2,6-Dichloro-1,4-phenylenediamine

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

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,6-Dichloro-1,4-benzenediamine (225 g., 1.27 mol) is suspended in methylene chloride (1.3 liters) containing triethylamine (245 mL, 1.7 mol). After the mixture is cooled to 5° C., trichloroacetylchloride (169 mL, 1.5 mol, Aldrich Chemical Co.) is added dropwise with stirring at a rate to maintain 5° C. Upon complete addition, the stirred reaction is allowed to reach room temperature. After 24 hours the mixture is filtered and the collected solid is washed with methylene chloride (700 mL). The filtrate is evaporated to a small volume. A solid is collected and washed with methylene chloride (250 mL) to yield 465 grams of N-(4-amino-3,5-dichlorophenyl)-trichloroacetamide. The product exhibits a mass spectral analysis of m/e+· 320 for C8H5Cl5N2O. to maintain 5° C Upon complete addition the stirred reaction to reach room temperature After 24 hours the mixture is filtered the collected solid is washed with methylene chloride (700 mL) The filtrate is evaporated to a small volume A solid is collected washed with methylene chloride (250 mL)

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,6-Dichloro-1,4-benzenediamine (225 g., 1.27 mol) is suspended in methylene chloride (1.3 liters) containing triethylamine (245 mL, 1.7 mol). After the mixture is cooled to 5° C., trichloroacetylchloride (169 mL, 1.5 mol, Aldrich Chemical Co.) is added dropwise with stirring at a rate to maintain 5° C. Upon complete addition, the stirred reaction is allowed to reach room temperature. After 24 hours the mixture is filtered and the collected solid is washed with methylene chloride (700 mL). The filtrate is evaporated to a small volume. A solid is collected and washed with methylene chloride (250 mL) to yield 465 grams of N-(4-amino-3,5-dichlorophenyl)-trichloroacetamide. The product exhibits a mass spectral analysis of m/e+. 320 for C8H5Cl5N2O. 3. N-(3,5-Dichloro-4-formamidophenyl)-trichloroacetamide may be prepared from N-(4-amino-3,5-dichlorophenyl)-trichloroacetamide as follows: to maintain 5° C Upon complete addition the stirred reaction to reach room temperature After 24 hours the mixture is filtered the collected solid is washed with methylene chloride (700 mL) The filtrate is evaporated to a small volume A solid is collected washed with methylene chloride (250 mL)

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,6-Dichloro-1,4-benzenediamine (225 g., 1.27 mol) is suspended in methylene chloride (1.3 liters) containing triethylamine (245 mL, 1.7 mol). After the mixture is cooled to 5° C., trichloroacetylchloride (169 mL, 1.5 mol, Aldrich Chemical Co.) is added dropwise with stirring at a rate to maintain 5° C. Upon complete addition, the stirred reaction is allowed to reach room temperature. After 24 hours the mixture is filtered and the collected solid is washed with methylene chloride (700 mL). The filtrate is evaporated to a small volume. A solid is collected and washed with methylene chloride (250 mL) to yield 465 grams of N-(4-amino-3,5-dichlorophenyl)-trichloroacetamide. The product exhibits a mass spectral analysis of m/e+. 320 for C8H5Cl5N2O. 3. N-(3,5-Dichloro-4-formamidophenyl)-trichloroacetamide may be prepared from N-(4-amino-3,5-dichlorophenyl)-trichloroacetamide as follows: to maintain 5° C Upon complete addition the stirred reaction to reach room temperature After 24 hours the mixture is filtered the collected solid is washed with methylene chloride (700 mL) The filtrate is evaporated to a small volume A solid is collected washed with methylene chloride (250 mL)

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

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

Procedure: A mixture of 3.5 g. of 2,6-dichloro-1,4-phenylenediamine and 3.3 g. of p-acetamidobenzaldehyde in 50 ml. of ethanol is refluxed for 21/2 hours. The reaction mixture is allowed to stand at room temperature for 16 hours, then evaporated in vacuo to give a solid. The solid in 25 ml. of N,N-dimethylformamide dimethylacetal is refluxed for 18 hours. The solvent is evaporated to provide a syrup which is dissolved in ethanol and n-hexane. The addition of more ethanol provides crystals. The crude product is collected, dissolved in 50 ml. of hot ethanol and filtered through diatomaceous earth. The filter is washed with ethanol and n-hexane is added to the filtrate until turbid. The clear liquid is decanted and evaporated in vacuo to give hard, yellow-orange crystals. The material is recrystallized from ethyl acetate/hexane to give 830 mg. of the product of the Example as bright yellow crystals, m.p. 171°-173° C. A mixture of 3.5 g evaporated in vacuo to give a solid The solvent is evaporated to provide a syrup which provides crystals The crude product is collected dissolved in 50 ml of hot ethanol and filtered through diatomaceous earth The filter is washed with ethanol and n-hexane is added to the filtrate until turbid The clear liquid is decanted evaporated in vacuo to give hard The material is recrystallized from ethyl acetate/hexane to give 830 mg

