2,5-dihydrothiophene 1,1-dioxide

Conditions: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 500 ml round-bottom flask equipped with condenser, thermometer and a stirrer were introduced 118 g. (1.0 mole) of 2,5-dihydrothiophene 1,1-dioxide, 200 ml. of 70% by weight aqueous ethanol and 37 g (0.5 mole) of 1,2-diaminopropane and 10 ml. of a 0.1 N sodium hydroxide solution. The reaction mixture was heated at 85°C for 20 hours. The solvent was then removed under a reduced pressure. The product, N,N'-bis(1,1-dioxotetrahydro-3-thienyl)-1,2-diaminopropane was obtained as a viscous liquid. The infrared spectrum of this product was superimposable with that of Example 3. This product also evaluated in high resiliency, flexible polyurethane foam (see Example 19). To a 500 ml round-bottom flask equipped with condenser thermometer and a stirrer were introduced 118 g The solvent was then removed under a reduced pressure

Conditions: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 500 ml round-bottom flask equipped with condenser, thermometer and a stirrer were introduced 118 g. (1.0 mole) of 2,5-dihydrothiophene 1,1-dioxide, 200 ml. of 70% by weight aqueous ethanol and 37 g (0.5 mole) of 1,2-diaminopropane and 10 ml. of a 0.1 N sodium hydroxide solution. The reaction mixture was heated at 85°C for 20 hours. The solvent was then removed under a reduced pressure. The product, N,N'-bis(1,1-dioxotetrahydro-3-thienyl)-1,2-diaminopropane was obtained as a viscous liquid. The infrared spectrum of this product was superimposable with that of Example 3. This product also evaluated in high resiliency, flexible polyurethane foam (see Example 19). To a 500 ml round-bottom flask equipped with condenser thermometer and a stirrer were introduced 118 g The solvent was then removed under a reduced pressure

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

Procedure: To a mixture of 0.5 mole of butadiene sulfone (commercially available from Aldrich, Milwaukee, Wis.) and 0.55 mole of 2-naphthylhydrazine is added 0.005 mole 40% aqueous potassium hydroxide solution. The mixture is kept for 16 hours at 60° C. N-(2-Naphthyl)-N-sulfolan-3-ylhydrazine is isolated and purified.

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

Procedure: To a mixture of 0.5 mole of butadiene sulfone (commercially available from Aldrich, Milwaukee, Wis.) and 0.55 mole of 2-naphthylhydrazine is added 0.005 mole 40% aqueous potassium hydroxide solution. The mixture is kept for 16 hours at 60° C. N-(2-Naphthyl)-N-sulfolan-3-ylhydrazine is isolated and purified.

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Butadiene sulfone (0.5 mol, obtained from Aldrich chemicals, Milwaukee, Wis.) and phenyl hydrazine (0.55 mol, 1.1 equiv. obtained from Aldrich Chemicals, Milwaukee, Wis.) were stirred for 5-10 minutes, and then 40% aqueous KOH solution (0.005 mol, 0.01 equiv. obtained from Aldrich Chemicals, Milwaukee, Wis.)) was added. The mixture was heated at 60° C. for 2 hours whereupon a solid separated. After 10 hours at room temperature, the solid was filtered, washed with excess of water and recrystallized from methanol to give the product as white crystals; yield 53%; mp 119.9-121.5° C.; 1H-NMR and 13C-NMR spectra in CDCl3 were in full agreement with the structure. separated the solid was filtered washed with excess of water recrystallized from methanol

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

Procedure: About 20 mmol (2.36 g) of 3-sulfolene (MW=118) and 42 mmol (4 g) of pyrrole-2-aldehyde (MW=95) were dissolved in an alkaline solution of 1.5 g of NaOH and 1.9 g of NaOCH3 in 70 ml of methanol. The mixture was stirred at room temperature for 5 days. The black-brown reaction mixture was concentrated. The black-brown reaction mixture was concentrated

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

Procedure: About 20 mmol (2.36 g) of 3-sulfolene (MW=118) and 42 mmol (4 g) of pyrrole-2-aldehyde (MW=95) were dissolved in an alkaline solution of 1.5 g of NaOH and 1.9 g of NaOCH3 in 70 ml of methanol. The mixture was stirred at room temperature for 5 days. The black-brown reaction mixture was concentrated. The black-brown reaction mixture was concentrated

