4-chloro-2-ethylaniline

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: 2-Ethyl-4-chloroaniline (0.3 mole), 5-chloromethyl-1,3-dioxolane (0.3 mole), potassium carbonate (0.3 mole) and tetraethylammonium chloride (2 grams) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture is heated at reflux for a period of 6 hours. After this time the mixture is filtered and distilled to yield the desired product N-(1,3-dioxolan-5-ylmethyl)-2-ethyl-4-chloroaniline. equipped with a mechanical stirrer thermometer and reflux condenser The reaction mixture is heated at reflux for a period of 6 hours After this time the mixture is filtered distilled

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

Procedure: 2-Ethyl-4-chloroaniline (0.3 mole), 5-chloromethyl-1,3-dioxolane (0.3 mole), potassium carbonate (0.3 mole) and tetraethylammonium chloride (2 grams) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture is heated at reflux for a period of 6 hours. After this time the mixture is filtered and distilled to yield the desired product N-(1,3-dioxolan-5-ylmethyl)-2-ethyl-4-chloroaniline. equipped with a mechanical stirrer thermometer and reflux condenser The reaction mixture is heated at reflux for a period of 6 hours After this time the mixture is filtered distilled

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

Procedure: To a stirred solution of 1.54 grams (0.01 mole) of 1-carboethoxycyclopropanecarboxylic acid (the monocarboxylic acid intermediate described in Example XVIII) and 0.99 gram (0.01 mole) of triethylamine in 75 milliliters of acetonitrile was added a solution of 1.06 grams (0.01 mole) of ethyl chloroformate in 25 milliliters of acetonitrile dropwise with cooling to 0° C.-5° C. After stirring at ice temperature for 30 minutes a solution of 1.52 grams (0.01 mole) of 4-chloro-2-ethylaniline in 20 milliliters of acetonitrile was fed dropwise with stirring and continued cooling. The reaction mixture was allowed to warm to room temperature, then stirred for approximately sixteen hours following which it was filtered and the filtrate freed of solvent by evaporation. The residue was dissolved in dichloromethane and extracted, successively, with water (2×50 milliliters), 2N HCl (2×50 milliliters) and water (1×50 milliliters). After drying (MgSO4), solvent was removed by evaporation and the solid recrystallized from hexane to give 1.15 grams (0.004 mole) of ethyl 1-(4-chloro-2-ethylphenylaminocarbonyl)cyclopropanecarboxylate as cream colored prisms having a melting point of 77° C.-80° C. with cooling to 0° C.-5° C continued cooling stirred for approximately sixteen hours was filtered the filtrate freed of solvent by evaporation The residue was dissolved in dichloromethane extracted After drying (MgSO4), solvent was removed by evaporation the solid recrystallized from hexane

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

Procedure: 2-Ethyl-4-chloroaniline (0.3 mole), 5-chloromethyl-1,3-dioxolane (0.3 mole), potassium carbonate (0.3 mole) and tetraethylammonium chloride (2 grams) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture is heated at reflux for a period of 6 hours. After this time the mixture is filtered and distilled to yield the desired product N-(1,3-dioxolan-5-ylmethyl)-2-ethyl-4-chloroaniline. equipped with a mechanical stirrer thermometer and reflux condenser The reaction mixture is heated at reflux for a period of 6 hours After this time the mixture is filtered distilled

