Potassium Carbonate → Diethyl 5,8-bis(2,2,2-trifluoroethoxy)quinoline-6,7-dicarboxylate

HRID 907468Notes

Reaction equation

HRID 907468 reaction equation
[OH:1][C:2]1[C:11]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[C:10]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:9]([OH:22])=[C:8]2[C:3]=1[CH:4]=[CH:5][CH:6]=[N:7]2.FC(F)(F)S(O[CH2:29][C:30]([F:33])([F:32])[F:31])(=O)=O.C([O-])([O-])=O.[K+].[K+].[NH4+].[Cl-]>CN(C=O)C>[F:31][C:30]([F:33])([F:32])[CH2:29][O:1][C:2]1[C:11]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[C:10]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:9]([O:22][CH2:29][C:30]([F:31])([F:32])[F:33])=[C:8]2[C:3]=1[CH:4]=[CH:5][CH:6]=[N:7]2

Participants

6

Reactant 4

HCID 11430Potassium CarbonateHCID 25517Ammonium ChlorideHCID 803662,2,2-Trifluoroethyl trifluoromethanesulfonateHCID 135932593Diethyl 5,8-dihydroxy-6,7-quinolinedicarboxylate

Product 1

HCID 44245003Diethyl 5,8-bis(2,2,2-trifluoroethoxy)quinoline-6,7-dicarboxylateYield 95.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A mixture containing diethyl 5,8-dihydroxyquinoline-6,7-dicarboxylate 2 (57.8 g, 189 mmol), 2,2,2-trifluoroethyl trifluoromethanesulfonate (100 g, 2.28 equiv) and K2CO3 (62.7 g, 2.4 equiv) in DMF (300 ml) was heated to 70 C for an hour. This mixture was cooled down to r.t. and added to half-saturated NH4Cl (1.5 L). After acidification with AcOH (60 ml), the product was extracted with toluene twice and once with 50% EtOAc/toluene. The combined organics were dried over Na2SO4 and filtered through a 1.2 L pad of silica to remove the polar material. The silica was washed with 10% EtOAc/toluene. Evaporation of the solvents afforded 84.68 g (95% yield) of pure product 3.

Workup

  1. temperaturewas heated to 70 C for an hour
  2. extractionAfter acidification with AcOH (60 ml), the product was extracted with toluene twice
  3. dry with materialThe combined organics were dried over Na2SO4
  4. filtrationfiltered through a 1.2 L pad of silica
  5. customto remove the polar material
  6. washThe silica was washed with 10% EtOAc/toluene
  7. customEvaporation of the solvents

Sources & evidence

ORD record
ord-7eed480ac46b4d4f9d988da2c0062d1a
Source dataset
uspto-grants-2011_09
Patent number
US08013159B2

Reaction notes

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