Trifluoroacetic acid → 2-Benzyl-5-bromo-4-methoxyphenol

HRID 1486833노트

반응식

HRID 1486833 반응식
[Br:1][C:2]1[C:7]([O:8][CH3:9])=[CH:6][C:5]([C:10]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=O)=[C:4]([OH:18])[CH:3]=1.FC(F)(F)C(O)=O.C([SiH](CC)CC)C.[NH4+].[Cl-]>C(Cl)Cl.O>[CH2:10]([C:5]1[CH:6]=[C:7]([O:8][CH3:9])[C:2]([Br:1])=[CH:3][C:4]=1[OH:18])[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

참가 물질

7

반응물 4

HCID 6422Trifluoroacetic acidHCID 12052TriethylsilaneHCID 25517Ammonium ChlorideHCID 67464087[4-Bromo-2-hydroxy-5-(methyloxy)phenyl](phenyl)methanone

생성물 1

HCID 900135612-Benzyl-5-bromo-4-methoxyphenol수율 72%

시약·촉매·용매 2

HCID 962Water용매HCID 6344Dichloromethane용매2회

실험 절차

To a solution of (4-bromo-2-hydroxy-5-methoxyphenyl)(phenyl)methanone (100 mg, 0.325 mmol) in 0.22 mL of anhydrous DCM (C=1.5M), were successively added dropwise trifluoroacetic acid (0.25 mL, 10 eq) and triethylsilane (0.21 mL, 4 eq). After 17 h of stirring at r.t., the reaction mixture was hydrolyzed with a saturated NH4Cl solution (5 mL) The layers were diluted with 20 mL of DCM and 20 mL of water and then separated. The aqueous layer was extracted twice with DCM (2×5 mL). The combined organic phase was washed twice with a saturated NaHCO3 solution (2×20 mL), brine (20 mL), dried over MgSO4, filtered and concentrated in vacuo. The crude product was purified by silica gel flash chromatography (Cyclohexane/AcOEt 97:3) to afford the desired product in 72% yield (68.5 mg) as an uncoloured oil. 1H NMR (300 MHz, CDCl3) δ 7.36-7.28 (m, 2H), 7.28-7.20 (m, 3H), 7.01 (s, 1H), 6.70 (s, 1H), 4.89 (s, 1H), 3.96 (s, 2H), 3.80 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 150.3 (C), 148.1 (C), 139.4 (C), 128.8 (CH), 128.7 (CH), 127.5 (C), 126.6 (CH), 120.7 (CH), 115.0 (CH), 109.4 (C), 57.0 (OCH3), 36.4 (CH2Bn); MS (ESI) m/z: 310.1, 312.1 [M+NH4, 79Br, 81Br]+; 602.0, 604.3, 606.1 [2M+NH4, 79Br, 81Br]+.

후처리

  1. customseparated
  2. extractionThe aqueous layer was extracted twice with DCM (2×5 mL)
  3. washThe combined organic phase was washed twice with a saturated NaHCO3 solution (2×20 mL), brine (20 mL)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe crude product was purified by silica gel flash chromatography (Cyclohexane/AcOEt 97:3)

출처 및 근거

ORD 기록
ord-08996921a12e4025b1a416341928f037
출처 데이터셋
uspto-grants-2016_08
특허 번호
US09428500B2

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