Dimethyl Sulfate → HCID 76287351, compound

HRID 1748745Notes

Reaction equation

HRID 1748745 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])[C:13](=[O:18])[NH:12][C:11]2[N:19]([CH3:23])[N:20]=[C:21]([CH3:22])[C:10]1=2.[OH-].[Na+].[CH3:26]OS(OC)(=O)=O.[NH4+].[OH-].C(=O)(O)[O-].[Na+]>C1COCC1.O.C(OCC)(=O)C>[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])[C:13](=[O:18])[N:12]([CH3:26])[C:11]2[N:19]([CH3:23])[N:20]=[C:21]([CH3:22])[C:10]1=2

Participants

8

Reactant 5

HCID 6497Dimethyl SulfateHCID 14798Sodium HydroxideHCID 14923Ammonium HydroxideHCID 516892Sodium BicarbonateHCID 136348430HCID 136348430, compound

Product 1

HCID 76287351HCID 76287351, compoundYield 72%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 21881883Oxolane--water (1/1)Solvent

Procedure

To 4-(2,4-dichlorophenyl)-1,3,6,6-tetramethyl-4,8-dihydropyrazolo[3,4-e][1,4]thiazepin-7-one (0.150 g, 0.4 mmol, made in the same manner as Preparation C.2) dissolved in THF/H2O (1:1, 10 mL), was added NaOH (0.81 mL, 2 M aqueous). The reaction mixture was stirred for about 24 h at rt. Subsequently, dimethylsulfate (0.077 mL, 0.8 mmol) was added, and the reaction mixture was stirred for about 1 hr at rt. To the reaction mixture was added NH4OH (1 mL, 25% aqueous), followed by 5% aqueous sodium bicarbonate (5 mL) and ethyl acetate (25 mL). 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/DCM (1:9)), to afford 4-(2,4-dichlorophenyl)-1,3,6,6,8-pentamethyl-4H-pyrazolo[3,4-e][1,4]thiazepin-7-one (0.110 g, 0.28 mmol, 72%), as a white solid. LC-MS (Table 1, Method a) Rt=5.05 min, m/z 384 (M+H)+; 1H NMR (400 MHz, CDCl3) δ ppm 1.05 (3 H, br. s.) 1.51 (3 H, br. s.) 2.32 (3 H, br. s.) 2.87 (3 H, br. s.) 3.65 (3 H, br. s.) 5.32 (1 H, br. s.) 7.29 (1 H, dd, J=8.3, 1.9 Hz) 7.34 (1 H, br. s.) 7.72 (1 H, d, J=8.3 Hz).

Workup

  1. stirringthe reaction mixture was stirred for about 1 hr at rt
  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/DCM (1:9))

Sources & evidence

ORD record
ord-5a66824179f144aaa5234acd400d4e4b
Source dataset
uspto-grants-2015_10
Patent number
US09150592B2

Reaction notes

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