1-Bromo-2-(tert-butyl)benzene

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: According to the general procedure B, 2-tert-butylbromobenzene (213 mg, 1.00 mmol) reacted with N,N-di-n-butylamine (130 mg, 1.00 mmol) using 1 mol % of catalyst and sodium tert-butoxide (115 mg, 1.20 mmol) at 60° C. to give the title compound (233 mg, 89%) as an oil: 1H-NMR (300 MHz, CDCl3): δ 7.25 (d, 2H, J=8.7 Hz), 6.62 (d, 2H, J=8.7 Hz), 3.25 (t, 4H, J=7.2 and 8.1 Hz), 1.58 (m, 4H), 1.35 (M, 4H), 1.30 (s, 9H), 0.97 (t, 6H, J=7.2 Hz). 13C{1H}-NMR (100 MHz, CDCl3): δ 146.01, 137.59, 125.92, 111.29, 50.84, 33.61, 31.56, 29.53, 20.39, 14.02. GC/MS(EI): m/z 261 (M+). at 60° C.

Conditions: temp:78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 1-bromo-2-tert-butylbenzene (2.88 g, 13.51 mmol) in anhydrous THF (45 mL) 2,2′-dipyridyl (ca 10 mg) was added under a nitrogen atmosphere. The mixture was cooled down minus 78° C., and a solution of n-butyllithium (2.5 M in hexanes, 5.94 mL, 14.86 mmol) was added dropwise via syringe within the period of ten minutes. Upon addition, the mixture was stirred for 30 minutes, then warmed up to minus 30° C., and a flow of formaldehyde (generated from 1.91 g of paraformaldehyde by heating at over 160° C.) was passed through the solution until the deep red color disappeared completely. The mixture was quenched with saturated ammonium chloride solution (5 mL), then poured into a mixture of dichloromethane (100 mL) and water (50 mL). The organic phase was separated and the aqueous phase was extracted with dichloromethane (20 mL) twice. The combined organic phase was dried over anhydrous Na2SO4, concentrated in vacuo, and purified by silica gel chromatography to yield 2-tert-butylbenzyl alcohol (1.67 g, 75%) as an oil. 1H NMR (400 MHz, CDCl3): δ 7.50 (m, 1H, Ph-H), 7.41 (m, 1H, Ph-H), 7.24 (m, 2H, Ph-H), 4.93 (d, J=4.8 Hz, 2H, CH2OH), 1.54 (br, 1H, CH2OH), 1.43 (s, 1H, C(CH3)3). Upon addition warmed up to minus 30° C. The mixture was quenched with saturated ammonium chloride solution (5 mL) poured into a mixture of dichloromethane (100 mL) and water (50 mL) The organic phase was separated the aqueous phase was extracted with dichloromethane (20 mL) twice The combined organic phase was dried over anhydrous Na2SO4 concentrated in vacuo purified by silica gel chromatography

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

Procedure: To a solution of 2-tert-butylaniline (7.46 g, 50 mmol 15.6 mL) in hydrobromic acid (40% w/w, 15 mL) cooled at <5° C. (ice/salt bath), a solution of 7.55 g (0.11 mol) of sodium nitrite in 10 mL of water was added at a rate that the temperature did not exceed 10° C. (ca two hour addition time). When the diazotization was completed, 0.20 g of copper powder was added. (CAUTION: the solution was refluxed very cautiously because of vigorous gas evolution!). When the vigorous evolution of nitrogen subsided, the system was kept at 50° C. for 30 minutes and was then diluted with 80 mL of water and extracted three times with diethyl ether (100 mL each). The organic layer was washed with 10% solution of KOH; dried over Na2SO4, concentrated in vacuo, and purified by chromatography on silica gel chromatography. The product obtained was further distilled at 85° C. (3 mm Hg) to yield 1-bromo-2-tert-butylbenzene (2.88 g, 27%). 1H NMR (400 MHz, CDCl3): δ 7.58 (m, 1H, Ph-H), 7.45 (m, 1H, Ph-H), 7.24 (m, 1H, Ph-H), 7.02 (m, 1H, Ph-H), 1.51 (s, 9H, C(CH3)3). did not exceed 10° C. (ca two hour addition time) (CAUTION: the solution was refluxed very cautiously because of vigorous gas evolution extracted three times with diethyl ether (100 mL each) The organic layer was washed with 10% solution of KOH dried over Na2SO4 concentrated in vacuo purified by chromatography on silica gel chromatography The product obtained was further distilled at 85° C. (3 mm Hg)

