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

HRID 1007818Notes

Reaction equation

HRID 1007818 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.NCCNC(=O)OC(C)(C)C>[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

6

Reactant 3

HCID 81531DiisopropylethylamineHCID 187201N-BOC-ethylenediamineHCID 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 86.5%

Reagents, catalysts & solvents 2

HCID 187201N-BOC-ethylenediamineCatalystHCID 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]ethyl}carbamate 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)

Sources & evidence

ORD record
ord-d77cc2b78d924214b3322febac4f798f
Source dataset
uspto-grants-2004_09
Patent number
US06797716B2

Reaction notes

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