Process for manufacturing a hydroxyester derivative intermediate and epoxy resins prepared therefrom
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example 1
A. Epoxidation of Allyl Acetate to Glycidyl Acetate
experiment a1
[0216] In this part of Example 1, a 100-mL, four-necked, glass reactor equipped with a cooling condenser, a thermometer, a magnetic stirrer, a nitrogen inlet and a heating lamp with a thermocontroller was employed. To the reactor were added 20 g (0.2 mole) of allyl acetate (commercially available from Aldrich Chemical Co.), 20 mL of methylene chloride, 0.50 g (1.0 mole percent based on the amount of allyl acetate) of methyltrioxorhenium (MTO) and 0.76 g (15 mole percent based on the amount of allyl acetate) of pyrazole. The resultant reaction mixture was stirred at ambient temperature under a nitrogen atmosphere for 5 minutes. Then 38 g (2 molar equivalents based on the amount of allyl acetate) of aqueous 35 percent hydrogen peroxide solution as an oxidant was added into the reactor at ambient temperature. A slight exothermic reaction occurred, and the temperature of the reaction mixture reached 30° C. The reaction was carried out at 25° C. for about 12 hours and then at 30° C. for ...
experiment a2
[0219] In this part of Example 1, a 250-mL, four-necked, glass reactor equipped with a cooling condenser, a thermometer, a magnetic stirrer, a nitrogen inlet and an ice-water cooling bath was employed. To the reactor were added 50 cc of acetonitrile and a mixture containing 0.08 g (0.45 mmole) of MnSO4·H2O and 2 g of water. The resultant reaction mixture was thoroughly mixed and 0.12 g of N,N′,N″-trimethyl-1,3,9-triazacyclononane (TMTACN, 0.69 mmole mole) was added to the reaction mixture, followed by the addition of a mixture containing 0.042 g (0.45 mmole) of oxalic acid, 0.060 g (0.45 mmole) of sodium oxalate and 2 g of water.
[0220] After thoroughly mixing the resultant reaction mixture, 15 g of allyl acetate (0.15 mole) was added into the reaction mixture. The reactor contents were cooled to 10° C., and 28.5 g (0.3 mole) of aqueous 35 percent hydrogen peroxide solution was added to the reaction mixture over about 30 minutes. Upon addition of the first portion of hydrogen peroxi...
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