摘要
膦、胂叶立德能与醛、酮等通过Wittig反应合成烯烃衍生物,在有机合成中具有很大的应用价值。其反应活性与结构的关系已有深入的讨论,有关分子结构的研究工作仍在继续中。我们按文献[4]合成甲氧羰基亚甲基三苯基胂,熔点153~154℃。
Colorless transparent crystals of an inner salt of carboxylmethyl triphenylarsonium Ph_3As^+CH_2COO- 11/2H_2O, the hydrolytic product of carbomethoxymethylene triphenylarsorane, were obtained from CH_3OH:C_2H_5OH (1:2) solution. Space group P , a=9. 430(1),b=9. 544 (1), c=20.797(1) , a=97.62(1), β=97.42(1),γ=99.23(1)°,V=1809.2 ,Z=4,D_o= 1.436g/cm^3. The structure was Solved by the heavy-atom method and refined by the full- matrix least-squares method with anisotropic temperature factors for non-hydrogen atoms and isotropic for all hydrogen atoms to R=0.030. The results show that the bond length As-CH_2 is comparable to the three As-Ph bond lengths and the carboxyl is delocalized. These differ obviously from those of arsonium ylides reported. The possible mechanism of the hydrolysis process was also suggested.
出处
《有机化学》
SCIE
CAS
CSCD
北大核心
1989年第5期471-474,共4页
Chinese Journal of Organic Chemistry
关键词
羧甲基三苯基
钾盐
晶体结构
crystal structure
carboxylmethyl-triphenyl-arsonium salt