Diisopropylethylamine → 1,1-Dimethylethyl N-{2-[(3-nitro[1,5]naphthyridin-4-yl)amino]ethyl}carbamate

HRID 1823391Notes

Reaction equation

HRID 1823391 reaction equation
C(N(C(C)C)CC)(C)C.Cl[N:11]1[CH2:20][CH:19]=[CH:18][C:17]2[N:16]=[CH:15][C:14]([N+:21]([O-:23])=[O:22])=[CH:13][C:12]1=2.[NH2:24][CH2:25][CH2:26][NH:27][C:28](=[O:34])[O:29][C:30]([CH3:33])([CH3:32])[CH3:31]>ClCCl>[N+:21]([C:14]1[CH:15]=[N:16][C:17]2[C:12]([C:13]=1[NH:24][CH2:25][CH2:26][NH:27][C:28](=[O:34])[O:29][C:30]([CH3:32])([CH3:31])[CH3:33])=[N:11][CH:20]=[CH:19][CH:18]=2)([O-:23])=[O:22]

Participants

5

Reactant 3

HCID 81531DiisopropylethylamineHCID 187201N-BOC-ethylenediamine2×HCID 540020875-Chloro-3-nitro[1,5]naphthyridine

Product 1

HCID 221726751,1-Dimethylethyl N-{2-[(3-nitro[1,5]naphthyridin-4-yl)amino]ethyl}carbamateYield 0.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent4×

Procedure

A solution of diisopropylethylamine (13.47 g, 0.10 mole) in dichloromethane (25 mL) was added to a solution of 5-chloro-3-nitro[1,5]naphthyridine (18.2 g, 0.086 mol) in dichloromethane (250 mL). A solution of tert-butyl N-(2-aminoethyl)carbamate (16.7 g, 0.10 mol) in dichloromethane (75 mL) was slowly added to the reaction mixture. The reaction mixture was heated at reflux overnight. Additional tert-butyl N-(2-aminoethyl)carbamate (1 g) was added and the reaction mixture was heated at reflux for an additional 3 hours. The reaction mixture was allowed to cool to ambient temperature and then it was diluted with additional dichloromethane, washed with water and with brine, dried, and then concentrated under vacuum to provide a dark solid. This solid was purified by flash chromatography (silica gel eluting with dichloromethane) to provide 24.8 g of 1,1-dimethylethyl N-{2-[(3-nitro[1,5]naphthyridin-4-yl)amino]ethylcarbamate as a canary yellow solid. A portion (0.3 g) was recrystallized from toluene (10 mL) and heptane (10 mL) to provide 0.2 g of canary yellow needles, m.p. 149–151° C. Analysis: Calculated for C15H19N5O4: % C, 54.05; % H, 5.75; % N, 21.01; Found: % C, 54.17; % H, 5.73; % N, 20.90.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux overnight
  3. temperaturethe reaction mixture was heated
  4. temperatureat reflux for an additional 3 hours
  5. washwashed with water and with brine
  6. customdried
  7. concentrationconcentrated under vacuum
  8. customto provide a dark solid
  9. customThis solid was purified by flash chromatography (silica gel eluting with dichloromethane)
  10. customto provide 24.8 g of 1,1-dimethylethyl N-{2-[(3-nitro[1,5]naphthyridin-4-yl)amino]ethylcarbamate as a canary yellow solid
  11. customA portion (0.3 g) was recrystallized from toluene (10 mL) and heptane (10 mL)

Sources & evidence

ORD record
ord-232e42d45ae545d3880c47d0b7e4413d
Source dataset
uspto-grants-2006_05
Patent number
US07038051B2

Reaction notes

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