Diethyl Ether → HCID 20338100, compound

HRID 2420028Notes

Reaction equation

HRID 2420028 reaction equation
[Mg].[CH2:2](Cl)[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.CCOCC.[Cl-].[CH2:16]([N+:23]1[CH:28]=[CH:27][C:26]([CH2:29][CH3:30])=[C:25]([CH2:31][CH3:32])[CH:24]=1)[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1>C1C=CC=CC=1>[CH2:16]([N:23]1[CH2:28][CH2:27][C:26]([CH2:29][CH3:30])=[C:25]([CH2:31][CH3:32])[CH:24]1[CH2:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1)[C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 7503Benzyl ChlorideHCID 5462224MagnesiumHCID 203381101-Benzyl-3,4-diethylpyridin-1-ium chloride

Product 1

HCID 20338100HCID 20338100, compound

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

The Grignard reagent prepared from magnesium (85.5 g.), benzyl chloride (407 g.) and ether (3020 ml.) was added to the slurry of 1-benzyl-3,4-diethylpyridinium chloride in benzene (2250 ml.). After refluxing the mixture was quenched in ice and ammonium chloride (453 g.). Ammonium hydroxide was added to the mixture. The ether layer was washed with water and concentrated. A solution of sodium borohydride (52 g.) in water (260 ml.) was added to a solution of the residue (712 g.) in ethanol (2 l.). The mixture was stirred, allowed to stand overnight and filtered. The filtrate was concentrated under vacuum. Water and ether were added to the residue. The ether layer was washed with water, dried and concentrated. The residue was distilled under vacuum. The main fractions darkened on exposure to air. Therefore, the sodium borohydride reduction was repeated excluding water. Sodium borohydride (42 g.) was added portionwise with stirring to a solution of the combined main fractions (517 g.) in ethanol (100%, 1 l.). The mixture was stirred for 6 hours, allowed to stand overnight and concentrated. Water and ether were added. The ether layer was washed with water, dried and concentrated. Since the reduction still appeared incomplete, it was repeated using dimethylformamide as the solvent. Sodium borohydride (40 g.) was added portionwise to a solution of the residue in dimethylformamide (1 l.). The mixture was stirred and allowed to stand overnight. Water was added and the mixture was extracted with ether. The ether extracts were washed with water, dried and concentrated. The residue was distilled under vacuum, affording 1,2-dibenzyl-3,4-diethyl-1,2,5,6-tetrahydropyridine (172 g., b.r. 154°-178° C./0.1 mm., mostly at 174° C.).

Workup

  1. temperatureAfter refluxing the mixture
  2. customwas quenched in ice
  3. additionAmmonium hydroxide was added to the mixture
  4. washThe ether layer was washed with water
  5. concentrationconcentrated
  6. additionA solution of sodium borohydride (52 g.) in water (260 ml.) was added to a solution of the residue (712 g.) in ethanol (2 l.)
  7. filtrationfiltered
  8. concentrationThe filtrate was concentrated under vacuum
  9. additionWater and ether were added to the residue
  10. washThe ether layer was washed with water
  11. customdried
  12. concentrationconcentrated
  13. distillationThe residue was distilled under vacuum
  14. additionSodium borohydride (42 g.) was added portionwise
  15. stirringwith stirring to a solution of the combined main fractions (517 g.) in ethanol (100%, 1 l.)
  16. stirringThe mixture was stirred for 6 hours
  17. waitto stand overnight
  18. concentrationconcentrated
  19. additionWater and ether were added
  20. washThe ether layer was washed with water
  21. customdried
  22. concentrationconcentrated
  23. additionSodium borohydride (40 g.) was added portionwise to a solution of the residue in dimethylformamide (1 l.)
  24. stirringThe mixture was stirred
  25. waitto stand overnight
  26. additionWater was added
  27. extractionthe mixture was extracted with ether
  28. washThe ether extracts were washed with water
  29. customdried
  30. concentrationconcentrated
  31. distillationThe residue was distilled under vacuum

Sources & evidence

ORD record
ord-4a3efda7a28848ffb2be57ee88be296b
Source dataset
uspto-grants-1978_08
Patent number
US04108857

Reaction notes

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