Conditions: temp:78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 1-bromo-2-tert-butylbenzene (2.88 g, 13.51 mmol) in anhydrous THF (45 mL) 2,2′-dipyridyl (ca 10 mg) was added under a nitrogen atmosphere. The mixture was cooled down minus 78° C., and a solution of n-butyllithium (2.5 M in hexanes, 5.94 mL, 14.86 mmol) was added dropwise via syringe within the period of ten minutes. Upon addition, the mixture was stirred for 30 minutes, then warmed up to minus 30° C., and a flow of formaldehyde (generated from 1.91 g of paraformaldehyde by heating at over 160° C.) was passed through the solution until the deep red color disappeared completely. The mixture was quenched with saturated ammonium chloride solution (5 mL), then poured into a mixture of dichloromethane (100 mL) and water (50 mL). The organic phase was separated and the aqueous phase was extracted with dichloromethane (20 mL) twice. The combined organic phase was dried over anhydrous Na2SO4, concentrated in vacuo, and purified by silica gel chromatography to yield 2-tert-butylbenzyl alcohol (1.67 g, 75%) as an oil. 1H NMR (400 MHz, CDCl3): δ 7.50 (m, 1 H, Ph-H), 7.41 (m, 1 H, Ph-H), 7.24 (m, 2 H, Ph-H), 4.93 (d, J=4.8 Hz, 2 H, CH2OH), 1.54 (br, 1 H, CH2OH), 1.43 (s, 1 H, C(CH3)3). Upon addition warmed up to minus 30° C. The mixture was quenched with saturated ammonium chloride solution (5 mL) poured into a mixture of dichloromethane (100 mL) and water (50 mL) The organic phase was separated the aqueous phase was extracted with dichloromethane (20 mL) twice The combined organic phase was dried over anhydrous Na2SO4 concentrated in vacuo purified by silica gel chromatography

Conditions: temp:78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 1-bromo-2-tert-butylbenzene (2.88 g, 13.51 mmol) in anhydrous THF (45 mL) 2,2′-dipyridyl (ca 10 mg) was added under a nitrogen atmosphere. The mixture was cooled down minus 78° C., and a solution of n-butyllithium (2.5 M in hexanes, 5.94 mL, 14.86 mmol) was added dropwise via syringe within the period of ten minutes. Upon addition, the mixture was stirred for 30 minutes, then warmed up to minus 30° C., and a flow of formaldehyde (generated from 1.91 g of paraformaldehyde by heating at over 160° C.) was passed through the solution until the deep red color disappeared completely. The mixture was quenched with saturated ammonium chloride solution (5 mL), then poured into a mixture of dichloromethane (100 mL) and water (50 mL). The organic phase was separated and the aqueous phase was extracted with dichloromethane (20 mL) twice. The combined organic phase was dried over anhydrous Na2SO4, concentrated in vacuo, and purified by silica gel chromatography to yield 2-tert-butylbenzyl alcohol (1.67 g, 75%) as an oil. 1H NMR (400 MHz, CDCl3): δ 7.50 (m, 1 H, Ph-H), 7.41 (m, 1 H, Ph-H), 7.24 (m, 2 H, Ph-H), 4.93 (d, J=4.8 Hz, 2 H, CH2OH), 1.54 (br, 1 H, CH2OH), 1.43 (s, 1 H, C(CH3)3). Upon addition warmed up to minus 30° C. The mixture was quenched with saturated ammonium chloride solution (5 mL) poured into a mixture of dichloromethane (100 mL) and water (50 mL) The organic phase was separated the aqueous phase was extracted with dichloromethane (20 mL) twice The combined organic phase was dried over anhydrous Na2SO4 concentrated in vacuo purified by silica gel chromatography

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

Procedure: To a solution of 2-tert-butylaniline (7.46 g, 50 mmol 15.6 mL) in hydrobromic acid (40% w/w, 15 mL) cooled at <5° C. (ice/salt bath), a solution of 7.55 g (0.11 mol) of sodium nitrite in 10 mL of water was added at a rate that the temperature did not exceed 10° C. (ca two hour addition time). When the diazotization was completed, 0.20 g of copper powder was added. (CAUTION: the solution was refluxed very cautiously because of vigorous gas evolution!). When the vigorous evolution of nitrogen subsided, the system was kept at 50° C. for 30 minutes and was then diluted with 80 mL of water and extracted three times with diethyl ether (100 mL each). The organic layer was washed with 10% solution of KOH; dried over Na2SO4, concentrated in vacuo, and purified by chromatography on silica gel chromatography. The product obtained was further distilled at 85° C. (3 mm Hg) to yield 1-bromo-2-tert-butylbenzene (2.88 g, 27%). 1H NMR (400 MHz, CDCl3): δ 7.58 (m, 1 H, Ph-H), 7.45 (m, 1 H, Ph-H), 7.24 (m, 1 H, Ph-H), 7.02 (m, 1 H, Ph-H), 1.51 (s, 9 H, C(CH3)3). did not exceed 10° C. (ca two hour addition time) (CAUTION: the solution was refluxed very cautiously because of vigorous gas evolution extracted three times with diethyl ether (100 mL each) The organic layer was washed with 10% solution of KOH dried over Na2SO4 concentrated in vacuo purified by chromatography on silica gel chromatography The product obtained was further distilled at 85° C. (3 mm Hg)

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

Procedure: According to the general procedure B, 2-tert-butylbromobenzene (213 mg, 1.00 mmol) reacted with N,N-di-n-butylamine (130 mg, 1.00 mmol) using 1 mol % of catalyst and sodium tert-butoxide (115 mg, 1.20 mmol) at 60° C. to give the title compound (233 mg, 89%) as an oil: 1H-NMR (300 MHz, CDCl3): δ 7.25 (d, 2H, J=8.7 Hz), 6.62 (d, 2H, J=8.7 Hz), 3.25 (t, 4H, J=7.2 and 8.1 Hz), 1.58 (m, 4H), 1.35 (M, 4H), 1.30 (s, 9H), 0.97 (t, 6H, J=7.2 Hz). 13C{1H}-NMR (100 MHz, CDCl3): δ 146.01, 137.59, 125.92, 111.29, 50.84, 33.61, 31.56, 29.53, 20.39, 14.02. GC/MS(EI): m/z 261 (M+). at 60° C.

