1-(bromomethyl)-3-tert-butylbenzene

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

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

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A dry 100 mL 3-necked flask equipped with a nitrogen inlet, a condenser, a thermometer, and a magnetic stirrer was charged with 2.0 g of 3-tert-butyltoluene (Wiley Organics, Coshocton, Ohio 43812), 2.40 g of N-bromosuccinimide (Aldrich), and 30 mL of CCl4. The mixture was treated with 0.16 g of benzoyl peroxide (Aldrich) and heated at 6-° C. under N2. Careful temperature control is important to minimize by-product formation. After 1 h at 60° C. the reaction mixture was cooled to 0° C., filtered to remove succinimide, and the filtrate was concentrated in vacuo to afford a light yellow liquid. Analysis of this material by tlc (SiO2, hexane) indicated a major new component at Rf =0.50, a minor component at Rf =0.55, and a trace of 3-tert-butyltoluene at Rf =0.75. The crude product was purified by flash chromatography on 100 g of silica gel (hexane) to afford 1.06 g (35%) of 3-tert-butylbenzyl bromide as a clear liquid. A dry 100 mL 3-necked flask equipped with a nitrogen inlet, a condenser heated at 6-° C filtered to remove succinimide the filtrate was concentrated in vacuo to afford a light yellow liquid The crude product was purified by flash chromatography on 100 g of silica gel (hexane)

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

Procedure: Dissolve 3-tert-butyltoluene (0.5 mL, 2.9 mmol) in carbon tetrachloride (20 mL). Add NBS (530 mg, 3 mmol) and irradiate the reaction mixture with a 250 watt sun-lamp with simultaneous heating to reflux for 1 h. Cool to ambient temperature, filter, and concentrate filtrate to dryness to give crude 1-bromomethyl-3-tert-butylbenzene. Dissolve crude 1-bromomethyl-3-tert-butylbenzene (600 mg) in anhydrous DMF. Add portion wise sodium azide (260 mg, 4 mmol) and stir at room temperature for 2 h. Pour the mixture into water (250 mL), extract with EtOAc (3×50 mL), wash combined organic extracts with brine, dry over MgSO4, filter and evaporate solvent to give crude 1-azidomethyl-3-tert-butylbenzene, that was used without further purification. Dissolve crude 1-azidomethyl-3-tert-butylbenzene in methanol containing 10% Pd/C (75 mg) at 5° C., and stir the resulting slurry under 1 atm H2 for 1 h. Filtrate, concentrate in vacuo and purify by chromatography on silica gel eluting sequentially with hexane/EtOAc (4:1 and 1:1), EtOAc, methanol and 2M ammonia in methanol to give the title compound (255 mg, 53% overall). MS (ES+) m/z: 164 (M+H)+. extract with EtOAc (3×50 mL) wash dry over MgSO4 filter evaporate solvent

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

Procedure: Dissolve 3-tert-butyltoluene (0.5 mL, 2.9 mmol) in carbon tetrachloride (20 mL). Add NBS (530 mg, 3 mmol) and irradiate the reaction mixture with a 250 watt sun-lamp with simultaneous heating to reflux for 1 h. Cool to ambient temperature, filter, and concentrate filtrate to dryness to give crude 1-bromomethyl-3-tert-butylbenzene. Dissolve crude 1-bromomethyl-3-tert-butylbenzene (600 mg) in anhydrous DMF. Add portion wise sodium azide (260 mg, 4 mmol) and stir at room temperature for 2 h. Pour the mixture into water (250 mL), extract with EtOAc (3×50 mL), wash combined organic extracts with brine, dry over MgSO4, filter and evaporate solvent to give crude 1-azidomethyl-3-tert-butylbenzene, that was used without further purification. Dissolve crude 1-azidomethyl-3-tert-butylbenzene in methanol containing 10% Pd/C (75 mg) at 5° C., and stir the resulting slurry under 1 atm H2 for 1 h. Filtrate, concentrate in vacuo and purify by chromatography on silica gel eluting sequentially with hexane/EtOAc (4:1 and 1:1), EtOAc, methanol and 2M ammonia in methanol to give the title compound (255 mg, 53% overall). MS (ES+) m/z: 164 (M+H)+. extract with EtOAc (3×50 mL) wash dry over MgSO4 filter evaporate solvent

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

Procedure: Dissolve 3-tert-butyltoluene (0.5 mL, 2.9 mmol) in carbon tetrachloride (20 mL). Add NBS (530 mg, 3 mmol) and irradiate the reaction mixture with a 250 watt sun-lamp with simultaneous heating to reflux for 1 h. Cool to ambient temperature, filter, and concentrate filtrate to dryness to give crude 1-bromomethyl-3-tert-butylbenzene. Dissolve crude 1-bromomethyl-3-tert-butylbenzene (600 mg) in anhydrous DMF. Add portion wise sodium azide (260 mg, 4 mmol) and stir at room temperature for 2 h. Pour the mixture into water (250 mL), extract with EtOAc (3×50 mL), wash combined organic extracts with brine, dry over MgSO4, filter and evaporate solvent to give crude 1-azidomethyl-3-tert-butylbenzene, that was used without further purification. Dissolve crude 1-azidomethyl-3-tert-butylbenzene in methanol containing 10% Pd/C (75 mg) at 5° C., and stir the resulting slurry under 1 atm H2 for 1 h. Filtrate, concentrate in vacuo and purify by chromatography on silica gel eluting sequentially with hexane/EtOAc (4:1 and 1:1), EtOAc, methanol and 2M ammonia in methanol to give the title compound (255 mg, 53% overall). MS (ES+) m/z: 164 (M+H)+. with simultaneous heating to reflux for 1 h filter concentrate filtrate to dryness

