2,2'-Biphenyldimethanol

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

Procedure: Lithium aluminum hydride (12.60 grams, 0.332 mol) and THF (175 ml) were placed in a dry 500 ml three-necked round-bottomed flask fitted with a condenser, addition funnel, nitrogen inlet, and magnetic stirrer. The mixture was cooled with an ice bath and diphenic acid (40.00 grams, 0.165 mol) in THF (100 ml) was added dropwise to the stirring mixture. After the addition was complete, the flask was removed from the ice bath and allowed to warm to room temperature. The reaction mixture was heated at reflux for 2 hours, then stirred overnight at room temperature. After cooling the mixture with an ice bath, water (12.6 ml) was added dropwise, followed by the successive dropwise addition of 15% aqueous sodium hydroxide (12.6 ml) and water (38 ml). The resulting yellow mixture was warmed to room temperature, and the solids were separated by vacuum filtration. The filtrate was placed on a rotary evaporator to remove the solvent. The remaining brownish-yellow solid was recystallized from toluene-hexane to give 28.60 grams (81% yield) of light brown solid product, melting point 105° to 108° C. 1H NMR (CDCl3): δ 2.77 (br s, 2H, --OH); 3.95 (s, 4H, --CH2 --); 6.50-7.25 (m, 8H, aromatic). fitted with a condenser, addition funnel, nitrogen inlet, and magnetic stirrer The mixture was cooled with an ice bath After the addition the flask was removed from the ice bath The reaction mixture was heated at reflux for 2 hours After cooling the mixture with an ice bath water (12.6 ml) was added dropwise followed by the successive dropwise addition of 15% aqueous sodium hydroxide (12.6 ml) and water (38 ml) The resulting yellow mixture was warmed to room temperature the solids were separated by vacuum filtration The filtrate was placed on a rotary evaporator to remove the solvent to give 28.60 grams (81% yield) of light brown solid product, melting point 105° to 108° C

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

Procedure: Lithium aluminum hydride (12.60 grams, 0.332 mol) and THF (175 ml) were placed in a dry 500 ml three-necked round-bottomed flask fitted with a condenser, addition funnel, nitrogen inlet, and magnetic stirrer. The mixture was cooled with an ice bath and diphenic acid (40.00 grams, 0.165 mol) in THF (100 ml) was added dropwise to the stirring mixture. After the addition was complete, the flask was removed from the ice bath and allowed to warm to room temperature. The reaction mixture was heated at reflux for 2 hours, then stirred overnight at room temperature. After cooling the mixture with an ice bath, water (12.6 ml) was added dropwise, followed by the successive dropwise addition of 15% aqueous sodium hydroxide (12.6 ml) and water (38 ml). The resulting yellow mixture was warmed to room temperature, and the solids were separated by vacuum filtration. The filtrate was placed on a rotary evaporator to remove the solvent. The remaining brownish-yellow solid was recystallized from toluene-hexane to give 28.60 grams (81% yield) of light brown solid product, melting point 105° to 108° C. 1H NMR (CDCl3): δ 2.77 (br s, 2H, --OH); 3.95 (s, 4H, --CH2 --); 6.50-7.25 (m, 8H, aromatic). fitted with a condenser, addition funnel, nitrogen inlet, and magnetic stirrer The mixture was cooled with an ice bath After the addition the flask was removed from the ice bath The reaction mixture was heated at reflux for 2 hours After cooling the mixture with an ice bath water (12.6 ml) was added dropwise followed by the successive dropwise addition of 15% aqueous sodium hydroxide (12.6 ml) and water (38 ml) The resulting yellow mixture was warmed to room temperature the solids were separated by vacuum filtration The filtrate was placed on a rotary evaporator to remove the solvent to give 28.60 grams (81% yield) of light brown solid product, melting point 105° to 108° C

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

Procedure: To 0.03 mol 2,2′-biphenyldimethanol was added 30 ml tetrahydrofuran and 0.09 mol pyridine, then added 0.075 mol benzoyl chloride with stirring. The reaction mixture was heated refluxing for 4 hours, cooled and added 20 ml saturated saline. The mixture was extracted with ethyl acetate, and extract was dried over anhydrous sodium sulfate. The solvent was removed. Column chromatography gave 2,2′-biphenyldimethanol dibenzoate as a colorless viscous liquid, and the yield was 93%. The reaction mixture was heated refluxing for 4 hours cooled added 20 ml saturated saline The mixture was extracted with ethyl acetate extract was dried over anhydrous sodium sulfate The solvent was removed

