Diethyl Ether → 1-(4-Chlorobenzyl)-2-hydroxy-2-hydroxymethyl-3,3-dimethylcyclopentane

HRID 257606Notes

Reaction equation

HRID 257606 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[Cl-].[Al+3].[Cl-].[Cl-].[Cl:11][C:12]1[CH:30]=[CH:29][C:15]([CH2:16][C:17]23[O:28][C:18]2([C:24](OC)=[O:25])[C:19]([CH3:23])([CH3:22])[CH2:20][CH2:21]3)=[CH:14][CH:13]=1.C(OCC)C>COCCOC>[Cl:11][C:12]1[CH:13]=[CH:14][C:15]([CH2:16][CH:17]2[CH2:21][CH2:20][C:19]([CH3:22])([CH3:23])[C:18]2([OH:28])[CH2:24][OH:25])=[CH:29][CH:30]=1

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 6451240Aluminum(III) ChlorideHCID 14721902HCID 14721902, compound2×HCID 21226445Aluminium lithium hydride2×

Product 1

HCID 147219041-(4-Chlorobenzyl)-2-hydroxy-2-hydroxymethyl-3,3-dimethylcyclopentaneYield 88.2%

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent2×

Procedure

2.7 g (71 mmols) lithium aluminium hydride were added to a suspension of 2.7 g (24 mmols) aluminium chloride partially dissolved in 120 ml 1,2-dimethoxyethane, the addition of lithium aluminium hydride causing a rise in temperature to 50° C. The resulting slurry was incubated at 50° C. for 30 minutes. A solution of 6.8 g (23 mmols) 1-(4-chlorobenzyl)-1,2-epoxy-3,3-dimethyl-2-methoxycarbonylcyclopentane prepared as described in (g) in 30 ml 1,2-dimethoxyethane was then added over a period of 30 minutes whilst maintaining the temperature of the reaction mixture at 50°-55° C. After 1 hour, thin layer chromatography indicated that the reaction was complete and the excess lithium aluminium hydride was therefore destroyed by adding 10 ml saturated aqueous ammonium chloride solution followed by 10 ml water. This produced a sludgy solid which filtered only slowly. After filtration, the solid was dissolved in 2N hydrochloric acid and extracted twice with diethyl ether. The extracts were combined with the filtrate and flashed to give 5.9 g crude product. Trituration with cold 60/80 petroleum and a little diethyl ether gave 5.45 g 1-(4-chlorobenzyl)-3,3-dimethyl-2-hydroxy-2-hydroxymethylcyclopentane as a white solid, m.pt. 103°-104° C. Yield: 82%.

Workup

  1. additionwas then added over a period of 30 minutes
  2. temperaturewhilst maintaining the temperature of the reaction mixture at 50°-55° C
  3. waitAfter 1 hour
  4. customthe excess lithium aluminium hydride was therefore destroyed
  5. additionby adding 10 ml saturated aqueous ammonium chloride solution
  6. customThis produced a sludgy solid which
  7. filtrationfiltered only slowly
  8. filtrationAfter filtration
  9. dissolutionthe solid was dissolved in 2N hydrochloric acid
  10. extractionextracted twice with diethyl ether
  11. customto give 5.9 g crude product

Sources & evidence

ORD record
ord-58f1adc59eea46d99e9573279ef0a1ff
Source dataset
uspto-grants-1993_11
Patent number
US05262543

Reaction notes

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