1-chloro-2,3-dimethylbenzene

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

Conditions: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a pilot scale reaction 200 kilograms (kg) of chloro-ortho-xylene (a mixture of 3-chloro-ortho-xylene and 4-chloro-ortho-xylene), 780 kg of acetic acid, 3.5 kg (1.0 mol %) cobalt acetate tetrahydrate, 1.75 kg (0.5 mol %) manganese acetate tetrahydrate, 0.4 kg (0.05 mol %) zirconium acetate solution, 1.75 kg (1.5 mol %) sodium acetate and varying amounts of sodium bromide were combined. The amount of sodium bromide was varied by example as shown in Table 2. The reactor was filled with nitrogen, pressurized to 1900 Kpa and heated to about 160° C. Air was introduced to the reactor through a dip tube at a flow rate gradually increasing to 200 normal m3/h. Initially, the off gas oxygen concentration was greater than 0 but less than 1 percent. The reaction mixture was agitated throughout the reaction time. After about 1 hour, the reaction temperature was increased to 175° C. After about 3 hours the off gas oxygen concentration increased to greater than 3 percent. The air flow was stopped. Air diluted with nitrogen so as to have an off gas oxygen concentration of about 5 percent was introduced into the reactor and the temperature of the reactor was increased to 190° C. The flow of diluted air was continued for about 3 hours. Final weight of the reactor contents was consistent with high conversions of chloro-o-xylene based on the absorption of 3 moles of O2 to generate the diacid and two moles of water. The majority of water formed by the reaction and the acetic acid were removed under atmospheric distillation. The chlorophthalic acid was dehydrated and any residual water and acetic acid were removed under heat and reduced pressure to form chlorophthalic anhydride. Chlorophthalic anhydride was separated from the catalyst by distillation under vacuum at distillation temperatures near 170° C. The isolated chlorophthalic acid was analyzed by gas chromatography. Results are shown in Table 2. [t2] The reactor was filled with nitrogen Air was introduced to the reactor through a dip tube at a flow rate gradually increasing to 200 normal m3/h Initially, the off gas oxygen concentration the reaction temperature was increased to 175° C After about 3 hours the off gas oxygen concentration increased to greater than 3 percent Air diluted with nitrogen so as was introduced into the reactor the temperature of the reactor was increased to 190° C The flow of diluted air was continued for about 3 hours the acetic acid were removed under atmospheric distillation any residual water and acetic acid were removed under heat

Conditions: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a laboratory scale reactor 492 grams (g) (3.5 mol) of chloro-ortho-xylene (a mixture of about 30% 3-chloro-ortho-xylene and about 70% 4-chloro-ortho-xylene), 1925 g of glacial acetic acid, 8.7 g (1 mol %) of cobalt acetate tetrahydrate, 4.3 g (0.5 mol %) of manganese acetate tetrahydrate, 1.0 g (0.06 mol %) zirconium acetate solution, 4.3 g (1.5 mol %) sodium acetate and varying amounts of sodium bromide were combined. The reactor was filled with nitrogen, pressurized to 1900 KPa and heated to about 160° C. Air was then introduced to the reactor through a dip tube. Initially, the off gas oxygen concentration was greater than 0 but less than 1 percent. The reaction mixture was agitated throughout the reaction time. After about 3 hours the oxygen concentration of the off gas increased to greater than 3 percent. The flow of air was stopped. Air diluted with nitrogen so as to have an off gas oxygen concentration of about 5 percent was introduced to the reactor and the temperature of the reactor was increased to about 190° C. The flow of diluted air continued for about 1 to 3 hours. Chlorophthalic acid was determined to be present in an amount of 25 wt % based on the total weight of the reaction mixture. The majority of water formed by the reaction and the acetic acid were removed under atmospheric distillation. The chlorophthalic acid was dehydrated and any residual water and acetic acid were removed under heat and reduced pressure to form chlorophthalic anhydride. Chlorophthalic anhydride was separated from the catalyst by distillation under vacuum at distillation temperatures near 170° C. The isolated chlorophthalic acid was analyzed by gas chromatography. Results are shown in Table 1. [t1] The reactor was filled with nitrogen Air was then introduced to the reactor through a dip tube Initially, the off gas oxygen concentration After about 3 hours the oxygen concentration of the off gas increased to greater than 3 percent Air diluted with nitrogen so as was introduced to the reactor the temperature of the reactor was increased to about 190° C The majority of water formed by the reaction the acetic acid were removed under atmospheric distillation any residual water and acetic acid were removed under heat

