A Study on Side Reactions of Hydroxyethylation of 3-Nitro-4- chlorobenzenesulfinic Acid with Ethylene Oxide

The reaction of 3-nitro-4-chlorobenzenesulfinic acid and ethylene oxide to obtain 2-nitro-4-（β-hydroxyethylsulfonyl）chlorobenzene had been studied. Except hydroxyethylation on the sulfur atom of 3-nitro-4-chlorobenzenesulfinic acid to form the target product, 2-nitro-4-（β- hydroxyethylsulfonyl）chlorobenzene, there presented three kinds of side reactions： 1. Condensation and elimination of HCI to form biphenyl sulfone derivatives; 2. Addition to give bisulfonyl ethane derivative via vinyl sulfone; and 3. Hydroxylethylation on O-atom to produce hydroxylethylsulfinate due to the tautomerism of sulfinic acid.

Synthesis and antibacterial activity of brominated 2′(4′)-nitro-3-hydroxy diphenyl ethers

Eight new brominated 2＇（4＇）-nitro-3-hydroxy diphenyl ethers have been designed and synthesized. The structures of new compounds were confirmed by ^1H NMR, IR and HRMS. The bioactivity tests showed that these compounds possessed antibacterial activities against the tested bacteria. These new compounds cannot be transformed into dioxins when they were manufactured and used.

Simple HPLC-Fluorescence Determination of Raspberry Ketone in Fragrance Mist after Pre-Column Derivatization with 4-Hydrazino-7-nitro-2,1,3-benzoxadiazole

Raspberry ketone {RK, 4-(4-hydroxyphenyl)butan-2-one} is a natural compound contained in raspberry, and is added to cosmetics for skin whitening. It is very important to measure the RK level in cosmetics for quality assessment, since RK structurally resembles 4-(4-hydroxyphenyl)-2-butanol, which causes leukoderma on consumers’ skin. Here, we present a simple HPLC-fluorescence method for determination of RK in a fragrance mist by pre-column derivatization with 4-hydrazino-7-nitro-2,1,3-benzoxadiazole hydrazine (NBD-H), which reacts with the carbonyl group of RK. The NBD-RK derivative was eluted from a reversed-phase ODS column, and detected with excitation at 470 nm and emission at 550 nm. The retention time of NBD-RK derivative obtained by reaction with NBD-H at 80°C for 20 min was 10.3 min. The standard curve was linear in the range of 0.2 to 10 μg/mL, with a correlation coefficient (r2) value of 0.9980. The lower limit of detection was 0.018 μg/mL (absolute amount of 1.8 pmol). The coefficients of variation were less than 8.1%. The content of RK in fragrance mist (1.00 mL) was 1.18 ± 0.07 mg (range: 1.12 to 1.28 mg, n = 5). Recovery tests were satisfactory (83.9% ± 3.9%;range: 79.6 to 88.8%, n = 5).

Crystal Structure and Thermal Decomposition Kinetics of 3-Nitro-4-diazo-5-oxygenpyrazole

A novel compound 3-nitro-4-diazo-5-oxypyrazole was synthesized by the nitration of 4-amino-3,5-dinitropyrazole using nitrification agents of fuming nitric acid and trifluoroacetic anhydride. The compound was purified by column chromatography and characterized by IR, NMR, MS and elemental analysis. Two different single crystals obtained by culturing with ethyl acetate as a solvent were measured by X-ray single-crystal diffractometer. The molecular weight of C3HN5O3 is 155.09 and the two crystals belong to monoclinic system, space groups P21/n and P21/c. For 1： a = 5.5007（2）, b = 9.0691（4）, c = 11.4158（4） A, β = 92.710°, V = 568.85 A3, Z = 4, Dc = 1.811 g/cm3, μ = 0.162 mm-1, F（000） = 312 and the final deviation factor is 0.0213. Crystals 1 and 2 have similar unit cell parameters, except that a = 10.1828（12）, b = 5.5925（6）, c = 10.5574（10） A and β = 108.330（4）° in crystal 2. The thermal behavior of the compound was studied by TG-DSC and melting endothermic peak and decomposition exothermic peak are at 425.7 and 534.5 K in DSC curve. The activation energy and pre-exponential factor of the exothermic decomposition reaction of the title compound obtained by Kissinger method and Flynn-Wall-Ozawa method are 50.38 k J/mol, 4.59 × 1022 s^（-1） and 55.89 k J/mol.

