Toluene → Ethyl 4-(3-oxopropyl)benzoate

HRID 731397Notes

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>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

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-ammounium 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. 1H NMR (DMSO-d6): δ1.38 (t, 3H), 2.81 (t, 2H), 3.03 (t, 2H), 4.39 (q, 2H), 7.27 (d, 2H), 7.98 (d, 2H), 9.81 (s, 1H).

Workup

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

Sources & evidence

ORD record: ord-713e9c3085cd4880a23fab1b9d42de55
Source dataset: uspto-grants-2009_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07582772B2

Reaction notes

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