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With ammonium acetate; acetic acid; In water; at 85 - 90℃; under 400 - 420 Torr; for 16h;
A 1000 mL four neck round bottom flask, equipped with a mechanical stirrer, a thermometer and a condenser, was charged with 2-ethylhexyl cyanoacetate (347 g, 1.76 gmol), benzophenone (200 g, 1.1 gmol) , recovered acetic acid (168.3 g containing 2% water, 2.75 gmol) and ammonium acetate (3 lg, 0.4 gmol). The stirred reaction mass was then heated to 85-90C. Azeotrope of acetic acid/water mixture was distilled off oyer a period of 16 h. under reduced pressure from 400-420 mm of Hg A till the Gas chromatographic analysis showed no further decrease in benzophenone concentration in reaction mass. The loss of acetic acid was continuously adjusted by adding the corresponding recovered acetic acid. The acetic acid was then recovered under reduced pressure (30-60 mm of Hg A). The HPLC analysis of reaction mass showed BPCA content of 0.19%. The crude reaction mixture was cooled and washed twice with 300 g portion of water and subsequently distilled to yield pale yellow colored viscous liquid (303 g, Yield 76.3%) which was found to be of 99.48% purity by Gas chromatographic analysis.
66.18 - 93.09%
With propionic acid;ammonium acetate; In n-heptane; at 110℃; under 760.051 Torr; for 5h;Product distribution / selectivity;
Into a 500ml four-neck round-bottom flask, equipped with a mechanical stirrer, a thermometer and a condenser is charged with 62.2 g (0.32mol) of 2-Ethylhexyl cyanoacetate (EHCA) and 81.Og (0.45 mol) of Benzophenone (BP) (molar ratio EHCA:BP = 0.71 : 1) and 27.7g (0.36 mol) of ammonium acetate and 81.0g (1.1 mol) of propionic acid and 81.0g of heptane. The mixture is heated under stirring. When the temperature reach H O0C, a mixture of propionic acid, water, heptane is distilled off over a period of 5 hours at normal pressure. Heptane phase is returned back to the flask. Then the reactant is cooled to 900C, and 100 ml of hot water is added to the reaction mixture. The mixture is kept at 85C for 10 minutes, and then transferred to a funnel for separation. To a flask equipped with a column 256.Og of crude 2-ethylhexyl 2-cyano-3,3- diphenylacrylate solution is added. Rectification is carried out at 1 mbar. 2-Ethylhexyl 2-cyano- <n="9"/>3,3-diphenylacrylate is distilled out at 2100C (vapor). After distillation, light yellow 2-ethylhexyl 2-cyano-3,3-diphenylacrylate is obtained. Reaction yields are as indicated in table 1 and assume recycle of unreacted benzophenone and 2-EHCA.The experiment is repeated by adjusting the amount of 2-EHCA in order to give the molar ratios as indicated in the table 1 below.
With propionic acid;ammonium acetate; In n-heptane; at 95 - 110℃; under 525.053 - 760.051 Torr; for 6h;Heating / reflux;Product distribution / selectivity;
A 2000ml reactor is charged with 3 U g of 2-ethylhexyl cyanoacetate, 70 g of ammoniumacetate, 404 g of benzophenones, 405 g of propionic acid and 405 g of n-heptane. The mixture is heated to about 950C under stirring at reduced pressure (about 700 mbar in order to maintain the reaction at reflux). When the temperature reached 950C a mixture of heptane, water and propionic acid is distilled off azeotropically over a period of 6h wherein the organic phase is recharged back in the reactor. During this time every hour 25 g of additional ammonium acetate is added stepwise (5 portions, 1 per hour). After the reaction is finished heptane and propionic acid are distilled off at reduced vacuum (up to 20 mbar while keeping the temperature below about 95C). When no more distillate is observed, 500g of water is added and the mixture is stirred for 10 min at 75C. After adding 340 g of n-heptane the organic phase is collected and the washing procedure is repeated. After evaporation of the solvent at reduced pressure (temperature is maintained below 95C) the crude product (comprising about 0.04 % of 2-cyano-3,3-diphenyl-2-propenamide) is collected followed by distillation using a wiped thin film evaporator. A second distillation yielded 388 g of light yellow octocrylene comprising about 0.38 % of 2-cyano-3,3-diphenyl- 2-propenamide (determined via HPLC). The reaction is repeated at normal pressure and a temperature of about HO0C (reflux temperature) resulting after purification in an amount of 0.7 % of 2-cyano-3,3- diphenyl- 2-propenamide
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