Water → 5H-Dibenzo(a,d)cycloheptene-2-acetic acid, alpha-methyl-5-oxo-

HRID 1439418Notes

Reaction equation

HRID 1439418 reaction equation
Br[CH:2]1[C:8]2[CH:9]=[CH:10][C:11]([CH:13]([CH3:17])[C:14]([OH:16])=[O:15])=[CH:12][C:7]=2[CH:6]=[CH:5][C:4]2[CH:18]=[CH:19][CH:20]=[CH:21][C:3]1=2.C(#N)C.O.CC[O:28]CC>C1(C)C=CC(S([O-])(=O)=O)=CC=1.[Ag+].C(O)(=O)C>[CH:12]1[C:7]2[CH:6]=[CH:5][C:4]3[CH:18]=[CH:19][CH:20]=[CH:21][C:3]=3[C:2](=[O:28])[C:8]=2[CH:9]=[CH:10][C:11]=1[CH:13]([CH3:17])[C:14]([OH:16])=[O:15]

Participants

7

Reactant 4

HCID 962WaterHCID 3283Diethyl EtherHCID 6342AcetonitrileHCID 21397491HCID 21397491, compound

Product 1

HCID 1739105H-Dibenzo(a,d)cycloheptene-2-acetic acid, alpha-methyl-5-oxo-Yield 15%

Reagents, catalysts & solvents 2

HCID 85606Benzenesulfonic acid, 4-methyl-, silver(1+) salt (1:1)CatalystHCID 176Acetic AcidSolvent

Conditions

Temperature
120 °C

Procedure

1.0 Gm. of silver p-toluenesulfonate and 0.5 gm. of 2-(5-bromo-5H-dibenzo[a,d]cyclohepten-2-yl)propionic acid are stirred in 50 ml. of acetonitrile in the dark for 6 hours. Water, ether and 2.0 ml. of acetic acid are added. The ethereal layer is washed, dried and evaporated. The products, 2-(5-p-toluene-sulfonyloxy-5H-dibenzo[a,d]cyclohepten-2-yl)propionic acid, is dissolved in 10 ml. of dimethylsulfoxide and heated to 120° C. for 5 minutes, then cooled, poured into water and extracted with ethyl acetate. The solution is washed, dried and evaporated. The residue is chromatographed on silica gel, eluting with 40:60:1 ethyl acetate: acetic acid, so as to isolate a 15% yield of 2-(5H-dibenzo[a,d]cyclohepten-5-on-2-yl propionic acid, m.p. (chloroform-hexane) 138°-139° C.; m.p. (acetone-hexane) 113°-115° C.

Workup

  1. washThe ethereal layer is washed
  2. customdried
  3. customevaporated
  4. dissolutionThe products, 2-(5-p-toluene-sulfonyloxy-5H-dibenzo[a,d]cyclohepten-2-yl)propionic acid, is dissolved in 10 ml
  5. temperaturecooled
  6. additionpoured into water
  7. extractionextracted with ethyl acetate
  8. washThe solution is washed
  9. customdried
  10. customevaporated
  11. customThe residue is chromatographed on silica gel
  12. washeluting with 40:60:1 ethyl acetate

Sources & evidence

ORD record
ord-1e51175af7f74863b906355564221769
Source dataset
uspto-grants-1977_11
Patent number
US04059611

Reaction notes

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