Hydrochloric Acid → Methyl 1-[2-(4-bromophenyl)-2-oxoethyl]cyclopentanecarboxylate

HRID 907668

反応式

HRID 907668 の反応式
Cl[C:2](=[O:13])[CH2:3][C:4]1([C:9]([O:11][CH3:12])=[O:10])[CH2:8][CH2:7][CH2:6][CH2:5]1.[Br:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.[Cl-].[Cl-].[Cl-].[Al+3].Cl>C(OCC)(=O)C.O.ClCCl>[Br:14][C:15]1[CH:20]=[CH:19][C:18]([C:2](=[O:13])[CH2:3][C:4]2([C:9]([O:11][CH3:12])=[O:10])[CH2:8][CH2:7][CH2:6][CH2:5]2)=[CH:17][CH:16]=1

参加物

8

反応物 4

HCID 313Hydrochloric AcidHCID 7961BromobenzeneHCID 6451240Aluminum(III) ChlorideHCID 21985709Methyl 1-(2-chloro-2-oxoethyl)cyclopentanecarboxylate

生成物 1

HCID 21985683Methyl 1-[2-(4-bromophenyl)-2-oxoethyl]cyclopentanecarboxylate

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6344Dichloromethane溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
0 °C

実験手順

To a 150 mL flask was added dichloromethane (70 mL), methyl 1-(2-chloro-2-oxoethyl)cyclopentanecarboxylate] (3.50 g, 16.8 mmol) [prepared as described by Bajaj, et al., J. Indian Chem. Soc. 52:1076-78, 1975] and bromobenzene (2.77 g, 17.6 mmol), and the reaction mixture cooled to 0° C. before aluminum trichloride (4.77 g, 35.7 mmol) was slowly added. The mixture was stirred for 1 h at 0° C., then for 12 h at rt. The reaction mixture was slowly poured into 50 mL chilled (0° C.) 1 N aqueous hydrochloric acid solution. Water (50 mL) was added, followed by ethyl acetate (100 mL), and the mixture stirred for 30 minutes. The layers were separated and the aqueous layer extracted with additional ethyl acetate (100 mL). The combined organic layer was washed with saturated aqueous sodium chloride (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to yield a brown oil which was purified by flash chromatography (10:1/hexane:ethyl acetate) to afford methyl 1-[2-(4-bromophenyl)-2-oxoethyl]cyclopentane carboxylate as a yellow, crystalline solid (1.62 g, 30%). LC-MS ret. time 3.45 min, m/z 324.8 (MH+); 1H NMR (300 MHz, CDCl3) δ 1.50-1.83 (overlapping signals, 6H), 2.22-2.33 (m, 2H), 3.37 (s, 2H), 3.66 (s, 3), 7.59 (d, 2H), 7.80 (d, 2H).

後処理

  1. additionwas slowly added
  2. waitfor 12 h at rt
  3. additionThe reaction mixture was slowly poured into 50 mL
  4. stirringthe mixture stirred for 30 minutes
  5. customThe layers were separated
  6. extractionthe aqueous layer extracted with additional ethyl acetate (100 mL)
  7. washThe combined organic layer was washed with saturated aqueous sodium chloride (100 mL)
  8. dry with materialdried over anhydrous sodium sulfate
  9. concentrationconcentrated under reduced pressure
  10. customto yield a brown oil which
  11. customwas purified by flash chromatography (10:1/hexane:ethyl acetate)

出典と根拠

ORDレコード
ord-a03d91663cd34bde8f42355767422dc6
出典データセット
uspto-grants-2011_09
特許番号
US08013166B2

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