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

Procedure: To 1-methyl-3-tert-butyl-benzene (551 mg, 3.72 mmol), NBS (730 mg, 1.1 eq) and AIBN (14 mg, catalytic amount) was added CCl4 (8 mL), which was then refluxed for 2 h. The suspended particles were removed by filtration, and washed with CCl4. The organic layers were combined and concentrated under reduced pressure to give 860 mg of a yellow liquid (which was identified by NMR to contain about 15% dibromo derivative). was then refluxed for 2 h The suspended particles were removed by filtration washed with CCl4 concentrated under reduced pressure

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

Procedure: To 1-methyl-3-tert-butyl-benzene (551 mg, 3.72 mmol), NBS (730 mg, 1.1 eq) and AIBN (14 mg, catalytic amount) was added CCl4 (8 mL), which was then refluxed for 2 h. The suspended particles were removed by filtration, and washed with CCl4. The organic layers were combined and concentrated under reduced pressure to give 860 mg of a yellow liquid (which was identified by NMR to contain about 15% dibromo derivative). was then refluxed for 2 h The suspended particles were removed by filtration washed with CCl4 concentrated under reduced pressure

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A dry 100 mL 3-necked flask equipped with a nitrogen inlet, a condenser, a thermometer, and a magnetic stirrer was charged with 2.0 g of 3-tert-butyltoluene (Wiley Organics, Coshocton, Ohio 43812), 2.40 g of N-bromosuccinimide (Aldrich), and 30 mL of CCl4. The mixture was treated with 0.16 g of benzoyl peroxide (Aldrich) and heated at 60° C. under N2. Careful temperature control is important to minimize by-product formation. After 1 h at 60° C. the reaction mixture was cooled to 0° C., filtered to remove succinimide, and the filtrate was concentrated in vacuo to afford a light yellow liquid. Analysis of this material by tlc (SiO2, hexane) indicated a major new component at Rf=0.50, a minor component at Rf=0.55, and a trace of 3-tert-butyltoluene at Rf=0.75. The crude product was purified by flash chromatography on 100 g of silica gel (hexane) to afford 1.06 g (35%) of 3-tert-butylbenzyl bromide as a clear liquid. A dry 100 mL 3-necked flask equipped with a nitrogen inlet, a condenser After 1 h at 60° C. the reaction mixture was cooled to 0° C. filtered to remove succinimide the filtrate was concentrated in vacuo to afford a light yellow liquid The crude product was purified by flash chromatography on 100 g of silica gel (hexane)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A dry 100 mL 3-necked flask equipped with a nitrogen inlet, a condenser, a thermometer, and a magnetic stirrer was charged with 2.0 g of 3-tert-butyltoluene (Wiley Organics, Coshocton, Ohio 43812), 2.40 g of N-bromosuccinimide (Aldrich), and 30 mL of CCl4. The mixture was treated with 0.16 g of benzoyl peroxide (Aldrich) and heated at 6-° C. under N2. Careful temperature control is important to minimize by-product formation. After 1 h at 60° C. the reaction mixture was cooled to 0° C., filtered to remove succinimide, and the filtrate was concentrated in vacuo to afford a light yellow liquid. Analysis of this material by tlc (SiO2, hexane) indicated a major new component at Rf =0.50, a minor component at Rf =0.55, and a trace of 3-tert-butyltoluene at Rf =0.75. The crude product was purified by flash chromatography on 100 g of silica gel (hexane) to afford 1.06 g (35%) of 3-tert-butylbenzyl bromide as a clear liquid. A dry 100 mL 3-necked flask equipped with a nitrogen inlet, a condenser heated at 6-° C filtered to remove succinimide the filtrate was concentrated in vacuo to afford a light yellow liquid The crude product was purified by flash chromatography on 100 g of silica gel (hexane)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A dry 100 mL 3-necked flask equipped with a nitrogen inlet, a condenser, a thermometer, and a magnetic stirrer was charged with 2.0 g of 3-tert-butyltoluene (Wiley Organics, Coshocton, Ohio 43812), 2.40 g of N-bromosuccinimide (Aldrich), and 30 mL of CCl4. The mixture was treated with 0.16 g of benzoyl peroxide (Aldrich) and heated at 6-° C. under N2. Careful temperature control is important to minimize by-product formation. After 1 h at 60° C. the reaction mixture was cooled to 0° C., filtered to remove succinimide, and the filtrate was concentrated in vacuo to afford a light yellow liquid. Analysis of this material by tlc (SiO2, hexane) indicated a major new component at Rf =0.50, a minor component at Rf =0.55, and a trace of 3-tert-butyltoluene at Rf =0.75. The crude product was purified by flash chromatography on 100 g of silica gel (hexane) to afford 1.06 g (35%) of 3-tert-butylbenzyl bromide as a clear liquid. A dry 100 mL 3-necked flask equipped with a nitrogen inlet, a condenser heated at 6-° C filtered to remove succinimide the filtrate was concentrated in vacuo to afford a light yellow liquid The crude product was purified by flash chromatography on 100 g of silica gel (hexane)

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