5,11-dihydrobenzo[b][1,4]benzodiazepin-6-one

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:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of 4.3 g of 5,11-dihydro-10H-dibenz[b,e][1,4]diazepin-11-one in 50 ml of tetrahydrofuran, under nitrogen and cooled to 0° C. is added 4.0 ml of 10N methyl sulfide-borane complex. The ice bath is removed after 30 minutes and the reaction mixture stirred at room temperature for 18 hours. The reaction mixture is cooled in an ice bath and 30 ml of anhydrous methanol added dropwise and evaporated to dryness in vacuo. Another 30 ml of methanol is added and evaporated to a residue. The residue is quenched with 30 ml of 40% sodium hydroxide followed by heating at 110° C. for 45 minutes and cooling to room temperature. The reaction mixture is diluted with 200 ml of water and extracted with methylene chloride (3×100 ml). The combined extracts are washed with 1N HCl, water and 0.5N NaOH. The organic layer is dried and evaporated in vacuo to give 3.2 g of the desired product, m.p. 114°-116° C. is added 4.0 ml of 10N methyl sulfide-borane complex The ice bath is removed after 30 minutes The reaction mixture is cooled in an ice bath 30 ml of anhydrous methanol added dropwise evaporated to dryness in vacuo Another 30 ml of methanol is added evaporated to a residue The residue is quenched with 30 ml of 40% sodium hydroxide by heating at 110° C. for 45 minutes cooling to room temperature The reaction mixture is diluted with 200 ml of water extracted with methylene chloride (3×100 ml) The combined extracts are washed with 1N HCl, water and 0.5N NaOH The organic layer is dried evaporated in vacuo

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

実験手順: To a stirred solution of 4.3 g of 5,11-dihydro-10H-dibenz[b,e][1,4]diazepin-11-one in 50 ml of tetrahydrofuran, under nitrogen and cooled to 0° C. is added 4.0 ml of 10N methyl sulfide-borane complex. The ice bath is removed after 30 minutes and the reaction mixture stirred at room temperature for 18 hours. The reaction mixture is cooled in an ice bath and 30 ml of anhydrous methanol added dropwise and evaporated to dryness in vacuo. Another 30 ml of methanol is added and evaporated to a residue. The residue is quenched with 30 ml of 40% sodium hydroxide followed by heating at 110° C. for 45 minutes and cooling to room temperature. The reaction mixture is diluted with 200 ml of water and extracted with methylene chloride (3×100 ml). The combined extracts are washed with 1N HCl, water and 0.5N NaOH. The organic layer is dried and evaporated in vacuo to give 3.2 g of the desired product, m.p. 114°-116° C. is added 4.0 ml of 10N methyl sulfide-borane complex The ice bath is removed after 30 minutes The reaction mixture is cooled in an ice bath 30 ml of anhydrous methanol added dropwise evaporated to dryness in vacuo Another 30 ml of methanol is added evaporated to a residue The residue is quenched with 30 ml of 40% sodium hydroxide by heating at 110° C. for 45 minutes cooling to room temperature The reaction mixture is diluted with 200 ml of water extracted with methylene chloride (3×100 ml) The combined extracts are washed with 1N HCl, water and 0.5N NaOH The organic layer is dried evaporated in vacuo

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

実験手順: 6.3 gm (0.03 mol) of 5,10-dihydro-11H-dibenzo[b,e][1,4]diazepin-11-one and 3.3 gm (0.036 mol) of acrylic acid chloride were refluxed, while stirring, in 200 ml of toluene for 3 hours. The reaction mixture was then evaporated in vacuo. The dry residue was admixed with 200 ml of ethanol, and 2.5 gm (0.035 mol) of pyrrolidine were added dropwise, while stirring, to the boiling solution. Subsequently, the reaction mixture was heated for 20 minutes, then evaporated in vacuo to about 1/10 of its original volume, and discolored by filtration through activated charcoal/silica gel. The crude product was recrystallized from a little ethyl acetate. The reaction mixture was then evaporated in vacuo were added dropwise Subsequently, the reaction mixture was heated for 20 minutes evaporated in vacuo to about 1/10 of its original volume discolored by filtration through activated charcoal/silica gel The crude product was recrystallized from a little ethyl acetate

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

実験手順: 5.26 gm (0.025 mol) of 5,10-dihydro-11H-dibenzo[b,e][1,4]diazepin-11-one and 2.7 gm (0.03 mol) of acrylic acid chloride were refluxed in 200 ml of toluene for 3 hours. Subsequently, the reaction mixture was evaporated in vacuo to dryness, and the residue was stirred with aqueous sodium bicarbonate solution. After suction-filtering, washing with water, and drying, 5-acryloyl-5,10-dihydro-11H-dibenzo[b,e][1,4]diazepin-11-one was obtained with a quantitative yield. Recrystallization from ethanol. Subsequently, the reaction mixture was evaporated in vacuo to dryness After suction-filtering washing with water drying

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

実験手順: A quantity of 4.9 gm (0.0425 mol) of 1-methyl-4-piperidinol was added dropwise to a mixture of 22.5 ml of a 20% solution of phosgene in toluene, 100 ml of dioxane, and 4.75 gm (0.045 mol) of anhydrous sodium carbonate while external cooling with ice was carried out. The mixture was stirred for a further 60 minutes at ambient temperature, 9.0 gm (0.0428 mol) of 5,10-dihydro-11H-dibenzo[b,e][1,4]diazepin-11-one were added to the reaction mixture, and this was then refluxed for four hours. The mixture was filtered, the filtrate was concentrated by evaporation in vacuo, and the crude product obtained was purified by column chromatography on 500 gm of silica gel [eluant: ethyl acetate/methanol (volume ratio of 10:1)]. After recrystallization from ethyl acetate, the resulting colorless crystals melted at 203°-204° C. and were identical--according to the mixed melting point, thin layer chromatogram, and IR spectrum--to a product prepared according to Example 4. Yield: 7.6 gm (51% of theory). while external cooling with ice this was then refluxed for four hours The mixture was filtered the filtrate was concentrated by evaporation in vacuo

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

実験手順: The 5-(4-bromobutyryl)-5,10-dihydro-11H-dibenzo(b,e)(1,4)-diazepine-11-one, starting material, was synthesized similarly to the starting material described in Example 1, from 5,10-dihydro-11H-dibenzo(b,e)(1,4)-diazepine-11-one and 4-bromobutyryl chloride. The yield is 74.3% of the theoretical yield and the melting point is 159°-161° C. (toluene). was synthesized similarly to the starting material The yield is 74.3% of the theoretical yield

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

実験手順: The 5-(4-bromobutyryl)-5,10-dihydro-11H-dibenzo(b,e)(1,4)-diazepine-11-one, starting material, was synthesized similarly to the starting material described in Example 1, from 5,10-dihydro-11H-dibenzo(b,e)(1,4)-diazepine-11-one and 4-bromobutyryl chloride. The yield is 74.3% of the theoretical yield and the melting point is 159°-161° C. (toluene). was synthesized similarly to the starting material The yield is 74.3% of the theoretical yield