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

HRID 1405949ノート

反応式

HRID 1405949 の反応式
[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

参加物

5

反応物 4

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

生成物 1

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

反応条件

温度
90 °C

実験手順

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+).

後処理

  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

出典と根拠

ORDレコード
ord-e0cedbe773804b7d8681e3262682aa2f
出典データセット
uspto-grants-2014_12
特許番号
US08916578B2

反応ノート

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