed acid was 1：2,the yield of cyclohexene was maximal.1-nitrocyclohexene was prepared by nitration reaction of cyclohexene with sodium nitrite and iodine in ethyl acetate and water in the presence of ethylene glycol（EG）,and its structure was characterized by 1HNMR,IR and elemental analysis.The appropriate reaction conditions at room temperature were as follows：cyclohexene was 24 mmol and iodine was 36 mmol,n（NaNO2）∶n（cyclohexene） was 6.0∶1.0,n（EG）∶n（cyclohexene） is 2.5～3.0 and the reaction time was 72 h,and the yield of 3 was 65.7% under the conditions.The one-pot synthetic method for obtaining 1-nitrocyclohexene,which employed I2-CH2OHCH2OH/NaNO2 instead of HgCl2/NaNO2 to nitrify cyclohexene,was not involved in handling the intermediate with basic solution,with avoiding using of the highly toxic reagents,and its pretreatment process was simple and convenient due to its homogeneous reaction system,along with higher yield.

关 键 词：环己醇 混酸 环己烯 1-硝基环己烯 工艺改进 

分 类 号：O625[理学—有机化学]