Hydrochloric Acid → HCID 21883641, compound

HRID 722314Notes

Reaction equation

HRID 722314 reaction equation
[F:1][C:2]([F:19])([F:18])[CH:3]1[C:8]([C:9]([O:11][CH2:12][CH3:13])=[O:10])=[CH:7][C:6]2[CH:14]=[CH:15][CH:16]=[CH:17][C:5]=2[O:4]1.[Cl-].[Al+3].[Cl-].[Cl-].[C:24](Cl)(=[O:31])[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1.Cl>ClCCCl>[C:24]([C:15]1[CH:16]=[CH:17][C:5]2[O:4][CH:3]([C:2]([F:1])([F:18])[F:19])[C:8]([C:9]([O:11][CH2:12][CH3:13])=[O:10])=[CH:7][C:6]=2[CH:14]=1)(=[O:31])[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 7412Benzoyl chlorideHCID 6451240Aluminum(III) ChlorideHCID 218835922H-1-Benzopyran-3-carboxylic acid, 2-(trifluoromethyl)-, ethyl ester

Product 1

HCID 21883641HCID 21883641, compoundYield 12%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent3×

Conditions

Temperature
80 °C

Procedure

Ethyl 2-(trifluoromethyl)-2H-1-benzopyran-3-carboxylate (Example 10, Step 1)(1.59 g, 5.8 mmol) was dissolved in 1,2-dichloroethane (3 mL) and added to a 0° C. suspension of aluminum chloride (2.59 g, 19.4 mmol) in 1,2-dichloroethane (3 mL). A solution of benzoyl chloride (1.01 g, 7.2 mmol) in 1,2-dichloroethane (3 mL) was added and the reaction was heated to 80° C. and stirred for 4 hours. The solution was poured onto 3 N HCl and ice and extracted with ethyl acetate. The ethyl acetate layers were combined, washed with 3N HCl, saturated sodium bicarbonate, brine, dried over MgSO4 and concentrated in vacuo. The crude ester was purified by flash chromatography over silica gel (with 1:9 ethyl acetate/hexane as eluant) to afford the ester as a white crystalline solid (0.26 g, 12%): mp 114.7–116.1° C. 1H NMR (CDCl3/300 MHz) 7.82 (dd, 1H, J=8.5 Hz 2.0 Hz), 7.76 (m, 4H), 7.61 (m, 1H), 7.50 (m, 2H), 7.09 (d, 1H, J=8.7 Hz), 5.79 (q, 1H, J=6.8 Hz), 4.34 (m, 2H), 1.36 (t, 3H, J=7.2 Hz).

Workup

  1. additionadded to a 0° C.
  2. extractionextracted with ethyl acetate
  3. washwashed with 3N HCl, saturated sodium bicarbonate, brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated in vacuo
  6. customThe crude ester was purified by flash chromatography over silica gel (with 1:9 ethyl acetate/hexane as eluant)

Sources & evidence

ORD record
ord-9aa0e63dc47b40a0a75b8f6d64d40e03
Source dataset
uspto-grants-2006_11
Patent number
US07138411B2

Reaction notes

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