prop-2-enyl prop-2-enoate

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

Procedure: A 7.57-liter stirred autoclave was charged under nitrogen with 4000 ml of methylene chloride, 400 grams of ethyl acrylate, 20 grams of maleic anhydride, 1.2 grams of allyl acrylate, and 1.0 gram of azobis(isobutyronitrile). It was then sealed, charged with 300 grams of boron trifluoride, and pressured to 21 kg/sq cm with ethylene. The subsequent copolymerization at 25° C was continued until pressure measurement indicated that ethylene uptake had ceased (about two hours later). The reaction was quenched by addition of one liter of diethyl ether. Volatiles were removed by steam-stripping in a well-ventilated hood. The terpolymer thereby obtained was dissolved in acetone, precipitated in water in a blender, and oven-dried. Yield: 415 grams. It was then sealed The subsequent copolymerization at 25° C about two hours The reaction was quenched by addition of one liter of diethyl ether Volatiles were removed by steam-stripping in a well-ventilated hood The terpolymer thereby obtained precipitated in water in a blender oven-dried

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a three-necked flask equipped as in Example 1 there was added 260 grams allylacrylate (2.32 moles), 0.5 grams catalyst prepared in accordance with U.S. Pat. No. 3,814,730 (2.6 weight percent Pt) and 1.04 grams phenothiazine. The mixture was heated with stirring to 65° C. and, using the vent of the condenser, purged with nitrogen. The heat source was then turned off and 237 grams (2.32 moles) CH3SiHCl2 was added dropwise, the temperature of the reaction mass being maintained at about 70° C. Upon completion of the addition of methyldichlorosilane the crude product was cooled to room temperature. One gram phenothiazine and 0.05 gram triphenyl phosphine were added to the product prior to distillation. Acryloxypropylmethyldichlorosilane (360 grams, 68% yield) was distilled at 109°-112° C./10 mm Hg. To a three-necked flask equipped as in Example 1 there prepared in accordance with U.S The mixture was heated purged with nitrogen the temperature of the reaction mass being maintained at about 70° C was cooled to room temperature to distillation

Conditions: temp:3.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: An ice-cooled (3° C.) stirred solution of N-boc-glycine, allyl ester (6.46 g, 30 mmol) in anhydrous tetrahydrofuran (60 mL) under nitrogen was treated with 1N lithium bis(trimethylsilylamide)/tetrahydrofuran (33 mL, 33 mmol) at a rate to keep pot temperature below 10° C., then stirred at 3° C. for 15 min and cooled (−40° C.). A solution of allyl acrylate (4.45 mL, 35 mmol) in anhydrous tetrahydrofuran (25 mL) was added dropwise, and the mixture allowed to reach room temperature, stirred 1 h, and refluxed for 2 h. The mixture was cooled to room temperature, quenched with glacial acetic acid (2.5 mL), and concentrated. The residual oil was dissolved in methylene chloride (300 mL) and the solution washed with water and saturated sodium bicarbonate (150 mL each), dried (Na2SO4), and concentrated. The residue was dissolved in minimum methylene chloride and loaded onto a silica gel column (350 mL volume) and eluted with 55:30:15 heptane/methylene chloride/ethyl acetate to afford 3-allyl 1-tert-butyl 4-oxopyrrolidine-1,3-dicarboxylate (5.07 g, 63%) as a colorless oil. NMR (CDCl3): δ 5.85-6.00 (m, 1 H), 5.20-5.40 (m, 2 H), 4.60-4.75 (m, 2 H), 4.20 (m, 1 H), 3.95-4.10 (m, 1 H), 3.87 (d J=6.5 Hz, 1 H), 3.62 (t, J=8 Hz, 1 H), 1.48 (s, 9 H). MS (m+1): 270.4; MS (m−bu+1): 214.2. temperature below 10° C. cooled (−40° C.) to reach room temperature stirred 1 h refluxed for 2 h The mixture was cooled to room temperature quenched with glacial acetic acid (2.5 mL) concentrated The residual oil was dissolved in methylene chloride (300 mL) the solution washed with water and saturated sodium bicarbonate (150 mL each) dried (Na2SO4) concentrated The residue was dissolved in minimum methylene chloride eluted with 55:30:15 heptane/methylene chloride/ethyl acetate

