Thionyl Chloride → Ethyl chloro[(3-methoxy-4-nitrophenyl) methyl]phosphinate

HRID 2279915Notes

Reaction equation

HRID 2279915 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:15]=[CH:16][C:17]=1[N+:18]([O-:20])=[O:19])[CH2:6][P:7](=O)([O:11]CC)[O:8][CH2:9][CH3:10].S(Cl)([Cl:23])=O>CN(C=O)C>[Cl:23][P:7]([CH2:6][C:5]1[CH:15]=[CH:16][C:17]([N+:18]([O-:20])=[O:19])=[C:3]([O:2][CH3:1])[CH:4]=1)(=[O:11])[O:8][CH2:9][CH3:10]

Participants

4

Reactant 2

HCID 24386Thionyl ChlorideHCID 86654016Diethyl (3-methoxy-4-nitrobenzyl)phosphonate2×

Product 1

HCID 86697855Ethyl chloro[(3-methoxy-4-nitrophenyl) methyl]phosphinate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of diethyl (3-methoxy-4-nitrobenzyl)phosphonate (Compound 1G, 5 g, 15.5 mmol) in thionyl chloride (50 mL, 690 mmol) was treated with catalytic amount of DMF and heated to reflux under nitrogen for 6 h. The mixture was concentrated under reduced pressure and co-evaporated with dichloroethane (50 mL) to give crude (ethyl chloro[(3-methoxy-4-nitrophenyl) methyl]phosphinate). This material was taken up in DCM (20 mL) and added to a solution of 2-propanol (4 mL, 52 mmol) and DIPEA (6 mL, 34.5 mmol) in DCM (20 mL). The resulting mixture was stirred at rt for 24 hrs. The solvents were evaporated and the residue was purified by column chromatography (SiO2, 5% methanol in dichloromethane) to give 3 g of the desired product as a light-yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.8 2(d, J=8.4 Hz, 1H), 7.1 (s, 1H), 6.92 (d, J=8.5 Hz, 1H), 4.6-4.4.75 (m, 1H), 4.05-4.08 (m, 2H), 3.93 (s, 3H), 3.18 (d, J=20 Hz, 2H), 1.18-1.25 (m, 9H).

Workup

  1. temperatureheated
  2. temperatureto reflux under nitrogen for 6 h
  3. concentrationThe mixture was concentrated under reduced pressure and co-evaporated with dichloroethane (50 mL)

Sources & evidence

ORD record
ord-3a2291bb1e3f4a8e8ab979e7684030bc
Source dataset
uspto-grants-2015_09
Patent number
US09133224B2

Reaction notes

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