1,2-dibromo-4,5-dimethylbenzene

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

Procedure: To a solution of diphenylphosphine borane (V-a) (0.17 g, 0.83 mmol) in dry THF (2 mL) was added dropwise under argon at −78° C. n-BuLi (0.83 mmol). The resulting solution was stirred at this temperature during one hour and 4,5-dibromo-o-xylene (VI-b) (0.31 g, 1.16 mmol) was then added dropwise followed by n-BuLi (0.17 mmol). After one hour at −78° C., the reaction mixture was quenched with water (10 mL) and extracted with methylene chloride (3×10 mL). The organic phases were dried over MgSO4, filtered and the solvent evaporated giving a residue which was purified by column chromatography on silica gel using petroleum ether/methylene chloride 3:1 as eluent. Analytical pure sample can be obtained by recrystallization in methylene chloride/hexane. White solid; yield 56%; Rf 0.45 (petroleum ether/ethyl acetate 3:1); IR (neat) 3050, 2986, 2946, 2917, 2417, 2388, 2357, 1588, 1481, 1471, 1436, 1343, 1136, 1125, 1102, 1062, 1028, 999, 923, 877, 749, 734, 701, 692 cm−1; 1H NMR (300MHz, CDCl3) δ 2.17 (s, 3H, CH3), 2.29 (s, 3H, CH3), 7.21 (d, J=12.3 Hz, Harom), 7.43-7.56 (m, 7H, Harom), 7.65-7.72 (m, 4H, Harom); 13C NMR (75.5 MHz, CDCl3) δ 19.4 (CH3), 19.5 (CH3), 124.7 (d, J=4.4 Hz, Carom), 131.1 (d, J=2.5 Hz, Carom), 133.2 (d, J=9.6 Hz, Carom), 135.9 (d, J=6.1 Hz, Carom), 136.3 (d, J=9.9 Hz, Carom), 137.8 (d, J=11.8 Hz, Carom), 142.6 (d, J=2.2 Hz, Carom); 31P NMR (121 MHz, CDCl3) δ 25.5; HRMS calcd for C20H21PBBrNa (M+Na)+ 405.0553, found 405.0563; Anal calcd for C20H21PBBr: C, 62.71; H, 5.53; found: C, 62.86; H, 5.58. After one hour at −78° C. the reaction mixture was quenched with water (10 mL) extracted with methylene chloride (3×10 mL) The organic phases were dried over MgSO4 filtered the solvent evaporated giving a residue which was purified by column chromatography on silica gel Analytical pure sample can be obtained by recrystallization in methylene chloride/hexane

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

Procedure: To a solution of diphenylphosphine borane (V-a) (0.17 g, 0.83 mmol) in dry THF (2 mL) was added dropwise under argon at −78° C. n-BuLi (0.83 mmol). The resulting solution was stirred at this temperature during one hour and 4,5-dibromo-o-xylene (VI-b) (0.31 g, 1.16 mmol) was then added dropwise followed by n-BuLi (0.17 mmol). After one hour at −78° C., the reaction mixture was quenched with water (10 mL) and extracted with methylene chloride (3×10 mL). The organic phases were dried over MgSO4, filtered and the solvent evaporated giving a residue which was purified by column chromatography on silica gel using petroleum ether/methylene chloride 3:1 as eluent. Analytical pure sample can be obtained by recrystallization in methylene chloride/hexane. White solid; yield 56%; Rf 0.45 (petroleum ether/ethyl acetate 3:1); IR (neat) 3050, 2986, 2946, 2917, 2417, 2388, 2357, 1588, 1481, 1471, 1436, 1343, 1136, 1125, 1102, 1062, 1028, 999, 923, 877, 749, 734, 701, 692 cm−1; 1H NMR (300MHz, CDCl3) δ 2.17 (s, 3H, CH3), 2.29 (s, 3H, CH3), 7.21 (d, J=12.3 Hz, Harom), 7.43-7.56 (m, 7H, Harom), 7.65-7.72 (m, 4H, Harom); 13C NMR (75.5 MHz, CDCl3) δ 19.4 (CH3), 19.5 (CH3), 124.7 (d, J=4.4 Hz, Carom), 131.1 (d, J=2.5 Hz, Carom), 133.2 (d, J=9.6 Hz, Carom), 135.9 (d, J=6.1 Hz, Carom), 136.3 (d, J=9.9 Hz, Carom), 137.8 (d, J=11.8 Hz, Carom), 142.6 (d, J=2.2 Hz, Carom); 31P NMR (121 MHz, CDCl3) δ 25.5; HRMS calcd for C20H21PBBrNa (M+Na)+ 405.0553, found 405.0563; Anal calcd for C20H21PBBr: C, 62.71; H, 5.53; found: C, 62.86; H, 5.58. After one hour at −78° C. the reaction mixture was quenched with water (10 mL) extracted with methylene chloride (3×10 mL) The organic phases were dried over MgSO4 filtered the solvent evaporated giving a residue which was purified by column chromatography on silica gel Analytical pure sample can be obtained by recrystallization in methylene chloride/hexane

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

Procedure: The synthesis is carried out in accordance with the general procedure in accordance with Example 2 from 63.3 g (240 mmol) of 1,2-dibromo-4,5-dimethylbenzene and 85.4 g (505 mmol) of 4-aminobiphenyl. The precipitated solid is recrystallised from toluene/acetonitrile (5:1), and the residue is washed with MeOH, giving 80.3 g (182 mmol) of a crystalline solid. The overall yield is 76%. The precipitated solid is recrystallised from toluene/acetonitrile (5:1) the residue is washed with MeOH

