Phosphorus fertilizers from less pure sedimentary sources become increasingly important, due to depletion of phosphorus from igneous rock of high quality. Consequently, robust methods with potential to remove various ...Phosphorus fertilizers from less pure sedimentary sources become increasingly important, due to depletion of phosphorus from igneous rock of high quality. Consequently, robust methods with potential to remove various types of hazardous elements are required. Among such impurities, hexavalent chromium (Cr(VI)) is very likely to become a future challenge. Different industrial ways to treat phosphate rock are currently being practised, and we have here studied how chromium behaves when using the nitro-phosphate process. The reduction mechanism of Cr (VI) in nitric acid and phosphoric acid solutions was investigated by measuring redox potential and UV-VIS spectra. The results show that Cr (VI) is not stable in strong nitric acid solutions. Reduction of Cr (VI) species decreased with decreasing temperature, NO<sub>2</sub> concentration, ionic strength and absence of light. These findings support the proposed reduction reaction:The reduction rate was observed proportional to the nitric acid decomposition: .展开更多
Methyluracil and 5-nitro-6-methyluracil react with variable molar quantities of benzoyl chloride in acetonitrile-pyridine at room temperature to give 1-N, 3-N-dibenzoyl-6- methyluracil 3b and 1-N-benzoyl-5-nitro-6-met...Methyluracil and 5-nitro-6-methyluracil react with variable molar quantities of benzoyl chloride in acetonitrile-pyridine at room temperature to give 1-N, 3-N-dibenzoyl-6- methyluracil 3b and 1-N-benzoyl-5-nitro-6-methyluracil 4b. The reactive rates of debenzoylation of 3b and 4b were investigated.展开更多
The thermal decomposition of ammonium 3-nitro-1,2,4-triazol-5-onate monohydrate[NH4（NTO）·H2O] was studied by means of thermal analysis-MS coupling and the combination technique of in situ thermolysis cell with ...The thermal decomposition of ammonium 3-nitro-1,2,4-triazol-5-onate monohydrate[NH4（NTO）·H2O] was studied by means of thermal analysis-MS coupling and the combination technique of in situ thermolysis cell with rapid-scan Fourier transform infrared spectroscopy. The results show that there are two endothermic steps and one exothermic step in the decomposition process of NH4（NTO）·H2O. The detected gas products consist of NH3, H2O, N2, CO2, CO, and NO2.展开更多
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-chloroben...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.展开更多
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 compo...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.展开更多
The title compound C18H16N4O3 （Mr = 336.35） has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Schiff base compound is a derivative of 4-aminoantipyrine. As expect...The title compound C18H16N4O3 （Mr = 336.35） has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Schiff base compound is a derivative of 4-aminoantipyrine. As expected, the molecular structure adopts a trans configuration about the central C=N double bond. It crystallizes in orthorhombic, space group P2dc with a = 7.632（1）, b = 7.816（1）, c = 28.082（5） A,β = 96.18（1）°, V= 1665.48（51） A^3, Z= 4, Dc = 1.341 g/cm^3, F（000） = 704,μ = 0.094 mm^-1, the final R = 0.0448 and wR = 0.1058. Of the total 3748 collections, 3105 were unique. In the molecule there exist two different planes of pyrazoline and C（11）-C（16） phenyl ring, which are approximately coplanar （r.m.s. de deviation from the combined mean plane is 0.03 A） with the dihedral angle between them of 9.8%.展开更多
Seven optimized configurations and their electronic structures of 4-amino-5-nitro- 1,2,3-triazole dimers on their potential energy surface have been obtained by using density functional theory （DPT） method at the B3...Seven optimized configurations and their electronic structures of 4-amino-5-nitro- 1,2,3-triazole dimers on their potential energy surface have been obtained by using density functional theory （DPT） method at the B3LYP/6-311＋＋G＊＊ level. The maximum intermolecular interaction energy is -35.42 kJ/mol via the basis set superposition error-correction （BSSE） and zero point energy-correction （ZPE）. Charge transfers between the two subsystems are small. The vibration analysis of optimized configurations was performed, and the thermodynamic property changes from monomer to dimer have been obtained with the temperature ranging from 200 to 800 K on the basis of statistical thermodynamics. It is found that the hydrogen bonds contribute to the dimers dominantly, and the extent of intermolecular interaction is mainly determined by the hydrogen bonds＇ strength rather than their number. The dimerization processes of Ⅳ, Ⅴand Ⅵ can occur spontaneously at 200 K.展开更多
