Sodium Thiosulfate → HCID 66937196, compound

HRID 408725Notes

Reaction equation

HRID 408725 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=CC(Cl)=CC=4)=[CH:25][C:13]=3[N:12]=2)[CH:10]=1)=[O:5])[CH3:2].ClC1C(SC2C=CC(Cl)=CC=2)=CC2N=C(N3C=C(C(O)=O)C=N3)NC=2C=1.[CH:61]1[CH:66]=[C:65]([Cl:67])[CH:64]=[C:63](C(OO)=O)[CH:62]=1.[S:72]([O-:76])([O-])(=[O:74])=S.[Na+].[Na+]>C([O-])(O)=O.[Na+].ClCCl>[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:72]([C:62]4[CH:61]=[CH:66][C:65]([Cl:67])=[CH:64][CH:63]=4)(=[O:76])=[O:74])=[CH:25][C:13]=3[N:12]=2)[CH:10]=1)=[O:5])[CH3:2]

Participants

7

Reactant 4

HCID 24477Sodium ThiosulfateHCID 70297m-Chloroperbenzoic acidHCID 44479584HCID 44479584, compoundHCID 66937228HCID 66937228, compound

Product 1

HCID 66937196HCID 66937196, compoundYield 89.3%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 516892Sodium BicarbonateSolvent

Conditions

Temperature
23 °C

Procedure

To a solution of 1-[6-chloro-5-(4-chloro-phenylsulfanyl)-1-(2-methoxy-ethoxymethyl)-1H-benzoimidazol-2-yl]-1H-pyrazole-4-carboxylic acid ethyl ester (Intermediate from Example 61) (2.69 g, 5.16 mmol) and dichloromethane (26 mL) was added mCPBA (2.43 g, 10.8 mmol) at 23° C. The reaction was stirred for 16 h at 23° C. Dichloromethane (30 mL) was added followed by a solution of sodium thiosulfate (1.71 g, 10.8 mmol) in 80% saturated aqueous NaHCO3 (30 mL). The mixture was stirred vigorously until both layers were clear. The organic layer was collected and the aqueous layer extracted with CH2Cl2 (2×80 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 (2.55 g, 89%) as a mixture of regioisomers. MS (ESI/CI): mass calcd. for C23H22Cl2N4O6S, 552.1; m/z found, 553.1 [M+H]+. 1H NMR (400 MHz, CDCl3): 8.91-8.89 (m, 2H), 8.73 (s, 1.4H), 8.68 (s, 0.6H), 8.20 (d, J=0.6 Hz, 0.6H), 8.18 (d, J=0.6 Hz, 1.4H), 7.91-7.87 (m, 4H), 7.72 (s, 0.6H), 7.68 (s, 1.4H), 7.48-7.43 (m, 4H), 6.27 (s, 1.2H), 6.15 (s, 2.8H), 4.39-4.32 (m, 4H), 3.71-3.66 (m, 1.2H), 3.67-3.62 (m, 2.8H), 3.48-3.45 (m, 1.2H), 3.44-3.40 (m, 2.8H), 3.28 (s, 1.8H), 3.24 (s, 4.2H), 1.40-1.34 (m, 6H).

Workup

  1. stirringThe mixture was stirred vigorously until both layers
  2. customThe organic layer was collected
  3. extractionthe aqueous layer extracted with CH2Cl2 (2×80 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-b803ea6a86284c2a91299aabe192c909
Source dataset
uspto-grants-2014_06
Patent number
US08759345B2

Reaction notes

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