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sulfuric acid; In water; 1,2-dichloro-ethane; at 62℃; for 10h;Product distribution / selectivity; |
The synthesis of 2-methacryloyloxy-2-(3-(2-hydroxy-2-propyl)1-1-adamantyl)propane was performed by the following method. First, according to the method described in Japanese Patent Application Laid-open No. 2002-167342, 1000 g of 1,3-dihydroxyadamantane was synthesized from adamantane. Next, a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a Dimroth condenser was charged with 100 g of 1,3-dihydroxyadamantane, 500 mL of 1,2-dichloroethane and 800 g of 96percent sulfuric acid, and further 300 g of formic acid was dropped into the flask for 1 h. Thereafter, the contents of the flask were reacted at 25° C. for 10 h. The resultant reaction solution was filtered to separate precipitated crystals therefrom. The thus separated crystals were washed with water to obtain 140 g of <strong>[39269-10-8]1,3-adamantanedicarboxylic acid</strong>. Then, a four-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser was charged with 140 g of <strong>[39269-10-8]1,3-adamantanedicarboxylic acid</strong>, 12 g of 96percent sulfuric acid, 200 g of methanol and 1000 mL of 1,2-dichloroethane, and the contents of the flask were reacted at 62° C. for 10 h.After completion of the reaction, the resultant reaction solution was separated into an organic phase and a water phase. The organic phase was washed with a saturated sodium hydrogencarbonate aqueous solution, and then concentrated. The thus obtained crystals were separated from the organic phase by filtration, thereby obtaining 150 g of methyl 1,3-adamantanedicarboxylate. Next, a four-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser and a dropping funnel was charged with 100 g of methyl 1,3-adamantanedicarboxylate and 500 mL of tetrahydrofuran, and then 600 mL of a 3M magnesium methyl bromide/diethyl ether solution was dropped into the flask for 1 h. Thereafter, the contents of the flask were stirred at 25° C. for 3 h, and then mixed with water to terminate the reaction. The resultant reaction solution was separated into an organic phase and a water phase. The thus separated organic phase was concentrated to obtain 90 g of 1,3-adamantanediisopropanol.Next, a five-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser and two dropping funnels was charged with 90 g of 1,3-adamantanediisopropanol and 100 mL of 1,2-dichloroethane, and then 63 g of methacryloyl chloride and 81 g of triethylamine were simultaneously dropped into the flask for 1 h. Thereafter, the contents of the flask were stirred at 25° C. for 3 h, and then mixed with water to terminate the reaction. The resultant reaction solution was separated into an organic phase and a water phase. The thus separated organic phase was washed with ion-exchanged water, filtered, concentrated and then purified by silica gel column chromatography to obtain 80 g of 2-methacryloyloxy-2-(3-(2-hydroxy-2-propyl)-1-adamantyl)propane as represented by the following formula (hereinafter referred to as "compound A"). The thus obtained compound A was identified by 1H-NMR and 13C-NMR (refer to FIGS. 1 and 2).; The synthesis of 2-methacryloyloxy-2-(3-(2-methacryloyloxy-2-propyl)-1-adamantyl)propane was performed by the following method. First, according to the method described in Japanese Patent Application Laid-open No. 2002-167342, 100 g of 1,3-dihydroxyadamantane was synthesized from adamantane. Next, a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a Dimroth condenser was charged with 100 g of 1,3-dihydroxyadamantane, 500 mL of 1,2-dichloroethane and 800 g of 96percent sulfuric acid, and further 300 g of formic acid was dropped into the flask for 1 h. Thereafter, the contents of the flask were reacted at 25° C. for 10 h. The resultant reaction solution was filtered to separate precipitated crystals therefrom. The thus separated crystals were washed with water to obtain 140 g of <strong>[39269-10-8]1,3-adamantanedicarboxylic acid</strong>.Then, a four-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser was charged with 140 g of <strong>[39269-10-8]1,3-adamantanedicarboxylic acid</strong>, 12 g of 96percent sulfuric acid, 200 g of methanol and 1000 mL of 1,2-dichloroethane, and the contents of the flask were reacted at 62° C. for 10 h. After completion of the reaction, the resultant reaction solution was separated into an organic phase and a water phase. The thus separated organic phase was washed with a saturated sodium hydrogencarbonate aqueous solution, and then concentrated. The obtained crystals were separated by filtration from the organic phase, thereby obtaining 150 g of methyl 1,3-adamantanedicarboxylate. Next, a four-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser and a dropping funnel was charged with 100 g of methyl 1,3-adamantanedicarboxylate and 500 mL of tetrahydrofuran, and then 600 mL of a 3M magnesium methyl bromide/diethyl ether solution was dropped into the flask for 1 h. Thereafter, the contents of the flask were stirred at 25° C. for 3 h, and then mixed with water ... |