2-Amino-3-bromopyridine → Benzyl 4-[2-[(3-bromopyridin-2-yl)amino]-2-oxoethyl}-3,6-dihydropyridine-1(2H)-carboxylate

HRID 1664799Notes

Reaction equation

C[Al](C)C.CO[C:7](=[O:25])[CH2:8][C:9]1[CH2:10][CH2:11][N:12]([C:15]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[O:16])[CH2:13][CH:14]=1.[Br:26][C:27]1[C:28]([NH2:33])=[N:29][CH:30]=[CH:31][CH:32]=1>ClC(Cl)C>[Br:26][C:27]1[C:28]([NH:33][C:7](=[O:25])[CH2:8][C:9]2[CH2:10][CH2:11][N:12]([C:15]([O:17][CH2:18][C:19]3[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=3)=[O:16])[CH2:13][CH:14]=2)=[N:29][CH:30]=[CH:31][CH:32]=1

Participants

Conditions

Temperature: 55 °C

Procedure

Trimethylaluminum (0.91 g, 12.61 mmol) was added to a solution of benzyl 4-(2-methoxy-2-oxoethyl)-3,6-dihydropyridine-1(2H)-carboxylate (2.43 g, 8.41 mmol) and 3-bromopyridin-2-amine (1.60 g, 9.25 mmol) in dichloroethane (45 mL) at 0° C. The reaction mixture was slowly warmed to 55° C. After 18 h, the reaction mixture was quenched with saturated aqueous sodium bicarbonate and extracted with dichloromethane (4×). The combined organic extracts were washed with Rochelle's salts (1N in water), saturated brine, dried over magnesium sulfate, filtered and concentrated. Purification by silica gel chromatography (50% hexanes/ethyl acetate→100% ethyl acetate) gave the title compound (1.91 g). MS 430.0 (M).

Workup

customthe reaction mixture was quenched with saturated aqueous sodium bicarbonate
extractionextracted with dichloromethane (4×)
washThe combined organic extracts were washed with Rochelle's salts (1N in water), saturated brine
dry with materialdried over magnesium sulfate
filtrationfiltered
concentrationconcentrated
customPurification by silica gel chromatography (50% hexanes/ethyl acetate→100% ethyl acetate)

Sources & evidence

ORD record: ord-0a9b1593a1b044deb48f94767c8c890a
Source dataset: uspto-grants-2011_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08039460B2

Reaction notes

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