Acetic Acid → HCID 54165322, compound

HRID 1588955Notes

Reaction equation

HRID 1588955 reaction equation
[C:1]([O:5][C:6](=[O:16])[C:7]1[CH:12]=[CH:11][C:10]([C:13](=[O:15])[CH3:14])=[CH:9][CH:8]=1)([CH3:4])([CH3:3])[CH3:2].C[O:18][C:19](=[O:24])/[CH:20]=[CH:21]/CBr.O.[C:26](O)(=O)C>[Zn].II.CCOCC>[C:1]([O:5][C:6]([C:7]1[CH:8]=[CH:9][C:10]([C:13]([OH:15])([CH3:26])[CH2:14][CH:21]=[CH:20][C:19]([OH:24])=[O:18])=[CH:11][CH:12]=1)=[O:16])([CH3:4])([CH3:2])[CH3:3]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 962WaterHCID 53691752-Butenoic acid, 4-bromo-, methyl ester2×HCID 13844704tert-Butyl 4-acetylbenzoate

Product 1

HCID 54165322HCID 54165322, compound

Reagents, catalysts & solvents 3

HCID 807IodineCatalystHCID 23994ZincCatalyst2×HCID 3283Diethyl EtherSolvent

Conditions

Temperature
70 °C

Procedure

To a suspension obtained by adding a solution of 4-acetylbenzoic acid tert-butyl ester (7.82 g) in benzene-ether-tetrahydrofuran (3:3:2, 80 ml) to 4.64 g (71 mmol) of zinc, were added gradually under heating and stirring 4-bromocrotonic acid methyl ester (6.36 g) and iodine (20 mg). After reflux under heating in an oil bath at 70° C. for 1 hour, methyl 4-bromocrotonate (2.13 g) and zinc (1.55 g) were added, followed by reflux under heating for 30 minutes. The temperature was cooled down to room temperature, and the reaction mixture was poured into water (300 ml) and adjusted to pH 5 with acetic acid. The organic layer obtained by extraction with ether was washed with 5% aqueous ammonia and then dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure and the resulting residue was purified by column chromatography (support; silica gel, 200 g, developing agent; ethyl acetate:hexane=1:4), to obtain the object compound (9.2 g).

Workup

  1. customTo a suspension obtained
  2. additionwere added gradually
  3. temperatureunder heating
  4. temperatureAfter reflux
  5. temperatureby reflux
  6. temperatureunder heating for 30 minutes
  7. temperatureThe temperature was cooled down to room temperature
  8. washwas washed with 5% aqueous ammonia
  9. dry with materialdried over anhydrous magnesium sulfate
  10. customThe solvent was evaporated under reduced pressure
  11. customthe resulting residue was purified by column chromatography (support; silica gel, 200 g, developing agent; ethyl acetate:hexane=1:4)

Sources & evidence

ORD record
ord-c6577c445ec5422a99e5271beda5fb80
Source dataset
uspto-grants-1993_06
Patent number
US05223620

Reaction notes

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