4-ethenylbenzaldehyde

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

Procedure: In a 100 ml 3-necked round-bottomed flask, 6.8 g (51.5 mmol) of 4-vinylbenzaldehyde, 12.4 g (205.8 mmol) of n-propanol and 0.1 g (0.5 mmol) of p-toluenesulfonic acid are dissolved in 45 ml of benzene. The solution is refluxed for 22 hours using a water separator and then ether is added thereto. The mixture is subsequently neutralised with 0.1N sodium hydroxide solution. The organic phase is then washed three times with water, dried over magnesium sulfate and concentrated. The resulting oil can be purified by column chromatography (stationary phase silica gel, mobile phase hexane/ether 5/4) to yield 2.54 g (10.8 mmol, 21% of the theoretical yield) of the desired substance in the form of a clear oil. The solution is refluxed for 22 hours The organic phase is then washed three times with water dried over magnesium sulfate concentrated The resulting oil can be purified by column chromatography (stationary phase silica gel, mobile phase hexane/ether 5/4) to yield 2.54 g (10.8 mmol, 21% of the theoretical yield) of the desired substance in the form of a clear oil

Conditions: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 250 ml 3-necked round-bottomed flask, 13.72 g of (103 mmol) of 4-vinylbenzaldehyde, 7.08 g (114 mmol) of ethylene glycol and 0.23 g (1.3 mmol) of p-toluenesulfonic acid are added to 100 ml of toluene. The resulting mixture is refluxed at 45° C. under reduced pressure for 3 hours using a water separator. It is then washed twice with 100 ml of water, and the organic phase is dried over magnesium sulfate and concentrated to yield 17.47 g of crude product in the form of a pale yellow oil. The latter is distilled at 80° C./0.05 mbar. Yield: 12.81 g (72.7 mmol, 70.6% of the theoretical yield). 1H-NMR (CDCl3, 100 mHz): δ7.39/s/4H, 6.68/dd (J1 =11 Hz, J2 =18 Hz)/1H, 5.74/s/1H, 5.72 (J1 =18 Hz, J2 =2 Hz)/1H, 5.22/dd (J1 =11 Hz, J2 =2 Hz)/1H, 3.96/m/4H. It is then washed twice with 100 ml of water the organic phase is dried over magnesium sulfate concentrated

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

Procedure: 13 gms of 4-vinyl benzaldehyde 0.955 moles) was added to a flask containing 13.9 gms of 2-hydroxyacetophenone (0.955) in 150 ml alcohol. In a separate RB flask, 13 gms of NaOH was dissolved in 100 ml of aqueous ethyl alcohol (75%). The NaOH solution was added to the reaction mixture at once. The color of the solution immediately changed from colorless to yellow to pink, and then, finally, to a dark red precipitate. The solution was allowed to sit at room temperature overnight. The next morning, 6 gms of NaOH in 200 ml of aqueous ethyl alcohol (75%) was added to the Precipitate and the reaction mixture was cooled in an icebath for 15 mins. In a separate RB flask, a solution of 50 ml of 30% hydrogen peroxide solution in 50 ml of aqueous ethyl alcohol (75%) was added to the reaction flask at once at 0°-5° C. The red colored precipitate dissolved immediately and the color of the solution slowly changed from red to yellow. The solution was gradually warmed to room temperature and was stirred for 6 hrs. The reaction mixture was neutralized with dil. HCl at 0°-4° C. A white precipitate formed and was filtered and washed with distilled water until it was free from acid. The color of the product slowly changed from colorless to light pink or to light brown during filtration. the reaction mixture was cooled in an icebath for 15 mins The red colored precipitate dissolved immediately A white precipitate formed was filtered washed with distilled water until it to light brown during filtration

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

Procedure: 13 gms of 4-vinyl benzaldehyde 0.955 moles) was added to a flask containing 13.9 gms of 2-hydroxyacetophenone (0.955) in 150 ml alcohol. In a separate RB flask, 13 gms of NaOH was dissolved in 100 ml of aqueous ethyl alcohol (75%). The NaOH solution was added to the reaction mixture at once. The color of the solution immediately changed from colorless to yellow to pink, and then, finally, to a dark red precipitate. The solution was allowed to sit at room temperature overnight. The next morning, 6 gms of NaOH in 200 ml of aqueous ethyl alcohol (75%) was added to the Precipitate and the reaction mixture was cooled in an icebath for 15 mins. In a separate RB flask, a solution of 50 ml of 30% hydrogen peroxide solution in 50 ml of aqueous ethyl alcohol (75%) was added to the reaction flask at once at 0°-5° C. The red colored precipitate dissolved immediately and the color of the solution slowly changed from red to yellow. The solution was gradually warmed to room temperature and was stirred for 6 hrs. The reaction mixture was neutralized with dil. HCl at 0°-4° C. A white precipitate formed and was filtered and washed with distilled water until it was free from acid. The color of the product slowly changed from colorless to light pink or to light brown during filtration. the reaction mixture was cooled in an icebath for 15 mins The red colored precipitate dissolved immediately A white precipitate formed was filtered washed with distilled water until it to light brown during filtration

