Sodium Thiosulfate → HCID 66937137, compound

HRID 538156Notes

Reaction equation

HRID 538156 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]([Cl:34])[C:24](SC4C=C(C)C=CC=4)=[CH:25][C:13]=3[N:12]=2)[CH:10]=1)=[O:5])[CH3:2].ClC1C(S[C:54]2[CH:55]=[C:56]([CH3:60])[CH:57]=[CH:58][CH:59]=2)=CC2N=C(N3C=C(C(O)=O)C=N3)NC=2C=1.O[O:62][S:63]([O-:65])=O.[K+].S([O-])([O-])(=O)=S.[Na+].[Na+]>C([O-])(O)=O.[Na+].ClCCl.O.CO>[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]([Cl:34])[C:24]([S:63]([C:54]4[CH:55]=[C:56]([CH3:60])[CH:57]=[CH:58][CH:59]=4)(=[O:65])=[O:62])=[CH:25][C:13]=3[N:12]=2)[CH:10]=1)=[O:5])[CH3:2]

Participants

9

Reactant 4

HCID 24477Sodium ThiosulfateHCID 23707502Potassium hydroxy sulfiteHCID 44479583HCID 44479583, compoundHCID 66937322HCID 66937322, compound

Product 1

HCID 66937137HCID 66937137, compoundYield 62%

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 516892Sodium BicarbonateSolvent

Conditions

Temperature
23 °C

Procedure

To a solution of 1-[6-chloro-1-(2-methoxy-ethoxymethyl)-5-m-tolylsulfanyl-1H-benzoimidazol-2-yl]-1H-pyrazole-4-carboxylic acid ethyl ester (Intermediate from EXAMPLE 60, product from Step F) (0.160 g, 0.319 mmol) and MeOH (1.6 mL) was added a solution of Oxone® (0.412 g, 0.671 mmol) and water (1.7 mL) at 23° C. The reaction mixture was stirred at 23° C. for 16 h. Dichloromethane (30 mL) was added followed by a solution of sodium thiosulfate (0.106 g, 0.670 mmol) in 80% saturated aq. NaHCO3 (30 mL). The mixture was stirred vigorously until both layers were clear. The organic layer was collected and the water layer extracted with CH2Cl2 (2×50 mL). The organic layers were combined, dried, filtered, and concentrated under reduced pressure. The residue was purified (FCC) (0-100% EtOAc/hexanes) to yield the titled compound (0.105 mg, 62%) as a mixture of regioisomers. MS (ESI/CI): mass calcd. for C24H25ClN4O6S, 532.1; m/z found, 533.1 [M+H]+. 1H NMR (400 MHz, CDCl3): 8.90 (d, J=0.6 Hz, 1.5H), 8.89 (d, J=0.6 Hz, 0.5H), 8.73 (br s, 1.5H), 8.69 (br s, 0.5H), 8.19 (d, J=0.6 Hz, 0.5H), 8.18 (d, J=0.6, 1.5H), 7.79-7.75 (m, 2H), 7.75-7.72 (m, 2H), 7.71 (s, 0.5H), 7.67 (s, 1.5H), 7.39-7.36 (m, 4H), 6.27 (s, 1H), 6.14 (s, 3H), 4.40-4.32 (m, 4H), 3.71-3.67 (m, 1H), 3.66-3.61 (m, 3H), 3.49-3.45 (m, 1H), 3.44-3.39 (m, 3H), 3.28 (s, 1.5H), 3.24 (s, 4.5H), 2.38 (br s, 6H), 1.38-1.33 (m, 6H).

Workup

  1. stirringThe mixture was stirred vigorously until both layers
  2. customThe organic layer was collected
  3. extractionthe water layer extracted with CH2Cl2 (2×50 mL)
  4. customdried
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified (FCC) (0-100% EtOAc/hexanes)

Sources & evidence

ORD record
ord-849ce8fce8c7415fb8c6c5e03015da9d
Source dataset
uspto-grants-2014_10
Patent number
US08865713B2

Reaction notes

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