Methanol → Methyl 2-bromopyridine-3-carboxylate

HRID 2230776Notes

Reaction equation

HRID 2230776 reaction equation
[Br:1][C:2]1[N:10]=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].CO.N(C(OCC)=O)=N[C:15](OCC)=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CCOCC>[Br:1][C:2]1[N:10]=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([O:6][CH3:15])=[O:5]

Participants

6

Reactant 4

HCID 887MethanolHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 2332622-Bromopyridine-3-carboxylic acid

Product 1

HCID 12349191Methyl 2-bromopyridine-3-carboxylateYield 111%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

2-Bromonicotinic acid (7.33 g, 36 mmol) was suspended in dry Et2O (40 mL), and MeOH (2.3 mL) and diethyl azodicarboxylate (5.8 mL, 37 mmol) were added. Triphenylphosphine (9.61 g in 40 mL Et2O, 37 mmol) was added dropwise over 2.5 hours. After stirring an additional two hours, the reaction was filtered and evaporated. The resulting clear liquid was chromatographed on silica gel (10-40% EtOAc/hexanes) to yield a clear oil (8.63 g, 100%). 1H NMR (CDCl13): δ8.49 (dd, 1H, J=4.8, J′=2.2), 8.09 (dd, 1H, J=7.7, J′=1.8), 7.36 (m, 1H), 3.97 (s, 3H).

Workup

  1. filtrationthe reaction was filtered
  2. customevaporated
  3. customThe resulting clear liquid was chromatographed on silica gel (10-40% EtOAc/hexanes)

Sources & evidence

ORD record
ord-869b5c8359b549bcb8e368c2e4b0c813
Source dataset
uspto-grants-2002_07
Patent number
US06426346B1

Reaction notes

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