Ethyl bromoacetate → Ethyl 4-(4'-fluoro-4-biphenylyl)-4-oxo-crotonate

HRID 2397366Notes

Reaction equation

HRID 2397366 reaction equation
C1(C(C2C=CC=CC=2)(C2C=CC=CC=2)COC([PH2]=C)=O)C=CC=CC=1.Br[CH2:27][C:28]([C:30]1[CH:35]=[CH:34][C:33]([C:36]2[CH:41]=[CH:40][C:39]([F:42])=[CH:38][CH:37]=2)=[CH:32][CH:31]=1)=[O:29].Br[CH2:44][C:45]([O:47][CH2:48][CH3:49])=[O:46].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1C=CC=CC=1>[F:42][C:39]1[CH:40]=[CH:41][C:36]([C:33]2[CH:34]=[CH:35][C:30]([C:28](=[O:29])/[CH:27]=[CH:44]/[C:45]([O:47][CH2:48][CH3:49])=[O:46])=[CH:31][CH:32]=2)=[CH:37][CH:38]=1

Participants

6

Reactant 4

HCID 7748Ethyl bromoacetateHCID 11776TriphenylphosphineHCID 135319772-Bromo-4'-(4-fluoro-phenyl)-acetophenoneHCID 178503017HCID 178503017, compound

Product 1

HCID 21437917Ethyl 4-(4'-fluoro-4-biphenylyl)-4-oxo-crotonate

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A mixture of 18.5 gm (0.0538 mol) of triphenyl-carbethoxy-methylenephosphoran and 260 cc of absolute benzene was heated to boiling, 7.6 gm (0.026 mol) of 2-bromo-4'-(4-fluoro-phenyl)-acetophenone were added, and the mixture was stirred for two hours at the boiling point. Thereafter, the precipitated triphenyl-carbethoxy-methylphosphonium bromide was separated by vacuum filtration, the clear filtrate was admixed with 4.35 gm (0.026 mol) of ethyl bromoacetate to tie up the triphenyl-phosphine, and the mixture was again boiled for two hours. Thereafter, the reaction mixture was allowed to cool, was then filtered, the filtrate was evaporated, and the residue was recrystallized first from methanol and subsequently from cyclohexane, yielding 4.2 gm (54% of theory) of the compound of the formula ##STR9## having a melting point of 115°-117° C.

Workup

  1. temperaturewas heated
  2. customThereafter, the precipitated triphenyl-carbethoxy-methylphosphonium bromide was separated by vacuum filtration
  3. waitthe mixture was again boiled for two hours
  4. temperatureto cool
  5. filtrationwas then filtered
  6. customthe filtrate was evaporated
  7. customthe residue was recrystallized first from methanol and subsequently from cyclohexane
  8. customyielding 4.2 gm (54% of theory) of the compound of the formula

Sources & evidence

ORD record
ord-ac50e513d2e6410c82d9cbdb1f37084b
Source dataset
uspto-grants-1977_05
Patent number
US04021479

Reaction notes

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