Ethyl Acetate → HCID 178480541, compound

HRID 1507472Notes

Reaction equation

HRID 1507472 reaction equation
[F:1][C:2]1[C:7]([O:8]C)=[C:6]([F:10])[CH:5]=[CH:4][C:3]=1[NH:11][C:12]([NH:26][C:27]1[NH:31][N:30]=[C:29]([C:32]2[CH:37]=[CH:36][C:35]([O:38]C)=[C:34]([F:40])[CH:33]=2)[CH:28]=1)=[N:13][C:14]([C:16]1[C:17]([C:22]([F:25])([F:24])[F:23])=[N:18][N:19]([CH3:21])[CH:20]=1)=[O:15].B(Br)(Br)Br.CCOC(C)=O>ClCCl>[F:1][C:2]1[C:7]([OH:8])=[C:6]([F:10])[CH:5]=[CH:4][C:3]=1[NH:11][C:12]([NH:26][C:27]1[NH:31][N:30]=[C:29]([C:32]2[CH:37]=[CH:36][C:35]([OH:38])=[C:34]([F:40])[CH:33]=2)[CH:28]=1)=[N:13][C:14]([C:16]1[C:17]([C:22]([F:25])([F:23])[F:24])=[N:18][N:19]([CH3:21])[CH:20]=1)=[O:15]

Participants

5

Reactant 3

HCID 8857Ethyl Acetate2×HCID 25134Boron tribromideHCID 178488664HCID 178488664, compound

Product 1

HCID 178480541HCID 178480541, compoundYield 28%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

N-(((2,4-Difluoro-3-methoxyphenyl)amino)((3-(3-fluoro-4-methoxyphenyl)-1H-pyrazol-5-yl)amino)methylene)-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide (110 mg, 0.194 mmol) was suspended in dichloromethane (4 mL), and a solution of boron tribromide in DCM (1 mL of 1 M, 5 equivalents) was added carefully. The mixture was stirred at room temperature overnight. Then, the reaction was quenched by the addition of ice, and the resulting slurry was then treated with aqueous sodium bicarbonate (pH approximately neutral). The mixture was stirred for 30 minutes, and then partitioned between water and EtOAc. Next, the organic phase was dried over sodium sulfate, and concentrated onto silica gel. The crude product was purified by chromatography (gradient: 8:2 hexanes:EtOAc to 2:8 hexanes:EtOAc to provide the title compound as a white solid (29 mg, 28% yield). 1H NMR (DMSO-d6) δ 13.16 (s, 1H), 12.69 (s, 1H), 10.72 (s, 1H), 10.32 (s, 1H), 10.23 (s, 1H), 8.09 (s, 1H), 7.56 (m, 2H), 7.40 (d, 1H), 7.04 (m, 2H), 6.62 (s, 1H), 3.89 (s, 3H). MS: calc.=539.39; obs. M+H=540.03. HPLC (Method E): retention time was 4.828 minutes.

Workup

  1. customThen, the reaction was quenched by the addition of ice
  2. additionthe resulting slurry was then treated with aqueous sodium bicarbonate (pH approximately neutral)
  3. stirringThe mixture was stirred for 30 minutes
  4. custompartitioned between water and EtOAc
  5. dry with materialNext, the organic phase was dried over sodium sulfate
  6. concentrationconcentrated onto silica gel
  7. customThe crude product was purified by chromatography (gradient

Sources & evidence

ORD record
ord-ac3e00c3aeb84c1694ba53ce1b310398
Source dataset
uspto-grants-2015_12
Patent number
US09221814B2

Reaction notes

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