4-(dimethylamino)cyclohexan-1-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:; See reaction.notes.procedure_details.

実験手順: A solution of 7.8 g. of 4-dimethylaminocyclohexanone and 11 g. of 1,1-bis(4-fluorophenyl)hydrazine in 350 ml. of absolute ethyl alcohol and 90 ml. of 5-N hydrogen chloride in absolute ethyl alcohol was heated under reflux for five hours, cooled, and filtered. The solids were suspended in ether and treated with dilute sodium hydroxide solution and the ether extract was separated, dried and evaporated to dryness. The resulting oil was dissolved in ethyl alcohol, treated with hydrogen chloride in ethyl alcohol and the solution was concentrated and cooled. The resulting solids were collected by filtration to give, after recrystallization from ethyl alcohol, 5.6 g. of 3-(dimethylamino)-6-fluoro-9-(4-fluorophenyl)-1,2,3,4-tetrahydrocarbazole hydrochloride, m.p. 283°-285° C. under reflux for five hours cooled filtered treated with dilute sodium hydroxide solution the ether extract was separated dried evaporated to dryness The resulting oil was dissolved in ethyl alcohol treated with hydrogen chloride in ethyl alcohol the solution was concentrated cooled The resulting solids were collected by filtration to give after recrystallization from ethyl alcohol, 5.6 g

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

実験手順: To a solution of 14.1 g. of 4-dimethylaminocyclohexanone in 100 ml. of a 6-N solution of hydrogen chloride in absolute ethyl alcohol was added 23.5 g. of 4-phenoxyphenylhydrazine hydrochloride and the mixture was heated at reflux for six hours. The mixture was filtered, the filtrate was made alkaline with 10% potassium hydroxide and extracted with chloroform, and the chloroform extract was washed with water and evaporated to dryness under reduced pressure to give 3-(dimethylamino)-6-phenoxy-1,2,3,4-tetrahydrocarbazole. at reflux for six hours The mixture was filtered extracted with chloroform the chloroform extract was washed with water evaporated to dryness under reduced pressure

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

実験手順: A solution of 15.5 g. of 4-dimethylaminocyclohexanone and 15.2 g. of 4-carboxyphenylhydrazine in 200 ml. of 5-N hydrogen chloride in ethyl alcohol was refluxed for twentyfour hours and the reaction mixture was evaporated to dryness under reduced pressure. The residue was dissolved in water, the aqueous solution was made alkaline with dilute sodium hydroxide and extracted with methylene dichloride and the extract was evaporated to dryness under reduced pressure to give, after recrystallization from isopropyl alcohol, 17.8 g. of 3-(dimethylamino)-6-ethoxycarbonyl-1,2,3,4-tetrahydrocarbazole, m.p. 188°-190° C. the reaction mixture was evaporated to dryness under reduced pressure The residue was dissolved in water extracted with methylene dichloride the extract was evaporated to dryness under reduced pressure to give after recrystallization from isopropyl alcohol, 17.8 g

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

実験手順: A solution of 14.1 g. of 4-dimethylaminocyclohexanone and 18.9 g. of 2-carboxyphenylhydrazine hydrochloride in 150 ml. of absolute ethyl alcohol was heated under reflux for six hours, cooled, and the resulting crystalline 4-dimethylaminocyclohexanone 2-carboxyphenylhydrazone hydrochloride was collected by filtration, washed with isopropyl alcohol and ether, suspended in 200 ml. of 2% hydrogen chloride in acetic acid and heated at reflux for eight hours. The mixture was cooled and the solids were collected by filtration, washed with isopropyl alcohol and dissolved in 400 ml. of water. The aqueous solution was treated with alkali until neutral and allowed to stand for two hours. The resulting crystals were filtered to give, on recrystallization from water, 30.3 g. of 3-(dimethylamino)-8-carboxy-1,2,3,4-tetrahydrocarbazole hydrate, m.p. >300° C. (dec.) under reflux for six hours cooled the resulting crystalline 4-dimethylaminocyclohexanone 2-carboxyphenylhydrazone hydrochloride was collected by filtration washed with isopropyl alcohol and ether of 2% hydrogen chloride in acetic acid and heated at reflux for eight hours The mixture was cooled the solids were collected by filtration washed with isopropyl alcohol dissolved in 400 ml The aqueous solution was treated with alkali until neutral and The resulting crystals were filtered to give, on recrystallization from water, 30.3 g

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

実験手順: To a solution of 3.78 gm (26.8 mMol) 4-dimethylamino-1-cyclohexanone and 6.69 gm (26.8 mMol) 4-benzyloxyphenylhydrazine hydrochloride in 50 mL ethanol were added 2.17 mL (26.8 mMol) pyridine. To this solution were added 5×10 mL portions of water and the reaction mixture then stored at 0° C. for 18 hours. The reaction mixture was then diluted with an additional 50 mL of water and the mixture extracted well with dichloromethane. The combined organic extracts were dried over sodium sulfate and the volatiles removed under reduced pressure. The residual oil was subjected to flash silica gel chromatography, eluting with 9:1 chloroform:methanol. Fractions shown to contain the desired product were combined and concentrated under reduced pressure to give 2.14 gm (24.9%) of the title compound. the mixture extracted well with dichloromethane The combined organic extracts were dried over sodium sulfate the volatiles removed under reduced pressure eluting with 9:1 chloroform concentrated under reduced pressure

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

実験手順: 4.96 gm (26.8 mMol) 4-dimethylamino-1-cyclohexanone ethylene ketal were dissolved in 50 mL formic acid and the solution stirred at reflux for 18 hours. The reaction mixture was then cooled to ambient and the volatiles removed under reduced pressure to give 3.78 gm (100%) of the title compound. at reflux for 18 hours The reaction mixture was then cooled to ambient and the volatiles removed under reduced pressure

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

実験手順: To a mixture of 6.0 gm (42.0 mMol) 4-dimethylaminocyclohexanone and 9.5 gm (42.0 mMol) 4-bromophenyl-hydrazine hydrochloride in 100 mL ethanol were added 3.4 mL (42 mMol) pyridine. The resultant mixture was then heated at reflux for 2 hours and then stirred at ambient temperature for 18 hours. The reaction mixture was then treated with aqueous potassium carbonate and extracted well with dichloromethane. The organic phases were combined, dried over sodium sulfate and concentrated under reduced pressure. The resultant residue was treated with toluene and concentrated again under reduced pressure to give 11.3 gm (87%) of the desired compound. at reflux for 2 hours extracted well with dichloromethane dried over sodium sulfate concentrated under reduced pressure The resultant residue was treated with toluene concentrated again under reduced pressure

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