Piperidine → Ethyl 3-nitro-4-(piperidin-1-yl)benzoate

HRID 219781

반응식

HRID 219781 반응식
F[C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][C:3]=1[N+:13]([O-:15])=[O:14].[NH:16]1[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]1>CN(C=O)C.O>[N+:13]([C:3]1[CH:4]=[C:5]([CH:11]=[CH:12][C:2]=1[N:16]1[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]1)[C:6]([O:8][CH2:9][CH3:10])=[O:7])([O-:15])=[O:14]

참가 물질

5

반응물 2

HCID 8082PiperidineHCID 21277355Ethyl 4-fluoro-3-nitrobenzoate

생성물 1

HCID 12493642Ethyl 3-nitro-4-(piperidin-1-yl)benzoate

시약·촉매·용매 2

HCID 962Water용매HCID 6228Dimethylformamide용매

반응 조건

온도
50 °C

실험 절차

A mixture of ethyl 4-fluoro-3-nitrobenzoate (Clontech 01072, 500 mg; 2.35 mmol; 1 eq.) and piperidine (599.2 mg; 7.04 mmol; 3 eq.) in DMF (2 mL) was heated to 50° C. for 3 hours. The reaction was then allowed to return to RT and diluted with water. It was extracted with EtOAc and the organic phase was dried over sodium sulfate and concentrated in vacuo, affording ethyl 3-nitro-4-piperidin-1-ylbenzoate as a yellow oil. The residue was taken up in THF (15 mL) and lithium hydroxide (280.86 mg; 11.73 mmol; 5 eq.) was added, followed by water (15 mL). The reaction mixture was then stirred at RT for 5 hours. It was concentrated and the residue was diluted with water. The aqueous phase was washed with Et2O and acidified to pH 5 with acetic acid. It was extracted with Et2O and the organic phase was dried over magnesium sulfate and concentrated, affording the title compound as a yellow solid (562 mg, 96%). 1H NMR: (DMSO-d6, 300 MHz) δ 13.07 (s, 1H), 8.29-8.28 (d, J=2.11 Hz, 1H), 8.03-8 (dd, J=8.91 Hz, J=2.20 Hz, 1H), 7.35-7.33 (d, J=8.91 Hz, 1H), 3.15-3.13 (m, 4H), 1.64-1.60 (m, 6H). LC/MS (Method A): 252.9 (M+H)+; 250.9 (M−H)−. HPLC (Method A) Rt 3.69 min (Purity: 99.7%).

후처리

  1. customto return to RT
  2. extractionIt was extracted with EtOAc
  3. dry with materialthe organic phase was dried over sodium sulfate
  4. concentrationconcentrated in vacuo

출처 및 근거

ORD 기록
ord-b9d6e5aeb87b4261a8c9995a8d711f38
출처 데이터셋
uspto-grants-2012_06
특허 번호
US08202865B2

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