4,4-dimethylimidazolidine-2-thione

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: 4,4-Dimethylimidazoline-2-thione was prepared by adding a solution of 50 g. of 1,2-diamino-2-methylpropane in 35 ml. of methylene chloride dropwise with stirring to a solution of 43 g. of carbon disulfide in 200 ml. of methylene chloride during about 3 hrs. The product formed as a white precipitate immediately on mixing of the two solutions. The solvent was removed by distillation in vacuo and replaced with water, and the mixture was refluxed for 7 hrs. It was concentrated to one-half the original volume, clarified by filtration while hot, and the product allowed to crystallize from the filtrate, yield 60.6 g., m.p. 114°-115°. A portion of this material, 43.9 g., (0.337 mole), was treated with 47.9 g. (0.337 mole) of methyl iodide in 400 ml. of ethanol. The methyl iodide was added by dropwise addition. The mixture was then concentrated in vacuo to an oil which was mixed with i-Pr2O to induce crystallization resulting in the formation of a light yellow solid, yield 90.7 g. (99%), of 2-methylthio-4,4-dimethyl-2-imidazoline hydroiodide. A portion of this material, 27.2 g. (0.1 mole), and 14.1 g. (0.1 mole) of p-chlorobenzylamine were dissolved in 100 ml. of abs. EtOH and added to a solution of 9.0 g. (0.4 mole) of sodium in 400 ml. of abs. EtOH at the reflux temperature. The solution was stirred for 10 min. and 14.2 g. (0.1 mole) of ethyl oximinocyanoacetate was added in portions during a period of about 5 min. The reaction solution became clear and bright yellow in color. It was refluxed for 41/2 hrs. and then concentrated in vacuo to yield an oily solid. The latter was dissolved in water and treated with acetic acid resulting in formation of the desired product as a red precipitate which was collected and air dried, m.p. 214°-215°, yield 16.7 g. (50%). by adding a solution of 50 g The product formed as a white precipitate immediately on mixing of the two solutions The solvent was removed by distillation in vacuo the mixture was refluxed for 7 hrs It was concentrated to one-half the original volume clarified by filtration while hot, and the product to crystallize from the filtrate, yield 60.6 g , (0.337 mole), was treated with 47.9 g The mixture was then concentrated in vacuo to an oil which was mixed with i-Pr2O crystallization resulting in the formation of a light yellow solid, yield 90.7 g It was refluxed for 41/2 hrs and then concentrated in vacuo to yield an oily solid was collected air dried

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

実験手順: 3.1 g of 2-bromo-4'-chloro-3'-sulfamoylacetophenone and 1.3 g of 4,4-dimethyl-2-imidazolidine-thione were reacted as described in Example 12 in 15 ml of methanol, the reaction mixture was precipitated with 70 ml of diethyl ether and the oily precipitate was crystallized with ethyl acetate at 40° to 50° C. Colorless, crystalline solid body: melting point: 164° C (decomposition). the reaction mixture was precipitated with 70 ml of diethyl ether the oily precipitate was crystallized with ethyl acetate at 40° to 50° C

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

実験手順: 4,4-Dimethylimidazoline-2-thione was prepared by adding a solution of 50 g. of 1,2-diamino-2-methylpropane in 35 ml. of methylene chloride dropwise with stirring to a solution of 43 g. of carbon disulfide in 200 ml. of methylene chloride during about 3 hrs. The product formed as a white precipitate immediately on mixing of the two solutions. The solvent was removed by distillation in vacuo and replaced with water, and the mixture was refluxed for 7 hrs. It was concentrated to one-half the original volume, clarified by filtration while hot, and the product allowed to crystallize from the filtrate, yield 60.6 g., m.p. 114°-115°. A portion of this material, 43.9 g., (0.337 mole), was treated with 47.9 g. (0.337 mole) of methyl iodide in 400 ml. of ethanol. The methyl iodide was added by dropwise addition. The mixture was then concentrated in vacuo to an oil which was mixed with i-Pr2O to induce crystallization resulting in the formation of a light yellow solid, yield 90.7 g. (99%), of 2-methylthio-4,4-dimethyl-2-imidazoline hydroiodide. A portion of this material, 27.2 g. (0.1 mole), and 14.1 g. (0.1 mole) of p-chlorobenzylamine were dissolved in 100 ml. of abs. EtOH and added to a solution of 9.0 g. (0.4 mole) of sodium in 400 ml. of abs. EtOH at the reflux temperature. The solution was stirred for 10 min. and 14.2 g. (0.1 mole) of ethyl oximinocyanoacetate was added in portions during a period of about 5 min. The reaction solution became clear and bright yellow in color. It was refluxed for 41/2 hrs. and then concentrated in vacuo to yield an oily solid. The latter was dissolved in water and treated with acetic acid resulting in formation of the desired product as a red precipitate which was collected and air dried, m.p. 214°-215°, yield 16.7 g. (50%). by adding a solution of 50 g The product formed as a white precipitate immediately on mixing of the two solutions The solvent was removed by distillation in vacuo the mixture was refluxed for 7 hrs It was concentrated to one-half the original volume clarified by filtration while hot, and the product to crystallize from the filtrate, yield 60.6 g , (0.337 mole), was treated with 47.9 g The mixture was then concentrated in vacuo to an oil which was mixed with i-Pr2O crystallization resulting in the formation of a light yellow solid, yield 90.7 g It was refluxed for 41/2 hrs and then concentrated in vacuo to yield an oily solid was collected air dried

