prop-2-enoyl prop-2-enoate

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

Procedure: This substituted acrylamide was synthesized from acrylic anhydride and 4-(2-aminoethyl)pyridine. Acrylic anhydride was obtained from acrylic acid and acetic anhydride. Synthesis of PEAM was initiated by the slow addition of 0.36 mole (45.0 g) of acrylic anhydride in 50 ml of ethyl ether containing 50 mg of BHT to 0.35 mole (42.76 g) of 4-(2-aminoethyl)pyridine in 150 ml of ethyl ether containing 150 mg of BHT at -55° C., with the formation of a precipitate. The rate of addition was kept sufficiently slow to ensure that the temperature did not exceed -30° C. during the reaction. After removal of the ether by room temperature evaporation, the precipitate was dissolved in 200 ml of methanol and subsequently vacuum distilled. The substituted acrylamide (15% yield) was collected at 170° C., 100 mtorr.

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

Procedure: This substituted acrylamide was synthesized from acrylic anhydride and 4-(2-aminoethyl)pyridine. Acrylic anhydride was obtained from acrylic acid and acetic anhydride. Synthesis of PEAM was initiated by the slow addition of 0.36 mole (45.0 g) of acrylic anhydride in 50 ml of ethyl ether containing 50 mg of BHT to 0.35 mole (42.76 g) of 4-(2-aminoethyl)pyridine in 150 ml of ethyl ether containing 150 mg of BHT at -55° C., with the formation of a precipitate. The rate of addition was kept sufficiently slow to ensure that the temperature did not exceed -30° C. during the reaction. After removal of the ether by room temperature evaporation, the precipitate was dissolved in 200 ml of methanol and subsequently vacuum distilled. The substituted acrylamide (15% yield) was collected at 170° C., 100 mtorr.

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

Procedure: This substituted acrylamide was synthesized from acrylic anhydride and 4-(2-aminoethyl)pyridine. Acrylic anhydride was obtained from acrylic acid and acetic anhydride. Synthesis of PEAM was initiated by the slow addition of 0.36 mole (45.0 g) of acrylic anhydride in 50 ml of ethyl ether containing 50 mg of BHT to 0.35 mole (42.76 g) of 4-(2-aminoethyl)pyridine in 150 ml of ethyl ether containing 150 mg of BHT at -55° C., with the formation of a precipitate. The rate of addition was kept sufficiently slow to ensure that the temperature did not exceed -30° C. during the reaction. After removal of the ether by room temperature evaporation, the precipitate was dissolved in 200 ml of methanol and subsequently vacuum distilled. The substituted acrylamide (15% yield) was collected at 170° C., 100 mtorr.

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

Procedure: Acrylic anhydride was synthesized in 70-80% yield as in the following example. Acryloyl chloride (2.7 g, 30 mmol) was added dropwise over 5 min to an ice-cooled solution of acrylic acid (2.0 g, 30 mmol) and triethylamine (2.8 g, 30 mmol) in THF (50 mL), and the solution was stirred at room temperature for 16 h. The NH4+Cl− precipitate was collected in a fritted glass filter, and the solvent was then removed from the filtrate by rotary evaporation. The residue was dissolved in CH2Cl2 (25 mL), washed twice with dilute aq. NaHCO3 (50 mL each) and once with satd. NaCl aq. soln. (50 mL), and dried over anhy. Na2SO4. After filtration and removing the solvent by rotary evaporation, 2.8 g (80%) of acrylic anhydride was obtained as a light yellow liquid. It was used without further purification. 1H NMR (CDCl3, 77.23 ppm): 6.04 (m, ═CH trans to CO2), 6.14 (m, ═CH gem to CO2), 6.50 (d, ═CH cis to CO2). 13C NMR (CDCl3/DMSO-d6): 127.4 (═CH), 134.7 (′CH2), 161.2 (C═O). The NH4+Cl− precipitate was collected in a fritted glass filter the solvent was then removed from the filtrate by rotary evaporation The residue was dissolved in CH2Cl2 (25 mL) washed twice with dilute aq. NaHCO3 (50 mL each) (50 mL), and dried over anhy After filtration removing the solvent by rotary evaporation

