Hydrochloric Acid → HCID 21883545, compound

HRID 722385Notes

Reaction equation

HRID 722385 reaction equation
[F:1][C:2]([F:6])([F:5])[CH2:3][OH:4].[H-].[Na+].[Cl:9][C:10]1[C:11](F)=[CH:12][C:13]2[O:18][CH:17]([C:19]([F:22])([F:21])[F:20])[C:16]([C:23]([O-:25])=[O:24])=[CH:15][C:14]=2[CH:26]=1.Cl.O1CCO[CH2:31][CH2:30]1>>[Cl:9][C:10]1[C:11]([O:4][CH2:3][C:2]([F:6])([F:5])[F:1])=[CH:12][C:13]2[O:18][CH:17]([C:19]([F:22])([F:21])[F:20])[C:16]([C:23]([O:25][CH2:30][CH3:31])=[O:24])=[CH:15][C:14]=2[CH:26]=1

Participants

6

Reactant 5

HCID 313Hydrochloric AcidHCID 64092,2,2-TrifluoroethanolHCID 24758Sodium hydrideHCID 312751,4-Dioxane3×HCID 21883706HCID 21883706, compound

Product 1

HCID 21883545HCID 21883545, compoundYield 18%

Conditions

Temperature
85 °C

Procedure

A solution of 2,2,2-trifluoroethanol(1.3 g, 13 mmol) in 1,4-dioxane (2 mL) was added to a slurry of NaH (0.5 g, 13 mmol) in 1,4-dioxane (2 mL). The reaction was stirred for 10 minutes then a solution of 6-chloro-7-fluoro-2-(trifluoromethyl)-2H-1-benzopyran-3-carboxylate (1.61 g, 5.0 mmol) in 1,4-dioxane (5 mL) was added and the reaction was heated to 85° C. for 22 hours. The reaction mixture was acidified with 3N HCl, extracted with ethyl acetate, washed with saturated NaHCO3, brine, dried over MgSO4 and concentrated in vacuo, to give a brown oil which was passed through a column of silica gel with 10% ethyl acetate/hexanes to give a white solid (0.37 g, 18%): 1H NMR (CDCl3/300 MHz) 7.62 (s, 1H), 7.28 (s, 1H), 6.58 (s, 1H), 5.69 (q, 1H, J=6.6 Hz), 4.42 (m, 2H), 4.31 (m, 2H), 1.34 (t, 3H, J=7.1 Hz). 19F NMR (CDCl3/282 MHz) −74.2 (t, 3F, J=8.0 Hz), −78.9 (d, 3F, J=6.5 Hz).

Workup

  1. extractionextracted with ethyl acetate
  2. washwashed with saturated NaHCO3, brine
  3. dry with materialdried over MgSO4
  4. concentrationconcentrated in vacuo
  5. customto give a brown oil which

Sources & evidence

ORD record
ord-234c62bb1bb445cc97c371af70154ebe
Source dataset
uspto-grants-2006_11
Patent number
US07138411B2

Reaction notes

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