5,5'-Azoxytetrazolates - a new nitrogen-rich dianion and its comparison to 5,5'-azotetrazolate

A modification of the synthesis of sodium 5,5'-azotetrazolate pentahydrate, described by Thiele in 1898, yields the unknown and unexpected corresponding 5N-oxido derivative sodium 5,5'-azoxybistetrazolate pentahydrate (Na(2)zTO center dot 5H(2)O, 1). Purification was achieved by recrystallization based on the better solubility of Na(2)zTO center dot 5H(2)O in water. Different nitrogen-rich salts, such as the diammonium (3), the dihydroxylammonium (4), the bis-diaminoguanidinium (5), the bis-triaminoguanidinium (6) and the diaminouronium salt (7), have been prepared using metathesis reactions starting from barium 5,5'azoxybistetrazolate pentahydrate (2) and ammonium, hydroxylammonium, diaminoguanidinium or diaminouronium sulfate and triaminoguanidinium chloride, respectively. The nitrogen rich azoxyderivatives 3-7 were characterized using NMR, IR and Raman spectroscopy, mass spectrometry and elemental analysis. Additionally the solid state structures of 3, 4, 5 and 7 were determined by single crystal X-ray diffraction. The heats of formation of 3 and 4 and their corresponding azo-tetrazolate derivatives were calculated by the atomization method based on CBS-4M enthalpies. With these values and the crystal densities, several detonation parameters such as the detonation velocity, detonation pressure and specific impulse were calculated (EXPLO5) and compared. The sensitivities towards shock (BAM drophammer), friction (BAM friction tester) and electrostatic discharge of the described compounds were determined

Iminium Salts by Meerwein Alkylation of Ehrlich’s Aldehyde

4-(Dimethylamino)benzaldehyde is alkylated at the N atom by dialkyl sulfates, MeI, or Me3O BF4. In contrast, ethylation by Et3O BF4 occurs selectively at the O atom yielding a quinoid iminium ion. 4-(Diethylamino)benzaldehyde is alkylated only at O by either Et or Me oxonium reagent. The iminium salts are prone to hydrolysis giving the corresponding hydrotetrafluoroborates. Five crystal structures were determined

Iminium Salts by Meerwein Alkylation of Ehrlich’s Aldehyde

4-(Dimethylamino)benzaldehyde is alkylated at the N atom by dialkyl sulfates, MeI, or Me3O BF4. In contrast, ethylation by Et3O BF4 occurs selectively at the O atom yielding a quinoid iminium ion. 4-(Diethylamino)benzaldehyde is alkylated only at O by either Et or Me oxonium reagent. The iminium salts are prone to hydrolysis giving the corresponding hydrotetrafluoroborates. Five crystal structures were determined

Separation of Hemicellulose and Cellulose from Wood Pulp by Means of Ionic Liquid/Cosolvent Systems

Pulp of high cellulose content, also known as dissolving pulp, is needed for many purposes, including the production of cellulosic fibers and films. Paper-grade pulp, which is rich in hemicellulose, could be a cheap source but must be refined. Hitherto, hemicellulose extraction procedures suffered from a loss of cellulose and the non-recoverability of unaltered hemicelluloses. Herein, an environmentally benign fractionation concept is presented, using mixtures of a cosolvent (water, ethanol, or acetone) and the cellulose dissolving ionic liquid 1-ethyl-3-methylimidazolium acetate (EMIM OAc). This cosolvent addition was monitored using Kamlet–Taft parameters, and appropriate stirring conditions (3 h at 60 °C) were maintained. This allowed the fractionation of a paper-grade kraft pulp into a separated cellulose and a regenerated hemicellulose fraction. Both of these exhibited high levels of purity, without any yield losses or depolymerization. Thus, this process represents an ecologically and economically efficient alternative in producing dissolving pulp of highest purity

Dialkyl Phosphate-Related Ionic Liquids as Selective Solvents for Xylan

Herein we describe a possibility of selective dissolution of xylan, the most important type of hemicellulose, from <i>Eucalyptus globulus</i> kraft pulp using ionic liquids (ILs). On the basis of the IL 1-butyl-3-methylimidazolium dimethyl phosphate, which is well-known to dissolve pulp, the phosphate anion was modified by substituting one oxygen atom for sulfur and selenium, respectively. This alteration reduces the hydrogen bond basicity of the IL and therefore prevents dissolution of cellulose fibers, whereas the less ordered xylan is still dissolved. ¹H NMR spectra of model solutions and Kamlet–Taft parameters were used to quantify the solvent polarity and hydrogen bond acceptor properties of the ILs. These parameters have been correlated to their ability to dissolve xylan and cellulose, which was monitored by ¹³C NMR spectroscopy. It was found that the selectivity for xylan dissolution increases to a certain extent with decreasing hydrogen-bond-accepting ability of anions of the ILs