Synthesis and properties of new paramagnetic hybrid bayerite from Al(0)/naphthalene dianhydride reaction

The reaction of Naphthalene 1,4,5,8-dianhydride (NTCDA) with elemental aluminum(0) powder is studied in an aqueous alcoholic KOH mixture to search for the NTCDA anion and dianion electron-adducts. After analyzing various reaction conditions it was found that the reaction yielded a greenish precipitate in 3:1 (v:v) ethanol:water mixture. This powder is composed mainly of aluminum trihydroxide crystallites of bayerite [α-Al(OH3)(s)] and the organic content is approximately 6%. This hybrid material proved to be paramagnetic even after exposure to air for one year and at temperatures up to 200 ºC. Typical carbonylic bound to metal IR bands and reflectance UV-VIS spectra demonstrate the entrapment of NTCDA radical anion into the aluminum trihydroxide, hence rendering its green color and a paramagnetic behavior. Thus, besides the understanding of an aluminum reaction in suspension, the entrapment of an organic material (NTCDA) that stays stable as the corresponding radical can provide an interesting option for the synthesis of aluminum trihydroxide composites.FAPESPCNPQCoordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES

Formation and decomposition of N-alkyinaphthalimides: experimental evidences and ab initio description of the reaction pathways

The kinetics of hydrolysis of 1,8-N-butyl-naphthalimide (1,8-NBN) to 1,8-N-butyl-naphthalamide (1,8-NBAmide) and of 2,3-N-butyl-naphthalimide (2,3-NBN) to 2,3-N-butyl-naphthalamide (2,3-NBAmide), as well as the formation of the respective anhydrides from the amides were investigated in a wide acidity range. 1,8-NBN equilibrates with 1,8-NBAmide in mild alkali. Under the same conditions 2,3-NBN quantitatively yields 2,3-NBAmide. Over a wide range of acidities the reactions of the 1,8- and 2,3-N-butyl-naphthalamides (or imides) yield similar products but with widely different rates and at distinct pH`s. Anhydride formation in acid was demonstrated for 1,8-NBAmide. The reactions mechanisms were rationalized in the manifold pathways of ab initio calculations. The differences in rates and pH ranges in the reactions of the 1,8- and 2,3-N-butyl-naphthalamides were attributed to differences in the stability of the tetrahedral intermediates in alkali as well as the relative stabilities of the five and six-membered ring intermediates. The rate of carboxylic acid assisted 1,8-N-Butyl-naphthalamide hydrolysis is one of the largest described for amide hydrolysis models. Copyright (C) 2010 John Wiley & Sons, Ltd.FAPESPFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)CNPqCAPESCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES