Studies on the Development for New Synthetic Reagents of Organic Sulfur and Selenium Compounds and their Organization

有机硫、硒化合物及其组织新型合成试剂的开发研究

基本信息

批准号：
02453018
负责人：
FURUKAWA Naomichi
金额：
$ 4.29万
依托单位：
University of Tsukuba
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1990
资助国家：
日本
起止时间：
1990 至 1992
项目状态：
已结题

项目摘要

1.It was found that phenyl 3- and 4-pyridyl sulfoxides underwent Grignard exchange reactions to afford readily 3-and 4-pyridyl magnesium bromide which reacted with various aldehydes and ketones to give the corresponding addition products. By using this exchange reactions, optically active 3-and 4-pyridylphenyl sulfoxides were prepared. On the other hand, 2-pyridyl phenyl sulfoxide gave under similar condition to provide the ligand coupling products.i.e., 2-pyridyl derivatives in high yields. The reaction of 2-PyS(O) Ph with LDA (lithium diisopropylamide) gave highly regioselectively the 3-lithiated sulfoxide which then reacts with electrophiles to result in the formation of the 3-substituted 2-phenylsulfinyl pyridines. These pyridyl derivatives gave finally optically active 2-phenyl pyridines on treatment with Grignard reagents. Also first synthesis of optically active 2-p-tolyl pyridyl sulfoxide was performed by employing the above mentioned procedure.2. On treatment with LDA and then with ArCHO,optically pure 2-PyCH_2S(O)-Tol-p gave a-phenyl alkoxyl substituted sulfoxides by asymmetric induction. After desulfinylation, optically active 1-aryl-2-(2-pyridyl)ethanols were synthesized.3. Monooxides of thianthrene and selenanthrene were converted to 4,6-disubstituted derivatives by treatment with LDA and electrophiles such as (PhS)_2. Furthermore,4,6-disubstituted thianthrene and selenanthrene 1-oxides were found to react with n-BuLito give the ring contracted 1,9-disubstituted dibenzothiophenes and dibenzoselenophenes. These 1,9-disubstituted dibenzothiophenes and dibenzoselenophenes provide [3.4, bc]thienothiophene and selenophene on pyrolysis and photolysis.

1.发现苯基3-和4-吡啶基亚砜发生格氏交换反应，容易生成3-和4-吡啶基溴化镁，与各种醛、酮反应生成相应的加成产物。通过利用该交换反应，制备了光学活性的3-和4-吡啶基苯基亚砜。另一方面，2-吡啶基苯基亚砜在类似的条件下以高产率提供配体偶联产物，即2-吡啶基衍生物。 2-PyS(O) Ph 与 LDA（二异丙基氨基锂）反应高度区域选择性地生成 3-锂化亚砜，然后与亲电子试剂反应形成 3-取代的 2-苯基亚磺酰基吡啶。这些吡啶基衍生物经格氏试剂处理后最终得到光学活性的2-苯基吡啶。采用上述方法还首次合成了光学活性2-对甲苯基吡啶亚砜。 2．先用LDA处理，然后用ArCHO处理，通过不对称诱导，光学纯的2-PyCH_2S(O)-Tol-p得到α-苯基烷氧基取代的亚砜。经过脱亚磺酰化反应，合成了光学活性的1-芳基-2-(2-吡啶基)乙醇。 3．通过用LDA和亲电子试剂如(PhS)_2处理，将噻蒽和硒蒽的一氧化物转化为4,6-二取代衍生物。此外，还发现4,6-二取代的噻蒽和硒蒽1-氧化物与n-BuLi反应生成环收缩的1,9-二取代的二苯并噻吩和二苯并硒吩。这些1,9-二取代的二苯并噻吩和二苯并硒吩通过热解和光解提供[3.4,bc]噻吩并噻吩和硒吩。