Unusual Ring‐Closure Reactions During the Oxidation of 1,1′‐Bi(3‐methylphosphol‐2‐ene) with Hexafluoroacetone — Formation of a Tricyclic Fluorine‐Containing Phosphorane
作者:Sebastian Vollbrecht、Alexander Vollbrecht、Jörg Jeske、Peter G. Jones、Reinhard Schmutzler、Wolf‐Walther Du Mont
DOI:10.1002/cber.19971300623
日期:1997.6
with 3, or with 1/2 equivalent of Si2Cl6 provided the new γ3P-γP-diphosphane 1,1′-bi(3-methylphosphol-2-ene) 4. Reduction of 4 with Si2Cl6 led to 3. Oxidation of 4 with selenium gave the 1,2-diphosphane diselenide, 5. The oxidation of 4 with hexafluoroacetone led to a mixture of products, from which a novel tricyclic phosphorane 6 was separated. the structure of 196 was determined by X-ray diffraction;
异戊二烯的还原-的PCl 3的加合物1与镁粉末,或有Si 2氯6,家具的P -氯-3-甲基phosphol -2-烯,2,在令人满意的产率。用Si 2 Cl 6进一步还原2,得到新的三氯甲硅烷基-3-甲基膦-2-烯3。的反应2与镁粉末,具有3,或与1/2当量的Si 2氯6提供的新的γ 3 P-γP-二膦1,1'-双(3- methylphosphol -2-烯)4。减少4与Si 2 Cl 6导致3。用硒氧化4,得到1,2-二膦二硒化物5。用六氟丙酮氧化4生成产物混合物,从中分离出新的三环磷烷6。196的结构通过X射线衍射测定。在扭曲的三角双锥体中磷的配位几何结构,具有非常长的赤道P-C(CF 3)2键为193.2(2)pm。