3-hydroxy-2-prop-2-enylbenzaldehyde

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

Procedure: In a 1 L three necked round bottom flask equipped with a mechanical stirrer, thermometer and reflux condenser was added 300 mL acetone, 23.19 g of 2-allyl-3-hydroxybenzaldehyde (0.143 mole, 1 eq.), 2.13 g of sodium iodide (14 mmol., 0.1 eq), 39.52 g of potassium carbonate (28.6 mmol., 2 eq.) and 22.39 g of p-methoxybenzyl chloride (14.3 mmol., 1 eq.). The reaction mixture was heated to reflux for 4 hours. After cooling to room temperature, the reaction mixture was filtered through a bed of Hyflosupercel and the solvent removed by rotary evaporation. The residual dark oil was taken up in 200 mL of toluene and washed sequentially with 10% aqueous sodium hydroxide, water and brine. The organic phase was dried over sodium sulfate and decolourized with 5 g Darco G60. After filtration through a Celite pad, the solvent was removed by rotary evaporation to give 35.5 g of oil which was then recrystallized from 175 mL of hot IPA. After cooling to room temperature and further cooling to 0-5° C., the solids were filtered and washed with IPA to afford after drying at 40° C., 24.74 g (61%) of 2-allyl-3-(4-methoxy-benzyloxy)-benzaldehyde as an off-white solid. thermometer and reflux condenser The reaction mixture was heated to reflux for 4 hours the reaction mixture was filtered through a bed of Hyflosupercel the solvent removed by rotary evaporation washed sequentially with 10% aqueous sodium hydroxide, water and brine The organic phase was dried over sodium sulfate After filtration through a Celite pad the solvent was removed by rotary evaporation

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

Procedure: In a 1 L three necked round bottom flask equipped with a mechanical stirrer, thermometer and reflux condenser was added 300 mL acetone, 23.19 g of 2-allyl-3-hydroxybenzaldehyde (0.143 mole, 1 eq.), 2.13 g of sodium iodide (14 mmol., 0.1 eq), 39.52 g of potassium carbonate (28.6 mmol., 2 eq.) and 22.39 g of p-methoxybenzyl chloride (14.3 mmol., 1 eq.). The reaction mixture was heated to reflux for 4 hours. After cooling to room temperature, the reaction mixture was filtered through a bed of Hyflosupercel and the solvent removed by rotary evaporation. The residual dark oil was taken up in 200 mL of toluene and washed sequentially with 10% aqueous sodium hydroxide, water and brine. The organic phase was dried over sodium sulfate and decolourized with 5 g Darco G60. After filtration through a Celite pad, the solvent was removed by rotary evaporation to give 35.5 g of oil which was then recrystallized from 175 mL of hot IPA. After cooling to room temperature and further cooling to 0-5° C., the solids were filtered and washed with IPA to afford after drying at 40° C., 24.74 g (61%) of 2-allyl-3-(4-methoxy-benzyloxy)-benzaldehyde as an off-white solid. thermometer and reflux condenser The reaction mixture was heated to reflux for 4 hours the reaction mixture was filtered through a bed of Hyflosupercel the solvent removed by rotary evaporation washed sequentially with 10% aqueous sodium hydroxide, water and brine The organic phase was dried over sodium sulfate After filtration through a Celite pad the solvent was removed by rotary evaporation

Conditions: temp:217.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 500 ml three-necked Morton flask equipped with mechanical stirrer, thermometer and reflux condenser was added 100 g of 3-allyloxybenzaldehyde (0.62 moles, 1 eq.) and 150 g of cis/trans decalin (1.5 vol). The mixture was purged with nitrogen and then heated to a reflux temperature of 217° C. The reaction was maintained at this reflux temperature for seven hours then cooled and 231 mL of toluene was added. The reaction mixture was then allowed to cool to room temperature. After stirring for 18 hours and further cooling to 0-5° C., reaction mixture was filtered and the cake washed with 200 mL of heptane. The wet cake was stirred in 200 mL of heptane for 1-2 hours at room temperature. After filtration and drying of the cake at 40° C., 54.27 g of crude 2-allyl-3-hydroxybenzaldehyde were obtained. This represents a recovery of 82% of the available 2-allyl product produced by the Claisen rearrangement. In a 500 ml three-necked Morton flask equipped with mechanical stirrer thermometer and reflux condenser The mixture was purged with nitrogen The reaction was maintained at this reflux temperature for seven hours then cooled 231 mL of toluene was added to cool to room temperature further cooling to 0-5° C. reaction mixture was filtered the cake washed with 200 mL of heptane The wet cake was stirred in 200 mL of heptane for 1-2 hours at room temperature After filtration drying of the cake at 40° C.

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

Procedure: In a 1 L three necked round bottom flask equipped with a mechanical stirrer, thermometer and reflux condenser was added 300 mL acetone, 23.19 g of 2-allyl-3-hydroxybenzaldehyde (0.143 mole, 1 eq.), 2.13 g of sodium iodide (14 mmol., 0.1 eq), 39.52 g of potassium carbonate (28.6 mmol., 2 eq.) and 22.39 g of p-methoxybenzyl chloride (14.3 mmol., 1 eq.). The reaction mixture was heated to reflux for 4 hours. After cooling to room temperature, the reaction mixture was filtered through a bed of Hyflosupercel and the solvent removed by rotary evaporation. The residual dark oil was taken up in 200 mL of toluene and washed sequentially with 10% aqueous sodium hydroxide, water and brine. The organic phase was dried over sodium sulfate and decolourized with 5 g Darco G60. After filtration through a Celite pad, the solvent was removed by rotary evaporation to give 35.5 g of oil which was then recrystallized from 175 mL of hot IPA. After cooling to room temperature and further cooling to 0-5° C., the solids were filtered and washed with IPA to afford after drying at 40° C., 24.74 g (61%) of 2-allyl-3-(4-methoxy-benzyloxy)-benzaldehyde as an off-white solid. thermometer and reflux condenser The reaction mixture was heated to reflux for 4 hours the reaction mixture was filtered through a bed of Hyflosupercel the solvent removed by rotary evaporation washed sequentially with 10% aqueous sodium hydroxide, water and brine The organic phase was dried over sodium sulfate After filtration through a Celite pad the solvent was removed by rotary evaporation

Conditions: temp:217.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 500 ml three-necked Morton flask equipped with mechanical stirrer, thermometer and reflux condenser was added 100 g of 3-allyloxybenzaldehyde (0.62 moles, 1 eq.) and 150 g of cis/trans decalin (1.5 vol). The mixture was purged with nitrogen and then heated to a reflux temperature of 217° C. The reaction was maintained at this reflux temperature for seven hours then cooled and 231 mL of toluene was added. The reaction mixture was then allowed to cool to room temperature. After stirring for 18 hours and further cooling to 0-5° C., reaction mixture was filtered and the cake washed with 200 mL of heptane. The wet cake was stirred in 200 mL of heptane for 1-2 hours at room temperature. After filtration and drying of the cake at 40° C., 54.27 g of crude 2-allyl-3-hydroxybenzaldehyde were obtained. This represents a recovery of 82% of the available 2-allyl product produced by the Claisen rearrangement. In a 500 ml three-necked Morton flask equipped with mechanical stirrer thermometer and reflux condenser The mixture was purged with nitrogen The reaction was maintained at this reflux temperature for seven hours then cooled 231 mL of toluene was added to cool to room temperature further cooling to 0-5° C. reaction mixture was filtered the cake washed with 200 mL of heptane The wet cake was stirred in 200 mL of heptane for 1-2 hours at room temperature After filtration drying of the cake at 40° C.