Benzoyl Peroxide → 2-Bromomethyl-5-nitro-benzenesulfonic Acid, 2,2-Dimethylpropyl Ester

HRID 277583Notes

Reaction equation

HRID 277583 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1[S:11]([O:14][CH2:15][C:16]([CH3:19])([CH3:18])[CH3:17])(=[O:13])=[O:12].C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.[Br:38]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl.C(OCC)(=O)C>[Br:38][CH2:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1[S:11]([O:14][CH2:15][C:16]([CH3:19])([CH3:18])[CH3:17])(=[O:13])=[O:12]

Participants

6

Reactant 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 571129482-Methyl-5-nitro-benzenesulfonic acid, 2,2-dimethylpropyl ester

Product 1

HCID 571929642-Bromomethyl-5-nitro-benzenesulfonic Acid, 2,2-Dimethylpropyl EsterYield 44%

Reagents, catalysts & solvents 2

HCID 5943Carbon TetrachlorideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 2-methyl-5-nitro-benzenesulfonic acid, 2,2-dimethylpropyl ester, Example 24 (1.0 g, 3.48 mmol) in dry carbon tetrachloride (50 mL) was added 126 mg (0.52 mmol) of benzoyl peroxide and 712 mg (4.0 mmol) of recrystallized N-bromosuccinimide. A reflux condensor was attached and the mixture was heated to reflux and stirred overnight. After cooling to room temperature the reaction mixture was diluted with ethyl acetate (250 mL) and washed with water, followed by saturated sodium bicarbonate, and then brine. The organic layer was dried (MgSO4) and concentrated to dryness on a rotary evaporator. Purification by flash column chromatography using 10% ethyl acetate in hexanes gave 560 mg (44%) of the title compound as a white solid: 1HNMR (CDCl3): d 8.83 (d, J=2 Hz, 1H), 8.48 (dd, J=2 Hz, 9 Hz, 1H), 7.92 (d, J=9 Hz, 1H), 4.96 (s, 2H), 3.85 (s, 2H), 1.0 (s, 9H); MS (ES-NEG): [M−H] 364/366; Anal. Calc. for C12H16BrNO5S: C, 39.35; H, 4.40; N, 3.82. Found: C, 39.88; H, 4.16; N, 3.85.

Workup

  1. temperaturethe mixture was heated
  2. temperatureto reflux
  3. washwashed with water
  4. dry with materialThe organic layer was dried (MgSO4)
  5. concentrationconcentrated to dryness on a rotary evaporator
  6. customPurification by flash column chromatography

Sources & evidence

ORD record
ord-6b688e3473e84eedbf8508862a80a047
Source dataset
uspto-grants-2002_03
Patent number
US06355633B1

Reaction notes

Loading…