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

Procedure: According to the general procedure B, 2-tert-butylbromobenzene (213 mg, 1.00 mmol) reacted with N,N-di-n-butylamine (130 mg, 1.00 mmol) using 1 mol % of catalyst and sodium tert-butoxide (115 mg, 1.20 mmol) at 60° C. to give the title compound (233 mg, 89%) as an oil: 1H-NMR (300 MHz, CDCl3): δ 7.25 (d, 2H, J=8.7 Hz), 6.62 (d, 2H, J=8.7 Hz), 3.25 (t, 4H, J=7.2 and 8.1 Hz), 1.58 (m, 4H), 1.35 (M, 4H), 1.30 (s, 9H), 0.97 (t, 6H, J=7.2 Hz). 13C{1H}-NMR (100 MHz, CDCl3): δ 146.01, 137.59, 125.92, 111.29, 50.84, 33.61, 31.56, 29.53, 20.39, 14.02. GC/MS(EI): m/z 261 (M+). at 60° C.

Conditions: temp:78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 1-bromo-2-tert-butylbenzene (2.88 g, 13.51 mmol) in anhydrous THF (45 mL) 2,2′-dipyridyl (ca 10 mg) was added under a nitrogen atmosphere. The mixture was cooled down minus 78° C., and a solution of n-butyllithium (2.5 M in hexanes, 5.94 mL, 14.86 mmol) was added dropwise via syringe within the period of ten minutes. Upon addition, the mixture was stirred for 30 minutes, then warmed up to minus 30° C., and a flow of formaldehyde (generated from 1.91 g of paraformaldehyde by heating at over 160° C.) was passed through the solution until the deep red color disappeared completely. The mixture was quenched with saturated ammonium chloride solution (5 mL), then poured into a mixture of dichloromethane (100 mL) and water (50 mL). The organic phase was separated and the aqueous phase was extracted with dichloromethane (20 mL) twice. The combined organic phase was dried over anhydrous Na2SO4, concentrated in vacuo, and purified by silica gel chromatography to yield 2-tert-butylbenzyl alcohol (1.67 g, 75%) as an oil. 1H NMR (400 MHz, CDCl3): δ 7.50 (m, 1H, Ph-H), 7.41 (m, 1H, Ph-H), 7.24 (m, 2H, Ph-H), 4.93 (d, J=4.8 Hz, 2H, CH2OH), 1.54 (br, 1H, CH2OH), 1.43 (s, 1H, C(CH3)3). Upon addition warmed up to minus 30° C. The mixture was quenched with saturated ammonium chloride solution (5 mL) poured into a mixture of dichloromethane (100 mL) and water (50 mL) The organic phase was separated the aqueous phase was extracted with dichloromethane (20 mL) twice The combined organic phase was dried over anhydrous Na2SO4 concentrated in vacuo purified by silica gel chromatography

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

Procedure: To a solution of 2-tert-butylaniline (7.46 g, 50 mmol 15.6 mL) in hydrobromic acid (40% w/w, 15 mL) cooled at <5° C. (ice/salt bath), a solution of 7.55 g (0.11 mol) of sodium nitrite in 10 mL of water was added at a rate that the temperature did not exceed 10° C. (ca two hour addition time). When the diazotization was completed, 0.20 g of copper powder was added. (CAUTION: the solution was refluxed very cautiously because of vigorous gas evolution!). When the vigorous evolution of nitrogen subsided, the system was kept at 50° C. for 30 minutes and was then diluted with 80 mL of water and extracted three times with diethyl ether (100 mL each). The organic layer was washed with 10% solution of KOH; dried over Na2SO4, concentrated in vacuo, and purified by chromatography on silica gel chromatography. The product obtained was further distilled at 85° C. (3 mm Hg) to yield 1-bromo-2-tert-butylbenzene (2.88 g, 27%). 1H NMR (400 MHz, CDCl3): δ 7.58 (m, 1H, Ph-H), 7.45 (m, 1H, Ph-H), 7.24 (m, 1H, Ph-H), 7.02 (m, 1H, Ph-H), 1.51 (s, 9H, C(CH3)3). did not exceed 10° C. (ca two hour addition time) (CAUTION: the solution was refluxed very cautiously because of vigorous gas evolution extracted three times with diethyl ether (100 mL each) The organic layer was washed with 10% solution of KOH dried over Na2SO4 concentrated in vacuo purified by chromatography on silica gel chromatography The product obtained was further distilled at 85° C. (3 mm Hg)