1,5-Diamino-1H-tetrazole (2, DAT) can easily be protonated by reaction with strong mineral acids, yielding the poorly investigated 1,5-diaminotetrazolium nitrate (2a) and perchlorate (2b). A new synthesis for 2 is introduced that avoids lead azide as a hazardous byproduct. The reaction of 1,5-diamino-1H-tetrazole with iodomethane (7a) followed by the metathesis of the iodide (7a) with silver nitrate (7b), silver dinitramide (7c), or silver azide (7d) leads to a new family of heterocyclic-based salts. In all cases, stable salts were obtained and fully characterized by vibrational (IR, Raman) spectroscopy, multinuclear NMR spectroscopy, mass spectrometry, elemental analysis, X-ray structure determination, and initial safety testing (impact and friction sensitivity). Most of the salts exhibit good thermal stabilities, and both the perchlorate (2b) and the dinitramide (7c) have melting points well below 100 degrees C, yet high decomposition onsets, defining them as new (7c), highly energetic ionic liquids. Preliminary sensitivity testing of the crystalline compounds indicates rather low impact sensitivities for all compounds, the highest being that of the perchlorate (2b) and the dinitramide (7c) with a value of 7 J. In contrast, the friction sensitivities of the perchlorate (2b, 60 N) and the dinitramide (7c, 24 N) are relatively high. The enthalpies of combustion (Delta(c)H degrees ) of 7b-d were determined experimentally using oxygen bomb calorimetry: Delta(c)H degrees (7b) = -2456 cal g(-)(1), Delta(c)H degrees (7c) = -2135 cal g(-)(1), and Delta(c)H degrees (7d) = -3594 cal g(-)(1). The standard enthalpies of formation (Delta(f)H degrees ) of 7b-d were obtained on the basis of quantum chemical computations using the G2 (G3) method: Delta(f)H degrees (7b) = 41.7 (41.2) kcal mol(-)(1), Delta(f)H degrees (7c) = 92.1 (91.1) kcal mol(-)(1), and Delta(f)H degrees (7d) = 161.6 (161.5) kcal mol(-)(1). The detonation velocities (D) and detonation pressures (P) of 2b and 7b-d were calculated using the empirical equations of Kamlet and Jacobs: D(2b) = 8383 m s(-)(1), P(2b) = 32.2 GPa; D(7b) = 7682 m s(-)(1), P(7b) = 23.4 GPa; D(7c) = 8827 m s(-)(1), P(7c) = 33.6 GPa; and D(7d) = 7405 m s(-)(1), P(7d) = 20.8 GPa. For all compounds, a structure determination by single-crystal X-ray diffraction was performed. 2a and 2b crystallize in the monoclinic space groups C2/c and P2(1)/n, respectively. The salts of 7 crystallize in the orthorhombic space groups Pna2(1) (7a, 7d) and Fdd2 (7b). The hydrogen-bonded ring motifs are discussed in the formalism of graph-set analysis of hydrogen-bond patterns and compared in the case of 2a, 2b, and 7b.

Organometdics 1992, I I, 3588-3600. diop = 2,3-O-isopropylidene-2,3-dihydroxy-l,4-b1s(di-pheny1phosphino)butane.

Perylene‐3,4‐dicarboximides 2 are obtained by a decarboxylizing condensation of moderately sterically hindered primary amines with perylene‐3,4,9,10‐tetracarboxylic 3,4:9,10‐bisanhydride (3) in the presence of water. Perylene‐3,4‐dicarboxylic anhydride (4) is prepared by hydrolysis of the imides with KOH in tert‐butyl alcohol. The anhydride may be condensed with any primary amine to the corresponding imide. The imides are highly fluorescent and very photostable dyes.

The catalytic enantioselective formation of new C À C bonds is an important class of reactions.[1] Especially attractive are multicomponent reactions which allow the formation of several bonds including new CÀC bonds in a one-pot procedure.[2] For achieving optimum atom economy [3] and avoiding the production of stoichiometric amounts of metal salts as by-products, we [4] and others [5] have examined the use of an alkyne as the precursor for the nucleophilic reaction component. Alkynes of type 1 can be deprotonated catalytically in situ by means of cesium salts and reacted subsequently with aldehydes and ketones, leading to propargyl alcohols. [6] Recently, we have shown that various enamines react with terminal alkynes in the presence of copper(i) salts and quinap (2), [7] providing propargylamines in up to 90 % ee.[4]In order to avoid the generation of sensitive enamines and to extend the scope of this propargylamine synthesis to nonenolizable aldehydes (i.e. aldehydes from which enamines cannot be prepared), we have examined a new threecomponent reaction [8] between an alkyne 1, an aldehyde 3, and a secondary amine 4. We have found that propargylamines of type 5 are formed in toluene at room temperature in the presence of CuBr (5 mol %), (R)-quinap ((R)-2) (5.5 mol %), and molecular sieves 4 in excellent yields (up to 99 %) and good enantioselectivities (up to 96 % ee; Scheme 1 and Table 1).The reaction is usually complete within 12 to 48 h for the racemic reaction without ligand and within one to six days for the enantioselective reaction with high yields in most cases. The alkyne can bear either an aryl substituent (R 1 = Ph) or an alkyl substituent (R 1 = Bu; entries 1 and 2 in Table 1). The resulting propargylamines 5 a and 5 b were obtained in 98 and 85 % yield and 86 and 82 % ee, respectively. Branched aliphatic aldehydes like isobutyraldehyde lead to the expected propargylamines 5 c and 5 d in 60 and 99 % yield and 84 and 83 % ee, respectively (entries 3 and 4). The use of

