Hydrochloric Acid → 4,4-Di(4-tolyl)-but-3-enoic acid

HRID 53138

Reaction equation

HRID 53138 reaction equation
[CH3:1][C:2]1[CH:16]=[CH:15][C:5]([C:6]([C:8]2[CH:13]=[CH:12][C:11]([CH3:14])=[CH:10][CH:9]=2)=O)=[CH:4][CH:3]=1.CC(C)([O-])C.[K+].C(OCC)(=O)[CH2:24][CH2:25][C:26]([O:28]CC)=[O:27].Cl>O.C(O)(C)(C)C>[C:11]1([CH3:14])[CH:12]=[CH:13][C:8]([C:6]([C:5]2[CH:15]=[CH:16][C:2]([CH3:1])=[CH:3][CH:4]=2)=[CH:24][CH2:25][C:26]([OH:28])=[O:27])=[CH:9][CH:10]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 31249Diethyl SuccinateHCID 691484,4'-DimethylbenzophenoneHCID 23665647Potassium tert-butoxide

Product 1

HCID 101069814,4-Di(4-tolyl)-but-3-enoic acid

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6386tert-ButanolSolvent

Procedure

To a 500 mL round-bottomed flask equipped with condenser and nitrogen inlet were added 29.7 grams (141 mmol) 4,4'-dimethylbenzophenone and 141 mL t-butanol forming a solution, followed by 17.4 grams (155 mmol) potassium t-butoxide and 29.5 grams (170 mmol) diethyl succinate. The reaction was refluxed for 18 hours, cooled, and acidified with 6N hydrochloric acid, then poured into water and extracted with ethyl acetate. The organic layer was dried over sodium sulfate and evaporated, and the residue taken up in 200 mL glacial acetic acid. It was then treated with 70 mL 48% hydrobromic acid and refluxed for 36 hours. The reaction was cooled, partitioned between water and ethyl acetate, and the combined organic layers washed with water and brine, dried over sodium sulfate, and evaporated. The residue was chromatographed on silica gel using methylene chloride/methanol as eluant to afford the product as low melting solid, 25.0 grams (66%), Rf =0.25 in 5% methanol/methylene chloride on silica gel. This material was used directly in the next step.

Workup

  1. customTo a 500 mL round-bottomed flask equipped with condenser and nitrogen inlet
  2. temperatureThe reaction was refluxed for 18 hours
  3. temperaturecooled
  4. extractionextracted with ethyl acetate
  5. dry with materialThe organic layer was dried over sodium sulfate
  6. customevaporated
  7. additionIt was then treated with 70 mL 48% hydrobromic acid
  8. temperaturerefluxed for 36 hours
  9. temperatureThe reaction was cooled
  10. custompartitioned between water and ethyl acetate
  11. washthe combined organic layers washed with water and brine
  12. dry with materialdried over sodium sulfate
  13. customevaporated
  14. customThe residue was chromatographed on silica gel
  15. customto afford the product as low melting solid, 25.0 grams (66%), Rf =0.25 in 5% methanol/methylene chloride on silica gel

Sources & evidence

ORD record
ord-2eea09bb3dec46f7858b5a4bdb0b69e7
Source dataset
uspto-grants-1997_04
Patent number
US05618811

Linked notes

Loading…