(E)-4-(4-chlorophenyl)but-3-en-2-one

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using the procedure of Example 2, sodium pellets (6.33 g, 0.275 mol), (E)-4-(4-chlorophenyl)-but-3-en-2-one (45.16 g, 0.25 mol) and diethyl oxalate (43.8 g, 0.30 mol) were reacted to give (E)-6-(4-chlorophenyl-2,4-dioxo-hex-5-enoic acid ethyl ester (4; 61.1 g, 87%) as yellow crystals: mp 117-118° C.; 1H NMR (400 MHz, CDCl3) δ 14.80 (s, 1H), 7.68 (d, J=15.9 Hz, 1H), 7.53-7.35 (m, 4H), 6.62 (d, J=15.9 Hz, 1H), 6.53 (s, 1H), 4.38 (q, J=7.2 Hz, 2H), 1.40 (t, J=7.1 Hz, 3H); HRMS-ESI (m/z): calcd for C14H13ClO4, 280.050. found, 280.050. were reacted

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 250 ml single neck flask was charged 14 g (99.6 mmoles, 1.0 eq) of p-chlorobenzaldehyde dissolved in 30 ml of acetone. To this was added 5 g of 10% aqueous sodium hydroxide solution (12.5 mmoles, 0.125 eq), dropwise and during the course of addition, temperature was kept no higher than 25° C., while the mixture was agitated continuously for 30 minutes. To the mixture was added 50 ml of water, followed by 100 ml of ethyl acetate, the phases were separated and the organic phase was washed with water three times and then dried, and concentrated to obtain 15.5 g of (E)-4-(4-chlorophenyl)-3-buten-2-one as a faintly yellow oil in 86.2% yield. dropwise and during the course of addition, temperature was kept no higher than 25° C., while the mixture the phases were separated the organic phase was washed with water three times dried concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 250 ml single neck flask was charged 14 g (99.6 mmoles, 1.0 eq) of p-chlorobenzaldehyde dissolved in 30 ml of acetone. To this was added 5 g of 10% aqueous sodium hydroxide solution (12.5 mmoles, 0.125 eq), dropwise and during the course of addition, temperature was kept no higher than 25° C., while the mixture was agitated continuously for 30 minutes. To the mixture was added 50 ml of water, followed by 100 ml of ethyl acetate, the phases were separated and the organic phase was washed with water three times and then dried, and concentrated to obtain 15.5 g of (E)-4-(4-chlorophenyl)-3-buten-2-one as a faintly yellow oil in 86.2% yield. dropwise and during the course of addition, temperature was kept no higher than 25° C., while the mixture the phases were separated the organic phase was washed with water three times dried concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A suspension of (E)-4-(4-chlorophenyl)but-3-en-2-one (5.42 g, 30 mmol, Aldrich Chemical Co.), 1-(2-ethoxy-2-oxoethyl)pyridinium chloride (6.05 g, 30 mmol) (prepared according to the procedure described in WO 94/04502) and ammonium acetate (46.3 g, 0.6 mol) in ethanol (150 mL) was stirred at room temperature for 15 min, then at reflux for 4 h. The reaction mixture was allowed to cool and stand at room temperature overnight. The resulting precipitate was collected by filtration, and the collected solid was washed with ethanol, then water, and dried in a vacuum oven at 45° C. for 16 h to afford 3.1 g (47%) of the title compound as an off-white solid. HPLC/MS: retention time=2.86 min, [M+H]+=220.3. prepared at reflux for 4 h to cool stand at room temperature overnight The resulting precipitate was collected by filtration the collected solid was washed with ethanol water, and dried in a vacuum oven at 45° C. for 16 h

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using the procedure of Example 2, sodium pellets (6.33 g, 0.275 mol), (E)-4-(4-chlorophenyl)-but-3-en-2-one (45.16 g, 0.25 mol) and diethyl oxalate (43.8 g, 0.30 mol) were reacted to give (E)-6-(4-chlorophenyl-2,4-dioxo-hex-5-enoic acid ethyl ester (4; 61.1 g, 87%) as yellow crystals: mp 117-118° C.; 1H NMR (400 MHz, CDCl3) δ 14.80 (s, 1H), 7.68 (d, J=15.9 Hz, 1H), 7.53-7.35 (m, 4H), 6.62 (d, J=15.9 Hz, 1H), 6.53 (s, 1H), 4.38 (q, J=7.2 Hz, 2H), 1.40 (t, J=7.1 Hz, 3H); HRMS-ESI (m/z): calcd for C14H13ClO4, 280.050. found, 280.050. were reacted

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 250 ml single neck flask was charged 14 g (99.6 mmoles, 1.0 eq) of p-chlorobenzaldehyde dissolved in 30 ml of acetone. To this was added 5 g of 10% aqueous sodium hydroxide solution (12.5 mmoles, 0.125 eq), dropwise and during the course of addition, temperature was kept no higher than 25° C., while the mixture was agitated continuously for 30 minutes. To the mixture was added 50 ml of water, followed by 100 ml of ethyl acetate, the phases were separated and the organic phase was washed with water three times and then dried, and concentrated to obtain 15.5 g of (E)-4-(4-chlorophenyl)-3-buten-2-one as a faintly yellow oil in 86.2% yield. dropwise and during the course of addition, temperature was kept no higher than 25° C., while the mixture the phases were separated the organic phase was washed with water three times dried concentrated