(2-methyl-3-phenylphenyl)methanol

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

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

Procedure: In a photoreactor was placed 3-iodo-2-methylbenzyl alcohol (5.0 g, 0.02 mole) and 800 ml of benzene. To this was added sodium thiosulfate (5.0 g, 0.04 mole) in 15 ml of water. The mixture was purged with argon for 30 minutes, then irradiated with a 200 watt medium pressure ultraviolet lamp for 36.5 hours. The reaction mixture was then transferred to a separatory funnel. The photoreactor was washed with approximately 20 ml each of water, chloroform, and acetone. These washes were added to the separatory funnel. The organic layer was washed with aqueous 0.5 M sodium thiosulfate, then with an aqueous solution saturated with sodium chloride. The organic layer was then dried and filtered. The filtrate was evaporated under reduced pressure to an oily residue. The residue was purified by column chromatography on silica gel, elution with 1:1 hexane:chloroform, to give 2-methyl[1,1'-biphenyl]-3-methanol (2.4 g). The nmr and ir spectra were consistent with that expected for the named compound. The mixture was purged with argon for 30 minutes irradiated with a 200 watt medium pressure ultraviolet lamp for 36.5 hours The reaction mixture was then transferred to a separatory funnel The photoreactor was washed with approximately 20 ml each of water, chloroform, and acetone These washes were added to the separatory funnel The organic layer was washed with aqueous 0.5 M sodium thiosulfate The organic layer was then dried filtered The filtrate was evaporated under reduced pressure to an oily residue The residue was purified by column chromatography on silica gel, elution with 1:1 hexane

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

Procedure: 2-Methyl[1,1'-biphenyl]-3-methanol was prepared as follows: To 100 ml of stirred 50% aqueous ethanol was added 2-methyl-3-nitrobenzyl alcohol (41.8 g, 0.25 mole) and 85.0 grams of iron powder. The mixture was brought to reflux, and 5.2 ml of concentrated hydrochloric acid was slowly added. Upon complete addition, the reaction mixture was stirred under reflux for 2 hours. The reaction mixture was then made just basic with ethanolic 15% potassium hydroxide. The hot mixture was filtered through diactomaceous earth to remove the iron. The filter cake was washed with ethanol. The filtrate was acidified with hydrogen chloride, then allowed to stand at room temperature for 16 hours. The ethanol was removed by evaporation under reduced pressure. Hexane was added to the residue, and the water-hexane azeotrope was removed by distillation. The addition of hexane and the subsequent removal of the water-hexane azeotrope by distillation was repeated three times. The 3-hydroxymethyl-2-methylaniline hydrochloride residue thus obtained was used as follows. to reflux Upon complete addition under reflux for 2 hours The hot mixture was filtered through diactomaceous earth to remove the iron The filter cake was washed with ethanol The ethanol was removed by evaporation under reduced pressure Hexane was added to the residue the water-hexane azeotrope was removed by distillation The addition of hexane the subsequent removal of the water-hexane azeotrope by distillation

Conditions: temp:53.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a nitrogen atmosphere, the reaction mixture from above was decanted into a clean, dry flask, leaving the unreacted magnesium turnings in the first flask. This solution, which contains (2-methyl[1,1'-biphenyl]-3-yl)magnesium chloride, was heated to reflux, and 16.5 g (0.55 mole based on formaldehyde) of polyoxymethylene diacetate (avg. mol. wgt. approx. 50,000, available commercially from E.I. du Pont de Nemours & Co., Inc., Wilmington, Delaware under the trade name Delrin 500 acetal homopolymer resin), milled to about 80 mesh, was added with stirring over three hours. Refluxing was continued for four additional hours after which the reaction mixture was allowed to cool and stand overnight. The mixture was then heated to 53° C. and was poured into a mixture of 100 g of ice, 52 g of concentrated hydrochloric acid, and 200 g of a mixture containing 95% n-octane and 5% toluene (wt/wt). This mixture was filtered and the organic phase separated. The organic solvents were distilled off, boiling range 65°-93° C. During a four hour period the solution was cooled with stirring to approximately 5° C. and was then filtered. The filter cake was washed with 100 mL of cold n-octane and air-dried for 0.5 hour. The filter cake was broken up and dried under a vacuum at 55° C. for four hours, yielding 78.9 g of (2-methyl[1,1'-biphenyl]-3-yl)methanol (89.9% purity), a yield of 70.8% of theory. Under a nitrogen atmosphere, the reaction mixture from above was decanted into a clean, dry flask leaving the unreacted magnesium turnings in the first flask was heated to reflux was added Refluxing to cool stand overnight This mixture was filtered the organic phase separated The organic solvents were distilled off During a four hour period the solution was cooled with stirring to approximately 5° C. was then filtered The filter cake was washed with 100 mL of cold n-octane air-dried for 0.5 hour dried under a vacuum at 55° C. for four hours