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

Procedure: To a stirred solution of 1.54 grams (0.01 mole) of 1-carboethoxycyclopropanecarboxylic acid (the monocarboxylic acid intermediate described in Example XVIII) and 0.99 gram (0.01 mole) of triethylamine in 75 milliliters of acetonitrile was added a solution of 1.06 grams (0.01 mole) of ethyl chloroformate in 25 milliliters of acetonitrile dropwise with cooling to 0° C.-5° C. After stirring at ice temperature for 30 minutes a solution of 1.52 grams (0.01 mole) of 4-chloro-2-ethylaniline in 20 milliliters of acetonitrile was fed dropwise with stirring and continued cooling. The reaction mixture was allowed to warm to room temperature, then stirred for approximately sixteen hours following which it was filtered and the filtrate freed of solvent by evaporation. The residue was dissolved in dichloromethane and extracted, successively, with water (2×50 milliliters), 2N HCl (2×50 milliliters) and water (1×50 milliliters). After drying (MgSO4), solvent was removed by evaporation and the solid recrystallized from hexane to give 1.15 grams (0.004 mole) of ethyl 1-(4-chloro-2-ethylphenylaminocarbonyl)cyclopropanecarboxylate as cream colored prisms having a melting point of 77° C.-80° C. Elemental analysis of the product indicated the following: with cooling to 0° C.-5° C continued cooling stirred for approximately sixteen hours was filtered the filtrate freed of solvent by evaporation The residue was dissolved in dichloromethane extracted After drying (MgSO4), solvent was removed by evaporation the solid recrystallized from hexane

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

Procedure: To a stirred solution of 1.54 grams (0.01 mole) of 1-carboethoxycyclopropanecarboxylic acid (the monocarboxylic acid intermediate described in Example XVIII) and 0.99 gram (0.01 mole) of triethylamine in 75 milliliters of acetonitrile was added a solution of 1.06 grams (0.01 mole) of ethyl chloroformate in 25 milliliters of acetonitrile dropwise with cooling to 0° C.-5° C. After stirring at ice temperature for 30 minutes a solution of 1.52 grams (0.01 mole) of 4-chloro-2-ethylaniline in 20 milliliters of acetonitrile was fed dropwise with stirring and continued cooling. The reaction mixture was allowed to warm to room temperature, then stirred for approximately sixteen hours following which it was filtered and the filtrate freed of solvent by evaporation. The residue was dissolved in dichloromethane and extracted, successively, with water (2×50 milliliters), 2N HCl (2×50 milliliters) and water (1×50 milliliters). After drying (MgSO4), solvent was removed by evaporation and the solid recrystallized from hexane to give 1.15 grams (0.004 mole) of ethyl 1-(4-chloro-2-ethylphenylaminocarbonyl)cyclopropanecarboxylate as cream colored prisms having a melting point of 77° C.-80° C. Elemental analysis of the product indicated the following: with cooling to 0° C.-5° C continued cooling stirred for approximately sixteen hours was filtered the filtrate freed of solvent by evaporation The residue was dissolved in dichloromethane extracted After drying (MgSO4), solvent was removed by evaporation the solid recrystallized from hexane

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

Procedure: 2-Ethyl-4-chloroaniline (0.3 mole), 5-chloromethyl-1,3-dioxolane (0.3 mole), potassium carbonate (0.3 mole) and tetraethylammonium chloride (2 grams) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture is heated at reflux for a period of 6 hours. After this time the mixture is filtered and distilled to yield the desired product N-(1,3-dioxolan-5-ylmethyl)-2-ethyl-4-chloroaniline. equipped with a mechanical stirrer thermometer and reflux condenser The reaction mixture is heated at reflux for a period of 6 hours After this time the mixture is filtered distilled

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

Procedure: 2'-Ethyl-4'-chloroacetanilide (31 grams) was heated to reflux in a mixture containing 80 milliliters of ethanol and 55 milliliters of concentrated HCL for about 2.5 hours. After cooling to room temperature, the mixture was basified to a pH of about 8 by an aqueous NaOH solution (20 percent). An oily aniline layer was observed. The mixture was transferred to a separatory funnel and was extracted with ether (3 times 75 milliliters). The ethereal extracts were combined and dried over MgSO4. After filtration, ether was removed under reduced pressure. 2-Ethyl-4-chloroaniline was purified and isolated by a reduced pressure distillation, yield 14.2 grams (58 percent). to reflux in a mixture The mixture was transferred to a separatory funnel was extracted with ether (3 times 75 milliliters) dried over MgSO4 After filtration, ether was removed under reduced pressure 2-Ethyl-4-chloroaniline was purified isolated by a reduced pressure distillation, yield 14.2 grams (58 percent)

