Acetic Acid → 5-Diallylaminomethyl-furan-3-carboxylic acid ethyl ester

HRID 1437139Notes

Reaction equation

HRID 1437139 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[CH:10]=[C:9]([CH:11]=O)[O:8][CH:7]=1)=[O:5])[CH3:2].[CH2:13]([NH:16][CH2:17][CH:18]=[CH2:19])[CH:14]=[CH2:15].C(O)(=O)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCl.C(O)C>[CH2:1]([O:3][C:4]([C:6]1[CH:10]=[C:9]([CH2:11][N:16]([CH2:17][CH:18]=[CH2:19])[CH2:13][CH:14]=[CH2:15])[O:8][CH:7]=1)=[O:5])[CH3:2]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 31279DiallylamineHCID 5049666Sodium triacetoxyborohydrideHCID 10964904Ethyl 5-formylfuran-3-carboxylate

Product 1

HCID 579405775-Diallylaminomethyl-furan-3-carboxylic acid ethyl ester

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of 5-formyl-3-furancarboxylic acid ethyl ester (prepared as described in Tetrahedron (1996), 52(12), 4245-56) (1.61 g) in dichloromethane (20 ml) was added diallylamine (1.18 ml). The solution was treated with glacial acetic acid (0.55 ml) and then sodium triacetoxyborohydride (4.2 g). The suspension was stirred at room temperature for 3.5 h. The suspension was treated with ethanol (80 ml) and stirred at room temperature for 25 mins. The solvent was removed in vacuo. The residue was partitioned between ethyl acetate (200 ml) and saturated aqueous sodium hydrogen carbonate (100 ml). The phases were separated and the organic phase washed with saturated aqueous sodium hydrogen carbonate (100 ml) and brine (50 ml). The combined aqueous phases were extracted with ethyl acetate (50 ml). The combined organic extracts were dried (MgSO4), filtered and the solvent removed in vacuo. The residue was dissolved in methanol and applied equally onto SCX sulphonic acid ion exchange cartridges (10 g×4, pre-treated with methanol). The cartridges were eluted with methanol followed by 10% 0.880 ammonia in methanol; evaporation of the basic fractions in vacuo gave the title compound as a mobile oil (2.06 g).

Workup

  1. stirringstirred at room temperature for 25 mins
  2. customThe solvent was removed in vacuo
  3. customThe residue was partitioned between ethyl acetate (200 ml) and saturated aqueous sodium hydrogen carbonate (100 ml)
  4. customThe phases were separated
  5. washthe organic phase washed with saturated aqueous sodium hydrogen carbonate (100 ml) and brine (50 ml)
  6. extractionThe combined aqueous phases were extracted with ethyl acetate (50 ml)
  7. dry with materialThe combined organic extracts were dried (MgSO4)
  8. filtrationfiltered
  9. customthe solvent removed in vacuo
  10. dissolutionThe residue was dissolved in methanol
  11. additionapplied equally onto SCX sulphonic acid ion exchange cartridges (10 g×4, pre-treated with methanol)
  12. washThe cartridges were eluted with methanol
  13. customevaporation of the basic fractions in vacuo

Sources & evidence

ORD record
ord-7fab38de30754733b0060745fc028b87
Source dataset
uspto-grants-2009_11
Patent number
US07622464B2

Reaction notes

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