2-(methylsulfanylmethyl)aniline

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Through this general procedure p-anisidine could be converted into 4-methoxy-2-(methylthiomethyl)aniline in 62 percent yield. The procedure is quite general. For a series of anilines (toluidine, aniline, p-chloroaniline, 4-nitroaniline, and p-ethoxycarbonylaniline) reaction of the aniline with the chlorine:sulfur compound complex chlorodimethylsulfonium chloride through the azasulfonium halide salt gave the corresponding 2-(methylthiomethyl)anilines in 54, 67, 45, 31 and 35% yields, respectively. The reaction is not restricted to chlorodialkylsulfonium chlorides. For example, when bromodimethylsulfonium bromide was used with aniline to form the azasulfonium bromide salt of aniline a 69 percent yield of 2-(methylthiomethyl)aniline was obtained. Treatment of aniline with halotetramethylenesulfonium halide (chloride or bromide) to form the azasulfonium salt followed by base treatment, gave 2-(2-tetrahydrothienyl)aniline in 20 percent yield. The use of β-keto sulfides and β-carboalkoxysulfides in the reaction provided a simple route to indoles and 2-oxindoles. Treatment of p-anisidine with chlorine:sulfur compound complex ##EQU8## to form the azasulfonium halide salt of the anisidine, followed by triethylamine, according to the above general procedure, gave 2-methyl-5-methoxy-3-methylthioindole in 38 percent yield. The reaction is not restricted to p-anisidine. With aniline, p-chloroaniline, and benzocaine, we obtained the corresponding unsubstituted, 5-chloro- and 5-ethoxycarbonyl-2-methyl-3-methylthioindoles in 68, 45 and 33 percent yields, respectively. Raney nickel desulfurization of the 3-methylthio compound gave 5-methoxy-2-methylindole in 72 percent yield. yields

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 7.60 g (0.0974 moles) of dry dimethyl sulfoxide in 70 ml of dry acetic acid at 0° C. and under a nitrogen atmosphere, was slowly added 9.76 g (0.0959 moles) of 100% sulfuric acid. The temperature rose to 15° C. The ice bath was removed and 9.9843 g (0.0838 moles) of phenyl isocyanate was added dropwise. An immediate evolution of gas began, which subsided after approximately fifteen minutes. After thirty minutes at room temperature, the reaction mixture was warmed to 50° C. for an additional hour. The entire solution was then poured into 100 ml of 10% aqueous sodium hydroxide solution and this was extracted with methylene chloride. The organic layer was dried over anhydrous sodium carbonate and filtered. Due to the instability of this sulfilimine, 0.33 g of succnimide was added and the solution was then concentrated to 150 ml and refluxed for sixteen hours. The solution was then washed with 10% aqueous sodium hydroxide, dried over anhydrous magnesium sulfate and filtered. To this was added dodecane as an internal standard and the solution was analyzed by gas chromatography. In this manner, there was obtained 1.751 g (22.4%) of aniline and 7.166 g (55.8%) of 2-methylthiomethylaniline. Other examples of the preparation and rearrangement of unstable N-aryl-S,S-dimethylsulfilimines were performed and these results can be found in Table II. at 0° C. rose to 15° C The ice bath was removed which subsided after approximately fifteen minutes After thirty minutes at room temperature this was extracted with methylene chloride The organic layer was dried over anhydrous sodium carbonate filtered Due to the instability of this sulfilimine, 0.33 g of succnimide was added the solution was then concentrated to 150 ml refluxed for sixteen hours The solution was then washed with 10% aqueous sodium hydroxide dried over anhydrous magnesium sulfate filtered To this was added dodecane as an internal standard

