1,2,3,9-tetrahydrocarbazol-4-one

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of 1,2,3,9-tetrahydro-4H-carbazol-4-one (6.02 g, 32.5 mmol) in 1:1 ethylene glycol: p-dioxane (100 mL) at 80° C. is added copper (II) chloride (21 g, 156.2 mmol). The mixture is heated for 20 minutes. The mixture is then partitioned between water and ethyl acetate. The layers are separated and the organic layer is washed three times with water (200 mL). The organic layer is dried over anhydrous sodium sulfate, filtered, and concentrated. The residue is dissolved in DMF (100 mL) to which is added lithium bromide (7.04 g, 81.25 mmol) and lithium carbonate (6.0 g, 81.25 mmol). The mixture is heated at 120° C. for 4.5 hours. The mixture is then partitioned between water and ether. The ether layer is washed three times with water (200 mL). The ether layer is dried over anhydrous sodium sulfate, filtered and concentrated. Column chromatography, silica gel (800 mL), using CH2Cl2 as eluent gave 1.1 g (18%) of the title compound; 1H NMR (CDCl3) δ5.26, 6.57, 7.01, 7.26, 7.41, 8.05, 8.26; Anal. Calcd for C12H9NO: C, 78.67; H, 4.95; N, 7.64. Found: C, 78.04; H, 4.94; N, 7.58. The mixture is heated for 20 minutes The mixture is then partitioned between water and ethyl acetate The layers are separated the organic layer is washed three times with water (200 mL) The organic layer is dried over anhydrous sodium sulfate filtered concentrated The residue is dissolved in DMF (100 mL) to which The mixture is then partitioned between water and ether The ether layer is washed three times with water (200 mL) The ether layer is dried over anhydrous sodium sulfate filtered concentrated

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

Procedure: To a solution of 1,3-cyclohexane dione (1.99 g, 17.7 mmol) in water (55 mL) is added phenylhydrazine (1.92 g, 17.7 mmol) in 10 mL of water. A gummy solid quickly formed, which after completion of the addition is scrapped with a spatula to give a solid. The solid is collected, washed with water, and dried in a vacuum oven to give 3.0 g of a tan solid. After drying, the tan solid is stirred at reflux in TFA (25 mL) overnight. Upon cooling, TFA is removed in vacuo and water is added to the residue. The resulting solid is collected, washed with water, and dried to give 1.82 g (55%) of the title compound; mp 218-220° C.; IR (drift) 3150, 3130, 3104, 3093, 3056, 2976, 2954, 2944, 1607, 1577, 1466, 1413, 1251, 1178, 755 cm−1; 1H NMR (CDCl3) δ2.26, 2.64, 3.00, 7.26, 7.35, 8.21, 8.74. Anal. Calcd for C12H11NO: C, 77.81; H, 5.99; N, 7.56. Found: C, 77.82; H, 6.15; N, 7.54. A gummy solid quickly formed which after completion of the addition to give a solid The solid is collected washed with water dried in a vacuum oven

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

Procedure: To a reactor containing water (1 L) was added Raney nickel (35 g) followed by 1,2,3,9-tetrahydrocarbazole-4-one (50 g) and sodium hydroxide (15 g). The contents were heated to reflux and maintained for about 20 hours. The catalyst was filtered off and the filtrate was acidified to obtain a solid, which was filtered and dried to obtain the title compound. When necessary, the title compound was further purified by dissolving in 10% sodium hydroxide solution, treating with activated charcoal and precipitation from dilute hydrochloric acid to give off-white to grey crystals of 4-hydroxy carbazole in 50% yield. The contents were heated to reflux maintained for about 20 hours The catalyst was filtered off to obtain a solid, which was filtered dried

