化学学报 ›› 1964, Vol. 30 ›› Issue (6): 532-539. 上一篇    下一篇

论文

Ⅳ.环己基膦酰二氯与高碳醇的醇解反应

陆熙炎, 王国樑   

  1. 中国科学院有机化学研究所
  • 投稿日期:1963-11-11 发布日期:2013-06-03

Ⅳ. ALCOHOLYSIS OF CYCLOHEXYLPHOSPHONYL DICHLORIDE WITH HIGHER ALCOHOLS

LOH HSI-YIEN, WANG KUO-LIANG   

  1. Institute of Organic Chemistry, Academia Sinica
  • Received:1963-11-11 Published:2013-06-03

环己基膦酰二氯在吡啶存在下与计算量高碳醇进行醇解反应,馏出物中有环己基膦酰氯-2-乙基己酯存在,水解后得环己基膦酸单-2-乙基己酯,环己胺解后得环己基膦酰环己胺2-乙基己酯.将蒸馏后的残渣水解,得环己基膦酸及环己基膦酸单-2-乙基己酯.本文叙述一种从烷基膦酰二氯合成高碳醇的烷基膦酸二酯及单酯的简便方法.

Detailed studies on the products of the alcoholysis of cyclohexylphosphonyl dichloride(Ⅰ) with 2-ethyl hexanol are described.It was found that the reaction proceeded incompletely when Ⅰ was reacted with calculated amount of alcohol in the presence of pyridine.Four fractions were obtained from the reaction product by distillation.The first fraction,as identified by gas chromatography,was unreacted 2-ethyl hexanol.The second fraction,as proved by hydrolysis to mono-2-ethylhexyl cydohexylphosphonate(Ⅳ) and by reaction with cyclohexylamine to form N-cyclohexyl 2-ethylhexyl cyclohexylphos-phonamidate(V),was shown to be 2-ethylhexyl cyclohexylphosphonochloridate(Ⅲ).The normal product of the alcoholysis reaction,di-2-ethylhexyl cyclohexylphosphonate,appeared in the third fraction only in 27.5% yield.The residue of the distillation was a neutral,yellow viscous liquid.On hydrolysis it yielded cyclohexylphosphonic acid(Ⅵ) and IV in the mole ratio of 1:14-19.