3-Nitrobenzaldehyde → HCID 54569294、化合物

HRID 2232413ノート

反応式

HRID 2232413 の反応式
[CH2:1]([Li])[CH2:2][CH2:3][CH3:4].[PH4+].[N+:7]([C:10]1[CH:11]=[C:12]([CH:15]=[CH:16][CH:17]=1)C=O)([O-:9])=[O:8].O1CC[CH2:20][CH2:19]1>[Br-].C([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)CCC.CCCCCC>[CH:1]([C:12]1[CH:11]=[C:10]([N+:7]([O-:9])=[O:8])[CH:17]=[CH:16][CH:15]=1)=[CH:2][CH2:3][CH2:4][CH2:19][CH3:20]

参加物

7

反応物 4

HCID 74493-NitrobenzaldehydeHCID 8028Tetrahydrofuran2 回HCID 5460504PhosphoniumHCID 178418339Butyllithium

生成物 1

HCID 54569294HCID 54569294、化合物収率 90%

試薬・触媒・溶媒 2

HCID 159628Butyltriphenylphosphonium bromide触媒HCID 8058Hexane溶媒

反応条件

温度
0 °C

実験手順

A suspension of butyltriphenylphosphonium bromide (27.3 g, 0.067 m) in 350 ml of dry tetrahydrofuran was cooled to 0° C. under an inert atmosphere of argon. To this stirred suspension was added 0.9 equivalent (0.06 m) of n-butyl lithium in hexane with continued cooling. The mixture was stirred at 0° and as ylide formation proceeded the solid phosphonium salt dissolved with formation of a red-orange solution. After 30 minutes a solution of one equivalent of 3-nitrobenzaldehyde (10.1 g, 0.067 m) in 200 ml of dry tetrahydrofuran was added dropwise to the ylide solution during 30 minutes. The reaction mixture was stirred and allowed to warm to room temperature. After 1 hour the reaction was quenched into 500 ml of saturated ammonium chloride solution and extracted several times with diethyl ether. The combined ether extracts were washed with water and with saturated sodium chloride solution and dried over magnesium sulfate. Filtration of the drying agent and concentration of the ether solution under vacuum afforded a clear brown oil which was purified by silica gel column chromatography to give 3-(1-hexenyl)nitrobenzene (11.0 g, 90% yield) as a clear, light-yellow oil. NMR of this material showed it to be mostly cis configuration at the double bond with some trans isomer present.

後処理

  1. dissolutiondissolved with formation of a red-orange solution
  2. stirringThe reaction mixture was stirred
  3. temperatureto warm to room temperature
  4. customAfter 1 hour the reaction was quenched into 500 ml of saturated ammonium chloride solution
  5. extractionextracted several times with diethyl ether
  6. washThe combined ether extracts were washed with water and with saturated sodium chloride solution
  7. dry with materialdried over magnesium sulfate
  8. filtrationFiltration of the drying agent and concentration of the ether solution under vacuum
  9. customafforded a clear brown oil which
  10. customwas purified by silica gel column chromatography

出典と根拠

ORDレコード
ord-16849b05d440445cb2812ea6aa2b7fe9
出典データセット
uspto-grants-1988_11
特許番号
US04788209

反応ノート

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