Acetic Acid → Ammonia

HRID 2234455Notes

Reaction equation

HRID 2234455 reaction equation
[C:1]([NH:8][C@@H:9]1[CH2:13][CH2:12][NH:11][CH2:10]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[C:14](O)(=O)C.C([O-])(=O)C.[Na+].C([BH3-])#N.[Na+].C(=O)([O-])O.[Na+]>C=O>[NH3:8].[CH3:14][N:11]1[CH2:12][CH2:13][C@@H:9]([NH:8][C:1](=[O:2])[O:3][C:4]([CH3:7])([CH3:6])[CH3:5])[CH2:10]1

Participants

8

Reactant 5

HCID 176Acetic AcidHCID 516892Sodium BicarbonateHCID 517045Sodium AcetateHCID 1514397(3R)-(+)-3-(tert-Butoxycarbonylamino)pyrrolidineHCID 5003444Sodium cyanoborohydride

Product 2

HCID 222AmmoniaYield 2.5%HCID 45091942(R)-tert-Butyl 1-methylpyrrolidin-3-ylcarbamate

Reagents, catalysts & solvents 1

HCID 712FormaldehydeSolvent

Procedure

(3R)-3-(Bocamino)pyrrolidine (Fluorochem; 2.5 g, 13.42 mmol) was dissolved in 37% aqueous formaldehyde (78 mL) and acetic acid (8.5 mL, 134.23 mmol). Sodium acetate (11.0 g, 134.23 mmol) was added and the mixture cooled in an ice/water bath. Sodium cyanoborohydride (844 mg, 13.42 mmol) was added and the mixture allowed to stir for 3 hours. Saturated aqueous sodium hydrogen carbonate was added until the mixture was basic. The mixture was extracted with DCM (×2) and the combined extracts dried (MgSO4) and concentrated. Column chromatography (2.5-5% 7N ammonia in methanol) yielded the title compound as a colourless liquid that crystallised on standing (1.20 g, 45%).

Workup

  1. temperaturethe mixture cooled in an ice/water bath
  2. extractionThe mixture was extracted with DCM (×2)
  3. dry with materialthe combined extracts dried (MgSO4)
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-f94826acfdf14999b01f609e3684f34a
Source dataset
uspto-grants-2010_05
Patent number
US07709471B2

Reaction notes

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