methyl thiohypochlorite

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

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

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

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

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3-(4-Bromophenoxy)phenol (0.1 mole) and methylene chloride (200 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer and addition funnel. The mixture is stirred until dissolved and cooled to about -20° C. A solution of methyl sulfenyl chloride freshly prepared by reacting dimethyl disulfide (0.15 mole) with chlorine (0.18 mole) in methylene chloride (100 ml) is then added dropwise to the reaction vessel over a period of about 40 minutes. After the addition is completed stirring is continued for 30 minutes with cooling and 30 minutes at room temperature. After this time the reaction mixture is washed with water (200 ml), with 5% aqueous sodium bicarbonate (200 ml) and again with water (200 ml). The washed solution is then dried by passing it through a phase separator. The dried solution is stripped of solvent under reduced pressure and the residue chromatographed using a clay column and hexane/ethyl acetate as the eluant. The fractions containing the product are combined and stripped of solvent to yield the desired product 5-(4-bromophenoxy) 2-(methylthio)phenol as the residue. equipped with a mechanical stirrer and addition funnel until dissolved is then added dropwise to the reaction vessel over a period of about 40 minutes After the addition is completed stirring with cooling and 30 minutes at room temperature After this time the reaction mixture is washed with water (200 ml), with 5% aqueous sodium bicarbonate (200 ml) and again with water (200 ml) The washed solution is then dried the residue chromatographed The fractions containing the product

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3-(2-Cyano-4-fluorophenoxy)phenol (0.1 mole) and methylene chloride (200 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer and addition funnel. The mixture is stirred until dissolved and cooled to about -20° C. A solution of methyl sulfenyl chloride freshly prepared by reacting dimethyl disulfide (0.15 mole) with chlorine (0.18 mole) in methylene chloride (100 ml) is then added dropwise to the reaction vessel over a period of about 40 minutes. After the addition is completed stirring is continued for 30 minutes with cooling and 30 minutes at room temperature. After this time the reaction mixture is washed with water (200 ml) with 5% aqueous sodium bicarbonate (200 ml) and again with water (200 ml). The washed solution is then dried by passing it through a phase separator. The dried solution is stripped of solvent under reduced pressure and the residue chromatographed using a clay column and hexane/ethyl acetate as the eluant. The fractions containing the product are combined and stripped of solvent to yield the desired product 5-(2-cyano-4-fluorophenoxy) 2-(methylthio)phenol as the residue. equipped with a mechanical stirrer and addition funnel until dissolved is then added dropwise to the reaction vessel over a period of about 40 minutes After the addition is completed stirring with cooling and 30 minutes at room temperature After this time the reaction mixture is washed with water (200 ml) with 5% aqueous sodium bicarbonate (200 ml) and again with water (200 ml) The washed solution is then dried the residue chromatographed The fractions containing the product

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3-(2-Nitro-4-trifluoromethylphenoxy)phenol (0.1 mole) and methylene chloride (200 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer and addition funnel. The mixture is stirred until dissolved and cooled to about -20° C. A solution of methyl sulfenyl chloride freshly prepared by reacting dimethyl disulfide (0.15 mole) with chlorine (0.18 mole) in methylene chloride (100 ml) is then added dropwise to the reaction vessel over a period of about 40 minutes. After the addition is completed stirring is continued for 30 minutes with cooling and 30 minutes at room temperature. After this time the reaction mixture is washed with water (200 ml), with 5% aqueous sodium bicarbonate (200 ml) and again with water (200 ml). The washed solution is then dried by passing it through a phase separator. The dried solution is stripped of solvent under reduced pressure and the residue chromatographed using a clay column and hexane/ethyl acetate as the eluant. The fractions containing the product are combined and stripped of solvent to yield the desired product 5-(2-nitro-4-trifluoromethylphenoxy) 2-(methylthio)phenol as the residue. equipped with a mechanical stirrer and addition funnel until dissolved is then added dropwise to the reaction vessel over a period of about 40 minutes After the addition is completed stirring with cooling and 30 minutes at room temperature After this time the reaction mixture is washed with water (200 ml), with 5% aqueous sodium bicarbonate (200 ml) and again with water (200 ml) The washed solution is then dried the residue chromatographed The fractions containing the product

