1-(支链烷基)萘和1-(支链烷基)萘-4-磺酸钠的合成  

Synthesis of Branched 1-Alkylnaphthalenes and Sodium 1-Alkylnaphthalene-4-sulfonates

作　　者：谭晓礼[1] 徐志成[1] 安静仪[1] 张路[1] 赵濉[1] 俞稼镛[1] 

机构地区：[1]中国科学院理化技术研究所,北京100101

出　　处：《精细化工》2004年第z1期44-46,共3页Fine Chemicals

基　　金：国家重点基础研究规划资助项目(G19990225)

摘　　要：采用高效的合成路线制备了支链化的1 烷基萘(Ⅳ)和相应的1 烷基萘 4 磺酸钠(Ⅴ)。合成的6种化合物的结构如下:1 异丁基萘,1 (2 己基)萘,1 丁基萘以及相应的磺酸钠盐。以1 溴代萘为起始原料制备Ⅳ的产率为51 8%,以Ⅳ为原料制备Ⅴ的产率为42%。该方法以1 萘基溴化镁(Ⅰ)和1 丁酮(或1 己酮,或丁醛)回流反应6h,得1 萘基烷醇(Ⅱ),产率80%。Ⅱ与红磷和碘的混合物在冰醋酸溶液反应,回流3h,得到烯烃混合物(Ⅲ),产率95%以上。Ⅲ在室温下用Pd C催化加氢2h,得到Ⅳ,产率90%。Ⅳ用氯磺酸磺化,反应物料比n(Ⅲ)∶n(氯磺酸)=1∶2,以三氯甲烷为溶剂,5℃以下反应5h得到Ⅴ的粗产品,产率70%;粗产品在V(乙醇)∶V(水)=1∶1中重结晶两次,得精产品,收率为60%。用IR,ESI-MS和1HNMR鉴定了Ⅳ和Ⅴ的结构。An efficient method was provided for the preparation of branched 1-alkylnaphthalenes(Ⅳ) and the corresponding sodium 1-alkylnaphthalene-4-sulfonates(Ⅴ).The structures of six compounds synthesized were 1-isobutylnaphthalene,1-(2-hexyl)naphthalene,1-butylnaphthalene and the corresponding sodium 1-alkylnaphthalene-4-sulfonates.Ⅳ were prepared from 1-bromonaphthalene as starting materialsin in total yield of 51.8%,and pure Ⅴ were prepared from Ⅳ in 42% yield.Thus,1-naphthylmagnesium bromide refluxed with 2-butanone (or 2-hexanone,butyraldehyde) for 6 h to give the corresponding carbinol(Ⅱ) in 80% yield.Ⅱ refluxed with a mixture of red phosphorus and iodine in glacial acetic acid for 3 h to give mixture of olefins(Ⅲ) in > 95% yield.Ⅳ was prepared by hydrogenation of Ⅲ over Pd/C catalyst in ethanol solution at room temperature for 2 h in 90% yield.Ⅳ reacted with chlorosulfonic acid 〔 n(Ⅳ)∶n(chlorosulfonic acid)=1∶2〕 in CHCl_3 at < 5 ℃ for 5 h to give crude Ⅴ in 70% yield.Crude Ⅴ was recrystallized twice from aqueous ethanol〔V(ethanol)∶V(water)=1∶1〕 to give the refined product in 60% yield.The structures of Ⅳ and Ⅴ were identified by IR,ESI-MS and^1HNMR.

关 键 词：1-溴代萘 加氢还原 支链烷基萘 支链烷基萘磺酸钠 磺化 

分 类 号：TQ423.115[化学工程]