Acetonitrile → HCID 178516167, compound

HRID 2261872Notes

Reaction equation

HRID 2261872 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]([C@H:8]2[CH2:9][CH2:10][C@H: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 178516167HCID 178516167, compoundYield 20.5%

Reagents, catalysts & solvents 2

HCID 24470Silver NitrateCatalystHCID 962WaterSolvent2×

Conditions

Temperature
2.5 °C

Procedure

To a stirred solution of silver nitrate (17.5 g, 0.104 moles) dissolved in 100 ml water, 50 g (0.209 moles) trans-4-(4-chlorophenyl)cyclohexane carboxylic acid was added. To this solution acetonitrile (250 ml) was added and under stirring and heated to reflux. 33.1 g (0.209 moles) 1,4-naphthoquinone was then added. 120 g (0.525 mole) ammonium persulfate dissolved in 400 ml water was added drop-wise to the stirred solution and continued reflux for 2 hours. The reaction solution was then cooled to 0-5° C. and extracted with methylene chloride. The organic layer was first washed with water, followed by 10% sodium carbonate aqueous solution, and further with water until the pH is neutral. The organic layer was distilled to eliminate methylene chloride and was then stirred in acetonitrile and filtered. The solid obtained was crystallized from acetonitrile to obtain 15 g of trans-2-[4-(4-chlorophenyl)cyclohexyl]-1,4-naphthoquinone (20% yield). M.P. 146-149 (uncorrected), 1H NMR (400 MHz), δH (d6-CDCl3) 8.07-8.14 (2H, m, Naphth), 7.65-7.74 (2H, m, Naphth), 7.27-7.30 (2H, d, arom.), 7.07-7.19 (2H, d, arom.), 6.80 (1H, s, naphtho.), 2.98-3.01 (1H, tt, CH), 2.54-2.58 (1H, tt, CH—), 1.25-2.03 (8H, multi, CH2).

Workup

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

Sources & evidence

ORD record
ord-76b84820c37a4cf6acaa84b3ece4aff0
Source dataset
uspto-grants-2010_12
Patent number
US07847127B2

Reaction notes

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