Conditions: temp:3.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: An ice-cooled (3° C.) stirred solution of N-boc-glycine, allyl ester (6.46 g, 30 mmol) in anhydrous tetrahydrofuran (60 mL) under nitrogen was treated with 1N lithium bis(trimethylsilylamide)/tetrahydrofuran (33 mL, 33 mmol) at a rate to keep pot temperature below 10° C., then stirred at 3° C. for 15 min and cooled (−40° C.). A solution of allyl acrylate (4.45 mL, 35 mmol) in anhydrous tetrahydrofuran (25 mL) was added dropwise, and the mixture allowed to reach room temperature, stirred 1 h, and refluxed for 2 h. The mixture was cooled to room temperature, quenched with glacial acetic acid (2.5 mL), and concentrated. The residual oil was dissolved in methylene chloride (300 mL) and the solution washed with water and saturated sodium bicarbonate (150 mL each), dried (Na2SO4), and concentrated. The residue was dissolved in minimum methylene chloride and loaded onto a silica gel column (350 mL volume) and eluted with 55:30:15 heptane/methylene chloride/ethyl acetate to afford 3-allyl 1-tert-butyl 4-oxopyrrolidine-1,3-dicarboxylate (5.07 g, 63%) as a colorless oil. NMR (CDCl3): δ 5.85-6.00 (m, 1 H), 5.20-5.40 (m, 2 H), 4.60-4.75 (m, 2 H), 4.20 (m, 1 H), 3.95-4.10 (m, 1 H), 3.87 (d J=6.5 Hz, 1 H), 3.62 (t, J=8 Hz, 1 H), 1.48 (s, 9 H). MS (m+1): 270.4; MS (m−bu+1): 214.2. temperature below 10° C. cooled (−40° C.) to reach room temperature stirred 1 h refluxed for 2 h The mixture was cooled to room temperature quenched with glacial acetic acid (2.5 mL) concentrated The residual oil was dissolved in methylene chloride (300 mL) the solution washed with water and saturated sodium bicarbonate (150 mL each) dried (Na2SO4) concentrated The residue was dissolved in minimum methylene chloride eluted with 55:30:15 heptane/methylene chloride/ethyl acetate

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

Procedure: A 7.57-liter stirred autoclave was charged under nitrogen with 4000 ml of methylene chloride, 400 grams of ethyl acrylate, 20 grams of maleic anhydride, 1.2 grams of allyl acrylate, and 1.0 gram of azobis(isobutyronitrile). It was then sealed, charged with 300 grams of boron trifluoride, and pressured to 21 kg/sq cm with ethylene. The subsequent copolymerization at 25° C was continued until pressure measurement indicated that ethylene uptake had ceased (about two hours later). The reaction was quenched by addition of one liter of diethyl ether. Volatiles were removed by steam-stripping in a well-ventilated hood. The terpolymer thereby obtained was dissolved in acetone, precipitated in water in a blender, and oven-dried. Yield: 415 grams. It was then sealed The subsequent copolymerization at 25° C about two hours The reaction was quenched by addition of one liter of diethyl ether Volatiles were removed by steam-stripping in a well-ventilated hood The terpolymer thereby obtained precipitated in water in a blender oven-dried

