9H-thioxanthen-9-ol

Conditions: temp:2.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A suspension of 9H-Thioxanthen-9-ol [32] (2.14 g, 9.98 mmol) in anhydrous Et2O (20 mL) under N2 and SOCl2 (0.8 mL, 11.48 mmol) was added with caution via syringe with stirring at 0-5° C. The alcohol dissolved before a white solid began to separate. After stirring (1 hr.) at room temperature, the solvent was removed under reduced pressure and C6H6 (10 mL) was added and solvent removed to dryness again. All manipulations were performed with rigorous exclusion of air. Anhydrous C6H6 (20 mL) and CuCN powder (1.79 g, 19.97 mmol) were added and the suspension was stirred at reflux (4 hr.).The reaction mixture was filtered while hot and the residue was washed with hot C6H6 (50 mL). The filterate was evaporated to give a crystalline residue containing thioxanthene and thioxanthen-9-one as well as the desired nitrile. One recrystallizations from hexane removed thioxanthene and one recrystallizations from 2-propanol removed most of the thioxanthen-9one to provide 1.3 g (59%) of the pure nitrile, mp. 97-98° C. to separate After stirring (1 hr.) at room temperature the solvent was removed under reduced pressure and C6H6 (10 mL) was added solvent removed to dryness again the suspension was stirred at reflux (4 hr ).The reaction mixture was filtered while hot and the residue was washed with hot C6H6 (50 mL) The filterate was evaporated to give a crystalline residue One recrystallizations from hexane removed thioxanthene and one recrystallizations from 2-propanol removed most of the thioxanthen-9one

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

Procedure: A suspension of thioxanthen-9-one [31] (2 g, 9.42 mmol) in anhydrous CH3OH (30 mL) was stirred under N2 and NaBH4 (1.42 g, 37.68 mmol) was added slowly in portions over 15 min. After complete addition the reaction mixture was heated at reflux (3 hr.) and cooled to room temperature. Ice-water was added and the reaction mixture was extracted with CH2Cl2 (3×50 mL). The combined CH2Cl2 extracts were washed with water, brine, dried (MgSO4). The solvent was removed under reduced pressure to give a yellow solid, which was recrystallized from pet.ether to give 1.87 g (93%) of the alcohol as pale yellow needles, mp 104-105° C. After complete addition the reaction mixture was heated at reflux (3 hr.) the reaction mixture was extracted with CH2Cl2 (3×50 mL) The combined CH2Cl2 extracts were washed with water, brine dried (MgSO4) The solvent was removed under reduced pressure to give a yellow solid, which was recrystallized from pet

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Crude 9-hydroxythioxanthene (9.58 g, 45 mmol) is mixed with ethyl nitroacetate (5.5 mL, 49 mmol) and heated at 100° C. for 1 hour. TLC (SiO2, hexane:2-propanol/3:1) after 45 minutes shows no starting material. The cooled reaction mixture is treated with 100 mL of ethanol and 39 mL of 1.25 M ethanolic potassium hydroxide solution. Ethanol is stripped and the residue taken up in water and extracted with diethyl ether. The aqueous layer is acidified to pH 2 to 3 with 85% phosphoric acid solution and refrigerated overnight. A crystalline solid is collected by filtration and dried at 50° C./10 mm Hg. A total of 8.4 g of the title compound is collected in three crops; mp 111°-115° C. The cooled reaction mixture extracted with diethyl ether A crystalline solid is collected by filtration dried at 50° C./10 mm Hg A total of 8.4 g of the title compound is collected in three crops

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Crude 9-hydroxythioxanthene (9.58 g, 45 mmol) is mixed with ethyl nitroacetate (5.5 mL, 49 mmol) and heated at 100° C. for 1 hour. TLC (SiO2, hexane:2-propanol/3:1) after 45 minutes shows no starting material. The cooled reaction mixture is treated with 100 mL of ethanol and 39 mL of 1.25 M ethanolic potassium hydroxide solution. Ethanol is stripped and the residue taken up in water and extracted with diethyl ether. The aqueous layer is acidified to pH 2 to 3 with 85% phosphoric acid solution and refrigerated overnight. A crystalline solid is collected by filtration and dried at 50° C./10 mm Hg. A total of 8.4 g of the title compound is collected in three crops; mp 111°-115° C. The cooled reaction mixture extracted with diethyl ether A crystalline solid is collected by filtration dried at 50° C./10 mm Hg A total of 8.4 g of the title compound is collected in three crops