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 7.60 g (0.0974 moles) of dry dimethyl sulfoxide in 70 ml of dry acetic acid at 0° C. and under a nitrogen atmosphere, was slowly added 9.76 g (0.0959 moles) of 100% sulfuric acid. The temperature rose to 15° C. The ice bath was removed and 9.9843 g (0.0838 moles) of phenyl isocyanate was added dropwise. An immediate evolution of gas began, which subsided after approximately fifteen minutes. After thirty minutes at room temperature, the reaction mixture was warmed to 50° C. for an additional hour. The entire solution was then poured into 100 ml of 10% aqueous sodium hydroxide solution and this was extracted with methylene chloride. The organic layer was dried over anhydrous sodium carbonate and filtered. Due to the instability of this sulfilimine, 0.33 g of succnimide was added and the solution was then concentrated to 150 ml and refluxed for sixteen hours. The solution was then washed with 10% aqueous sodium hydroxide, dried over anhydrous magnesium sulfate and filtered. To this was added dodecane as an internal standard and the solution was analyzed by gas chromatography. In this manner, there was obtained 1.751 g (22.4%) of aniline and 7.166 g (55.8%) of 2-methylthiomethylaniline. Other examples of the preparation and rearrangement of unstable N-aryl-S,S-dimethylsulfilimines were performed and these results can be found in Table II. at 0° C. rose to 15° C The ice bath was removed which subsided after approximately fifteen minutes After thirty minutes at room temperature this was extracted with methylene chloride The organic layer was dried over anhydrous sodium carbonate filtered Due to the instability of this sulfilimine, 0.33 g of succnimide was added the solution was then concentrated to 150 ml refluxed for sixteen hours The solution was then washed with 10% aqueous sodium hydroxide dried over anhydrous magnesium sulfate filtered To this was added dodecane as an internal standard

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Iron powder (60 g, 1.0 g-atom) was added slowly through a solid addition funnel to a solution of 53.5 g (0.29 mol) of o-methylthiomethylnitrobenzene in 210 ml of glacial acetic acid and 600 ml of absolute ethanol under reflux over a period of 45 minutes. The mixture was then refluxed for 3 hours. The iron powder was filtered off and the filtrate was diluted with 800 ml of water. The aqueous mixture was extracted twice with 200 ml ethyl acetate and twice with 200 ml ether. The combined organic extracts were washed with water, dried and concentrated to yield 48 g (75% pure) of orange oil. under reflux over a period of 45 minutes The mixture was then refluxed for 3 hours The iron powder was filtered off the filtrate was diluted with 800 ml of water The aqueous mixture was extracted twice with 200 ml ethyl acetate and twice with 200 ml ether The combined organic extracts were washed with water dried concentrated to yield 48 g (75% pure) of orange oil

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Iron powder (60 g, 1.0 g-atom) was added slowly through a solid addition funnel to a solution of 53.5 g (0.29 mol) of o-methylthiomethylnitrobenzene in 210 ml of glacial acetic acid and 600 ml of absolute ethanol under reflux over a period of 45 minutes. The mixture was then refluxed for 3 hours. The iron powder was filtered off and the filtrate was diluted with 800 ml of water. The aqueous mixture was extracted twice with 200 ml ethyl acetate and twice with 200 ml ether. The combined organic extracts were washed with water, dried and concentrated to yield 48 g (75% pure) of orange oil. under reflux over a period of 45 minutes The mixture was then refluxed for 3 hours The iron powder was filtered off the filtrate was diluted with 800 ml of water The aqueous mixture was extracted twice with 200 ml ethyl acetate and twice with 200 ml ether The combined organic extracts were washed with water dried concentrated to yield 48 g (75% pure) of orange oil

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Through this general procedure p-anisidine could be converted into 4-methoxy-2-(methylthiomethyl)aniline in 62 percent yield. The procedure is quite general. For a series of anilines (toluidine, aniline, p-chloroaniline, 4-nitroaniline, and p-ethoxycarbonylaniline) reaction of the aniline with the chlorine:sulfur compound complex chlorodimethylsulfonium chloride through the azasulfonium halide salt gave the corresponding 2-(methylthiomethyl)anilines in 54, 67, 45, 31 and 35% yields, respectively. The reaction is not restricted to chlorodialkylsulfonium chlorides. For example, when bromodimethylsulfonium bromide was used with aniline to form the azasulfonium bromide salt of aniline a 69 percent yield of 2-(methylthiomethyl)aniline was obtained. Treatment of aniline with halotetramethylenesulfonium halide (chloride or bromide) to form the azasulfonium salt followed by base treatment, gave 2-(2-tetrahydrothienyl)aniline in 20 percent yield. The use of β-keto sulfides and β-carboalkoxysulfides in this reaction provided a simple route to indoles and 2-oxindoles. Treatment of p-anisidine with chlorine:sulfur compound complex ##EQU11## to form the azasulfonium halide salt of the anisidine, followed by triethylamine, according to the above general procedure, gave 2-methyl-5-methoxy-3-methylthioindole in 38 percent yield. The reaction is not restricted to p-anisidine. With aniline, p-chloroaniline, and benzocaine, we obtained the corresponding unsubstituted, 5-chloro- and 5-ethoxycarbonyl-2-methyl-3-methylthioindoles in 68, 45 and 33 percent yields, respectively. Raney nickel desulfurization of the 3-methylthio compound gave 5-methoxy-2-methylindole in 72 percent yield. yields

