2-Amino-4-methylpyridine → (6-Bromopyridin-2-yl)-(4-methylpyridin-2-yl)amine

HRID 1716529Notes

Reaction equation

Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Br:8])[N:3]=1.[NH2:9][C:10]1[CH:15]=[C:14]([CH3:16])[CH:13]=[CH:12][N:11]=1.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[Br:8][C:4]1[N:3]=[C:2]([NH:9][C:10]2[CH:15]=[C:14]([CH3:16])[CH:13]=[CH:12][N:11]=2)[CH:7]=[CH:6][CH:5]=1

Participants

Conditions

Temperature: 80 °C

Procedure

A suspension of 2,6-dibromopyridine (12.5 g), 2-amino-4-picoline (32.8 g, 139 mmol), palladium acetate (2.59 g, 11.6 mmol), rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (8.64 g, 13.9 mmol), sodium tert-butoxide (13.3 g, 139 mmol) in toluene (200 ml) was heated and stirred in an Ar stream at 80° C. for 12 hours. Water was added to the reaction solution and the solution was extracted with ethyl acetate. After the organic layer was washed with a saturated brine and dried over anhydrous magnesium sulfate, the residue obtained by vacuum concentration was purified by flash chromatography on silica gel (n-hexane:ethyl acetate=3:1) and subsequently washed with isopropyl ether and the title compound (15.4 g, 51%) was obtained.

Workup

temperaturewas heated
extractionthe solution was extracted with ethyl acetate
washAfter the organic layer was washed with a saturated brine
dry with materialdried over anhydrous magnesium sulfate
customthe residue obtained by vacuum concentration
customwas purified by flash chromatography on silica gel (n-hexane:ethyl acetate=3:1)
washsubsequently washed with isopropyl ether

Sources & evidence

ORD record: ord-93e7b71752174768b691c11d26e98431
Source dataset: uspto-grants-2010_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07803801B2

Reaction notes

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