반응 #2006434

반응 방정식

1,3-benzenedimethanol

isophthaloyl dichloride

lithium aluminum hydride

→

divinyl ether

1,3-benzenedimethanol

수율 94.0%

용매

THF

tetrahydrofuran

반응 조건

후처리

1. 1
   기타was prepared in a two-liter, 3-necked round-bottomed flask
2. 2
   기타equipped with a 500-ml constant pressure addition funnel, an overhead stirrer
3. 3
   온도with cooling in an ice bath
4. 4
   workup.ADDITIONOnce addition
5. 5
   기타was removed
6. 6
   온도was re-cooled
7. 7
   workup.ADDITION200 ml of ethyl acetate was slowly added
8. 8
   workup.ADDITIONwas then added slowly
9. 9
   여과The suspension was filtered
10. 10
    세척well washed with ethyl acetate
11. 11
    세척The combined filtrate and washings were then washed with brine
12. 12
    건조dried over anhydrous magnesium sulfate
13. 13
    기타evaporated on a rotary evaporator

실험 절차

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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