M-Phenylenediamine → N1-(5-Bromo-3-nitro-2-pyridinyl)-1,3-benzenediamine

HRID 341182Notes

Reaction equation

HRID 341182 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[C:5](Cl)=[N:6][CH:7]=1.[C:12]1([NH2:19])[CH:17]=[CH:16][CH:15]=[C:14]([NH2:18])[CH:13]=1.CCN(C(C)C)C(C)C>CN1C(=O)CCC1>[Br:1][C:2]1[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[C:5]([NH:18][C:14]2[CH:15]=[CH:16][CH:17]=[C:12]([NH2:19])[CH:13]=2)=[N:6][CH:7]=1

Participants

5

Reactant 3

HCID 7935M-PhenylenediamineHCID 81531DiisopropylethylamineHCID 70194125-Bromo-2-chloro-3-nitropyridine

Product 1

HCID 59320866N1-(5-Bromo-3-nitro-2-pyridinyl)-1,3-benzenediamineYield 80.1%

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of 5-bromo-2-chloro-3-nitro-pyridine (2.4 g, 10.1 mmol), benzene-1,3-diamine (2.7 g, 25 mmol) and DIPEA (5.3 ml, 30 mmol) in dry NMP (20 ml) was stirred and heated at 120° C. under N2 for 2 hours. After cooling to RT the mixture was partitioned between EtOAc and H2O. The organic layer was washed with brine (×1) then dried (MgSO4), filtered and evaporated. The residue was purified by chromatography on silica (10→50% EtOAc/petrol) to give the title compound (2.5 g) as a red solid. 1H NMR (400 MHz, DMSO-d6): 9.78 (1H, s), 8.66 (1H, d), 8.60 (1H, d), 7.00 (1H, t), 6.83-6.71 (2H, m), 6.39 (1H, d), 5.13 (2H, s).

Workup

  1. temperatureAfter cooling to RT the mixture
  2. customwas partitioned between EtOAc and H2O
  3. washThe organic layer was washed with brine (×1)
  4. dry with materialthen dried (MgSO4)
  5. filtrationfiltered
  6. customevaporated
  7. customThe residue was purified by chromatography on silica (10→50% EtOAc/petrol)

Sources & evidence

ORD record
ord-98e20cddf49a43bf8dbe00d8f338394f
Source dataset
uspto-grants-2014_11
Patent number
US08895745B2

Reaction notes

Loading…