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

Procedure: To 3 g LiAlH4 was added 100 ml anhydrous ethyl ether. While cooling with ice-bath and stirring intensely, 0.05 mol diethyl 2,2′-biphenyldicarboxylate was slowly added dropwise. The reaction mixture was heated refluxing for 5 hours, then cooled. Excess LiAlH4 was decomposed with water. The mixture was filtered, and the filtrate was extracted with ethyl ether. The extract was dried over anhydrous sodium sulfate. The solvent was removed. Column chromatography gave 2,2′-biphenyldimethanol as a white solid, the yield was 75%, and m.p. was 98-103° C. IR spectrum had a strong absorption peak at 3400 cm−1, and had no absorption peak at about 1700 cm−1. This demonstrated that the reduction reaction was carried out completely. While cooling with ice-bath The reaction mixture was heated refluxing for 5 hours cooled The mixture was filtered the filtrate was extracted with ethyl ether The extract was dried over anhydrous sodium sulfate The solvent was removed

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

Procedure: To 0.03 mol 2,2′-biphenyldimethanol was added 30 ml tetrahydrofuran and 0.09 mol pyridine, then added 0.075 mol benzoyl chloride with stirring. The reaction mixture was heated refluxing for 4 hours, cooled and added 20 ml saturated saline. The mixture was extracted with ethyl acetate, and extract was dried over anhydrous sodium sulfate. The solvent was removed. Column chromatography gave 2,2′-biphenyldimethanol dibenzoate as a colorless viscous liquid, and the yield was 93%. The reaction mixture was heated refluxing for 4 hours cooled added 20 ml saturated saline The mixture was extracted with ethyl acetate extract was dried over anhydrous sodium sulfate The solvent was removed

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

Procedure: To 3 g LiAlH4 was added 100 ml anhydrous ethyl ether. While cooling with ice-bath and stirring intensely, 0.05 mol diethyl 2,2′-biphenyldicarboxylate was slowly added dropwise. The reaction mixture was heated refluxing for 5 hours, then cooled. Excess LiAlH4 was decomposed with water. The mixture was filtered, and the filtrate was extracted with ethyl ether. The extract was dried over anhydrous sodium sulfate. The solvent was removed. Column chromatography gave 2,2′-biphenyldimethanol as a white solid, the yield was 75%, and m.p. was 98-103° C. IR spectrum had a strong absorption peak at 3400 cm−1, and had no absorption peak at about 1700 cm−1. This demonstrated that the reduction reaction was carried out completely. While cooling with ice-bath The reaction mixture was heated refluxing for 5 hours cooled The mixture was filtered the filtrate was extracted with ethyl ether The extract was dried over anhydrous sodium sulfate The solvent was removed

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

Procedure: Lithium aluminum hydride (12.60 grams, 0.332 mol) and THF (175 ml) were placed in a dry 500 ml three-necked round-bottomed flask fitted with a condenser, addition funnel, nitrogen inlet, and magnetic stirrer. The mixture was cooled with an ice bath and diphenic acid (40.00 grams, 0.165 mol) in THF (100 ml) was added dropwise to the stirring mixture. After the addition was complete, the flask was removed from the ice bath and allowed to warm to room temperature. The reaction mixture was heated at reflux for 2 hours, then stirred overnight at room temperature. After cooling the mixture with an ice bath, water (12.6 ml) was added dropwise, followed by the successive dropwise addition of 15% aqueous sodium hydroxide (12.6 ml) and water (38 ml). The resulting yellow mixture was warmed to room temperature, and the solids were separated by vacuum filtration. The filtrate was placed on a rotary evaporator to remove the solvent. The remaining brownish-yellow solid was recrystallized from toluene-hexane to give 28.60 grams (81% yield) of light brown solid product, melting point 105° to 108° C. 1H NMR (CDCl3): δ2.77 (br s, 2H, --OH); 3.95 (s, 4H, --CH2 --); 6.50-7.25 (m, 8H, aromatic). fitted with a condenser, addition funnel, nitrogen inlet, and magnetic stirrer The mixture was cooled with an ice bath After the addition the flask was removed from the ice bath The reaction mixture was heated at reflux for 2 hours After cooling the mixture with an ice bath water (12.6 ml) was added dropwise followed by the successive dropwise addition of 15% aqueous sodium hydroxide (12.6 ml) and water (38 ml) The resulting yellow mixture was warmed to room temperature the solids were separated by vacuum filtration The filtrate was placed on a rotary evaporator to remove the solvent The remaining brownish-yellow solid was recrystallized from toluene-hexane to give 28.60 grams (81% yield) of light brown solid product, melting point 105° to 108° C

