Dimethylformamide → HCID 58615379, compound

HRID 852986Notes

Reaction equation

HRID 852986 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N:8]=[CH:7][CH:6]=[C:5]2[O:12][CH3:13].C([Li])CCC.CN(C)[CH:21]=[O:22]>O1CCCC1.[Cl-].[NH4+].C(#N)C>[CH3:13][O:12][C:5]1[C:4]2[C:9](=[CH:10][CH:11]=[C:2]([CH:21]=[O:22])[CH:3]=2)[N:8]=[CH:7][CH:6]=1

Participants

7

Reactant 3

HCID 6228DimethylformamideHCID 457909296-Bromo-4-methoxyquinolineHCID 178418339Butyllithium

Product 1

HCID 58615379HCID 58615379, compoundYield 64%

Reagents, catalysts & solvents 3

HCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolvent2×HCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
-60 °C

Procedure

To a solution of 6-bromo-4-methoxy-quinoline (8.91 g, 37.42 mmol) in THF (tetrahydrofuran) (155 mL) was added dropwise a 2.5M solution of n-butyllithium in hexanes (16.46 mL, 4.16 mmol, 1.1 equiv.) at −70° C. During the addition, the temperature of the reaction mixture was raised slightly to −60° C. and it gave a very dark brown solution. The resulting colored solution was stirred for 30 min at this temperature. Then, a solution of dimethylformamide (5.78 mL, 74.84 mmol) in THF (10 mL) was added dropwise. After addition, the mixture was allowed to warm to room temperature and stirred for 15 h. Then, the mixture was diluted with saturated ammonium chloride solution and the two layers were separated. The aqueous layer was extracted with ethyl acetate (3×150 mL). The combined organic extracts were washed with brine solution and dried over anhydrous magnesium sulfate. Filtration of the drying agent and removal of the solvent under the vacuum gave the crude brown solid. This solid was dissolved in acetonitrile (˜50 mL) at hot condition and then stored in the refrigerator overnight. The solids were collected by filtration and washed with diethyl ether. After drying in air, 4.47 g (64% yield) of 4-methoxy-quinoline-6-carbaldehyde was isolated as a white solid: EI-HRMS m/e calcd for C11H9NO2 (M+) 187.0633, found 187.0638.

Workup

  1. additionDuring the addition
  2. customit gave a very dark brown solution
  3. additionAfter addition
  4. temperatureto warm to room temperature
  5. stirringstirred for 15 h
  6. customthe two layers were separated
  7. extractionThe aqueous layer was extracted with ethyl acetate (3×150 mL)
  8. washThe combined organic extracts were washed with brine solution
  9. dry with materialdried over anhydrous magnesium sulfate
  10. filtrationFiltration of the drying agent and removal of the solvent under the vacuum
  11. customgave the crude brown solid
  12. customstored in the refrigerator overnight
  13. filtrationThe solids were collected by filtration
  14. washwashed with diethyl ether
  15. customAfter drying in air

Sources & evidence

ORD record
ord-e9ada1a470e84d03b1219b37beee7914
Source dataset
uspto-grants-2007_08
Patent number
US07253285B2

Reaction notes

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