(2-BROMOETHYL)-PHOSPHORYLCHLORIDE synthesis

Yield: 90%

Reaction Conditions:

with trichlorophosphate in dichloromethane for 6 h;Reflux;

Steps:

2-Bromoethyl dichlorophosphate
(Hansen et al., 1982; Modro and Modro, 1992) Freshly distilled 2-bromoethanol (1.05 eq, 6.08 g, 50 mmol) dissolved in dry CH2CI2 (5 mL) was added drop-wise during 1 h to an ice-cooled solution of freshly distilled POCl₃ (7,35 g, 48 mmol) dissolved in dry CH₂C1₂ (10 mL). The reaction mixture was refluxed for 5 h. Vacuum-distillation (b.p. 66-69 °C, 0.4 mbar) gave 2-Bromoethyl dichlorophosphate (10.4 g, 90%). H NMR: 4.550 (dt, ³JH-P = 10.43 Hz, 2H, H-Cl), 3.580 (t, 2H, H-C2). ¹³C NMR: 70.030 (b, CH₂, CI), 27.500 (b, CH₂, C2). ³¹P NMR: 7.440. MS (EI): 241 + 243 (1 : 1, M-l); HRMS : calcd. for Cz^BrClzOzP 241.8458 (M-l); found 241.84549.

References:

PUNGENTE, Michael D.;PARTALI, Vassilla;SLIWKA, Hans-Richard;OPSTAD, Christer L.;LEOPOLD, Phillip L.;LOU, Howard H.;BILCHUK, Natalia;JUBELL, Emile WO2014/71072, 2014, A2 Location in patent:Page/Page column 42