Toluene → Ethyl 4-(3-oxopropyl)benzoate

HRID 1663612Notes

Reaction equation

HRID 1663612 reaction equation
I[C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=1.[CH2:13]([OH:16])[CH:14]=[CH2:15].C(=O)(O)[O-].[Na+].C1(C)C=CC=CC=1>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:9]([O:8][C:6](=[O:7])[C:5]1[CH:11]=[CH:12][C:2]([CH2:15][CH2:14][CH:13]=[O:16])=[CH:3][CH:4]=1)[CH3:10]

Participants

8

Reactant 4

HCID 1140TolueneHCID 7858Allyl AlcoholHCID 142891Ethyl 4-iodobenzoateHCID 516892Sodium Bicarbonate

Product 1

HCID 2757377Ethyl 4-(3-oxopropyl)benzoateYield 98.6%

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
77.5 °C

Procedure

Ethyl 4-iodobenzoate (200 g, 0.725 mol) and allyl alcohol (63 g, 1.087 mol) are added to a stirred suspension of Sodium bicarbonate (152 g, 1.812 mol), tetrabutyl-ammonium bromide (117 g, 0.362 mol) and Palladium (II) acetate (3.2 g, 0.014 mol) in DMF (600 mL). The reaction mixture is warmed to 75-80° C. for 3-3.5 hours and cooled to 40° C.-50° C. Toluene (1 L) is added to the reaction mixture with vigorous agitation and the mixture is stirred for 15 min at room temperature. The resulting mixture is filtered through a celite pad. The pad is washed with toluene (2×200 mL). The filtrate and wash are combined, washed with water (3×1 L), evaporated to constant weight at 30° C.-40° C. and 10 mmHg. The crude product 147.5 g (98.8%, 84% by HPLC) of 4-(3-Oxo-propyl)-benzoic acid ethyl ester as dark brown oil is obtained.

Workup

  1. temperaturecooled to 40° C.-50° C
  2. filtrationThe resulting mixture is filtered through a celite pad
  3. washThe pad is washed with toluene (2×200 mL)
  4. washThe filtrate and wash
  5. washwashed with water (3×1 L)
  6. customevaporated to constant weight at 30° C.-40° C.

Sources & evidence

ORD record
ord-b28aff9df7fe4bb7823addb1e5043e6d
Source dataset
uspto-grants-2011_10
Patent number
US08034960B2

Reaction notes

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