The title compound （C12H15NO13S, Mr = 413.31） was synthesized by the nitration of napthalene-1,4-dicarboxylate acid in mixed nitric and sulfuric acids. It crystallizes in monoclinic, space group P2 1/c with a = 8.10...The title compound （C12H15NO13S, Mr = 413.31） was synthesized by the nitration of napthalene-1,4-dicarboxylate acid in mixed nitric and sulfuric acids. It crystallizes in monoclinic, space group P2 1/c with a = 8.100（1）, b = 24.369（3）, c = 8.634（1） A, β = 105.380（2）°, V = 1643.1（4） A^3, Z = 4, Dc = 1.671 g/cm^3, F（000） = 856, μ（MoKa） = 0.273 mm^- 1, T = 294（2） K, the final R = 0.0400 and wR = 0.1021 for 2866 observed reflections with I 〉 2σ（I）. In this crystal there exist a number of H-bonds which link the molecules to form a three-dimensional infinite network structure. The thermal decomposition of the title compound was investigated by using TG-DTG and DSC techniques.展开更多
The synthetic process for 2,2-dimethyl-5-nitro-5-nitroso-1,3-dioxane（DMNNDO） was improved by using tri（hydroxymethyl）nitromethane and acetone as starting materials through a ＂one-pot＂ method combined with alkali...The synthetic process for 2,2-dimethyl-5-nitro-5-nitroso-1,3-dioxane（DMNNDO） was improved by using tri（hydroxymethyl）nitromethane and acetone as starting materials through a ＂one-pot＂ method combined with alkaline hydrolysis and nitrosation reactions. The yield of DMNNDO was increased from 37% to 45%. The structure of DMNNDO was characterized by IR,^1H NMR,^13 C NMR,and elemental analysis. Also the thermal decomposition of DMNNDO was studied by using DSC and TG-DTG to find that there are primarily two exothermic decomposition processes between 90 and 300 oC. The crystal structure of DMNNDO was studied by X-ray single-crystal diffraction for the first time. The molecular structure exists as a dimeric form due to the presence of nitroso group. The crystal belongs to monoclinic system,space group C2/c with a = 14.515（3）,b = 9.955（2）,c = 11.897（2） °,β = 98.500（3）°,V = 1.6998（2） nm^3,Z = 8,D_c = 1.486 g×cm^-3,μ = 0.128 mm^-1,F（000） = 800,S = 1.055,R = 0.0358 and wR = 0.0917. In particular,DMNNDO could be easily hydrolyzed in hydrous systems and the hydrolysis mechanism in CDCl_3 was revealed by means of NMR monitoring.展开更多
N-Acetyl-P. m or o-nitro-phenylethylamines and (HCHO). were treated in 60% H,SO./HOAc. via α -amidoalkylation to give 2-acetyl-mono(5, 6, 7 or 8)-nitro-l .2,3.4- tetrahydroisoquinolines. Additionally. solme interesti...N-Acetyl-P. m or o-nitro-phenylethylamines and (HCHO). were treated in 60% H,SO./HOAc. via α -amidoalkylation to give 2-acetyl-mono(5, 6, 7 or 8)-nitro-l .2,3.4- tetrahydroisoquinolines. Additionally. solme interesting phenomena were observed when the comparison between 2-acetyl-5, 6. 7 or 8-nitro-l,2.3.4-tetrahydroisoqui and 2-alkylsulfonyl-5. 6 or 7nitro-l,2.3,4-tetrahydroisoquinolines was made.展开更多
The bile complexes have been Synthesised by the reaction of rare earth nitrate with 2-[2-3-nitro- 4-methoxylphenyl) vinyl ]-1-methylpyridinium nitrate in ethanol solution and have been characterized by IR. UV and 1H N...The bile complexes have been Synthesised by the reaction of rare earth nitrate with 2-[2-3-nitro- 4-methoxylphenyl) vinyl ]-1-methylpyridinium nitrate in ethanol solution and have been characterized by IR. UV and 1H NMR spectre TG-DTA, molar conductance and X-ray powder diffraction . The results show that the Crystal form of Nd complex containing one molecular water as a ligand is eleven coordinated and is different from the others.展开更多
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 a...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 (r<sup>2</sup>) 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).展开更多
