3-bromo-5-tert-butylbenzaldehyde

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

Procedure: A suspension of 3-bromo-5-tert-butylbenzaldehyde (4.17 g, 17.30 mmol), malonic acid (2.15 g, 20.72 mmol) and ammonium acetate (2.66 g, 34.59 mmol) in isopropanol (35 mL) was heated at reflux under nitrogen for 3 h to afford a thick colorless solid. The solid was filtered hot, washed with hot isopropanol (2×25 mL) and dried in vacuo to give the desired racemic product as a colorless solid (2.68 g). was heated at reflux under nitrogen for 3 h to afford a thick colorless solid The solid was filtered hot washed with hot isopropanol (2×25 mL) dried in vacuo

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

Procedure: A suspension of 3-bromo-5-tert-butylbenzaldehyde (4.17 g, 17.30 mmol), malonic acid (2.15 g, 20.72 mmol) and ammonium acetate (2.66 g, 34.59 mmol) in isopropanol (35 mL) was heated at reflux under nitrogen for 3 h to afford a thick colorless solid. The solid was filtered hot, washed with hot isopropanol (2×25 mL) and dried in vacuo to give the desired racemic product as a colorless solid (2.68 g). was heated at reflux under nitrogen for 3 h to afford a thick colorless solid The solid was filtered hot washed with hot isopropanol (2×25 mL) dried in vacuo

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

Procedure: A suspension of 3-bromo-5-tert-butylbenzaldehyde (41.5 g, 0.17 mol), malonic acid (21.5 g, 0.20 mol) and ammonium acetate (26.6 g, 0.34 mol) in isopropanol (350 mL) was heated at reflux under nitrogen for 14 h to afford a thick colorless solid. The solid was filtered hot, washed with hot isopropanol (2×100 mL) and dried in vacuo to give the desired racemic product as a colorless solid (37.8 g). was heated at reflux under nitrogen for 14 h to afford a thick colorless solid The solid was filtered hot washed with hot isopropanol (2×100 mL) dried in vacuo

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

Procedure: 1,3-Dibromo-5-tert-butylbenzene (50 g, 0.17 mol) was dissolved in anhydrous ether (200 mL) in a dried flask under nitrogen. The reaction mixture was cooled to −78° C. and stirred under nitrogen atmosphere. A 2.46 M solution of n-BuLi in hexanes (171.2 mL, 0.171 mol) was added dropwise to the above solution and the reaction mixture was stirred at −78° C. for 30 minute after complete addition of n-BuLi. After 30 minute of stirring at −78° C., the reaction mixture was warmed to −30° C. DMF (16 mL, 0.2 mol) was added to the above reaction mixture dropwise, keeping the reaction mixture below −20° C. After addition of DMF, the reaction mixture was warmed slowly to 0° C. (30 minute) and then stirring was continued overnight to obtain a yellow-orange solution. The reaction mixture was poured into 400 mL of chilled 10% aqueous HCl and the mixture was stirred for 15 minutes. The ether layer was separated, washed with water (2×250 mL), dried over anhydrous Na2SO4, filtered and evaporated in vacuo to give the product as a pale yellow viscous liquid. The crude product was dissolved in dichloromethane (250 mL) and passed through a small pad of silica gel (250 g). Evaporation of the solvent in vacuo gave the product as a pale yellow viscous liquid (41.2 g). the reaction mixture was stirred at −78° C. for 30 minute After 30 minute of stirring at −78° C. the reaction mixture was warmed to −30° C the reaction mixture below −20° C the reaction mixture was warmed slowly to 0° C. (30 minute) stirring to obtain a yellow-orange solution the mixture was stirred for 15 minutes The ether layer was separated washed with water (2×250 mL) dried over anhydrous Na2SO4 filtered evaporated in vacuo

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

Procedure: A suspension of 3-bromo-5-tert-butylbenzaldehyde (4.17 g, 17.30 mmol), malonic acid (2.15 g, 20.72 mmol) and ammonium acetate (2.66 g, 34.59 mmol) in isopropanol (35 mL) was heated at reflux under nitrogen for 3 h to afford a thick colorless solid. The solid was filtered hot, washed with hot isopropanol (2×25 mL) and dried in vacuo to give the desired racemic product as a colorless solid (2.68 g). was heated at reflux under nitrogen for 3 h to afford a thick colorless solid The solid was filtered hot washed with hot isopropanol (2×25 mL) dried in vacuo