Conditions: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a pilot scale reaction 200 kilograms (kg) of chloro-ortho-xylene (a mixture of 3-chloro-ortho-xylene and 4-chloro ortho-xylene), 780 kg of acetic acid, 3.5 kg (1.0 mol %) cobalt acetate tetrahydrate, 1.75 kg (0.5 mol %) manganese acetate tetrahydrate, 0.4 kg (0.05 mol %/l) zirconium acetate solution, 1.75 kg (1.5 mol %) sodium acetate and varying amounts of sodium bromide were combined. The amount of sodium bromide was varied by example as shown in Table 2. The reactor was filled with nitrogen, pressurized to 1900 Kpa and heated to about 160° C. Air was introduced to the reactor through a dip tube at a flow rate gradually increasing to 200 normal m3/h. Initially, the off gas oxygen concentration was greater than 0 but less than 1 percent. The reaction mixture was agitated throughout the reaction time. After about 1 hour, the reaction temperature was increased to 175° C. After about 3 hours the off gas oxygen concentration increased to greater than 3 percent. The air flow was stopped. Air diluted with nitrogen so as to have an off gas oxygen concentration of about 5 percent was introduced into the reactor and the temperature of the reactor was increased to 190° C. The flow of diluted air was continued for about 3 hours. Final weight of the reactor contents was consistent with high conversions of chloro-o-xylene based on the absorption of 3 moles of O2 to generate the diacid and two moles of water. The majority of water formed by the reaction and the acetic acid were removed under atmospheric distillation. The chlorophthalic acid was dehydrated and any residual water and acetic acid were removed under heat and reduced pressure to form chlorophthalic anhydride. Chlorophthalic anhydride was separated from the catalyst by distillation under vacuum at distillation temperatures near 170° C. The isolated chlorophthalic acid was analyzed by gas chromatography. Results are shown in Table 2. The reactor was filled with nitrogen Air was introduced to the reactor through a dip tube at a flow rate gradually increasing to 200 normal m3/h Initially, the off gas oxygen concentration the reaction temperature was increased to 175° C After about 3 hours the off gas oxygen concentration increased to greater than 3 percent Air diluted with nitrogen so as was introduced into the reactor the temperature of the reactor was increased to 190° C The flow of diluted air was continued for about 3 hours the acetic acid were removed under atmospheric distillation any residual water and acetic acid were removed under heat

Conditions: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a laboratory scale reactor 492 grams (g) (3.5 mol) of chloro-ortho-xylene (a mixture of about 30% 3-chloro-ortho-xylene and about 70% 4-chloro-ortho-xylene), 1925 g of glacial acetic acid, 8.7 g (1 mol %) of cobalt acetate tetrahydrate, 4.3 g (0.5 mol %) of manganese acetate tetrahydrate, 1.0 g (0.06 mol %) zirconium acetate solution, 4.3 g (1.5 mol %) sodium acetate and varying amounts of sodium bromide were combined. The reactor was filled with nitrogen, pressurized to 1900 KPa and heated to about 160° C. Air was then introduced to the reactor through a dip tube. Initially, the off gas oxygen concentration was greater than 0 but less than 1 percent. The reaction mixture was agitated throughout the reaction time. After about 3 hours the oxygen concentration of the off gas increased to greater than 3 percent. The flow of air was stopped. Air diluted with nitrogen so as to have an off gas oxygen concentration of about 5 percent was introduced to the reactor and the temperature of the reactor was increased to about 190° C. The flow of diluted air continued for about 1 to 3 hours. Chlorophthalic acid was determined to be present in an amount of 25 wt % based on the total weight of the reaction mixture. The majority of water formed by the reaction and the acetic acid were removed under atmospheric distillation. The chlorophthalic acid was dehydrated and any residual water and acetic acid were removed under heat and reduced pressure to form chlorophthalic anhydride. Chlorophthalic anhydride was separated from the catalyst by distillation under vacuum at distillation temperatures near 170° C. The isolated chlorophthalic acid was analyzed by gas chromatography. Results are shown in Table 1. The reactor was filled with nitrogen Air was then introduced to the reactor through a dip tube Initially, the off gas oxygen concentration After about 3 hours the oxygen concentration of the off gas increased to greater than 3 percent Air diluted with nitrogen so as was introduced to the reactor the temperature of the reactor was increased to about 190° C The majority of water formed by the reaction the acetic acid were removed under atmospheric distillation any residual water and acetic acid were removed under heat

