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-吡啶基磺氧化亚磺氧化物经过了Grignard交换反应，可容易获得3和4-吡啶基溴化镁，与各种醛和酮反应，以提供相应的添加产物。通过使用这种交换反应，制备了光学活跃的3和4-吡啶基苯基亚磺氧化物。另一方面，2-吡啶基苯基磺氧化物在相似的条件下给出了配体偶联产物。 2-PYS（O）pH与LDA（二异丙酰胺锂）的反应给出了高度区域性的3叶氧化所有硫氧化甲氧化物，然后与电力液反应，从而形成了3均取代的2-苯基硫辛基吡啶基。这些吡啶基衍生物最终在用尖齿试剂治疗时给出了光学活性的2-苯基吡啶。同样，通过采用上述程序进行了光学活性2-P-tolyl吡啶基磺酰氧化物的首次合成。2。在用LDA和Archo处理时，光学纯的2-Pych_2s（O）-TOL-P通过非对称诱导产生了苯基苯基烷氧基取代亚氧化亚氧化亚氧化亚氧化亚氧化亚氧化亚氧化亚氧化亚氧化亚氧化亚氧化亚氧化亚氧化亚氧化亚氧化亚氧化亚氧化亚氧化亚氧化甲基氧化物。脱硫基化后，合成光学活性的1-芳基-2-（2-吡啶基）乙醇。3。通过用LDA和（pHS）_2的电力处理，将硫代和硒的单氧化物转化为4,6二取代的衍生物。此外，发现4,6二取代的硫代和硒1-氧化物与n-bulito反应，使该环收缩为1,9-二取代的二苯甲酸酯和二苯并苯苯甲酸烯。这些1,9二取代的Dibenzothiophenes和Dibenzoselenophenes在热解和光解提供[3.4，BC]噻吩噻吩和硒。