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Triethylamine → (3R,4R)-4-(4-Bromo-2-nitro-phenylamino)-3-hydroxy-piperidine-1-carboxylic acid tert-butyl ester

HRID 1670630
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HRID 1670630 반응식
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][C@@H:11]([NH2:14])[C@H:10]([OH:15])[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[Br:16][C:17]1[CH:18]=[CH:19][C:20](F)=[C:21]([N+:23]([O-:25])=[O:24])[CH:22]=1.C(N(CC)CC)C>C(OCC)(=O)C>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][C@@H:11]([NH:14][C:20]2[CH:19]=[CH:18][C:17]([Br:16])=[CH:22][C:21]=2[N+:23]([O-:25])=[O:24])[C@H:10]([OH:15])[CH2:9]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]
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참가 물질

5

반응물 3

HCID 8471TriethylamineHCID 27363284-Bromo-1-fluoro-2-nitrobenzeneHCID 10727458rac-tert-butyl (3R,4R)-4-amino-3-hydroxypiperidine-1-carboxylate

생성물 1

HCID 67335873(3R,4R)-4-(4-Bromo-2-nitro-phenylamino)-3-hydroxy-piperidine-1-carboxylic acid tert-butyl ester수율 148.3%

시약·촉매·용매 1

HCID 8857Ethyl Acetate
용매
2회

실험 절차

Heat a mixture of (3R,4R)-4-amino-3-hydroxy-piperidine-1-carboxylic acid tert-butyl ester (0.02 mol, 6.0 g), 5-bromo-2-fluoronitrobenzene (0.03 mol, 6.71 g) and triethyl amine (0.058 mol, 5.88 mL) in ethyl acetate (180 mL) to reflux for 16 h. Cool the reaction mixture to room temperature, dilute with ethyl acetate, and wash with water and brine. Dry the organic layer over anhydrous sodium sulfate, filter, and concentrate to obtain the title compound (12.35 g, crude). 1H NMR (400 MHz, CDCl3) δ 1.46 (s, 9H), 1.50-1.51 (m, 1H), 2.08-2.12 (m, 1H), 2.93 (dd, 1H), 3.01 (br s, 1H), 3.55-3.61 (m, 1H), 3.62-3.68 (m, 1H), 3.68 (br s, 1H), 4.13-4.18 (m, 1H), 6.97 (d, 1H), 7.48 (dd, 1H), 8.08 (d, 1H), 8.30 (d, 1H). ES-MS m/z 316 [M−Boc]+.

후처리

  1. temperatureHeat
  2. temperatureto reflux for 16 h
  3. washwash with water and brine
  4. dry with materialDry the organic layer over anhydrous sodium sulfate
  5. filtrationfilter
  6. concentrationconcentrate

출처 및 근거

ORD 기록
ord-7fd6381059414fa7a270d51ca59e067a
출처 데이터셋
uspto-grants-2011_08
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US07994164B2

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