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

Procedure: The synthesis is carried out in accordance with the general procedure in accordance with Example 2 from 63.3 g (240 mmol) of 1,2-dibromo-4,5-dimethylbenzene and 54 ml (505 mmol) of p-toluidine. The precipitated solid is recrystallised from toluene/acetonitrile (5:1), and the residue is washed with MeOH, giving 69 g (218 mmol) of a crystalline solid. The overall yield is 91%. The precipitated solid is recrystallised from toluene/acetonitrile (5:1) the residue is washed with MeOH

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

Procedure: The synthesis is carried out in accordance with the general procedure in accordance with Example 2 from 63.3 g (240 mmol) of 1,2-dibromo-4,5-dimethylbenzene and 46 ml (505 mmol) of aniline. The precipitated solid is recrystallised from toluene/acetonitrile (5:1), and the residue is washed with MeOH, giving 65 g (223 mmol) of a crystalline solid. The overall yield is 93%. The precipitated solid is recrystallised from toluene/acetonitrile (5:1) the residue is washed with MeOH

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

Procedure: The synthesis is carried out in accordance with the general procedure in accordance with Example 2 from 63.3 g (240 mmol) of 1,2-dibromo-4,5-dimethylbenzene and 46 ml (505 mmol) of aniline. The precipitated solid is recrystallised from toluene/acetonitrile (5:1), and the residue is washed with MeOH, giving 65 g (223 mmol) of a crystalline solid. The overall yield is 93%. The precipitated solid is recrystallised from toluene/acetonitrile (5:1) the residue is washed with MeOH

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

Procedure: To a solution of diphenylphosphine borane (V-a) (0.17 g, 0.83 mmol) in dry THF (2 mL) was added dropwise under argon at −78° C. n-BuLi (0.83 mmol). The resulting solution was stirred at this temperature during one hour and 4,5-dibromo-o-xylene (VI-b) (0.31 g, 1.16 mmol) was then added dropwise followed by n-BuLi (0.17 mmol). After one hour at −78° C., the reaction mixture was quenched with water (10 mL) and extracted with methylene chloride (3×10 mL). The organic phases were dried over MgSO4, filtered and the solvent evaporated giving a residue which was purified by column chromatography on silica gel using petroleum ether/methylene chloride 3:1 as eluent. Analytical pure sample can be obtained by recrystallization in methylene chloride/hexane. White solid; yield 56%; Rf 0.45 (petroleum ether/ethyl acetate 3:1); IR (neat) 3050, 2986, 2946, 2917, 2417, 2388, 2357, 1588, 1481, 1471, 1436, 1343, 1136, 1125, 1102, 1062, 1028, 999, 923, 877, 749, 734, 701, 692 cm−1; 1H NMR (300MHz, CDCl3) δ 2.17 (s, 3H, CH3), 2.29 (s, 3H, CH3), 7.21 (d, J=12.3 Hz, Harom), 7.43-7.56 (m, 7H, Harom), 7.65-7.72 (m, 4H, Harom); 13C NMR (75.5 MHz, CDCl3) δ 19.4 (CH3), 19.5 (CH3), 124.7 (d, J=4.4 Hz, Carom), 131.1 (d, J=2.5 Hz, Carom), 133.2 (d, J=9.6 Hz, Carom), 135.9 (d, J=6.1 Hz, Carom), 136.3 (d, J=9.9 Hz, Carom), 137.8 (d, J=11.8 Hz, Carom), 142.6 (d, J=2.2 Hz, Carom); 31P NMR (121 MHz, CDCl3) δ 25.5; HRMS calcd for C20H21PBBrNa (M+Na)+ 405.0553, found 405.0563; Anal calcd for C20H21PBBr: C, 62.71; H, 5.53; found: C, 62.86; H, 5.58. After one hour at −78° C. the reaction mixture was quenched with water (10 mL) extracted with methylene chloride (3×10 mL) The organic phases were dried over MgSO4 filtered the solvent evaporated giving a residue which was purified by column chromatography on silica gel Analytical pure sample can be obtained by recrystallization in methylene chloride/hexane

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

Procedure: The synthesis is carried out in accordance with the general procedure in accordance with Example 2 from 63.3 g (240 mmol) of 1,2-dibromo-4,5-dimethylbenzene and 85.4 g (505 mmol) of 4-aminobiphenyl. The precipitated solid is recrystallised from toluene/acetonitrile (5:1), and the residue is washed with MeOH, giving 80.3 g (182 mmol) of a crystalline solid. The overall yield is 76%. The precipitated solid is recrystallised from toluene/acetonitrile (5:1) the residue is washed with MeOH

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

Procedure: The synthesis is carried out in accordance with the general procedure in accordance with Example 2 from 63.3 g (240 mmol) of 1,2-dibromo-4,5-dimethylbenzene and 54 ml (505 mmol) of p-toluidine. The precipitated solid is recrystallised from toluene/acetonitrile (5:1), and the residue is washed with MeOH, giving 69 g (218 mmol) of a crystalline solid. The overall yield is 91%. The precipitated solid is recrystallised from toluene/acetonitrile (5:1) the residue is washed with MeOH

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

Procedure: The synthesis is carried out in accordance with the general procedure in accordance with Example 2 from 63.3 g (240 mmol) of 1,2-dibromo-4,5-dimethylbenzene and 46 ml (505 mmol) of aniline. The precipitated solid is recrystallised from toluene/acetonitrile (5:1), and the residue is washed with MeOH, giving 65 g (223 mmol) of a crystalline solid. The overall yield is 93%. The precipitated solid is recrystallised from toluene/acetonitrile (5:1) the residue is washed with MeOH