4-bromobenzohydrazide

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 4-Bromo-benzoic acid hydrazide (12.90 g, 60 mmol) and N,N-dimethylacetamide dimethyl acetal (12 mL, 82.0 mmol) were dissolved in N,N-dimethylformamide (100 mL) and the solution heated to 60° C. for 2 hours. The solution was concentrated in vacuo and the residue taken up in toluene (80 mL) and treated with para-toluenesulfonic acid monohydrate (200 mg, 1.50 mmol). The mixture was heated to reflux for 2 hours, allowed to cool, and the product crystallised from the solution and was collected by filtration. The crude product was washed with ether and dried in vacuo to yield a white solid. The filtrate was concentrated in vacuo and the residue combined with the white solid, dissolved in toluene (50 mL) and treated with para-toluenesulfonic acid monohydrate (100 mg, 0.75 mmol). The mixture was heated to reflux for 3 hours, allowed to cool and concentrated in vacuo. The residue was purified by column chromatography on silica gel eluting with pentane:ethyl acetate 80:20 to 40:60 to yield the title product, 12.00 g. The solution was concentrated in vacuo The mixture was heated to reflux for 2 hours to cool the product crystallised from the solution was collected by filtration The crude product was washed with ether dried in vacuo to yield a white solid The filtrate was concentrated in vacuo dissolved in toluene (50 mL) The mixture was heated to reflux for 3 hours to cool concentrated in vacuo The residue was purified by column chromatography on silica gel eluting with pentane:ethyl acetate 80:20 to 40:60

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 4-Bromo-benzoic acid hydrazide (12.90 g, 60 mmol) and N,N-dimethylacetamide dimethyl acetal (12 mL, 82.0 mmol) were dissolved in N,N-dimethylformamide (100 mL) and the solution heated to 60° C. for 2 hours. The solution was concentrated in vacuo and the residue taken up in toluene (80 mL) and treated with para-toluenesulfonic acid monohydrate (200 mg, 1.50 mmol). The mixture was heated to reflux for 2 hours, allowed to cool, and the product crystallised from the solution and was collected by filtration. The crude product was washed with ether and dried in vacuo to yield a white solid. The filtrate was concentrated in vacuo and the residue combined with the white solid, dissolved in toluene (50 mL) and treated with para-toluenesulfonic acid monohydrate (100 mg, 0.75 mmol). The mixture was heated to reflux for 3 hours, allowed to cool and concentrated in vacuo. The residue was purified by column chromatography on silica gel eluting with pentane:ethyl acetate 80:20 to 40:60 to yield the title product, 12.00 g. The solution was concentrated in vacuo The mixture was heated to reflux for 2 hours to cool the product crystallised from the solution was collected by filtration The crude product was washed with ether dried in vacuo to yield a white solid The filtrate was concentrated in vacuo dissolved in toluene (50 mL) The mixture was heated to reflux for 3 hours to cool concentrated in vacuo The residue was purified by column chromatography on silica gel eluting with pentane:ethyl acetate 80:20 to 40:60

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

実験手順: 2.0 g (13.9 mmol) of 4-bromobenzoylhydrazine was put into a 300 mL three-neck flask, 7 mL of N-methyl-2-pyrrolidone was added thereto, and the mixture was stirred at a room temperature. A mixed solution of 5.0 mL of N-methyl-2-pyrrolidone and 2.5 mL (21.5 mmol) of benzoyl chloride was dripped into the solution through a 50 mL dropping funnel. The mixture was stirred at 80° C. for 3 hours. After the reaction, a solid was precipitated out with the addition of the reactive mixture to approximately 200 mL of water. The precipitated solid was collected by suction filtration. The collected solid was washed with water, a saturated sodium hydrogen carbonate solution, and saturated saline, in the order given. The obtained solid was recrystallized with a mixed solvent of acetate and hexane, so that 3.6 g of a white solid, which was the object of the synthesis, was obtained at a yield of 80%. The mixture was stirred at 80° C. for 3 hours After the reaction a solid was precipitated out with the addition of the reactive mixture to approximately 200 mL of water The precipitated solid was collected by suction filtration The collected solid was washed with water The obtained solid was recrystallized with a mixed solvent of acetate and hexane, so that 3.6 g of a white solid, which the object of the synthesis was obtained at a yield of 80%

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

実験手順: A stirred suspension of 4-bromobenzoic hydrazide (4.0 g, 18.6 mmol) in triethyl orthoacetate (15 ml) was heated under reflux for 24 h. The reaction mixture was cooled and the precipitate filtered, washed with 60-80° C. petroleum ether (20 ml) and dried to give the title compound as a yellow solid (3.86 g, 87%). was heated under reflux for 24 h The reaction mixture was cooled the precipitate filtered washed with 60-80° C. petroleum ether (20 ml) dried

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

実験手順: A mixture of 4-bromobenzoic acid hydrazide (3.23 g) and triethylorthopropionate (25 ml) was heated at reflux for 7 hours. The mixture was evaporated to give a solid which was recrystallised from ethyl acetate to give 2-(4-bromphenyl)-5-ethyl-1,3,4-oxadiazole (3.65 g), as a solid, m.p. 101°-102° C.; microanalysis found: C, 47.3; H, 3.6; N, 10.9%; C10H9BrN2O requires: C, 47.5; H, 3.58; N, 11.1%; NMR(CDCl3): 1.44(3H,t), 2.96(2H,q), 7.65(2H,d) and 7.90(2h,D); m/z 253(M+H). was heated at reflux for 7 hours The mixture was evaporated to give a solid which was recrystallised from ethyl acetate

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Following the general method as outlined in Example 1, into a suspension of 5-iodo-1H-indole-2,3-dione in acetic acid was added 4-bromobenzohydrazide. After stirring at 100° C., the reaction mixture was cooled to rt and a yellow solid precipitated out. Filtration on a fritté, washing with AcOH, water and drying under vacuo at 60° C. overnight gave 193 mg of the title compound (82%) as a yellow solid in 99.6% purity by HPLC (Rt: 6.03, gradient of 10 min, MaxPlot detection between 230 and 400 nm). the reaction mixture was cooled to rt a yellow solid precipitated out Filtration on a fritté washing with AcOH, water drying under vacuo at 60° C. overnight