Acetonitrile → 2-((1R,4r)-4-(4-chlorophenyl)cyclohexyl)naphthalene-1,4-dione

HRID 2261874Notes

Reaction equation

HRID 2261874 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C@H:8]2[CH2:13][CH2:12][C@H:11]([C:14](O)=O)[CH2:10][CH2:9]2)=[CH:4][CH:3]=1.C(#N)C.[C:20]1(=[O:31])[C:29]2[C:24](=[CH:25][CH:26]=[CH:27][CH:28]=2)[C:23](=[O:30])[CH:22]=C1.S(OOS([O-])(=O)=O)([O-])(=O)=O.[NH4+].[NH4+]>O.[N+]([O-])([O-])=O.[Ag+]>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH:8]2[CH2:9][CH2:10][CH:11]([C:14]3[C:20](=[O:31])[C:29]4[C:24]([C:23](=[O:30])[CH:22]=3)=[CH:25][CH:26]=[CH:27][CH:28]=4)[CH2:12][CH2:13]2)=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 6342AcetonitrileHCID 85301,4-NaphthoquinoneHCID 62648Ammonium PersulfateHCID 178525693HCID 178525693, compound

Product 1

HCID 251644132-((1R,4r)-4-(4-chlorophenyl)cyclohexyl)naphthalene-1,4-dioneYield 20.3%

Reagents, catalysts & solvents 2

HCID 24470Silver NitrateCatalystHCID 962WaterSolvent2×

Conditions

Temperature
31 °C

Procedure

A mixture of 14.17 g silver nitrate (0.0838 moles) in 200 ml water, and 100 g (0.419 moles) trans-4-(4-chlorophenyl)cyclohexane carboxylic acid were prepared. To this mixture acetonitrile 500 ml was added under stirring and heated to reflux. 80 g (0.506 moles) 1,4-naphthoquinone was then added. 239 g (1.048 moles) ammonium persulfate dissolved in 600 ml water was added drop-wise to the stirred solution and continued reflux for half an hour. The reaction solution was then cooled to 30-32° C. and extracted with methylene chloride. The organic layer was first washed with water, followed with 10% sodium carbonate aqueous solution, and further with water until neutral pH. The organic layer was distilled to eliminate methylene chloride, stirred in acetonitrile, and filtered. The solid obtained was crystallized from acetonitrile to obtain 29.8 g of the trans isomer of Formula II (20.3% yield). M.P. 147- 149° C. (uncorrected).

Workup

  1. customwere prepared
  2. temperatureheated to reflux
  3. additionwas added drop-wise to the stirred solution
  4. temperaturecontinued reflux for half an hour
  5. extractionextracted with methylene chloride
  6. washThe organic layer was first washed with water
  7. distillationThe organic layer was distilled
  8. stirringstirred in acetonitrile
  9. filtrationfiltered
  10. customThe solid obtained
  11. customwas crystallized from acetonitrile

Sources & evidence

ORD record
ord-d9b163c048464aea959d4ca52d69f3a9
Source dataset
uspto-grants-2010_12
Patent number
US07847127B2

Reaction notes

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