Water → Pentanoic acid, 2-acetyl-, ethyl ester

Participants

Reaction Steps

Keto ester 9 was synthesized according to the method of Barbry et. al. [71]. A mixture of potassium carbonate (14 g, 0.10 mol), ethyl acetoacetate (4.3 g, 33 mmol), 1-iodopropane (5.7 g, 33.7 mmol), tetrabutylammonium chloride hydrate (10 g), water (50 mL) and chloroform (50 mL) was stirred at room temperature for 40 h. The aqueous layer was then separated, acidified with 5M hydrochloric acid and extracted with ether. The organic portions were combined, concentrated and the residual tetrabutylammonium chloride was precipitated by addition of ether. After filtration, the ethereal filtrate was dried (MgSO4) and evaporated to give a yellow liquid which was fractionated by distillation. The fraction which boiled at 93° C. at ˜15 mmHg (Lit. [72] 106-107° C., 22 mmHg) was collected (2.13 g) and 1H NMR has indicated that this colourless liquid contained about 5% of ethyl acetoacetate and 95% of 9; δH (270 MHz, CDCl3) 0.93 (3H, t, J=7.3 Hz, CH3), 1.28 (5H, m, —CH2CH2CH3 and CH3), 1.83 (2H, m, —CH2CH2CH3), 2.23 (3H, s, CH3CO), 3.42 (1H, t, J=7.3 Hz, —CH) and 4.20 (2H, q, J=7.3 Hz, COOCH2CH3); MS (EI) m/z (rel. intensity) 172.1(25, M+), 143.1[50, (M-Et)+], 130.1[28, (M+H—CH3CO)+], 115.1(23), 101.1(40), 85.0(20), 69.0(30), 55.0(30), 43.0[100, (CH3CO)+]. This crude was used for the next reaction without further purification.

Provenance & Evidence