m-Chloroperbenzoic acid → HCID 87451679, compound

HRID 407197Notes

Reaction equation

HRID 407197 reaction equation
[Br:1][C:2]1[S:6][C:5]([S:7][CH2:8][C:9]2[C:10]([C:19]([F:22])([F:21])[F:20])=[N:11][N:12]([CH3:18])[C:13]=2[O:14][CH:15]([F:17])[F:16])=[N:4][CH:3]=1.ClC1C=CC=C(C(OO)=[O:31])C=1>C1(C)C=CC=CC=1>[Br:1][C:2]1[S:6][C:5]([S:7]([CH2:8][C:9]2[C:10]([C:19]([F:22])([F:20])[F:21])=[N:11][N:12]([CH3:18])[C:13]=2[O:14][CH:15]([F:17])[F:16])=[O:31])=[N:4][CH:3]=1

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 87452288HCID 87452288, compound

Product 1

HCID 87451679HCID 87451679, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

The 5-bromo-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-thiazole obtained in this manner (4.0 g, 9.429 mmol) is initially charged in 100 ml of toluene. With stirring, 3-chloroperbenzoic acid (1.976 g, 8.015 mmol, 77% pure) is then added a little at a time, and the mixture is stirred at room temperature for a further 4 hours. For work-up, the reaction mixture is washed successively with water, aqueous NaHSO3 solution, aqueous NaHCO3 solution and finally with NaCl solution. The organic phase is dried over magnesium sulfate, filtered off and concentrated. The residue is triturated with n-heptane, filtered off and dried. The racemic 5-bromo-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl)-1,3-thiazole obtained (3.75 g) is purified by preparative chiral HPLC (column: Chiralcel® OD; mobile phase: n-hexane/2-propanol 90:10; flow rate: 0.6 ml/min; column temperature: 25° C.) and separated into the enantiomers. This gives 1.505 g (36.2% of theory) of 5-bromo-2-[(S)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (Rt=10.258 min) and 1.305 g (31.4% of theory) of 5-bromo-2-[(R)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (Rt=12.557 min).

Workup

  1. stirringthe mixture is stirred at room temperature for a further 4 hours
  2. washFor work-up, the reaction mixture is washed successively with water, aqueous NaHSO3 solution, aqueous NaHCO3 solution and finally with NaCl solution
  3. dry with materialThe organic phase is dried over magnesium sulfate
  4. filtrationfiltered off
  5. concentrationconcentrated
  6. customThe residue is triturated with n-heptane
  7. filtrationfiltered off
  8. customdried

Sources & evidence

ORD record
ord-10a720c89b364d8e876985569d58a839
Source dataset
uspto-grants-2014_06
Patent number
US08754234B2

Reaction notes

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