Ethyl orthoformate → Allyl 3-(methylamino)benzoate

HRID 341893Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 341893
[NH2:1][C:2]1[CH:3]=[C:4]([CH:11]=[CH:12][CH:13]=1)[C:5]([O:7][CH2:8][CH:9]=[CH2:10])=[O:6].[CH:14](OCC)(OCC)OCC>FC(F)(F)C(O)=O>[CH3:14][NH:1][C:2]1[CH:3]=[C:4]([CH:11]=[CH:12][CH:13]=1)[C:5]([O:7][CH2:8][CH:9]=[CH2:10])=[O:6]

Komponenten

4

Edukt 2

HCID 31214Ethyl orthoformateHCID 18930599Allyl 3-aminobenzoate

Produkt 1

HCID 22168609Allyl 3-(methylamino)benzoateAusbeute 17 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6422Trifluoroacetic acidKatalysator

Versuchsvorschrift

Allyl 3-aminobenzoate (5 g, 28.2 mM) was dissolved in triethyl orthoformate (50 ml) and trifluoroacetic acid (5 drops) was added. The solution was stirred and refluxed up through 3 å molecular sieves for 5 hours. Solvent was removed, and the residue dissolved in ethanol (50 ml), followed by the addition of acetic acid (8.08 ml) and sodium cyanoborohydride (6.85 g, 0.108M) in several portions. The mixture was stirred at ambient temperature for 16 hours, and solvent removed. The residue was dissolved in diethyl ether, washed with water, brine, and dried over MgSO4. Crude product was purified by chromatography on silica, eluting with a gradient from dichloromethane to dichloromethane/ethyl acetate (95:5), to give allyl 3-methylaminobenzoate (0.93 g, 17%). Nmr (CDCl3): δ 2.88 (s, 3H); 4.81 (dt, 2H); 5.23-5.45 (m, 2H); 5.94-6.13 (m, 1H); 6.83 (dd, 1H); 7.25 (dd, 1H); 7.33 (t, 1H); 7.43 (dm, 1H).

Aufarbeitung

  1. temperaturerefluxed up through 3 å molecular sieves for 5 hours
  2. customSolvent was removed
  3. dissolutionthe residue dissolved in ethanol (50 ml)
  4. additionfollowed by the addition of acetic acid (8.08 ml) and sodium cyanoborohydride (6.85 g, 0.108M) in several portions
  5. stirringThe mixture was stirred at ambient temperature for 16 hours
  6. customsolvent removed
  7. dissolutionThe residue was dissolved in diethyl ether
  8. washwashed with water, brine
  9. dry with materialdried over MgSO4
  10. customCrude product was purified by chromatography on silica
  11. washeluting with a gradient from dichloromethane to dichloromethane/ethyl acetate (95:5)

Quellen und Nachweise

ORD-Eintrag
ord-774ed228af6844a0a6e734c41b228f86
Quelldatensatz
uspto-grants-1999_01
Patentnummer
US05856321

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