Preparation, Crystal Structure, and Thermal Analysis of Carbohydrazide Trinitrophloroglucinolate

A new compound （CHZ）（HTNPG）·0.5H2O was synthesized by mixing carbohydrazide（CHZ） and trinitrophloroglucinol（TNPG） and characterized by elemental analysis and Fourier transform infrared （FTIR） spectrum. Its crystal structure was determined by single crystal X-ray diffraction analysis. The crystal belongs to triclinic system, P1 space group, with a=0.45578（9） nm, b=1.0142（2） nm, c=1.3041（3） nm, α=86.53（3）°, β=99.56（3）°, γ=81.94（3）°, V= 0.5958（2） nm^3, Z=2, Dc=2.008 g/cm^3, R1=0.0476, and wR2=0.1139. The compound is a di-substituted salt of TNPG, which consists of a cation （CHZ）^2＋ and an anion （HTNPG）^2-. The thermal analysis of the compound was studied by means of differential scanning calorimetry（DSC） and thermogravimetry-derivative thermogravimetry（TG-DTG）. Under nitrogen atmosphere at a heating rate of 10 ℃/min, the thermal decomposition of the compound contained one endothermic process of dehydrating stage and two intense exothermic decomposition processes in a temperature range of 140--232 ℃ on the DSC trace. The decomposition products of the title compound are nearly gaseous products. The existing complicated hydrogen bond networks and electrostatic attraction between （CHZ）^2＋ and （HTNPG）^2- enhance the thermal stability of the title compound.

A New Two-dimensional Cd(Ⅱ) Coordination Polymer Constructed by Pyridine-2,5-dicarbohydrazide

A new two-dimensional Cd（Ⅱ） coordination polymer, [Cd（2,5-pdch）（H2O）]n·2n（ClO4）·nH2O （2,5-pdch = pyridine-2,5-dicarbohydrazide）, was prepared and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction analysis. The crystal belongs to monoclinic, space group P21/c with a = 10.905（2）, b = 11.602（1）, c = 15.034（2） A, β = 117.794 （10°, V = 1682.8（4A3, Z = 4, C7H13CdCl2NsO12, Mr = 542.52, Dc = 2.141 g/cm^3,/μ = 1.691 mm^-1, F（000） = 1072, 2（MoKa） = 0.71073A, the final R = 0.0608 and wR = 0.1329 for 2972 observed reflections with I 〉 2σ（I）. Single-crystal X-ray diffraction analysis reveals that the Cd（Ⅱ） atom displays a distorted pentagonal-bipyramidal geometry coordinated by three N atoms and three O atoms from three different 2,5-pdch ligands, and one water molecule. Interestingly, each two Cd（Ⅱ） atoms are bridged by two carbohydrazide groups of the 2,5-pdch ligands to form a dimeric unit, and such dimeric units are further connected by the 2,5-pdch ligand to generate a two-dimensional （4,4）-network.

Comparative DFT Study of [Mg(CHZ)_3](ClO_4)_2 and [Mg(CHZ)_3](NO_3)_2(CHZ=Carbohydrazide)

The molecular geometry,electronic structure,thermochemistry and infrared spectra of [Mg（CHZ）3]（ClO4）2 and [Mg（CHZ）3]（NO3）2 were comparatively studied using the Heyd-Scuseria-Ernzerhof（HSE） screened hybrid density functional with 6-31G＊＊ basis set.The experimental results show that the complexes have six-coordinated octahedron feature,and the metal-ligand interactions are predominantly ionic in nature.The calculated heats of formation predict that [Mg（CHZ）3]（NO3）2 is more stable than [Mg（CHZ）3]（ClO4）2.Detailed NBO analyses indicate that the ligand-anion interaction plays an important role in the stability for these two energetic complexes.Moreover,the stretching vibration frequencies of N-H bonds shift to lower wave number compared to the free CHZ ligand,which are caused by the delocalizations from N-H bond orbital to lone-pair electron antibond orbital of magnesium.

Flash Pyrolysis Study of M2TNR （M： Carbohydrazide or Semicarbazide） by T-jump/FTIR Spectroscopy

Flash pyrolysis of （CHZ）2TNR and （SCZ）2TNR was conducted by T-jump/FTIR spectroscopy under 0.1 MPa Ar atmosphere. The results show that eleven IR-active gas products obtained during flash pyrolysis process of the two title compounds are NO, CO, HCN, NH3, NO2, N2O, HNCO, HNO2, CO2, H2O and HCHO, of which NO and CO are the main gas products. The molar fraction of the individual product in the pyrolysis gas mixture was described as a function of time. At least some of the NO2, N2O and H2O can result from the oxidization reaction of NH3 during flash pyrolysis of （CHZ）2TNR. It can be concluded that the two compounds are not worthy of further in-depth consideration of the adoption in detonators as eco-friendly primary explosive, and should not be used as gas generation composition of automobile crash airbag system taking into account the toxicity.

