Convenient synthesis of β-allenic α-difluoromethylenephosphonic acid monoesters:Potential synthons for cyclic phosphate mimics
Convenient synthesis of β-allenic α-difluoromethylenephosphonic acid monoesters:Potential synthons for cyclic phosphate mimics
摘要
β-Allenic α-difluoromethylenephosphonic acid monoesters were prepared under mild conditions for the first time by hydrolyzing the corresponding diethyl phosphonates in aqueous sodium hydroxide solution.
β-Allenic α-difluoromethylenephosphonic acid monoesters were prepared under mild conditions for the first time by hydrolyzing the corresponding diethyl phosphonates in aqueous sodium hydroxide solution.
基金
We thank the National Natural Science Foundation of China for financial support(No.20572124).
参考文献7
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7[7]Typical procedure for the synthesis of 2a.To a mixture of 1a (1.27 g,5 mmol),EtOH (5 mL) and water (10 mL) was added 1 mol/L NaOH solution (10 mL) slowly.The mixture was stirred at room temperature for about 0.5 h to the completion of the reaction (monitored by TLC).Then the reaction mixture was diluted with water (15 mL),acidified with 10% HCl to pH 2-3 and extracted with EtOAc (20 mL (3).The organic layer was washed with saturated NaCl solution and dried over anhydrous Na2SO4.After removal of solvent in vacuo,2a (1.05 g,93% yield) was obtained as an oil without further purification.IR (film):2250,1979,1640,1233,1033 cm (1; 1H-NMR (CDCl3,300 MHz) δppm:10.4 (s,1H),5.30-5.23 (m,1 H),4.27-4.18 (m,2 H),1.75 (s,6 H),1.35 (t,3 H,J = 7.2 Hz); 13C-NMR (CDCl3,125 MHz) δppm:204.3-204.0 (m),116.7 (td,JC-F = 247.1 Hz,JC-P = 189.1 Hz),102.3,84.9 (td,JC-F = 26.7 Hz,JC-P = 15.9 Hz),64.8 (d,JC-P = 6.6 Hz),19.4,16.2; 19F-NMR (CDCl3,282 MHz) δppm:(106.9 (dd,JP-F = 117.0 Hz,JH-F = 10.1 Hz); 13P-NMR (CDCl3,121 MHz) δppm:6.97 (t,JP-F = 117.0 Hz); EIMS m/z (%):227(M+ + 1,21.16),206(43.86),134(59.72),119(73.56),117(43.58),97(100.00),96(44.83),77(88.85),65(58.65).HRMS (MALDI):calcd.for C8H13F2O3PNa(M+ + Na):249.0471,found:249.0462.
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