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 0.25 mol/L 1,3-cyclohexanedione/50% sulfuric acid solution was placed in a 200-mL container purged with nitrogen. Then, a 0.25 mol/L phenylhydrazine/50% sulfuric acid solution was added dropwise into the container under stirring at 20000 rpm by CLEARMIX (manufactured by M Technique Co., Ltd.) while the temperature of the liquid in the container was maintained at 25° C. As a result of HPLC analysis, the production rate of 1,2,3,4-tetrahydrocarbazol-4-one was 24% or less. purged with nitrogen Then, a 0.25 mol/L phenylhydrazine/50% sulfuric acid solution was added dropwise into the container As a result of HPLC analysis

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

Procedure: A 0.25 mol/L 1,3-cyclohexanedione/50% sulfuric acid solution was sent as a first fluid from the center at a ratio of supply pressure/back pressure of 0.07 MPa/0.02 MPa, a rotation speed of 500 rpm, and a sending temperature of 25° C., and a 0.25 mol/L phenylhydrazine/50% sulfuric acid solution was introduced as a second fluid into a space between the processing surfaces at 18 mL/min. The first fluid and the second fluid were mixed in a thin film fluid, and then a solution obtained after processing was discharged from the space between the processing surfaces at 29 mL/min. As a result of HPLC analysis, the production rate of 1,2,3,4-tetrahydrocarbazol-4-one was 80% or higher. The first fluid and the second fluid were mixed in a thin film fluid a solution obtained after processing As a result of HPLC analysis

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

Procedure: In a 500 ml two-neck flask, 1,2,3,4-tetrahydro-9H-carbazole-4-one (Compound E, 20 g), t-butyl bromobenzene (60 g), potassium carbonate (43 g), Cu powder (2.1 g), and NMP (70 ml) were mixed and stirred. The reaction mixture was refluxed and stirred for 24 to 30 hours in a state in which the temperature was raised. When the reaction was completed, the reactant was cooled at room temperature, and then the reactant was mixed with ethylacetate (500 ml) and brine (500 ml) and strongly stirred. Floating materials was filtered and removed using celite, and the organic layer was separated. The water layer was extracted using ethylacetate, and the organic layer was collected and dried over magnesium sulfate. The organic layer was concentrated, and the residual was purified using a column chromatography, thereby obtaining 13 g of N-(t-butylphenyl) carbazolone (Compound F). The reaction mixture was refluxed stirred for 24 to 30 hours in a state in which the temperature was raised strongly stirred Floating materials was filtered removed the organic layer was separated The water layer was extracted the organic layer was collected dried over magnesium sulfate The organic layer was concentrated the residual was purified

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of 1,2,3,9-tetrahydro-4H-carbazol-4-one (6.02 g, 32.5 mmol) in 1:1 ethylene glycol: p-dioxane (100 mL) at 80° C. is added copper (II) chloride (21 g, 156.2 mmol). The mixture is heated for 20 minutes. The mixture is then partitioned between water and ethyl acetate. The layers are separated and the organic layer is washed three times with water (200 mL). The organic layer is dried over anhydrous sodium sulfate, filtered, and concentrated. The residue is dissolved in DMF (100 mL) to which is added lithium bromide (7.04 g, 81.25 mmol) and lithium carbonate (6.0 g, 81.25 mmol). The mixture is heated at 120° C. for 4.5 hours. The mixture is then partitioned between water and ether. The ether layer is washed three times with water (200 mL). The ether layer is dried over anhydrous sodium sulfate, filtered and concentrated. Column chromatography, silica gel (800 mL), using CH2Cl2 as eluent gave 1.1 g (18%) of the title compound; 1H NMR (CDCl3) δ5.26, 6.57, 7.01, 7.26, 7.41, 8.05, 8.26; Anal. Calcd for C12H9NO: C, 78.67; H, 4.95; N, 7.64. Found: C, 78.04; H, 4.94; N, 7.58. The mixture is heated for 20 minutes The mixture is then partitioned between water and ethyl acetate The layers are separated the organic layer is washed three times with water (200 mL) The organic layer is dried over anhydrous sodium sulfate filtered concentrated The residue is dissolved in DMF (100 mL) to which The mixture is then partitioned between water and ether The ether layer is washed three times with water (200 mL) The ether layer is dried over anhydrous sodium sulfate filtered concentrated