m-Chloroperbenzoic acid → HCID 136216215, compound

HRID 1748770Notes

Reaction equation

HRID 1748770 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[CH:9]1[S:15][C:14]([CH3:17])([CH3:16])[CH2:13][NH:12][C:11]2[N:18]([CH3:22])[N:19]=[C:20]([CH3:21])[C:10]1=2.C1C=C(Cl)C=C(C(OO)=[O:31])C=1.C(=O)(O)[O-].[Na+]>C(Cl)Cl>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[CH:9]1[S:15](=[O:31])[C:14]([CH3:17])([CH3:16])[CH2:13][NH:12][C:11]2[N:18]([CH3:22])[N:19]=[C:20]([CH3:21])[C:10]1=2

Participants

5

Reactant 3

HCID 70297m-Chloroperbenzoic acidHCID 516892Sodium BicarbonateHCID 136216145HCID 136216145, compound

Product 1

HCID 136216215HCID 136216215, compoundYield 62.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

To 4-(2,4-dichlorophenyl)-1,3,6,6-tetramethyl-7,8-dihydro-4H-pyrazolo[3,4-e][1,4]thiazepine (0.1 g, 0.28 mmol), Example D.4) in DCM (5 mL) at 0° C., was added m-CPBA (48.5 mg, 0.28 mmol) dissolved in 3 mL DCM (dropwise in 10 min). The resulting mixture was stirred for about 10 min at rt. Subsequently, 5% aqueous sodium bicarbonate (10 mL) and DCM (20 mL) were added. The layers were separated and the organic layer was washed with water (25 mL), dried (MgSO4), filtered and concentrated in vacuo. The resulting residue was purified by column chromatography (SiO2, ethyl acetate followed by 10% MeOH in ethyl acetate) to afford 4-(2,4-dichlorophenyl)-1,3,6,6-tetramethyl-7,8-dihydro-4H-pyrazolo[3,4-e][1,4]thiazepine 5-oxide (65 mg, 0.175 mmol, 62%), as white solid: LC-MS (Table 1, Method a) Rt=2.72 (major) and 2.97 (minor), diastereomeric ratio (64:36); m/z 372 (M+H)+; Isomer A: 1H NMR (400 MHz, CDCl3) δ ppm 1.08 (3 H, s) 1.35 (3 H, s) 1.74 (3 H, s) 3.05 (1 H, dd, J=14.7, 6.1 Hz) 3.55 (1 H, dd, J=14.7, 3.8 Hz) 3.66 (3H, s) 3.65-3.69 (1 H, m) 5.67 (1 H, s) 7.17-7.23 (2 H, m) 7.18-7.23 (1 H, m); Isomer B: 1H NMR (400 MHz, CDCl3) δ ppm 1.37 (3 H, s) 1.38 (3 H, s) 1.39 (3 H, s) 3.02 (1 H, dd, J=14.6, 7.1 Hz) 3.51 (1 H, dd, J=14.6, 2.8 Hz) 3.61 (1 H, dd, J=2.8 Hz) 3.64 (3 H, s) 5.50 (1 H, s) 7.34 (1 H, dd, J=8.6, 2.2 Hz) 7.47 (1 H, d, J=2.2 Hz) 7.89 (1 H, d, J=8.6 Hz).

Workup

  1. customat 0° C.
  2. customThe layers were separated
  3. washthe organic layer was washed with water (25 mL)
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe resulting residue was purified by column chromatography (SiO2, ethyl acetate followed by 10% MeOH in ethyl acetate)

Sources & evidence

ORD record
ord-d7cea546077747a5af18f6b55e9cb3ce
Source dataset
uspto-grants-2015_10
Patent number
US09150592B2

Reaction notes

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