10601-70-4Relevant articles and documents
Aerobic oxidation of N-alkylamides catalyzed by N-hydroxyphthalimide under mild conditions. Polar and enthalpic effects
Minisci, Francesco,Punta, Carlo,Recupero, Francesco,Fontana, Francesca,Franco Pedulli, Gian
, p. 2671 - 2676 (2007/10/03)
The oxidation of N-alkylamides by O2, catalyzed by N-hydroxyphthalimide (NHPI) and Co(II) salt, leads under mild conditions to carbonyl derivatives (aldehydes, ketones, carboxylic acids, imides) whose distribution depends on the nature of the alkyl group and on the reaction conditions. Primary N-benzylamides lead to imides and aromatic aldehydes at room temperature without any appreciable amount of carboxylic acids, while under the same conditions nonbenzylic derivatives give carboxylic acids and imides with no trace of aldehydes, even at very low conversion. These results are explained through hydrogen abstraction by the phthalimide-N-oxyl (PINO) radical, whose reactivity with benzyl derivatives is governed by polar effects, so that benzylamides are much more reactive than the corresponding aldehydes. The enthalpic effect is, however, dominant with nonbenzylic amides, making the corresponding aldehydes much more reactive than the starting amides. The importance of the bond dissociation energy (BDE) of the O-H bond in NHPI is emphasized.
HIGH-TEMPERATURE TRANSNITRILATION OF 2-BROMOCAPROIC ACID
Polivin, Yu. N.,Vinokurov, V. A.,Makarshin, S. V.,Karakhanov, R. A.,Silin, M. A.,Ageev, E. A.
, p. 1528 - 1530 (2007/10/02)
Chromato-mass spectrometry and IR and PMR spectroscopy were used to study the high-temperature reaction of 2-bromocaproic, 2-iodocaproic, and 2-bromo-2-phenylacetic acids with acetonitrile.The formation of anomalous transnitrilation products (capronitrile and benzyl cyanide) is a consequence of the initial conversion of 2-halo-substituted caproic and phenylacetic acids to caproic and phenylacetic acids, respectively.