Two new coordination polymers,{[Co（O2N-Hbtb）（phen）（H2O）3]·2H2O}n 1 and {[Cu3（O2N-btb）2（bipy）2（H2O）4]·4H2O}n 2（O2N-H3btb=5-nitro-1,2,3-benzenetricarboxylic acid,phen=1,10-phenanthroline,bipy=2,2...Two new coordination polymers,{[Co（O2N-Hbtb）（phen）（H2O）3]·2H2O}n 1 and {[Cu3（O2N-btb）2（bipy）2（H2O）4]·4H2O}n 2（O2N-H3btb=5-nitro-1,2,3-benzenetricarboxylic acid,phen=1,10-phenanthroline,bipy=2,2＇-bipyridine）,were prepared through hydrothermal reactions of Co（Ⅱ） or Cu（Ⅱ） salt with O2N-H3btb in the presence of different auxiliary N-donor ligands.Their crystal structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis and IR spectroscopy.In the two complexes,O2N-H3btb ligand acts as monodentate and bis-monodentate modes,respectively.Complex 1 displays a two-dimensional layered structure through the inter-and intramolecular hydrogen bonding interactions while complex 2 has an O2N-btb bridged one-dimensional chain which is extended into a three-dimensional network by hydrogen bonding interactions.The magnetic properties of complex 2 are investigated over the temperature range of 2～300 K and ferromagnetic interactions are observed.展开更多
文摘Phosphorus fertilizers from less pure sedimentary sources become increasingly important, due to depletion of phosphorus from igneous rock of high quality. Consequently, robust methods with potential to remove various types of hazardous elements are required. Among such impurities, hexavalent chromium (Cr(VI)) is very likely to become a future challenge. Different industrial ways to treat phosphate rock are currently being practised, and we have here studied how chromium behaves when using the nitro-phosphate process. The reduction mechanism of Cr (VI) in nitric acid and phosphoric acid solutions was investigated by measuring redox potential and UV-VIS spectra. The results show that Cr (VI) is not stable in strong nitric acid solutions. Reduction of Cr (VI) species decreased with decreasing temperature, NO<sub>2</sub> concentration, ionic strength and absence of light. These findings support the proposed reduction reaction:The reduction rate was observed proportional to the nitric acid decomposition: .
基金We thank the National Natural Science Foundation of China(NO．20172007)for financial support
文摘Methyluracil and 5-nitro-6-methyluracil react with variable molar quantities of benzoyl chloride in acetonitrile-pyridine at room temperature to give 1-N, 3-N-dibenzoyl-6- methyluracil 3b and 1-N-benzoyl-5-nitro-6-methyluracil 4b. The reactive rates of debenzoylation of 3b and 4b were investigated.
文摘The thermal decomposition of ammonium 3-nitro-1,2,4-triazol-5-onate monohydrate[NH4（NTO）·H2O] was studied by means of thermal analysis-MS coupling and the combination technique of in situ thermolysis cell with rapid-scan Fourier transform infrared spectroscopy. The results show that there are two endothermic steps and one exothermic step in the decomposition process of NH4（NTO）·H2O. The detected gas products consist of NH3, H2O, N2, CO2, CO, and NO2.
文摘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.
文摘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.
文摘The title compound C18H16N4O3 （Mr = 336.35） has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Schiff base compound is a derivative of 4-aminoantipyrine. As expected, the molecular structure adopts a trans configuration about the central C=N double bond. It crystallizes in orthorhombic, space group P2dc with a = 7.632（1）, b = 7.816（1）, c = 28.082（5） A,β = 96.18（1）°, V= 1665.48（51） A^3, Z= 4, Dc = 1.341 g/cm^3, F（000） = 704,μ = 0.094 mm^-1, the final R = 0.0448 and wR = 0.1058. Of the total 3748 collections, 3105 were unique. In the molecule there exist two different planes of pyrazoline and C（11）-C（16） phenyl ring, which are approximately coplanar （r.m.s. de deviation from the combined mean plane is 0.03 A） with the dihedral angle between them of 9.8%.
基金Project of National Natural Science Foundation of China (No. 10576030, 20173028)
文摘Seven optimized configurations and their electronic structures of 4-amino-5-nitro- 1,2,3-triazole dimers on their potential energy surface have been obtained by using density functional theory （DPT） method at the B3LYP/6-311＋＋G＊＊ level. The maximum intermolecular interaction energy is -35.42 kJ/mol via the basis set superposition error-correction （BSSE） and zero point energy-correction （ZPE）. Charge transfers between the two subsystems are small. The vibration analysis of optimized configurations was performed, and the thermodynamic property changes from monomer to dimer have been obtained with the temperature ranging from 200 to 800 K on the basis of statistical thermodynamics. It is found that the hydrogen bonds contribute to the dimers dominantly, and the extent of intermolecular interaction is mainly determined by the hydrogen bonds＇ strength rather than their number. The dimerization processes of Ⅳ, Ⅴand Ⅵ can occur spontaneously at 200 K.