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

Procedure: 4'-vinyl-3-hydroxyflavone. 2-hydroxyacetophenone (Aldrich) was used as received. Ethyl alcohol was distilled prior to use. 4-vinyl benzaldehyde was synthesized using the procedure described in Example 1(a). Ethyl alcohol was distilled

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

Procedure: 4'-vinyl-3-hydroxyflavone. 2-hydroxyacetophenone (Aldrich) was used as received. Ethyl alcohol was distilled prior to use. 4-vinyl benzaldehyde was synthesized using the procedure described in Example 1(a). Ethyl alcohol was distilled

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

Procedure: 7.6 gms (0.312 moles) of Mg tunings were transferred to an RB flask containing 50 ml of dry THF under nitrogen atmosphere. 2 ml of ethyl bromide was then added to the Mg metal and the reaction mixture was warmed to 50°-55° C. The mixture reacted vigorously and activated Mg metal was formed. A solution of 20 ml (0.156 moles) of 4-chlorostyrene in 50 ml of THF was added dropwise at room temperature to the activated Mg. The reaction mixture was stirred for an additional two hours. A dark gray solution appeared and was allowed to settle down. In a separate IL RB flask, a solution of 12 ml (0.15 moles) of anhydrous DMF was prepared in 300 ml of THF. The DMF solution was cooled in an icebath under dry nitrogen atmosphere for 15 mins. Grignard reagent was added dropwise to the DMF solution over a period of 1 hr with vigorous stirring. The reaction flask was then allowed to stir for three hrs. at 5° C. and RT overnight. The reaction was quenched by pouring the entire reaction mixture into 300 ml of dilute HCl in an icebath. The product was separated by solvent extraction with ether. The ether layer was dried over anhyd. MgSO4 and filtered. Finally, ether was evaporated under reduced pressure. A viscous yellow liquid was obtained and was dried under vacuum for 2 hrs and stored in a freezer at -10° C. containing a small amount of hydroquinone as an inhibitor. A yield of 65% high purity (above 95%) 4-vinyl benzaldehyde was obtained. the reaction mixture was warmed to 50°-55° C The mixture reacted vigorously was formed to stir for three hrs at 5° C. RT overnight The reaction was quenched by pouring the entire reaction mixture into 300 ml of dilute HCl in an icebath The product was separated by solvent extraction with ether The ether layer was dried over anhyd MgSO4 and filtered Finally, ether was evaporated under reduced pressure A viscous yellow liquid was obtained was dried under vacuum for 2 hrs stored in a freezer at -10° C. containing a small amount of hydroquinone as an inhibitor

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

Procedure: 7.6 gms (0.312 moles) of Mg tunings were transferred to an RB flask containing 50 ml of dry THF under nitrogen atmosphere. 2 ml of ethyl bromide was then added to the Mg metal and the reaction mixture was warmed to 50°-55° C. The mixture reacted vigorously and activated Mg metal was formed. A solution of 20 ml (0.156 moles) of 4-chlorostyrene in 50 ml of THF was added dropwise at room temperature to the activated Mg. The reaction mixture was stirred for an additional two hours. A dark gray solution appeared and was allowed to settle down. In a separate IL RB flask, a solution of 12 ml (0.15 moles) of anhydrous DMF was prepared in 300 ml of THF. The DMF solution was cooled in an icebath under dry nitrogen atmosphere for 15 mins. Grignard reagent was added dropwise to the DMF solution over a period of 1 hr with vigorous stirring. The reaction flask was then allowed to stir for three hrs. at 5° C. and RT overnight. The reaction was quenched by pouring the entire reaction mixture into 300 ml of dilute HCl in an icebath. The product was separated by solvent extraction with ether. The ether layer was dried over anhyd. MgSO4 and filtered. Finally, ether was evaporated under reduced pressure. A viscous yellow liquid was obtained and was dried under vacuum for 2 hrs and stored in a freezer at -10° C. containing a small amount of hydroquinone as an inhibitor. A yield of 65% high purity (above 95%) 4-vinyl benzaldehyde was obtained. the reaction mixture was warmed to 50°-55° C The mixture reacted vigorously was formed to stir for three hrs at 5° C. RT overnight The reaction was quenched by pouring the entire reaction mixture into 300 ml of dilute HCl in an icebath The product was separated by solvent extraction with ether The ether layer was dried over anhyd MgSO4 and filtered Finally, ether was evaporated under reduced pressure A viscous yellow liquid was obtained was dried under vacuum for 2 hrs stored in a freezer at -10° C. containing a small amount of hydroquinone as an inhibitor

