Sodium Hydroxide → HCID 14721901, compound

HRID 728048Notes

Reaction equation

HRID 728048 reaction equation
[Cl:1][C:2]1[CH:19]=[CH:18][C:5]([CH2:6][C:7]2[C:8](=O)[CH2:9][C:10]([CH3:16])([CH3:15])[CH2:11][C:12]=2[O:13]C)=[CH:4][CH:3]=1.[H-].[Al+3].[Li+].[H-].[H-].[H-].[OH-].[Na+].[Cr](Cl)([O-])(=O)=O.[NH+]1C=CC=CC=1>C(OCC)C.O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:6][C:7]2[C:12](=[O:13])[CH2:11][C:10]([CH3:16])([CH3:15])[CH2:9][CH:8]=2)=[CH:18][CH:19]=1

Participants

7

Reactant 4

HCID 14798Sodium HydroxideHCID 14721900HCID 14721900, compoundHCID 21226445Aluminium lithium hydrideHCID 178418287HCID 178418287, compound

Product 1

HCID 14721901HCID 14721901, compoundYield 91%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×

Procedure

98 g (0.35 mol) of the 2-(4-chlorobenzyl)-3- methoxy-5,5-dimethylcyclohex-2-en-1-one obtained in Example 2 were added to a slurry of 6.65 g (0.175 mol) lithium aluminum hydride in 490 mls diethyl ether at a rate sufficient to maintain reflux and the final reaction mixture refluxed for a further 30 minutes. 5 ml water were then added, followed by 5 ml 15% aqueous sodium hydroxide and a further 15 ml water and the resulting precipitate was filtered off. The filtrate was then shaken in 200 ml 5M hydrochloric acid for five minutes and the organic layer then separated, washed twice with 100 ml aliquots of saturated sodium bicarbonate solution, dried over anhydrous magnesium sulphate and stripped. The resulting oil was then dissolved in 430 mls dichloromethane, 18 g (0.085 mols) pyridinium chlorochromate were added and the reaction mixture stirred for 3 hours. 600 ml diethyl ether were added and the solid was then filtered off. The filtrate was washed three times with 10% sodium hydroxide, once with 2.5M hydrochloric acid and once with saturated sodium bicarbonate solution. It was then dried over anhydrous magnesium sulphate and stripped to give 82 g of crude product. Distillation of the crude product under reduced pressure (0.15 mm mercury) gave 79 g 2-(4-chlorobenzyl)-5,5-dimethylcyclohex-2-en-1-one, b.pt. 130° C. at 0.15 mm mercury. Yield: 91%.

Workup

  1. temperatureto maintain
  2. temperaturereflux
  3. customthe final reaction mixture
  4. temperaturerefluxed for a further 30 minutes
  5. filtrationa further 15 ml water and the resulting precipitate was filtered off
  6. customthe organic layer then separated
  7. washwashed twice with 100 ml aliquots of saturated sodium bicarbonate solution
  8. dry with materialdried over anhydrous magnesium sulphate
  9. dissolutionThe resulting oil was then dissolved in 430 mls dichloromethane
  10. stirringthe reaction mixture stirred for 3 hours
  11. filtrationthe solid was then filtered off
  12. washThe filtrate was washed three times with 10% sodium hydroxide
  13. dry with materialIt was then dried over anhydrous magnesium sulphate
  14. customto give 82 g of crude product
  15. distillationDistillation of the crude product under reduced pressure (0.15 mm mercury)

Sources & evidence

ORD record
ord-3fe1b4a468404912baeeac5eea5351c5
Source dataset
uspto-grants-1991_09
Patent number
US05047426

Reaction notes

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