Synthesis of New Substituted 4-Amino-3,5-dinitropyridine Derivatives

Facile synthetic routes for the preparation of some new 4-amino-3,5-dinitropyridine derivatives have been revealed. Nitration of 2-chloropyridin-4-amine （1） as a starting material, in an unexpected one-step reaction, to give dinitrated derivatives, followed by nucleophilic substitution reactions with sodium azide, potassium fluoride, ammonia, methylamine, and 4-nitroimidazol, respectively, gave substituted 4-amino-3,5-dinitropyridine derivatives. Meanwhile, its azide derivative underwent a ring closure conversion into 7-amino-6-nitro-[1,2,5]oxadiazolo[3,4-b]- pyridine-1-oxide. It is of significance that all of the nucleophilic substitution reactions were carried out under mild conditions.

Synthesis,crystal structure and thermal behavior of 4-amino-3,5-dinitropyrazole copper salt

A novel energetic combustion catalyst, 4-amino-3,S-dinitropyrazole copper salt （[Cu（adnp）2（H2O）2]）, was synthesized in a yield of 93.6% for the first time. The single crystal of [Cu（adnp）2（H2O）2] was determined by single crystal X-ray diffraction. It crystallizes in a triclinic system, space group p^-1 with crystal parameters a = 5.541（3） A, b = 7.926（4） A, c = 10.231（5） A,β = 101.372（8）°, V = 398.3（3） A3, Z = 1, μ = 1.467 mm^-1, F（0 0 0） = 243, and Dc = 2.000 g cm^-3. The thermal behavior and non-isothermal decomposition reaction kinetics of [Cu（adnp）2（H2O）2] were studied by means of different heating rate differential scanning calorimetry （DSC）. The kinetic equation of major exothermic decomposition reaction for [Cu（adnp）2（H2O）2] was obtained. The entropy of activation （△S≠）, enthalpy of activation （△H≠）, free energy of activation （△G≠）, the self-accelerating decomposition temperature （TSADT） and the critical temperature of thermal explosion （Tb） are 59.42 j mol^-1 K^-1, 169.5 kJ mol^-1, 1141.26 kJ mol ^-1 457.3 K and 468.1 K, respectively.

In situ ATR-FTIR Combined with SIMPLISMAAlgorithm to Investigate the Synthesis Mechanism of 4-Amino-3,5-dimethyl Pyrazole

In situ attenuated total refletion-Fourier transform infrared spectroscopy（ATR-FTIR） was used to monitorand acquire spectral information on the synthesis of 4-amino-3,5-dimethyl pyrazole. Principal component analy-sis（PCA） was used to determine the number of principle components（PCs）. The score vectors of the PCs were ana-lysed using the simple-to-use interactive self-modelling mixture analysis（SIMPLISMA） algorithm to obtain spectraland concentration profiles for the reactants, intermediates and product. The vibrational frequencies of the interme-diates were calculated via density ftmctional theory（DFT） at the level of the B3LYP/6-31 l＋＋G（d,p） basis set, and thegeometrical configurations of the intermediates were simultaneously optimized. Finally, a reasonable synthesismechanism for 4-amino-3,5-dimethyl pyrazole was determined based on the changes observed in the feature peaks.The results from the SIMPLISMA algorithm correlated well with the quantttm chemistry calculations. This provedthat the SIMPLISMA algorithm combined with ATR-FTIR can be used to detemfine the synthesis mechanism for4-amino-3,5-dimethyl pyrazole and can even provide a new, useful method to explore dynamic synthesis reactionmechanisms.

Syntheses, Structures and Properties of Four Manganese Coordination Polymers Derived from 4-Amino-3,5- bis（imidazol-1 -ylmethyl）-1,2,4-triazole

The reaction of 4-amino-3,5-bis（imidazol-l-ylmethyl）-1,2,4-triazole （abit） and manganese（Ⅱ） salts yields four coordination polymers {[Mn（abit）3]（C104）z}n （1）, {[Mn（abit）3]（PF6）2},, （2）, [Mn（abit）（dca）2（H2O）2],, （3a） and [Mn（abit）（dca）2（H2O）2]n （3b）. Compounds 1 and 2 are one-dimensional triple-stranded chain. Compounds 3a and 3b are polymorphous and construct one-dimensional single chain. The conformational analysis is performed. The thermal properties have been investigated.

