Diethyl Ether → Diethyl[(4-nitrophenyl)(difluoro)methyl]phosphonate

HRID 511421Notes

Reaction equation

HRID 511421 reaction equation
[CH3:1][CH2:2][O:3][P:4]([O:10][CH2:11][CH3:12])([C:6](Br)([F:8])[F:7])=[O:5].I[C:14]1[CH:19]=[CH:18][C:17]([N+:20]([O-:22])=[O:21])=[CH:16][CH:15]=1.CCOCC>CN(C=O)C.Cl[Cu]>[N+:20]([C:17]1[CH:18]=[CH:19][C:14]([C:6]([P:4](=[O:5])([O:10][CH2:11][CH3:12])[O:3][CH2:2][CH3:1])([F:8])[F:7])=[CH:15][CH:16]=1)([O-:22])=[O:21]

Participants

6

Reactant 3

HCID 3283Diethyl EtherHCID 124951-Iodo-4-nitrobenzeneHCID 144101Bromodifluoromethyl diethylphosphonate

Product 1

HCID 10881410Diethyl[(4-nitrophenyl)(difluoro)methyl]phosphonateYield 86.4%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 6228DimethylformamideSolvent

Procedure

Under N2, a mixture of bromodifluoromethyl diethylphosphonate (0.427 g, 1.6 mmol) and Cd powder (180 mg, 1.6 mmol) in DMF (0.5 mL) was stirred at room temperature for 2 h. Most of Cd disappeared. 4-Iodo-1-nitrobenzene (249 mg, 1.00 mmol) and CuCl (115 mg, 1.16 mmol) were then added. The mixture was again stirred at room temperature for 3 h. Ether (20 mL) was added to the reaction mixture and the precipitated solids were filtered off and washed with 10 mL of ether. The combined ether layers were washed with NH4Cl (aq), dried over MgSO4, and evaporated to give the title product (267 mg, yield: 86%). 1H NMR (CD3OD, 400 MHz): δ=1.33 (t, J=7.2 Hz, 6 H), 4.20-4.28 (m, 4 H), 7.86 (d, J=8.4 Hz, 2 H), 8.39 (d, J=8.4 Hz, 2 H). MS (ES+): m/z 310.06 [MH+]. HPLC: tR=3.92 min (ZQ3, polar—5 min).

Workup

  1. stirringThe mixture was again stirred at room temperature for 3 h
  2. filtrationthe precipitated solids were filtered off
  3. washwashed with 10 mL of ether
  4. washThe combined ether layers were washed with NH4Cl (aq)
  5. dry with materialdried over MgSO4
  6. customevaporated

Sources & evidence

ORD record
ord-74edbd9c43fd48d09099dde919adc8eb
Source dataset
uspto-grants-2015_08
Patent number
US09096624B2

Reaction notes

Loading…