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

Procedure: Ethyl 2-(4-cyanobenzoyl)-2-(9H-thioxanthen-9-yl)acetate Ethyl-4-cyanobenzoyl acetate (6 g, 28 mmol) and 9-hydroxy thioxanthene (6.6 g, 31 mmol) were mixed in acetic acid (50 ml) and ethanol (50 ml) using the procedure described in Example 3 (ii) to give ethyl 2-(4-cyanobenzoyl)-2-(9H-thioxanthen-9-yl)acetate as a pale yellow solid.

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

Procedure: Ethyl 2-(4-cyanobenzoyl)-2-(9H-thioxanthen-9-yl)acetate Ethyl-4-cyanobenzoyl acetate (6 g, 28 mmol) and 9-hydroxy thioxanthene (6.6 g, 31 mmol) were mixed in acetic acid (50 ml) and ethanol (50 ml) using the procedure described in Example 3 (ii) to give ethyl 2-(4-cyanobenzoyl)-2-(9H-thioxanthen-9-yl)acetate as a pale yellow solid.

Conditions: temp:2.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A suspension of 9H-Thioxanthen-9-ol [32] (2.14 g, 9.98 mmol) in anhydrous Et2O (20 mL) under N2 and SOCl2 (0.8 mL, 11.48 mmol) was added with caution via syringe with stirring at 0-5° C. The alcohol dissolved before a white solid began to separate. After stirring (1 hr.) at room temperature, the solvent was removed under reduced pressure and C6H6 (10 mL) was added and solvent removed to dryness again. All manipulations were performed with rigorous exclusion of air. Anhydrous C6H6 (20 mL) and CuCN powder (1.79 g, 19.97 mmol) were added and the suspension was stirred at reflux (4 hr.).The reaction mixture was filtered while hot and the residue was washed with hot C6H6 (50 mL). The filterate was evaporated to give a crystalline residue containing thioxanthene and thioxanthen-9-one as well as the desired nitrile. One recrystallizations from hexane removed thioxanthene and one recrystallizations from 2-propanol removed most of the thioxanthen-9one to provide 1.3 g (59%) of the pure nitrile, mp. 97-98° C. to separate After stirring (1 hr.) at room temperature the solvent was removed under reduced pressure and C6H6 (10 mL) was added solvent removed to dryness again the suspension was stirred at reflux (4 hr ).The reaction mixture was filtered while hot and the residue was washed with hot C6H6 (50 mL) The filterate was evaporated to give a crystalline residue One recrystallizations from hexane removed thioxanthene and one recrystallizations from 2-propanol removed most of the thioxanthen-9one

Conditions: temp:2.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A suspension of 9H-Thioxanthen-9-ol [32] (2.14 g, 9.98 mmol) in anhydrous Et2O (20 mL) under N2 and SOCl2 (0.8 mL, 11.48 mmol) was added with caution via syringe with stirring at 0-5° C. The alcohol dissolved before a white solid began to separate. After stirring (1 hr.) at room temperature, the solvent was removed under reduced pressure and C6H6 (10 mL) was added and solvent removed to dryness again. All manipulations were performed with rigorous exclusion of air. Anhydrous C6H6 (20 mL) and CuCN powder (1.79 g, 19.97 mmol) were added and the suspension was stirred at reflux (4 hr.).The reaction mixture was filtered while hot and the residue was washed with hot C6H6 (50 mL). The filterate was evaporated to give a crystalline residue containing thioxanthene and thioxanthen-9-one as well as the desired nitrile. One recrystallizations from hexane removed thioxanthene and one recrystallizations from 2-propanol removed most of the thioxanthen-9one to provide 1.3 g (59%) of the pure nitrile, mp. 97-98° C. to separate After stirring (1 hr.) at room temperature the solvent was removed under reduced pressure and C6H6 (10 mL) was added solvent removed to dryness again the suspension was stirred at reflux (4 hr ).The reaction mixture was filtered while hot and the residue was washed with hot C6H6 (50 mL) The filterate was evaporated to give a crystalline residue One recrystallizations from hexane removed thioxanthene and one recrystallizations from 2-propanol removed most of the thioxanthen-9one

