Triethyl phosphite → Diethyl (2-fluoro-5-methoxy-4-nitrobenzyl)phosphonate

HRID 1947892Notes

Reaction equation

HRID 1947892 reaction equation
Cl[CH2:2][C:3]1[CH:8]=[C:7]([O:9][CH3:10])[C:6]([N+:11]([O-:13])=[O:12])=[CH:5][C:4]=1[F:14].[P:15]([O:22]CC)([O:19][CH2:20][CH3:21])[O:16][CH2:17][CH3:18]>>[F:14][C:4]1[CH:5]=[C:6]([N+:11]([O-:13])=[O:12])[C:7]([O:9][CH3:10])=[CH:8][C:3]=1[CH2:2][P:15](=[O:22])([O:19][CH2:20][CH3:21])[O:16][CH2:17][CH3:18]

Participants

3

Reactant 2

HCID 31215Triethyl phosphiteHCID 672551071-(Chloromethyl)-2-fluoro-5-methoxy-4-nitrobenzene2×

Product 1

HCID 86654021Diethyl (2-fluoro-5-methoxy-4-nitrobenzyl)phosphonateYield 35%

Conditions

Temperature
100 °C

Procedure

A mixture of 1-(chloromethyl)-2-fluoro-5-methoxy-4-nitrobenzene (Compound 130C, 1.578 g, 7.186 mmol) and triethyl phosphite (1.43 g, 8.62 mmol) was heated at 100° C. for 16 h in a sealed tube. After concentrating the reaction mixture under reduced pressure, the crude product was purified by silica gel chromatography on an ISCO combi-flash system using DCM/MeOH as eluent (100:0→95:5) to give an orange oil, 800 mg (35% yield). 1H NMR (CDCl3, 400 MHz): δ=1.30 (t, J=7.07 Hz, 6H), 3.20-3.27 (m, 2H), 3.97 (s, 3H), 4.11 (dd, J=8.08, 7.07 Hz, 4H), 7.17 (dd, J=5.94, 2.65 Hz, 1H), 7.67 (dd, J=8.72, 0.88 Hz, 1H). MS (ES+): m/z 322.09 [MH+] (TOF, polar).

Workup

  1. concentrationAfter concentrating the reaction mixture under reduced pressure
  2. customthe crude product was purified by silica gel chromatography on an ISCO combi-flash system
  3. customto give an orange oil, 800 mg (35% yield)

Sources & evidence

ORD record
ord-c30f3c8566024232af514ba57c12ac7d
Source dataset
uspto-grants-2013_03
Patent number
US08399433B2

Reaction notes

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