Thionyl Chloride → Phosphonic acid, (chlorophenylmethyl)-, diethyl ester

HRID 233449Notes

Reaction equation

HRID 233449 reaction equation
O[CH:2]([P:9](=[O:16])([O:13][CH2:14][CH3:15])[O:10][CH2:11][CH3:12])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.S(Cl)([Cl:19])=O>>[Cl:19][CH:2]([P:9](=[O:16])([O:13][CH2:14][CH3:15])[O:10][CH2:11][CH3:12])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1

Participants

3

Reactant 2

HCID 24386Thionyl ChlorideHCID 238674diethoxyphosphoryl-phenyl-methanol

Product 1

HCID 11747439Phosphonic acid, (chlorophenylmethyl)-, diethyl esterYield 66.2%

Procedure

A solution of Compound 19 (1.00 g, 0.0041M) in thionyl chloride (1.63 g, 0.014M) is allowed to stir at room temperature for 16 hours. The thionyl chloride is removed in vacuo and the crude is poured over ice-water. The aqueous is extracted with ether (2 times). The ether layer is washed with sodium bicarbonate (saturated solution) (2 times) and water. The organic layer is dried (Na2SO4), filtered and concentrated to obtain 0.712 g of a clear oil. The crude is chromatographed over flash silica gel (0.040-063 mm, 100 g) and eluted with 1% acetone/CH2Cl2 to obtain 0.516 g (0.0020M, 48%) of the title compound as a clear oil. 1H NMR (CDCl3 /TMS): δ 7.56-7.52 (m, 2H, Ar), 4.40 -7.32 (m, 3H, ArH), 4.90 (d, J=14 Hz, 1H, CHCl), 4.23-4.12 (m, 2H, CH2), 4.10-4.00 (m, 1H, CH2), 3.95-3.84 (m, 1H, CH2), 1.32 (dt, J=7.0, 0.6 Hz, 3H, CH3), 1.17 (dt, J=7.0, 0.6 Hz, 3H, CH3); 13C NMR (CDCl3): δ 134.16 (d, J=3.0 Hz, Ar), 129.01-128.55 (m, Ar), 64.13-63.86 (m, CH2), 53.67 (d, J=53.7 Hz, CHCl), 16.45-16.19 (m, CH3); 31P NMR (CDCl3): δ 17.82. Anal. calc'd. for C11H16O3CIP: C, 50.30; H, 6.14; P, 11.79. Found: C, 50.06; H, 6.24; P, 11.66.

Workup

  1. customThe thionyl chloride is removed in vacuo
  2. additionthe crude is poured over ice-water
  3. extractionThe aqueous is extracted with ether (2 times)
  4. washThe ether layer is washed with sodium bicarbonate (saturated solution) (2 times) and water
  5. dry with materialThe organic layer is dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-24efce0366064c1aa684814a580ed84f
Source dataset
uspto-grants-1997_01
Patent number
US05593980

Reaction notes

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