Ammonia → Tert-butyl (1-carbamimidoylcyclopropyl)carbamate hcl

HRID 1040471Notes

Reaction equation

HRID 1040471 reaction equation
[C:1]([O:5][C:6](=[O:13])[NH:7][C:8]1([C:11]#[N:12])[CH2:10][CH2:9]1)([CH3:4])([CH3:3])[CH3:2].CC[O-].[Na+].[NH4+:18].[Cl-:19].N>CCO>[ClH:19].[C:1]([O:5][C:6](=[O:13])[NH:7][C:8]1([C:11](=[NH:18])[NH2:12])[CH2:10][CH2:9]1)([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 4

HCID 222AmmoniaHCID 25517Ammonium ChlorideHCID 2723922Sodium ethoxide2×HCID 20825555tert-butyl N-(1-cyanocyclopropyl)carbamate

Product 1

HCID 67390485Tert-butyl (1-carbamimidoylcyclopropyl)carbamate hclYield 81.2%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

(1-Cyano-cyclopropyl)-carbamic acid tert-butyl ester (2.12 g, 11.6 mmol) was dissolved in anhydrous EtOH (29 mL) and NaOEt (21 wt % in EtOH, 6.5 mL, 17.5 mmol) was added via syringe in one portion. The yellow solution was stirred at room temperature for 1 h. An additional amount of NaOEt (21 wt % in EtOH, 2.2 mL, 2.9 mmol) was added and stirring was continued for 2 h. To the reaction was added solid NH4Cl (2.5 g, 47 mmol) followed by NH3 (7N in MeOH, 1.7 mL, 12 mmol). The flask was sealed and the suspension was allowed to stir for 88 h. The solids were filtered off, using anhydrous EtOH to rinse. The filtrate was concentrated and re-suspended in EtOAc (10 mL). This mixture was heated to reflux for 30 min then allowed to cool to room temperature. The solids were collected by filtration to give 2.22 g of the title compound as a white powder, m/z 200.44 [M+1]+.

Workup

  1. stirringstirring
  2. waitwas continued for 2 h
  3. customThe flask was sealed
  4. stirringto stir for 88 h
  5. filtrationThe solids were filtered off
  6. washto rinse
  7. concentrationThe filtrate was concentrated
  8. temperatureThis mixture was heated
  9. temperatureto reflux for 30 min
  10. temperatureto cool to room temperature
  11. filtrationThe solids were collected by filtration

Sources & evidence

ORD record
ord-4b2b218779eb41cbab74c2db44ccbe2e
Source dataset
uspto-grants-2013_10
Patent number
US08552205B2

Reaction notes

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