Benzenepropanoic acid → 4-Phenylbutyrophenone

HRID 983679Notes

Reaction equation

HRID 983679 reaction equation
[C:1]1([CH2:7][CH2:8][C:9](O)=O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:12]1(B(O)O)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.O.[C:22](OC(=O)C(C)(C)C)(=[O:27])C(C)(C)C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[CH-]1C=CC=C1.[Fe+2].C1COCC1>[C:12]1([C:22]([CH2:9][CH2:8][CH2:7][C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)=[O:27])[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

8

Reactant 4

HCID 107Benzenepropanoic acidHCID 962WaterHCID 15234Pivalic anhydrideHCID 66827Phenylboronic Acid

Product 1

HCID 794134-PhenylbutyrophenoneYield 83%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 15826098Cyclopenta-1,3-diene;cyclopenta-2,4-dien-1-yl(diphenyl)phosphane;iron(2+)CatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
60 °C

Procedure

A 100 ml flask having a septum cap and magnetic stirrer was initially charged with palladium acetate (67.3 mg, 0.30 mmol), diphenylferrocenylphosphine (194 mg, 0.35 mmol), 3-phenylpropionic acid (1.50 g, 10 mmol) and benzeneboronic acid (1.46 g, 12 mmol). THF (40 ml), water (45 mg, 2.5 mmol) and pivalic anhydride (2.79 g, 15 mmol) were added in succession with the aid of syringes. The reaction vessel was then purged with inert gas and the reaction mixture was heated to 60° C. for a few hours. The progress of the reaction was followed with the aid of gas chromatography. As soon as complete conversion had been attained, the catalyst was removed by filtration through silica gel, the solvent was distilled off and the residue was recrystallized from hexane. The pivalic acid remained in the mother liquor and could be recovered. In this way, 1.73 g (83%) of 3-phenylpropyl phenyl ketone were obtained as colorless crystals. 1H NMR (200 MHz, CDCl3, 25° C., TMS): δ=7.95 (m, 2H), 7.61-7.19 (m, 8H), 3.32 (t, 3J(H,H)=6 Hz, 2H), 3.13 (t, 3J (H,H)=6 Hz, 2H) ppm; 13C NMR (50 MHz, CDCl3, 25° C., TMS): δ=198.8, 141.0, 136.5, 132.7, 128.3, 128.2, 128.1, 127.7, 125.8, 40.1, 29.8 ppm; MS (70 eV): m/z (%): 210(53) [M+], 105(100), 77(46), 51(17), HRMS: calc. for C15H14O [M+]: 210.104465; found: 210.10447; anal. calc. for C15H14O (210.3): C 85.68%; H 6.71%; N 0.00%; found: C 85.37; H 6.67; N 0.00%.

Workup

  1. customA 100 ml flask having
  2. customa septum cap
  3. customThe reaction vessel was then purged with inert gas
  4. customthe catalyst was removed by filtration through silica gel
  5. distillationthe solvent was distilled off
  6. customthe residue was recrystallized from hexane
  7. customcould be recovered

Sources & evidence

ORD record
ord-7bc85d187bc844c0b89e301ee6bf9c1c
Source dataset
uspto-grants-2005_03
Patent number
US06864394B2

Reaction notes

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