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

Procedure: In a photoreactor was placed 3-iodo-2-methylbenzyl alcohol (5.0 g, 0.02 mole) and 800 ml of benzene. To this was added sodium thiosulfate (5.0 g, 0.04 mole) in 15 ml of water. The mixture was purged with argon for 30 minutes, then irradiated with a 200 watt medium pressure ultraviolet lamp for 36.5 hours. The reaction mixture was then transferred to a separatory funnel. The photoreactor was washed with approximately 20 ml each of water, chloroform, and acetone. These washes were added to the separatory funnel. The organic layer was washed with aqueous 0.5M sodium thiosulfate, then with an aqueous solution saturated with sodium chloride. The organic layer was then dried and filtered. The filtrate was evaporated under reduced pressure to an oily residue. The residue was purified by column chromatography on silica gel, elution with 1:1 hexane:chloroform, to give 2-methyl[1,1'-biphenyl]-3-methanol (2.4 g). The nmr and ir spectra were consistent with that expected for the named compound. The mixture was purged with argon for 30 minutes irradiated with a 200 watt medium pressure ultraviolet lamp for 36.5 hours The reaction mixture was then transferred to a separatory funnel The photoreactor was washed with approximately 20 ml each of water, chloroform, and acetone These washes were added to the separatory funnel The organic layer was washed with aqueous 0.5M sodium thiosulfate The organic layer was then dried filtered The filtrate was evaporated under reduced pressure to an oily residue The residue was purified by column chromatography on silica gel, elution with 1:1 hexane

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

Procedure: 2-Methyl[1,1'-biphenyl]-3-methanol was prepared as follows: To 100 ml of stirred 50% aqueous ethanol was added 2-methyl-3-nitrobenzyl alcohol (41.8 g, 0.25 mole) and 85.0 grams of iron powder. The mixture was brought to reflux, and 5.2 ml of concentrated hydrochloric acid was slowly added. Upon complete addition, the reaction mixture was stirred under reflux for 2 hours. The reaction mixture was then made just basic with ethanolic 15% potassium hydroxide. The hot mixture was filtered through diatomaceous earth to remove the iron. The filter cake was washed with ethanol. The filtrate was acidified with hydrogen chloride, then allowed to stand at room temperature for 16 hours. The ethanol was removed by evaporation under reduced pressure. Hexane was added to the residue, and the water-hexane azeotrope was removed by distillation. The addition of hexane and the subsequent removal of the water-hexane azeotrope by distillation was repeated three times. The 3-hydroxymethyl-2-methylaniline hydrochloride residue thus obtained was used as follows. to reflux Upon complete addition under reflux for 2 hours The hot mixture was filtered through diatomaceous earth to remove the iron The filter cake was washed with ethanol The ethanol was removed by evaporation under reduced pressure Hexane was added to the residue the water-hexane azeotrope was removed by distillation The addition of hexane the subsequent removal of the water-hexane azeotrope by distillation

