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    • 87. 发明授权
    • Preparation of (thiono)phosphoric esters
    • (硫醇)磷酸酯的制备
    • US4772702A
    • 1988-09-20
    • US875426
    • 1986-06-17
    • Fritz Maurer
    • Fritz Maurer
    • B01J31/00C07B61/00C07F9/12C07F9/18C07F9/58C07F9/6512C07F9/65
    • C07F9/12C07F9/18C07F9/585C07F9/65125
    • In the preparation of a (thiono)phosphoric ester of the formula ##STR1## in which X represents oxygen or sulphur,R and R.sup.1 are identical or different and represent alkyl, andR.sup.2 represents optionally substituted aryl or represents optionally substituted hetaryl having at least one nitrogen atom,wherein a hydroxyl derivative of the formulaR.sup.2 --OHor an ammonium, alkali metal or alkaline earth metal salt thereof is reacted with a (thiono)phosphoric halide of the formula ##STR2## in which Hal represents halogen,the improvement which comprises effecting the reaction in the presence of a bicyclic organic amine as catalyst. Advantageously the reaction is effected in a diluent in the presence of potassium carbonate as an acid acceptor at 20.degree. to 100.degree. C., and 0.8 to 1.5 mols of the halide and 0.005 to 0.5 mol of 1,4-diazabicayclo-(2,2,2)-octane are used as bicyclic organic amine per mol of the hydroxyl compound.
    • 在制备式(IMA)中的(硫代)磷酸酯的情况下,其中X表示氧或硫,R和R 1相同或不同,表示烷基,R 2表示任意取代的芳基,或表示任选取代的具有至少一个 氮原子,其中式R 2 -OH的羟基衍生物或其铵,碱金属或碱土金属盐与其中Hal代表卤素的式(IMAGE)的(硫代)磷酰卤反应,其改进包括 在双环有机胺作催化剂存在下进行反应。 有利地,反应在稀释剂中,在碳酸钾作为酸受体的存在下,在20-100℃,和0.8-1.5摩尔的卤化物和0.005-0.5摩尔的1,4-二氮杂双环(2, 2,2) - 辛烷用作每摩尔羟基化合物的双环有机胺。