tert-butyl N-(4-aminobutyl)carbamate → Tert-butyl 4-[(2-chloro-5,6-dimethyl-3-nitropyridin-4-yl)amino]butylcarbamate

HRID 11353

Reaction equation

HRID 11353 reaction equation
[NH2:1][CH2:2][CH2:3][CH2:4][CH2:5][NH:6][C:7](=[O:13])[O:8][C:9]([CH3:12])([CH3:11])[CH3:10].[Cl:14][C:15]1[C:20]([N+:21]([O-:23])=[O:22])=[C:19](Cl)[C:18]([CH3:25])=[C:17]([CH3:26])[N:16]=1.C(N(CC)CC)C>CN(C)C=O>[Cl:14][C:15]1[C:20]([N+:21]([O-:23])=[O:22])=[C:19]([NH:1][CH2:2][CH2:3][CH2:4][CH2:5][NH:6][C:7](=[O:13])[O:8][C:9]([CH3:10])([CH3:12])[CH3:11])[C:18]([CH3:25])=[C:17]([CH3:26])[N:16]=1

Participants

5

Reactant 3

HCID 4351tert-butyl N-(4-aminobutyl)carbamateHCID 8471TriethylamineHCID 121091232,4-Dichloro-5,6-dimethyl-3-nitropyridine

Product 1

HCID 12109124Tert-butyl 4-[(2-chloro-5,6-dimethyl-3-nitropyridin-4-yl)amino]butylcarbamateYield 48%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A solution of tert-butyl 4-aminobutylcarbamate (8.52 g, 45.24 mmol) in N,N-dimethylformamide was added to a solution of 2,4-dichloro-5,6-dimethyl-3-nitropyridine (10.00 g, 45.24 mmol) and triethylamine (12.6 mL, 90.5 mmol) in N,N-dimethylformamide (320 mL). The reaction mixture was stirred overnight and then concentrated under reduced pressure. The residue was partitioned between water and ethyl acetate. The layers were separated and the aqueous layer was extracted with ethyl acetate. The organics were combined, washed with brine and then concentrated under reduced pressure to provide a brown oily residue. This material was purified by flash chromatography (400 mL silica gel, eluting initially with 10% ethyl acetate in hexane and then increasing the gradient to 15% and then to 25%) to provide 8.1 g of tert-butyl 4-[(2-chloro-5,6-dimethyl-3-nitropyridin-4-yl)amino]butylcarbamate as a yellow solid.

Workup

  1. concentrationconcentrated under reduced pressure
  2. customThe residue was partitioned between water and ethyl acetate
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted with ethyl acetate
  5. washwashed with brine
  6. concentrationconcentrated under reduced pressure
  7. customto provide a brown oily residue
  8. customThis material was purified by flash chromatography (400 mL silica gel
  9. washeluting initially with 10% ethyl acetate in hexane
  10. temperatureincreasing the gradient to 15%

Sources & evidence

ORD record
ord-70c165635d014dcb99ca60dfce845323
Source dataset
uspto-grants-2006_08
Patent number
US07098221B2

Linked notes

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