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

HRID 233449ノート

反応式

HRID 233449 の反応式
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

参加物

3

反応物 2

HCID 24386Thionyl ChlorideHCID 238674diethoxyphosphoryl-phenyl-methanol

生成物 1

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

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-24efce0366064c1aa684814a580ed84f
出典データセット
uspto-grants-1997_01
特許番号
US05593980

反応ノート

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