Hexane → 4-(3-Oxobutyl)benzoic acid methyl ester

HRID 1479254Notes

Reaction equation

HRID 1479254 reaction equation
[CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[CH:8][C:7](Br)=[CH:6][CH:5]=1.[CH3:12][CH:13]([OH:16])[CH:14]=[CH2:15].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCCCCC>C(N(CC)CC)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OCC)(=O)C>[CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[CH:8][C:7]([CH2:15][CH2:14][C:13](=[O:16])[CH3:12])=[CH:6][CH:5]=1

Participants

8

Reactant 4

HCID 8058HexaneHCID 117163-Buten-2-olHCID 11776TriphenylphosphineHCID 12081Methyl 4-bromobenzoate

Product 1

HCID 109326404-(3-Oxobutyl)benzoic acid methyl esterYield 26.1%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 8471TriethylamineSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
75 °C

Procedure

To a solution of methyl-4-bromobenzoate (1.0 g, 4.65 mmol) in triethylamine (13 mL) was added 3-buten-2-ol (1 mL, 11.63 mmol), palladium (II) acetate (0.104 g, 0.465 mmol), and then triphenylphosphine (0.244 g, 0.93 mmol). The reaction was stirred in a 75° C. oil bath overnight under nitrogen atmosphere. Monitoring by TLC (3:1 hexane:ethyl acetate) showed the product and aryl bromide. The reaction was cooled to room temperature and then concentrated. Water was then added followed by extraction with ethyl acetate. The organic layer was washed with water and brine, dried over Na2SO4, filtered and concentrated. The crude product was purified by flash column chromatography (5:1 to 3:1 hexane:ethyl acetate) to obtain the product (250 mg, 26% yield). 1H NMR (600 MHz, CDCl3): δ 7.95 (d, 2H, J=8.4 Hz), 7.25 (d, 2H, J=8.4 Hz), 3.90 (s, 3H), 2.95 (t, 2H, J=7.45 Hz), 2.77 (t, 2H, J=7.68 Hz), 2.14 (s, 3H).

Workup

  1. temperatureThe reaction was cooled to room temperature
  2. concentrationconcentrated
  3. additionWater was then added
  4. extractionfollowed by extraction with ethyl acetate
  5. washThe organic layer was washed with water and brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude product was purified by flash column chromatography (5:1 to 3:1 hexane:ethyl acetate)

Sources & evidence

ORD record
ord-85944161b8704381a799c584553fd361
Source dataset
uspto-grants-2016_08
Patent number
US09408927B2

Reaction notes

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