Benzyl Bromide → HCID 76837484, compound

HRID 2375233Notes

Reaction equation

HRID 2375233 reaction equation
[C:1]([O:4][C:5]1[CH:10]=[CH:9][C:8]([C:11]([NH:13][O:14][CH2:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[O:12])=[CH:7][CH:6]=1)(=[O:3])[CH3:2].[CH2:22](Br)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.CN(C)P(=O)(N(C)C)N(C)C>C1C=CC=CC=1>[C:1]([O:4][C:5]1[CH:6]=[CH:7][C:8]([C:11]([O:12][CH2:22][C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[N:13][O:14][CH2:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[CH:9][CH:10]=1)(=[O:3])[CH3:2].[C:1]([O:4][C:5]1[CH:6]=[CH:7][C:8]([C:11]([N:13]([CH2:22][C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[O:14][CH2:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[O:12])=[CH:9][CH:10]=1)(=[O:3])[CH3:2]

Participants

6

Reactant 3

HCID 7498Benzyl BromideHCID 12679HexamethylphosphoramideHCID 32578092HCID 32578092, compound

Product 2

HCID 58611875HCID 58611875, compoundYield 28%HCID 76837484HCID 76837484, compoundYield 66%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

To a solution of 4-{[(benzyloxy)amino]carbonyl}phenyl acetate (18) (2.000 g, 7.0 mmol) and benzyl bromide (3.59 g, 21.0 mmol) in hexamethylphosphoric triamide (10 ml) Cs2CO3 (2.51 g, 7.7 mmol) was added and the reaction mixture was stirred at ambient temperature for 24 hours. The mixture was diluted with benzene (50 ml) and washed successively with water (2×30 ml), 2N HCl (30 ml), water (2×30 ml), brine (30 ml), and dried (Na2SO4). The solvent was evaporated and the residue was chromatographed on silica gel (100 g) with petroleum ether-benzene (1:1) and benzene-ethyl acetate (9:1) as eluents to give 4-{(benzyloxy)[(benzyloxy)imino]methyl}phenyl acetate (19) (1.743 g, 66%) as an oil, Rf 0.83 (toluene-ethyl acetate, 9:1), and 4-{[benzyl(benzyloxy)amino]-carbonyl}phenyl acetate (20) (0.744 g, 28%) as a white solid, Rf 0.48 (toluene-ethyl acetate, 9:1). (19): 1H NMR (DMSO-d6, HMDSO) δ: 2.24 (3H, s); 5.12 (2H, s); 5.32 (2H, s); 7.17 (2H, d, J=8.7 Hz); 7.25-7.54 (10H, m); 7.66 (2H, d, J=8.7 Hz). GC-MS, m/z (%): 375 (0.2), 268 (0.3), 253 (1), 227 (0.6), 211 (1.3), 196 (0.5), 180 (2.3), 163 (19.5), 121 (36), 107 (5.2), 91 (100), 77 (6), 65 (16). IR (film, cm−1): 1758, 1616, 1578, 1507. (20): 1H NMR (DMSO-d6, HMDSO) δ: 2.28 (3H, s); 4.72 (2H, s); 4.99 (2H, s); 6.88-7.10 (2H, m); 7.12-7.50 (8H, m); 7.22 (2H, d, J=8.0 Hz); 7.63 (2H, d, J=8.0 Hz). GC-MS, m/z (%):269 (36), 227 (27), 121 (100), 106 (25), 91 (46), 77 (14), 65 (26). IR (nujol, cm−1): 1756, 1663, 1604, 1578, 1507.

Workup

  1. washwashed successively with water (2×30 ml), 2N HCl (30 ml), water (2×30 ml), brine (30 ml)
  2. dry with materialdried (Na2SO4)
  3. customThe solvent was evaporated
  4. customthe residue was chromatographed on silica gel (100 g) with petroleum ether-benzene (1:1) and benzene-ethyl acetate (9:1) as eluents

Sources & evidence

ORD record
ord-9d27bd11db71414c926bc21f76d9f6a8
Source dataset
uspto-grants-2008_12
Patent number
US07465719B2

Reaction notes

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