- Silica-sulfuric acid catalyzed nitrodeiodination of iodopyrazoles
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We report here the synthesis of nitropyrazoles in good to excellent yields from iodopyrazoles over silica-sulfuric acid catalyst for the first time. The present procedure require less acid, offers a simplified workup procedure, and may be applied for the
- Ravi,Gore, Girish M.,Sikder, Arun K.,Tewari, Surya P.
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- A simple and environmentally benign nitration of pyrazoles by impregnated bismuth nitrate
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We report herein a facile, rapid, and environmentally friendly synthesis of nitropyrazoles in good yields using silica-bismuth nitrate and silica-sulfuric acid-bismuth nitrate at room temperature for the first time. The relatively non-toxic nature, ease o
- Ravi,Gore, Girish M.,Tewari, Surya P.,Sikder, Arun K.
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- An antiferromagnetic metalloring pyrazolate (Pz) framework with [Cu12(μ2-OH)12(Pz)12] nodes for separation of C2H2/CH4 mixture
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The search for functional metalloring organic frameworks (MROFs) has been of continuous interest in the fields of both molecular rings and metal-organic frameworks (MOFs) due to their importance in many multifunctional applications. Herein, a hierarchical pyrazolate framework MROF-12 with the topology of the Schl?fli symbol {460.66} is reported, which is constructed by an elongated rigid ligand and attractive metalloring cluster nodes [Cu12(μ2-OH)12(Pz)12]. MROF-12 not only adopts the unique functionalities of the metalloring clusters but also inherits the porous properties of MOFs. The large [Cu12(μ2-OH)12(Pz)12] metalloring nodes with the diameter of 12.202 ? endow MROF-12 with excellent stability and antiferromagnetism, and they are bridged by linear pyrazolate ligands (H2NDI) to form micro-mesoporous MROF with permanent porosity. The activated sample MROF-12a can exhibit a relatively high Brunauer-Emmett-Teller/Langmuir surface area (460.7/571.9 m2 g-1) as well as pore volume of 0.240 cm3 g-1. Dynamic fixed bed breakthrough experiments indicate that the separation of C2H2/CH4 or CO2/CH4 mixtures can be efficiently achieved through a column packed with MROF-12a solid.
- Li, Ziyin,Ye, Yingxiang,Yao, Zizhu,Guo, Junzhi,Lin, Quanjie,Zhang, Jindan,Zhang, Zhangjing,Wei, Fangfang,Xiang, Shengchang
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- Synthesis and Structural Characterisation of Lithium, Zinc, and Aluminium Pyrazolate Complexes
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The reaction of nBuLi with 3,5-dimethylpyrazole (MepzH) in EtO or tmeda/hexane (tmeda = N,N,N,N-tetramethylethane-1,2-diamine) and with 3,5-dimethyl-4-nitropyrazolate (MepzHNO) in THF results in the formation of three structurally diverse lithium pyrazola
- Rad, Nazli E.,Junk, Peter C.,Deacon, Glen B.,Taidakov, Ilya V.,Wang, Jun
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- Synthesis of high-performance insensitive energetic materials based on nitropyrazole and 1,2,4-Triazole
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A new family of symmetric (4-nitro-1H-pyrazole-3,5-diyl)bis(1H-1,2,4-Triazole)-based derivatives were obtained. All these new compounds were characterized by (1H, 13C)NMR spectroscopy, infrared spectroscopy, elemental analysis and differential scanning calorimetry (DSC). The structures of 5,5′-(4-nitro-1H-pyrazole-3,5-diyl)bis(3-nitro-1H-1,2,4-Triazole) (6) and N,N′-((4-nitro-1H-pyrazole-3,5-diyl)bis(1H-1,2,4-Triazole-5,3-diyl))dinitramide (7) were further confirmed by single crystal X-ray diffraction. In addition, the theoretical calculations by using the Gaussian 09 package show that target compounds have high heats of formation ranging from 1.40 to 2.84 kJ g-1. Among them, the safety and detonation performances of 6 (D: 8747 m s-1, P: 33.0 GPa, Td: 238.2 °C, IS: 30 J) and energetic salts dihydroxylammonium((4-nitro-1H-pyrazole-3,5-diyl)bis(1H-1,2,4-Triazole-5,3-diyl))bis(nitroamide) (9) (D: 9077 m s-1, P: 33.6 GPa, IS: >40 J) and dihydrazinium((4-nitro-1H-pyrazole-3,5-diyl)bis(1H-1,2,4-Triazole-5,3-diyl))bis(nitroamide) (10) (D: 8759 m s-1, P: 30.2 GPa, IS: >40 J) are comparable to those of 1,3,5-Trinitroperhydro-1,3,5-Triazine (RDX: D = 8795 m s-1, P = 34.9 GPa, Td = 210 °C, IS: 7.4 J) due to the positive effect of ternary hydrogen bonds.
