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

利用含硫官能团杂环化合物的高反应活性开发新反应和新有机试剂的研究

基本信息

批准号：
61470019
负责人：
FURUKAWA Naomichi
金额：
$ 4.03万
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：
1986
资助国家：
日本
起止时间：
1986 至 1988
项目状态：
已结题

项目摘要

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.

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。