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

Procedure: 13 gms of 4-vinyl benzaldehyde (0.955 moles) was added to a flask containing 13.9 gms of 2-hydroxyacetophenone (0.955) in 150 ml alcohol. In a separate RB flask, 13 gms of NaOH was dissolved in 100 ml of aqueous ethyl alcohol (75%). The NaOH solution was added to the reaction mixture at once. The color of the solution immediately changed from colorless to yellow to pink, and then, finally, to a dark red precipitate. The solution was allowed to sit at room temperature overnight. The next morning, 6 gms of NaOH in 200 ml of aqueous ethyl alcohol (75%) was added to the precipitate and the reaction mixture was cooled in an icebath for 15 mins. In a separate RB flask, a solution of 50 ml of 30% hydrogen peroxide solution in 50 ml of aqueous ethyl alcohol (75%) was added to the reaction flask at once at 0°-5° C. The red colored precipitate dissolved immediately and the color of the solution slowly changed from red to yellow. The solution was gradually warmed to room temperature and was stirred for 6 hrs. The reaction mixture was neutralized with dil. HCl at 0°-4° C. A white precipitate formed and was filtered and washed with distilled water until it was free from acid. The color of the product slowly changed from colorless to light pink or to light brown during filtration. the reaction mixture was cooled in an icebath for 15 mins The red colored precipitate dissolved immediately A white precipitate formed was filtered washed with distilled water until it to light brown during filtration

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

Procedure: 7.6 gms (0.312 moles) of Mg tunings were transferred to an RB flask containing 50 ml of dry THF under nitrogen atmosphere. 2 ml of ethyl bromide was then added to the Mg metal and the reaction mixture was warmed to 50°-55° C. The mixture reacted vigorously and activated Mg metal was formed. A solution of 20 ml (0.156 moles) of 4-chlorostyrene in 50 ml of THF was added dropwise at room temperature to the activated Mg. The reaction mixture was stirred for an additional two hours. A dark gray solution appeared and was allowed to settle down. In a separate 1L RB flask, a solution of 12 ml (0.15 moles) of anhydrous DMF was prepared in 300 ml of THF. The DMF solution was cooled in an icebath under dry nitrogen atmosphere for 15 mins. Grignard reagent was added dropwise to the DMF solution over a period of 1 hr with vigorous stirring. The reaction flask was then allowed to stir for three hrs. at 5° C. and RT overnight. The reaction was quenched by pouring the entire reaction mixture into 300 ml of dilute HCl in an icebath. The product was separated by solvent extraction with ether. The ether layer was dried over anhyd. MgSO4 and filtered. Finally, ether was evaporated under reduced pressure. A viscous yellow liquid was obtained and was dried under vacuum for 2 hrs and stored in a freezer at -10° C. containing a small amount of hydroquinone as an inhibitor. A yield of 65% high purity (above 95%) 4-vinyl benzaldehyde was obtained. the reaction mixture was warmed to 50°-55° C The mixture reacted vigorously was formed In a separate 1L RB flask to stir for three hrs at 5° C. RT overnight The reaction was quenched by pouring the entire reaction mixture into 300 ml of dilute HCl in an icebath The product was separated by solvent extraction with ether The ether layer was dried over anhyd MgSO4 and filtered Finally, ether was evaporated under reduced pressure A viscous yellow liquid was obtained was dried under vacuum for 2 hrs stored in a freezer at -10° C. containing a small amount of hydroquinone as an inhibitor