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

Procedure: To a reaction system comprising a suspension of 2,2'-bis(hydroxymethyl)-1,1'-biphenyl (85.3 grams, 0.398 mole) in methylene chloride (500 mL) at 0° C. containing pyridine (2 mL) was added a solution of thionyl chloride (163 grams, 1.36 moles) in methylene chloride (100 mL) dropwise with stirring. The system was allowed to warm to room temperature overnight and then was stripped to a residue with a stream of nitrogen at room temperature. The residue was dissolved in toluene (100 mL), cooled to 0° C., and quenched by the addition of ice cold, saturated sodium chloride solution (100 mL). The layers were separated, the organic phase was washed with water at 0° C. (1×100 mL), the layers separated, and the organic phase dried with magnesium sulfate. The solvent was evaporated to give a thick oil which was then distilled at 125° C. to 127° C. (0.1 mm Hg) to give 91.9 grams of colorless oil which contained 71.3 g of product dichloride (71% of theoretical yield). was stripped to a residue with a stream of nitrogen at room temperature cooled to 0° C. quenched by the addition of ice cold, saturated sodium chloride solution (100 mL) The layers were separated the organic phase was washed with water at 0° C. (1×100 mL) the layers separated the organic phase dried with magnesium sulfate The solvent was evaporated to give a thick oil which was then distilled at 125° C. to 127° C. (0.1 mm Hg)

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

Procedure: Lithium aluminum hydride (12.60 grams, 0.332 mol) and THF (175 ml) were placed in a dry 500 ml three-necked round-bottomed flask fitted with a condenser, addition funnel, nitrogen inlet, and magnetic stirrer. The mixture was cooled with an ice bath and diphenic acid (40.00 grams, 0.165 mol) in THF (100 ml) was added dropwise to the stirring mixture. After the addition was complete, the flask was removed from the ice bath and allowed to warm to room temperature. The reaction mixture was heated at reflux for 2 hours, then stirred overnight at room temperature. After cooling the mixture with an ice bath, water (12.6 ml) was added dropwise, followed by the successive dropwise addition of 15% aqueous sodium hydroxide (12.6 ml) and water (38 ml). The resulting yellow mixture was warmed to room temperature, and the solids were separated by vacuum filtration. The filtrate was placed on a rotary evaporator to remove the solvent. The remaining brownish-yellow solid was recrystallized from toluene-hexane to give 28.60 grams (81% yield) of light brown solid product, melting point 105° to 108° C. fitted with a condenser, addition funnel, nitrogen inlet, and magnetic stirrer The mixture was cooled with an ice bath After the addition the flask was removed from the ice bath The reaction mixture was heated at reflux for 2 hours After cooling the mixture with an ice bath water (12.6 ml) was added dropwise followed by the successive dropwise addition of 15% aqueous sodium hydroxide (12.6 ml) and water (38 ml) The resulting yellow mixture was warmed to room temperature the solids were separated by vacuum filtration The filtrate was placed on a rotary evaporator to remove the solvent The remaining brownish-yellow solid was recrystallized from toluene-hexane to give 28.60 grams (81% yield) of light brown solid product, melting point 105° to 108° C.

