Ethyl orthoformate → Allyl 3-allyloxy-4-methylaminobenzoate

HRID 1736373Notes

Reaction equation

HRID 1736373 reaction equation
[CH2:1]([O:4][C:5]1[CH:6]=[C:7]([CH:14]=[CH:15][C:16]=1[NH2:17])[C:8]([O:10][CH2:11][CH:12]=[CH2:13])=[O:9])[CH:2]=[CH2:3].[CH2:18](OC(OCC)OCC)C>FC(F)(F)C(O)=O>[CH2:1]([O:4][C:5]1[CH:6]=[C:7]([CH:14]=[CH:15][C:16]=1[NH:17][CH3:18])[C:8]([O:10][CH2:11][CH:12]=[CH2:13])=[O:9])[CH:2]=[CH2:3]

Participants

4

Reactant 2

HCID 31214Ethyl orthoformateHCID 19432469Allyl 3-allyloxy-4-aminobenzoate

Product 1

HCID 19432509Allyl 3-allyloxy-4-methylaminobenzoateYield 41%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidCatalyst

Procedure

Allyl 3-allyloxy-4-aminobenzoate (7 g, 30 mM) was dissolved in triethylorthoformate (70 ml), treated with trifluoroacetic acid (10 drops), and heated under reflux for 5 hours. Solvent was removed by evaporation, and the residual oil was dissolved in ethanol (70 ml), then treated with glacial acetic acid (8.59 ml, 150 mM) followed by sodium cyanoborohydride (9.43 g, 150 mM) in several portions. The mixture was then left to stir at ambient temperature under a blanket of argon for 18 hours. Solvent was removed, and the residue treated with water (50 ml) and extracted into diethyl ether. The combined extracts were washed with water and brine before being dried over MgSO4. After removal of the solvent, the residue was purified by chromatography over silica, eluting with a gradient of dichloromethane/ethyl acetate (100:0 to 95:5), to give allyl 3-allyloxy-4-methylaminobenzoate (3.08 g, 41%).

Workup

  1. temperatureheated
  2. temperatureunder reflux for 5 hours
  3. customSolvent was removed by evaporation
  4. dissolutionthe residual oil was dissolved in ethanol (70 ml)
  5. additiontreated with glacial acetic acid (8.59 ml, 150 mM)
  6. waitThe mixture was then left
  7. customSolvent was removed
  8. additionthe residue treated with water (50 ml)
  9. extractionextracted into diethyl ether
  10. washThe combined extracts were washed with water and brine
  11. dry with materialbefore being dried over MgSO4
  12. customAfter removal of the solvent
  13. customthe residue was purified by chromatography over silica
  14. washeluting with a gradient of dichloromethane/ethyl acetate (100:0 to 95:5)

Sources & evidence

ORD record
ord-64725da9400f48ed95fcc7030dd77632
Source dataset
uspto-grants-1996_07
Patent number
US05541178

Reaction notes

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