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

Procedure: A 7.57-liter stirred autoclave was charged under nitrogen with 4000 ml of methylene chloride, 400 grams of ethyl acrylate, 20 grams of maleic anhydride, 1.2 grams of allyl acrylate, and 1.0 gram of azobis(isobutyronitrile). It was then sealed, charged with 300 grams of boron trifluoride, and pressured to 21 kg/sq cm with ethylene. The subsequent copolymerization at 25° C was continued until pressure measurement indicated that ethylene uptake had ceased (about two hours later). The reaction was quenched by addition of one liter of diethyl ether. Volatiles were removed by steam-stripping in a well-ventilated hood. The terpolymer thereby obtained was dissolved in acetone, precipitated in water in a blender, and oven-dried. Yield: 415 grams. It was then sealed The subsequent copolymerization at 25° C about two hours The reaction was quenched by addition of one liter of diethyl ether Volatiles were removed by steam-stripping in a well-ventilated hood The terpolymer thereby obtained precipitated in water in a blender oven-dried

Conditions: temp:3.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: An ice-cooled (3° C.) stirred solution of N-boc-glycine, allyl ester (6.46 g, 30 mmol) in anhydrous tetrahydrofuran (60 mL) under nitrogen was treated with 1N lithium bis(trimethylsilylamide)/tetrahydrofuran (33 mL, 33 mmol) at a rate to keep pot temperature below 10° C., then stirred at 3° C. for 15 min and cooled (−40° C.). A solution of allyl acrylate (4.45 mL, 35 mmol) in anhydrous tetrahydrofuran (25 mL) was added dropwise, and the mixture allowed to reach room temperature, stirred 1 h, and refluxed for 2 h. The mixture was cooled to room temperature, quenched with glacial acetic acid (2.5 mL), and concentrated. The residual oil was dissolved in methylene chloride (300 mL) and the solution washed with water and saturated sodium bicarbonate (150 mL each), dried (Na2SO4), and concentrated. The residue was dissolved in minimum methylene chloride and loaded onto a silica gel column (350 mL volume) and eluted with 55:30:15 heptane/methylene chloride/ethyl acetate to afford 3-allyl 1-tert-butyl 4-oxopyrrolidine-1,3-dicarboxylate (5.07 g, 63%) as a colorless oil. NMR (CDCl3): δ 5.85-6.00 (m, 1 H), 5.20-5.40 (m, 2 H), 4.60-4.75 (m, 2 H), 4.20 (m, 1 H), 3.95-4.10 (m, 1 H), 3.87 (d, J=6.5 Hz, 1 H), 3.62 (t, J=8 Hz, 1 H), 1.48 (s, 9 H). MS (m+1): 270.4; MS (m−bu+1): 214.2. temperature below 10° C. cooled (−40° C.) to reach room temperature stirred 1 h refluxed for 2 h The mixture was cooled to room temperature quenched with glacial acetic acid (2.5 mL) concentrated The residual oil was dissolved in methylene chloride (300 mL) the solution washed with water and saturated sodium bicarbonate (150 mL each) dried (Na2SO4) concentrated The residue was dissolved in minimum methylene chloride eluted with 55:30:15 heptane/methylene chloride/ethyl acetate

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

Procedure: The procedure of D(1) above, was repeated except that 1.2 grams of ethylene diacrylate were used in place of the allyl acrylate. Yield: 479 grams. The branched tetrapolymer obtained had about 50 mole percent of ethylene units. The polymer chain consisted principally of units -(E)-(B')-, where E is ethylene and B' is randomly selected from ethyl acrylate, ethylene diacrylate, and maleic anhydride (3.8 weight percent). The branched tetrapolymer obtained

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

Procedure: A 7.57-liter stirred autoclave was charged under nitrogen with 4000 ml. of methylene chloride, 400 grams of ethyl acrylate, 20 grams of maleic anhydride, 1.2 grams of allyl acrylate, and 1.0 gram of azobis(isobutyronitrile). It was then sealed, charged with 300 grams of boron trifluoride, and pressured to 21 kg./sq. cm. with ethylene. The subsequent copolymerization at 25° C. was continued until pressure measurement indicated that ethylene uptake had ceased (about two hours later). The reaction was quenched by addition of one liter of diethyl ether. Volatiles were removed by steam-stripping in a well-ventilated hood. The terpolymer thereby obtained was dissolved in acetone, precipitated in water in a blender, and oven-dried. Yield: 415 grams. was charged under nitrogen with 4000 ml It was then sealed The subsequent copolymerization at 25° C. about two hours The reaction was quenched by addition of one liter of diethyl ether Volatiles were removed by steam-stripping in a well-ventilated hood The terpolymer thereby obtained precipitated in water in a blender oven-dried

