Reactivity of Organophosphates. IV. Acid-catalyzed Hydrolysis of Triethyl Phosphate: a Comparison with Ethyl Acetate
Reactivity of Organophosphates. IV. Acid-catalyzed Hydrolysis of Triethyl Phosphate: a Comparison with Ethyl Acetate
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有机磷酸酯的反应性。
DOI：
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发表时间：
1974
期刊：
影响因子：
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通讯作者：
T. Tidwell
中科院分区：
文献类型：
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作者：
E. P. Lyznicki;K. Oyama;T. Tidwell
研究了磷酸三乙酯在水和35%二氧六环- 65%水中的水解反应。在101°时，水解速率常数为8.35 × 10−6 s−1，ΔH* = 23.4 kcal/mol， ΔS* =−20 e.u。，溶剂同位素效应为1.3，C-O键裂解由18O标记显示，0.5 M硫酸无催化作用。这些结果与BAL2水解机理一致，在中性35%二氧六环-65%水条件下的反应也有相同的途径。高氯酸在0.904 M酸条件下催化二氧环-水反应C-O键断裂，ΔH* = 24.1 kcal/mol， ΔS* = - 17 e.u，在0.556 M酸条件下具有溶剂同位素效应。这些结果表明，在这些条件下，AAL2水解途径被遵循。对磷酸三乙酯与乙酸乙酯的反应性进行了比较。
The hydrolysis of triethyl phosphate in water and in 35% dioxane – 65% water has been examined. Hydrolysis in neutral water proceeds with a rate constant of 8.35 × 10−6 s−1 at 101°, ΔH* = 23.4 kcal/mol, ΔS* = −20 e.u., a solvent isotope effect of 1.3, C—O bond cleavage as shown by 18O labeling, and no catalysis by 0.5 M sulfuric acid. These results are consistent with the BAL2 mechanism of hydrolysis and the same pathway is indicated for the reaction in neutral 35% dioxane –65% water. Perchloric acid catalyzes the reaction in dioxane–water with C—O bond cleavage in 0.904 M acid, ΔH* = 24.1 kcal/mol, ΔS* = −17 e.u., and the solvent isotope effect in 0.556 M acid. These results indicate that the AAL2 pathway of hydrolysis is followed under these conditions. The reactivity of triethyl phosphate is compared with that of ethyl acetate.