Conditions: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a pilot scale reaction 200 kilograms (kg) of chloro-ortho-xylene (a mixture of 3-chloro-ortho-xylene and 4-chloro-ortho-xylene), 780 kg of acetic acid, 3.5 kg (1.0 mol %) cobalt acetate tetrahydrate, 1.7.5 kg (0.5 mol %) manganese acetate tetrahydrate, 0.4 kg (0.05 mol %) zirconium acetate solution, 1.75 kg (1.5 mol %) sodium acetate and varying amounts of sodium bromide were combined. The amount of sodium bromide was varied by example as shown in Table 2. The reactor was filled with nitrogen, pressurized to 1900 Kpa and heated to about 160° C. Air was introduced to the reactor through a dip tube at a flow rate gradually increasing to 200 normal m3/h. Initially, the off gas oxygen concentration was greater than 0 but less than 1 percent. The reaction mixture was agitated throughout the reaction time. After about 1 hour, the reaction temperature was increased to 175° C. After about 3 hours the off gas oxygen concentration increased to greater than 3 percent. The air flow was stopped. Air diluted with nitrogen so as to have an off gas oxygen concentration of about 5 percent was introduced into the reactor and the temperature of the reactor was increased to 190° C. The flow of diluted air was continued for about 3 hours. Final weight of the reactor contents was consistent with high conversions of chloro-o-xylene based on the absorption of 3 moles of O2 to generate the diacid and two moles of water. The majority of water formed by the reaction and the acetic acid were removed under atmospheric distillation. The chlorophthalic acid was dehydrated and any residual water and acetic acid were removed under heat and reduced pressure to form chlorophthalic anhydride. Chlorophthalic anhydride was separated from the catalyst by distillation under vacuum at distillation temperatures near 170° C. The isolated chlorophthalic acid was analyzed by gas chromatography. Results are shown in Table 2. The reactor was filled with nitrogen Air was introduced to the reactor through a dip tube at a flow rate gradually increasing to 200 normal m3/h Initially, the off gas oxygen concentration the reaction temperature was increased to 175° C After about 3 hours the off gas oxygen concentration increased to greater than 3 percent Air diluted with nitrogen so as was introduced into the reactor the temperature of the reactor was increased to 190° C The flow of diluted air was continued for about 3 hours the acetic acid were removed under atmospheric distillation any residual water and acetic acid were removed under heat

Conditions: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a pilot scale reaction 200 kilograms (kg) of chloro-ortho-xylene (a mixture of 3-chloro-ortho-xylene and 4-chloro-ortho-xylene), 780 kg of acetic acid, 3.5 kg (1.0 mol %) cobalt acetate tetrahydrate, 1.7.5 kg (0.5 mol %) manganese acetate tetrahydrate, 0.4 kg (0.05 mol %) zirconium acetate solution, 1.75 kg (1.5 mol %) sodium acetate and varying amounts of sodium bromide were combined. The amount of sodium bromide was varied by example as shown in Table 2. The reactor was filled with nitrogen, pressurized to 1900 Kpa and heated to about 160° C. Air was introduced to the reactor through a dip tube at a flow rate gradually increasing to 200 normal m3/h. Initially, the off gas oxygen concentration was greater than 0 but less than 1 percent. The reaction mixture was agitated throughout the reaction time. After about 1 hour, the reaction temperature was increased to 175° C. After about 3 hours the off gas oxygen concentration increased to greater than 3 percent. The air flow was stopped. Air diluted with nitrogen so as to have an off gas oxygen concentration of about 5 percent was introduced into the reactor and the temperature of the reactor was increased to 190° C. The flow of diluted air was continued for about 3 hours. Final weight of the reactor contents was consistent with high conversions of chloro-o-xylene based on the absorption of 3 moles of O2 to generate the diacid and two moles of water. The majority of water formed by the reaction and the acetic acid were removed under atmospheric distillation. The chlorophthalic acid was dehydrated and any residual water and acetic acid were removed under heat and reduced pressure to form chlorophthalic anhydride. Chlorophthalic anhydride was separated from the catalyst by distillation under vacuum at distillation temperatures near 170° C. The isolated chlorophthalic acid was analyzed by gas chromatography. Results are shown in Table 2. The reactor was filled with nitrogen Air was introduced to the reactor through a dip tube at a flow rate gradually increasing to 200 normal m3/h Initially, the off gas oxygen concentration the reaction temperature was increased to 175° C After about 3 hours the off gas oxygen concentration increased to greater than 3 percent Air diluted with nitrogen so as was introduced into the reactor the temperature of the reactor was increased to 190° C The flow of diluted air was continued for about 3 hours the acetic acid were removed under atmospheric distillation any residual water and acetic acid were removed under heat

