Water → [5-(3,4-Dichlorophenyl)-2,3-dihydro-1H-pyrrolizine-6,7-diyl]dimethanol

HRID 569791Notes

Reaction equation

HRID 569791 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:9]2[N:10]3[C:14](=[C:15]([C:21](OC)=[O:22])[C:16]=2[C:17](OC)=[O:18])[CH2:13][CH2:12][CH2:11]3)[CH:5]=[CH:6][C:7]=1[Cl:8].[H-].[Al+3].[Li+].[H-].[H-].[H-].[H-].O>ClCCl.CCOCC>[Cl:1][C:2]1[CH:3]=[C:4]([C:9]2[N:10]3[C:14](=[C:15]([CH2:21][OH:22])[C:16]=2[CH2:17][OH:18])[CH2:13][CH2:12][CH2:11]3)[CH:5]=[CH:6][C:7]=1[Cl:8]

Participants

7

Reactant 4

HCID 962WaterHCID 166653HydrideHCID 320363dimethyl 5-(3,4-dichlorophenyl)-2,3-dihydro-1H-pyrrolizine-6,7-dicarboxylateHCID 21226445Aluminium lithium hydride

Product 1

HCID 320364[5-(3,4-Dichlorophenyl)-2,3-dihydro-1H-pyrrolizine-6,7-diyl]dimethanolYield 89%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 6344DichloromethaneSolvent

Procedure

A solution of dimethyl 2,3-dihydro-5-(3,4-dichlorophenyl)-1H-pyrrolizine-6,7-dicarboxylate (57.8 g, 0.157 mol) in dry dichloromethane (250 mL) was added dropwise, over a 30-min period, to a mechanically stirred mixture of lithium aluminum hydride (14.04 g, 2.35 equiv) in anhydrous ether (400 ml) heated under reflux. The stirred mixture was heated at reflux for 1 h after the addition was completed and cooled in an ice bath. The excess hydride was decomposed with wet ether and then with water until the salts were white. The mixture was filtered (through sintered glass) and the inorganic residue was washed with several portions (ca. 100 mL) of hot dichloromethane until the total filtrate volume was 1.2 L. The filtrate was concentrated in vacuo to a volume of 500 mL, warmed to boiling, and diluted with slow addition of 350 mL of petroleum ether. Compound 2,3-Dihydro-5-(3',4'-dichlorophenyl)-6,7-bis(hydroxy-methyl)-1H-pyrrolizine precipitated as clear, white, chunky prisms (33.8 g); the concentrated mother liquor, after similar treatment, gave an additional 9.71 g of 2,3-dihydro-5-(3',4'-dichlorophenyl)-6,7-bis(hydroxymethyl)-1H-pyrrolizine to a total yield of 89%.

Workup

  1. temperatureheated
  2. temperatureunder reflux
  3. temperatureThe stirred mixture was heated
  4. temperatureat reflux for 1 h
  5. additionafter the addition
  6. temperaturecooled in an ice bath
  7. filtrationThe mixture was filtered (through sintered glass)
  8. washthe inorganic residue was washed with several portions (ca. 100 mL) of hot dichloromethane until the total filtrate volume
  9. concentrationThe filtrate was concentrated in vacuo to a volume of 500 mL
  10. temperaturewarmed
  11. additiondiluted with slow addition of 350 mL of petroleum ether
  12. customCompound 2,3-Dihydro-5-(3',4'-dichlorophenyl)-6,7-bis(hydroxy-methyl)-1H-pyrrolizine precipitated as clear, white, chunky prisms (33.8 g)

Sources & evidence

ORD record
ord-97a4177324184dd0a7d886194b334dc8
Source dataset
uspto-grants-1988_03
Patent number
US04734423

Reaction notes

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