A method for preparing organophosphate compounds by efficiently esterifying p(o)-oh compounds with phenol
A technology of organic phosphoric acid and compounds, which is applied in organic chemistry, chemical instruments and methods, compounds of Group 5/15 elements of the periodic table, etc., can solve the problems of harsh reaction conditions, raw material quality and safety, product stability and purity, and synthesis Problems such as high technical difficulty, to achieve the effects of mild and easy-to-control reaction process, good industrial application prospects, and cheap and easy-to-obtain catalysts
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Embodiment 1
[0025] 109 mg (0.5 mmol) of diphenylphosphoric acid, 47 mg (0.5 mmol) of phenol, 1.0 mmol of triethylamine and 81 mg (0.5 mmol) of carbonyldiimidazole were added to 1.0 mL of organic solvent ( Tetrahydrofuran, dichloromethane, dichloroethane, N,N -dimethylformamide, 1,4-dioxane, acetone, ethyl acetate, acetonitrile), stirred and reacted at room temperature for 12 hours. Through GC detection analysis, when acetonitrile is used as the reaction solvent, the productive rate of this coupling reaction can reach the productive rate of 43.4%.
Embodiment 2
[0027] 109 mg (0.5 mmol) of diphenylphosphoric acid, 47 mg (0.5 mmol) of phenol, 1.0 mmol of base (diisopropylethylamine, 1,8-diazabicycloundec-7-ene , N,N - Dimethylaniline, N,N -Diethylaniline, N,N -Dimethylbenzylamine, triethylamine, potassium carbonate, sodium carbonate, potassium phosphate, potassium hydroxide, sodium hydroxide or cesium carbonate) and 81 mg (0.5 mmol) carbonyldiimidazole were added to the Schlenk tube under nitrogen atmosphere, Add 1.0 mL of acetonitrile under a nitrogen atmosphere, and stir the reaction at room temperature for 12 hours. Through GC detection analysis, in N,N When -dimethylaniline is used as base, the productive rate of this coupling reaction can reach the productive rate of 71%. The efficiency of the organic base in this system is obviously higher than that of the inorganic base, the main reason is that the inorganic base is easy to form the corresponding phosphate from the P(O)-OH compound.
Embodiment 3
[0029] 109 mg (0.5 mmol) of diphenylphosphoric acid, 47 mg (0.5 mmol) of phenol, different molar ratios (0mol%, 50mol%, 100mol%, 150mol%, 200mol%) N,N -Dimethylaniline and 81 mg (0.5 mmol) of carbonyldiimidazole were added into 1.0 mL of acetonitrile under a nitrogen atmosphere, and the reaction was stirred at room temperature for 12 hours. Analysis by GC detection, only in N,N -When the amount of dimethylaniline is 1.5 times the reaction equivalent of diphenylphosphoric acid, the yield of the coupling reaction can reach 99% yield.
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