1-(bromomethyl)-2-[2-(bromomethyl)phenyl]benzene

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 25.0 g (73.5 mmol) of 2,2'-bis(bromomethyl)biphenyl, 14.2 g (151 mmol) of phenol, 14.7 g (261 mmol) of pulverized potassium hydroxide and 3.41 g (15 mmol) of triethylbenzylammonium chloride is admixed with 120 ml of dichloromethane and stirred for 5 hours at 40° C.

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

Procedure: Diisobutylphosphine (1.66 grams, 11.37 mmol) was dissolved in THF (25 ml) under nitrogen and cooled with a dry ice/acetone bath. n-Butyllithium (7.11 ml of a 1.6M solution in hexane, 11.37 mmol) was added dropwise to the stirring solution which was then allowed to stir for 1 hour in the cold bath. 2,2'-Bis(bromomethyl)-1,1'-biphenyl (1.89 grams, 5.55 mmol) in THF (10 ml) was added dropwise at -70° C. The solution was allowed to stir overnight at room temperature and was then heated at reflux for 1 hour. Saturated aqueous NH4Cl was added to the solution at room temperature. Diethyl ether was added and the layers were separated in a separatory funnel. The aqueous layer was extracted twice with diethyl ether, and the combined organic solution was then washed twice with water. The solvent was removed on a steam bath under a stream of nitrogen. The oily residue was then placed on a Kugelrohr distillation apparatus to remove low boiling material at about 175° C. and 1 mm Hg leaving 1.88 grams (72% yield) of a thick orange glassy product. 1H NMR (CDCl3): δ 0.65-1.67 (complex, 36H, aliphatic); 2.42 (s, 4H, benzylic); 6.67-7.30 (complex, 8H aromatic). 31P NMR (CDCl3): δ+31. cooled with a dry ice/acetone bath to stir overnight at room temperature was then heated at reflux for 1 hour the layers were separated in a separatory funnel The aqueous layer was extracted twice with diethyl ether the combined organic solution was then washed twice with water The solvent was removed on a steam bath under a stream of nitrogen The oily residue was then placed on a Kugelrohr distillation apparatus to remove low boiling material at about 175° C.

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

Procedure: Di[p-(3-phenylpropyl)phenyl]chlorophosphine 1 (6.0 g, 13.1 mmol) was dissolved in 150 ml THF and Li (0.185 g, 26.2 mmol) was chopped directly into the reaction flask under Ar. A deep red solution was resulted in 10 min and all the lithium was consumed in 4 h. The solution was then filtered and 2,2'-dibromomethyl-1,1'-biphenyl (2.23 g, 6.5 mmol) in 20 ml THF was added dropwise with an ice-water bath. The color of the solution was slowly changed to pale yellow. The mixture was stirred for additional 10 h before the solvent was removed by vacuum. 50 ml diethyl ether was added and it was washed with 3×10 ml H2O. The ether phase was dried over MgSO4 and the solvent was then removed by vacuum. The resulting pale yellow viscous oil was purified over silica gel column. 2.3 g (69% yield) of 11 was eluted with Et2O/hexane (1/10), 11 was characterized by 1H, 13C, 31P NMR and Mass spectrometry. A deep red solution was resulted in 10 min all the lithium was consumed in 4 h The solution was then filtered was removed by vacuum 50 ml diethyl ether was added it was washed with 3×10 ml H2O The ether phase was dried over MgSO4 the solvent was then removed by vacuum The resulting pale yellow viscous oil was purified over silica gel column

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 25.0 g (73.5 mmol) of 2,2'-bis(bromomethyl)biphenyl, 14.2 g (151 mmol) of phenol, 14.7 g (261 mmol) of pulverized potassium hydroxide and 3.41 g (15 mmol) of triethylbenzylammonium chloride is admixed with 120 ml of dichloromethane and stirred for 5 hours at 40° C.

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

Procedure: Diisobutylphosphine (1.66 grams, 11.37 mmol) was dissolved in THF (25 ml) under nitrogen and cooled with a dry ice/acetone bath. n-Butyllithium (7.11 ml of a 1.6M solution in hexane, 11.37 mmol) was added dropwise to the stirring solution which was then allowed to stir for 1 hour in the cold bath. 2,2'-Bis(bromomethyl)-1,1'-biphenyl (1.89 grams, 5.55 mmol) in THF (10 ml) was added dropwise at -70° C. The solution was allowed to stir overnight at room temperature and was then heated at reflux for 1 hour. Saturated aqueous NH4Cl was added to the solution at room temperature. Diethyl ether was added and the layers were separated in a separatory funnel. The aqueous layer was extracted twice with diethyl ether, and the combined organic solution was then washed twice with water. The solvent was removed on a steam bath under a stream of nitrogen. The oily residue was then placed on a Kugelrohr distillation apparatus to remove low boiling material at about 175° C. and 1 mm Hg leaving 1.88 grams (72% yield) of a thick orange glassy product. 1H NMR (CDCl3): δ 0.65-1.67 (complex, 36H, aliphatic); 2.42 (s, 4H, benzylic); 6.67-7.30 (complex, 8H aromatic). 31P NMR (CDCl3): δ+31. cooled with a dry ice/acetone bath to stir overnight at room temperature was then heated at reflux for 1 hour the layers were separated in a separatory funnel The aqueous layer was extracted twice with diethyl ether the combined organic solution was then washed twice with water The solvent was removed on a steam bath under a stream of nitrogen The oily residue was then placed on a Kugelrohr distillation apparatus to remove low boiling material at about 175° C.

