Dimethylamine → 4-(6-Dimethylamino-3-nitro-pyridin-2-ylamino)-piperidine-1-carboxylic acid tert-butyl ester

HRID 967415Notes

Reaction equation

HRID 967415 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH:11]([NH:14][C:15]2[C:20]([N+:21]([O-:23])=[O:22])=[CH:19][CH:18]=[C:17](Cl)[N:16]=2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH3:25][NH:26][CH3:27]>CO.C(Cl)Cl.C1COCC1>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH:11]([NH:14][C:15]2[C:20]([N+:21]([O-:23])=[O:22])=[CH:19][CH:18]=[C:17]([N:26]([CH3:27])[CH3:25])[N:16]=2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 2

HCID 674DimethylamineHCID 57500931Tert-butyl 4-[(6-chloro-3-nitropyridin-2-yl)amino]piperidine-1-carboxylate

Product 1

HCID 691571204-(6-Dimethylamino-3-nitro-pyridin-2-ylamino)-piperidine-1-carboxylic acid tert-butyl esterYield 104.3%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 21226129Dichloromethane methanolSolvent

Procedure

To a stirring solution of 6 g (0.016 mol) of 4-(6-chloro-3-nitro-pyridin-2-ylamino)-piperidine-1-carboxylic acid tert-butyl ester in MeOH/CH2Cl2 (84 mL/15 mL) was added 2.2 g (0.05 mol) of dimethylamine in THF (25 mL). The reaction mixture was stirred at room temperature for 16 h, and was then concentrated. The crude product was then dissolved in CH2Cl2 (400 mL) and washed with saturated NaHCO3 (2×200 mL). The washes were combined and extracted with EtOAc (100 mL). The combined organic layers were dried over Na2SO4 and concentrated to afford 6.1 g (99%) of the desired product as a bright yellow solid. MS (electrospray): exact mass calculated for C17H27N5O4, 365.21; m/z found, 388.19 [M+Na]+. 1H NMR (400 MHz, CDCl3): 8.74 (d, J=7.07 Hz, 1H), 8.18 (d, J=9.4 Hz, 1H), 5.97 (d, J=7.3 Hz, 1H), 4.28-4.16 (m, 1H), 4.07-3.93 (m, 2H), 3.17 (s, 6H), 3.01 (t, J=11.9 Hz, 2H), 2.05 (dd, J=12.4 Hz and 3.03 Hz, 2H), 1.60-1.50 (m, 2H), 1.47 (s, 9H).

Workup

  1. concentrationwas then concentrated
  2. dissolutionThe crude product was then dissolved in CH2Cl2 (400 mL)
  3. washwashed with saturated NaHCO3 (2×200 mL)
  4. extractionextracted with EtOAc (100 mL)
  5. dry with materialThe combined organic layers were dried over Na2SO4
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-d040f54703ca4a55a8622be3bd143d62
Source dataset
uspto-grants-2005_10
Patent number
US06953793B2

Reaction notes

Loading…