Potassium → HCID 19966028, compound

HRID 1734890Notes

Reaction equation

HRID 1734890 reaction equation
CC(C)([O-])C.[K+].[CH:7]1([CH2:14][CH2:15][C:16](=[O:23])[CH2:17][C:18](OCC)=O)[CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8]1.[K].[C:25]([C:29]1[CH:34]=[CH:33][C:32](CI)=[CH:31][C:30]=1[N+:37]([O-:39])=[O:38])([CH3:28])([CH3:27])[CH3:26]>C(OCC)C.O1CCCC1>[C:25]([C:29]1[CH:34]=[CH:33][C:32]([CH2:18][CH2:17][C:16](=[O:23])[CH2:15][CH2:14][CH:7]2[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13]2)=[CH:31][C:30]=1[N+:37]([O-:39])=[O:38])([CH3:28])([CH3:26])[CH3:27]

Participants

7

Reactant 4

HCID 5462222PotassiumHCID 19966029HCID 19966029, compoundHCID 19966064HCID 19966064, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 19966028HCID 19966028, compoundYield 68.1%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

454 mg (4.06 mmol) of potassium-t-butoxide were added to 10 ml of a tetrahydrofuran solution containing 1.00 g (4.16 mmol) of ethyl 5-cycloheptyl-3-oxovalerate (prepared as described in Preparation 5). The mixture was then stirred for 10 minutes to prepare the corresponding potassium salt. 1.11 g (3.47 mmol) of 2-t-butyl-5-iodomethyl-1-nitrobenzene (prepared as described in Preparation 51) were added to the mixture in an ice bath, and the mixture was stirred for 2 hours at the temperature of the ice bath. The reaction solution was diluted with diethyl ether and washed with water. The solvent was removed by distillation under reduced pressure, and the resulting residue was dissolved in 10 ml of ethanol. 1.73 ml of a 2N aqueous solution of sodium hydroxide were added, and the mixture was heated for 4 hours under reflux. The reaction mixture was then cooled in an ice bath, sufficient concentrated aqueous hydrochloric acid was added to adjust its pH to a value of 5.0, and the mixture was heated for a further 2 hours under reflux. At the end of this time, the reaction solution was diluted with diethyl ether and washed with water. The solvent was then removed by distillation under reduced pressure. The resulting residue was subjected to column chromatography through 70 g of silica gel. Elution with a 2:1 by volume mixture of methylene chloride and hexane afforded 850 mg (yield 68%) of the title compound as an oily substance.

Workup

  1. washwashed with water
  2. customThe solvent was removed by distillation under reduced pressure
  3. dissolutionthe resulting residue was dissolved in 10 ml of ethanol
  4. addition1.73 ml of a 2N aqueous solution of sodium hydroxide were added
  5. temperaturethe mixture was heated for 4 hours
  6. temperatureunder reflux
  7. temperatureThe reaction mixture was then cooled in an ice bath
  8. additionsufficient concentrated aqueous hydrochloric acid was added
  9. temperaturethe mixture was heated for a further 2 hours
  10. temperatureunder reflux
  11. additionAt the end of this time, the reaction solution was diluted with diethyl ether
  12. washwashed with water
  13. customThe solvent was then removed by distillation under reduced pressure
  14. washElution with a 2:1
  15. additionby volume mixture of methylene chloride and hexane

Sources & evidence

ORD record
ord-f3ec796d39aa4be5a9d29b1cc36e1510
Source dataset
uspto-grants-1996_07
Patent number
US05534529

Reaction notes

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