1-chloro-4-ethenylbenzene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: A solution of 13.9 g. 4-chlorostyrene and 10.4 g. styrene in 120 ml. dry benzene containing 0.24 g. azobisisobutyronitrile (Vazo® 64, du Pont) was stirred under nitrogen at 58°-64° C. for 24 hours. The solution was solvent stripped to a colorless syrupy residue which was dissolved in 50 ml. benzene and the solution added slowly with stirring to 300 ml. absolute ethanol. The precipitated polymer was filtered, washed with ethanol, and dried. The yield was 15.2 g. Analysis of the polymer showed presence of 15.83% chlorine, equivalent to a copolymer containing 47 mole % styrene and 53 mole % 4-chlorostyrene units in the repeat unit. was dissolved in 50 ml The precipitated polymer was filtered washed with ethanol dried containing 47 mole % styrene and 53 mole % 4-chlorostyrene units in the repeat unit

Conditions: temp:0.00; pressure:0.00; stir:

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:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of 4-chlorostyrene (1.20 ml, 10.0 mmol), Rh2(OAc)4 (0.221 g, 0.500 mmol), and toluene (20 ml) was added ethyl diazoacetate (1.09 ml, 10.50 mmol). Gas evolution was observed. The mixture was heated to 80° C. for 1 hour. The mixture was purified on silica gel (EtOAc in hexanes gradient) to provide 0.216 g of the title compound as an oil (9%). The mixture was purified on silica gel (EtOAc in hexanes gradient)

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

Procedure: To a suspension of 1-chloro-4-vinylbenzene (0.1195 ml, 0.9957 mmol), tetrakis(acetonitrile)copper(I) hexafluorophosphate (0.01856 g, 0.04979 mmol), and 4 angstrom molecular sieves (300 mg) in dry acetonitrile (2.5 ml) degassed with argon was added [N-[(p-nitrophenyl)sulfonyl]imino]phenyliodinane (0.6037 g, 1.494 mmol) portion-wise over 2 hours as a solid. It was stirred overnight under argon, then was loaded directly onto a Biotage SP1 system eluting with a 2-30% linear gradient of EtOAc in hexanes to yield 276 mg of the title compound (81.8% yield). degassed with argon eluting with a 2-30% linear gradient of EtOAc in hexanes

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of 4-chlorostyrene (1.20 ml, 10.0 mmol), Rh2(OAc)4 (0.221 g, 0.500 mmol), and toluene (20 ml) was added ethyl diazoacetate (1.09 ml, 10.50 mmol). Gas evolution was observed. The mixture was heated to 80° C. for 1 hour. The mixture was purified on silica gel (EtOAc in hexanes gradient) to provide 0.216 g of the title compound as an oil (9%). The mixture was purified on silica gel (EtOAc in hexanes gradient)

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

Procedure: 5-(p-Chlorophenyl)norbornene (called "CPN" hereinafter) was prepared from p-chlorostyrene and dicyclopentadiene in a pressure vessel and purified by fractional distillation. purified by fractional distillation

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: There was added dropwise with vigorous stirring under a nitrogen atmosphere, 62.9 grams (0.34 mole) of 4-chlorostyrene and 250 ml. of dry distilled tetrahydrofuran to 8.9 grams (0.37 mole) of magnesium metal turnings under enough tetrahydrofuran to cover the turnings. The exothermic reaction was controlled by external cooling to keep the temperature below 60° C. After the exotherm had subsided, the reaction mixture was heated at 60° C. for 0.5 hour until most of the magnesium had been consumed. Using a salt-ice bath, the reaction mixture was cooled to 0° C. and a solution of 44 grams (0.23 mole) of t-butyl perbenzoate in 80 ml. of tetrahydrofuran was added a such a rate to maintain the temperature between 0° C. and 5° C. After the addition had been completed, the temperature was allowed to rise to 25° C. with stirring over the course of 2 hours. Reaction mixture was then poured into 1000 ml. of a 3% aqueous hydrochloric acid solution. The oil which formed was extracted from the aqueous solution with 200 ml. portions of ethylether. The ether layers were washed twice with a 10% aqueous sodium hydroxide solution and then with water until the washings were neutral. The ether layer was then dried over sodium sulfate and the ether removed using a rotary evaporator. To the pale-yellow oil which remained was added a small amount of ionol as an inhibitor and the product fractionally distilled. There was obtained 20% yield of 4-t-butoxystyrene having a boiling point of 45°-46° C. at 0.03 millimeters. The proton NMR spectrum was recorded and is in agreement with the structure of the product. Elemental analysis calculated for C12H16O: %C, 81.82; %H, 9.09. Found: %C, 81.64; %H, 8.89. There was added dropwise of dry The exothermic reaction by external cooling the temperature below 60° C had been consumed to maintain the temperature between 0° C. and 5° C After the addition to rise to 25° C. with stirring over the course of 2 hours Reaction mixture was then poured into 1000 ml The oil which formed was extracted from the aqueous solution with 200 ml The ether layers were washed twice with a 10% aqueous sodium hydroxide solution The ether layer was then dried over sodium sulfate the ether removed a rotary evaporator To the pale-yellow oil which remained was added a small amount of ionol as an inhibitor the product fractionally distilled