ETHYL (4-IODOBENZOYL)ACETATE

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

Procedure: Ethyl 3-(4-iodophenyl)-3-oxopropanoate (3.0 g, 9.4 mmol) was added slowly to a solution of hydroxylamine hydrochloride (660 mg, 9.44 mmol), NaOH (795 mg, 19.8 mmol), and water (12 mL) at 0° C. The reaction mixture was kept at 0° C. for 1 h. The precipitate was collected by filtration, rinsed with water, and dried under vacuum to afford the title compound as white solid (2.0 g, 64%). 1H NMR (CDCl3, 400 MHz): δ 7.84 (d, 2H), 7.40 (d, 2H), 3.78 (s, 2H). 13C NMR (acetone-d6, 100 MHz): δ 176.1, 164.6, 139.1, 129.2, 129.0, 98.6, 34.4. The precipitate was collected by filtration rinsed with water dried under vacuum

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of EtOAc (6 mL) in Et2O (15 mL) was added to a solution of LDA (2 M in THF, 60 mL, 120 mmol) in Et2O (80 mL) at −78° C. The resulting solution was stirred at −78° C. for 45 minutes. To this solution, a solution of 4-iodobenzoyl chloride (16 g, 60.5 mmol) in Et2O (30 mL) was added at −78° C. The reaction mixture was allowed to warm to room temperature and stirred for 15 h. The reaction mixture was poured into iced-sulfuric acid (300 g, 10%), stirred for 15 minutes, and extracted with Et2O (3×80 mL). The combined organic layers were dried over MgSO4 and concentrated in vacuo to afford the title compound as light orange oil (9 g, 47%). Compound exists as a mixture of ketone and enol forms (3:1). 1H NMR (CDCl3, 400 MHz): (ketone form) δ 7.87 (d, 2H), 7.67 (d, 2H), 4.26 (q, 2H), 3.95 (s, 2H), 1.24 (t, 3H); (enol form) δ 12.55 (s, 1H), 7.78 (d, 2H), 7.50 (q, 2H), 5.65 (s, 1H), 4.59 (q, 2H), 1.34 (t, 3H). to warm to room temperature stirred for 15 h stirred for 15 minutes extracted with Et2O (3×80 mL) The combined organic layers were dried over MgSO4 concentrated in vacuo

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of EtOAc (6 mL) in Et2O (15 mL) was added to a solution of LDA (2 M in THF, 60 mL, 120 mmol) in Et2O (80 mL) at −78° C. The resulting solution was stirred at −78° C. for 45 minutes. To this solution, a solution of 4-iodobenzoyl chloride (16 g, 60.5 mmol) in Et2O (30 mL) was added at −78° C. The reaction mixture was allowed to warm to room temperature and stirred for 15 h. The reaction mixture was poured into iced-sulfuric acid (300 g, 10%), stirred for 15 minutes, and extracted with Et2O (3×80 mL). The combined organic layers were dried over MgSO4 and concentrated in vacuo to afford the title compound as light orange oil (9 g, 47%). Compound exists as a mixture of ketone and enol forms (3:1). 1H NMR (CDCl3, 400 MHz): (ketone form) δ 7.87 (d, 2H), 7.67 (d, 2H), 4.26 (q, 2H), 3.95 (s, 2H), 1.24 (t, 3H); (enol form) δ 12.55 (s, 1H), 7.78 (d, 2H), 7.50 (q, 2H), 5.65 (s, 1H), 4.59 (q, 2H), 1.34 (t, 3H). to warm to room temperature stirred for 15 h stirred for 15 minutes extracted with Et2O (3×80 mL) The combined organic layers were dried over MgSO4 concentrated in vacuo

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl 4-iodobenzoylacetate (10 mmol, manufactured by Aldrich) and ethanol (10 mL) were charged in a 100 mL round-bottom flask to which a solution of 2-hydrazinopyrimidine (10 mmol, manufactured by Aldrich) in ethanol (10 mL) was then added. After being stirred at 100° C. for 8 hours, the reaction liquid was cooled at room temperature. The resulting solid was filtered, washed with ethanol and hexane, and then dried under vacuum to afford the title compound. was then added the reaction liquid was cooled at room temperature The resulting solid was filtered washed with ethanol and hexane dried under vacuum

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl 4-iodobenzoylacetate (10 mmol, manufactured by Aldrich) and ethanol (10 mL) were charged in a 100 mL round-bottom flask to which a solution of 2-hydrazinopyrimidine (10 mmol, manufactured by Aldrich) in ethanol (10 mL) was then added. After being stirred at 100° C. for 8 hours, the reaction liquid was cooled at room temperature. The resulting solid was filtered, washed with ethanol and hexane, and then dried under vacuum to afford the title compound. was then added the reaction liquid was cooled at room temperature The resulting solid was filtered washed with ethanol and hexane dried under vacuum

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

Procedure: Ethyl 3-(4-iodophenyl)-3-oxopropanoate (3.0 g, 9.4 mmol) was added slowly to a solution of hydroxylamine hydrochloride (660 mg, 9.44 mmol), NaOH (795 mg, 19.8 mmol), and water (12 mL) at 0° C. The reaction mixture was kept at 0° C. for 1 h. The precipitate was collected by filtration, rinsed with water, and dried under vacuum to afford the title compound as white solid (2.0 g, 64%). 1H NMR (CDCl3, 400 MHz): δ 7.84 (d, 2H), 7.40 (d, 2H), 3.78 (s, 2H). 13C NMR (acetone-d6, 100 MHz): δ 176.1, 164.6, 139.1, 129.2, 129.0, 98.6, 34.4. The precipitate was collected by filtration rinsed with water dried under vacuum

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of EtOAc (6 mL) in Et2O (15 mL) was added to a solution of LDA (2 M in THF, 60 mL, 120 mmol) in Et2O (80 mL) at −78° C. The resulting solution was stirred at −78° C. for 45 minutes. To this solution, a solution of 4-iodobenzoyl chloride (16 g, 60.5 mmol) in Et2O (30 mL) was added at −78° C. The reaction mixture was allowed to warm to room temperature and stirred for 15 h. The reaction mixture was poured into iced-sulfuric acid (300 g, 10%), stirred for 15 minutes, and extracted with Et2O (3×80 mL). The combined organic layers were dried over MgSO4 and concentrated in vacuo to afford the title compound as light orange oil (9 g, 47%). Compound exists as a mixture of ketone and enol forms (3:1). 1H NMR (CDCl3, 400 MHz): (ketone form) δ 7.87 (d, 2H), 7.67 (d, 2H), 4.26 (q, 2H), 3.95 (s, 2H), 1.24 (t, 3H); (enol form) δ 12.55 (s, 1H), 7.78 (d, 2H), 7.50 (q, 2H), 5.65 (s, 1H), 4.59 (q, 2H), 1.34 (t, 3H). to warm to room temperature stirred for 15 h stirred for 15 minutes extracted with Et2O (3×80 mL) The combined organic layers were dried over MgSO4 concentrated in vacuo