Diethyl chlorophosphate → HCID 178435656, compound

Following a general procedure (Doisneau et al. (1992) J. Organomet. Chem. 425: 113-117), to a solution of 12 (2.0 g, 7.8 mmol) in dry THF (50 mL) at −78° C. were added dropwise 1.1 equiv of freshly prepared LDA (40 mL, 8.0 mmol) in THF. After 1 h at −78° C., diethyl chlorophosphate (1.1 equiv, 1.2 mL, 8.0 mmol) was added at −78° C. for 1 h. The reaction mixture was allowed to warm to rt for an additional 1 h and then was recooled to −78° C. and an additional 2.3 equiv of LDA (80 mL, 20 mmol) was added. The reaction mixture was warmed to rt and stirred overnight then hydrolyzed at 0° C. The reaction mixture was extracted with ether (3×50 mL) and the combined organic layers were washed with water (3×50 mL) and satd NaCl (3×50 mL) and dried (MgSO4). The resulting residue after evaporation was purified by column chromatography (silica, petroleum ether) to afford 1.7 g (90%) of a yellow oil. 1H NMR δ 1.19 (t, J=7.5 Hz, 3H), 2.36 (q, J=7.5 Hz, 2H), 2.73 (s, 1H), 4.10 (m, 4H), 4.15 (t, J=2.1 Hz, 2H), 4.37 (t, J=2.1 Hz, 2H); 13C NMR δ 15.3, 21.9, 66.5, 69.7, 69.8, 70.0, 72.9, 74.3; FAB-MS obsd 238.0466, calcd exact mass 238.0445; Anal. Calcd for C14H14Fe: C, 70.62; H, 5.93. Found: C, 70.65; H, 5.92.

1. customwas recooled to −78° C.
2. temperatureThe reaction mixture was warmed to rt
3. customthen hydrolyzed at 0° C
4. extractionThe reaction mixture was extracted with ether (3×50 mL)
5. washthe combined organic layers were washed with water (3×50 mL) and satd NaCl (3×50 mL)
6. dry with materialdried (MgSO4)
7. customThe resulting residue after evaporation
8. customwas purified by column chromatography (silica, petroleum ether)

ORD record

ord-867e0e11c7bc4b96acb07e911b8c30d7

Source dataset

uspto-grants-2009_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07518905B2