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

1.发现苯基3-和4-吡啶基亚砜经格氏交换反应，容易得到3-和4-吡啶基溴化镁，溴化镁与各种醛、酮反应，得到相应的加成产物。利用这种交换反应，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条件下得到配体偶联产物，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，再与亲电试剂反应生成3-取代的2-苯亚磺酰基吡啶。这些吡啶衍生物最终得到光学活性的2-苯基吡啶处理与格氏试剂。采用上述方法首次合成了光学活性的2-对甲苯基吡啶亚砜.光学纯的2-PyCH_2S（O）-Tol-p经LDA和ArCHO处理后，通过不对称诱导得到了α-苯基烷氧基取代亚砜。经双噻吩基化后，合成了光学活性的1-芳基-2-（2-吡啶基）乙醇类化合物.用LDA和（PhS）_2等亲电试剂处理噻蒽和硒蒽的单氧化物，得到4，6-二取代衍生物。此外，还发现4，6-二取代噻蒽和硒蒽1-氧化物与正丁基锂反应生成缩环的1，9-二取代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]噻吩并噻吩和硒代噻吩。

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.