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

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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.