Methyl 5-bromopyridine-3-carboxylate → HCID 5323747, compound

HRID 630229Notes

Reaction equation

Br[C:2]1[CH:3]=[C:4]([C:8]([O:10][CH3:11])=[O:9])[CH:5]=[N:6][CH:7]=1.[CH2:12]([Zn]CC)[CH3:13]>O1CCOCC1>[CH2:12]([C:2]1[CH:3]=[C:4]([C:8]([O:10][CH3:11])=[O:9])[CH:5]=[N:6][CH:7]=1)[CH3:13]

Participants

Conditions

Temperature: 70 °C

Procedure

To a solution of methyl 5-bromopyridine-3-carboxylate (10.0 g, 46.29 mmol) in anhydrous dioxane (100 mL) at room temperature was added (1,1′-bis(diphenylphosphino)ferrocene)dichloropalladium (II) (677 mg, 0.925 mmol). Then, diethylzinc (5.71 g, 38 mL, 46.29 mmol, 15% solution in toluene) was added dropwise. The reaction mixture was heated at 70° C. for 45 minutes, then cooled to room temperature and quenched with MeOH. The mixture was extracted with ethyl acetate (2×250 mL) and washed with water, 0.1 N HCl, and brine. The organic layer was dried over anhydrous sodium sulfate and filtered. The filtrate was evaporated, and the residue was purified by CombiFlash using 0-30% ethyl acetate and hexane to provide methyl 5-ethylpyridine-3-carboxylate as a yellow oil (4.20 g, 55% yield); 1H NMR (400 MHz, CDCl3): δ 1. (t, 3H), 1.45 (t, 3H), 2.78 (q, 2H), 3.99 (s, 3H), 8.15 (s, 1H), 8.65 (s, 1H), 8.89 (s, 1H); M+165.1.

Workup

temperaturecooled to room temperature
customquenched with MeOH
extractionThe mixture was extracted with ethyl acetate (2×250 mL)
washwashed with water, 0.1 N HCl, and brine
dry with materialThe organic layer was dried over anhydrous sodium sulfate
filtrationfiltered
customThe filtrate was evaporated
customthe residue was purified by CombiFlash

Sources & evidence

ORD record: ord-9d476cbf07804a4080ab03437a1bf93a
Source dataset: uspto-grants-2016_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09315521B2

Reaction notes

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