3-羟基-4-苯基-2-丁酮的合成

Synthesis of 3-Hydroxy-4-phenyl-2-butanone

分别以(E)-1-苯基-1-丁烯-3-酮和4-苯基-2-丁酮为起始原料合成了3-羟基-4-苯基-2-丁酮。以(E)-1-苯基-1-丁烯-3-酮为起始原料,经过环氧化和还原两步反应得到产物;第1步环氧化反应,用双氧水作氧化剂,产率64%;第2步α,β-环氧酮在Pd/C催化作用下用甲酸还原,得到产物3-羟基-4-苯基-2-丁酮,产率67%;该路线总产率为43%。以4-苯基-2-丁酮为起始原料,经过烯醇硅醚中间体氧化得到产物;4-苯基-2-丁酮在六甲基二硅胺作用下与三甲基碘硅烷反应得到4-苯基-2-丁烯-2-基三甲基硅醚,产率为75%;第2步烯醇硅醚用间氯过氧苯甲酸氧化,得到产物3-羟基-4-苯基-2-丁酮,产率达71%;该路线总产率为53%。以(E)-1-苯基-1-丁烯-3-酮为起始原料的合成路线总产率略低,但操作简单,试剂价廉易得,是更为实用可行的合成路线。

Two different methods of preparing 3-hydroxy-4-phenyl-2-butanone were studied starting from（E）-1-phenyl-1-buten-3-one and 4-phenyl-2-butanone,respectively.（E）-1-Phenyl-1-buten-3-one was converted into 3-hydroxy-4-phenyl-2-butanone through epoxidation and reduction.The first step of reaction used H2O2 as oxidant,with a yield of 64% of 1-phenyl-1,2-epoxy-3-butanone;1-phenyl-1,2-epoxy-3-butanone was reduced by HCOOH in the presence of Pd/C to produce 3-hydroxy-4-phenyl-2-butanone,whose yield reached 67%.The overall yield was 43%.4-Phenyl-2-butanone was converted into 3-hydroxy-4-phenyl-2-butanone through the oxidation of the intermediate silylenol ether.4-Phenyl-2-butanone reacted with trimethylsilyl iodide in the presence of hexamethyldisilazane,with a yield of 75% of 4-phenyl-2-buten-2-yl trimethylsilyl ether.The obtained silylenol ether was oxidized with m-chloroperoxybenzoic acid,with a yield of 71% of 3-hydroxy-4-phenyl-2-butanone.The overall yield was 53%.The synthetic route starting from（E）-1-phenyl-1-buten-3-one is a more practical route due to its easy operation and commercially available cheap reagents,though with a little lower overall yield.