Chlorodimethylphosphine → Dimethyl(3-nitrobenzyl)phosphane oxide

HRID 511214Notes

Reaction equation

HRID 511214 reaction equation
Cl[P:2]([CH3:4])[CH3:3].[O-:5]CC.[Na+].Br[CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[C:13]([N+:17]([O-:19])=[O:18])[CH:12]=1>C1COCC1>[CH3:3][P:2](=[O:5])([CH3:4])[CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[C:13]([N+:17]([O-:19])=[O:18])[CH:12]=1

Participants

5

Reactant 3

HCID 69936ChlorodimethylphosphineHCID 77568Benzene, 1-(bromomethyl)-3-nitro-HCID 2723922Sodium ethoxide

Product 1

HCID 67256329Dimethyl(3-nitrobenzyl)phosphane oxideYield 28%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of chlorodimethylphosphine (250 mg, 2.60 mmol) in THF (0.7 mL) was added dropwise to a stirred suspension of sodium ethoxide (194 mg, 2.85 mmol) in THF (0.8 mL) at 0° C. The resulting mixture was stirred at room temperature for 30 min. then treated with 1-(bromomethyl)-3-nitrobenzene (560 mg, 2.59 mmol). The mixture was then stirred under nitrogen at 100° C. in a sealed tube for 2 h., concentrated in vacuo and the residue purified by chromatography over silica gel eluting with 5% MeOH in dichloromethane to afford 153 mg of dimethyl(3-nitrobenzyl)phosphane oxide (yield: 28%). 1H-NMR (CDCl3, 400 MHz): δ=1.53 (d, J=12.4 Hz, 6 H), 3.27 (d, J=14.0 Hz, 2 H), 7.55 (t, J=7.6 Hz, 1 H), 7.71 (d, J=7.6 Hz, 1 H), 8.11 (d, J=2.0 Hz, 1 H), 8.16 (dd, J=0.8, 7.2 Hz, 1 H). MS (ES+): m/z 214.00 (MH+). HPLC: tR=2.16 min (ZQ3, polar—5 min).

Workup

  1. stirringThe mixture was then stirred under nitrogen at 100° C. in a sealed tube for 2 h.
  2. concentrationconcentrated in vacuo
  3. customthe residue purified by chromatography over silica gel eluting with 5% MeOH in dichloromethane

Sources & evidence

ORD record
ord-01462e2659b644d098059711fc17343f
Source dataset
uspto-grants-2015_08
Patent number
US09096624B2

Reaction notes

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