- Xu, Minxian,Cheng, Guangbin,Xiong, Hualin,Wang, Bohan,Ju, Xuehai,Yang, Hongwei
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- gem-DINITRO COMPOUNDS IN ORGANIC SYNTHESIS. 2. SYNTHESIS OF 4-NITROPYRAZOLES FROM DINITROMETHANE AND ITS DERIVATIVES
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A series of 4-nitropyrazoles was synthesized from dinitromethane and other gem-dinitro derivatives.New cyclization reactions of aliphatic azines with dinitromethane and an intramolecular cyclization of dinitroacetazines have been discovered, with which 4-nitropyrazoles substituted at the 3- and 5-positions of the pyrazole ring can be obtained in one stage.
- Laikhter, A. L.,Cherkasova, T. I.,Semenov, V. V.
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- Energetic Tricyclic Polynitropyrazole and Its Salts: Proton-Locking Effect of Guanidium Cations
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An axisymmetric polynitro-pyrazole molecule, 3,5-di(3,5-dinitropyrazol-4-yl)]-4-nitro-1H-pyrazole (5), and its salts (6-12) were prepared and fully characterized. These compounds not only show promising energetic properties but also show a unique tautomeric switch via combining different cations with the axisymmetric compound (5). Its salts (6-9) remain axisymmetric when the cations are potassium, ammonium, or amino-1,2,4-triazolium. However, when the cations are guanidiums, the salts (10-12) dramatically become asymmetric owing to the fixed proton. The introduction of guanidium cations breaks the tautomeric equilibrium by blocking the prototropic transformations and results in the switch-off effect to tautomerism. The structural constraints of 1H NMR and 13C NMR spectra provide strong evidence for the unusual structural constraint phenomenon. These stabilized asymmetric tautomers are very important from the point of molecular recognition, and this research may promote further developments in synthetic and isolation methodologies for novel bioactive pyrazole-based compounds.
- Tang, Yongxing,Huang, Wei,Chinnam, Ajay Kumar,Singh, Jatinder,Staples, Richard J.,Shreeve, Jean'Ne M.
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- Chemical properties of derivatives of N-difluoromethyl-and N-2-H-tetrafluoroethylpyrazoles
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Nitration, chlorination, bromination, and iodination reactions have been investigated for pyrazole derivatives containing a difluoromethylene fragment directly on a nitrogen atom. Conditions have been found for introducing a cyano group into the nucleus of N-2-H-tetrafluoroethylpyrazole and converting it into carboxyl or tetrazole functions. Springer Science+Business Media, Inc. 2006.
- Petko,Sokolenko,Yagupolskii
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- Faujasite catalyzed nitrodeiodination of iodopyrazoles
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Nitrodeiodination of iodopyrazoles using nitric acid/Faujasite has been investigated. The present procedure is simple, rapid and convenient and requires no sulfuric acid or oleum and may be applied for the synthesis of several nitropyrazoles in good yield
- Ravi,Tewari, Surya P.