Synthesis,Bioactivity Evaluation,3D-QSAR,and Molecular Docking of Novel Pyrazole-4-carbohydrazides as Potential Fungicides Targeting Succinate Dehydrogenase

To screen novel antifungal agents targeting the succinate dehydrogenase(SDH),a series of pyrazole-4-carbohydrazides were rationally designed,synthesized,and characterized under the guidance of the structures of succinate dehydrogenase inhibitors(SDHIs).Bioassay results in vitro indicated that most of the target compounds exhibited excellent activity against Rhizoctonia solani(R.solani),Fusarium graminearum(F.graminearum),Botrytis cinerea(B.cinerea)and Colletotrichum capsica(C.cinerea).Compounds 7d,7l,7t and 7x were identified as the most promoting candidates,and their anti-F.graminearum EC50 values were as low as 0.56,0.47,0.46 and 0.49μg/mL,respectively,presenting the similar antifungal activity as that of the commonly used fungicide carbendazim(0.43μg/mL).The 3D-QSAR models were built for a systematic structure-activity relationship profile to explore more potent pyrazole-4-carbohydrazides as novel fungicides.Molecular docking of 7d,7l and 7r with SDH was performed to reveal the binding modes in active pocket and analyze the interactions between the molecules and the SDH protein.

Synthesis,Structural Characterization,Fluorescence Properties and Herbicidal Activity of Bis(substituted salicylaldehyde)Carbohydrazide Dibutyltin Complexes

A series of dibutyltin complexes,(Bu_(2)Sn)_(2)L,[(Bu_(2)Sn)_(2)L]3 and H_(2)LSnBu_(2),were synthesized by microwave-assisted methanolic solvothermal method,where H4L is[_(2)-(OH)-R-ArCH=NNH]_(2)CX,and X=O,R=4-NEt_(2)(Tl),5-Br(T_(2));X=S,R=H(T3);R=5-Br(T4).Their structures were characterized by elemental analysis,IR and(^(1)H,^(13)C)-NMR spectra.The molecular structure of T_(2) was confirmed by X-ray diffraction.The crystal of T_(2) belongs to monoclinic system,space group la.Five-coordinated distorted triangular bipyramids and six-coordinated distorted octahedral configurations were formed by the coordination of oxygen and nitrogen atoms of ligand with two dibutyltins,thus forming a trimeric hexanuclear butyltin complex by the cross coordination of three units(Bu_(2)Sn)_(2)L with enol imines.The T_(2) and T4 exhibit fluorescence emission in DMF solvents and DMF-water mixture.The fluorescence intensity of T_(2)-DMF-H_(2)0 system decreases almost linearly with the increase of water volume fraction(WVF).The aggregation fluorescence enhancement effect of T4-DMF-H_(2)0 solution system increases with the increase of WVF at the range of 0-_(2)0%WVF.When WVF is more than _(2)0%,the fluorescence intensity decreases with the increase of WVF.In addition,T1〜T4 have broad growth activities on target plants,such as Portulaca oleracea L.,Amaranthus spinosus L.,Cassia tora L.,Brassica campestris L.ssp.chinensis var.utilis Tsen et Lee,and Amaranthus tricolor L.,and can be used as a candidate herbicide for further research.

Flash Pyrolysis Study of MnTC and NiCT by Using T-Jump/FTIR Spectroscopy

Flash pyrolysis of MnTC（ [Mn2（TNR）2（CHZ）2（H2O）4]·2H2O） and NiCT（ [Ni（CHZ）3]（TNR）·5H2O） is conducted by using T-jump/FTIR spectroscopy under 0.1 MPa Ar atmosphere. The mole fractions of the individual products in the pyrolysis gas mixture are described as a function of time. Results show that NiCT appears to produce more N2O, NH3 and HONO upon flash pyrolysis, thus secondary oxidation reduction reactions may take place to a certain extent during its thermal decomposition, which in turn leads to unsteady combustion and possibly to failure of the device. While H2O and CO2 are the major two gas products of flash pyrolysis of MnTC, it warrants further in-depth trials for the adoption in detonators as coo-friendly and chemically compatible primary explosive. The two compounds both liberate volatile metal carbonate, oxide and isocyanate compounds.

Kinetics Study on the Exothermic Decomposition Reaction of [Cd（CHZ）3]（ClO4）2

The Temperature-jump/FTIR （T-jump/FTIR） spectroscopy was introduced to resolve the decomposition kinetics parameters of [Cd（CHZ）3]（ClO4）2 （CdCP） at high temperature following very rapid heating process. The increase in the absorbances during the flash pyrolysis of CdCP yielded the kinetics parameters in the range of 360-430 ℃ at 0.1 MPa Ar atmosphere： Ea=28.6 kJ/mol and In A= 17. The kinetics parameters of the exothermic decomposition reaction were also determined by using DSC method. The value of Ea determined by T-jump/FTIR spectroscopy is smaller than that by Kissinger method and Ozawa-Doyle method, which makes these values qualitatively consistent with other energetic materials. The T-jump/FTIR spectroscopy might be resembled as the surface of explosion reaction very closely. In addition, the decomposition kinetics of evolution of the major four individual gas products was also resolved by T-jump/FTIR spectroscopy, which might be essential for detailed combustion modeling of solid energetic materials.

Novel Synthesis of Some Phthalazinone Derivatives

Dimethyl homophthalate condensed with isatin to give the unexpected five membered lactone 3 rather than the half ester 1 and the β-lactone 2. Treatment of compound 3 with excess hydrazine hydrate afforded phthalazinone carbohydrazide 4 which represents a novel method for the synthesis of phthalazinone derivatives. The carhohy- drazide 4 upon treatment with carbon disulphide afforded 1,3,4-oxadiazole derivative 5, which reacted with ethyl- chloroacetate to give the S-alkylated product 6. The structure of compound 3 compared with 2 was discussed using hyperchem professional （7） AM1 calculations, X-ray single crystal structure and complete spectral data.