1-bromo-4-ethenylbenzene

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

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

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

Procedure: A 5 L three-neck round-bottom flask was equipped with a mechanical stirrer, thermocouple thermometer, addition funnel with a nitrogen bubbler, and a cooling bath container. The nitrogen-flushed flask was charged with 200 mL anhydrous tetrahydrofuran, 67.5 g (2.77 mol) of magnesium turnings, and a small crystal of iodine. The addition funnel was charged with 500 g (2.73 mol) of freshly distilled 4-bromostyrene. Approximately 10 mL of 4-bromostyrene was added to the flask with vigorous stirring. As soon as the Grignard reaction was started, the flask was charged with an additional 1800 mL of anhydrous tetrahydrofuran. The remainder of the 4-bromostyrene was added dropwise to the stirred reaction at such a rate as to maintain the reaction at a temperature of 40° C. while cooling the flask with an ice/water bath. The addition required 2 hours, after which the cooling bath was removed and the reaction stirred another 1.5 hours. The reaction mixture was then cooled to 0° C. with a dry-ice/acetone bath, and the addition funnel was replaced with a gas inlet tube connected with appropriate back-flow safeguards to a cylinder of hexafluoroacetone. Hexafluoroacetone gas was passed into the reaction mixture over 2 hours while maintaining the reaction temperature below 15° C. with the cooling bath. After the reaction exotherm diminished, the gas addition was stopped. A total of 480 g (2.89 mol) hexafluoroacetone had been added. The cooling bath was removed and the reaction stirred overnight. The reaction was maintained below 10° C. as 500 mL of 6 N hydrochloric acid was added dropwise with stirring over 1 hour. The organic layer was separated and the aqueous layer extracted with three 300 mL portions of diethyl ether. The combined organic layers were washed with three 300 mL portions of brine, dried over sodium sulfate, filtered, and evaporated on the rotary evaporator. The residue was distilled under vacuum collecting fractions 58-78° C. at a vacuum of 800-300 mTorr. A total of 589 g (74%) of product containing approximately 15 mol % complexed tetrahydrofuran (THF) was obtained. A 5 L three-neck round-bottom flask was equipped with a mechanical stirrer thermocouple thermometer, addition funnel with a nitrogen bubbler, and a cooling bath container The nitrogen-flushed flask As soon as the Grignard reaction to maintain the reaction at a temperature of 40° C. while cooling the flask with an ice/water bath The addition required 2 hours after which the cooling bath was removed the addition funnel was replaced with a gas inlet tube Hexafluoroacetone gas was passed into the reaction mixture over 2 hours while maintaining the reaction temperature below 15° C. with the cooling bath the gas addition The cooling bath was removed the reaction stirred overnight The reaction was maintained below 10° C. as 500 mL of 6 N hydrochloric acid was added dropwise with stirring over 1 hour The organic layer was separated the aqueous layer extracted with three 300 mL portions of diethyl ether The combined organic layers were washed with three 300 mL portions of brine dried over sodium sulfate filtered evaporated on the rotary evaporator The residue was distilled under vacuum collecting fractions 58-78° C. at a vacuum of 800-300 mTorr A total of 589 g (74%) of product containing approximately 15 mol % complexed tetrahydrofuran (THF) was obtained

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

Procedure: Into a four-neck flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser with a calcium chloride tube and a dropping funnel were charged 4.9 g of magnesium cut powder and 50 ml of tetrahydrofuran. 36.6 Grams of p-bromostyrene diluted with tetrahydrofuran to about 4 times the weight was added dropwise under gentle reflux in a dry nitrogen gas stream. After the magnesium had disappeared, a solution consisting of 37.0 g of acridone and 600 ml of tetrahydrofuran was added dropwise over a period of two hours with stirring. After refluxing for further 5 hours, the reaction mixture was allowed to cool and then poured onto hydrochloric acid-ice to effect hydrolysis. The organic layer was extracted with ether and the extract was dried over anhydrous sodium sulfate. The solvent was then distilled off to obtain a yellow semi-solid. Almost the same weight (60 g) of phosphorus pentoxide was added to 500 ml of a solution of the semi-solid in benzene. The mixture was stirred at room temperature for 5 hours and then allowed to stand overnight. The supernatant liquid separated by decantation was washed with water, dried, and then concentrated to dryness. The residue was purified by silica gel chromatography to obtain 22.5 g of 9-(p-vinylphenyl)acridine. Yield 42.1%. Into a four-neck flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser with a calcium chloride tube and a dropping funnel was added dropwise under gentle reflux in a dry nitrogen gas stream was added dropwise over a period of two hours After refluxing for further 5 hours to cool poured onto hydrochloric acid-ice hydrolysis The organic layer was extracted with ether the extract was dried over anhydrous sodium sulfate The solvent was then distilled off to obtain a yellow semi-solid The mixture was stirred at room temperature for 5 hours The supernatant liquid separated by decantation was washed with water dried concentrated to dryness The residue was purified by silica gel chromatography

