Dimethylformamide → HCID 86626216, compound

HRID 658094Notes

Reaction equation

HRID 658094 reaction equation
C([Li])CCC.C1C[O:9][CH2:8]C1.CC1CCCN(C)C1(C)C.[F:21][C:22]1[CH:34]=[C:33]([F:35])[CH:32]=[CH:31][C:23]=1[C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25].CN(C=O)C>C1COCC1.O.C(O)(=O)C>[F:21][C:22]1[C:34]([CH:8]=[O:9])=[C:33]([F:35])[CH:32]=[CH:31][C:23]=1[C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25]

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 187617721,2,2,3-TetramethylpiperidineHCID 57447335Tert-butyl 2,4-difluorobenzoateHCID 178420697HCID 178420697, compound

Product 1

HCID 86626216HCID 86626216, compoundYield 100%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-10 °C

Procedure

At −78° C., 17.62 ml of 1.59 M n-butyl lithium-THF solution was added dropwise to 100 ml of THF solution containing 4.73 ml of tetramethylpiperidine. This was stirred at −10° C. for 10 minutes, cooled to −78° C., mixed with 5.00 g of tert-butyl 2,4-difluorobenzoate dissolved in 20 ml of THF and then stirred for 1 hour. Subsequently, 7.23 ml of DMF was added dropwise thereto, and the mixture was stirred for 1 hour, mixed with 5.34 ml of acetic acid and then risen to room temperature. This was mixed with an appropriate amount of purified water, extracted with ethyl acetate and dried with anhydrous magnesium sulfate. After concentration, the thus formed residue was purified by a silica gel column chromatography to obtain 5.65 g (100%) of tert-butyl 2,4-difluoro-3-formylbenzoate (Reference Example 4-1) from a hexane-ethyl acetate (20:1-10:1) eluate.

Workup

  1. temperaturecooled to −78° C.
  2. stirringstirred for 1 hour
  3. stirringthe mixture was stirred for 1 hour
  4. customrisen to room temperature
  5. extractionextracted with ethyl acetate
  6. dry with materialdried with anhydrous magnesium sulfate
  7. concentrationAfter concentration
  8. customthe thus formed residue was purified by a silica gel column chromatography

Sources & evidence

ORD record
ord-f3ddbfb5e0024a948e38037e830ee908
Source dataset
uspto-grants-2011_12
Patent number
US08076367B2

Reaction notes

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