12,14-二羟基紫韧革烯的分离和结构测定

由紫韧革菌(Stereum purpureum)代谢产物中分离出一个新的三环倍半萜烯醇(sterpurenol), 12,14-二羟基紫韧革烯。用二维核磁共振确定了它具有紫韧革烯(sterpurene,1)的骨架及它的整个分子结构。     

10-甲基-PGD2的合成子的合成

PGD2的合成子(9)的合成是以2-甲基环戊1,3-二酮(1)为原料, 经烯醇醚化、烯丙基化、酸去保护、羰基的锂铝氢还原、臭氧化、氧化、甲酰化获得.     

相似分析/质谱法鉴别二十种脂肪族双烯-1-醇及乙酸酯

本文报道了二十个脂肪族双烯-1-醇和乙酸酯EI-质谱的特征, 并提出了相似分析法鉴别这些共轭双烯、孤立双烯的双键位置及几何异构体的质谱。     

两价钯催化下烯醇钯中间体和亲电试剂的反应研究

根据在两价钯催化的亲核试剂－炔烃－α,β-不饱和羰基化合物的串联加成反应中所假设的烯醇钯中间体的机理,研究了炔酸烯丙酯化合物1和亲电试剂在两价钯催化下的反应。使用乙酰氮作为亲电试剂得到了β－乙酰氧基烯基－γ－丁丙酯3,这一结果为烯醇钯中间体的机理提供了一个实验证据。     

有机磷化合物的研究 XXI:两可阴离子的区域选择性磷酰化反应

本文报道某些两可阴离子磷酰化反应的区域选择性.苯基丙酮双阴离子与二乙基磷酰氯反应,除O-磷酰化产物的顺,反异构体外,还得两个C-磷酰化产物.烯丙基苯碳阴离子与二乙基磷酰氯反应未获得预期产物,苯乙酮的环已胺Schiff碱作为两可阴离子,在磷酰化反应中可获得以C-磷酰化为主的三种产物.本文对双阴离子的化学结构与磷酰化反应区域选择性的影响作了讨论.     

有机磷化合物的研究IX.某些具有活泼亚甲基化合物的碳磷酰化反应

The formation of P -- C bond is one of the important problems in synthetic organophosphorous chemistry. This paper describes the study of the formation of P -- C linkage via phosphorylation of carbon atom containing active hydrogen. p-Substituted phenylacetonitrile possessing an active methylene group undergoes stepwise C -- phosphorylation smoothly with diethyl phosphoryl chloride in the presence of naphthalene-sodium. Phosphonyl chloride reacts analogously. Being a deprotonizing agent naphthalene-sodium is distinguished by its availability, effectiveness and mild reaction conditions. The presence of an electron-withdrawing group in the benzene ring reduces the yield of phosphorylation seriously. The chemical shift of ^3^1P NMR of the resulted α-cyano-benzylphosphonates (1) correlates linearly with the Hammett \s\ constants of the substituents. As indicated by ^1H NMR studies the protons in the ester ethyl groups are magnetically nonequivalent. Compound 1 can be alkylated with alkyl halide or condensed with aromatic aldehyde by Hornor-Wittig type reaction due to the presence of active hydrogen atom. The structure-reactivity studies of diethyl phosphoryl chloride on reacting with various β- and β-diketones and β-keto esters (5) as regiospecific reaction were reported. The influences of metal ions in the enolates on the reactivity of the latter were examined and discussed. Only vinyl phosphates with predominantly Z configuration have been isolated exclusively. The C atom with an active hydrogen in the β-diketones investigated is inert to phosphorylation. These experimental results are well supported by reaction selectivity in terms of Eqo/Ecoc based on EHMO calculation.     

关于DAKIN-WEST反应的研究

七种α-伯氨基酸和一个α-仲氨基酸分别与醋酐和吡啶回流反应产生相应的烯醇酯3和7.根据核磁共振氢谱、碳谱和NOE技术初步确定了十个烯醇酯3的双键构型.氰基乙酸与醋酐和吡啶反应产生3-氰基乙酰丙酮(8).     

昆虫信息素结构鉴定与合成 XXI, 淡色库蚊产卵引诱信息素四个光学异构体的立体选择性合成

应用Sharless不对称环氧化反应,合成淡色库蚊产卵引诱信息素的所有四个光学异构体1a～1d, e.e.96～97%. 从炔醇2出发到1a～1d的总得率为15～20%.     

三环型吗啡类似物合成的新方法

本文报道4,6-二羟基-9bβ-N-甲基苯乙胺乙基六氢双苯骈呋喃(1)的合成路线。以芳基取代的环己烯醇(2)为原料, 经重排、环氧化、环合、还原、磺酰化、取代和脱保护等九步反应, 1的总产率为46%。