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3-(2-Bromo-4-nitrophenoxy)phenol (0.01 mole) and methylene chloride (200 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer and addition funnel. The mixture is stirred until dissolved and cooled to about -20° C. A solution of methyl sulfenyl chloride freshly prepared by reacting dimethyl disulfide (0.015 mole) with chlorine (0.18 mole) in methylene chloride (100 ml) is then added dropwise to the reaction vessel over a period of about 40 minutes. After the addition is completed stirring is continued for 30 minutes with cooling and 30 minutes at room temperature. After this time the reaction mixture is washed with water (200 ml) with 5% aqueous sodium bicarbonate (200 ml) and again with water (200 ml). The washed solution is then dried by passing it through a phase separator. The dried solution is stripped of solvent under reduced pressure and the residue chromatographed using a clay column and hexane/ethyl acetate as the eluant. The fractions containing the product are combined and stripped of solvent to yield the desired product 5-(2-bromo-4-nitrophenoxy)-2-(methylthio)phenol as the residue. equipped with a mechanical stirrer and addition funnel until dissolved is then added dropwise to the reaction vessel over a period of about 40 minutes After the addition is completed stirring with cooling and 30 minutes at room temperature After this time the reaction mixture is washed with water (200 ml) with 5% aqueous sodium bicarbonate (200 ml) and again with water (200 ml) The washed solution is then dried the residue chromatographed The fractions containing the product

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

Procedure: A 1.1 g (0.012 mol) sample of methylsulfenyl chloride was added dropwise to a cooled (-5° to -10° C.) solution of 3.6 g (0.01 mol) 4-dipropylamino-N-methyl-3,5-dinitrobenzenesulfonamide and 1.1 g (0.014 mol) pyridine in 25 ml dichloromethane. The reaction mixture was then stirred at about 0° C. until the sulfonamide reactant could not be detected by thin layer chromatography on silica gel (benzene/acetone eluant). The reaction mixture was then washed with water, dried over magnesium sulfate and evaporated under reduced pressure to give a yellow semi-solid residue. The residue was recrystallized from ethanol to give 2.3 g of the product, as a yellow solid, m.p. 119°-121° C. Elemental analysis for C14H22N4O6S2 showed: % S, calc. 15.8, found 15.9. The reaction mixture was then washed with water dried over magnesium sulfate evaporated under reduced pressure to give a yellow semi-solid residue The residue was recrystallized from ethanol

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3-(4-Bromophenoxy)phenol (0.1 mole) and methylene chloride (200 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer and addition funnel. The mixture is stirred until dissolved and cooled to about -20° C. A solution of methyl sulfenyl chloride freshly prepared by reacting dimethyl disulfide (0.15 mole) with chlorine (0.18 mole) in methylene chloride (100 ml) is then added dropwise to the reaction vessel over a period of about 40 minutes. After the addition is completed stirring is continued for 30 minutes with cooling and 30 minutes at room temperature. After this time the reaction mixture is washed with water (200 ml), with 5% aqueous sodium bicarbonate (200 ml) and again with water (200 ml). The washed solution is then dried by passing it through a phase separator. The dried solution is stripped of solvent under reduced pressure and the residue chromatographed using a clay column and hexane/ethyl acetate as the eluant. The fractions containing the product are combined and stripped of solvent to yield the desired product 5-(4-bromophenoxy) 2-(methylthio)phenol as the residue. equipped with a mechanical stirrer and addition funnel until dissolved is then added dropwise to the reaction vessel over a period of about 40 minutes After the addition is completed stirring with cooling and 30 minutes at room temperature After this time the reaction mixture is washed with water (200 ml), with 5% aqueous sodium bicarbonate (200 ml) and again with water (200 ml) The washed solution is then dried the residue chromatographed The fractions containing the product