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

HRID 1486830

反応式

HRID 1486830 の反応式
[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

参加物

8

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 887Methanol溶媒HCID 962Water溶媒HCID 6344Dichloromethane溶媒

実験手順

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]+.

後処理

  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

出典と根拠

ORDレコード
ord-ce3841d57f7545aeb57e305352fba6b6
出典データセット
uspto-grants-2016_08
特許番号
US09428500B2

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