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: 3.1 g of 2-bromo-4'-chloro-3'-sulfamoylacetophenone and 1.3 g of 4,4-dimethyl-2-imidazolidine-thione were reacted as described in Example 12 in 15 ml of methanol, the reaction mixture was precipitated with 70 ml of diethyl ether and the oily precipitate was crystallized with ethyl acetate at 40° to 50° C. Colorless, crystalline solid body: melting point: 164° C. (decomposition). the reaction mixture was precipitated with 70 ml of diethyl ether the oily precipitate was crystallized with ethyl acetate at 40° to 50° C

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

実験手順: A suspension of 110 g (0.83 M) of 4,4-dimethyl-2-imidazolidinethione in 700 ml isopropanol was treated with 148 g (1.04 M) methyl iodide and stirred at room temperature under reflux for 1/2 hour. When all had dissolved, heated to gentle reflux for 1 hour. Cool, dilute to 2 liters with anhydrous ether, seed, and cool in ice. Filter and wash with dry ether. Yield of 4,4-dimethyl-2-(methylthio)imidazoline hydroiodide was 221 g, 98%, mp 93.5°-95° C. Pure material melts at 94.5°-95° C. under reflux for 1/2 hour When all had dissolved heated to gentle reflux for 1 hour Cool cool in ice Filter wash with dry ether

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

実験手順: A mixture of 39.0 g (0.3 M) 4,4-dimethylimidazolidine-2-thione, 44.2 g (0.3 M) 2,6-dimethylphenyl isocyanate and 100 ml dimethylformamide was refluxed with stirring for 24 hours. After cooling to room temperature, the solution was filtered from a small amount of insoluble solid and poured into 300 ml water with efficient stirring. The precipitated product was filtered, washed well with water, and dried in vacuo. Yield 62.6 g, mp 228°-231° C. Recrystallization from 600 ml of boiling methanol yielded 46 g of N-(2,6-dimethylphenyl)-4,4-dimethyl-2-thioxo-1-imidazolidinecarboxamide as white crystalline product, mp 241.5°-243° C. A small sample was recrystallized from benzene to give an analytical sample, mp 245.5°-246° C. was refluxed the solution was filtered from a small amount of insoluble solid poured into 300 ml water with efficient stirring The precipitated product was filtered washed well with water dried in vacuo Recrystallization from 600 ml of boiling methanol