基金This work was supported by the NNSFC (No. 20471008)
文摘The title compound （C12H15NO13S, Mr = 413.31） was synthesized by the nitration of napthalene-1,4-dicarboxylate acid in mixed nitric and sulfuric acids. It crystallizes in monoclinic, space group P2 1/c with a = 8.100（1）, b = 24.369（3）, c = 8.634（1） A, β = 105.380（2）°, V = 1643.1（4） A^3, Z = 4, Dc = 1.671 g/cm^3, F（000） = 856, μ（MoKa） = 0.273 mm^- 1, T = 294（2） K, the final R = 0.0400 and wR = 0.1021 for 2866 observed reflections with I 〉 2σ（I）. In this crystal there exist a number of H-bonds which link the molecules to form a three-dimensional infinite network structure. The thermal decomposition of the title compound was investigated by using TG-DTG and DSC techniques.
文摘The synthetic process for 2,2-dimethyl-5-nitro-5-nitroso-1,3-dioxane（DMNNDO） was improved by using tri（hydroxymethyl）nitromethane and acetone as starting materials through a ＂one-pot＂ method combined with alkaline hydrolysis and nitrosation reactions. The yield of DMNNDO was increased from 37% to 45%. The structure of DMNNDO was characterized by IR,^1H NMR,^13 C NMR,and elemental analysis. Also the thermal decomposition of DMNNDO was studied by using DSC and TG-DTG to find that there are primarily two exothermic decomposition processes between 90 and 300 oC. The crystal structure of DMNNDO was studied by X-ray single-crystal diffraction for the first time. The molecular structure exists as a dimeric form due to the presence of nitroso group. The crystal belongs to monoclinic system,space group C2/c with a = 14.515（3）,b = 9.955（2）,c = 11.897（2） °,β = 98.500（3）°,V = 1.6998（2） nm^3,Z = 8,D_c = 1.486 g×cm^-3,μ = 0.128 mm^-1,F（000） = 800,S = 1.055,R = 0.0358 and wR = 0.0917. In particular,DMNNDO could be easily hydrolyzed in hydrous systems and the hydrolysis mechanism in CDCl_3 was revealed by means of NMR monitoring.
基金the new drug discovery foundation of Shanghai instituteof Pharmaceutical Industry and the Analysis Centre of the Second Milita
文摘N-Acetyl-P. m or o-nitro-phenylethylamines and (HCHO). were treated in 60% H,SO./HOAc. via α -amidoalkylation to give 2-acetyl-mono(5, 6, 7 or 8)-nitro-l .2,3.4- tetrahydroisoquinolines. Additionally. solme interesting phenomena were observed when the comparison between 2-acetyl-5, 6. 7 or 8-nitro-l,2.3.4-tetrahydroisoqui and 2-alkylsulfonyl-5. 6 or 7nitro-l,2.3,4-tetrahydroisoquinolines was made.
文摘The bile complexes have been Synthesised by the reaction of rare earth nitrate with 2-[2-3-nitro- 4-methoxylphenyl) vinyl ]-1-methylpyridinium nitrate in ethanol solution and have been characterized by IR. UV and 1H NMR spectre TG-DTA, molar conductance and X-ray powder diffraction . The results show that the Crystal form of Nd complex containing one molecular water as a ligand is eleven coordinated and is different from the others.
文摘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 (r<sup>2</sup>) 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).
基金Supported by the National Natural Science Foundation of China (Nos. 20471026 and 20771054)the Henan Tackle Key Problem of Science and Technology (Nos. 072102270030 and 072102270034)2009GGJS-104
文摘Two new coordination polymers,{[Co（O2N-Hbtb）（phen）（H2O）3]·2H2O}n 1 and {[Cu3（O2N-btb）2（bipy）2（H2O）4]·4H2O}n 2（O2N-H3btb=5-nitro-1,2,3-benzenetricarboxylic acid,phen=1,10-phenanthroline,bipy=2,2＇-bipyridine）,were prepared through hydrothermal reactions of Co（Ⅱ） or Cu（Ⅱ） salt with O2N-H3btb in the presence of different auxiliary N-donor ligands.Their crystal structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis and IR spectroscopy.In the two complexes,O2N-H3btb ligand acts as monodentate and bis-monodentate modes,respectively.Complex 1 displays a two-dimensional layered structure through the inter-and intramolecular hydrogen bonding interactions while complex 2 has an O2N-btb bridged one-dimensional chain which is extended into a three-dimensional network by hydrogen bonding interactions.The magnetic properties of complex 2 are investigated over the temperature range of 2～300 K and ferromagnetic interactions are observed.
