Bromine → 3-(8-Bromo-4,4-dimethyl-2-oxo-1,4-dihydro-2H-3,1-benzoxazin-6-yl)-5-fluorobenzonitrile

HRID 2191350Notes

Reaction equation

HRID 2191350 reaction equation
[CH3:1][C:2]1([CH3:22])[C:7]2[CH:8]=[C:9]([C:12]3[CH:13]=[C:14]([CH:17]=[C:18]([F:20])[CH:19]=3)[C:15]#[N:16])[CH:10]=[CH:11][C:6]=2[NH:5][C:4](=[O:21])[O:3]1.C([O-])(=O)C.[Na+].[Br:28]Br>C(O)(=O)C>[Br:28][C:11]1[C:6]2[NH:5][C:4](=[O:21])[O:3][C:2]([CH3:22])([CH3:1])[C:7]=2[CH:8]=[C:9]([C:12]2[CH:13]=[C:14]([CH:17]=[C:18]([F:20])[CH:19]=2)[C:15]#[N:16])[CH:10]=1

Participants

5

Reactant 3

HCID 24408BromineHCID 517045Sodium AcetateHCID 98391343-(4,4-dimethyl-2-oxo-2,4-dihydro-1H-benzo[d][1,3]oxazin-6-yl)-5-fluorobenzonitrile

Product 1

HCID 220219003-(8-Bromo-4,4-dimethyl-2-oxo-1,4-dihydro-2H-3,1-benzoxazin-6-yl)-5-fluorobenzonitrileYield 75.3%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

To a mixture of 3-(4,4-dimethyl-2-oxo-1,4-dihydro-2H-3,1-benzoxazin-6-yl)-5-fluorobenzonitrile (0.5 g, 1.7 mmol) and sodium acetate (0.2 g, 2.4 mmol) in acetic acid (5 mL) was added, at room temperature under nitrogen, bromine (0.12 mL, 2.34 mmol). The reaction mixture was stirred for 20 hours and then poured into ice water (30 mL). The precipitate was collected on a filter and washed with water (3×5 mL) to yield 3-(8-bromo-4,4-dimethyl-2-oxo-1,4-dihydro-2H-3,1-benzoxazin-6-yl)-5-fluorobenzonitrile as an off-white solid (0.48 g, 75%): mp 216-217° C.; 1H-NMR (DMSO-d6) δ 9.78 (s, 1H), 8.18 (t, 1H, J=1.6 Hz), 8.02-8.08 (m, 2H), 7.81 (m, 1H), 7.75 (d, 1H, J=1.8 Hz), 1.66 (s, 6H). MS (ESI) m/z 373, 375 [M−H]−.

Workup

  1. additionwas added, at room temperature under nitrogen
  2. customThe precipitate was collected on
  3. filtrationa filter
  4. washwashed with water (3×5 mL)

Sources & evidence

ORD record
ord-71c43753b28e469a849db9a8d2cc8505
Source dataset
uspto-grants-2012_12
Patent number
US08329690B2

Reaction notes

Loading…