2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 7-Fluoroquinolin-2(1H)-one

HRID 1191341Notes

Reaction equation

HRID 1191341 reaction equation
C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N.[F:15][C:16]1[CH:25]=[C:24]2[C:19]([CH2:20][CH2:21][C:22](=[O:26])[NH:23]2)=[CH:18][CH:17]=1>O1CCOCC1>[F:15][C:16]1[CH:25]=[C:24]2[C:19]([CH:20]=[CH:21][C:22](=[O:26])[NH:23]2)=[CH:18][CH:17]=1

Participants

4

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 138300Carbostyril, 3,4-dihydro-7-fluoro-

Product 1

HCID 190675757-Fluoroquinolin-2(1H)-oneYield 18.9%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

DDQ (0.42 g, 1.9 mmol) was added to a solution of 7-fluoro-3,4-dihydro-1H-quinolin-2-one (0.20 g 1.2 mmol) in dioxane (25 mL) and the resulting mixture was refluxed under an Argon atmosphere for 16 h. The mixture was concentrated under reduced pressure and sat aqueous Na2CO3 solution (25 mL) was added, and this was extracted with an organic mixture (MeOH/CH2Cl2 1:10, 3×50 mL). The combined organic phase was dried (Na2SO4), filtered, concentrated under reduced pressure and purified by combi flash LC (SiO2; CH2Cl2/MeOH 10:1) to give the title compound (0.037 g, 18%). 1H NMR (DMSO-D6) δ 11.8 (s, 1H), 7.88 (d, J=9.6 Hz, 1H), 7.74-7.65 (m, 1H), 7.05-6.95 (m, 2H), 6.43, (d, J=9.6 Hz); 13C NMR (CDMSO-D6) δ 163.0 (d, J=247 Hz), 161.9, 140.4 (d, J=13 Hz), 130.4 (d, J=11 Hz), 120.9, 116.1, 109.8 (d, J=23), 101.0 (d, J=25 Hz).

Workup

  1. temperaturethe resulting mixture was refluxed under an Argon atmosphere for 16 h
  2. concentrationThe mixture was concentrated under reduced pressure
  3. additionwas added
  4. extractionthis was extracted with an organic mixture (MeOH/CH2Cl2 1:10, 3×50 mL)
  5. dry with materialThe combined organic phase was dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. custompurified by combi flash LC (SiO2; CH2Cl2/MeOH 10:1)

Sources & evidence

ORD record
ord-e1a030b429724b7c838a795b5e3fda33
Source dataset
uspto-grants-2014_03
Patent number
US08680115B2

Reaction notes

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