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- Rationally tuning host-guest interactions to free hydroxide ions within intertrimerically cuprophilic metal-organic frameworks for high OH- conductivity
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Hydroxide-anion-exchange membrane fuel cells (HEMFCs) are now considered as one of the most promising green energy-conversion technologies for stationary and mobile applications, showing high fuel conversion efficiency at high pH and low cost due to their ability to operate under basic conditions using non-precious metal catalysts. But one key impediment to commercialization is insufficient hydroxide ion (OH-) conductivity of the central HEM component. Here, we report the development of free OH- anion-containing metal-organic frameworks (FOMOFs) with rationally tunable host-guest interactions for HEMs with high OH- conductivity. Among three solids obtained by post-synthesis treatment of ultrastable MOF FJU-66 with various bases, free OH- anions are observed in FJU-66·[EVIm]OH with strong host-guest interactions between the MOF backbone and guest cations. Despite the lowest OH- concentration, FJU-66·[EVIm]OH exhibits the highest OH- conductivity close to 0.1 S cm-1. The high OH- conductivity achieved suggests the potential application of the FOMOFs for practical HEMs of fuel cells.
- Li, Ziyin,Zhang, Zhangjing,Ye, Yingxiang,Cai, Kaicong,Du, Fenfen,Zeng, Heng,Tao, Jin,Lin, Quanjie,Zheng, Ying,Xiang, Shengchang
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- Four syntheses of 4-Amino-3,5-dinitropyrazole
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In this paper, syntheses of 4-amino-3,5-dinitropyrazole from four different starting materials are described. The starting materials were 4-nitropyrazole, 4-nitro-3,5-dimethylpyrazole, 3,5-dinitropyrazole, and 4-chloropyrazole, respectively. They are compared in terms of yield, number of steps and suitability for scale-up into pilot scale production. The overall yield, calculated from commercially available starting materials, ranged from 21% in the case of synthesis via 3,5-dinitropyrazole up to 61% for the one starting from 4-chloropyrazole. With numerous factors taken into account, the latter was chosen for a pilot scale study and the product could be produced in batches of 200 g.
- Ek, Stefan,Latypov, Nikolaj V.
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- Tandem copper (Cu) catalysed N-arylation-vinylogous nitroaldol condensation of 3,5-disubstituted 4-nitropyrazoles
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A tandem process involving copper catalysed N-arylation and vinylogous nitroaldol condensation is described. The reaction of 3,5-dialkyl substituted 4-nitropyrazoles and ortho-halo substituted (hetero)aryl aldehydes or ketones furnished 3-nitropyrazolo[1,5-a]quinoline and heteroaryl-fused 3-nitropyrazolo[1,5-a]pyridine derivatives in moderate to high yields.
- Obulesu, Owk,Nanubolu, Jagadeesh Babu,Suresh, Surisetti
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- Based on triazole nitrogen heterocyclic energetic compounds and their synthesis methods
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The present invention discloses a triazole-based nitrogen heterocyclic energy-containing compound and a method of synthesis thereof. The energetic compound is 4-nitro-3,5-bis(3,4-diamino-1,2,4-triazole-5-yl) 1H- pyrazole. By the synthesis method of the present invention synthesized based on the actual measurement of impact sensitivity of triazole nitrogen heterocyclic energetic compounds >40J, friction sensitivity > 360N, calculated burst velocity of 8197m/s, The burst pressure is 24.2Gpa, the thermal decomposition temperature is 318.6 °C, the performance is better than TNT, the thermal decomposition temperature and sensitivity are better than RDX, and it is stable at room temperature, and its synthesis method is simple, the synthesis process is safe and controllable, it can achieve mass production, and its thermal decomposition temperature is high, and it has application prospects in the field of heat-resistant explosives.
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Paragraph 0020-0022
(2022/01/05)
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- PYRROLO(PYRAZOLO)PYRIMIDINE DERIVATIVE AS LRRK2 INHIBITOR
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The present invention relates to a pyrrolo(pyrazolo)pyrimidine derivative having efficacy as an LRRK2 inhibitor, a preparation method therefor, and a pharmaceutical composition for preventing or treating degenerative brain diseases, containing the same.
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Paragraph 0093-0094; 0153-0154
(2020/11/23)
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- Depsipeptides Featuring a Neutral P1 Are Potent Inhibitors of Kallikrein-Related Peptidase 6 with On-Target Cellular Activity
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Kallikrein-related peptidase 6 (KLK6) is a secreted serine protease that belongs to the family of tissue kallikreins (KLKs). Many KLKs are investigated as potential biomarkers for cancer as well as therapeutic drug targets for a number of pathologies. KLK6, in particular, has been implicated in neurodegenerative diseases and cancer, but target validation has been hampered by a lack of selective inhibitors. This work introduces a class of depsipeptidic KLK6 inhibitors, discovered via high-throughput screening, which were found to function as substrate mimics that transiently acylate the catalytic serine of KLK6. Detailed structure-activity relationship studies, aided by in silico modeling, uncovered strict structural requirements for potency, stability, and acyl-enzyme complex half-life. An optimized scaffold, DKFZ-251, demonstrated good selectivity for KLK6 compared to other KLKs, and on-target activity in a cellular assay. Moreover, DKFZ-633, an inhibitor-derived activity-based probe, could be used to pull down active endogenous KLK6.