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

Procedure: 180 ml of 50% sodium hydroxide solution are treated at about 60° C. in sequence with 7.7 g of cyanamide, 1.3 g of tricaprylmethylammonium chloride, 360 ml of benzene and 62 g of 2,2'-bis(bromomethyl)-biphenyl, and the mixture is stirred at 60°-70° C. for 6 hours. After cooling the reaction mixture this is transferred to a separating funnel and shaken with 50 ml of methylene chloride, whereby the separated product is taken up in the methylene chloride phase. The aqueous phase is back-extracted twice with methylene chloride. The combined extracts are subsequently washed with water, dried over anhydrous sodium sulphate and evaporated, and the residue is taken up in 100 ml of toluene and the solution is heated to reflux temperature, filtered and treated at about 50° C. with 200 ml of tert.-butyl methyl ether. Finally, the crystals which are precipitated by ice-cooling are filtered off under suction and dried. In this manner there is obtained pure 5,7-dihydro-6H-dibenz[c,e]azepine-6-carbonitrile, m.p. 121°-124° C. After cooling the reaction mixture this is transferred to a separating funnel The aqueous phase is back-extracted twice with methylene chloride The combined extracts are subsequently washed with water dried over anhydrous sodium sulphate evaporated the solution is heated to reflux temperature filtered treated at about 50° C. with 200 ml of tert.-butyl methyl ether Finally, the crystals which are precipitated by ice- cooling are filtered off under suction dried

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

Procedure: 180 ml of 50% sodium hydroxide solution are treated at about 60° C. in sequence with 7.7 g of cyanamide, 1.3 g of tricaprylmethylammonium chloride, 360 ml of benzene and 62 g of 2,2'-bis(bromomethyl)-biphenyl, and the mixture is stirred at 60°-70° C. for 6 hours. After cooling the reaction mixture this is transferred to a separating funnel and shaken with 50 ml of methylene chloride, whereby the separated product is taken up in the methylene chloride phase. The aqueous phase is back-extracted twice with methylene chloride. The combined extracts are subsequently washed with water, dried over anhydrous sodium sulphate and evaporated, and the residue is taken up in 100 ml of toluene and the solution is heated to reflux temperature, filtered and treated at about 50° C. with 200 ml of tert.-butyl methyl ether. Finally, the crystals which are precipitated by ice-cooling are filtered off under suction and dried. In this manner there is obtained pure 5,7-dihydro-6H-dibenz[c,e]azepine-6-carbonitrile, m.p. 121°-124° C. After cooling the reaction mixture this is transferred to a separating funnel The aqueous phase is back-extracted twice with methylene chloride The combined extracts are subsequently washed with water dried over anhydrous sodium sulphate evaporated the solution is heated to reflux temperature filtered treated at about 50° C. with 200 ml of tert.-butyl methyl ether Finally, the crystals which are precipitated by ice- cooling are filtered off under suction dried

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

Procedure: Diisobutylphosphine (1.66 grams, 11.37 mmol) was dissolved in THF (25 ml) under nitrogen and cooled with a dry ice/acetone bath. n-Butyllithium (7.11 ml of a 1.6M solution in hexane, 11.37 mmol) was added dropwise to the stirring solution which was then allowed to stir for 1 hour in the cold bath. 2,2'-Bis(bromomethyl)-1,1'-biphenyl (1.89 grams, 5.55 mmol) in THF (10 ml) was added dropwise at -70° C. The solution was allowed to stir overnight at room temperature and was then heated at reflux for 1 hour. Saturated aqueous NH4Cl was added to the solution at room temperature. Diethyl ether was added and the layers were separated in a separatory funnel. The aqueous layer was extracted twice with diethyl ether, and the combined organic solution was then washed twice with water. The solvent was removed on a steam bath under a stream of nitrogen. The oily residue was then placed on a Kugelrohr distillation apparatus to remove low boiling material at about 175° C. and 1 mm Hg leaving 1.88 grams (72% yield) of a thick orange glassy product. 1H NMR (CDCl3): δ0.65-1.67 (complex, 36H, aliphatic); 2.42 (s, 4H, benzylic); 6.67-7.30 (complex, 8H aromatic). 31P NMR (CDCl3): δ+31. cooled with a dry ice/acetone bath to stir overnight at room temperature was then heated at reflux for 1 hour the layers were separated in a separatory funnel The aqueous layer was extracted twice with diethyl ether the combined organic solution was then washed twice with water The solvent was removed on a steam bath under a stream of nitrogen The oily residue was then placed on a Kugelrohr distillation apparatus to remove low boiling material at about 175° C.

