tert-Butanol → Tert-butyl 5-(trifluoromethyl)thiophen-2-ylcarbamate

HRID 1626359노트

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HRID 1626359 반응식
[F:1][C:2]([F:12])([F:11])[C:3]1[S:7][C:6](C(O)=O)=[CH:5][CH:4]=1.C([N:15]([CH2:18]C)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:27])C=CC=CC=1.[CH3:37][C:38]([OH:41])([CH3:40])[CH3:39]>>[F:12][C:2]([F:1])([F:11])[C:3]1[S:7][C:6]([NH:15][C:18](=[O:27])[O:41][C:38]([CH3:40])([CH3:39])[CH3:37])=[CH:5][CH:4]=1

참가 물질

5

반응물 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 20490515-(Trifluoromethyl)thiophene-2-carboxylic acid

생성물 1

HCID 86718387Tert-butyl 5-(trifluoromethyl)thiophen-2-ylcarbamate

반응 조건

온도
90 °C

실험 절차

To 5-(trifluoromethyl)thiophene-2-carboxylic acid in tBuOH (50 mL) was added triethylamine (1.53 mL, 11 mmol) and diphenylphosphoryl azide (DPPA) (2.4 mL, 11 mmol). This mixture was heated to 90° C., and was stirred overnight (ca. 16 hours). Thin layer chromatography (TLC) indicated that the reaction was complete. The solvent was removed under reduced pressure, the residue was dissolved in ethyl acetate (EtOAc) and washed 1× with NaHCO3 aq sat, 1× with citric acid (10% aqueous), and 1× brine. The solution was dried over MgSO4, filtered and concentrated. After silica gel chromatography (5 to 20% EtOAc/hexanes) the title compound was afforded (1.46 g, 44% over 3 steps) as a yellow/orange solid, mp 118-120° C.; Rf=0.31 (10% EtOAc/hex); 1H NMR (DMSO-d6) δ 11.03 (br s, 1H), 7.38 (app d, 1H, J=4.1 Hz), 6.51 (app d, 1H, J=3.3 Hz), 1.49 (s, 9H); GCMS (EI) m/z 267 (M+).

후처리

  1. customThe solvent was removed under reduced pressure
  2. dissolutionthe residue was dissolved in ethyl acetate (EtOAc)
  3. washwashed 1× with NaHCO3 aq
  4. dry with materialThe solution was dried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated

출처 및 근거

ORD 기록
ord-3c16ecffdb9c493a83b3b0c28be9bf78
출처 데이터셋
uspto-grants-2014_07
특허 번호
US08785465B2

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