an eqüilibrium exists which proceeds through an imide addition product, the equilibrium being displaced toward the side of the weaker carboxylic acid.3We have found that replacing acetonitrile with shortchain dinitriles (specifically succinonitrile, glutaronitrile, and -methylglutaronitrile) provides two distinct advantages in the use of this reaction as a synthetic method. First, the use of pressure equipment to reach the required high temperatures (150-300°) is avoided.Second, distinct improvements in yield of product nitrile, especially for aliphatic systems, have been realized due to the fact that the once-exchanged short-chain cyano acid undergoes an internal cyclic imide formation, removing it from the equilibrium and thus driving the reaction to completion. mol) of «-methylglutaronitrile (II) containing 11.6 g of 85% HsPOj for 18 hr. The resulting black solution was cooled and vacuum distilled to give 1246 g (98% of theoretical) of tan solid -methylglutarimide (III), bp 137°(7 mm), and 929.7 g (97% of theoretical) of yellow liquid dodecanedinitrile (IV), bp 193°( 8 mm). Aqueous NaOH washing and redistillation afforded colorless liquid IV, mp 21-22°.
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