1-(3,4-dichlorophenyl)-3-methylurea

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

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

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1-(3,4-dichlorophenyl)-3-methyl urea (15.2 g, 0.07 mol) was combined with 15.0 g (0.1 mol) of chloral and 5 drops of concentrated sulfuric acid. The mixture was heated for an hour to effect reaction, then stripped under vacuum. To the crude 1-(3,4-dichlorophenyl)-3-(1-hydroxy-2,2,2-trichloroethyl)-3-methyl urea was added an excess of thionyl chloride and the mixture was heated gradually to a maximum of 65° C. Diethyl ether was added to the crude product, and the insoluble product was collected on a filter, washed twice with diethyl ether and dried. The 15.3 g of product, which melted at 132°-140° C., analyzed as follows: %Cl, calculated 55.2, found 46.0. The product is the seventh compound tabulated in Table I. The mixture was heated for an hour reaction the insoluble product was collected on a filter washed twice with diethyl ether dried

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1-(3,4-dichlorophenyl)-3-methyl urea (15.2 g, 0.07 mol) was combined with 15.0 g (0.1 mol) of chloral and 5 drops of concentrated sulfuric acid. The mixture was heated for an hour to effect reaction, then stripped under vacuum. To the crude 1-(3,4-dichlorophenyl)-3-(1-hydroxy-2,2,2-trichloroethyl)-3-methyl urea was added an excess of thionyl chloride and the mixture was heated gradually to a maximum of 65° C. Diethyl ether was added to the crude product, and the insoluble product was collected on a filter, washed twice with diethyl ether and dried. The 15.3 g of product, which melted at 132°-140° C., analyzed as follows: %Cl, calculated 55.2, found 46.0. The product is the seventh compound tabulated in Table I. The mixture was heated for an hour reaction the insoluble product was collected on a filter washed twice with diethyl ether dried

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

Procedure: 11 g of N-methyl-N'-(3,4-dichlorophenyl)-urea, 60 g of potassium carbonate and 50 ml of dimethylsulfur chloride were added at 10° C. to 150 ml of dimethylsulfoxide and the mixture was allowed to stand until exothermic generation of heat ceased. The reaction mixture was added to water and was extracted with ether. The ether solution was washed with water, dried and concentrated to dryness by distillation under reduced pressure. The residue was crystallized from isopropyl ether and then ethyl acetate to obtain 7.7 g of N-methyl-N-(2-thiapropyl)-N'-(3,4-dichlorophenyl)-urea melting at 103° C. of heat was extracted with ether The ether solution was washed with water dried concentrated to dryness by distillation under reduced pressure The residue was crystallized from isopropyl ether

Conditions: temp:-40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 67 g of sulfuryl chloride in 100 ml of methylene chloride was added dropwise to a solution of 61 g of diethyldisulfide in 600 ml of methylene chloride cooled to -40° C. and after the temperature was raised to -5° C., the mixture was stirred for 5 minutes. The mixture was cooled to -40° C. and a solution of 57 g of N-methyl-N'-(3,4-dichlorophenyl)-urea in 460 ml of pyridine was added dropwise thereto. The mixture was stirred at -40° C. for 1 hour and for another hour at -20° C. The mixture was poured into an ice-water mixture and the pH was adjusted to 3.5 by addition of concentrated hydrochloric acid. The organic phase was decanted and the aqueous phase was extracted with methylene chloride. The combined organic phases were washed with water, dried and evaporated to dryness under reduced pressure. The residue was crystallized from isopropyl ether and subjected to chromatography over silica gel. Elution with a 7-3 benzene-ethyl acetate mixture gave 22 g of N-methyl-N-ethylthio-N'-(3,4-dichlorophenyl)-urea melting at 71° C. after the temperature was raised to -5° C. The mixture was cooled to -40° C. The mixture was stirred at -40° C. for 1 hour and for another hour at -20° C The organic phase was decanted the aqueous phase was extracted with methylene chloride The combined organic phases were washed with water dried evaporated to dryness under reduced pressure The residue was crystallized from isopropyl ether Elution with a 7-3 benzene-ethyl acetate mixture

Conditions: temp:-30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 20 ml of methylsulfenyl chloride and 200ml of ethyl ether was added slowly while keeping the temperature below -30° C. to a solution of 40 g of N-methyl-N'-(3,4-dichlorophenyl)-urea in 500 ml of pyridine and the mixture was stirred for 1 hour at -30° C. After letting the temperature rise to 5° C., the mixture was stirred for 17 hours and the mixture was poured into a mixture of ice and water. The mixture was extracted with methylene chloride and the methylene chloride extract was washed with water and dried. The volatile fractions were removed by distillation under reduced pressure and the residue was crystallized from isopropyl ether to obtain 29.4 g of N-methyl-N-methylthio-N'-(3,4-dichlorophenyl)-urea melting at 93° C. A microanalytical sample was obtained by chromatography over silica gel and elution with a 9-1 benzene-ethyl acetate mixture. was added slowly the temperature below -30° C. to 5° C. the mixture was stirred for 17 hours The mixture was extracted with methylene chloride the methylene chloride extract was washed with water dried The volatile fractions were removed by distillation under reduced pressure the residue was crystallized from isopropyl ether