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Through this general procedure p-anisidine could be converted into 4-methoxy-2-(methylthiomethyl)aniline in 62 percent yield. The procedure is quite general. For a series of anilines (toluidine, aniline, p-chloroaniline, 4-nitroaniline, and p-ethoxycarbonylaniline) reaction of the aniline with the chlorine:sulfur compound complex chlorodimethylsulfonium chloride through the azasulfonium halide salt gave the corresponding 2-(methylthiomethyl)anilines in 54, 67, 45, 31 and 35% yields, respectively. The reaction is not restricted to chlorodialkylsulfonium chlorides. For example, when bromodimethylsulfonium bromide was used with aniline to form the azasulfonium bromide salt of aniline a 69 percent yield of 2-(methylthiomethyl)aniline was obtained. Treatment of aniline with halotetramethylenesulfonium halide (chloride or bromide) to form the azasulfonium salt followed by base treatment, gave 2-(2-tetrahydrothienyl)aniline in 20 percent yield. The use of β-keto sulfides and β-carboalkoxysulfides in the reaction provided a simple route to indoles and 2-oxindoles. Treatment of p-anisidine with chlorine:sulfur compound complex ##EQU8## to form the azasulfonium halide salt of the anisidine, followed by triethylamine, according to the above general procedure, gave 2-methyl-5-methoxy-3-methylthioindole in 38 percent yield. The reaction is not restricted to p-anisidine. With aniline, p-chloroaniline, and benzocaine, we obtained the corresponding unsubstituted, 5-chloro- and 5-ethoxycarbonyl-2-methyl-3-methylthioindoles in 68, 45 and 33 percent yields, respectively. Raney nickel desulfurization of the 3-methylthio compound gave 5-methoxy-2-methylindole in 72 percent yield. yields

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 7.60 g (0.0974 moles) of dry dimethyl sulfoxide in 70 ml of dry acetic acid at 0° C. and under a nitrogen atmosphere, was slowly added 9.76 g (0.0959 moles) of 100% sulfuric acid. The temperature rose to 15° C. The ice bath was removed and 9.9843 g (0.0838 moles) of phenyl isocyanate was added dropwise. An immediate evolution of gas began, which subsided after approximately fifteen minutes. After thirty minutes at room temperature, the reaction mixture was warmed to 50° C. for an additional hour. The entire solution was then poured into 100 ml of 10% aqueous sodium hydroxide solution and this was extracted with methylene chloride. The organic layer was dried over anhydrous sodium carbonate and filtered. Due to the instability of this sulfilimine, 0.33 g of succnimide was added and the solution was then concentrated to 150 ml and refluxed for sixteen hours. The solution was then washed with 10% aqueous sodium hydroxide, dried over anhydrous magnesium sulfate and filtered. To this was added dodecane as an internal standard and the solution was analyzed by gas chromatography. In this manner, there was obtained 1.751 g (22.4%) of aniline and 7.166 g (55.8%) of 2-methylthiomethylaniline. Other examples of the preparation and rearrangement of unstable N-aryl-S,S-dimethylsulfilimines were performed and these results can be found in Table II. at 0° C. rose to 15° C The ice bath was removed which subsided after approximately fifteen minutes After thirty minutes at room temperature this was extracted with methylene chloride The organic layer was dried over anhydrous sodium carbonate filtered Due to the instability of this sulfilimine, 0.33 g of succnimide was added the solution was then concentrated to 150 ml refluxed for sixteen hours The solution was then washed with 10% aqueous sodium hydroxide dried over anhydrous magnesium sulfate filtered To this was added dodecane as an internal standard