化学学报 ›› 1965, Vol. 31 ›› Issue (3): 199-202. 上一篇    下一篇

论文

新法制备二烷基磷酰氰酯

童曾寿, 戴昌世   

  • 收稿日期:1964-03-01 出版日期:1965-06-15 发布日期:2013-06-03

A NEW METHOD FOR THE PREPARATION OF O, O’-DIALKYLPHOSPHORYL CYANIDES

TUNG TZENG-SHOU, TAI CHANG-SHIH   

  • Received:1964-03-01 Online:1965-06-15 Published:2013-06-03

(1) 用二烷基亚磷酸酯与四氯化碳和氰化鈉反应,制备二烷基磷酰氰酯,并讨論其反应机理。二烷基亚磷酸酯的相对活泼性依下列次序递減:二甲基->二乙基->二正丙基->二异丁基亚磷酸酯。 (2) 在制备二烷基磷酰氰酯时,如反应条件较强,容易获得副产品,四烷基焦磷酸酯。

The O,O'-dialkyl phosphoryl cyanides(Ⅱ) were prepared in good yields by the reaction of sodium cyanide with dialkylphosphonates (Ⅰ) in the presence of carbon tetrachloride under appropriate conditions.The reaction mechanism was briefly discussed.In the above reaction,the order of the relative reactivities of dialkylphosphonates is as follows:
dimethyl > diethyl > di-n-propy > di-iso-butyl.
In the course of the preparation,side reactions were found,in which by-products such as tetraalkylpyrophosphates (Ⅲ,R=Me,Et,n-Pr,and i-Bu) were obtained.However,under suitable conditions.these side reactions can be almost completely suppressed.A detailed procedure is given.