Hydrochloric Acid → HCID 13281350, compound

HRID 544685Notes

Reaction equation

HRID 544685 reaction equation
[Cl:1][C:2]1[C:3]([CH2:14][CH2:15][CH2:16][C:17](Cl)=[O:18])=[C:4]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:5]=[CH:6][CH:7]=1.[Cl-].[Al+3].[Cl-].[Cl-].Cl>C(=S)=S>[Cl:1][C:2]1[C:3]2[CH2:14][CH2:15][CH2:16][C:17](=[O:18])[C:9]3[CH:10]=[CH:11][CH:12]=[CH:13][C:8]=3[C:4]=2[CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 6451240Aluminum(III) ChlorideHCID 13281349HCID 13281349, compound

Product 1

HCID 13281350HCID 13281350, compound

Reagents, catalysts & solvents 1

HCID 6348Carbon DisulfideSolvent3×

Procedure

Using the extreme-dilution technique described by Hedden and Brown, J. Am. Chem. Soc., 75, 3744-48 (1953), 4-(3-chloro-[1,1'-biphenyl]-2-yl)butanoic acid chloride (18.9 g, 0.069 mole) was diluted in carbon disulfide (100 ml) and placed in the dropping funnel. The dilution flask was filled with carbon disulfide (approximately 700 ml). Aluminum chloride (19.8 g, 0.15 mole) in carbon disulfide (700 ml) was placed in the reaction flask and heated at reflux. The contents of the dropping funnel were added to the reaction during an eight day period. After complete addition the contents of the dilution flask were added to the reaction flask and the mixture allowed to stir at room temperature for approximately 18 hours. One liter of 2 N hydrochloric acid was added to the mixture and the total stirred for 0.5 hour. The mixture was poured into a separatory funnel and the organic phase separated. The remaining aqueous phase was saturated with sodium chloride and extracted with methylene chloride (3×250 ml). The organic phase and extracts were combined, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated under reduced pressure to yield an oil. The oil was subjected to column chromatography on silica gel eluted with toluene:methylene chloride (1:1). The fractions which contained the desired product were combined and evaporated under reduced pressure to give a solid. The solid was recrystallized from methylcyclohexane:n-heptane (30:70) to yield 9-chloro-5,6,7,8-tetrahydrodibenzo[a,c]cycloocten-5-one (m.p. 117.5°-118.5°). The solvent was evaporated from the mother liquor to give an oil. This oil was subjected to column chromatography on silica gel eluted with n-heptane:ethyl acetate (40:1). The fractions which contained the desired product were combined and evaporated under reduced pressure to give additional product.

Workup

  1. temperatureheated
  2. temperatureat reflux
  3. additionThe contents of the dropping funnel were added to the reaction during an eight day period
  4. additionAfter complete addition the contents of the dilution flask
  5. additionwere added to the reaction flask
  6. stirringthe total stirred for 0.5 hour
  7. additionThe mixture was poured into a separatory funnel
  8. customthe organic phase separated
  9. extractionextracted with methylene chloride (3×250 ml)
  10. dry with materialdried over anhydrous magnesium sulfate
  11. filtrationfiltered
  12. customthe filtrate evaporated under reduced pressure
  13. customto yield an oil
  14. washeluted with toluene:methylene chloride (1:1)
  15. customevaporated under reduced pressure
  16. customto give a solid
  17. customThe solid was recrystallized from methylcyclohexane:n-heptane (30:70)

Sources & evidence

ORD record
ord-6190694ec12d4e8b8e72d686b6c3255d
Source dataset
uspto-grants-1984_05
Patent number
US04451484

Reaction notes

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