Dichloromethane → HCID 90408779, compound

HRID 516569Notes

Reaction equation

HRID 516569 reaction equation
[NH2:1][C:2]1[C:7]([F:8])=[C:6]([C:9]2[CH:14]=[CH:13][C:12]([Si](C)(C)C)=[C:11]([F:19])[C:10]=2[F:20])[N:5]=[C:4]([C:21]([O:23][CH3:24])=[O:22])[C:3]=1[Cl:25].[Br:26]Br.ClCCl.S([O-])([O-])(=O)=S.[Na+].[Na+]>C(#N)C.O>[NH2:1][C:2]1[C:7]([F:8])=[C:6]([C:9]2[CH:14]=[CH:13][C:12]([Br:26])=[C:11]([F:19])[C:10]=2[F:20])[N:5]=[C:4]([C:21]([O:23][CH3:24])=[O:22])[C:3]=1[Cl:25]

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 24408BromineHCID 24477Sodium ThiosulfateHCID 90408447HCID 90408447, compound

Product 1

HCID 90408779HCID 90408779, compoundYield 63.7%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

Methyl 4-amino-3-chloro-6-(2,3-difluoro-4-(trimethylsilyl)phenyl)-5-fluoropicolinate (2.5 g, 6.43 mmol) was dissolved in acetonitrile (32 mL) and bromine (3.31 mL, 64.3 mmol) was added. The reaction mixture was stirred at room temperature for 4 h at which time LCMS indicated the reaction was mostly complete. The reaction mixture was partitioned between dichloromethane and water and sodium thiosulfate (10.17 g, 64.3 mmol) was added. The aqueous phase was extracted with dichloromethane and the organic extracts were combined and concentrated under vacuum. The product was purified by flash chromatography (SiO2, eluting with 5-40% ethyl acetate in hexanes) to provide the title compound as a light yellow solid (1.62 g, 63.7%).

Workup

  1. additionwas added
  2. extractionThe aqueous phase was extracted with dichloromethane
  3. concentrationconcentrated under vacuum
  4. customThe product was purified by flash chromatography (SiO2, eluting with 5-40% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-9b573a0ac9cd450eab680d487fa31d62
Source dataset
uspto-grants-2015_08
Patent number
US09113629B2

Reaction notes

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