Synthesis of High Refractive Spiroheterocyclic Derivatives Through Thioacetalization of Multi-Carbonyl Compounds
作者:Ji-Myoung Ye、Muchchintala Maheswara、Jung-Yun Do
DOI:10.5012/bkcs.2012.33.8.2494
日期:2012.8.20
Preparation of several new spirocyclic mercapto derivatives is described. Thiol protection on multi-carbonyl compounds allows of high sulfur content necessary to induce high refractive index. Condensation of 1,3-dimercapto-2-propanol and cyclohexanone followed by successive oxidation and thioacetalization affords a dispirocycle with four sulfurs. Selective S,S-protection of cyclohexane-1,4-dione is achieved with 1,3-dimercapto-2-propanol and 2,3-dimercapto-1-propanol to provide dispirocycles with four sulfurs. Olefine-oxidation of norbornene gives a useful dialdehyde intermediate which is transformed to 1,3-dithiolane for a linearly-bound-cyclic molecule. Refractive index of linearly-bound-cycles was below 1.60 and dispirocycles exhibited high refractive index of 1.57-1.69.
本文描述了几种新型螺环硫醇衍生物的制备。在多羰基化合物上进行硫醇保护,可以使硫含量达到诱导高折射率所需的较高水平。将1,3-二巯基-2-丙醇与环己酮缩合,随后进行连续氧化和硫缩醛化,得到含有四个硫原子的双螺环化合物。通过1,3-二巯基-2-丙醇和2,3-二巯基-1-丙醇对环己烷-1,4-二酮进行选择性S,S保护,可以制得含有四个硫原子的双螺环化合物。烯烃氧化降冰片烯得到一个有用的二醛中间体,将其转化为1,3-二硫杂环戊烷,形成线性连接的环状分子。线性连接的环的折射率低于1.60,而双螺环化合物的折射率高达1.57-1.69。