Potassium Carbonate → ethyl 6-chloro-7-(2-chloro-4,5-dimethylphenoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate

HRID 855005Notes

Reaction equation

HRID 855005 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][C:11]=1F)[O:8][CH:7]([C:13]([F:16])([F:15])[F:14])[C:6]([C:17]([O:19][CH2:20][CH3:21])=[O:18])=[CH:5]2.[Cl:22][C:23]1[CH:28]=[C:27]([CH3:29])[C:26]([CH3:30])=[CH:25][C:24]=1[OH:31].C(=O)([O-])[O-].[K+].[K+].[Al]>CN(C=O)C.C(OCC)C.O>[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][C:11]=1[O:31][C:24]1[CH:25]=[C:26]([CH3:30])[C:27]([CH3:29])=[CH:28][C:23]=1[Cl:22])[O:8][CH:7]([C:13]([F:16])([F:15])[F:14])[C:6]([C:17]([O:19][CH2:20][CH3:21])=[O:18])=[CH:5]2

Participants

8

Reactant 4

HCID 11430Potassium CarbonateHCID 707542-Chloro-4,5-dimethylphenolHCID 5359268Aluminum2×HCID 21883602ethyl 6-chloro-7-fluoro-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Product 1

HCID 69518202ethyl 6-chloro-7-(2-chloro-4,5-dimethylphenoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Procedure

To 325 mg (1.0 mmole) of ethyl 6-chloro-7-fluoro-2-(trifluoromethyl)-2H-chromene-3-carboxylate in 2.5 mL of DMF was added 172 mg (1.1 mmole) of 2-chloro-4,5-dimethylphenol and 193.5 mg (1.4 mmole) of potassium carbonate. The suspension was prepared in a capped vial and placed in an aluminum heating block equipped with a shaker. The aluminum block was heated to 110° C. for 16 h. After allowing the vial to cool, the mixture was treated with 10 mL of water and 2 mL of diethyl ether. The organic layer was removed and the aqueous layer extracted two times with diethyl ether. Combined organic extracts were filtered through 5 g of silica and the silica washed with 10 mL of diethyl ether. The filtrates were concentrated under a stream of N2 to afford an off-white solid, which was used in the next step without further purification: 1H NMR (CDCl3/300 MHz) 1.36 (t, 3H, J=7.2 Hz), 2.25, (s, 3H), 2.27 (s, 3H), 4.32 (m, 2H), 5.66 (q, 1H, J=6.8 Hz), 6.27 (s, 1H), 6.93 (2, 1H), 7.25 (s, 1H), 7.33 (s, 1H), 7.66 (s, 1H); 19F NMR (CDCl3/300 MHz) −78.9 (d, 3F, J=6.2 Hz).

Workup

  1. customThe suspension was prepared in a capped vial and
  2. customequipped with a shaker
  3. temperatureto cool
  4. customThe organic layer was removed
  5. extractionthe aqueous layer extracted two times with diethyl ether
  6. filtrationCombined organic extracts were filtered through 5 g of silica
  7. washthe silica washed with 10 mL of diethyl ether
  8. concentrationThe filtrates were concentrated under a stream of N2
  9. customto afford an off-white solid, which
  10. customwas used in the next step without further purification

Sources & evidence

ORD record
ord-9870afe32ed4466b915ddc3b569c4284
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

Loading…