2-chloro-N-(chloromethyl)-N-(2,6-dimethylphenyl)acetamide

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

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

Procedure: About 12.3 g (0.050 mole) of 2',6'-dimethyl-N-(chloromethyl) 2-chloroacetanilide dissolved in twenty (20) ml of ethylene dichloride was added to 22.5 g (0.25 mole) of 2-methoxy-1-methyl ethanol. The solution was allowed to stand one hour at room temperature. Excess alcohol and HCl was removed under vacuum on a rotary evaporator. The residual oil was treated with an additional 22.5 g fresh alcohol for 30 minutes at 60° C. Excess alcohol and HCl was removed as before at 65° C./1 mm Hg. The light yellow oily residue weighed 14.86 g (99.1% yield). Refractive index of the oil, n26D 1.5263. Proton NMR was consistent with structure. Excess alcohol and HCl was removed under vacuum on a rotary evaporator The residual oil was treated with an additional 22.5 g fresh alcohol for 30 minutes at 60° C Excess alcohol and HCl was removed as before at 65° C./1 mm Hg

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

Procedure: About 12.3 g (0.050 mole) of 2',6'-dimethyl-N-(chloromethyl) 2-chloroacetanilide dissolved in twenty (20) ml of ethylene dichloride was added to 22.5 g (0.25 mole) of 2-methoxy-1-methyl ethanol. The solution was allowed to stand one hour at room temperature. Excess alcohol and HCl was removed under vacuum on a rotary evaporator. The residual oil was treated with an additional 22.5 g fresh alcohol for 30 minutes at 60° C. Excess alcohol and HCl was removed as before at 65° C./1 mm Hg. The light yellow oily residue weighed 14.86 g (99.1% yield). Refractive index of the oil, n26D 1.5263. Proton NMR was consistent with structure. Excess alcohol and HCl was removed under vacuum on a rotary evaporator The residual oil was treated with an additional 22.5 g fresh alcohol for 30 minutes at 60° C Excess alcohol and HCl was removed as before at 65° C./1 mm Hg

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 7.5 parts by weight of pyrazole and 4.0 parts by weight of sodium hydroxide in 20 parts by volume of water was added dropwise at 20°-25° C., with vigorous stirring, to a solution of 24.6 parts by weight of 2-chloro-N-chloromethyl-2',6'-dimethylacetanilide and M parts by weight of phase transfer catalyst in 70 parts by volume of toluene, and stirring was continued for 3-5 hours at the same temperature. After complete conversion (checked by thin layer chromatography), the organic phase was washed three times with water, dried and concentrated under reduced pressure at 70° to give G parts by weight of 2-chloro-2',6'-dimethyl-N-(pyrazol-1-yl-methyl)-acetanilide, as shown in the Table which follows. After complete conversion (checked by thin layer chromatography), the organic phase was washed three times with water dried concentrated under reduced pressure at 70°

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

Procedure: A solution of 12.1 parts by weight of 4-isopropylpyrazole and 5.6 parts by weight of potassium hydroxide in 30 parts by volume of water was added at 25° C., with vigorous stirring, to a solution of 24.6 parts by weight of 2-chloro-N-chloromethyl-2',6'-dimethylacetanilide and 0.5 part by weight of triethylbenzylammonium chloride in 100 parts by volume of chloroform and stirring was continued for 4 hours at 25° C. The organic phase was washed with three times 50 parts by volume of water, dried over sodium sulfate and evaporated under reduced pressure at 50° C. to give 26.2 parts by weight of 2-chloro-2',6'-dimethyl-N-(4-isopropylpyrazol-1-yl-methyl)-acetanilide of melting point 58° C. The organic phase was washed with three times 50 parts by volume of water dried over sodium sulfate evaporated under reduced pressure at 50° C.

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

Procedure: A solution of 10.8 parts by weight of 4-methoxypyrazole and 4.0 parts by weight of sodium hydroxide in 20 parts by volume of water was added dropwise at 10°-15° C., with vigorous stirring, to a solution of 24.6 parts by weight of 2-chloro-N-chloromethyl-2',6'-dimethylacetanilide and one part by weight of benzyltriethylammonium bromide in 70 parts by volume of toluene and the stirring was continued for 3 hours. The organic phase was washed with three times 40 parts by volume of water, dried over sodium sulfate and evaporated in vacuo at 80° C. to give 28.1 parts by weight of 2-chloro-2',6'-dimethyl-N-(4-methoxypyrazol-1-yl-methyl)acetanilide of melting point 115°-116° C. (melting point of a sample recrystallized from ethanol: 118° C.), which according to the 1H-NMR spectrum and thin layer chromatography carried out using a 3:7 mixture of ethyl acetate:toluene was more than 97% pure. The organic phase was washed with three times 40 parts by volume of water dried over sodium sulfate evaporated in vacuo at 80° C.