The crystallochemistry of and the bonding in the orthorhombic four-connected nets of BaIn(2) (CeCu(2) structure) and of CaPtSn (TiNiSi structure, a derivative of the CeCu(2) structure) are analyzed with approximate molecular orbital calculations. Following the Zintl concept, in BaIn(2) the In(-) ions are isoelectronic with group IV tin and should adopt a four-connected structure. In contrast to alpha-tin, which has a cubic diamond structure, the indium ions in BaIn(2) build up an orthorhombic three-dimensional four-connected net containing distorted tetrahedra and ladder polymers of four-membered rings. In the CeCu(2) structure (space group Imma) two bond angles in these distorted tetrahedra are fixed at 90 degrees. The four-connected net in the CeCu(2) structure is topologically related to the layers in black phosphorus (space group Cmca). In CaPtSn (TiNiSi structure) the orthorhombic four-connected net is formed by (PtSn)(2)(-) ions in an ordered arrangement. Calculations on BaIn(2) and CaPtSn show that the four-connected nets are increasingly stabilized as the valence electron count is increased from 16 to 30 valence electrons per 4 formula units. For more than 30e, the nets are destabilized due to filling of M-E antibonding states. Structural data obtained by precise single crystal investigations for the TiNiSi series CaPdIn (20e), CaPdSn (24e), CaPdSb (28e), and CaAgSb (32e), confirm the results of the extended Hückel calculations. We find an interesting and understandable angular asymmetry of the tetrahedral sites in these ternary compounds.

Energetic salts of the 5,5‘-azotetrazolate anion with different guandidinium cations were investigated, including bis(guanidinium) 5,5‘-azotetrazolate (GZT), bis(aminoguanidinium) 5,5‘-azotetrazolate (AGZT), bis(aminoguanidinium) 5,5‘-azotetrazolate monohydrate (AGZTH), bis(diaminoguanidinium) 5,5‘-azotetrazolate (DAGZT), bis(triaminoguanidinium) 5,5‘-azotetrazolate (TAGZT), and bis(azidoformamidinium) 5,5‘-azotetrazolate (AFZT). AGZT was obtained according to the literature as the monohydrate (AGZTH), and DAGZT was synthesized for the first time. All salts were fully characterized by vibrational spectroscopy (IR, Raman), multinuclear NMR spectroscopy, and elemental analysis. Safety testing (impact and friction sensitivity) was performed to find safe handling procedures. The crystal structures of AFZT and AGZTH, which crystallize in the monoclinic space groups P21/n and C2/c, were determined. The thermal decomposition of the salts was monitored by differential scanning calorimetry, and the gaseous products of the explosions of all compounds were identified with mass spectrometry and IR spectroscopy.

Propargylamines are important as both synthetic intermediates for the preparation of polyfunctional amino derivatives and as biologically active compounds. [1] Their preparation in enantiomerically enriched form is therefore of great importance. Although several diastereo-and enantioselective syntheses have been developed, [2] until now no metal-catalyzed enantioselective synthesis of propargylamines is known. [3] We report herein a new copper(i)-catalyzed enantioselective addition of alkynes [4] to enamines. First, we examined the racemic synthesis of propargylamines by metal-complex catalysis. Various metal salts, including Sc(OTf) 3 , Zn(OTf) 2 , Yb(OTf) 3 , and Cu I and Cu II salts, [5] were tested as catalysts. Copper(i) and copper(ii) bromide proved to give the fastest conversions. We chose test enamines [6] with readily removable protecting groups such as an allyl or a benzyl group. Enamines 1 a ± h (1.2 ± 1.5 equiv) reacted readily with terminal alkynes 2 a ± k in toluene in the presence of copper(i) bromide (5 mol %) to give propargylic amines of type 3 (Scheme 1, Table 1) under mild reaction conditions. R 1 N R 2 R 4 R 3 R 5 R 1 N R 4 R 3 R 2 R 5 CuBr (5 mol%) toluene RT or 60 °C 3 -24 h + 1a-h 2a-k 3a-r 66 -98 % Scheme 1. Synthesis of propargylamines by the addition of alkynes to enamines.

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