Isophthaloyl chloride → 1,3-Benzenedimethanol

Participants

Reaction Steps

In the following examples, cyclohexyl vinyl ether (CHVE), 2-ethylhexyl vinyl ether (EHVE), diethyleneglycol divinyl ether (DGDVE) and 9-anthracenemethanol were obtained from Aldrich Chemical Company. 1,4-butanediol divinyl ether (BDVE), trimethyleneglycol trivinyl ether (TMPVE), cyclohexanedimethanol divinyl ether (CHDVE) and nonanediol divinyl ether (NDVE) were obtained from Nippon Carbide Industries, Co. Inc. 1,3-benzenedimethyl divinyl ether (BDMDVE) was synthesized from 1,3-benzenedimethanol, which was prepared in a two-liter, 3-necked round-bottomed flask equipped with a 500-ml constant pressure addition funnel, an overhead stirrer, a thermocouple and a nitrogen inlet into which was added 27 g (0.74 mol) of lithium aluminum hydride (95%) and 1000 ml of anhydrous tetrahydrofuran (THF). The addition funnel was charged with a solution of 100 g (0.493 mol) of isophthaloyl dichloride in 400 ml of anhydrous THF. Diacylchloride was added slowly over a period of 2 hours with cooling in an ice bath. Once addition was complete the ice bath was removed and the suspension allowed to reach room temperature for four hours at which time it was re-cooled and 200 ml of ethyl acetate was slowly added to decompose the remaining hydride. The addition funnel was recharged with 200 ml of 2M NaOH, which was then added slowly with vigorous stirring until the ensuing suspension became granular in appearance. The suspension was filtered and well washed with ethyl acetate. The combined filtrate and washings were then washed with brine, dried over anhydrous magnesium sulfate and evaporated on a rotary evaporator to yield 64 g (94%) of 1,3-benzenedimethanol as a clear, colorless oil which solidified upon standing. The BDMDVE was then prepared in a two-liter round bottomed flask equipped with a positive-pressure nitrogen inlet and a magnetic stir bar was added 64 g (0.46 mol) of 1,3-benzenedimethanol, 10 g (0.03 mol) of mercuric acetate and 1 liter of ethyl vinyl ether. The solution was stirred at room temperature for four days at which time it was washed well with saturated sodium bicarbonate solution and brine. The solution was then stirred for three days over 20 g of anhydrous magnesium sulfate (the reaction is driven to completion by stirring over the acidic magnesium sulfate), filtered, and evaporated on a rotary evaporator. The resulting oil was distilled twice through an 8″ Vigreux to yield 53 g (60%) of BDMDVE, boiling point=84° C. at 1 mm Hg.

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