Conditions: temp:-30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 20 ml of methylsulfenyl chloride and 200ml of ethyl ether was added slowly while keeping the temperature below -30° C. to a solution of 40 g of N-methyl-N'-(3,4-dichlorophenyl)-urea in 500 ml of pyridine and the mixture was stirred for 1 hour at -30° C. After letting the temperature rise to 5° C., the mixture was stirred for 17 hours and the mixture was poured into a mixture of ice and water. The mixture was extracted with methylene chloride and the methylene chloride extract was washed with water and dried. The volatile fractions were removed by distillation under reduced pressure and the residue was crystallized from isopropyl ether to obtain 29.4 g of N-methyl-N-methylthio-N'-(3,4-dichlorophenyl)-urea melting at 93° C. A microanalytical sample was obtained by chromatography over silica gel and elution with a 9-1 benzene-ethyl acetate mixture. was added slowly the temperature below -30° C. to 5° C. the mixture was stirred for 17 hours The mixture was extracted with methylene chloride the methylene chloride extract was washed with water dried The volatile fractions were removed by distillation under reduced pressure the residue was crystallized from isopropyl ether

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 27.4 g of 3,4-dichloroaniline in 140 ml of isopropyl ether was added slowly to 9 g of methyl isocyanate in 100 ml of isopropyl ether and the mixture was refluxed for 2 hours and was then cooled to 0° C. The precipitate formed was recovered by vacuum filtration and was washed with isopropyl ether. The mother liquors were concentrated to obtain a second crop. The two combined crops weighing 19.5 g and melting at 156° C. were crystallized from ethyl acetate to obtain N-methyl-N'-(3,4-dichlorophenyl)-urea melting at 160° C., identical to the product described by Onley et al., J. Ass. Off. Anal. Chem., Vol. 52 (1969), p. 545. the mixture was refluxed for 2 hours The precipitate formed was recovered by vacuum filtration was washed with isopropyl ether The mother liquors were concentrated to obtain a second crop were crystallized from ethyl acetate

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 27.4 g of 3,4-dichloroaniline in 140 ml of isopropyl ether was added slowly to 9 g of methyl isocyanate in 100 ml of isopropyl ether and the mixture was refluxed for 2 hours and was then cooled to 0° C. The precipitate formed was recovered by vacuum filtration and was washed with isopropyl ether. The mother liquors were concentrated to obtain a second crop. The two combined crops weighing 19.5 g and melting at 156° C. were crystallized from ethyl acetate to obtain N-methyl-N'-(3,4-dichlorophenyl)-urea melting at 160° C., identical to the product described by Onley et al., J. Ass. Off. Anal. Chem., Vol. 52 (1969), p. 545. the mixture was refluxed for 2 hours The precipitate formed was recovered by vacuum filtration was washed with isopropyl ether The mother liquors were concentrated to obtain a second crop were crystallized from ethyl acetate

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 27 g of chlorosulfuric acid were slowly added at 0° C to a mixture of 12 g of ethylene sulfide and 200 ml of methylene chloride and the mixture was stirred at 0° C for 10 minutes and was then cooled to -20° C. A mixture of 32.6 g of N-methyl-N'-(3,4-dichlorophenyl)-urea in 210 ml of pyridine was added to the reaction mixture after which the temperature returned to 0° C. The mixture was stirred at 0° C for 10 minutes and was then poured into a mixture of ice, water, hydrochloric acid and methylene chloride. The mixture was stirred for 30 minutes and the decanted organic phase was washed, dried, filtered and concentrated to dryness under reduced pressure. The residue was chromatographed over silica gel and the product was eluted witn 9-1 benzene-ethyl acetate mixture and was crystallized from isopropyl ether to obtain 10 g of N-(2-chloroethylthio)-N-methyl-N'-(3,4-dichlorophenyl)-urea melting at 62° C. was then cooled to -20° C was added to the reaction mixture after which the temperature returned to 0° C The mixture was stirred at 0° C for 10 minutes The mixture was stirred for 30 minutes the decanted organic phase was washed dried filtered concentrated to dryness under reduced pressure The residue was chromatographed over silica gel the product was eluted witn 9-1 benzene-ethyl acetate mixture was crystallized from isopropyl ether

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1-(3,4-dichlorophenyl)-3-methyl urea (15.2 g, 0.07 mol) was combined with 15.0 g (0.1 mol) of chloral and 5 drops of concentrated sulfuric acid. The mixture was heated for an hour to effect reaction, then stripped under vacuum. To the crude 1-(3,4-dichlorophenyl)-3-(1-hydroxy-2,2,2-trichloroethyl)-3-methyl urea was added an excess of thionyl chloride and the mixture was heated gradually to a maximum of 65° C. Diethyl ether was added to the crude product, and the insoluble product was collected on a filter, washed twice with diethyl ether and dried. The 15.3 g of product, which melted at 132°-140° C., analyzed as follows: %Cl, calculated 55.2, found 46.0. The mixture was heated for an hour reaction the insoluble product was collected on a filter washed twice with diethyl ether dried