Carbon Tetrachloride → Ethyl 4-(bromomethyl)-3-(4-methoxyphenyl)-7-(pivaloyloxy)isoxazolo[4,5-c]pyridine-6-carboxylate

HRID 2388229Notes

Reaction equation

HRID 2388229 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[C:13]3[C:14]([CH3:30])=[N:15][C:16]([C:25]([O:27][CH2:28][CH3:29])=[O:26])=[C:17]([O:18][C:19](=[O:24])[C:20]([CH3:23])([CH3:22])[CH3:21])[C:12]=3[O:11][N:10]=2)=[CH:5][CH:4]=1.C1C(=O)N([Br:38])C(=O)C1.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.C(Cl)(Cl)(Cl)Cl>C(Cl)Cl>[Br:38][CH2:30][C:14]1[C:13]2[C:9]([C:6]3[CH:7]=[CH:8][C:3]([O:2][CH3:1])=[CH:4][CH:5]=3)=[N:10][O:11][C:12]=2[C:17]([O:18][C:19](=[O:24])[C:20]([CH3:23])([CH3:22])[CH3:21])=[C:16]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[N:15]=1

Participants

6

Reactant 4

HCID 5943Carbon TetrachlorideHCID 7187Benzoyl Peroxide2×HCID 67184N-bromobutanimide2×HCID 67530063Ethyl 3-(4-methoxyphenyl)-4-methyl-7-(pivaloyloxy)isoxazolo[4,5-c]pyridine-6-carboxylate

Product 1

HCID 67529608Ethyl 4-(bromomethyl)-3-(4-methoxyphenyl)-7-(pivaloyloxy)isoxazolo[4,5-c]pyridine-6-carboxylateYield 49.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Ethyl 3-(4-methoxyphenyl)-4-methyl-7-(pivaloyloxy)isoxazolo[4,5-c]pyridine-6-carboxylate (58 mg, 0.14 mmol), NBS (28 mg, 0.15 mmol) and benzoyl peroxide (3.4 mg, 0.014 mmol) were added to 3 mL of carbon tetrachloride. The mixture was refluxed for 16 h. After the mixture was cooled to room temperature, another 1 equiv of NBS and 0.1 equiv of benzoyl peroxide were added, and the reaction mixture was refluxed for an additional 16 h. After the mixture was cooled, 20 mL of CH2Cl2 and 1 g of silica gel were added, and the solvent was removed in vacuo. The crude was purified by flash chromatography (0-30% EtOAc/hexanes) to give 34 mg of the title compound. MS: (+) m/z 491.28, 493.25 (M+1, 79Br/81Br).

Workup

  1. temperatureThe mixture was refluxed for 16 h
  2. temperaturethe reaction mixture was refluxed for an additional 16 h
  3. temperatureAfter the mixture was cooled
  4. customthe solvent was removed in vacuo
  5. customThe crude was purified by flash chromatography (0-30% EtOAc/hexanes)

Sources & evidence

ORD record
ord-f8d1809e814b42d1a64acdd3fe816790
Source dataset
uspto-grants-2012_09
Patent number
US08269008B2

Reaction notes

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