Pyridine → N-nitroso-N-(tert-butoxycarbonyl)amino-cyclopropane

HRID 12820

Reaction equation

HRID 12820 reaction equation
F[B-](F)(F)F.[N:6]#[O+:7].[C:8]([O:12][C:13]([NH:15][CH:16]1[CH2:18][CH2:17]1)=[O:14])([CH3:11])([CH3:10])[CH3:9].N1C=CC=CC=1.CCOC(C)=O>C(#N)C>[N:6]([N:15]([CH:16]1[CH2:18][CH2:17]1)[C:13]([O:12][C:8]([CH3:11])([CH3:9])[CH3:10])=[O:14])=[O:7]

Participants

6

Reactant 4

HCID 1049PyridineHCID 8857Ethyl AcetateHCID 11137142Nitrilooxonium tetrafluoroborateHCID 15698228tert-Butyl N-cyclopropylcarbamate

Product 1

HCID 57941319N-nitroso-N-(tert-butoxycarbonyl)amino-cyclopropaneYield 106.7%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
-30 °C

Procedure

Nitrosonium tetrafluoroborate (9.32 g, 79.8 mmol) was added carefully in several portions to a cooled (−30° C.) solution of N-(tert-butoxycarbonyl)cyclopropylamine (9.57 g, 60.9 mmol) and anhydrous pyridine (11.7 mL) in dry acetonitrile (150 mL). The solution was stirred at −30° C. for 30 minutes, and then at 0° C. for 2 hours. Ice water and EtOAc were added and the organic phase was separated and washed quickly with 1N HCl to remove pyridine. The organic phase was washed with 1N NaHCO3 and brine, dried (MgSO4), filtered, and evaporated under high vacuum with a water bath temperature below 40° C. to give N-nitroso-N-(tert-butoxycarbonyl)amino-cyclopropane (12.1 g, quantitative) as an oil.

Workup

  1. waitat 0° C. for 2 hours
  2. customthe organic phase was separated
  3. washwashed quickly with 1N HCl
  4. customto remove pyridine
  5. washThe organic phase was washed with 1N NaHCO3 and brine
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. customevaporated under high vacuum with a water bath temperature below 40° C.

Sources & evidence

ORD record
ord-aab3b91cf6294126a849440ff6925f04
Source dataset
uspto-grants-2010_06
Patent number
US07728029B2

Linked notes

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