Bromine → 6-Bromo-7-(1,1-dimethylethyl)-2-(trifluoromethyl)-2h-1-benzopyran-3-carboxylic acid

HRID 1421572Notes

Reaction equation

HRID 1421572 reaction equation
[CH3:1][C:2]([C:5]1[CH:21]=[CH:20][C:8]2[CH:9]=[C:10]([C:17]([OH:19])=[O:18])[CH:11]([C:13]([F:16])([F:15])[F:14])[O:12][C:7]=2[CH:6]=1)([CH3:4])[CH3:3].[Br:22]Br>[Fe].C(Cl)(Cl)Cl>[Br:22][C:21]1[C:5]([C:2]([CH3:1])([CH3:3])[CH3:4])=[CH:6][C:7]2[O:12][CH:11]([C:13]([F:14])([F:15])[F:16])[C:10]([C:17]([OH:19])=[O:18])=[CH:9][C:8]=2[CH:20]=1

Participants

5

Reactant 2

HCID 24408BromineHCID 99044067-(1,1-Dimethylethyl)-2-trifluoromethyl-2h-1-benzopyran-3-carboxylic acid

Product 1

HCID 218836796-Bromo-7-(1,1-dimethylethyl)-2-(trifluoromethyl)-2h-1-benzopyran-3-carboxylic acid

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 6212ChloroformSolvent

Procedure

7-(1,1-Dimethylethyl-2-(trifluoromethyl)-2H-1-benzopyran-3-carboxylic acid (Example 12) (0.6 g, 2 mmol), chloroform (50 mL), iron filings (0.01 g, 0.2 mmol), and bromine (0.48 g, 3.00 mmol) were stirred at reflux for 16 h. The mixture was allowed to cool and was washed with brine (2×50 mL). After drying over MgSO4, the mixture was filtered, concentrated in vacuo, and the residue crystallized from ether-hexanes yielding the title compound as a white solid (0.5 g, 66%): mp 198.6-199.9° C. 1H NMR (acetone-d6 /300 MHz) 7.85 (s, 1H), 7.72 (s, 1H, 7.13 (s, 1H), 5.83 (q, 1H, J=7.2 Hz), 1.5 (s, 9H). Anal. Calc'd for C15H14O3F3Br: C, 47.52; H, 3.72; N, 21.07. Found: C, 47.42; H, 3.68; N, 21.15.

Workup

  1. temperatureat reflux for 16 h
  2. temperatureto cool
  3. washwas washed with brine (2×50 mL)
  4. dry with materialAfter drying over MgSO4
  5. filtrationthe mixture was filtered
  6. concentrationconcentrated in vacuo
  7. customthe residue crystallized from ether-hexanes yielding the title compound as a white solid (0.5 g, 66%)

Sources & evidence

ORD record
ord-c6e6d6acc02942ccb115d5600e99abc5
Source dataset
uspto-grants-2000_06
Patent number
US06077850

Reaction notes

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