Auxiliary Ligands Mediated One- and Two-dimensional Cd(Ⅱ) Coordination Polymers Incorporating Methyl-3- hydroxy-5-carboxy-2-Thiophenecarboxylate Ligand

Two N-donor ligands mediated Cd（Ⅱ） coordination polymers, namely,[Cd（L）（dmpz）2]n （1） and {[Cd（L）（atr）05（H20）]（H2O）}n （2） （H2L = methyl-3-hydroxy-5-carboxy-2-thiophenecarboxylate, dmpz = 3,5-dimethylpyrazole, and atr= 4-amino-l,2,4-triazole）, havebeen produced. Their structures were characterized by single-crystal X-ray diffraction analysis,elemental analyses and infrared spectra. Compound 1 possesses a one-dimensional （1D） chainstructure and is finally extended into a three-dimensional （3D） supramolecular architecturethough hydrogen bonding interactions. Compound 2 features a two-dimensional （2D） networkwith 4-connected sql topology based on dinuclear Cd（Ⅱ） clusters as nodes, which is alsoassembled into a 3D supramolecular architecture through hydrogen bonding interactions.Furthermore, compounds 1 and 2 exhibit high thermal stabilities and intense fluorescent emissionin the solid, and can be explored as potential luminescent materials.

Two New Iron Coordination Polymers Based on Fe-pyta Chains Incorporating Pyridine-2,4,6-tricarboxylate

Reaction of FeCIz＇6H20, pyridine-2,4,6-tricarboxylic acid（H3pyta） and NaOH in the hydrothermal system at 185 ℃ resulted in the formation of 1D coordination polymer[Fe（Hpyta）（H2O）2]（1） based on Fe-Hpyta chains. When the abpt[abpt=-4-amino-3,5-bis（4-pyridyl）-l,2,4-triazole] ligand was employed in the reaction system, a 3D supramolecular porous network （H2bpt）[Fe（pyta）（H2O）2]·4H2O（2） was obtained. The framework was constructed with negative （Fe-pyta） chains and the positive H3bpt^＋ in situ, formed from the abpt reagent, to form 1D channels filled with guest water molecules via hydrogen-bonds. X-Ray diffraction crystal structure analysis shows that complex 1 crystallized in the monoclinic system, space group C2/c, a=1.1490（5） nm, b=0.9008（4） nm, c=1.0058（5） nm, B=107.254（9）°, V=0.9942（8） nm3, Z=4; and complex 2 crystallizes in the triclinic system, space group P1 with a=0.90392（11） nm, b=0.96027（11 ） nm, c=1.55540（18） nm, a=73.558（2）°,B= 86.126（2）°,r= 68.745（2）°, V=1.2059（2） nm^3 and Z=2.

Synthesis,Crystal Structure and Evaluations of Its Cytotoxicity,Anti-microbial and Anti-hydroxyl Radical Activities of a New Co-crystal Compound(C6H6Cl2N2O2S)·(Phen)·H2O

Co-crystal is a very potential kind of drug solid forms, and has a far-reaching influence on designing and preparing drugs. A new 1：1：1 co-crystal compound consisting of 4-amino-3,5-dichloro-benzenesulfonamide, 1,10-phenanthroline and water was synthesized, and its crystal structure was characterized by X-ray diffraction method. The compositions of the co-crystal are self-assembled into a three-dimensional network structure via intermolecular interactions including hydrogen bonds, π-π stacking, Cl？？？Cl interactions and van der Waals＇ forces. According to the evaluations of cytotoxicity assays, anti-microbial and anti-hydroxyl radicals, this co-crystal is a potential drug.