Polygonal mesopores microflower catalysts for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene to 2-nitro-4-methylsulfonylbenzoic acid in a continuous-flow microreactor

The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene(NMST)to 2-nitro-4-methylsulfonyl benzoic acid(NMSBA)with atmospheric air or molecular oxygen in alkaline medium presents a significant challenge for the chemical industry.Here,we report the synthesis of FeOOH/Fe_(3)O_(4)/metal-organic framework(MOF)polygonal mesopores microflower templated from a MIL-88B(Fe)at room temperature,which exposes polygonal mesopores with atomistic edge steps and lattice defects.The obtained FeOOH/Fe_(3)O_(4)/MOF catalyst was adsorbed onto glass beads and then introduced into the microchannel reactor.In the alkaline environment,oxygen was used as oxidant to catalyze the oxidation of NMST to NMSBA,showing impressive performance.This sustainable system utilizes oxygen as a clean oxidant in an inexpensive and environmentally friendly NaOH/methanol mixture.The position and type of substituent critically affect the products.Additionally,this sustainable protocol enabled gram-scale preparation of carboxylic acid and benzyl alcohol derivatives with high chemoselectivities.Finally,the reactions can be conducted in a pressure reactor,which can conserve oxygen and prevent solvent loss.Moreover,compared with the traditional batch reactor,the self-built microchannel reactor can accelerate the reaction rate,shorten the reaction time,and enhance the selectivity of catalytic oxidation reactions.This approach contributes to environmental protection and holds potential for industrial applications.

Intrinsic kinetics of catalytic hydrogenation of 2-nitro-4-acetylamino anisole to 2-amino-4-acetylamino anisole over Raney nickel catalyst

The catalytic hydrogenation of 2-nitro-4-acetylamino anisole(NMA)is a less-polluting and efficient method to produce 2-amino-4-acetamino anisole(AMA).However,the kinetics of catalytic hydrogenation of NMA to AMA remains obscure.In this work,the kinetic models including power-law model and Langmuir-Hinshelwood-Hougen-Watson(LHHW)model of NMA hydrogenation to AMA catalyzed by Raney nickel catalyst were investigated.All experiments were carried out under the elimination of mass transfer resistance within the temperature range of 70–100°C and the hydrogen pressure of 0.8–1.5 MPa.The reaction was found to follow 0.52-order kinetics with respect to the NMA concentration and 1.10-order kinetics in terms of hydrogen pressure.Based on the LHHW model,the dual-site dissociation adsorption of hydrogen was analyzed to be the rate determining step.The research of intrinsic kinetics of NMA to AMA provides the guidance for the reactor design and inspires the catalyst modification.

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).

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).

2-硝基-4-氯苯酚合成工艺优化研究

以对二氯苯为原料,通过混合酸硝化、常压相转移催化水解,得到了目标产物2-硝基-4-氯苯酚。考察了碱量、碱浓度、相转移催化剂类型及用量对水解反应的影响,通过优化水解条件为反应6 h,1.4 g四丁基溴化铵,25%的氢氧化钾溶液,300 mL水。产品最高收率可达88.9%。

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.

Non-isothermal Kinetics of the Thermal Decomposition of 3-Nitro-1,2,4-triazol-5-one Magnesium Complex

The thermal decomposition of 3-nitro-1,2,4-triazol-5-one magnesium complex and its kinetics were studied under the non-isothermal condition by DSC and TG/DTG methods. The kinetic parameters were obtained from analysis of the DSC and TG/DTG curves by the Kissinger method,the Ozawa method,the differential method and the integral method. The most probable mechanism functions for the thermal decomposition of the first stage,the second stage and the third stage were suggested by comparing the kinetic parameters. The entropy of activation (ΔS ≠),enthalpy of activation (ΔH ≠) and free energy of activation (ΔG ≠) at Tpdo are -66.74 J·mol -1 ·K -1 ,119.2 kJ·mol -1 and 152.44 kJ·mol -1 ,respectively.

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.