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

Procedure: Into a four-neck flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser with a calcium chloride tube and a dropping funnel were charged 4.9 g of magnesium cut powder and 50 ml of tetrahydrofuran. 36.6 Grams of p-bromostyrene diluted with tetrahydrofuran to about 4 times the weight was added dropwise under gentle reflux in a dry nitrogen gas stream. After the magnesium had disappeared, a solution consisting of 37.0 g of acridone and 600 ml of tetrahydrofuran was added dropwise over a period of two hours with stirring. After refluxing for further 5 hours, the reaction mixture was allowed to cool and then poured onto hydrochloric acid-ice to effect hydrolysis. The organic layer was extracted with ether and the extract was dried over anhydrous sodium sulfate. The solvent was then distilled off to obtain a yellow semi-solid. Almost the same weight (60 g) of phosphorus pentoxide was added to 500 ml of a solution of the semi-solid in benzene. The mixture was stirred at room temperature for 5 hours and then allowed to stand overnight. The supernatant liquid separated by decantation was washed with water, dried, and then concentrated to dryness. The residue was purified by silica gel chromatography to obtain 22.5 g of 9-(p-vinylphenyl)acridine. Yield 42.1%. Into a four-neck flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser with a calcium chloride tube and a dropping funnel was added dropwise under gentle reflux in a dry nitrogen gas stream was added dropwise over a period of two hours After refluxing for further 5 hours to cool poured onto hydrochloric acid-ice hydrolysis The organic layer was extracted with ether the extract was dried over anhydrous sodium sulfate The solvent was then distilled off to obtain a yellow semi-solid The mixture was stirred at room temperature for 5 hours The supernatant liquid separated by decantation was washed with water dried concentrated to dryness The residue was purified by silica gel chromatography

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

Procedure: A vinylbiphenyl polymer was prepared in the same manner as in Example 10 except that poly-p-bromostyrene obtained as in Example 10 by using p-bromostyrene instead of p-chlorostyrene, and o-bromoanisol were used. The polymer gave a peak of OCH3 through 1H-NMR measurement in the same manner as in Example 10. obtained as in Example 10 The polymer gave a peak of OCH3 through 1H-NMR measurement in the same manner as in Example 10

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

Procedure: Polymerizable Gold Complex (3-1) was synthesized by reacting the gold complex obtained by the reaction between sodium tetrachloroaurate (III) and triphenylphosphine having a polymerizable functional group, with phenylbutadiyne synthesized by a known method (see, P. Cadiot and W. Chodkiewicz, Chemistry of Acetylenes, H. G. Viehe, ed., Marcel Dekker, New York (1969)). More specifically, 20 ml of dried THF was added to 341 mg (14 mmol) of magnesium and thereto, a 10 ml THF solution containing 2.70 g (15 mmol) of 4-bromostyrene was added dropwise to prepare a Grignard reagent. To the resulting solution, a 10 ml THF solution containing 2.50 g (11 mmol) of chlorodiphenylphosphine was added dropwise and stirred at room temperature of 1.5 hours. After removing the solvent by distillation under reduced pressure, the residue was purified by silica gel column chromatography and recrystallized from a hexane solution to obtain 2.30 g (8.3 mmol) of (4-vinylphenyl)diphenylphosphine Compound (B). was added dropwise was added dropwise After removing the solvent by distillation under reduced pressure the residue was purified by silica gel column chromatography recrystallized from a hexane solution

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

Procedure: A Grignard reagent prepared from 4-bromostyrene (2.75 g, 15.0 mmol) and magnesium (0.39 g, 16.0 mmol) in THF (20 mL) was added dropwise (during a period of 20 min) to a stirred solution of bis[(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl)oxalate (5.00 g, 13.7 mmol) in THF (15 mL) at −60° C. The mixture was left warming to room temperature and poured into a mixture of ice (200 g) and a saturated solution of NH4Cl (10 mL). Extraction with diethyl ether (2×), washing with water (3×), drying (Na2SO4) and concentrating afforded 6.42 g of the crude compound as an oil. Repetitive column chromatography (SiO2, heptane/ether 7:3 and heptane/ether 95:5) gave 2.03 g (47%) of an oil. The mixture was left Extraction with diethyl ether (2×) washing with water (3×) drying (Na2SO4) concentrating afforded 6.42 g of the crude compound as an oil

