Potassium Carbonate → 4-Bromo-3,5-dimethylphenyl 3-(3-nitrophenyl)propiolate

HRID 1483186ノート

反応式

HRID 1483186 の反応式
I[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[CH:3]=1.C([O-])([O-])=O.[K+].[K+].[C:17]([O:21][C:22]1[CH:27]=[C:26]([CH3:28])[C:25]([Br:29])=[C:24]([CH3:30])[CH:23]=1)(=[O:20])[C:18]#[CH:19]>C1COCC1.[Cu]I>[N+:8]([C:4]1[CH:3]=[C:2]([C:19]#[C:18][C:17]([O:21][C:22]2[CH:23]=[C:24]([CH3:30])[C:25]([Br:29])=[C:26]([CH3:28])[CH:27]=2)=[O:20])[CH:7]=[CH:6][CH:5]=1)([O-:10])=[O:9]

参加物

6

反応物 3

HCID 11430Potassium CarbonateHCID 125741-Iodo-3-nitrobenzeneHCID 725452334-Bromo-3,5-dimethylphenyl propiolate

生成物 1

HCID 894777654-Bromo-3,5-dimethylphenyl 3-(3-nitrophenyl)propiolate収率 29%

試薬・触媒・溶媒 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
65 °C

実験手順

1-Iodo-3-nitrobenzene (41.05 g, 164.3 mmol) in THF (100 mL) was degassed under reduced pressure at −78° C., and then nitrogen gas was introduced. To the solution was added K2CO3 (41.27 g, 298.6 mmol), CuI (2.27 g, 11.9 mmol) and PdCl2(Ph3P)2 (1.11 g, 1.57 mmol), and the mixture was stirred at 65° C. 4-bromo-3,5-dimethylphenyl propiolate (6-1) (37.79 g, 149.3 mmol) in THF (68 mL) was added by syringe pump over a period of 5.4 hr, and the mixture was stirred an additional 1 h after addition was complete. After being cooled to room temperature, the mixture was filtered. The filtrate was concentrated and purified by silica gel column chromatography. The fractions containing the desired compound were concentrated. To the concentrate added hexane and the precipitated solid was collected by filtration. The solid was washed with hexane and dried to give the title compound 6-2 (15.96 g, 29% yield) as a brown solid.

後処理

  1. additionnitrogen gas was introduced
  2. stirringthe mixture was stirred an additional 1 h
  3. additionafter addition
  4. temperatureAfter being cooled to room temperature
  5. filtrationthe mixture was filtered
  6. concentrationThe filtrate was concentrated
  7. custompurified by silica gel column chromatography
  8. additionThe fractions containing the desired compound
  9. concentrationwere concentrated
  10. additionTo the concentrate added hexane
  11. filtrationthe precipitated solid was collected by filtration
  12. washThe solid was washed with hexane
  13. customdried

出典と根拠

ORDレコード
ord-6dbdfa8f095c4178bdd62a44f2c4d7f3
出典データセット
uspto-grants-2016_08
特許番号
US09416121B2

反応ノート

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