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

実験手順: 4,4-Dimethylimidazoline-2-thione was prepared by adding a solution of 50 g. of 1,2-diamino-2-methylpropane in 35 ml. of methylene chloride dropwise with stirring to a solution of 43 g. of carbon disulfide in 200 ml. of methylene chloride during about 3 hrs. The product formed as a white precipitate immediately on mixing of the two solutions. The solvent was removed by distillation in vacuo and replaced with water, and the mixture was refluxed for 7 hrs. It was concentrated to one-half the original volume, clarified by filtration while hot, and the product allowed to crystallize from the filtrate, yield 60.6 g., m.p. 114°-115°. A portion of this material, 43.9 g., (0.337 mole), was treated with 47.9 g. (0.337 mole) of methyl iodide in 400 ml. of ethanol. The methyl iodide was added by dropwise addition. The mixture was then concentrated in vacuo to an oil which was mixed with i-Pr2O to induce crystallization resulting in the formation of a light yellow solid, yield 90.7 g. (99%), of 2-methylthio-4,4-dimethyl-2-imidazoline hydroiodide. A portion of this material, 27.2 g. (0.1 mole), and 14.1 g. (0.1 mole) of p-chlorobenzylamine were dissolved in 100 ml. of abs. EtOH and added to a solution of 9.0 g. (0.4 mole) of sodium in 400 ml. of abs. EtOH at the reflux temperature. The solution was stirred for 10 min. and 14.2 g. (0.1 mole) of ethyl oximinocyanoacetate was added in portions during a period of about 5 min. The reaction solution became clear and bright yellow in color. It was refluxed for 41/2 hrs. and then concentrated in vacuo to yield an oily solid. The latter was dissolved in water and treated with acetic acid resulting in formation of the desired product as a red precipitate which was collected and air dried, m.p. 214°-215°, yield 16.7 g. (50%). by adding a solution of 50 g The product formed as a white precipitate immediately on mixing of the two solutions The solvent was removed by distillation in vacuo the mixture was refluxed for 7 hrs It was concentrated to one-half the original volume clarified by filtration while hot, and the product to crystallize from the filtrate, yield 60.6 g , (0.337 mole), was treated with 47.9 g The mixture was then concentrated in vacuo to an oil which was mixed with i-Pr2O crystallization resulting in the formation of a light yellow solid, yield 90.7 g It was refluxed for 41/2 hrs and then concentrated in vacuo to yield an oily solid was collected air dried

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

実験手順: 3.1 g of 2-bromo-4'-chloro-3'-sulfamoylacetophenone and 1.3 g of 4,4-dimethyl-2-imidazolidine-thione were reacted as described in Example 12 in 15 ml of methanol, the reaction mixture was precipitated with 70 ml of diethyl ether and the oily precipitate was crystallized with ethyl acetate at 40° to 50° C. Colorless, crystalline solid body: melting point: 164° C (decomposition). the reaction mixture was precipitated with 70 ml of diethyl ether the oily precipitate was crystallized with ethyl acetate at 40° to 50° C

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

実験手順: 4,4-Dimethylimidazoline-2-thione was prepared by adding a solution of 50 g. of 1,2-diamino-2-methylpropane in 35 ml. of methylene chloride dropwise with stirring to a solution of 43 g. of carbon disulfide in 200 ml. of methylene chloride during about 3 hrs. The product formed as a white precipitate immediately on mixing of the two solutions. The solvent was removed by distillation in vacuo and replaced with water, and the mixture was refluxed for 7 hrs. It was concentrated to one-half the original volume, clarified by filtration while hot, and the product allowed to crystallize from the filtrate, yield 60.6 g., m.p. 114°-115°. A portion of this material, 43.9 g., (0.337 mole), was treated with 47.9 g. (0.337 mole) of methyl iodide in 400 ml. of ethanol. The methyl iodide was added by dropwise addition. The mixture was then concentrated in vacuo to an oil which was mixed with i-Pr2O to induce crystallization resulting in the formation of a light yellow solid, yield 90.7 g. (99%), of 2-methylthio-4,4-dimethyl-2-imidazoline hydroiodide. A portion of this material, 27.2 g. (0.1 mole), and 14.1 g. (0.1 mole) of p-chlorobenzylamine were dissolved in 100 ml. of abs. EtOH and added to a solution of 9.0 g. (0.4 mole) of sodium in 400 ml. of abs. EtOH at the reflux temperature. The solution was stirred for 10 min. and 14.2 g. (0.1 mole) of ethyl oximinocyanoacetate was added in portions during a period of about 5 min. The reaction solution became clear and bright yellow in color. It was refluxed for 41/2 hrs. and then concentrated in vacuo to yield an oily solid. The latter was dissolved in water and treated with acetic acid resulting in formation of the desired product as a red precipitate which was collected and air dried, m.p. 214°-215°, yield 16.7 g. (50%). by adding a solution of 50 g The product formed as a white precipitate immediately on mixing of the two solutions The solvent was removed by distillation in vacuo the mixture was refluxed for 7 hrs It was concentrated to one-half the original volume clarified by filtration while hot, and the product to crystallize from the filtrate, yield 60.6 g , (0.337 mole), was treated with 47.9 g The mixture was then concentrated in vacuo to an oil which was mixed with i-Pr2O crystallization resulting in the formation of a light yellow solid, yield 90.7 g It was refluxed for 41/2 hrs and then concentrated in vacuo to yield an oily solid was collected air dried