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

Procedure: The reaction of an alkylamine, such as o-ethylaniline, with an acetic acid anhydride to form an acetanilide, such as 2'-ethylacetanilide. The resulting acetanilide can then be reacted with a hydrogen halide, such as hydrogen chloride, in the presence of hydrogen peroxide to form a halogenated product in the para position of the acetyl group, such as 2'-ethyl-4'-chloroacetanilide. The halogenated acetanilide can be hydrolyzed in an aqueous alcoholic solution of hydrochloric acid to form a halogenated o-ethylaniline, such as 2-ethyl-4-chloroaniline. This halogenated o-ethylaniline is then reaction with a phenyl 2-hydroxy-11H-benzo(a)carbazole-3-carboxylate derivatives, such as phenyl 2-hydroxy-8-fluoro-11H-benzo(a)carbazole-3-carboxylate, phenyl 2-hydroxy-8-chloro-11H-benzo(a)carbazole-3-carboxylate, or phenyl 2-hydroxy-11H-benzo(a)carbazole-3-carboxylate to form the corresponding carbazole anilide coupler such as 2-hydroxy-8-fluoro-11H-benzo(a)carbazole- 3-carbox-2'-ethyl-4'-chloroanilide, 2-hydroxy-8-chloro-11H-benzo(a)carbazole-3-carbox-2'-ethyl-4'-chloroanilide, 2-hydroxy-11H-benzo(a)carbazole-3-carbox-2'-ethyl-4'-chloroanilide, etc. These new carbazole anilide couplers can then be used to synthesize the trisazo pigments of the present invention.

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

Procedure: 2'-Ethyl-4'-chloroacetanilide (31 grams) was heated to reflux in a mixture containing 80 milliliters of ethanol and 55 milliliters of concentrated HCL for about 2.5 hours. After cooling to room temperature, the mixture was basified to a pH of about 8 by an aqueous NaOH solution (20 percent). An oily aniline layer was observed. The mixture was transferred to a separatory funnel and was extracted with ether (3 times 75 milliliters). The ethereal extracts were combined and dried over MgSO4. After filtration, ether was removed under reduced pressure. 2-Ethyl-4-chloroaniline was purified and isolated by a reduced pressure distillation, yield 14.2 grams (58 percent). to reflux in a mixture The mixture was transferred to a separatory funnel was extracted with ether (3 times 75 milliliters) dried over MgSO4 After filtration, ether was removed under reduced pressure 2-Ethyl-4-chloroaniline was purified isolated by a reduced pressure distillation, yield 14.2 grams (58 percent)

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

Procedure: The reaction of an alkylamine, such as o-ethylaniline, with an acetic acid anhydride to form an acetanilide, such as 2'-ethylacetanilide. The resulting acetanilide can then be reacted with a hydrogen halide, such as hydrogen chloride, in the presence of hydrogen peroxide to form a halogenated product in the para position of the acetyl group, such as 2'-ethyl-4'-chloroacetanilide. The halogenated acetanilide can be hydrolyzed in an aqueous alcoholic solution of hydrochloric acid to form a halogenated o-ethylaniline, such as 2-ethyl-4-chloroaniline. This halogenated o-ethylaniline is then reaction with a phenyl 2-hydroxy-11H-benzo(a)carbazole-3-carboxylate derivatives, such as phenyl 2-hydroxy-8-fluoro-11H-benzo(a)carbazole-3-carboxylate, phenyl 2-hydroxy-8-chloro-11H-benzo(a)carbazole-3-carboxylate, or phenyl 2-hydroxy-11H-benzo(a)carbazole-3-carboxylate to form the corresponding carbazole anilide coupler such as 2-hydroxy-8-fluoro-11H-benzo(a)carbazole- 3-carbox-2'-ethyl-4'-chloroanilide, 2-hydroxy-8-chloro-11H-benzo(a)carbazole-3-carbox-2'-ethyl-4'-chloroanilide, 2-hydroxy-11H-benzo(a)carbazole-3-carbox-2'-ethyl-4'-chloroanilide, etc. These new carbazole anilide couplers can then be used to synthesize the trisazo pigments of the present invention.