RESUMO
The structures of the cocrystalline adducts of 3-nitrophenol (3-NP) with 1,3,5,7-tetraazatricyclo[3.3.1.13,7]decane [HMTA, (1)] as the 2:1:1 hydrate, 2C6H5NO3·C6H12N4·H2O, (1a), with 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane [TATU (2)] as the 2:1 cocrystal, 2C6H5NO3·C7H14N4, (2a), and with 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane [TATD, (3)] as the 2:1 cocrystal, 2C6H5NO3·C8H16N4, (3a), are reported. In the binary crystals (2a) and (3a), the 3-nitrophenol molecules are linked via O-H...N hydrogen bonds into aminal cage azaadamantanes. In (1a), the structure is stabilized by O-H...N and O-H...O hydrogen bonds, and generates ternary cocrystals. There are C-H...O hydrogen bonds present in all three cocrystals, and in (1a), there are also C-H...O and C-H...π interactions present. The presence of an ethylene bridge in the structures of (2) and (3) defines the formation of a hydrogen-bonded motif in the supramolecular architectures of (2a) and (3a). The differences in the C-N bond lengths of the aminal cage structures, as a result of hyperconjugative interactions and electron delocalization, were analysed. These three cocrystals were obtained by the solvent-free assisted grinding method. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation from a mixture of hexanes.
RESUMO
Solvent-free treatment of 1,3,6,8-tetra-aza-tri-cyclo-[4.3.1.13,8]undecano (TATU) with 4-chloro-3,5-di-methyl-phenol led to the formation of the title co-crystal, C7H14N4·2C8H9ClO. The asymmetric unit contains one aminal cage mol-ecule and two phenol mol-ecules linked via two O-Hâ¯N hydrogen bonds. In the aminal cage, the N-CH2-CH2-N unit is slightly distorted from a syn periplanar geometry. Aromatic π-π stacking between the benzene rings from two different neighbouring phenol mol-ecules [centroid-centroid distance = 4.0570â (11)â Å] consolidates the crystal packing.
RESUMO
An efficient methodology to obtain novel antifungal analogs of brassinin 1 is described. Starting from l-tryptophan 2, N,N'-dialkylthiourea 4, 4-[(1H-indol-3-yl)methylene]-2-sulfanylidene-1,3-thiazolidin-5-one 5 and alkyl (2S)-3-(1H-indol-3-yl)-2-{[(alkylsulfanyl)carbonothioyl]amino}propanoate 6 type compounds were obtained as main products in different ratios depending on the reaction conditions via a tandem dithiocarbamate formation and Michael addition reaction. In order to understand the dependence of the reaction conditions on the mechanism pathway, a DFT/B3LYP study was performed. The results suggested the existence of competitive mechanistic routes which involve the presence of an ionic dithiocarbamate intermediate 9. Antifungal activities of all products were then evaluated against Fusarium oxysporum through mycelial growth inhibition using a microscale amended-medium assay. IC50 values were thus determined for each compound. These results showed that 6-related compounds can be considered as promissory antifungal agents.
Assuntos
Fusarium/efeitos dos fármacos , Indóis/síntese química , Indóis/farmacologia , Triptofano/química , Antifúngicos/síntese química , Antifúngicos/química , Antifúngicos/farmacologia , Indóis/química , Modelos Moleculares , Estrutura Molecular , Micélio/efeitos dos fármacos , Tiocarbamatos/químicaRESUMO
The title chiral quaternary ammonium salt, C(13)H(25)N(4) (+)·I(-), was synthesized through the Menschutkin reaction between the cage aminal (2S,7S)-1,8,10,12-tetra-aza-tetra-cyclo-[8.3.1.1(8,12).0(2,7)]penta-decane and ethyl iodide. The quaternization occurred regioselectively on the nitrogen with major sp3 character. The crystal structure consists of anions and cations separated by normal distances. Ions are not linked through C-Hâ¯I hydrogen bonds.
RESUMO
BACKGROUND: Novel mono N-alkyl quaternary ammonium salts (3a-f) were prepared using the Menschutkin reaction from the cage adamanzane type aminal 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (TATU) and alkyl iodides, such as methyl, ethyl, propyl, butyl, pentyl and hexyl iodide (2a-f), in dry acetonitrile at room temperature. RESULTS: The structures of these new quaternary ammonium salts were established using various spectral and electrospray ionization mass spectrometry (ESI-MS) analyses. Compound (3b) was also analyzed using X-ray crystallography. CONCLUSION: It was noted that alkyl chain length did not significantly affect the reaction because all employed alkyl iodide electrophiles reacted in a similar fashion with the aminal 1 to produce the corresponding mono N-quaternary ammonium salts, which were characterized by spectroscopic and analytical techniques.
RESUMO
The title compound, 1,5:3,7-dimethano-1,3,5,7-benzotetrazonine-hydroquinone (2/1), 2C(11)H(14)N(4).C(6)H(6)O(2), crystallizes with the hydroquinone molecule located on a center of inversion. In contrast to other hydroquinone-adamanzane adducts, which form extended hydrogen-bonded networks, in the present case, one hydroquinone molecule is linked to two 1,5:3,7-dimethano-1,3,5,7-benzotetrazonine molecules, forming a 2:1 cluster through O-H...N hydrogen bonds.