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

Procedure: A suspension of thioxanthen-9-one [31] (2 g, 9.42 mmol) in anhydrous CH3OH (30 mL) was stirred under N2 and NaBH4 (1.42 g, 37.68 mmol) was added slowly in portions over 15 min. After complete addition the reaction mixture was heated at reflux (3 hr.) and cooled to room temperature. Ice-water was added and the reaction mixture was extracted with CH2Cl2 (3×50 mL). The combined CH2Cl2 extracts were washed with water, brine, dried (MgSO4). The solvent was removed under reduced pressure to give a yellow solid, which was recrystallized from pet.ether to give 1.87 g (93%) of the alcohol as pale yellow needles, mp 104-105° C. After complete addition the reaction mixture was heated at reflux (3 hr.) the reaction mixture was extracted with CH2Cl2 (3×50 mL) The combined CH2Cl2 extracts were washed with water, brine dried (MgSO4) The solvent was removed under reduced pressure to give a yellow solid, which was recrystallized from pet

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Crude 9-hydroxythioxanthene (9.58 g, 45 mmol) is mixed with ethyl nitroacetate (5.5 mL, 49 mmol) and heated at 100° C. for 1 hour. TLC (SiO2, hexane:2-propanol/3:1) after 45 minutes shows no starting material. The cooled reaction mixture is treated with 100 mL of ethanol and 39 mL of 1.25 M ethanolic potassium hydroxide solution. Ethanol is stripped and the residue taken up in water and extracted with diethyl ether. The aqueous layer is acidified to pH 2 to 3 with 85% phosphoric acid solution and refrigerated overnight. A crystalline solid is collected by filtration and dried at 50° C./10 mm Hg. A total of 8.4 g of the title compound is collected in three crops; mp 111°-115° C. The cooled reaction mixture extracted with diethyl ether A crystalline solid is collected by filtration dried at 50° C./10 mm Hg A total of 8.4 g of the title compound is collected in three crops

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Crude 9-hydroxythioxanthene (9.58 g, 45 mmol) is mixed with ethyl nitroacetate (5.5 mL, 49 mmol) and heated at 100° C. for 1 hour. TLC (SiO2, hexane:2-propanol/3:l) after 45 minutes shows no starting material. The cooled reaction mixture is treated with 100 mL of ethanol and 39 mL of 1.25M ethanolic potassium hydroxide solution. Ethanol is stripped and the residue taken up in water and extracted with diethyl ether. The aqueous layer is acidified to pH 2 to 3 with 85% phosphoric acid solution and refrigerated overnight. A crystalline solid is collected by filtration and dried at 50° C./10 mm Hg. A total of 8.4 g of the title compound is collected in three crops; mp 111°-115° C. The cooled reaction mixture extracted with diethyl ether A crystalline solid is collected by filtration dried at 50° C./10 mm Hg A total of 8.4 g of the title compound is collected in three crops

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Crude 9-hydroxythioxanthene (9.58 g, 45 mmol) is mixed with ethyl nitroacetate (5.5 mL, 49 mmol) and heated at 100° C. for 1 hour. TLC (SiO2, hexane:2-propanol/3:1) after 45 minutes shows no starting material. The cooled reaction mixture is treated with 100 mL of ethanol and 39 mL of 1.25M ethanolic potassium hydroxide solution. Ethanol is stripped and the residue taken up in water and extracted with diethyl ether. The aqueous layer is acidified to pH 2 to 3 with 85% phosphoric acid solution and refrigerated overnight. A crystalline solid is collected by filtration and dried at 50° C./10 mm Hg. A total of 8.4 g of the title compound is collected in three crops; mp 111°-115° C. The cooled reaction mixture extracted with diethyl ether A crystalline solid is collected by filtration dried at 50° C./10 mm Hg A total of 8.4 g of the title compound is collected in three crops