2-(bromomethyl)benzoyl chloride

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Using the procedure of Example V, but substituting a mixture of propyl α-chloro-o-toluate and propyl α-bromo-o-toluate, prepared from propyl alcohol and α-bromo-o-toluoyl chloride, for the toluate mixture of Example V provides an oil which upon triturating several times with ether and precipitating as an oil from ethyl acetate with ether and drying yields 18.7 g of o-propoxycarbonylbenzyltributylphosphonium bromide, an oil having a structure in accordance with formula (1) which is confirmed by nmr spectral analysis. provides an oil which upon triturating several times with ether precipitating as an oil from ethyl acetate with ether drying

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Using the procedure of Example V, but substituting a mixture of propyl α-chloro-o-toluate and propyl α-bromo-o-toluate, prepared from propyl alcohol and α-bromo-o-toluoyl chloride, for the toluate mixture of Example V provides an oil which upon triturating several times with ether and precipitating as an oil from ethyl acetate with ether and drying yields 18.7 g of o-propoxycarbonylbenzyltributylphosphonium bromide, an oil having a structure in accordance with formula (1) which is confirmed by nmr spectral analysis. provides an oil which upon triturating several times with ether precipitating as an oil from ethyl acetate with ether drying

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-bromo-5-trityl-pyrrolo[2,3-b]pyrazin-7-amine (3 g, 6.588 mmol) dissolved in THF (30 mL) under N2 at rt. DIPEA (5.7 mL, 32.9 mmol) added followed by a solution of 2-(bromomethyl)benzoyl chloride (1.9 g, 8.137 mmol) in THF (10 mL). Reaction mixture stirred overnight then partitioned between EtOAc and water. Aqueous phase extracted with EtOAc. Combined organics washed with saturated NaHCO3 solution then brine, dried and concentrated. Residue taken up in DCM and purified by chromatography (0-40% EtOAc-petroleum ether gradient). Further purification by chromatography (isocratic DCM elution) gives the title compound as a yellow foam (1.45 g, 34%); 1H NMR (400 MHz, DMSO) δ 4.93 (2H, s), 7.21-7.38 (15H, m), 7.44-7.61 (3H, m), 7.62 (1H, d), 8.19 (1H, s), 8.59 (1H, s), 10.93 (1H, s) ppm; MS (ES+) 653.0. Reaction mixture then partitioned between EtOAc and water Aqueous phase extracted with EtOAc Combined organics washed with saturated NaHCO3 solution brine, dried concentrated purified by chromatography (0-40% EtOAc-petroleum ether gradient) Further purification by chromatography (isocratic DCM elution)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: --A solution of α-bromotoluic acid (1.08 g) in dry benzene (10 ml) was stirred for 2 hours with thionyl chloride (0.73 ml) and dry DMF (five drops). The reaction mixture was evaporated to dryness, taken up in toluene and evaporated again. The crude product was crystallized from n-hexane (10 ml, charcoal) thereby obtaining pure α-bromotoluic acid chloride (0.95 g) as white flakes. The reaction mixture was evaporated to dryness evaporated again The crude product was crystallized from n-hexane (10 ml, charcoal)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Using the procedure of Example V, but substituting a mixture of propyl α-chloro-o-toluate and propyl α-bromo-o-toluate, prepared from propyl alcohol and α-bromo-o-toluoyl chloride, for the toluate mixture of Example V provides an oil which upon triturating several times with ether and precipitating as an oil from ethyl acetate with ether and drying yields 18.7 g of o-propoxycarbonylbenzyltributylphosphonium bromide, an oil having a structure in accordance with formula (1) which is confirmed by nmr spectral analysis. provides an oil which upon triturating several times with ether precipitating as an oil from ethyl acetate with ether drying

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Using the procedure of Example V, but substituting a mixture of propyl α-chloro-o-toluate and propyl α-bromo-o-toluate, prepared from propyl alcohol and α-bromo-o-toluoyl chloride, for the toluate mixture of Example V provides an oil which upon triturating several times with ether and precipitating as an oil from ethyl acetate with ether and drying yields 18.7 g of o-propoxycarbonylbenzyltributylphosphonium bromide, an oil having a structure in accordance with formula (1) which is confirmed by nmr spectral analysis. provides an oil which upon triturating several times with ether precipitating as an oil from ethyl acetate with ether drying

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-bromo-5-trityl-pyrrolo[2,3-b]pyrazin-7-amine (3 g, 6.588 mmol) dissolved in THF (30 mL) under N2 at rt. DIPEA (5.7 mL, 32.9 mmol) added followed by a solution of 2-(bromomethyl)benzoyl chloride (1.9 g, 8.137 mmol) in THF (10 mL). Reaction mixture stirred overnight then partitioned between EtOAc and water. Aqueous phase extracted with EtOAc. Combined organics washed with saturated NaHCO3 solution then brine, dried and concentrated. Residue taken up in DCM and purified by chromatography (0-40% EtOAc-petroleum ether gradient). Further purification by chromatography (isocratic DCM elution) gives the title compound as a yellow foam (1.45 g, 34%); 1H NMR (400 MHz, DMSO) δ 4.93 (2H, s), 7.21-7.38 (15H, m), 7.44-7.61 (3H, m), 7.62 (1H, d), 8.19 (1H, s), 8.59 (1H, s), 10.93 (1H, s) ppm; MS (ES+) 653.0. Reaction mixture then partitioned between EtOAc and water Aqueous phase extracted with EtOAc Combined organics washed with saturated NaHCO3 solution brine, dried concentrated purified by chromatography (0-40% EtOAc-petroleum ether gradient) Further purification by chromatography (isocratic DCM elution)