Allyl bromide → HCID 10082149, compound

HRID 373954

Reaction equation

HRID 373954 reaction equation
[C:1]([CH2:9][C:10]([O:12][CH3:13])=[O:11])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[N:4][CH:3]=1.[Na].[CH2:15](Br)[CH:16]=[CH2:17]>CO>[CH3:13][O:12][C:10](=[O:11])[CH:9]([C:1](=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[N:4][CH:3]=1)[CH2:17][CH:16]=[CH2:15]

Participants

5

Reactant 3

HCID 7841Allyl bromide2×HCID 1086453-Pyridinepropanoic acid, beta-oxo-, methyl esterHCID 5360545Sodium

Product 1

HCID 10082149HCID 10082149, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
25 °C

Procedure

Methyl 2-(nicotinoyl)acetate (17.9 g, prepared by the method of E Wenkert et al, J. Org. Chem., 1983, 48, 5006) was added under argon to a solution of sodium metal (2.3 g) in methanol (200 ml) and the resulting mixture was stirred at 25° C. for 30 mins. Allyl bromide (12.0 g) was then added and stirring was continued overnight. A further amount (about 2 g) of allyl bromide was added, the mixture was stirred for 48 hours, and then concentrated. The residual oil was partitioned between water and ether and the aqueous layer was extracted three times with ether. The combined extracts were washed with saturated brine, dried (MgSO4) and concentrated. The residue was purified by flash column chromatography, eluting with a mixture of petroleum ether (b.p. 60°-80°) and ethyl acetate (1:1, v/v) to give methyl-2-nicotinoyl-4-pentenoate (A) as a pale yellow oil (13.8 g); NMR 2.6-2.9 (2H,m), 3.7 (3H,s), 4.4 (1H,m), 4.9-5.2 (2H,m), 5.5-6.0 (1H,m), 7.2-7.5 (1H,m), 8.1-8.3 (1H,m), 8.7-8.8 (1H,m) and 9.1-9.2 (1H,m).

Workup

  1. stirringstirring
  2. waitwas continued overnight
  3. stirringthe mixture was stirred for 48 hours
  4. concentrationconcentrated
  5. customThe residual oil was partitioned between water and ether
  6. extractionthe aqueous layer was extracted three times with ether
  7. washThe combined extracts were washed with saturated brine
  8. dry with materialdried (MgSO4)
  9. concentrationconcentrated
  10. customThe residue was purified by flash column chromatography
  11. washeluting with a mixture of petroleum ether (b.p. 60°-80°) and ethyl acetate (1:1

Sources & evidence

ORD record
ord-19fcb8cd5765478a8553de024e42ed10
Source dataset
uspto-grants-1992_11
Patent number
US05166213

Linked notes

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