Diazomethane → Methyl 4-chloronicotinate

HRID 1655601Notes

Reaction equation

HRID 1655601 reaction equation
[Cl:1][C:2]1[C:7]([C:8]([OH:10])=[O:9])=[CH:6][N:5]=[CH:4][CH:3]=1.[N+](=[CH2:13])=[N-]>CO.CCOCC>[Cl:1][C:2]1[CH:3]=[CH:4][N:5]=[CH:6][C:7]=1[C:8]([O:10][CH3:13])=[O:9]

Participants

5

Reactant 2

HCID 9550DiazomethaneHCID 8182294-Chloronicotinic acid

Product 1

HCID 12574055Methyl 4-chloronicotinateYield 85%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 3283Diethyl EtherSolvent

Procedure

4-Chloronicotinic acid, prepared as described by W. C. J. Ross in J. Chem. Soc. (C), 1816 (1966), (2.54 g, 16.1 mmol) in methanol (30 mL) at 0° C. was treated with diazomethane in ether until gas evolution ceased; the ice bath was removed halfway through the esterification. The excess diazomethane was removed with a nitrogen stream and the solvent was removed under reduced pressure. The residue was taken up in saturated sodium bicarbonate solution and extracted with ethyl acetate (2×). The combined organic extracts were washed with 1M aqueous sodium hydroxide solution (2×) and brine, dried over sodium sulfate, filtered and concentrated in vacuo to afford 2.35 g (85%) of the title compound as a yellow oil. A portion (1.47 g) was distilled at b.p. 75°-85° C. at ~1 mm mercury to afford 1.15 g as a pale yellow crystalline solid.

Workup

  1. customthe ice bath was removed halfway through the esterification
  2. customThe excess diazomethane was removed with a nitrogen stream
  3. customthe solvent was removed under reduced pressure
  4. extractionextracted with ethyl acetate (2×)
  5. washThe combined organic extracts were washed with 1M aqueous sodium hydroxide solution (2×) and brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-da7db7780a8644f1952d147ab7b417a1
Source dataset
uspto-grants-1993_10
Patent number
US05250548

Reaction notes

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