Investigations on the Development of New Reactions and New Organic Reagents by Using High Reactivities of Heterocycles Bearing Sulfur Functional Groups

1.合成了一系列含吡啶及其氮杂杂环的有机硫化合物，并对其物化性质进行了研究。发现了这些化合物的几个新反应。在甲醇中，α-亚磺酰基、磺酰基-吡啶和N-氧化物很容易与KOH反应生成各种亚磺酸和亚磺酸。特别是首次发现了稳定的亚硫酸钠的制备方法。β-和γ-吡啶基苯亚砜与烷基格氏试剂在亚硫基硫原子上反应生成β-和伽马吡啶基格氏试剂，后者进一步与亲电试剂反应生成各种新的吡啶类化合物。另一方面，α-衍生物与烷基格氏试剂反应，以较高的产率得到相应的α-苯基吡啶。这两个反应被认为是通过一种常见的中间体“硫磺”进行的。当用吡啶格氏试剂处理吡啶亚砜时，除了在伽马-吡啶亚砜和伽马-吡咯-溴化镁的反应中，都以较高的产率得到了对称和不对称的双氮杂芳基。这些化合物可用于重金属的络合剂，该步骤便于制备这些络合剂。将碘苯与乙基格氏试剂反应，制备了α-β-吡啶格氏试剂和伽马-吡啶格氏试剂。吡啶基苯亚砜与LDA反应生成相应的α-锂基亚硫醚，具体位于吡啶环上。锂亚砜进一步与各种亲电试剂反应，高产率地转化为相应的吡啶衍生物。

1. Numerous organic sulfur compounds bearing pyridyl and related azaheterocycles were prepared and investigated their physical and chemical properties. Several new reactions of these compounds were found. alpha-Sulfinyl and sulfonyl-pyridines and N-oxides react readily with KOH in MeOH to afford various sulfenic and sulfinic acids. Especially, first preparation of stable sodium sulfenate was found.2. beta- and gamma.-Pyridyl phenyl sulfoxides were found to react with alkyl Grignard reagents at the sulfinyl sulfur atom to give both beta- and gammapyridyl Grignard reagents which react further with electrophiles to provide various new pyridyl compounds. On the other hand, alpha-derivative reacts with alkyl grignard reagents to afford the corresponding alpha-phenylpyridine in good yield. These two reactions are considered to proeed via a common intermediate " -sulfurance".3. When pyridyl sulfoxides were treated with pyridyl grignard reagents except in the reactions of gamma-pyridyl sulfoxide and gamma-PyMgBr, the corresponding both symmetric and unsymmetric bis-azaaryls were obtained in good yields. These compounds are useful for chelating agents of heavy metals and this procedures are convenient for preparation of these chelating agents.4. alpha- beta- and gamma-pyridyl Grignard reagents were prepared from the reactions of iodobenzenes with ethyl Grignard reagent.5. Pyridyl phenyl sulfoxides were found to react with LDA to give the corresponding alpha-lithiated sulfoxides specifically at the pyridyl ring. The lithiated sulfoxides react further with various electrophiles to be converted to the corresponding pyridyl derivatives in high yields.