1-chloro-2-methyl-3-phenylbenzene

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 stirred solution of 3-chloro-2-methyl-[1,1'-biphenyl] (13.5 g, 0.067 mole) and N-bromosuccinimide (11.8 g, 0.067 mole) in 125 ml of carbon tetrachloride was irradiated and heated to reflux for 61/2 hours with a 250 watt brooder lamp. The light/heat source was turned off and the reaction mixture stirred at room temperature for approximately 64 hours. The reaction mixture was again irradiated and heated for two hours with the brooder lamp. The mixture was cooled, a solid precipitate filtered off, and the filter cake washed with two 50 ml portions of carbon tetrachloride. The filtrate was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and filtered. The filtrate was evaporated under reduced pressure to give 2-bromomethyl-3-chloro-[1,1'-biphenyl] as an oil. heated to reflux for 61/2 hours with a 250 watt brooder lamp The reaction mixture was again irradiated heated for two hours with the brooder lamp The mixture was cooled a solid precipitate filtered off the filter cake washed with two 50 ml portions of carbon tetrachloride The filtrate was washed with saturated aqueous sodium chloride solution dried over anhydrous magnesium sulfate filtered The filtrate was evaporated under reduced pressure

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

Procedure: During a 45 minute period 3-chloro-2-methylaniline (141.6 g, 1.0 mole) was added to a stirred solution of isoamyl nitrite (175.6 g, 1.5 moles) in benzene (842 g, 10.0 moles). The reaction mixture was stirred at room temperature for two hours, heated at reflux for one hour, then cooled to room temperature. Approximately 2 l of n-heptane was added to the reaction mixture. Most of the solvents were distilled from the mixture under reduced pressure, followed by distillation at atmospheric pressure (until a head temperature of 95° was reached). The pot residue was dissolved in 2 l of n-heptane and the solution filtered through 250 g of silica gel. The filtrate was subjected to column chromatography on 250 g of silica gel, elution with n-heptane, to give an oil. The oil was rechromatographed on 250 g of silica gel, elution with n-heptane, to give an oil. The oil was distilled in a Kugelrohr distillation apparatus (90°/0.05 mm) to give 3-chloro-2-methyl-[ 1,1'-biphenyl] (23.5 g) as an oil. heated at reflux for one hour cooled to room temperature Most of the solvents were distilled from the mixture under reduced pressure followed by distillation at atmospheric pressure (until a head temperature of 95° The pot residue was dissolved in 2 l of n-heptane the solution filtered through 250 g of silica gel The filtrate was subjected to column chromatography on 250 g of silica gel, elution with n-heptane to give an oil The oil was rechromatographed on 250 g of silica gel, elution with n-heptane to give an oil The oil was distilled in a Kugelrohr distillation apparatus (90°/0.05 mm)

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

Procedure: During a 45 minute period 3-chloro-2-methylaniline (141.6 g, 1.0 mole) was added to a stirred solution of isoamyl nitrite (175.6 g, 1.5 moles) in benzene (842 g, 10.0 moles). The reaction mixture was stirred at room temperature for two hours, heated at reflux for one hour, then cooled to room temperature. Approximately 2 l of n-heptane was added to the reaction mixture. Most of the solvents were distilled from the mixture under reduced pressure, followed by distillation at atmospheric pressure (until a head temperature of 95° was reached). The pot residue was dissolved in 2 l of n-heptane and the solution filtered through 250 g of silica gel. The filtrate was subjected to column chromatography on 250 g of silica gel, elution with n-heptane, to give an oil. The oil was rechromatographed on 250 g of silica gel, elution with n-heptane, to give an oil. The oil was distilled in a Kugelrohr distillation apparatus (90°/0.05 mm) to give 3-chloro-2-methyl-[ 1,1'-biphenyl] (23.5 g) as an oil. heated at reflux for one hour cooled to room temperature Most of the solvents were distilled from the mixture under reduced pressure followed by distillation at atmospheric pressure (until a head temperature of 95° The pot residue was dissolved in 2 l of n-heptane the solution filtered through 250 g of silica gel The filtrate was subjected to column chromatography on 250 g of silica gel, elution with n-heptane to give an oil The oil was rechromatographed on 250 g of silica gel, elution with n-heptane to give an oil The oil was distilled in a Kugelrohr distillation apparatus (90°/0.05 mm)

