Acetic Acid → Carbamate

HRID 588187Notes

Reaction equation

HRID 588187 reaction equation
[C:1](=[O:4])([O-:3])[NH2:2].[CH3:5][N:6]1[CH2:10][CH:9]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[C:17]([F:20])([F:19])[F:18])[CH:8]([N+:21]([O-])=O)[CH2:7]1.C(O)(=O)C>CO.[Zn]>[C:1](=[O:3])([O-:4])[NH2:2].[CH3:5][N:6]1[CH2:10][CH:9]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[C:17]([F:18])([F:19])[F:20])[CH:8]([NH2:21])[CH2:7]1

Participants

7

Reactant 3

HCID 176Acetic AcidHCID 276CarbamateHCID 118271741HCID 118271741, compound

Product 2

HCID 276CarbamateHCID 118271900HCID 118271900, compound

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 887MethanolSolvent

Conditions

Temperature
0 °C

Procedure

(3S and R,4R and S)-1-Methyl-3-nitro-4-(2-(trifluoromethyl)phenyl) pyrrolidine (296.8 mg, 1.082 mmol) was dissolved in MeOH (5 mL) and the reaction mixture was cooled to 0° C. Acetic acid (5 mL) and zinc (354 mg, 5.41 mmol) were added and the reaction mixture was warmed to room temperature and stirred under N2 for 16 h. The suspension was filtered over Celite and washed with MeOH. The filtrate was concentrated in vacuo, the residue suspended in EtOAc, cooled in an ice bath, and basified with conc. NH4OH. The organic phase was separated, washed with brine, dried over Na2SO4, filtered, and concentrated in vacuo to afford (3S and R,4R and S)-1-methyl-4-(2-(trifluoromethyl)phenyl)pyrrolidin-3-amine, which was carried onto the next step without further purification. MS ESI calc'd. For C12H15F3N2 [M+1]+ 245. found 245.

Workup

  1. temperaturethe reaction mixture was warmed to room temperature
  2. filtrationThe suspension was filtered over Celite
  3. washwashed with MeOH
  4. concentrationThe filtrate was concentrated in vacuo
  5. temperaturecooled in an ice bath
  6. customThe organic phase was separated
  7. washwashed with brine
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-8f4e89a2f53f40558cae4fbe69b1bede
Source dataset
uspto-grants-2016_01
Patent number
US09226922B2

Reaction notes

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