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

Procedure: About 80 mmol (9.4 g) of 3-sulfolene (MW=118) and 170 mmol (19.04 g) (15.9 ml) of thiophene-2-aldehyde (MW=112, d=1.2 g/cm3) were added to an alkaline solution of 1 g of NaOH in 200 ml of ethanol. The mixture was stirred at room temperature for 3 days. A yellow precipitate formed which was filtered off with suction and washed thoroughly with ethanol and water. A yellow precipitate formed which was filtered off with suction washed thoroughly with ethanol and water

Conditions: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 500 ml round-bottom flask equipped with condenser, thermometer and a stirrer were introduced 118 g. (1.0 mole) of 2,5-dihydrothiophene 1,1-dioxide, 200 ml. of 70% by weight aqueous ethanol and 37 g (0.5 mole) of 1,2-diaminopropane and 10 ml. of a 0.1 N sodium hydroxide solution. The reaction mixture was heated at 85°C for 20 hours. The solvent was then removed under a reduced pressure. The product, N,N'-bis(1,1-dioxotetrahydro-3-thienyl)-1,2-diaminopropane was obtained as a viscous liquid. The infrared spectrum of this product was superimposable with that of Example 3. This product also evaluated in high resiliency, flexible polyurethane foam (see Example 19). To a 500 ml round-bottom flask equipped with condenser thermometer and a stirrer were introduced 118 g The solvent was then removed under a reduced pressure

Conditions: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 500 ml round-bottom flask equipped with condenser, thermometer and a stirrer were introduced 118 g. (1.0 mole) of 2,5-dihydrothiophene 1,1-dioxide, 200 ml. of 70% by weight aqueous ethanol and 37 g (0.5 mole) of 1,2-diaminopropane and 10 ml. of a 0.1 N sodium hydroxide solution. The reaction mixture was heated at 85°C for 20 hours. The solvent was then removed under a reduced pressure. The product, N,N'-bis(1,1-dioxotetrahydro-3-thienyl)-1,2-diaminopropane was obtained as a viscous liquid. The infrared spectrum of this product was superimposable with that of Example 3. This product also evaluated in high resiliency, flexible polyurethane foam (see Example 19). To a 500 ml round-bottom flask equipped with condenser thermometer and a stirrer were introduced 118 g The solvent was then removed under a reduced pressure

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

Procedure: Except that 0.13 g (1.0 mmol) of iron (II) chloride was used in manufacturing of sulfolene instead of 0.186 g (1.0 mmol) of ferrocene, a 3-sulfolene aqueous solution was prepared in the same manner as in Example 1. The amount of 3-sulfolene in the obtained aqueous solution was 103 g (0.85 mol) and the yield from 1,3-butadiene was 85%. An amount of 0.01 g of polymers was found on the filter paper after filtering the 3-sulfolene aqueous solution. Next, the obtained 3-sulfolene aqueous solution was hydrogenated in the same manner as in Example 1. The hydrogen pressure did not stop lowering in 240 minutes of the reaction time. At that time, the reaction rate was 57%. Table 1 shows the measurements of the amount of generated polymers and the reaction time of hydrogenation.

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

Procedure: Except that 0.045 g (1.0 mmol) of dimethylamine was used instead of 0.186 g (1.0 mmol) of ferrocene used in manufacturing of sulfolene, a 3-sulfolene aqueous solution was prepared in the same manner as in Example 1. The amount of 3-sulfolene in the obtained aqueous solution was 100 g (0.85 mol) and the yield from 1,3-butadiene was 85%. An amount of 0.1 g of polymers was found on the filter paper after filtering the 3-sulfolene aqueous solution. Next, the obtained 3-sulfolene aqueous solution was hydrogenated in the same manner as in Example 1. The hydrogen pressure did not stop lowering in 340 minutes of the reaction time. At that time, the reaction rate was 75%. Table 1 shows the measurements of the amount of generated polymers and the reaction time of hydrogenation.