1-ethenylsulfonylethene

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:0.00; pressure:0.00; stir:

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

Conditions: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Aluminum chloride (310 g, 2.3 mol) is added to chlorobenzene (2.5 L) to give a cloudy green suspension. Vinyl sulfone (230 mL, 2.3 mol) is added via a funnel. 2,6-Difluoroaniline (250 mL, 2.3 mol) is added a via funnel. The light brown solution is heated to 110° C. Upon completion, the heat is removed and the black solution is self-cooled to 70° C. The reaction mixture is quenched in methylene chloride (4 L) and ice water (5 L). The aqueous phase is extracted with methylene chloride. The combined organic layers are concentrated and added branched octane (3 L), and then cooled to 0° C. for 30 minutes. The solids are filtered and washed with branched octane (2×500 mL). The crude black solids are dissolved into methylene chloride (3 L) and then loaded onto a SiO2 plug (1.8 kg). The column is eluted with dichloromethane (16 L) until clear. The methylene chloride solution is concentrated to give light brown solids (387 g or 68% yield). The solids are dissolved in hot ethyl acetate (3 L) followed by the addition of hexanes (900 mL). The black solution is self-cooled to room temperature overnight. The light amber crystal needles are filtered and washed with hexanes (4×250 mL). The solids are dried in vacuo at 50° C. overnight to give 314 g of the title compound (55% recystallized yield 1st crop). to give a cloudy green suspension Upon completion, the heat is removed the black solution is self-cooled to 70° C The reaction mixture is quenched in methylene chloride (4 L) The aqueous phase is extracted with methylene chloride The combined organic layers are concentrated added branched octane (3 L) cooled to 0° C. for 30 minutes The solids are filtered washed with branched octane (2×500 mL) The crude black solids are dissolved into methylene chloride (3 L) The column is eluted with dichloromethane (16 L) until clear The methylene chloride solution is concentrated to give light brown solids (387 g or 68% yield) The black solution is self-cooled to room temperature overnight The light amber crystal needles are filtered washed with hexanes (4×250 mL) The solids are dried in vacuo at 50° C. overnight

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

Procedure: The preparation of stabilizer compounds of formula S of the invention is illustrated by the following synthesis of Stabilizer S-3. ##STR16## A mixture of para-aminophenol (25 g, 229 mmol) and divinylsulfone (32.5 g, 275 mmol) was heated at reflux in ethanol (100 ml) for two days. The reaction mixture was cooled and poured into ice water (1 l). The mixture was made acidic with the addition of acetic acid and the resulting tan solid was isolated by filtration and washed with water. Recrystallization from methanol afforded the desired 4-(1',1'-dioxothiomorpholino)phenol as a light tan crystalline solid (35 g, 67%). Mp. 149-151° C. The preparation of stabilizer compounds of formula S of the invention is illustrated by the following synthesis of Stabilizer S-3 was heated The reaction mixture was cooled the resulting tan solid was isolated by filtration washed with water Recrystallization from methanol

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

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

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

Procedure: A suspension of 8.74 g of 4-aminophenol in 190 ml of ethanol is added dropwise at 50° to 11.34 g of divinyl sulfone, whereupon rinsing is carried out with 50 ml of ethanol and then the mixture is heated to boiling under reflux under argon for 3 hours. After cooling, the mixture is treated with 480 ml of water and stirred for 1 hour at 0°. The precipitated crystals are removed by filtration under suction, washed with 20 percent ethanol and water and dried. By recrystallization from dichloromethane/methanol/ether there is obtained 4-(p-hydroxyphenyl)-tetrahydro-4H-1,4-thiazine 1,1-dioxide of melting point 153°-155°. whereupon rinsing the mixture is heated under reflux under argon for 3 hours After cooling the mixture is treated with 480 ml of water The precipitated crystals are removed by filtration under suction washed with 20 percent ethanol and water dried By recrystallization from dichloromethane/methanol/ether there

Conditions: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Aluminum chloride (310 g, 2.3 mol) is added to chlorobenzene (2.5 L) to give a cloudy green suspension. Vinyl sulfone (230 mL, 2.3 mol) is added via funnel, followed by 2,6-difluoroaniline (250 mL, 2.3 mol). The light brown solution is heated to 110° C. Upon completion of the reaction, the heat is removed and the black solution is self-cooled to 70° C. The reaction mixture is then quenched in methylene chloride (4 L) and ice water (5 L), the aqueous phase is extracted with methylene chloride (3 L, 2 L, 2 L, 2 L) and the combined organic layers are concentrated, rediluted with branched octane (3 L), and then cooled to 0° C. for 30 minutes. The solids are filtered and washed with branched octane (2×500 mL) and are then dissolved in methylene chloride (3 L) and loaded onto a silica gel plug (1.8 kg). The column is eluted with dichloromethane (16 L) until clear. The methylene chloride solution is concentrated, and the solids are dissolved in hot ethyl acetate (3 L) followed by the addition of hexanes (900 mL). The black solution is self-cooled to room temperature overnight, and the resulting light amber crystal needles are filtered and washed with hexanes (4×250 mL). The solids are dried under reduced pressure at 50° C. overnight to give the title compound, 1H NMR (CDCl3) δ 7.08 (m, 1H), 6.91 (m, 2H), 3.67 (m, 4H), 3.18 (m, 4H). to give a cloudy green suspension Upon completion of the reaction the heat is removed the black solution is self-cooled to 70° C The reaction mixture is then quenched in methylene chloride (4 L) ice water (5 L), the aqueous phase is extracted with methylene chloride (3 L, 2 L, 2 L, 2 L) the combined organic layers are concentrated rediluted with branched octane (3 L) cooled to 0° C. for 30 minutes The solids are filtered washed with branched octane (2×500 mL) are then dissolved in methylene chloride (3 L) The column is eluted with dichloromethane (16 L) until clear The methylene chloride solution is concentrated the solids are dissolved in hot ethyl acetate (3 L) followed by the addition of hexanes (900 mL) The black solution is self-cooled to room temperature overnight the resulting light amber crystal needles are filtered washed with hexanes (4×250 mL) The solids are dried under reduced pressure at 50° C. overnight