Aluminum dichloride → HCID 14330437, compound

HRID 2291997Notes

Reaction equation

HRID 2291997 reaction equation
[CH2:1]1[CH:8]2[N:4]([CH2:5][CH2:6][CH2:7]2)[C:3](=O)[CH2:2]1.[C:10]1([Li])[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.[AlH](Cl)Cl.[Cl-].[Al+3].[Cl-].[Cl-].[H-].[H-].[H-].[H-].[Li+].[Al+3].[C:30]([OH:37])(=[O:36])/[CH:31]=[CH:32]/[C:33]([OH:35])=[O:34]>C1COCC1.C1CCCCC1.CCOCC.CCOCC.CC(O)C.O>[C:30]([OH:37])(=[O:36])/[CH:31]=[CH:32]/[C:33]([OH:35])=[O:34].[C:10]1([CH:3]2[N:4]3[CH:8]([CH2:7][CH2:6][CH2:5]3)[CH2:1][CH2:2]2)[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

Participants

12

Reactant 6

HCID 11238Aluminum dichlorideHCID 444972Fumaric AcidHCID 566402Hexahydro-pyrrolizin-3-oneHCID 6451240Aluminum(III) ChlorideHCID 21226445Aluminium lithium hydrideHCID 178506676HCID 178506676, compound

Product 1

HCID 14330437HCID 14330437, compoundYield 9%

Reagents, catalysts & solvents 5

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×HCID 3776IsopropanolSolventHCID 8028TetrahydrofuranSolventHCID 21895417Cyclohexane diethyletherSolvent

Conditions

Temperature
-40 °C

Procedure

Into a round bottom flask was placed 5 g (0.04 moles) hexahydro-3H-pyrrolizin-3-one, described in CA, 86 89512 (1977) in 100 mL of dry THF. This was cooled to -40° C. and 20 mL of 2.0M phenyllithium in cyclohexane/ether was added over 40 min keeping the temperature below -20° C. The reaction mixture was stirred at -20° C. for 40 min and added to a suspension of AlCl2H made by adding 5.34 g (0.04 moles) aluminum chloride in 25 mL of dry ether to a suspension of 1.52 g (0.04 moles) LAH in ether. The reaction mixture was stirred overnight under nitrogen. To the reaction mixture was added 120 mL of water and it was stirred for one hr. The solid was filtered off and washed well with ether. The filtrate was made basic with 3N sodium hydroxide and extracted several times with ether. The ether layers were combined, washed with brine and dried (K2CO3). The solvent was removed in vacuo. The residue was taken up in ether, washed with water and extracted with 3N hydrogen chloride. The acidic layer was made basic by sodium hydroxide addition and extracted with ether. The ether layer was washed with brine, dried (K2CO3) and the solvent evaporated in vacuo. The resulting oil was flashed chromatographed on silica gel using 1:7 acetone:hexane as the eluant. The resulting oil was treated with one equivalent of fumaric acid in 2-propanol to give the salt which was recrystallized from 2-propanol to give 680 mg of hexahydro-3-phenyl-1H-pyrrolizine (E)-2-butenedioate (9%), mp 143°-145.5° C.

Workup

  1. customInto a round bottom flask was placed
  2. customthe temperature below -20° C
  3. stirringThe reaction mixture was stirred overnight under nitrogen
  4. stirringwas stirred for one hr
  5. filtrationThe solid was filtered off
  6. washwashed well with ether
  7. extractionextracted several times with ether
  8. washwashed with brine
  9. dry with materialdried (K2CO3)
  10. customThe solvent was removed in vacuo
  11. washwashed with water
  12. extractionextracted with 3N hydrogen chloride
  13. additionThe acidic layer was made basic by sodium hydroxide addition
  14. extractionextracted with ether
  15. washThe ether layer was washed with brine
  16. dry with materialdried (K2CO3)
  17. customthe solvent evaporated in vacuo
  18. customThe resulting oil was flashed chromatographed on silica gel using 1:7 acetone
  19. customto give the salt which
  20. customwas recrystallized from 2-propanol

Sources & evidence

ORD record
ord-e276ad2dd83146bca4af8ab86220d85f
Source dataset
uspto-grants-1989_01
Patent number
US04800207

Reaction notes

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