Sodium Hydroxide → 305809-45-4

HRID 1816232Notes

Reaction equation

HRID 1816232 reaction equation
[NH:1]1[CH2:5][CH2:4][N:3]=[C:2]1[CH2:6][NH:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[S:14][CH3:15].ClC1C=C(C=CC=1)C(OO)=[O:21].[OH-:27].[Na+]>CO.O.C(OCC)(=O)C>[NH:3]1[CH2:4][CH2:5][N:1]=[C:2]1[CH2:6][NH:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[S:14]([CH3:15])(=[O:21])=[O:27]

Participants

7

Reactant 3

HCID 14798Sodium HydroxideHCID 70297m-Chloroperbenzoic acid2×HCID 11108001HCID 11108001, compound

Product 1

HCID 9816461305809-45-4

Reagents, catalysts & solvents 3

HCID 887MethanolSolvent2×HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent3×

Procedure

N-(4,5-Dihydro-1H-imidazol-2-ylmethyl)-2-(methylthio)aniline (16.8 g, 76 mmol) was stirred in methanol (250 mL) and cooled in an ice bath. A solution of m-chloroperoxybenzoic acid (37 g of ˜70 wt %) in methanol (200 mL) was added dropwise over 1 hour while the temperature of the mixture was maintained below 28° C. After 20 minutes, additional m-chloroperoxybenzoic acid (2.0 g) was added and stirring continued for 20 minutes. The reaction mixture was reduced in vacuo to a slurry (˜40 mL volume), diluted with water (250 mL) and ethyl acetate (250 mL), and treated with 10N sodium hydroxide (15 mL). The ethyl acetate phase and five additional ethyl acetate extracts (100 mL each) were combined and washed with 0.1N NaOH (50 mL). Additional 10N sodium hydroxide (10 mL) was added to the aqueous phase and two ethyl acetate extracts (100 mL each) were collected and washed with 0.1N NaOH (10 mL) and all of the ethyl acetate phases combined. Drying (MgSO4) followed by evaporation gave N-(4,5-dihydro-1H-imidazol-2-ylmethyl)-2-(methylsulfonyl)aniline (12.3 g, 48.5 mmol), which was dissolved in ethyl acetate (450 mL). Fumaric acid (5.6 g, 48.5 mmol) was dissolved in methanol (80 mL) and the ethyl acetate solution of N-(4,5-dihydro-1H-imidazol-2-ylmethyl)-2-(methylsulfonyl)aniline was added to the rapidly stirred methanolic solution of fumaric acid. The mixture was stored at 4° C. for 16 hours and the resulting crystals were collected and dried in vacuo to give N-(4,5-dihydro-1H-imidazol-2-ylmethyl)-2-(methylsulfonyl)aniline as the fumaric acid salt (12.8 g, 45%).

Workup

  1. temperaturecooled in an ice bath
  2. temperaturewas maintained below 28° C
  3. waitcontinued for 20 minutes
  4. washwashed with 0.1N NaOH (50 mL)
  5. additionAdditional 10N sodium hydroxide (10 mL) was added to the aqueous phase and two ethyl acetate extracts (100 mL each)
  6. customwere collected
  7. washwashed with 0.1N NaOH (10 mL)
  8. dry with materialDrying (MgSO4)
  9. customfollowed by evaporation

Sources & evidence

ORD record
ord-0fcbf9c7f2fe41c2af4987e44b8fabe7
Source dataset
uspto-grants-2005_04
Patent number
US06884801B1

Reaction notes

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