Triethyl phosphite → Diethyl 3-Nitrobenzylphosphonate

HRID 511209Notes

Reaction equation

[N+:1]([C:4]1[CH:5]=[C:6]([CH:9]=[CH:10][CH:11]=1)[CH2:7]Br)([O-:3])=[O:2].[P:12]([O:19]CC)([O:16][CH2:17][CH3:18])[O:13][CH2:14][CH3:15]>>[N+:1]([C:4]1[CH:5]=[C:6]([CH:9]=[CH:10][CH:11]=1)[CH2:7][P:12](=[O:19])([O:16][CH2:17][CH3:18])[O:13][CH2:14][CH3:15])([O-:3])=[O:2]

Participants

Reactant 2

HCID 31215Triethyl phosphite

HCID 77568Benzene, 1-(bromomethyl)-3-nitro-

Product 1

HCID 13675396Diethyl 3-NitrobenzylphosphonateYield 98%

Conditions

Temperature: 140 °C

Procedure

A mixture of 3-nitrobenzyl bromide (648 mg, 3.00 mmol) and triethyl phosphite (0.669 mL, 3.90 mmol) was stirred at 140° C. under nitrogen for 16 h. The excess triethyl phosphite was removed under reduced pressure and the residue purified by chromatography over silica gel eluting with 2% MeOH in dichloromethane to afford diethyl (3-nitrobenzyl)phosphonate, 0.80 g (yield: 98%). 1H-NMR (CD3OD, 400 MHz): δ=1.27 (t, J=6.8 Hz, 6 H), 3.43 (d, J=22.0 Hz, 2 H), 4.08 (q, J=6.8 Hz, 4 H), 7.58 (t, J=8.0 Hz, 1 H), 7.72 (d, J=7.6 Hz, 1 H), 8.15 (d, J=8.4 Hz, 1 H), 8.22 (d, J=2.4 Hz, 1 H). MS (ES+): m/z 273.99 (MH+). HPLC: tR=2.92 min (ZQ3, polar—5 min).

Workup

customThe excess triethyl phosphite was removed under reduced pressure
customthe residue purified by chromatography over silica gel eluting with 2% MeOH in dichloromethane

Sources & evidence

ORD record: ord-2d113f11fe4e4cddb578b69490e086aa
Source dataset: uspto-grants-2015_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09096624B2

Reaction notes

Loading…