Acetonitrile → HCID 56971122, compound

HRID 1615495Notes

Reaction equation

HRID 1615495 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[C:13]3[N:14]=[C:15]([C:17]4[C:18]([CH3:26])=[N:19][N:20]5[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=45)[S:16][C:12]=3[CH2:11][CH2:10][CH2:9]2)=[CH:4][CH:3]=1.[O:27]1CCOCC1.C(#N)C.S(OOS([O-])(=O)=O)([O-])(=O)=O.[K+].[K+]>O.O.O.O.O.O.S([O-])([O-])(=O)=O.[Cu+2]>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[C:13]3[N:14]=[C:15]([C:17]4[C:18]([CH3:26])=[N:19][N:20]5[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=45)[S:16][C:12]=3[C:11](=[O:27])[CH2:10][CH2:9]2)=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 6342AcetonitrileHCID 24412Potassium PersulfateHCID 312751,4-DioxaneHCID 68183042HCID 68183042, compound

Product 1

HCID 56971122HCID 56971122, compoundYield 40%

Reagents, catalysts & solvents 2

HCID 24463Copper sulfate pentahydrateCatalystHCID 962WaterSolvent2×

Conditions

Temperature
90 °C

Procedure

In a 100 mL round bottomed flask was placed 4-(4-chlorophenyl)-2-(2-methylpyrazolo[1,5-a]pyridin-3-yl)-4,5,6,7-tetrahydro-1,3-benzothiazole (250 mg, 0.66 mmol) along with 1,4-dioxane (15 mL) and acetonitrile (15 mL). To the mixture were added a solution of copper (II) sulfate pentahydrate (670 mg, 2.7 mmol) in water (10 mL) and a solution of potassium persulfate (770 mg, 2.8 mmol) in water (10 mL). The mixture was stirred for 6 hr at 90° C. The mixture was allowed to cool to rt and then insoluble materials were removed by filtration through a celite pad. The celite pad was washed with water and EtOAc. The aqueous phase was separated from the filtrate and then extracted with EtOAc (50 mL×2). The combined organic phases were washed with a 10% aqueous solution of NaHSO3 (50 mL), then a saturated aqueous solution of NaHCO3 (50 mL), then a saturated aqueous solution of NH4Cl (50 mL), and then dried over anhydrous MgSO4. Insoluble materials were removed by filtration and the filtrate was concentrated under reduced pressure. The residue was purified by pre-packed silica gel (12 g) column chromatography, eluting with 0% to 50% EtOAc/hexane to yield the title compound (100 mg; 40%) as a yellow crystalline solid. LCMS: (FA) ES+ 394, 396; 1H NMR (400 MHz, d6-DMSO) δ ppm 8.42 (dt, 1H), 8.15 (dt, 1H), 7.32-7.35 (m, 3H), 7.17 (d, 2H), 6.90 (td, 1H), 4.45 (dd, 1H), 2.57-2.75 (m, 5H), 2.29-2.37 (m, 1H), 2.00-2.15 (m, 1H).

Workup

  1. customIn a 100 mL round bottomed flask was placed
  2. temperatureto cool to rt
  3. custominsoluble materials were removed by filtration through a celite pad
  4. washThe celite pad was washed with water and EtOAc
  5. customThe aqueous phase was separated from the filtrate
  6. extractionextracted with EtOAc (50 mL×2)
  7. washThe combined organic phases were washed with a 10% aqueous solution of NaHSO3 (50 mL)
  8. dry with materiala saturated aqueous solution of NaHCO3 (50 mL), then a saturated aqueous solution of NH4Cl (50 mL), and then dried over anhydrous MgSO4
  9. customInsoluble materials were removed by filtration
  10. concentrationthe filtrate was concentrated under reduced pressure
  11. customThe residue was purified by pre-packed silica gel (12 g) column chromatography
  12. washeluting with 0% to 50% EtOAc/hexane

Sources & evidence

ORD record
ord-c2ea9acaead046049dc13522d1022a01
Source dataset
uspto-grants-2014_07
Patent number
US08765746B2

Reaction notes

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