2,4-Dihydroxybenzaldehyde → HCID 69517747, compound

HRID 854858Notes

Reaction equation

HRID 854858 reaction equation
[OH:1][C:2]1[CH:9]=[C:8]([OH:10])[CH:7]=[CH:6][C:3]=1[CH:4]=O.[F:11][C:12]([F:21])([F:20])/[CH:13]=[CH:14]/[C:15]([O:17][CH2:18][CH3:19])=[O:16].C([O-])([O-])=O.[K+].[K+]>CN(C=O)C.Cl>[OH:10][C:8]1[CH:9]=[C:2]2[C:3]([CH:4]=[C:14]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[CH:13]([C:12]([F:11])([F:21])[F:20])[O:1]2)=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 72132,4-DihydroxybenzaldehydeHCID 11430Potassium CarbonateHCID 5371261Ethyl (2E)-4,4,4-trifluoro-2-butenoate

Product 1

HCID 69517747HCID 69517747, compoundYield 31.6%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of 2,4-dihydroxy benzaldehyde (20.0 g, 0.145 mole) and ethyl 4,4,4-trifluorocrotonate (36.58 g, 0.217 mole) was dissolved in anhydrous DMF (40 mL). The solution was warmed to 60° C., treated with anhydrous K2CO3 (40.0 g, 0.290 mole), and maintained at 80° C. for 48 h. The reaction was cooled to room temperature, diluted with 3N HCl, and extracted with ethyl acetate. The combined extracts were washed with brine, dried over anhydrous MgSO4, filtered, and concentrated in vacuo to afford an oil. The oil was passed through the silica plug and the plug was washed with 20% EtOAc in hexane to give yellow solid (13.22 g, 31.6%): LCMS m/z 311.05 (M+Na). 1H NMR (CDCl3/400 MHz) 7.67 (s, 1H), 7.09 (d, 1H, J=8.8 Hz), 6.46 (m, 2H), 5.67 (q, 1H, J=6 Hz), 4.29 (q, 2H, J=7.2 Hz), 1.33 (t, 3H, J=7.2 Hz).

Workup

  1. temperaturemaintained at 80° C. for 48 h
  2. temperatureThe reaction was cooled to room temperature
  3. extractionextracted with ethyl acetate
  4. washThe combined extracts were washed with brine
  5. dry with materialdried over anhydrous MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto afford an oil
  9. washthe plug was washed with 20% EtOAc in hexane

Sources & evidence

ORD record
ord-f19f327773ae470599ee908ad9b003fa
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

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