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

Procedure: Lithium aluminum hydride (12.60 grams, 0.332 mol) and THF (175 ml) were placed in a dry 500 ml three-necked round-bottomed flask fitted with a condenser, addition funnel, nitrogen inlet, and magnetic stirrer. The mixture was cooled with an ice bath and diphenic acid (40.00 grams, 0.165 mol) in THF (100 ml) was added dropwise to the stirring mixture. After the addition was complete, the flask was removed from the ice bath and allowed to warm to room temperature. The reaction mixture was heated at reflux for 2 hours, then stirred overnight at room temperature. After cooling the mixture with an ice bath, water (12.6 ml) was added dropwise, followed by the successive dropwise addition of 15% aqueous sodium hydroxide (12.6 ml) and water (38 ml). The resulting yellow mixture was warmed to room temperature, and the solids were separated by vacuum filtration. The filtrate was placed on a rotary evaporator to remove the solvent. The remaining brownish-yellow solid was recrystallized from toluene-hexane to give 28.60 grams (81% yield) of light brown solid product, melting point 105° to 108° C. 1H NMR (CDCl3): δ 2.77 (br s, 2H, --OH); 3.95 (s, 4H, --CH2 --); 6.50-7.25 (m, 8H, aromatic). fitted with a condenser, addition funnel, nitrogen inlet, and magnetic stirrer The mixture was cooled with an ice bath After the addition the flask was removed from the ice bath The reaction mixture was heated at reflux for 2 hours After cooling the mixture with an ice bath water (12.6 ml) was added dropwise followed by the successive dropwise addition of 15% aqueous sodium hydroxide (12.6 ml) and water (38 ml) The resulting yellow mixture was warmed to room temperature the solids were separated by vacuum filtration The filtrate was placed on a rotary evaporator to remove the solvent The remaining brownish-yellow solid was recrystallized from toluene-hexane to give 28.60 grams (81% yield) of light brown solid product, melting point 105° to 108° C

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

Procedure: Lithium aluminum hydride (12.60 grams, 0.332 mol) and THF (175 ml) were placed in a dry 500 ml three-necked round-bottomed flask fitted with a condenser, addition funnel, nitrogen inlet, and magnetic stirrer. The mixture was cooled with an ice bath and diphenic acid (40.00 grams, 0.165 mol) in THF (100 ml) was added dropwise to the stirring mixture. After the addition was complete, the flask was removed from the ice bath and allowed to warm to room temperature. The reaction mixture was heated at reflux for 2 hours, then stirred overnight at room temperature. After cooling the mixture with an ice bath, water (12.6 ml) was added dropwise, followed by the successive dropwise addition of 15% aqueous sodium hydroxide (12.6 ml) and water (38 ml). The resulting yellow mixture was warmed to room temperature, and the solids were separated by vacuum filtration. The filtrate was placed on a rotary evaporator to remove the solvent. The remaining brownish-yellow solid was recystallized from toluene-hexane to give 28.60 grams (81% yield) of light brown solid product, melting point 105° to 108° C. 1H NMR (CDCl3): δ 2.77 (br s, 2H, --OH); 3.95 (s, 4H, --CH2 --); 6.50-7.25 (m, 8H, aromatic). fitted with a condenser, addition funnel, nitrogen inlet, and magnetic stirrer The mixture was cooled with an ice bath After the addition the flask was removed from the ice bath The reaction mixture was heated at reflux for 2 hours After cooling the mixture with an ice bath water (12.6 ml) was added dropwise followed by the successive dropwise addition of 15% aqueous sodium hydroxide (12.6 ml) and water (38 ml) The resulting yellow mixture was warmed to room temperature the solids were separated by vacuum filtration The filtrate was placed on a rotary evaporator to remove the solvent to give 28.60 grams (81% yield) of light brown solid product, melting point 105° to 108° C

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

Procedure: To 0.03 mol 2,2′-biphenyldimethanol was added 30 ml tetrahydrofuran and 0.09 mol pyridine, then added 0.075 mol benzoyl chloride with stirring. The reaction mixture was heated refluxing for 4 hours, cooled and added 20 ml saturated saline. The mixture was extracted with ethyl acetate, and extract was dried over anhydrous sodium sulfate. The solvent was removed. Column chromatography gave 2,2′-biphenyldimethanol dibenzoate as a colorless viscous liquid, and the yield was 93%. The reaction mixture was heated refluxing for 4 hours cooled added 20 ml saturated saline The mixture was extracted with ethyl acetate extract was dried over anhydrous sodium sulfate The solvent was removed