Ammonium Hydroxide → (E)-4-(4-Chlorophenyl)-N,N-diethyl-N-heptyl-2-buten-1-aminium chloride

HRID 464032Notes

Reaction equation

HRID 464032 reaction equation
[Cl:1]C1C=CC(CC=CCCl)=CC=1.[Cl:13][C:14]1[CH:19]=[CH:18][C:17]([CH2:20][CH:21](Cl)[CH:22]=[CH2:23])=[CH:16][CH:15]=1.[CH2:25]([N:27]([CH2:35][CH3:36])[CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])[CH3:26].[OH-].[NH4+]>C(#N)C>[Cl-:1].[Cl:13][C:14]1[CH:19]=[CH:18][C:17]([CH2:20]/[CH:21]=[CH:22]/[CH2:23][N+:27]([CH2:25][CH3:26])([CH2:35][CH3:36])[CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])=[CH:16][CH:15]=1

Participants

6

Reactant 4

HCID 14923Ammonium HydroxideHCID 12496130N,N-Diethyl-1-heptanamineHCID 136602341-Chloro-4-(2-chloro-3-butenyl)benzeneHCID 538538941-Chloro-4-(4-chloro-2-butenyl)benzene

Product 1

HCID 13660267(E)-4-(4-Chlorophenyl)-N,N-diethyl-N-heptyl-2-buten-1-aminium chlorideYield 60%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

Dissolve 35.55 g (0.1768 mole) of a mixture of 1-chloro-4-(4-chloro-2-butenyl)benzene and 1-chloro-4-(2-chloro-3-butenyl)benzene and 27.7 g (0.1607 mole) of N,N-diethyl-1-heptanamine in 220 ml of acetonitrile. Heat the reaction mixture to reflux for 6 hours. Follow the progress of the reaction by thin layer chromatography (acetonitrile: ammonium hydroxide, 95:5). At the completion of the reaction, evaporate solvent and dissolve the residue in 400 ml distilled water. Add solid sodium bicarbonate until pH of solution is 8.5. Wash the aqueous mixture with 4×200 ml petroleum ether and then 5×200 ml Et2O. Add 1N HCl to aqueous layer until pH=1 and then extract with 3×200 ml methylene chloride. Dry over magnesium sulfate, filter and evaporate solvent. Dissolve the material in 150 ml of 2-butanone and then add diethyl ether until solution becomes cloudy. Warm solution until clear and then cool and store in freezer for 3 hours to complete crystallization and then filter title compound. Recrystallize a second time (2-butanone/ether) to provide the title compound in 60% yield.

Workup

  1. temperatureHeat the reaction mixture
  2. temperatureto reflux for 6 hours
  3. customAt the completion of the reaction
  4. customevaporate solvent
  5. dissolutiondissolve the residue in 400 ml
  6. distillationdistilled water
  7. additionAdd solid sodium bicarbonate until pH of solution
  8. washWash the aqueous mixture with 4×200 ml petroleum ether
  9. additionAdd 1N HCl to aqueous layer until pH=1
  10. extractionextract with 3×200 ml methylene chloride
  11. dry with materialDry over magnesium sulfate
  12. filtrationfilter
  13. customevaporate solvent
  14. dissolutionDissolve the material in 150 ml of 2-butanone
  15. temperatureWarm solution until clear and then cool
  16. customcrystallization
  17. filtrationfilter title compound
  18. customRecrystallize a second time (2-butanone/ether)

Sources & evidence

ORD record
ord-12a81ce6eded4eb994053f3609838655
Source dataset
uspto-grants-1985_10
Patent number
US04545995

Reaction notes

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