Acetonitrile → HCID 18761406, compound

HRID 431716Notes

Reaction equation

HRID 431716 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:20]([Br:24])(Br)(Br)Br.CC#N.[CH2:28]([O:35][C:36]1[CH:41]=[CH:40][C:39]([CH2:42]CO)=[C:38]([N+:45]([O-:47])=[O:46])[CH:37]=1)[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1>CCOC(C)=O.CCCCCC>[CH2:28]([O:35][C:36]1[CH:41]=[CH:40][C:39]([CH2:42][CH2:20][Br:24])=[C:38]([N+:45]([O-:47])=[O:46])[CH:37]=1)[C:29]1[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=1

Participants

6

Reactant 4

HCID 6342AcetonitrileHCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 18761444HCID 18761444, compound

Product 1

HCID 18761406HCID 18761406, compoundYield 97.3%

Reagents, catalysts & solvents 1

HCID 21226206Ethyl acetate hexaneSolvent

Procedure

Triphenylphosphine (1.92 g, 7.33 mmol), CBr4 (7.28 g, 21.96 mmol), and dry CH3CN (16.6 mL) were added to a round bottom flask containing 2-(4-benzyloxy-2-nitrophenyl)ethanol (1.00 g, 3.66 mmol). A red solution resulted which was allowed to stir overnight under a positive pressure of nitrogen. The solution was checked by TLC (20% EtOAc/hexane) and concentrated down on a rotoevaporator. The excess CBr4 was removed by vacuum kugelrohr distillation (60° C., 0.25 mmHg). Column chromatography (SiO2, 10% EtOAc/5% CHCl3/85% petroleum ether gradient elution) afforded 2-(4-benzyloxy-2-nitrophenyl)ethyl bromide as a brownish solid (1.33 g, 3.56 mmol, 92%). Mp 30-34° C.; TLC (20% EtOAc/hexane) Rf=0.48; 1H-NMR (CDCl3, 500 MHz) 7.52 (d, 2.5, 1H), 7.34 (m, 5H), 7.24 (d, 8.5, 1H), 7.11 (dd, 2.5, 8.5, 1H), 5.04 (s, 2H), 3.57 (t, 7.0, 2H), 3.30 (t, 7.0, 2H); 13C-NMR (CDCl3, 125 MHz) 158.0, 149.4, 135.6, 133.8, 128.7, 128.4, 127.5, 125.8, 120. 5, 110.8, 70.6, 35.9, 32.0; IR (neat) 3070, 3027, 2919, 2855, 1618, 1570, 1526, 1499, 1451, 1408, 1381, 1343, 1289, 1262, 1240, 1149, 1025, 842, 804, 733, 695; EI-MS m/z (relative intensity) 335 (M+, 9); isotope pattern of M+ and M++2 agrees with the presence of one bromine atom. Accurate mass (EI-MS) for C15H14NO3Br: calcd. 335.0157, obsd. 335.0160.

Workup

  1. customA red solution resulted which
  2. concentrationconcentrated down on a rotoevaporator
  3. customThe excess CBr4 was removed by vacuum kugelrohr distillation (60° C., 0.25 mmHg)
  4. washColumn chromatography (SiO2, 10% EtOAc/5% CHCl3/85% petroleum ether gradient elution)

Sources & evidence

ORD record
ord-766fb16e06734eea83140bff60c17296
Source dataset
uspto-grants-2003_12
Patent number
US06660742B2

Reaction notes

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