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

Procedure: 7.6 gms (0.312 moles) of Mg tunings were transferred to an RB flask containing 50 ml of dry THF under nitrogen atmosphere. 2 ml of ethyl bromide was then added to the Mg metal and the reaction mixture was warmed to 50°-55° C. The mixture reacted vigorously and activated Mg metal was formed. A solution of 20 ml (0.156 moles) of 4-chlorostyrene in 50 ml of THF was added dropwise at room temperature to the activated Mg. The reaction mixture was stirred for an additional two hours. A dark gray solution appeared and was allowed to settle down. In a separate 1L RB flask, a solution of 12 ml (0.15 moles) of anhydrous DMF was prepared in 300 ml of THF. The DMF solution was cooled in an icebath under dry nitrogen atmosphere for 15 mins. Grignard reagent was added dropwise to the DMF solution over a period of 1 hr with vigorous stirring. The reaction flask was then allowed to stir for three hrs. at 5° C. and RT overnight. The reaction was quenched by pouring the entire reaction mixture into 300 ml of dilute HCl in an icebath. The product was separated by solvent extraction with ether. The ether layer was dried over anhyd. MgSO4 and filtered. Finally, ether was evaporated under reduced pressure. A viscous yellow liquid was obtained and was dried under vacuum for 2 hrs and stored in a freezer at -10° C. containing a small amount of hydroquinone as an inhibitor. A yield of 65% high purity (above 95%) 4-vinyl benzaldehyde was obtained. the reaction mixture was warmed to 50°-55° C The mixture reacted vigorously was formed In a separate 1L RB flask to stir for three hrs at 5° C. RT overnight The reaction was quenched by pouring the entire reaction mixture into 300 ml of dilute HCl in an icebath The product was separated by solvent extraction with ether The ether layer was dried over anhyd MgSO4 and filtered Finally, ether was evaporated under reduced pressure A viscous yellow liquid was obtained was dried under vacuum for 2 hrs stored in a freezer at -10° C. containing a small amount of hydroquinone as an inhibitor

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

Procedure: 4-Formylstyrene, 1c (2.98 g, 22.5 mmol) and 2c (5.00 g, 21.5 mmol) were weighed into a 250 mL 3-neck RB flask and ethanol (90 mL) added forming a colourless solution. The flask was then attached to two B19 stoppers (side-arms) and a B24 double-layer coil condenser (centre-socket) and this in turn connected to a nitrogen-vacuum manifold. The apparatus was flushed with nitrogen and the reaction mixture stirred overnight at room temperature. Next day 3-(diethylenetriamino)propyl-functionalised silica gel (1.85 g, 1.23 mmol/g loading) was added to the reaction mixture which was stirred at room temperature under nitrogen for a period of 6 hours in order to scavenge the excess 4-formylstyrene. Sodium borohydride (1.22 g, 32.2 mmol) was then added to the reaction mixture which was then stirred at room temperature for a period of 65 hours under nitrogen. Water (100 mL) was then added to the reaction mixture via syringe in order to quench the reaction. The reaction mixture was then stirred for 30 minutes at room temperature before the ethanol was stripped from the mixture in vacuo using a rotary evaporator to yield a white emulsion. CH2Cl2 (100 mL) was added to this residue and the resultant mixture transferred to a 250 mL-separating funnel. Water (10 mL) was added to the funnel which was then shaken and the layers partitioned and the lower organic layer decanted off. The aqueous layer was discarded and the organic layer then extracted with a further 2×100 mL portions of brine. The layers were partitioned and the lower organic layer collected and dried over anhydrous MgSO4 for a period of 1 hour. The drying mixture was filtered and the collected solid washed with 3×20 mL portions of CH2Cl2. The filtrate and washings were combined and stripped to dryness in vacuo using a rotary evaporator for a period of 1 hour to yield a very pale yellow oil. This was then further dried in vacuo (0.25 torr) at room temperature for a period of 20 hours. Yield: 6.82 g (91%, pale yellow oil). NMR (CDCl3) δ 1.21 (t, 6H, —CH3), 1.32 (bm, 4H, —CH2—), 1.48 (bm, 4H, —CH2—), 2.61 (triplet of doublets, 4H, hexamethylene bridge >NCH2—), 2.71 (d, 2H, 2,2-diethoxyethyl NCH2—), 3.54 (m, 2H, HA of OC(HA)(HB)—), 3.69 (m, 2H, HB of OC(HA)(HB)—), 3.76 (s, 2H, >NCH2Ar), 4.59 (t, 1H, —CH(OR)2), 5.20 (d, 1H, ═C—H), 5.72 (d, 1H, ═C—H), 6.70 (dd, 1H, ═C—H), 7.26 (d, 2H, ArH), 7.36 (d, 2H, ArH). added forming a colourless solution The apparatus was flushed with nitrogen Next day 3-(diethylenetriamino)propyl-functionalised silica gel (1.85 g, 1.23 mmol/g loading) was added to the reaction mixture which was stirred at room temperature under nitrogen for a period of 6 hours in order was then stirred at room temperature for a period of 65 hours under nitrogen to quench the reaction a rotary evaporator to yield a white emulsion separating funnel Water (10 mL) was added to the funnel which was then shaken the layers partitioned the lower organic layer decanted off the organic layer then extracted with a further 2×100 mL portions of brine The layers were partitioned the lower organic layer collected dried over anhydrous MgSO4 for a period of 1 hour The drying mixture was filtered the collected solid washed with 3×20 mL portions of CH2Cl2 a rotary evaporator for a period of 1 hour to yield a very pale yellow oil This was then further dried in vacuo (0.25 torr) at room temperature for a period of 20 hours