权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Generation of Tricooordinate Boron Anions and Synthetic Use of Novel Boron Compounds

三配位硼阴离子的生成及新型硼化合物的合成应用

基本信息

批准号：
06403014
负责人：
IMAMOTO Tsuneo
金额：
$ 21.12万
依托单位：
Chiba University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1996
项目状态：
已结题

项目摘要

The generation and reactions of tricoordinate boron anions have been investigated using phosphine-boranes. Tricyclohexylphosphine-monoiodoboranes were reduced by two equivalents of lithium 4,4'-di-tert-butylbiphenylide (LDBB) in tetrahydrofuran at -78ﾟC.The generated chemical species reacted with a variety of electrophiles such as chlorotrimethylsilane, diphenyl disulfide, methyl trifluoromethanesulfonate, ethylene oxide, benzaldehyde, diethyl carbonate, and carbon dioxide to affordphosphine-boranes possessing a sub stituent at the boron atom. Reaction of tri-tert-butylphosphine-monoiodoborane with LDBB,followed by treatment with water or benzyl bromide, provided di-tert-butylphosphine-borane or benzyl (di-tert-butyl) phosphine-borane, respectively. These reactions clearly indicate that tricoordinate boron anions were generated as the reactive intermediates.Phosphine-boranes possessing trifluoromethanesulfonyloxy group at the boron atom were synthesized by treatment of phosphine-borans with trifluoromethanesulfonic acids. The structures of the obtained compounds were unequivocally determined by single crystal X-ray analyzes. These compounds underwent nucleophilic substitution reaction with various nucleophiles such as organocopper reagents to give B-substituted phosphineboranes in good yields.Novel heterocyclic compounds containing P-B-S linkages were also synthesized, and their structures and chemical properties were characterized.

用膦硼烷研究了三配位硼负离子的生成和反应。在-78 ° C下，三环己基膦单碘硼烷被2当量的4，4 '-二叔丁基联苯锂（LDBB）还原，生成的化合物与三甲基氯硅烷、二苯基二硫醚、三氟甲磺酸甲酯、环氧乙烷、苯甲醛、碳酸二乙酯和二氧化碳等亲电试剂反应，得到硼原子上带有取代基的膦硼烷.三叔丁基膦-单碘硼烷与LDBB反应，然后用水或苄基溴处理，分别提供二叔丁基膦-硼烷或苄基（二叔丁基）膦-硼烷。这些反应清楚地表明，三配位硼阴离子作为反应中间体生成。膦硼烷与三氟甲磺酸反应，合成了在硼原子上具有三氟甲磺酰氧基的膦硼烷。所得化合物的结构通过单晶X-射线分析明确确定。这些化合物与有机铜试剂等亲核试剂发生亲核取代反应，以较好的产率合成了B-取代膦硼烷，并合成了新型含P-B-S键的杂环化合物，对其结构和化学性质进行了表征。