Nitroethane → Benzyl (2-methyl-3-(2-nitroprop-1-en-1-yl)phenyl)carbamate

HRID 2361399Notes

Reaction equation

HRID 2361399 reaction equation
[CH:1]([C:3]1[C:4]([CH3:20])=[C:5]([NH:9][C:10](=[O:19])[O:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH:6]=[CH:7][CH:8]=1)=O.[N+:21]([CH2:24][CH3:25])([O-:23])=[O:22].C([O-])(=O)C.[NH4+]>>[CH3:20][C:4]1[C:3]([CH:1]=[C:24]([N+:21]([O-:23])=[O:22])[CH3:25])=[CH:8][CH:7]=[CH:6][C:5]=1[NH:9][C:10](=[O:19])[O:11][CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

4

Reactant 3

HCID 6587NitroethaneHCID 517165Ammonium AcetateHCID 86681516Benzyl 3-formyl-2-methylphenylcarbamate

Product 1

HCID 77889903Benzyl (2-methyl-3-(2-nitroprop-1-en-1-yl)phenyl)carbamateYield 53.2%

Procedure

A solution of benzyl (3-formyl-2-methylphenyl)carbamate (8.00 g, 29.7 mmol), nitroethane (10.7 ml, 149 mmol), and ammonium acetate (11.5 g, 149 mmol) was heated in an oil bath at 95° C. overnight. The reaction mixture was concentrated under reduced pressure, and the residue was diluted with a mixture of dichloromethane (150 mL) and water (75 mL) and basified with solid sodium bicarbonate slowly. The organic layer was collected, and the aqueous layer was extracted with dichloromethane (2×100 mL). The combined organic layers were dried over anhydrous sodium sulfate. Concentration under reduced pressure followed by purification by flash silica gel chromatography using a mixture of ethyl acetate in hexane (20%-35%-50%-65%-75%) afforded benzyl (2-methyl-3-(2-nitroprop-1-en-1-yl)phenyl)carbamate (5.16 g, 15.8 mmol, 53% yield) as a pale yellow solid.

Workup

  1. concentrationThe reaction mixture was concentrated under reduced pressure
  2. additionthe residue was diluted with a mixture of dichloromethane (150 mL) and water (75 mL)
  3. customThe organic layer was collected
  4. extractionthe aqueous layer was extracted with dichloromethane (2×100 mL)
  5. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  6. concentrationConcentration under reduced pressure
  7. customfollowed by purification by flash silica gel chromatography
  8. additiona mixture of ethyl acetate in hexane (20%-35%-50%-65%-75%)

Sources & evidence

ORD record
ord-aada762c47b14ab5aaf1f0bec4272795
Source dataset
uspto-grants-2014_04
Patent number
US08685969B2

Reaction notes

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