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

Procedure: Acrylic anhydride was synthesized in 70-80% yield as in the following example. Acryloyl chloride (2.7 g, 30 mmol) was added dropwise over 5 min to an ice-cooled solution of acrylic acid (2.0 g, 30 mmol) and triethylamine (2.8 g, 30 mmol) in THF (50 mL), and the solution was stirred at room temperature for 16 h. The NH4+Cl− precipitate was collected in a fritted glass filter, and the solvent was then removed from the filtrate by rotary evaporation. The residue was dissolved in CH2Cl2 (25 mL), washed twice with dilute aq. NaHCO3 (50 mL each) and once with satd. NaCl aq. soln. (50 mL), and dried over anhy. Na2SO4. After filtration and removing the solvent by rotary evaporation, 2.8 g (80%) of acrylic anhydride was obtained as a light yellow liquid. It was used without further purification. 1H NMR (CDCl3, 77.23 ppm): 6.04 (m, ═CH trans to CO2), 6.14 (m, ═CH gem to CO2), 6.50 (d, ═CH cis to CO2). 13C NMR (CDCl3/DMSO-d6): 127.4 (═CH), 134.7 (′CH2), 161.2 (C═O). The NH4+Cl− precipitate was collected in a fritted glass filter the solvent was then removed from the filtrate by rotary evaporation The residue was dissolved in CH2Cl2 (25 mL) washed twice with dilute aq. NaHCO3 (50 mL each) (50 mL), and dried over anhy After filtration removing the solvent by rotary evaporation

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

Procedure: According to another embodiment of the invention, the olefin acid anhydrides are reacted with alcohols to give high yields of the acrylate esters at room temperature. In particular, acrylic anhydride has been reacted with a series of alcohols ranging from C-1 to C-18 to give high yields of the acrylate esters at room temperature. The synthesis of acrylate esters by the reaction of alcohols with acrylic anhydride were found to proceed essentially to completion at room temperature to yield only the desired acrylate esters. The following mechanism is proposed for this reaction: ##STR3## No significant competing reactions were observed, such as the Michael addition reactions that often accompany the production of acrylate esters under reflux conditions. The following are representative of this embodiment: (1) the reaction of n-butyl alcohol with acrylic anhydride was completed in 3.5 hours and yielded 91.2% of n-butyl acrylate; (2) the reaction of n-octyl alcohol with acrylic anhydride was completed in 4 hours to obtain an 81.3% yield of n-octyl acrylate; and (3) the reaction of cis-12,13-epoxy-cis-9-octadecenol with acrylic anhydride was completed in 55 hours to give an 88.4% yield of cis-12, 13-epoxy-cis-9-octadecenyl acrylate.

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

Procedure: According to another embodiment of the invention, the olefin acid anhydrides are reacted with alcohols to give high yields of the acrylate esters at room temperature. In particular, acrylic anhydride has been reacted with a series of alcohols ranging from C-1 to C-18 to give high yields of the acrylate esters at room temperature. The synthesis of acrylate esters by the reaction of alcohols with acrylic anhydride were found to proceed essentially to completion at room temperature to yield only the desired acrylate esters. The following mechanism is proposed for this reaction: ##STR3## No significant competing reactions were observed, such as the Michael addition reactions that often accompany the production of acrylate esters under reflux conditions. The following are representative of this embodiment: (1) the reaction of n-butyl alcohol with acrylic anhydride was completed in 3.5 hours and yielded 91.2% of n-butyl acrylate; (2) the reaction of n-octyl alcohol with acrylic anhydride was completed in 4 hours to obtain an 81.3% yield of n-octyl acrylate; and (3) the reaction of cis-12,13-epoxy-cis-9-octadecenol with acrylic anhydride was completed in 55 hours to give an 88.4% yield of cis-12, 13-epoxy-cis-9-octadecenyl acrylate. The following mechanism is proposed for this reaction ##STR3## No significant competing reactions were observed, such as the Michael addition reactions that

