N-bromobutanimide → Methyl 2'-(bromomethyl)-[1,1'-biphenyl]-4-carboxylate

HRID 1029583Notes

Reaction equation

HRID 1029583 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[CH3:17])=[CH:7][CH:6]=1)=[O:4].[Br:18]N1C(=O)CCC1=O>N(C(C)(C)C#N)=NC(C)(C)C#N.C(Cl)(Cl)(Cl)Cl>[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[CH2:17][Br:18])=[CH:7][CH:6]=1)=[O:4]

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 1392850Methyl 4-(2-methylphenyl)benzoate

Product 1

HCID 44886973Methyl 2'-(bromomethyl)-[1,1'-biphenyl]-4-carboxylateYield 78%

Reagents, catalysts & solvents 2

HCID 6547AzobisisobutyronitrileCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

A 5 L three-necked 24/40 round-bottom flask equipped with a mechanical stirrer, a reflux condenser with a nitrogen inlet at the top, and a thermometer was charged with 53.42 g (0.204 mol) of 2'-methylbiphenyl-4-carboxylic acid methyl ester, 3.4 L carbon tetrachloride, 38.09 g (0.214 mol) of N-bromosuccinimide and 2.0 g of 2,2'-azobis(2-methylpropionitrile). The flask was degassed and flushed with nitrogen, the stirrer was started and the contents were refluxed for 5 hours. The reaction mixture was then cooled to room temperature, filtered and evaporated. The residual oil was purified by recrystallization from dichloromethane-hexane to afford 48.48 g (78%) of the product which had: mp 80°-81° C.; NMR (CDCl3) δ3.94 (s, 3H), 4.40 (s, 2H), 7.20-7.26 (m, 1H), 7.32-7.41 (m, 2H), 7.48-7.54 (m, 3H), 8.12 (d, J=12 Hz, 2H); MS (EI) m/e 304, 306 (M+). Anal. (C15H13BrO2) C, H.

Workup

  1. customA 5 L three-necked 24/40 round-bottom flask equipped with a mechanical stirrer, a reflux condenser with a nitrogen inlet at the top
  2. customThe flask was degassed
  3. customflushed with nitrogen
  4. temperaturethe contents were refluxed for 5 hours
  5. filtrationfiltered
  6. customevaporated
  7. customThe residual oil was purified by recrystallization from dichloromethane-hexane

Sources & evidence

ORD record
ord-a178d472c9bc4d2686a81813f59ce921
Source dataset
uspto-grants-1992_04
Patent number
US05102880

Reaction notes

Loading…