Synthesis of A New Reagent 1-(6-Nitro-2-Benzothiazolyl)-3-(4-Nitrophenyl)-Triazene and Study on Its Color Reaction with Cadmium

This paper introduces the synthesis of a new color reagent 1-(6-nitro-2-benzothiazolyl)3-(4-nitrophenyl)-triazene (NBTNPT) and the color reaction of NBTNPT with Cd (II) has been studied. In the presence of Triton X-100, the reagent with Cd (II) forms an orange-yellow complex (1:1) at pH=11.5-12.3, the molar absorptivity is 2.81x10(5)L . mol(-1)m(-1) by dual-wavelength spectrophotometry, Beers law is obeyed in the range of 0-280 mu g/L for Cd (II).

Molecular Design and Property Prediction of High Density 4-Nitro-5-(5-nitro-1,2,4-triazol-3-yl)-2H-1,2,3-triazolate Derivatives as the Potential High Energy Explosives

To search for potential energetic materials with large energy density and acceptable thermodynamics and kinetics stability,twelve derivatives of 4-nitro-5-(5-nitro-1,2,4-triazol-3-yl)-2H-1,2,3-triazolate(named A~L)are designed and analyzed by using density functional theory(DFT)calculations at the B3LYP/6-311G**level of theory.The molecular heats of formation(HOF),electronic structures,impact sensitivity(H_(50)),oxygen balance(OB)and density(ρ)are investigated by isodesmic reaction method and physicochemical formulas.Furthermore,the detonation velocity(D)and detonation pressure(P)are calculated to study the detonation performance by Kamlet-Jacobs(K-J)equation.These results show that new molecule J(H_(50)=36.9 cm,ρ=1.90g/cm^(3),Q=1912.46 cal/g,P=37.82 GPa,D=9.22 km/s,OB=0.00),compound A(H_(50)=27.9 cm,ρ=1.93 g/cm^(3),Q=1612.93 cal/g,P=38.90 GPa,D=9.19 km/s)and compound H(H_(50)=37.3 cm,ρ=1.97 g/cm^(3),Q=1505.06cal/g,P=37.20 GPa,D=9.01 km/s)present promising effects that are far better RDX and HMX as the high energy density materials.Our calculations can provide useful information for the molecular synthesis of novel high energy density materials.

Theoretical Study on the Nitrogen-rich Derivatives Based on 1,2,4-Triazole and 1,2,3-Triazole Rings:an Extended Family of Power Performance Energetic Materials

The geometric and electronic structures of the derivatives of 4-nitro-5-(5-nitroimino-1,2,4-triazol-3-yl)-2H-1,2,3-triazolate(named A~J)are explored employing density functional theory(DFT)calculations at the B3LYP/6-311G^(**)level of theory.Based on the optimized molecular structures,the heats of formation(HOF)are obtained,and the electronic properties,density and molecular sensitivity by characteristic heights(H_(50))are discussed.Besides,the detonation performances(detonation velocity,detonation pressure)are estimated via Kamlet-Jacobs(K-J)formula.Compounds B(H50=29.4 cm,ρ=1.91 g/cm^(3),Q=1563.04 cal/g,P=36.05 GPa,D=8.95 km/s)and H(H_(50)=31.9 cm,ρ=1.80 g/cm^(3),Q=1610.09 cal/g,P=37.31 GPa,D=9.12 km/s)have positive HOFs and remarkable insensitivity and good detonation performance,strongly suggesting them as the acceptable new-type explosive.The initiating power surpasses conventional primary explosives,such as HMX.The outstanding detonation power of compounds B and H contributes to its future prospects as a promising green primary explosive.

Designing energetic covalent organic frameworks for stabilizing high-energy compounds

As an emerging high-energy compound,3-nitro-1,2,4-triazol-5-one(NTO)is used in military explosives and rocket propellants.However,the strong acidic corrosion of NTO,and the high sensitivity and poor thermostability of its salts,severely restrict their practical applications.Therefore,a novel strategy to design and construct energetic covalent organic frameworks(COFs)is proposed in this study.We have successfully prepared a two-dimensional crystalline energetic COF(named ECOF-1)assembled from triaminoguanidine salt,in which NTO anions are trapped in the porous framework via the ionic interaction and hydrogen bonds.The results show that ECOF-1 exhibits superior thermal stability than energetic salt of NTO.It also exhibits insensitivity and excellent heat of detonation of 7,971.71 kJ·kg−1.ECOF-1 greatly inhibits the corrosiveness of NTO.In prospect,energetic COFs are promising as a functional platform to design high-energy and insensitive energetic materials.