- De Vita, Elena,Schüler, Peter,Lovell, Scott,Lohbeck, Jasmin,Kullmann, Sven,Rabinovich, Eitan,Sananes, Amiram,He?ling, Bernd,Hamon, Veronique,Papo, Niv,Hess, Jochen,Tate, Edward W.,Gunkel, Nikolas,Miller, Aubry K.
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supporting information
p. 8859 - 8874
(2018/10/09)
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- Dearomatization of oxa- or selenadiazolopyridines with neutral nucleophiles as an efficient approach to pharmacologically relevant nitrogen compounds
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Highly electrophilic 6-nitro-4-azabenzofuroxan and 6-nitro-4-azabenzo[1,2,5]selenadiazole add π-excessive (het)arenes and other neutral nucleophiles at 7-position to give C–C and N–C-bonded adducts, 1,4-dihydropyridines fused with furoxan or selenadiazole ring.
- Starosotnikov, Alexey M.,Shkaev, Dmitry V.,Bastrakov, Maxim A.,Fedyanin, Ivan V.,Shevelev, Svyatoslav A.,Dalinger, Igor L.
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p. 638 - 640
(2018/12/13)
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- Facile and environmentally friendly synthesis of nitropyrazoles using montmorillonite K-10 impregnated with bismuth nitrate
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Nitropyrazoles in higher yields were synthesized using montmorillonite K-10 impregnated with bismuth nitrate and the present procedure may be applied for the nitration of a wide variety of azoles in the drug and pharmaceutical industries.
- Ravi,Tewari, Surya P.
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experimental part
p. 37 - 41
(2012/04/10)
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- Synthesis, structural, and biological evaluation of the arene-linked pyrazolyl methane ligands and their d9/d10 metal complexes
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A series of the p-bis[(1-pyrazolyl)methyl] benzene ligands (L 1-L6) in the DMSO system were synthesized. In the mean time, by using the ligands as a linker, a new family of transition metal coordination polymers, namely, [Cu2(L1)2Cl 4] (1), [Cu2(L2)2Cl4] (2), [Ag(L2)(NO3)] (3), [Zn2(L 2)2(SCN)4] (4) and [Cd2(L 2)(SCN)4] (5) [L1 = 1,4-bis((1H-pyrazol-1-yl) methyl)benzene; L2 = 1,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)methyl) benzene] have been constructed by the reaction of the p-bis[(1-pyrazolyl)methyl] benzene and corresponding to the transition metal compounds in a mixed solution of CH3OH/C2H5OH at mild temperature condition. All the coordination polymers and p-bis[(1-pyrazolyl)methyl]benzene ligands were characterized by elemental analysis, IR spectroscopy, 1H NMR and 13C NMR, and some of them were characterized by UV spectroscopy, thermogravimetric analysis, X-ray powder and X-ray single-crystal diffraction. Structural analyses reveal that the ligands L3-L5 (L 3 = 1,4-bis((4-iodo-1H-pyrazol-1-yl)methyl)benzene, L4 = 1,4-bis((4-iodo-3,5-dimethyl-1H-pyrazol-1-yl)methyl)benzene, L5 = 1,4-bis((4-nitro-1H-pyrazol-1-yl)methyl)benzene,L6 = 1,4-bis((4-nitro-3,5-dimethyl-1H-pyrazol-1-yl) methyl) benzene) are discrete organic compound molecules and the complexes 1-5 are 1D M-L-M coordination polymers, which are further interlinked via hydrogen bonds resulting in 2D or even 3D supermolecular networks. The luminescent properties of the coordination polymers 3, 4 and 5 were examined by luminescence spectra. The analytic results indicate that different metal complexes with the same ligand have different influence on the characteristic photoluminescence. Furthermore, the cytotoxicity of the ligands L1-L6 and complexes 1-5 were evaluated against hepG2 cells. For the ligands of L1-L6, the different substituents of the pyrazole ring slightly influenced the cytotoxicity of the cell. It is found that nitro-compounds have shown the highest cytotoxicity under the same concentration condition. The cytotoxic activity of the complexes 1-5 are strongly increased by the introduction of the transition metals.
