Potassium Carbonate → HCID 53800296, compound

HRID 395414Notes

Reaction equation

HRID 395414 reaction equation
C1(CC2C(C=COC)=C(C(F)(F)F)N=C(C(F)F)C=2C(OC)=O)CC1.BrBr.C(=O)([O-])[O-].[K+].[K+].[Br:34][CH:35]([C:41]1[C:42]([CH2:58][CH:59]2[CH2:61][CH2:60]2)=[C:43]([C:54]([O:56][CH3:57])=[O:55])[C:44]([CH:51]([F:53])[F:52])=[N:45][C:46]=1[C:47]([F:50])([F:49])[F:48])[CH:36](OC)[O:37][CH3:38]>CCOCC.CO>[Br:34][C:35]([C:41]1[C:42]([CH2:58][CH:59]2[CH2:60][CH2:61]2)=[C:43]([C:54]([O:56][CH3:57])=[O:55])[C:44]([CH:51]([F:52])[F:53])=[N:45][C:46]=1[C:47]([F:48])([F:49])[F:50])=[CH:36][O:37][CH3:38]

Participants

7

Reactant 4

HCID 11430Potassium CarbonateHCID 24408BromineHCID 22668796HCID 22668796, compoundHCID 69880965HCID 69880965, compound

Product 1

HCID 53800296HCID 53800296, compoundYield 80%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 3283Diethyl EtherSolvent

Procedure

To a solution of 18.0 g(49.3 mmol) of methyl 4-(cyclopropylmethyl)-2-(difluoromethyl)-5-(2-methoxyethenyl)-6-(trifluoromethyl)-3-pyridinecarboxylate (example 127 of U.S. Pat. No. 6,169,432) in 250 ml of ether was added 7.9 g (49.4 mmol) of bromine. The reaction mixture was stirred at room temperature for 2 h and to the mixture was added 6.8 g of freshly ground potassium carbonate and 100 ml of methanol. The reaction mixture was stirred for another 45 min and was washed with water and brine. The organic layer was dried (MgSO4), filtered through celite, and concentrated in vacuo. The residue was kugelrohr distilled and the distillate was purified by chromatography (7% EtOAc in hexane) to give 18.7 g (80% yield) of 1:1 mixture of methyl 5-(1-bromo-2,2-dimethoxyethyl)-4-(cyclopropylmethyl)-2-(difluoromethyl)-6-(trifluoromethyl)-3-pyridinecarboxylate and product. HPLC purification (10% EtOAc in hexane) gave 4.1 g of the desired product as a colorless oil which crystallized and was recrystallized from hexane to give crystals, mp 79-79.5° C.

Workup

  1. stirringThe reaction mixture was stirred for another 45 min
  2. washwas washed with water and brine
  3. dry with materialThe organic layer was dried (MgSO4)
  4. filtrationfiltered through celite
  5. concentrationconcentrated in vacuo
  6. distillationThe residue was kugelrohr distilled
  7. distillationthe distillate was purified by chromatography (7% EtOAc in hexane)
  8. customto give
  9. customHPLC purification (10% EtOAc in hexane)

Sources & evidence

ORD record
ord-b25e177f67c34280b7338afb46f1dc0c
Source dataset
uspto-grants-2003_08
Patent number
US06605624B1

Reaction notes

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