Warawa E J, Mueller N J
J Med Chem. 1975 Jan;18(1):71-4. doi: 10.1021/jm00235a016.
The 1,4 addition of p-chlorophenylmagnesium bromide to 2-benzylidene-3-quinuclidinone gave 2-(4-chlorobenzhydryl)-3-quinuclidinone as two diastereoisomers. Selective reduction of this ketone with aluminum isopropoxide gave the two cis-2-(4-chlorobenzhydryl)-3-quinuclidinols, which differ only in the configuration of the benzhydryl group, designated alpha and beta in order of their elution on chromatography. Reduction with NaBH4 gave a mixture of four isomeric alcohols, of which the two cis isomers were selectively oxidized. The two trans-2-(4-chlorobenzhydryl)-3-quinuclidinols were chromatographically separated and desingated alpha and beta in order of elution. Only the beta-cis and beta-trans alcohols showed CNS stimulant properties. The beta-cis isomer was shown to be related both qualitatively and quantitatively more to methylphenidate (Ritalin) than to d-amphetamine.
对氯苯基溴化镁与2-亚苄基-3-奎宁环酮发生1,4加成反应,生成2-(4-氯二苯甲基)-3-奎宁环酮的两种非对映异构体。用异丙醇铝对该酮进行选择性还原,得到两种顺式-2-(4-氯二苯甲基)-3-奎宁环醇,它们仅在二苯甲基的构型上有所不同,根据它们在色谱上的洗脱顺序分别命名为α和β。用硼氢化钠还原得到四种异构醇的混合物,其中两种顺式异构体被选择性氧化。两种反式-2-(4-氯二苯甲基)-3-奎宁环醇通过色谱法分离,并根据洗脱顺序命名为α和β。只有β-顺式和β-反式醇表现出中枢神经系统刺激特性。结果表明,β-顺式异构体在定性和定量方面与哌醋甲酯(利他林)的关系比与d-苯丙胺的关系更大。