Benzoyl Peroxide → 2-Tert-butoxycarbonylmethyl-5-bromomethyl benzoic acid tert-butyl ester

HRID 1170039Notes

Reaction equation

HRID 1170039 reaction equation
[C:1]([O:5][C:6](=[O:22])[C:7]1[CH:12]=[C:11]([CH3:13])[CH:10]=[CH:9][C:8]=1[CH2:14][C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])([CH3:4])([CH3:3])[CH3:2].[Br:23]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl>[C:1]([O:5][C:6](=[O:22])[C:7]1[CH:12]=[C:11]([CH2:13][Br:23])[CH:10]=[CH:9][C:8]=1[CH2:14][C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])([CH3:3])([CH3:4])[CH3:2]

Participants

5

Reactant 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 121113512-Tert-butoxycarbonylmethyl-5-methyl benzoic acid tert-butyl ester

Product 1

HCID 537042462-Tert-butoxycarbonylmethyl-5-bromomethyl benzoic acid tert-butyl esterYield 38.3%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

2-Tert-butoxycarbonylmethyl-5-methyl benzoic acid tert-butyl ester (4.751, 15.5 mmol) was dissolved in 75 ml of CCl4. To the solution was added N-bromosuccinimide (2.90 g, 16.3 mmol, 1.05 equivalents) and benzoyl peroxide (180 mg). The reaction mixture was refluxed under an argon atmosphere overnight; the reaction mixture was then cooled to room temperature, and the solid precipitate was filtered off, and washed with hexanes, the combined organic was taken to dryness and the residue was purified by chromatography to obtain 2-tert-butoxycarbonylmethyl-5-bromomethyl benzoic acid tert-butyl ester 2.286 g (38.3% yield) as an oil. 1H NMR (CDCl3): 7.920 (1H, d, J=2.2 Hz), 7.460 (1H, dd, J=1.95, 7.81 Hz), 7.193 (1H, d, J=7.81 Hz), 4.500 (2H, s), 3.953 (2H, s), 1.590 (9H, s), 1.444 (9H, s). FABMS (+Ve), m/z 387 [MH+, 81Br], 385 [MH+, 79Br], 331 [MH+−C4H8, 81Br], 329 [MH+−C4H8, 79Br], 275 [MH+−2C4H8, 81Br], 273 [MH+−2C4H8, 79Br]. Anal. calcd. for C18H25BrO4: C, 56.1; H, 6.5; Br, 20.7. Found: C, 56.27; H, 6.60; Br, 20.75.

Workup

  1. temperatureThe reaction mixture was refluxed under an argon atmosphere overnight
  2. filtrationthe solid precipitate was filtered off
  3. washwashed with hexanes
  4. customthe residue was purified by chromatography

Sources & evidence

ORD record
ord-bfc3571be2544ae69873589445f48362
Source dataset
uspto-grants-2010_11
Patent number
US07825216B2

Reaction notes

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