4-Nitrobenzaldehyde → 1-methyl-4-[(1E)-2-(4-nitrophenyl)ethenesulfonyl]benzene

HRID 227668

Reaction equation

HRID 227668 reaction equation
[C:1]1([CH3:11])[CH:6]=[CH:5][C:4]([S:7]([CH3:10])(=[O:9])=[O:8])=[CH:3][CH:2]=1.C([Li])CCC.C(OP(Cl)(OCC)=O)C.[N+:26]([C:29]1[CH:36]=[CH:35][C:32]([CH:33]=O)=[CH:31][CH:30]=1)([O-:28])=[O:27]>O1CCCC1.CCCCCC.O>[CH3:11][C:1]1[CH:6]=[CH:5][C:4]([S:7](/[CH:10]=[CH:33]/[C:32]2[CH:35]=[CH:36][C:29]([N+:26]([O-:28])=[O:27])=[CH:30][CH:31]=2)(=[O:9])=[O:8])=[CH:3][CH:2]=1

Participants

8

Reactant 4

HCID 5414-NitrobenzaldehydeHCID 13139Diethyl chlorophosphateHCID 18521p-Tolyl methyl sulfoneHCID 178418339Butyllithium

Product 1

HCID 138738071-methyl-4-[(1E)-2-(4-nitrophenyl)ethenesulfonyl]benzeneYield 98.1%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

To 15 g (85.47 mmol) of methyl p-tolyl sulfone dissolved in 450 cm3 of tetrahydrofuran are added, at a temperature in the region of 0° C. under an argon atmosphere, 117.5 cm3 (188 mmol) of a 1.06 M solution of n-butyl-lithium in hexane. After stirring for 30 minutes at a temperature in the region of 0° C. are added, under an argon atmosphere, 13 cm3 (85.47 mmol) of diethylchlorophosphate dissolved in 70 cm3 of tetrahydrofuran. After stirring for 30 minutes at a temperature in the region of 0° C., the reaction mixture is cooled to a temperature in the region of −78° C., followed by addition, under an argon atmosphere, of 13.05 g (85.47 mmol) of 4-nitrobenzaldehyde dissolved in 130 cm3 of tetrahydrofuran. After stirring for 1 hour at a temperature in the region of −78° C., the temperature of the reaction mixture is allowed to rise to a temperature in the region of 20° C., 100 cm3 of water are added and the mixture is concentrated under reduced pressure (2.7 kPa) to give a beige-coloured solid. The solid is stirred in 250 cm3 of water for 20 minutes, filtered, washed with three times 40 cm3 of water and oven-dried under reduced pressure (2.7 kPa) at 35° C. for 5 hours to give 25.43 g of 1-[(E)-2-(4-methylphenyl)sulfonylvinyl]-4-nitrobenzene in the form of a beige-coloured solid melting at 176° C.; M.W.=303, IE: m/z=303 M+, m/z=239 [M-SO2]+, m/z=139 [CH3-Ph-SO]+.

Workup

  1. additionare added, at a temperature in the region of 0° C. under an argon atmosphere
  2. additionare added, under an argon atmosphere
  3. stirringAfter stirring for 30 minutes at a temperature in the region of 0° C.
  4. temperaturethe reaction mixture is cooled to a temperature in the region of −78° C.
  5. stirringAfter stirring for 1 hour at a temperature in the region of −78° C.
  6. additionare added
  7. concentrationthe mixture is concentrated under reduced pressure (2.7 kPa)
  8. customto give a beige-coloured solid
  9. filtrationfiltered
  10. washwashed with three times 40 cm3 of water
  11. customoven-dried under reduced pressure (2.7 kPa) at 35° C. for 5 hours

Sources & evidence

ORD record
ord-ac38b2dc724141898525460096fd685f
Source dataset
uspto-grants-2009_07
Patent number
US07560571B2

Linked notes

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