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(一)八种亚磷酸二烃酯(包括二甲基-,二乙基-,二丙基-,二-异-丙基-,二-伯-丁基-,二-异-丁基-,二-仲-丁基-和二-伯-戊基-亚磷酸酯)在四氯化碳和一种叔胺存在下,与苯胺作用,生成二烃氧基磷酸酰胺(Ⅱ)。反应能力随下列的亚磷酸二烃酯次序逐渐减弱:二甲基-,二乙基-,二-伯-丙基-, 二-伯-丁基-,二-伯-戊基-,二-异-丁基-,二-异-丙基-,和二-仲-丁基亚磷酸酯。在上述反应中曾应用七种叔胺,三乙醇胺,甲基六氢吡啶,2-4-6-三甲基毗啶,α-甲基吡啶,吡啶,二甲基苯胺和二乙基苯胺。叔胺的辅助效应随下序递减:三乙醇胺,甲基六氢吡啶和2-4-6三甲基吡啶;另外四种叔胺(α-甲基吡啶,吡啶,二甲基苯胺和二乙基苯胺)无辅助效应。显然,辅助剂的碱性强弱是一相当重要的因素。 (二)此法亦可用作制备二烃氧基磷酸苯胼(Ⅳ),例如二丙烯基-,二中基-,二乙基-,二-异丙基-,二-异丁墓-,二-伯-戊基-,二-异-成基-,乙基伯-丁基-和乙基伯-戊苯胼磷酸酯。
(I) Eight oligoesters of phosphorous acid (including dimethyl-, diethyl-, dipropyl-, di-iso-propyl-, di- , Di-sec-butyl- and di-hepta-pentyl-phosphite) with aniline in the presence of carbon tetrachloride and a tertiary amine to form the dihydrocarbyloxy phosphoric acid amide (II). The reactivity diminishes with the following order of phosphite dihydrocarbyl esters: dimethyl-, diethyl-, di-primary-propyl-, di-primary-butyl-, Iso-butyl-, di-iso-propyl-, and di-sec-butyl phosphite. Seven tertiary amines, triethanolamine, methylpiperidine, 2-4-6-trimethylpyridine, alpha-picoline, pyridine, dimethylaniline and diethylaniline have been used in the above reaction. The secondary effect of the tertiary amine decreases with the sequence: triethanolamine, methylpiperidine and 2-4-6 picoline; the other four tertiary amines (α-picoline, pyridine, dimethylaniline and diethyl Aniline) No helper effect. Obviously, the alkaline strength of adjuvants is a very important factor. (II) This method can also be used for the preparation of phenylhydrazides of dihydrocarbyloxyphosphates such as di-, di-, diethyl-, di-isopropyl-, , Di-i-pentyl-, di-i-imino-, ethylheptane-butyl- and ethyl-β-phenylbenzenephosphonate.