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

Procedure: 2-Methyl[1,1'-biphenyl]-3-methanol was prepared as follows: To 100 ml of stirred 50% aqueous ethanol was added 2-methyl-3-nitrobenzyl alcohol (41.8 g, 0.25 mole) and 85.0 grams of iron powder. The mixture was brought to reflux, and 5.2 ml of concentrated hydrochloric acid was slowly added. Upon complete addition, the reaction mixture was stirred under reflux for 2 hours. The reaction mixture was then made just basic with ethanolic 15% potassium hydroxide. The hot mixture was filtered through diatomaceous earth to remove the iron. The filter cake was washed with ethanol. The filtrate was acidified with hydrogen chloride, then allowed to stand at room temperature for 16 hours. The ethanol was removed by evaporation under reduced pressure. Hexane was added to the residue, and the water-hexane azeotrope was removed by distillation. The addition of hexane and the subsequent removal of the water-hexane azeotrope by distillation was repeated three times. The 3-hydroxymethyl-2-methylaniline hydrochloride residue thus obtained was used as follows. to reflux Upon complete addition under reflux for 2 hours The hot mixture was filtered through diatomaceous earth to remove the iron The filter cake was washed with ethanol The ethanol was removed by evaporation under reduced pressure Hexane was added to the residue the water-hexane azeotrope was removed by distillation The addition of hexane the subsequent removal of the water-hexane azeotrope by distillation

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

Procedure: In a photoreactor was placed 3-iodo-2-methylbenzyl alcohol (5.0 g, 0.02 mole) and 800 ml of benzene. To this was added sodium thiosulfate (5.0 g, 0.04 mole) in 15 ml of water. The mixture was purged with argon for 30 minutes, then irradiated with a 200 watt medium pressure ultraviolet lamp for 36.5 hours. The reaction mixture was then transferred to a separatory funnel. The photoreactor was washed with approximately 20 ml each of water, chloroform, and acetone. These washes were added to the separatory funnel. The organic layer was washed with aqueous 0.5 M sodium thiosulfate, then with an aqueous solution saturated with sodium chloride. The organic layer was then dried and filtered. The filtrate was evaporated under reduced pressure to an oily residue. The residue was purified by column chromatography on silica gel, elution with 1:1 hexane:chloroform, to give 2-methyl[1,1'-biphenyl]-3-methanol (2.4 g). The nmr and ir spectra were consistent with that expected for the named compound. The mixture was purged with argon for 30 minutes irradiated with a 200 watt medium pressure ultraviolet lamp for 36.5 hours The reaction mixture was then transferred to a separatory funnel The photoreactor was washed with approximately 20 ml each of water, chloroform, and acetone These washes were added to the separatory funnel The organic layer was washed with aqueous 0.5 M sodium thiosulfate The organic layer was then dried filtered The filtrate was evaporated under reduced pressure to an oily residue The residue was purified by column chromatography on silica gel, elution with 1:1 hexane

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

Procedure: 2-Methyl[1,1'-biphenyl]-3-methanol was prepared as follows: To 100 ml of stirred 50% aqueous ethanol was added 2-methyl-3-nitrobenzyl alcohol (41.8 g, 0.25 mole) and 85.0 grams of iron powder. The mixture was brought to reflux, and 5.2 ml of concentrated hydrochloric acid was slowly added. Upon complete addition, the reaction mixture was stirred under reflux for 2 hours. The reaction mixture was then made just basic with ethanolic 15% potassium hydroxide. The hot mixture was filtered through diatomaceous earth to remove the iron. The filter cake was washed with ethanol. The filtrate was acidified with hydrogen chloride, then allowed to stand at room temperature for 16 hours. The ethanol was removed by evaporation under reduced pressure. Hexane was added to the residue, and the water-hexane azeotrope was removed by distillation. The addition of hexane and the subsequent removal of the water-hexane azeotrope by distillation was repeated three times. The 3-hydroxymethyl-2-methylaniline hydrochloride residue thus obtained was used as follows. to reflux Upon complete addition under reflux for 2 hours The hot mixture was filtered through diatomaceous earth to remove the iron The filter cake was washed with ethanol The ethanol was removed by evaporation under reduced pressure Hexane was added to the residue the water-hexane azeotrope was removed by distillation The addition of hexane the subsequent removal of the water-hexane azeotrope by distillation

