Pyridine → alpha-Cyano-6-bromo-2,3-dimethoxycinnamic acid

HRID 2290917Notes

Reaction equation

HRID 2290917 reaction equation
[Br:1][C:2]1[C:7]([CH:8]=O)=[C:6]([O:10][CH3:11])[C:5]([O:12][CH3:13])=[CH:4][CH:3]=1.[C:14]([CH2:16][C:17]([OH:19])=[O:18])#[N:15].N1C=CC=CC=1>C1C=CC=CC=1>[C:14]([C:16](=[CH:8][C:7]1[C:2]([Br:1])=[CH:3][CH:4]=[C:5]([O:12][CH3:13])[C:6]=1[O:10][CH3:11])[C:17]([OH:19])=[O:18])#[N:15]

Participants

5

Reactant 3

HCID 1049PyridineHCID 9740Cyanoacetic acidHCID 46719526-Bromo-2,3-dimethoxybenzaldehyde

Product 1

HCID 53869906alpha-Cyano-6-bromo-2,3-dimethoxycinnamic acidYield 71.8%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A mixture of 6-bromo-2,3-dimethoxybenzaldehyde (48.4 g, 0.20 mole), NH4OAc (1.93 g, 0.025 mole), cyanoacetic acid (0.186 mole, 15.8 g), pyridine (42 mL), and benzene (193 mL) was stirred at reflux for 2 hours using a Dean-Stark trap for water removal. Upon cooling to room temperature a solid was filtered and washed with hexane. The solid was dissolved in 1N KOH, and was extracted with ether. The aqueous layer was acidified with 10% HCl and was extracted with CH2Cl2. The combined CH2Cl2 layers were washed with water, saturated aqueous NaCl, dried (MgSO4), filtered, and evaporated to yield 41.7 g yellow solid, (67%); mp 130°-2°; M+ 311.

Workup

  1. temperatureat reflux for 2 hours
  2. customfor water removal
  3. filtrationwas filtered
  4. washwashed with hexane
  5. dissolutionThe solid was dissolved in 1N KOH
  6. extractionwas extracted with ether
  7. extractionwas extracted with CH2Cl2
  8. washThe combined CH2Cl2 layers were washed with water, saturated aqueous NaCl
  9. dry with materialdried (MgSO4)
  10. filtrationfiltered
  11. customevaporated

Sources & evidence

ORD record
ord-dde66f44ec154ac1af74ffbea120cdc5
Source dataset
uspto-grants-1986_10
Patent number
US04618683

Reaction notes

Loading…