3-Nitrobenzaldehyde → HCID 54569294, compound

HRID 2232413Notes

Reaction equation

HRID 2232413 reaction equation
[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]

Participants

7

Reactant 4

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

Product 1

HCID 54569294HCID 54569294, compoundYield 90%

Reagents, catalysts & solvents 2

HCID 159628Butyltriphenylphosphonium bromideCatalystHCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-16849b05d440445cb2812ea6aa2b7fe9
Source dataset
uspto-grants-1988_11
Patent number
US04788209

Reaction notes

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