Acetic Acid → HCID 9801143, compound

HRID 393310Notes

Reaction equation

HRID 393310 reaction equation
[Cl:1]Cl.C(O)(=O)C.[CH3:7][O:8][C:9]1[CH:32]=[CH:31][C:12]([O:13][C:14]2[CH:15]=[CH:16][C:17]3[O:22][CH:21]([C:23]([F:26])([F:25])[F:24])[C:20]([C:27]([OH:29])=[O:28])=[CH:19][C:18]=3[CH:30]=2)=[CH:11][CH:10]=1>>[Cl:1][C:32]1[CH:31]=[C:12]([CH:11]=[CH:10][C:9]=1[O:8][CH3:7])[O:13][C:14]1[CH:15]=[CH:16][C:17]2[O:22][CH:21]([C:23]([F:26])([F:25])[F:24])[C:20]([C:27]([OH:29])=[O:28])=[CH:19][C:18]=2[CH:30]=1

Participants

4

Reactant 3

HCID 176Acetic Acid3×HCID 24526Chlorine3×HCID 9842095HCID 9842095, compound

Product 1

HCID 9801143HCID 9801143, compoundYield 53%

Procedure

To a stirred solution of chlorine in acetic acid (3.5 mL of 0.24 M solution, 0.84 mmol) was added 6-(4-methoxyphenoxy)-2-(trifluoromethyl)-2H-1-benzopyran-3-carboxylic acid (0.31 g, 0.85 mmol) (Example 7). After 1hour additional chlorine in acetic acid (1.5 mL of 0.24 M solution, 0.36 mmol) was added. After three additional hours additional chlorine in acetic acid (0.25 ml of 0.25 M solution, 0.06 mmol) was added. After 2.5 hours the reaction was quenched with aqueous 10% sodium bisulfite solution and the resulting mixture extracted with ethyl acetate. The organic phase was washed with water, brine, dried over MgSO4, filtered, and concentrated in vacuo yielding a brown oil. The oil was dissolved in a minimum of hexanes which induced crystallization. Vacuum filtration of the mixture provided the title compound as yellow crystals (0.18 g, 53%): mp 205-207° C. 1H NMR (acetone-d6/300 MHz) 7.89 (s, 1H), 6.97-7.18 (m, 6H), 5.83 (q, 1H, J=7.0 Hz), 3.90 (s, 3H). FABLRMS m/z 400 (M+). FABHRMS m/z 399.0249 (M−H, Calc'd 399.0247). Anal. Calc'd for C18H12ClF3O5: C, 53.95; H, 3.02; Cl, 8.85. Found: C, 53.78; H, 3.08; Cl, 8.98.

Workup

  1. customAfter 2.5 hours the reaction was quenched with aqueous 10% sodium bisulfite solution
  2. extractionthe resulting mixture extracted with ethyl acetate
  3. washThe organic phase was washed with water, brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customyielding a brown oil
  8. customcrystallization
  9. filtrationVacuum filtration of the mixture

Sources & evidence

ORD record
ord-f66f0ac066c6474cb12ace72f6e01baf
Source dataset
uspto-grants-2004_10
Patent number
US06806288B1

Reaction notes

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