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 5.3 g. of 2,6-dichloro-p-phenylenediamine and 4.98 g. of 3,5-dimethoxybenzaldehyde in 100 ml. of ethanol is heated on a steam bath, solution occurs, followed by crystallization. Warming is continued on the steam bath for 16 hours. The reaction mixture is cooled, 50 ml. of glacial acetic acid and 500 mg. of platinum oxide are added and the mixture is hydrogenated in a Parr apparatus at 40 p.s.i. for 15 minutes. The mixture is filtered and washed with ethanol, then the combined filtrate and washings are evaporated to dryness. The residue is treated with 200 ml. of saturated sodium carbonate then is extracted twice with 200 ml. of ethyl acetate. The combined extract is evaporated to dryness. The residue is dissolved in methanol and the solution is cooled at 5° C. to provide crystals. The crystals are collected by filtration and washed with methanol to give 7.8 g. of product. This product is heated at reflux with 20 ml. of N,N-dimethylformamide dimethylacetal for 18 hours. The resulting solution is evaporated to an amber syrup. The syrup is treated with ether/hexane to crystallize 7.1 g. of the product of the Example as colorless needles, m.p. 124°-125° C. A mixture of 5.3 g followed by crystallization Warming The reaction mixture is cooled of platinum oxide are added for 15 minutes The mixture is filtered washed with ethanol the combined filtrate and washings are evaporated to dryness The residue is treated with 200 ml of saturated sodium carbonate then is extracted twice with 200 ml The combined extract is evaporated to dryness The residue is dissolved in methanol to provide crystals The crystals are collected by filtration washed with methanol to give 7.8 g This product is heated at reflux with 20 ml The resulting solution is evaporated to an amber syrup The syrup is treated with ether/hexane to crystallize 7.1 g

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,6-Dichloro-1,4-benzenediamine (225 g., 1.27 mol) is suspended in methylene chloride (1.3 liters) containing triethylamine (245 mL, 1.7 mol). After the mixture is cooled to 5° C., trichloroacetylchloride (169 mL, 1.5 mol, Aldrich Chemical Co.) is added dropwise with stirring at a rate to maintain 5° C. Upon complete addition, the stirred reaction is allowed to reach room temperature. After 24 hours the mixture is filtered and the collected solid is washed with methylene chloride (700 mL). The filtrate is evaporated to a small volume. A solid is collected and washed with methylene chloride (250 mL) to yield 465 grams of N-(4-amino-3,5-dichlorophenyl)-trichloroacetamide. The product exhibits a mass spectral analysis of m/e+· 320 for C8H5Cl5N2O. to maintain 5° C Upon complete addition the stirred reaction to reach room temperature After 24 hours the mixture is filtered the collected solid is washed with methylene chloride (700 mL) The filtrate is evaporated to a small volume A solid is collected washed with methylene chloride (250 mL)

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,6-Dichloro-1,4-benzenediamine (225 g., 1.27 mol) is suspended in methylene chloride (1.3 liters) containing triethylamine (245 mL, 1.7 mol). After the mixture is cooled to 5° C., trichloroacetylchloride (169 mL, 1.5 mol, Aldrich Chemical Co.) is added dropwise with stirring at a rate to maintain 5° C. Upon complete addition, the stirred reaction is allowed to reach room temperature. After 24 hours the mixture is filtered and the collected solid is washed with methylene chloride (700 mL). The filtrate is evaporated to a small volume. A solid is collected and washed with methylene chloride (250 mL) to yield 465 grams of N-(4-amino-3,5-dichlorophenyl)-trichloroacetamide. The product exhibits a mass spectral analysis of m/e+. 320 for C8H5Cl5N2O. 3. N-(3,5-Dichloro-4-formamidophenyl)-trichloroacetamide may be prepared from N-(4-amino-3,5-dichlorophenyl)-trichloroacetamide as follows: to maintain 5° C Upon complete addition the stirred reaction to reach room temperature After 24 hours the mixture is filtered the collected solid is washed with methylene chloride (700 mL) The filtrate is evaporated to a small volume A solid is collected washed with methylene chloride (250 mL)