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

Procedure: A Grignard reagent prepared from 4-bromostyrene (2.75 g, 15.0 mmol) and magnesium (0.39 g, 16.0 mmol) in THF (20 mL) was added dropwise (during a period of 20 min) to a stirred solution of bis[(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl)oxalate (5.00 g, 13.7 mmol) in THF (15 mL) at −60° C. The mixture was left warming to room temperature and poured into a mixture of ice (200 g) and a saturated solution of NH4Cl (10 mL). Extraction with diethyl ether (2×), washing with water (3×), drying (Na2SO4) and concentrating afforded 6.42 g of the crude compound as an oil. Repetitive column chromatography (SiO2, heptane/ether 7:3 and heptane/ether 95:5) gave 2.03 g (47%) of an oil. The mixture was left Extraction with diethyl ether (2×) washing with water (3×) drying (Na2SO4) concentrating afforded 6.42 g of the crude compound as an oil

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

Procedure: A Grignard reagent prepared from 4-bromostyrene (6.95 g, 38.0 mmol) and magnesium (0.97 g, 39.9 mmol) in THF (100 mL) was added dropwise (during a period of 20 min) to a stirred solution of bis[(Z)-3-hexenyl]oxalate (9.20 g, 36.2 mmol) in THF (35 mL) at −60° C. The mixture was left warming to room temperature and poured into a mixture of ice (100 g) and a saturated solution of NH4Cl (100 mL). Extraction with diethyl ether (200 mL, 2×), washing with a saturated solution of NaCl (50 mL, 4×, pH 7), drying (Na2SO4) and concentrating afforded 11.47 g of the crude compound as a brownish oil. Bulb-to-bulb distillation of 8.68 g of the crude product (0.06 mbar, 60° C.) and column chromatography (SiO2, heptane/ether 95:5, then 1:1, then pure ether) gave 3.53 g (50%) of an oil. The mixture was left Extraction with diethyl ether (200 mL, 2×) washing with a saturated solution of NaCl (50 mL, 4×, pH 7) drying (Na2SO4) concentrating afforded 11.47 g of the crude compound as a brownish oil Bulb-to-bulb distillation of 8.68 g of the crude product (0.06 mbar, 60° C.) and column chromatography (SiO2, heptane/ether 95:5

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

Procedure: A Grignard reagent prepared from 4-bromostyrene (6.95 g, 38.0 mmol) and magnesium (0.97 g, 39.9 mmol) in THF (100 mL) was added dropwise (during a period of 20 min) to a stirred solution of bis[(Z)-3-hexenyl]oxalate (9.20 g, 36.2 mmol) in THF (35 mL) at −60° C. The mixture was left warming to room temperature and poured into a mixture of ice (100 g) and a saturated solution of NH4Cl (100 mL). Extraction with diethyl ether (200 mL, 2×), washing with a saturated solution of NaCl (50 mL, 4×, pH 7), drying (Na2SO4) and concentrating afforded 11.47 g of the crude compound as a brownish oil. Bulb-to-bulb distillation of 8.68 g of the crude product (0.06 mbar, 60° C.) and column chromatography (SiO2, heptane/ether 95:5, then 1:1, then pure ether) gave 3.53 g (50%) of an oil. The mixture was left Extraction with diethyl ether (200 mL, 2×) washing with a saturated solution of NaCl (50 mL, 4×, pH 7) drying (Na2SO4) concentrating afforded 11.47 g of the crude compound as a brownish oil Bulb-to-bulb distillation of 8.68 g of the crude product (0.06 mbar, 60° C.) and column chromatography (SiO2, heptane/ether 95:5

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

Procedure: A Grignard reagent prepared from 4-bromostyrene (2.78 g, 15.2 mmol) and magnesium (0.39 g, 15.9 mmol) in THF (23 mL) was added dropwise (during 20 min) to a stirred solution of (E)-bis(3,7-dimethylocta-2,6-dien-1-yl)oxalate (5.00 g, 13.8 mmol) in THF (40 mL) at −60° C. The mixture was left warming to room temperature, and then poured into a mixture of ice (70 g) and a saturated solution of NH4Cl (60 mL). Extraction with diethyl ether (200 mL), washing with a saturated solution of NaCl (100 mL, 3×), drying (Na2SO4), adding of hydroquinone (10 mg) and concentrating afforded 6.44 g of the crude compound. Repetitive column chromatography (SiO2, heptane/ether 9:1 and 98:2), addition of hydroquinone to the product fraction, concentration and drying under vacuum (0.2 mbar, 1 h) gave 0.90 g (21%) of an oil. The mixture was left Extraction with diethyl ether (200 mL) washing with a saturated solution of NaCl (100 mL, 3×) drying (Na2SO4) adding of hydroquinone (10 mg) concentrating afforded 6.44 g of the crude compound to the product fraction, concentration drying under vacuum (0.2 mbar, 1 h)