Methanol → HCID 66937250, compound

HRID 1521400Notes

Reaction equation

HRID 1521400 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[CH:7]=[N:8][N:9]([C:11]2[N:15]([CH2:16][O:17][CH2:18][CH2:19][O:20][CH3:21])[C:14]3[CH:22]=[C:23]([S:30][CH2:31][CH3:32])[C:24]([C:26]([F:29])([F:28])[F:27])=[CH:25][C:13]=3[N:12]=2)[CH:10]=1)=[O:5])[CH3:2].CO.[OH:35][O:36][S:37]([O-:39])=O.[K+].S([O-])(O[O-])(=O)=O.[K+].[K+].[CH3:49][CH2:50]OC(C)=O>O>[CH2:1]([O:3][C:4]([C:6]1[CH:7]=[N:8][N:9]([C:11]2[N:15]([CH2:16][O:17][CH2:18][CH2:19][O:20][CH3:21])[C:14]3[CH:22]=[C:23]([S:30]([CH2:31][CH3:32])=[O:35])[C:24]([C:26]([F:29])([F:27])[F:28])=[CH:25][C:13]=3[N:12]=2)[CH:10]=1)=[O:5])[CH3:2].[CH2:1]([O:3][C:4]([C:6]1[CH:7]=[N:8][N:9]([C:11]2[N:15]([CH2:16][O:17][CH2:18][CH2:19][O:20][CH3:21])[C:14]3[CH:22]=[C:23]([S:37]([CH2:49][CH3:50])(=[O:39])=[O:36])[C:24]([C:26]([F:28])([F:29])[F:27])=[CH:25][C:13]=3[N:12]=2)[CH:10]=1)=[O:5])[CH3:2]

Participants

8

Reactant 5

HCID 887MethanolHCID 8857Ethyl AcetateHCID 10313463Potassium peroxymonosulphateHCID 23707502Potassium hydroxy sulfiteHCID 66937162HCID 66937162, compound

Product 2

HCID 66937250HCID 66937250, compoundYield 48%HCID 66937385HCID 66937385, compoundYield 45%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
23 °C

Procedure

To a mixture of 1-[1-(2-methoxy-ethoxymethyl)-6-ethylsulfanyl-5-trifluoromethyl-1H-benzoimidazol-2-yl]-1H-pyrazole-4-carboxylic acid ethyl ester (0.501 g, 1.14 mmol) and MeOH (5.7 mL) was added a solution of Oxone®/potassium peroxymonosulfate (1.47 g, 2.40 mmol) in water (5.7 mL). The mixture was stirred for 44 h at 23° C. EtOAc (50 mL) and water (30 mL) were added and the biphasic mixture stirred. The layers were separated and the aqueous layer was further extracted with EtOAc (50 mL). The combined organic layers were washed with brine, dried, filtered, and concentrated under reduced pressure. The residue was purified (FCC) (10-80% EtOAc/hex) to yield the titled compound (0.232 g, 45% yield, 2:1 mixture of regioisomers) and 1-[1-(2-methoxy-ethoxymethyl)-6-ethylsulfonyl-5-trifluoromethyl-1H-benzoimidazol-2-yl]-1H-pyrazole-4-carboxylic acid ethyl ester (0.260 g, 48% yield, 5:2 mixture of regioisomers). MS (ESI/CI): mass calcd. for C13H23ClN4O5S, 454.1; m/z found, 455.1 [M+H]+. 1H NMR (400 MHz, CDCl3): 8.90 (d, J=0.6 Hz, 1H), 8.20 (d, J=0.6 Hz, 1H), 8.13 (s, 1H), 7.74 (s, 1H), 6.25-6.16 (m, 2H), 4.37 (q, J=7.1 Hz, 2H), 3.68-3.62 (m, 2H), 3.46-3.41 (m, 2H), 3.27 (s, 3H), 3.26-3.13 (m, 1H), 2.94-2.83 (m, 1H), 1.39 (t, J=7.1 Hz, 3H), 1.27 (t, J=7.4 Hz, 3H).

Workup

  1. stirringthe biphasic mixture stirred
  2. customThe layers were separated
  3. extractionthe aqueous layer was further extracted with EtOAc (50 mL)
  4. washThe combined organic layers were washed with brine
  5. customdried
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified (FCC) (10-80% EtOAc/hex)

Sources & evidence

ORD record
ord-15b41ddb9dab48919d8967c272298bfa
Source dataset
uspto-grants-2015_07
Patent number
US09073923B2

Reaction notes

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