Benzoic Acid → HCID 54046783, compound

HRID 1414813Notes

Reaction equation

HRID 1414813 reaction equation
[CH3:1][C:2]([CH3:10])([CH3:9])[CH2:3][CH:4]=[CH:5][C:6](=O)[CH3:7].[CH2:11]([O:13][C:14](C=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)=[O:15])[CH3:12].[C:36](O)(=O)C1C=CC=CC=1>C1C=CC=CC=1>[CH2:11]([O:13][C:14](=[O:15])[CH:7]=[C:6]([CH3:36])[CH:5]=[CH:4][CH2:3][C:2]([CH3:10])([CH3:9])[CH3:1])[CH3:12]

Participants

5

Reactant 3

HCID 243Benzoic AcidHCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl esterHCID 54144416HCID 54144416, compound

Product 1

HCID 54046783HCID 54046783, compound

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

6.0 g. of 6,6-dimethyl-3-hepten-2-one, 15.0 g. of ethoxycarbonylmethylene-triphenyl-phosphorane and 2.5 g. of benzoic acid are dissolved in 90 ml. of absolute benzene and heated under reflux for 65 hours. The cooled reaction mixture is poured onto 75 ml. of ice-water and 15 ml. of 2-N aqueous sodium hydroxide and the benzene layer separated. The aqueous phase is re-extracted twice with diethyl ether and the extracts are washed with 10% by weight aqueous potassium bicarbonate solution, three times with water and once with saturated sodium chloride solution, dried over sodium sulfate and evaporated. The residue is taken up with a small amount of hexane and filtered. The filtrate is chromatographed on silica gel with hexane-diethyl ether (9:1 parts by volume). 3,7,7-Trimethyl-2,4-octadienoic acid ethyl ester is obtained as an isomer mixture which is distilled in a bulb-tube at 65° C./0.05 mmHg; nD20 = 1.4855.

Workup

  1. temperatureunder reflux for 65 hours
  2. customThe cooled reaction mixture
  3. additionis poured onto 75 ml
  4. customof 2-N aqueous sodium hydroxide and the benzene layer separated
  5. extractionThe aqueous phase is re-extracted twice with diethyl ether
  6. washthe extracts are washed with 10% by weight aqueous potassium bicarbonate solution, three times with water and once with saturated sodium chloride solution
  7. dry with materialdried over sodium sulfate
  8. customevaporated
  9. filtrationfiltered
  10. customThe filtrate is chromatographed on silica gel with hexane-diethyl ether (9:1 parts by volume)

Sources & evidence

ORD record
ord-282943bb0ca84b99a8abde539dee4a8b
Source dataset
uspto-grants-1977_01
Patent number
US04002647

Reaction notes

Loading…