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

Procedure: Under a nitrogen atmosphere, 101.3 g (0.50 mole) of 3-chloro-2-methylbiphenyl (92% purity) in 75 g of dry tetrahydrofuran was added dropwise over two hours with stirring to a gently refluxing mixture of 13.1 g (0.54 mole) of fresh magnesium turnings, the heel from a previous run containing 0.21 mole of unreacted magnesium, and 75 g of dry tetrahydrofuran in a dry reaction vessel. Upon complete addition, the reaction mixture was heated at reflux for five additional hours. Gas chromatographic analysis of a quenched sample of the reaction mixture showed 1.2% of unreacted 3-chloro-2-methylbiphenyl and 92.4% of 2-methylbiphenyl. The reaction mixture was allowed to cool overnight. a gently refluxing in a dry reaction vessel Upon complete addition the reaction mixture was heated at reflux for five additional hours to cool overnight

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

Procedure: A mixture of 3-chloro-2-methyl[1,1'-biphenyl] (10.4 grams, 0.051 mole) and N-bromosuccinimide (9.2 grams, 0.052 mole) in carbon tetrachloride (150 ml) was heated and irradiated with an infrared lamp for two hours. The mixture was cooled and filtered. The filtrate was evaporated under reduced pressure to give a quantitative yield of 2-bromomethyl-3-chloro[1,1'-biphenyl] as a yellow oil. was heated irradiated with an infrared lamp for two hours The mixture was cooled filtered The filtrate was evaporated under reduced pressure

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

Procedure: Under a dry nitrogen atmosphere isoamyl nitrite (37 grams, 0.31 mole) was added to a stirred solution of 3-chloro-2-methylaniline (35 grams, 0.25 mole) in benzene (500 ml). The mixture was heated at reflux for 1.5 hours, then allowed to cool and stirred at 50° for approximately 18 hours. The reaction mixture was cooled to room temperature, then evaporated under reduced pressure to a red residue. The residue was distilled under reduced pressure to give a yellow oil (bp 115°-130°/0.9 mm). The pot residue was washed with chloroform and the distillate dissolved in chloroform. The chloroform fractions were combined, washed with 10% aqueous hydrochloric acid and evaporated to give 3-chloro-2-methyl[1,1'-biphenyl] as a yellow oil. The mixture was heated at reflux for 1.5 hours to cool evaporated under reduced pressure to a red residue The residue was distilled under reduced pressure to give a yellow oil (bp 115°-130°/0.9 mm) The pot residue was washed with chloroform the distillate dissolved in chloroform washed with 10% aqueous hydrochloric acid evaporated

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

Procedure: Under a dry nitrogen atmosphere isoamyl nitrite (37 grams, 0.31 mole) was added to a stirred solution of 3-chloro-2-methylaniline (35 grams, 0.25 mole) in benzene (500 ml). The mixture was heated at reflux for 1.5 hours, then allowed to cool and stirred at 50° for approximately 18 hours. The reaction mixture was cooled to room temperature, then evaporated under reduced pressure to a red residue. The residue was distilled under reduced pressure to give a yellow oil (bp 115°-130°/0.9 mm). The pot residue was washed with chloroform and the distillate dissolved in chloroform. The chloroform fractions were combined, washed with 10% aqueous hydrochloric acid and evaporated to give 3-chloro-2-methyl[1,1'-biphenyl] as a yellow oil. The mixture was heated at reflux for 1.5 hours to cool evaporated under reduced pressure to a red residue The residue was distilled under reduced pressure to give a yellow oil (bp 115°-130°/0.9 mm) The pot residue was washed with chloroform the distillate dissolved in chloroform washed with 10% aqueous hydrochloric acid evaporated

