4-Bromophenol → 4'-(Methylsulfonyl)-[1,1'-biphenyl]-4-ol

HRID 423452

반응식

HRID 423452 반응식
[CH3:1][S:2]([C:5]1[CH:10]=[CH:9][C:8](B(O)O)=[CH:7][CH:6]=1)(=[O:4])=[O:3].Br[C:15]1[CH:20]=[CH:19][C:18]([OH:21])=[CH:17][CH:16]=1.C([O-])([O-])=O.[Na+].[Na+]>COCCOC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:1][S:2]([C:5]1[CH:10]=[CH:9][C:8]([C:15]2[CH:20]=[CH:19][C:18]([OH:21])=[CH:17][CH:16]=2)=[CH:7][CH:6]=1)(=[O:4])=[O:3]

참가 물질

6

반응물 3

HCID 78084-BromophenolHCID 10340Sodium CarbonateHCID 27343644-(Methanesulfonyl)phenylboronic acid

생성물 1

HCID 149826764'-(Methylsulfonyl)-[1,1'-biphenyl]-4-ol수율 64%

시약·촉매·용매 2

HCID 178418397HCID 178418397, 화합물촉매HCID 80711,2-Dimethoxyethane용매

반응 조건

온도
90 °C

실험 절차

[4-(Methylsulfonyl)phenyl]boronic acid (0.69 g, 3.40 mmol) was added to a solution of 4-bromophenol (0.5 g, 2.83 mmol) in DME (25 mL), followed by addition of 2M Na2CO3 (25 mL) and Pd(PPh3)4 (0.17 g, 0.14 mmol). The reaction mixture was heated at 90° C. for 3 h, then cooled to ambient temperature, and extracted with ether. The combined organic extract was washed with brine, dried over Na2SO4, filtered, and the filtrate was concentrated to give the crude product as an off-white solid. The crude product was purified by chromatography on a silica gel column eluted with 50% EtOAc/hexane to give 0.45 g (64%) of 4′-(methylsulfonyl)-4-biphenylol as a white solid. Alternatively, 4′-(methylsulfonyl)-4-biphenylol was prepared from 4-bromophenyl methyl sulfone (2 g, 8.5 mmol), (4-hydroxyphenyl)boronic acid (1.76 g, 12.75 mmol), 2M Na2CO3 (100 mL) and Pd(PPh3)4 (0.1 g, 0.08 mmol) in DME (100 mL) in a manner similar to the conditions above. 1H NMR (400 MHz, CDCl3): δ 7.97 (d, 2H, J=8.6 Hz), 7.71 (d, 2H, J=8.3 Hz), 7.51 (d, 2H, J=8.6 Hz), 6.94 (d, 2H, J=8.5 Hz), 4.92 (s, 1H), 3.08 (s, 3H); LRMS (ESI), m/z 249 (M+H).

후처리

  1. temperaturecooled to ambient temperature
  2. extractionextracted with ether
  3. extractionThe combined organic extract
  4. washwas washed with brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationthe filtrate was concentrated
  8. customto give the crude product as an off-white solid
  9. customThe crude product was purified by chromatography on a silica gel column
  10. washeluted with 50% EtOAc/hexane

출처 및 근거

ORD 기록
ord-cc1c6b97e4c744338c51e2fe36413402
출처 데이터셋
uspto-grants-2012_01
특허 번호
US08101634B2

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