Methylamine → N-Methyl-6-nitropyridin-3-amine

HRID 1690492Notes

Reaction equation

Br[C:2]1[CH:3]=[CH:4][C:5]([N+:8]([O-:10])=[O:9])=[N:6][CH:7]=1.[CH3:11][NH2:12]>>[CH3:11][NH:12][C:2]1[CH:3]=[CH:4][C:5]([N+:8]([O-:10])=[O:9])=[N:6][CH:7]=1

Participants

Reactant 2

HCID 6329Methylamine

HCID 8176205-Bromo-2-nitropyridine

Product 1

HCID 60631613N-Methyl-6-nitropyridin-3-amineYield 80%

Procedure

Using analogous procedures to those described in the portion of Note [9] immediately above that is concerned with the preparation of starting materials, 5-bromo-2-nitropyridine was reacted with methylamine to give 5-methylamino-2-nitropyridine in 80% yield; 1H NMR: (DMSOd6) 2.51 (s, 3H), 7.02 (m, 1H), 7.43 (br s, 1H), 7.86 (m, 1H), 8.13 (d, 1H); Mass Spectrum: M−H− 152; which in turn was converted into 5-(N-tert-butoxycarbonyl-N-methylamino)-2-nitropyridine in 51% yield; 1H NMR: (CDCl3) 1.52 (s, 9H), 3.4 (s, 3H), 7.98 (m, 1H), 8.24 (m, 1H), 8.6 (m, 1H); which in turn was converted into 2-amino-5-(N-tert-butoxycarbonyl-N-methylamino)pyridine in 100% yield; 1H NMR: (CDCl3) 1.42 (br s, 9H), 3.19 (s, 3H), 4.39 (br s, 2H), 6.46 (d, 1H), 7.3 (m, 1H), 7.94 (m, 1H); Mass Spectrum: M+H+ 224; and which in turn was converted into N-[5-(N-tert-butoxycarbonyl-N-methylamino) pyridin-2-yl]-2-[4-(6,7-dimethoxyquinazolin-4-yloxy)phenyl]acetamide; Mass Spectrum: M+H+ 546.

Sources & evidence

ORD record: ord-42f493c637b54fa09ec60b808831af72
Source dataset: uspto-grants-2012_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08153643B2

Reaction notes

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