Conditions: temp:3.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: An ice-cooled (3° C.) stirred solution of N-boc-glycine, allyl ester (6.46 g, 30 mmol) in anhydrous tetrahydrofuran (60 mL) under nitrogen was treated with 1N lithium bis(trimethylsilylamide)/tetrahydrofuran (33 mL, 33 mmol) at a rate to keep pot temperature below 10° C., then stirred at 3° C. for 15 min and cooled (−40° C.). A solution of allyl acrylate (4.45 mL, 35 mmol) in anhydrous tetrahydrofuran (25 mL) was added dropwise, and the mixture allowed to reach room temperature, stirred 1 h, and refluxed for 2 h. The mixture was cooled to room temperature, quenched with glacial acetic acid (2.5 mL), and concentrated. The residual oil was dissolved in methylene chloride (300 mL) and the solution washed with water and saturated sodium bicarbonate (150 mL each), dried (Na2SO4), and concentrated. The residue was dissolved in minimum methylene chloride and loaded onto a silica gel column (350 mL volume) and eluted with 55:30:15 heptane/methylene chloride/ethyl acetate to afford 3-allyl 1-tert-butyl 4-oxopyrrolidine-1,3-dicarboxylate (5.07 g, 63%) as a colorless oil. NMR (CDCl3): δ 5.85-6.00 (m, 1 H), 5.20-5.40 (m, 2 H), 4.60-4.75 (m, 2 H), 4.20 (m, 1 H), 3.95-4.10 (m, 1 H), 3.87 (d, J=6.5 Hz, 1 H), 3.62 (t, J=8 Hz, 1 H), 1.48 (s, 9 H). MS (m+1): 270.4; MS (m−bu+1): 214.2. temperature below 10° C. cooled (−40° C.) to reach room temperature stirred 1 h refluxed for 2 h The mixture was cooled to room temperature quenched with glacial acetic acid (2.5 mL) concentrated The residual oil was dissolved in methylene chloride (300 mL) the solution washed with water and saturated sodium bicarbonate (150 mL each) dried (Na2SO4) concentrated The residue was dissolved in minimum methylene chloride eluted with 55:30:15 heptane/methylene chloride/ethyl acetate

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

Procedure: The procedure of D(1) above, was repeated except that 1.2 grams of ethylene diacrylate were used in place of the allyl acrylate. Yield: 479 grams. The branched tetrapolymer obtained had about 50 mole percent of ethylene units. The polymer chain consisted principally of units -(E)-(B')-, where E is ethylene and B' is randomly selected from ethyl acrylate, ethylene diacrylate, and maleic anhydride (3.8 weight percent). The branched tetrapolymer obtained

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

Procedure: A 7.57-liter stirred autoclave was charged under nitrogen with 4000 ml. of methylene chloride, 400 grams of ethyl acrylate, 20 grams of maleic anhydride, 1.2 grams of allyl acrylate, and 1.0 gram of azobis(isobutyronitrile). It was then sealed, charged with 300 grams of boron trifluoride, and pressured to 21 kg./sq. cm. with ethylene. The subsequent copolymerization at 25° C. was continued until pressure measurement indicated that ethylene uptake had ceased (about two hours later). The reaction was quenched by addition of one liter of diethyl ether. Volatiles were removed by steam-stripping in a well-ventilated hood. The terpolymer thereby obtained was dissolved in acetone, precipitated in water in a blender, and oven-dried. Yield: 415 grams. was charged under nitrogen with 4000 ml It was then sealed The subsequent copolymerization at 25° C. about two hours The reaction was quenched by addition of one liter of diethyl ether Volatiles were removed by steam-stripping in a well-ventilated hood The terpolymer thereby obtained precipitated in water in a blender oven-dried