Cesium carbonate → Diethyl(4-nitrophenyl)phosphonate

HRID 472666

Reaction equation

HRID 472666 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[P:17]([O-:24])([O:21][CH2:22][CH3:23])[O:18][CH2:19][CH3:20]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:19]([O:18][P:17]([C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1)(=[O:24])[O:21][CH2:22][CH3:23])[CH3:20]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 114661-Bromo-4-nitrobenzeneHCID 3780918Diethylphosphite

Product 1

HCID 284865Diethyl(4-nitrophenyl)phosphonate

Reagents, catalysts & solvents 1

HCID 178418397HCID 178418397, compoundCatalyst

Procedure

A mixture of 1-bromo-4-nitrobenzene (400 mg, 2.00 mmol), tetrakis(triphenylphosphine)palladium(0) (120 mg, 0.20 mmol) and cesium carbonate (734 mg, 2.2 mmol) in a 30 mL microwave vial was purged and backfilled with nitrogen. Tetrahydrofuran (20 mL) was added followed by diethyl phosphite (0.360 mL, 2.8 mmol). The mixture was vortexed, then microwaved for 45 minutes at 120° C. Reaction was repeated three times to achieve total scale then the combined reaction mixtures were purified via chromatography (120 g silica gel 5%->75% ethyl acetate in hexane). (4-Nitro-phenyl)-phosphonic acid diethyl ester isolated as a light yellow oil (969 mg, 47%). 1H NMR (400 MHz, (D3C)2SO, δ, ppm): 8.35 (d, J=8.0 Hz, 2H), 7.16 (s, 1H), 5.93 (s, 2H), 3.40 (s, 4H), 2.36 (s, 4H), 2.20 (s, 3H), 8.05-7.95 (m, 2H), 4.09 (m, 4H), 1.25 (t, J=13.8, 7.4 Hz, 6H).

Workup

  1. customwas purged
  2. additionTetrahydrofuran (20 mL) was added
  3. custommicrowaved for 45 minutes at 120° C
  4. customReaction
  5. customthe combined reaction mixtures
  6. customwere purified via chromatography (120 g silica gel 5%->75% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-2493498a82fd449393526b3bf9ea033c
Source dataset
uspto-grants-2014_01
Patent number
US08633173B2

Linked notes

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