1,2-Dibromoethane → 4-(4-(2-Bromoethoxy)-benzyl)-3-(2,4-dichlorophenyl)-7-methoxy-chromen-2-one

HRID 1296686ノート

反応式

HRID 1296686 の反応式
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9]1[C:10](=[O:29])[O:11][C:12]2[C:17]([C:18]=1[CH2:19][C:20]1[CH:25]=[CH:24][C:23]([OH:26])=[CH:22][CH:21]=1)=[CH:16][CH:15]=[C:14]([O:27][CH3:28])[CH:13]=2.[Br:30][CH2:31][CH2:32]Br.C([O-])([O-])=O.[K+].[K+].C(Cl)Cl.O>CC(C)=O>[Br:30][CH2:31][CH2:32][O:26][C:23]1[CH:24]=[CH:25][C:20]([CH2:19][C:18]2[C:17]3[C:12](=[CH:13][C:14]([O:27][CH3:28])=[CH:15][CH:16]=3)[O:11][C:10](=[O:29])[C:9]=2[C:3]2[CH:4]=[CH:5][C:6]([Cl:8])=[CH:7][C:2]=2[Cl:1])=[CH:21][CH:22]=1

参加物

6

反応物 4

HCID 78391,2-Dibromoethane2 回HCID 11430Potassium Carbonate2 回HCID 113393373-(2,4-Dichlorophenyl)-4-(4-hydroxybenzyl)-7-methoxychromen-2-oneHCID 21908982Water methylene chloride

生成物 1

HCID 589130934-(4-(2-Bromoethoxy)-benzyl)-3-(2,4-dichlorophenyl)-7-methoxy-chromen-2-one収率 61%

試薬・触媒・溶媒 1

HCID 180Acetone溶媒

実験手順

A mixture of 3-(2,4-dichlorophenyl)-4-(4-hydroxybenzyl)-7-methoxy-chromen-2-one (6.4 g, 15.0 mmol), 1,2-dibromoethane (12.9 mL, 149.8 mmol) and K2CO3 (4.14 g, 30 mmol) in acetone (65 mL) was stirred at reflux temperature for 20.5 h. An additional portion of K2CO3 (241.6 mg, 1.75 mmol) and 1,2-dibromoethane (3.2 mL, 37.5 mmol) was added at that time and once more 7.5 h later. Heating was continued for an additional 20 h, for a total reaction time of 48 h. The resultant mixture was cooled to room temperature and poured into CH2Cl2/H2O. The layers were separated, and the aqueous phase was extracted with CH2Cl2 (2×). The combined organic layers were washed with brine (2×) and dried (MgSO4), and the solvent was removed in vacuo. The resultant residue was purified using flash chromatography (300 g silica gel, 4.5:1:1→4:1:1→3:1:1 hexanes:CH2Cl2:AcOEt) to provide the title compound as a white solid (4.851 g, 61%) in addition to recovered starting material (2.054 g, 32%). 1H NMR (300 MHz, CDCl3) δ 7.50 (d, J=2.0 Hz, 1H), 7.44 (d, J=9.0 Hz, 1H), 7.26 (dd, J=2.0, 8.0 Hz, 1H), 7.12 (d, J=8.0 Hz, 1H), 6.98–6.91 (m, 2H), 6.88 (d, J=2.0 Hz, 1H), 6.79–6.74 (m, 3H), 4.23 (t, J=6.5 Hz, 2H), 4.04 (d, J=15.5 Hz, 1H), 3.87 (s, 3H), 3.78 (d, J=15.5 Hz, 1H), 3.61 (t, J=6.5 Hz, 2H); MS (ESI) m/z 532.7 (M+H)+; HPLC tR 8.38 min.

後処理

  1. temperatureat reflux temperature for 20.5 h
  2. temperatureHeating
  3. customThe layers were separated
  4. extractionthe aqueous phase was extracted with CH2Cl2 (2×)
  5. washThe combined organic layers were washed with brine (2×)
  6. dry with materialdried (MgSO4)
  7. customthe solvent was removed in vacuo
  8. customThe resultant residue was purified

出典と根拠

ORDレコード
ord-df929075fba74423b94b98c4aa20df85
出典データセット
uspto-grants-2007_07
特許番号
US07247646B2

反応ノート

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