Triphenylphosphine → [3-(2,6-Difluoro-3-nitrophenoxy)propyl]carbamic acid tert-butyl ester

HRID 243226Notes

Reaction equation

HRID 243226 reaction equation
[F:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=[C:4]([F:11])[C:3]=1[OH:12].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:32]([O:36][C:37](=[O:43])[NH:38][CH2:39][CH2:40][CH2:41]O)([CH3:35])([CH3:34])[CH3:33].N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[C:32]([O:36][C:37](=[O:43])[NH:38][CH2:39][CH2:40][CH2:41][O:12][C:3]1[C:4]([F:11])=[CH:5][CH:6]=[C:7]([N+:8]([O-:10])=[O:9])[C:2]=1[F:1])([CH3:35])([CH3:34])[CH3:33]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 3838134tert-butyl N-(3-hydroxypropyl)carbamateHCID 537967812,6-Difluoro-3-nitrophenol

Product 1

HCID 68157251[3-(2,6-Difluoro-3-nitrophenoxy)propyl]carbamic acid tert-butyl esterYield 92%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a solution of 2,6-difluoro-3-nitrophenol (170 mg, 0.971 mmol) and triphenylphosphine (383 mg, 1.46 mmol) in THF (8 mL) was added a solution of (3-hydroxypropyl)carbamic acid tert-butyl ester (204 mg, 1.165 mmol) in THF (1 mL). The mixture was cooled in an ice bath and a solution of diethyl azodicarboxylate (255 mg, 1.46 mmol) in THF (1 mL) was added. The reaction was stirred at RT for 30 min, then concentrated in vacuo. The resulting residue was purified by column chromatography (Si—PCC, eluant 25-40% EtOAc in cyclohexane) affording the title compound as a colourless gum (296 mg, 92%). 1H NMR (CDCl3, 300 MHz): 7.81 (1H, ddd, J=9.4, 7.8, 5.3 Hz), 7.04 (1H, dt, J=9.4, 2.2 Hz), 4.77 (1H, bs), 4.27 (2H, t, J=6.0 Hz), 3.37 (2H, q, J=6.4 Hz), 2.00 (2H, quintet, J=6.3 Hz), 1.45 (9H, s)

Workup

  1. temperatureThe mixture was cooled in an ice bath
  2. concentrationconcentrated in vacuo
  3. customThe resulting residue was purified by column chromatography (Si—PCC, eluant 25-40% EtOAc in cyclohexane)

Sources & evidence

ORD record
ord-1d39278d662249e5a56eb405fe82a9d0
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Reaction notes

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