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

Procedure: Diisobutylphosphine (1.66 grams, 11.37 mmol) was dissolved in THF (25 ml) under nitrogen and cooled with a dry ice/acetone bath. n-Butyllithium (7.11 ml of a 1.6M solution in hexane, 11.37 mmol) was added dropwise to the stirring solution which was then allowed to stir for 1 hour in the cold bath. 2,2'-Bis(bromomethyl)-1,1'-biphenyl (1.89 grams, 5.55 mmol) in THF (10 ml) was added dropwise at -70° C. The solution was allowed to stir overnight at room temperature and was then heated at reflux for 1 hour. Saturated aqueous NH4Cl was added to the solution at room temperature. Diethyl ether was added and the layers were separated in a separatory funnel. The aqueous layer was extracted twice with diethyl ether, and the combined organic solution was then washed twice with water. The solvent was removed on a steam bath under a stream of nitrogen. The oily residue was then placed on a Kugelrohr distillation apparatus to remove low boiling material at about 175° C. and 1 mm Hg leaving 1.88 grams (72% yield) of a thick orange glassy product. 1H NMR (CDCl3): δ0.65-1.67 (complex, 36H, aliphatic); 2.42 (s, 4H, benzylic); 6.67-7.30 (complex, 8H aromatic). 31P NMR (CDCl3): δ+31. cooled with a dry ice/acetone bath to stir overnight at room temperature was then heated at reflux for 1 hour the layers were separated in a separatory funnel The aqueous layer was extracted twice with diethyl ether the combined organic solution was then washed twice with water The solvent was removed on a steam bath under a stream of nitrogen The oily residue was then placed on a Kugelrohr distillation apparatus to remove low boiling material at about 175° C.

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

Procedure: Di[p-(3-phenylpropyl)phenyl]chlorophosphine 1 (6.0 g, 13.1 mmol) was dissolved in 150 ml THF and Li (0.185 g, 26.2 mmol) was chopped directly into the reaction flask under Ar. A deep red solution was resulted in 10 min and all the lithium was consumed in 4 h. The solution was then filtered and 2,2'-dibromomethyl-1,1'-biphenyl (2.23 g, 6.5 mmol) in 20 ml THF was added dropwise with an ice-water bath. The color of the solution was slowly changed to pale yellow. The mixture was stirred for additional 10 h before the solvent was removed by vacuum. 50 ml diethyl ether was added and it was washed with 3×10 ml H2O. The ether phase was dried over MgSO4 and the solvent was then removed by vacuum. The resulting pale yellow viscous oil was purified over silica gel column. 2.3 g (69% yield) of 11 was eluted with Et2O/hexane (1/10), 11 was characterized by 1H, 13C, 31P NMR and Mass spectrometry. A deep red solution was resulted in 10 min all the lithium was consumed in 4 h The solution was then filtered was removed by vacuum 50 ml diethyl ether was added it was washed with 3×10 ml H2O The ether phase was dried over MgSO4 the solvent was then removed by vacuum The resulting pale yellow viscous oil was purified over silica gel column

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

Procedure: 180 ml of 50% sodium hydroxide solution are treated at about 60° C. in sequence with 7.7 g of cyanamide, 1.3 g of tricaprylmethylammonium chloride, 360 ml of benzene and 62 g of 2,2'-bis(bromomethyl)-biphenyl, and the mixture is stirred at 60°-70° C. for 6 hours. After cooling the reaction mixture this is transferred to a separating funnel and shaken with 50 ml of methylene chloride, whereby the separated product is taken up in the methylene chloride phase. The aqueous phase is back-extracted twice with methylene chloride. The combined extracts are subsequently washed with water, dried over anhydrous sodium sulphate and evaporated, and the residue is taken up in 100 ml of toluene and the solution is heated to reflux temperature, filtered and treated at about 50° C. with 200 ml of tert.-butyl methyl ether. Finally, the crystals which are precipitated by ice-cooling are filtered off under suction and dried. In this manner there is obtained pure 5,7-dihydro-6H-dibenz[c,e]azepine-6-carbonitrile, m.p. 121°-124° C. After cooling the reaction mixture this is transferred to a separating funnel The aqueous phase is back-extracted twice with methylene chloride The combined extracts are subsequently washed with water dried over anhydrous sodium sulphate evaporated the solution is heated to reflux temperature filtered treated at about 50° C. with 200 ml of tert.-butyl methyl ether Finally, the crystals which are precipitated by ice- cooling are filtered off under suction dried

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

Procedure: 2,2'-Bis(bromomethyl)-1,1'-biphenyl (3.40 grams, 10 mmole) was added to the addition funnel and dissolved in 10 mL of dry THF. The dibromo compound may be obtained by the free radical catalyzed halogenation of 2,2'-bitolyl. The flask containing the dibenzophospholyl anion is chilled with a water-ice bath. The mixture was stirred vigorously as the dibromo compound was added dropwise to the chilled solution over 30 minutes. The solution color lightened by the end of the addition. The resulting mixture was allowed to stir at room temperature for an additional five hours. Methanol (5 mL) was added to quench out any remaining anion and resulted in a pale yellow mixture.