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

Procedure: A stirred solution of 3-chloro-2-methyl-[1,1'-biphenyl] (13.5 g, 0.067 mole) and N-bromosuccinimide (11.8 g, 0.067 mole) in 125 ml of carbon tetrachloride was irradiated and heated to reflux for 61/2 hours with a 250 watt brooder lamp. The light/heat source was turned off and the reaction mixture stirred at room temperature for approximately 64 hours. The reaction mixture was again irradiated and heated for two hours with the brooder lamp. The mixture was cooled, a solid precipitate filtered off, and the filter cake washed with two 50 ml portions of carbon tetrachloride. The filtrate was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and filtered. The filtrate was evaporated under reduced pressure to give 2-bromomethyl-3-chloro-[1,1'-biphenyl] as an oil. heated to reflux for 61/2 hours with a 250 watt brooder lamp The reaction mixture was again irradiated heated for two hours with the brooder lamp The mixture was cooled a solid precipitate filtered off the filter cake washed with two 50 ml portions of carbon tetrachloride The filtrate was washed with saturated aqueous sodium chloride solution dried over anhydrous magnesium sulfate filtered The filtrate was evaporated under reduced pressure

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

Procedure: During a 45 minute period 3-chloro-2-methylaniline (141.6 g, 1.0 mole) was added to a stirred solution of isoamyl nitrite (175.6 g, 1.5 moles) in benzene (842 g, 10.0 moles). The reaction mixture was stirred at room temperature for two hours, heated at reflux for one hour, then cooled to room temperature. Approximately 2 l of n-heptane was added to the reaction mixture. Most of the solvents were distilled from the mixture under reduced pressure, followed by distillation at atmospheric pressure (until a head temperature of 95° was reached). The pot residue was dissolved in 2 l of n-heptane and the solution filtered through 250 g of silica gel. The filtrate was subjected to column chromatography on 250 g of silica gel, elution with n-heptane, to give an oil. The oil was rechromatographed on 250 g of silica gel, elution with n-heptane, to give an oil. The oil was distilled in a Kugelrohr distillation apparatus (90°/0.05 mm) to give 3-chloro-2-methyl-[1,1'-biphenyl] (23.5 g) as an oil. heated at reflux for one hour cooled to room temperature Most of the solvents were distilled from the mixture under reduced pressure followed by distillation at atmospheric pressure (until a head temperature of 95° The pot residue was dissolved in 2 l of n-heptane the solution filtered through 250 g of silica gel The filtrate was subjected to column chromatography on 250 g of silica gel, elution with n-heptane to give an oil The oil was rechromatographed on 250 g of silica gel, elution with n-heptane to give an oil The oil was distilled in a Kugelrohr distillation apparatus (90°/0.05 mm)

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

Procedure: During a 45 minute period 3-chloro-2-methylaniline (141.6 g, 1.0 mole) was added to a stirred solution of isoamyl nitrite (175.6 g, 1.5 moles) in benzene (842 g, 10.0 moles). The reaction mixture was stirred at room temperature for two hours, heated at reflux for one hour, then cooled to room temperature. Approximately 2 l of n-heptane was added to the reaction mixture. Most of the solvents were distilled from the mixture under reduced pressure, followed by distillation at atmospheric pressure (until a head temperature of 95° was reached). The pot residue was dissolved in 2 l of n-heptane and the solution filtered through 250 g of silica gel. The filtrate was subjected to column chromatography on 250 g of silica gel, elution with n-heptane, to give an oil. The oil was rechromatographed on 250 g of silica gel, elution with n-heptane, to give an oil. The oil was distilled in a Kugelrohr distillation apparatus (90°/0.05 mm) to give 3-chloro-2-methyl-[1,1'-biphenyl] (23.5 g) as an oil. heated at reflux for one hour cooled to room temperature Most of the solvents were distilled from the mixture under reduced pressure followed by distillation at atmospheric pressure (until a head temperature of 95° The pot residue was dissolved in 2 l of n-heptane the solution filtered through 250 g of silica gel The filtrate was subjected to column chromatography on 250 g of silica gel, elution with n-heptane to give an oil The oil was rechromatographed on 250 g of silica gel, elution with n-heptane to give an oil The oil was distilled in a Kugelrohr distillation apparatus (90°/0.05 mm)