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

Procedure: In a photoreactor was placed 3-iodo-2-methylbenzyl alcohol (5.0 g, 0.02 mole) and 800 ml of benzene. To this was added sodium thiosulfate (5.0 g, 0.04 mole) in 15 ml of water. The mixture was purged with argon for 30 minutes, then irradiated with a 200 watt medium pressure ultraviolet lamp for 36.5 hours. The reaction mixture was then transferred to a separatory funnel. The photoreactor was washed with approximately 20 ml each of water, chloroform, and acetone. These washes were added to the separatory funnel. The organic layer was washed with aqueous 0.5 M sodium thiosulfate, then with an aqueous solution saturated with sodium chloride. The organic layer was then dried and filtered. The filtrate was evaporated under reduced pressure to an oily residue. The residue was purified by column chromatography on silica gel, elution with 1:1 hexane:chloroform, to give 2-methyl[1,1'-biphenyl]-3-methanol (2.4 g). The nmr and ir spectra were consistent with that expected for the named compound. The mixture was purged with argon for 30 minutes irradiated with a 200 watt medium pressure ultraviolet lamp for 36.5 hours The reaction mixture was then transferred to a separatory funnel The photoreactor was washed with approximately 20 ml each of water, chloroform, and acetone These washes were added to the separatory funnel The organic layer was washed with aqueous 0.5 M sodium thiosulfate The organic layer was then dried filtered The filtrate was evaporated under reduced pressure to an oily residue The residue was purified by column chromatography on silica gel, elution with 1:1 hexane

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

Procedure: 2-Methyl[1,1'-biphenyl]-3-methanol was prepared as follows: To 100 ml of stirred 50% aqueous ethanol was added 2-methyl-3-nitrobenzyl alcohol (41.8 g, 0.25 mole) and 85.0 grams of iron powder. The mixture was brought to reflux, and 5.2 ml of concentrated hydrochloric acid was slowly added. Upon complete addition, the reaction mixture was stirred under reflux for 2 hours. The reaction mixture was then made just basic with ethanolic 15% potassium hydroxide. The hot mixture was filtered through diatomaceous earth to remove the iron. The filter cake was washed with ethanol. The filtrate was acidified with hydrogen chloride, then allowed to stand at room temperature for 16 hours. The ethanol was removed by evaporation under reduced pressure. Hexane was added to the residue, and the water-hexane azeotrope was removed by distillation. The addition of hexane and the subsequent removal of the water-hexane azeotrope by distillation was repeated three times. The 3-hydroxymethyl-2-methylaniline hydrochloride residue thus obtained was used as follows. to reflux Upon complete addition under reflux for 2 hours The hot mixture was filtered through diatomaceous earth to remove the iron The filter cake was washed with ethanol The ethanol was removed by evaporation under reduced pressure Hexane was added to the residue the water-hexane azeotrope was removed by distillation The addition of hexane the subsequent removal of the water-hexane azeotrope by distillation

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

Procedure: A solution of 2.97 g (15.0 mmol) of (2-methyl-3phenylphenyl)methanol in 1.5 ml of pyridine and 10 ml of diethyl ether, was dropwise added to a solution of 2.80 g (15.0 mmol) of 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarbonyl chloride in 10 ml of diethyl ether, and the mixture was stirred at room temperature for 3 hours. After an addition of 20 ml of hexane thereto, the inorganic salt was filtered off, and the filtrate was concentrated under reduced pressure. The product was purified by column chromatography (silica gel, dichloromethane/hexane=1/2) to obtain 4.23 g of (2-methyl-3-phenylphenyl)methyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate as a colorless oil. the inorganic salt was filtered off the filtrate was concentrated under reduced pressure The product was purified by column chromatography (silica gel, dichloromethane/hexane=1/2)