Benzoyl chloride → (4-Bromo-2,5-dimethoxyphenyl)(phenyl)methanone

HRID 1486830

반응식

HRID 1486830 반응식
[Br:1][C:2]1[CH:7]=[C:6]([O:8][CH3:9])[CH:5]=[CH:4][C:3]=1[O:10][CH3:11].[C:12](Cl)(=[O:19])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.OS(C(F)(F)F)(=O)=O.[OH-].[Na+]>C(Cl)Cl.O.CO>[Br:1][C:2]1[C:3]([O:10][CH3:11])=[CH:4][C:5]([C:12]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[O:19])=[C:6]([O:8][CH3:9])[CH:7]=1

참가 물질

8

반응물 4

HCID 7412Benzoyl chlorideHCID 14798Sodium HydroxideHCID 62406Trifluoromethanesulfonic acidHCID 91353Benzene, 2-bromo-1,4-dimethoxy-

생성물 1

HCID 67466544(4-Bromo-2,5-dimethoxyphenyl)(phenyl)methanone수율 76%

시약·촉매·용매 3

HCID 887Methanol용매HCID 962Water용매HCID 6344Dichloromethane용매

실험 절차

To a solution of 2-bromo-1,4-bis(methyloxy)benzene (2.0 g, 9.21 mmol) and benzoyl chloride (1.229 mL, 10.596 mmol, 1.15 eq) in DCM (9.5 mL, C=1.0M) at 0° C. was added triflic acid (0.815 mL, 9.21 mmol) over 5 min. The reaction mixture was allowed to warm to ambient temperature (40 min) and then slowly heated to gentle reflux (oil bath at 42° C.) and stirred for 48 h. The reaction mixture was cooled to r.t., and MeOH (0.3 mL) was added and stirring was continued for 30 min. The reaction mixture was poured into 80 mL of ice cooled water. The aqueous layer was neutralized with a 1 M NaOH solution. The layers were separated. The aqueous layer was extracted twice with DCM (2×20 mL). The combined organic phase was washed twice with a 1/1 water/brine mixture (2×30 mL), dried over MgSO4, filtered and concentrated in vacuo to a brown-orange oil. Then, MTBE (7 mL) was added and the mixture was stirred into an ultra-sound bath. The resulting solid was filtered, rinsed with 1:1 MTBE/hexanes mixture and air dried to afford [4-bromo-2,5-bis(methyloxy)phenyl](phenyl)methanone in 76% yield (2.258 g) as a white solid. 1H NMR (300 MHz, DMSO) δ 7.72 (d, J=8.5 Hz, 1H), 7.65 (t, J=7.4 Hz, 1H), 7.51 (t, J=7.6 Hz, 1H), 7.45 (s, 1H), 7.10 (s, 1H), 3.81 (s, 2H), 3.63 (s, 2H), 13C NMR (75 MHz, DMSO) δ 194.5 (C═O), 150.7 (C), 149.7 (C), 136.7 (C), 133.5 (CH), 129.3 (2CH), 128.6 (2CH), 128.2 (C), 117.3 (CH), 113.3 (C), 112.5 (CH), 56.7 (OCH3), 56.5 (OCH3); MS (ESI) m/z: 321.1, 323.0 [M+H, 79Br, 81Br]+; 243.1, 245.0 [M-Ph, 79Br, 81Br]+.

후처리

  1. temperatureslowly heated
  2. temperatureto gentle reflux (oil bath at 42° C.)
  3. temperatureThe reaction mixture was cooled to r.t.
  4. stirringstirring
  5. waitwas continued for 30 min
  6. customThe layers were separated
  7. extractionThe aqueous layer was extracted twice with DCM (2×20 mL)
  8. washThe combined organic phase was washed twice with a 1/1 water/brine mixture (2×30 mL)
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo to a brown-orange oil
  12. additionThen, MTBE (7 mL) was added
  13. stirringthe mixture was stirred into an ultra-sound bath
  14. filtrationThe resulting solid was filtered
  15. washrinsed with 1:1 MTBE/hexanes mixture and air
  16. customdried

출처 및 근거

ORD 기록
ord-ce3841d57f7545aeb57e305352fba6b6
출처 데이터셋
uspto-grants-2016_08
특허 번호
US09428500B2

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