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

Procedure: A solution of 9.0 parts by weight of 4-methylpyrazole and 4.0 parts by weight of sodium hydroxide in 20 parts by volume of water was added dropwise at 0° C., with vigorous stirring, to a solution of 24.6 parts by weight of 2-chloro-N-chloromethyl-2',6'-dimethylacetanilide and 0.15 part by weight of tri-n-butylmethylphosphonium bromide in 80 parts by volume of o-dichlorobenzene, and the stirring was continued for 5 hours at 10° C. The organic phase was washed with three times 50 parts by volume of water, dried over sodium sulfate and evaporated under reduced pressure at 70° C. to give 25.6 parts by weight of 2-chloro-2',6'-dimethyl-N-(4-methylpyrazol-1-yl-methyl)-acetanilide of melting point 100° C.; the product was pure according to the 1H-NMR spectrum and according to thin layer chromatography carried out using a 3:7 ethyl acetate:toluene mixture. The organic phase was washed with three times 50 parts by volume of water dried over sodium sulfate evaporated under reduced pressure at 70° C.

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

Procedure: A solution of 13.7 parts by weight of 4,5-dichloroimidazole and 4.4 parts by weight of sodium hydroxide in 20 parts of water was added dropwise to a solution of 24.6 parts by weight of 2-chloro-N-chloromethyl-2',6'-dimethylacetanilide and 2.0 parts by weight of triethylbenzylammonium chloride in 50 parts by volume of dichloromethane at 20°-25° C., with vigorous stirring, which was continued for 2 hours. The organic phase was washed with three times 30 parts by volume of water, dried over sodium sulfate and evaporated under reduced pressure at 70° C., to give 29.9 parts by weight of 2-chloro-2',6'-dimethyl-N-(4,5-dichloroimidazol-1-yl-methyl)-acetanilide of melting point 99° C.; the product was pure according to the 1H-NMR spectrum and according to thin layer chromatography carried out with a 3:7 ethyl acetate:toluene mixture. The organic phase was washed with three times 30 parts by volume of water dried over sodium sulfate evaporated under reduced pressure at 70° C.

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

Procedure: 43.9 parts by weight of 2-chloro-2',6'-dimethyl-N-chloromethyl acetanilide and 25.8 parts by weight of pyrazole are stirred for 7 hours at 90° C. in 120 parts by volume of toluene. After the mixture has cooled it is filtered, and the filtrate is washed 3 times with water, each time with 50 parts by volume, and dried over sodium sulfate. The solvent is evaporated and the residue pasted with 50 parts by volume of petroleum ether to give 39.1 parts by weight of 2-chloro-2',6'-dimethyl-N-(pyrazol-1-yl-methyl)-acetanilide, m.p.: 81° C. After the mixture has cooled it is filtered the filtrate is washed 3 times with water each time with 50 parts by volume, and dried over sodium sulfate The solvent is evaporated

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

Procedure: 16.5 parts by weight of 2-chloro-2',6'-dimethyl-N-chloromethyl acetanilide and 9.3 parts by weight of 1,2,4-triazole are refluxed for 8 hours in 60 parts by volume of anhydrous tetrahydrofuran. After the mixture has been cooled, it is filtered, the filtrate is concentrated in vacuo, and the residue is dissolved in 60 parts by volume of chloroform, washed 3 times with water, each time with 40 parts by volume, and dried over sodium sulfate. After evaporation of the solvent in vacuo, there is isolated 21.0 parts by weight of 2-chloro-2',6'-dimethyl-N-(1,2,4-triazol-1-yl-methyl)-acetanilide, m.p.: 115°-118° C.; after recrystallization from ethanol, it melts at 120° C. After the mixture has been cooled it is filtered the filtrate is concentrated in vacuo the residue is dissolved in 60 parts by volume of chloroform washed 3 times with water each time with 40 parts by volume, and dried over sodium sulfate After evaporation of the solvent in vacuo

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

Procedure: About 12.3 g (0.050 mole) of 2',6'-dimethyl-N-(chloromethyl) 2-chloroacetanilide dissolved in twenty (20) ml of ethylene dichloride was added to 22.5 g (0.25 mole) of 2-methoxy-1-methyl ethanol. The solution was allowed to stand one hour at room temperature. Excess alcohol and HCl was removed under vacuum on a rotary evaporator. The residual oil was treated with an additional 22.5 g fresh alcohol for 30 minutes at 60° C. Excess alcohol and HCl was removed as before at 65° C./1 mm Hg. The light yellow oily residue weighed 14.86 g (99.1% yield). Refractive index of the oil, n26D 1.5263. Proton NMR was consistent with structure. Excess alcohol and HCl was removed under vacuum on a rotary evaporator The residual oil was treated with an additional 22.5 g fresh alcohol for 30 minutes at 60° C Excess alcohol and HCl was removed as before at 65° C./1 mm Hg