Richard Gilardi

Hepta- and Octanitrocubanes

Four of the eight nitro groups of octanitrocubane 1 are introduced by functional group modification, three more by the astonishingly rapid, low-temperature N(2)O(4) nitration of sequentially formed polynitrocubyl anions, and the eighth and last by nitrosation of the heptanitrocubyl anion followed by ozonation.

Synthesis of polyazapolycyclic caged polynitramines

Abstract Syntheses of new polyazapolycyclic caged polynitramines are described. Sequentially reacting 4,10-dibenzyl-2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazaisowurtzitane (5a) with NOBF4 and NO2BF4 in sulfolane solvent produces 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo-[5.5.0.05,9.03,11]dodecane, 6). Syntheses of two new polyazapolycyclic caged trinitramines, 3,5,12-trinitro-3,5,12-triazawurtzitane (7a) and 2,4,10-trinitro-2,4,10-triazaadamantane (12a), as well as their labile parent secondary amines, are discussed. A new caged polynitrosamine, 3,5,12-trinitroso-3,5,12-triazawurtzitane (7d), has been obtained by ring-cleavage nitrosation of the new hexamine-wurtzitane compound 3,5,7,9-tetraazahexacyclo-[9.3.1.13,7.02,9.04,13.05,10]-hexadecane (10).

Iron(III) complexes of some thiosemicarbazones derived from 2-acetylpyridine, its 6-methyl derivative and itsN-oxide

SummaryA series of iron(III) complexes of thiosemicarbazones derived from 2-acetylpyridine, 6-methyl-2-acetylpyridine and 2-acetylpyridineN-oxide have been prepared from Fe(ClO4)3 and FeCl3. All of the isolated solids have cations involving two monobasic tridentate ligands, and either perchlorate or tetrachloroferrate(III) anions and are 1∶1 electrolytes. Coordinationvia the pyridine nitrogen (or theN-oxide oxygen), the imine nitrogen and the sulphur atom are confirmed by infrared spectra and x-ray diffraction. The presence of two different iron(III) species is indicated by the electron spin resonance spectra of the tetrachloroferrate(III) solids. E.s.r. along with electronic spectra prove the spin-paired configuration of these cationic iron(III) complexes.

Octanitrocubane: A New Nitrocarbon

Octanitrocubane, the first new nitrocarbon in 18 years, is introduced as a potential explosive of great power. Its synthesis and characterization are described.

4,4′,6,6′-Tetra-Substituted Hydrazo- and Azo-1,3,5-Triazines

The syntheses of 4,4′,6,6′-tetra(amino)- (1), tetra(hydroxylamino)- (2), tetra(hydrazino)- (3), and tetra(azido)hydrazo-1,3,5-triazines (4) are described. Compound (4) was oxidized to 4,4′,6,6′-tetra(azido)azo-1,3,5-triazine (5). The thermal and sensitivity properties of (4) and (5) are reported in addition to all physical properties of new compounds

Design and synthesis of AB3-type (A = 1,3,5-benzenetricarbonyl unit; B = Glu diOME or Glu7 octa OMe) peptide dendrimers: Crystal structure of the first generation†‡

The first generation molecule of glutamic acid-based dendrons on a 1, 3,5-benzenetricarbonyl core leads to a cylindrical assembly as demonstrated by single crystal x-ray diffraction. The benzene pi-pi stack (A) is stabilized by vertical NH...O===C hydrogen bonding with each subunit participating in three intermolecular hydrogen bonds related by three-fold rotation symmetry.

Unique assemblies of alternating positively and negatively charged layers, directed by hydrogen bonds, ionic interactions, and Π-stacking in the crystal structures of complexes between mellitic acid (benzenehexacarboxylic acid) and five planar aromatic bases

AbstractBenzenehexacarboxylic acid, mellitic acid (MA), has been used as a core motif to study possible radial self-assembly using complementary aromatic bases. By mixing water solutions of the components, crystals of the salts of MA with 4-aminopyridine (AP), 4-dimethylamino-pyridine (DM), 2,2′-bipyridine (DP), o-phenanthroline (PL), and melamine (ML) have been obtained. The MA−n ions have assembled in either extended sheets for MA−2 or extended ribbons for MA−4 by direct hydrogen bonding between MA and MA and additionally through mediation of hydrogen bonds to water molecules that distribute the negative charges throughout the MA sheet or ribbon. Most of the O atoms in carboxyl groups in the MA ions in the five complexes have been rotated significantly out of the plane of the central benzene ring. There are multiple base molecules, two or four, for each mellitic acid ion in the five complexes. Most of the NH+ moieties in all five bases make direct NH+ ⋅ ⋅ ⋅ O–C hydrogen bonds with MA−n. The planar base ions are generally arranged in stacks in which the components range from being parallel, with interplanar separations of 3.5 Å, to having a considerable tilt with respect to each other with nearest interplanar separation of atoms greater than 3.9 Å. These geometric characteristics are reflected in the color of the crystals. The three-dimensional networking makes some of the crystals very hard. Cell dimensions: 1, C32H30N8O12 ⋅ 2H2O, C2/c, a =13.764(2) Å, b =18.053(3) Å, c =14.876(4) Å, β =105.99(2)° 2, C26H26N4O12 ⋅ 3H2O, P21/n, a =15.891(1) Å, b =10.444(1) Å, c =18.242(1) Å, β =97.00(1); 3, C64H44N8O24⋅7H2O, P21/c, a =23.016(4) Å, b =15.241(2) Å, c =19.124(2) Å, β =100.60(1)° 4, C36H22N4O12, P21/n, a =14.581(1) Å, b =10.472(1) Å, c =20.607(2) Å, β =106.43(1); 5, C18H18N12O12 ⋅ 2H2O,

Synthesis of 3,6-bis(3-azido-1,2,4-triazol-1-yl)-1,2,4,5-tetrazine

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