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

Procedure: According to another embodiment of the invention, the olefin acid anhydrides are reacted with alcohols to give high yields of the acrylate esters at room temperature. In particular, acrylic anhydride has been reacted with a series of alcohols ranging from C-1 to C-18 to give high yields of the acrylate esters at room temperature. The synthesis of acrylate esters by the reaction of alcohols with acrylic anhydride were found to proceed essentially to completion at room temperature to yield only the desired acrylate esters. The following mechanism is proposed for this reaction: ##STR3## No significant competing reactions were observed, such as the Michael addition reactions that often accompany the production of acrylate esters under reflux conditions. The following are representative of this embodiment: (1) the reaction of n-butyl alcohol with acrylic anhydride was completed in 3.5 hours and yielded 91.2% of n-butyl acrylate; (2) the reaction of n-octyl alcohol with acrylic anhydride was completed in 4 hours to obtain an 81.3% yield of n-octyl acrylate; and (3) the reaction of cis-12,13-epoxy-cis-9-octadecenol with acrylic anhydride was completed in 55 hours to give an 88.4% yield of cis-12, 13-epoxy-cis-9-octadecenyl acrylate. The following mechanism is proposed for this reaction ##STR3## No significant competing reactions were observed, such as the Michael addition reactions that

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

Procedure: Moreover, in the case of benzoyl chloride, the resulting mixed anhydride is more reactive than benzoyl chloride. Thus, the carboxylate ion of acrylic acid preferentially reacts with the mixed anhydride to give acrylic anhydride and the benzoate ion, which subsequently reacts with unreacted benzoyl chloride to give benzoic anhydride, according to reaction scheme I.

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

Procedure: Moreover, in the case of benzoyl chloride, the resulting mixed anhydride is more reactive than benzoyl chloride. Thus, the carboxylate ion of acrylic acid preferentially reacts with the mixed anhydride to give acrylic anhydride and the benzoate ion, which subsequently reacts with unreacted benzoyl chloride to give benzoic anhydride, according to reaction scheme I.

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

Procedure: As seen below, benzoyl chloride, acetyl chloride and pivaloyl chloride were tested for use in the present invention. The best results were obtained with benzoyl chloride, which provided a yield of the acrylic anhydride of 77.2%. Acetyl chloride gave a less preferred product mixture that comprised 50% mixed anhydride, 25% acetic anhydride and 25% acrylic anhydride; the pivaloyl chloride reaction also gave a less preferred product mixture that comprised 50% mixed anhydride, 30% pivaloyl anhydride and 20% acrylic anhydride, based on gas chromatographic analysis. Benzoyl chloride is also more preferred than acetyl chloride and trimethyacetyl (pivaloyl) chloride, because the benzoyl chloride reaction yields benzoic anhydride which has a much greater boiling point than acrylic anhydride, facilitating the separation of the acrylic anhydride. also gave a less preferred product mixture that comprised 50%

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

Procedure: As seen below, benzoyl chloride, acetyl chloride and pivaloyl chloride were tested for use in the present invention. The best results were obtained with benzoyl chloride, which provided a yield of the acrylic anhydride of 77.2%. Acetyl chloride gave a less preferred product mixture that comprised 50% mixed anhydride, 25% acetic anhydride and 25% acrylic anhydride; the pivaloyl chloride reaction also gave a less preferred product mixture that comprised 50% mixed anhydride, 30% pivaloyl anhydride and 20% acrylic anhydride, based on gas chromatographic analysis. Benzoyl chloride is also more preferred than acetyl chloride and trimethyacetyl (pivaloyl) chloride, because the benzoyl chloride reaction yields benzoic anhydride which has a much greater boiling point than acrylic anhydride, facilitating the separation of the acrylic anhydride. also gave a less preferred product mixture that comprised 50%