Ethyl orthoformate → Allyl 3-(methylamino)benzoate

HRID 266860노트

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HRID 266860 반응식
[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]

참가 물질

4

반응물 2

HCID 31214Ethyl orthoformateHCID 18930599Allyl 3-aminobenzoate

생성물 1

HCID 22168609Allyl 3-(methylamino)benzoate수율 17%

시약·촉매·용매 1

HCID 6422Trifluoroacetic acid촉매

실험 절차

Allyl 3-aminobenzoate (5 g, 28.2 mM) was dissolved in triethyl orthoformate (50 ml) and trifluoroacetic acid (5 drops) was added. The soluiton was stirred and refluxed up through 3å 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).

후처리

  1. temperaturerefluxed up through 3å 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)

출처 및 근거

ORD 기록
ord-e8a94c43f1b84bc7ae77953f6b134095
출처 데이터셋
uspto-grants-1997_07
특허 번호
US05652233

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