Conditions: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a laboratory scale reactor 492 grams (g) (3.5 mol) of chloro-ortho-xylene (a mixture of about 30% 3-chloro-ortho-xylene and about 70% 4-chloro-ortho-xylene), 1925 g of glacial acetic acid, 8.7 g (1 mol %) of cobalt acetate tetrahydrate, 4.3 g (0.5 mol %) of manganese acetate tetrahydrate, 1.0 g (0.06 mol %) zirconium acetate solution, 4.3 g (1.5 mol %) sodium acetate and varying amounts of sodium bromide were combined. The reactor was filled with nitrogen, pressurized to 1900 KPa and heated to about 160° C. Air was then introduced to the reactor through a dip tube. Initially, the off gas oxygen concentration was greater than 0 but less than 1 percent. The reaction mixture was agitated throughout the reaction time. After about 3 hours the oxygen concentration of the off gas increased to greater than 3 percent. The flow of air was stopped. Air diluted with nitrogen so as to have an off gas oxygen concentration of about 5 percent was introduced to the reactor and the temperature of the reactor was increased to about 190° C. The flow of diluted air continued for about 1 to 3 hours. Chlorophthalic acid was determined to be present in an amount of 25 wt % based on the total weight of the reaction mixture. The majority of water formed by the reaction and the acetic acid were removed under atmospheric distillation. The chlorophthalic acid was dehydrated and any residual water and acetic acid were removed under heat and reduced pressure to form chlorophthalic anhydride. Chlorophthalic anhydride was separated from the catalyst by distillation under vacuum at distillation temperatures near 170° C. The isolated chlorophthalic acid was analyzed by gas chromatography. Results are shown in Table 1: The reactor was filled with nitrogen Air was then introduced to the reactor through a dip tube Initially, the off gas oxygen concentration After about 3 hours the oxygen concentration of the off gas increased to greater than 3 percent Air diluted with nitrogen so as was introduced to the reactor the temperature of the reactor was increased to about 190° C The majority of water formed by the reaction the acetic acid were removed under atmospheric distillation any residual water and acetic acid were removed under heat

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

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

Procedure: A solution of 70 parts of xylyl chloride in 240 parts of benzene is added to a mixture of 60 parts of boron fluoride dihydrate and 250 parts of 75 per cent strength by weight sulfuric acid at from 75° to 78° C, whilst stirring vigorously. After 6 hours, the organic phase is separated off and 82 parts (91.1% of theory) of o-benzyl-toluene boiling at 98° C at 0.2 mm Hg are isolated by distillation. the organic phase is separated off

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

Procedure: The intermediate 2-(2-methylphenylmethylthio)-pyridine N-oxide is prepared by the procedure described in Example 2 from α -chloro o-xylene and 2-mercaptopyridine N-oxide sodium salt. Melting point 134° - 136°C. Yield 85% theory. Structure confirmed by IR and NMR.

Conditions: temp:200.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 0.4 g of anhydrous aluminium chloride was added to 20 g of 2,3-dimethylphenyl chloroformate and the mixture was heated at 200° C. for 4.5 hours at normal pressure. The reaction mixture was then cooled and worked up as described in Example 1. 2,3-Dimethylchlorobenzene was obtained in a yield of 18%, which is considerable despite the unfavourable substitution pattern. The reaction mixture was then cooled