Malononitrile, tert-butyl

A. tert-Butylmalononitrile. In a dry 2-1. three-necked flask equipped with a thermometer, mechanical stirrer, and a Claisen adapter fitted with a dropping funnel and condenser protected with a drying tube is placed 200 ml. of nitromethane (Note 1). The flask is cooled to 0° in an ice-salt bath (Note 2), and anhydrous powdered aluminum chloride (90.0 g., 0.68 mole) is added with slow stirring through a powder funnel that temporarily replaces the thermometer. The temperature may rise to ca. 50° but quickly drops to 0°. Malononitrile (45.0 g., 0.68 mole) (Note 3) in 50 ml. of nitromethane is added through the dropping funnel at a rate such that the temperature is kept below 10° (approximately one hour), followed by slow dropwise addition of tert-butyl chloride (Note 4) (150 g., 1.62 moles) in 50 ml. of nitromethane at a rate such that the temperature is maintained... 

When malononitrile was used as a substrate, a high conversion of 98% was obtained after 12 h, whereas almost no activity was observed in the conversion of ethyl cyanoacetate and cyano-acetic acid tert-butyl ester, suggesting that the catalyst was size selective. The observation of reactant shape selectivity revealed that the catalytic turnovers take place in the MOF channels rather than at the outer surface of the MOF particles. Upon desolvation, for example, by the removal of water... 

Line I filled squares proton transfer from (EtS02)2 CHMe to a series of oxyanions. Data from Reference 26. Filled circles proton transfer from tert. butyl malononitrile to a series of oxyanions. Data from Reference 28. Open squares proton transfer from malononitrile to morpholine, phosphate and bicarbonate. Data from Reference 28. Open circle proton transfer from 1,4-dicyanobutene to a series of amines. Data from Reference 28. Open triangles proton transfer from a series of disulphones to H2O. Data from Reference 27. 

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