- Wang, Xin-Yu,Liu, Shu-Qing,Zhang, Chun-Yan,Song, Ge,Bai, Feng-Ying,Xing, Yong-Heng,Shi, Zhan
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p. 151 - 164
(2013/01/15)
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- Self-assembly hexanuclear metallacontainer hosting halogenated guest species and sustaining structure of 3D coordination framework
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Chloride-centered hexanuclear hydroxopyrazolate reveals potential as a receptor of halomethane and halometallate species and as a molecular building block for coordination polymers.
- Govor, Evgen V.,Lysenko, Andrey B.,Quinonero, David,Rusanov, Eduard B.,Chernega, Alexander N.,Moellmer, Jens,Staudt, Reiner,Krautscheid, Harald,Frontera, Antonio,Domasevitch, Konstantin V.
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supporting information; experimental part
p. 1764 - 1766
(2011/03/22)
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- Facile, fast and safe process development of nitration and bromination reactions using continuous flow reactors
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Chemists working in a pilot plant often face safety issues during scale-up operations. With the help of emerging microfluidic applications and microdevices, running hazardous, highly exothermic or potentially unstable reactions can be easily transposed into a safe continuous flow mode. This paper describes how a potentially hazardous pyrazole nitration and the bromination of a variety of electron-rich heteroaromatic substrates were efficiently performed using a cheap and easily available system for bench chemists. Advantages of the continuous flow mode in organic synthetic chemistry will be exemplified by the large-scale production of raw materials under safe, green and reproducible conditions.
- Pelleter, Jacques,Renaud, Fabrice
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experimental part
p. 698 - 705
(2010/04/22)
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- Synthesis and biological activities of novel bis-heterocyclic pyrrodiazole derivatives
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Novel structures of bis-heterocyclic pyrrodiazole derivatives containing pyrazole were designed and synthesized. The title compounds were characterized by 1H NMR, IR, MS, and elemental analysis. Biological activities of three intermediate compounds and 25 pyrrodiazole derivatives were tested in vivo and in vitro. Some of the title compounds exhibited certain herbicidal activities against barnyardgrass and rape.
- He, Feng-Qi,Liu, Xing-Hai,Wang, Bao-Lei,Li, Zheng-Ming
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- α-Substituted boron difluoride acetylacetonates
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By treatment of α-substituted acetylacetone derivatives with boron trifluoride etherate a series of earlier unknown boron difluoride complexes is obtained. The series includes binuclear complexes containing boron in the chelate fragment connected via sulfur or selenium atom. Gas chromatographic and spectral characteristics of the obtained compounds were investigated. By means of chromato-mass spectrometry their reaction with hydrazine in acidic and alkaline media was studied.
- Svistunova,Fedorenko
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p. 1515 - 1523
(2009/06/28)
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- Gas-chromatographic study of hydrazine reaction with metal β-diketonates
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When treated with hydrazine, metal β-diketonates undergo decomposition to form the corresponding pyrazoles, irrespective of the kinetic stability of the chelates. With substituted metal chelates, the main reaction products are pyrazoles bearing in positio
- Svistunova,Shapkin,Nikolaeva
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p. 899 - 900
(2007/10/03)
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- Synthesis for 7-alkylamino-3-methylpyrazolo [4,3-d]pyrimidines
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An improved synthesis is disclosed for 7-alkylamino-3-methylpyrazolo[4,3-d]pyrimidines, which are known to be potent cytokinin antagonists.
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- 4-Nitropyrazoles
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Covers a method of inducing abscission of fruit by applying a chemical composition containing an effective amount of a 4-nitropyrazole as the active ingredient in an agronomically acceptable carrier. Also covers certain 4-nitropyrazoles.
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