Hydrochloric Acid → Methyl 3-chloro-4-fluoro-alpha-azidocinnamate

HRID 2396851Notes

Reaction equation

HRID 2396851 reaction equation
[Na].[Cl:2][C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][C:10]=1[F:11])[CH:6]=O.[N:12]([CH2:15][C:16]([O:18][CH3:19])=[O:17])=[N+:13]=[N-:14].Cl>CO>[Cl:2][C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][C:10]=1[F:11])[CH:6]=[C:15]([N:12]=[N+:13]=[N-:14])[C:16]([O:18][CH3:19])=[O:17]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 5938663-Chloro-4-fluorobenzaldehydeHCID 4020482Methyl 2-azidoacetateHCID 5360545Sodium

Product 1

HCID 54554773Methyl 3-chloro-4-fluoro-alpha-azidocinnamateYield 33.3%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

While cooling with an ice bath 1.35 g of sodium were dissolved in 30 ml of methanol and subsequently a solution of 4.65 g of 3-chloro-4-fluorobenzaldehyde and 6.75 g of methyl azidoacetate in 10 ml of methanol were added within 20 min. The reaction mixture was stirred at room temperature for 3 hours and then neutralized with 2N HCl. The mixture was extracted with ethyl acetate, washed with water and saturated sodium chloride solution and the organic phase was dried over sodium sulfate. The solvent was removed and the residue was chromatographed over 250 g of silica gel with n-hexane-toluene 2:1. There were obtained 2.5 g (33%) of methyl 3-chloro-4-fluoro-a-azidocinnamate as yellow crystals with m.p. 72°-74°.

Workup

  1. extractionThe mixture was extracted with ethyl acetate
  2. washwashed with water and saturated sodium chloride solution
  3. dry with materialthe organic phase was dried over sodium sulfate
  4. customThe solvent was removed
  5. customthe residue was chromatographed over 250 g of silica gel with n-hexane-toluene 2:1

Sources & evidence

ORD record
ord-bf961dd54b9a4058ae58ca485f5c2e7d
Source dataset
uspto-grants-1996_02
Patent number
US05494928

Reaction notes

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