Ammonium Hydroxide → (4-Amino-butyl)-(4-tert-butoxycarbonylamino-butyl)-carbamic acid tert-butyl ester

HRID 604761Notes

Reaction equation

HRID 604761 reaction equation
[C:1]([O:5][C:6](=[O:25])[N:7]([CH2:13][CH2:14][CH2:15][CH2:16][NH:17][C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:8][CH2:9][CH2:10][C:11]#[N:12])([CH3:4])([CH3:3])[CH3:2].[NH4+].[OH-]>C(O)C.[Ni]>[C:1]([O:5][C:6](=[O:25])[N:7]([CH2:8][CH2:9][CH2:10][CH2:11][NH2:12])[CH2:13][CH2:14][CH2:15][CH2:16][NH:17][C:18]([O:20][C:21]([CH3:22])([CH3:23])[CH3:24])=[O:19])([CH3:2])([CH3:4])[CH3:3]

Participants

5

Reactant 2

HCID 14923Ammonium HydroxideHCID 86761291(4-tert-Butoxycarbonylamino-butyl)-(3-cyano-propyl)-carbamic acid tert-butyl ester

Product 1

HCID 86761292(4-Amino-butyl)-(4-tert-butoxycarbonylamino-butyl)-carbamic acid tert-butyl ester

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 702EthanolSolvent

Procedure

The nitrile 11 (2.00 g, 5.6 mmol) was dissolved in ethanol (100 mL). NH4OH (10 mL) and Raney nickel (8 g) were added and ammonia gas was bubbled through the solution for 20 minutes at 0° C. The suspension was hydrogenated at 50 parr for 24 hours. Air was bubbled through the solution and the Raney nickel was removed by filtering through a sintered glass funnel keeping the Raney nickel residue moist at all times. The ethanol and NH4OH were removed in vacuo and the oily residue dissolved in CH2Cl2 and washed with 10% aq, Na2CO3 (3×50 mL). The organic layer was dried over anhydrous Na2SO4, filtered and the solvent removed in vacuo to give the product 12 as a clear oil without further purification (1.92 g, 95%), Rf=0.4 (1:10:89 NH4OH:MeOH:CHCl3); 1H NMR (CDCl3) d 4.65 (br s, 1H, NHCO), 3.14 (m, 6H, 3×CH2), 2.69 (t, 2H, CH2), 2.35 (t, 2H, CH2), 1.58-1.26 (m, 26H, 4×CH2, 6×CH3).

Workup

  1. customammonia gas was bubbled through the solution for 20 minutes at 0° C
  2. customAir was bubbled through the solution
  3. customthe Raney nickel was removed
  4. filtrationby filtering through a sintered glass funnel
  5. customThe ethanol and NH4OH were removed in vacuo
  6. dissolutionthe oily residue dissolved in CH2Cl2
  7. washwashed with 10% aq
  8. dry with materialThe organic layer was dried over anhydrous Na2SO4
  9. filtrationfiltered
  10. customthe solvent removed in vacuo

Sources & evidence

ORD record
ord-44a6722cb4d8490fb70fe85f1ac7262c
Source dataset
uspto-grants-2011_03
Patent number
US07910363B1

Reaction notes

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