- Synthesis of amino, azido, nitro, and nitrogen-rich azole-substituted derivatives of 1H-benzotriazole for high-energy materials applications
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The amino, azido, nitro, and nitrogen-rich azole substituted derivatives of 1H-benzotriazole have been synthesized for energetic material applications. The synthesized compounds were fully characterized by 1H and 13C NMR spectroscopy, IR, MS, and elemental analysis. 5-Chloro-4-nitro-1H-benzo[1,2,3]triazole (2) and 5-azido-4,6-dinitro-1H-benzo[1, 2,3]triazole (7) crystallize in the Pca21 (orthorhombic) and P2 1/c (monoclinic) space group, respectively, as determined by single-crystal X-ray diffraction. Their densities are 1.71 and 1.77 g cm -3, respectively. The calculated densities of the other compounds range between 1.61 and 1.98 g cm-3. The detonation velocity (D) values calculated for these synthesized compounds range from 5.45 to 8.06 km s-1, and the detonation pressure (P) ranges from 12.35 to 28 GPa.
- Srinivas, Dharavath,Ghule, Vikas D.,Tewari, Surya P.,Muralidharan, Krishnamurthi
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- Selective Synthesis of N-H and N-Aryl Benzotriazoles by the [3 + 2] Annulation of Sodium Azide with Arynes
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The synthetic utility of NaN3 as the azide component in the [3 + 2] annulation with arynes generated from 2-(trimethylsilyl)aryltriflates resulting in the transition-metal-free synthesis of N-H and N-aryl benzotriazoles has been demonstrated. Using CsF as the fluoride source in CH3CN, the N-H benzotriazoles are formed in high selectivity instead of the expected azidobenzene. Interestingly, N-aryl benzotriazoles are formed using KF and THF as solvent in an open-flask reaction. Moreover, a method for the N1-arylation of benzotriazole is also presented.
- Guin, Avishek,Gaykar, Rahul N.,Bhattacharjee, Subrata,Biju, Akkattu T.
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p. 12692 - 12699
(2019/10/11)
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- Synthesis of Structurally Diverse Benzotriazoles via Rapid Diazotization and Intramolecular Cyclization of 1,2-Aryldiamines
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An operationally simple method has been developed for the preparation of N-unsubstituted benzotriazoles by diazotization and intramolecular cyclization of a wide range of 1,2-aryldiamines under mild conditions, using a polymer-supported nitrite reagent and p-tosic acid. The functional group tolerance of this approach was further demonstrated with effective activation and cyclization of N-alkyl, -aryl, and -acyl ortho-aminoanilines leading to the synthesis of N1-substituted benzotriazoles. The synthetic utility of this one-pot heterocyclization process was exemplified with the preparation of a number of biologically and medicinally important benzotriazole scaffolds, including an α-amino acid analogue.
- Faggyas, Réka J.,Sloan, Nikki L.,Buijs, Ned,Sutherland, Andrew
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p. 5344 - 5353
(2019/05/21)
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- Does the partial molar volume of a solute reflect the free energy of hydrophobic solvation?
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Halogenated heterocyclic ligands are widely used as the potent and frequently selective inhibitors of protein kinases. However, the exact contribution of the hydrophobic solvation of a free ligand is rarely accounted for the balance of interactions contributing to the free energy of ligand binding. Herein, we propose a new experimental method based on volumetric data to estimate the hydrophobicity of a ligand. We have tested this approach for a series of ten variously halogenated benzotriazoles, the binding affinity of which to the target protein kinase CK2 was assessed with the use of thermal shift assay. According to the hierarchical clustering procedure, the excess volume, defined as the difference between the experimentally determined partial molar volume and the calculated in silico molecular volume, was found to be distant from any commonly used hydrophobicity descriptors of the ligand. The excess volume, however, properly predicts solute binding affinity. On the way, we have proved that the binding of halogenated benzotriazoles to the protein kinase CK2 is driven mostly by hydrophobic interactions.
- Szymaniec-Rutkowska, Anna,Bugajska, Ewa,Kasperowicz, S?awomir,Mieczkowska, Kinga,Maciejewska, Agnieszka M.,Poznański, Jaros?aw
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- Making endo-cyclizations favorable again: A conceptually new synthetic approach to benzotriazoles via azide group directed lithiation/cyclization of 2-azidoaryl bromides
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Although benzotriazoles are important and ubiquitous, currently there is only one conceptual approach to their synthesis: bridging the two ortho-amino groups with an electrophilic nitrogen atom. Herein, we disclose a new practical alternative-the endo-cyclization of 2-azidoaryl lithiums obtained in situ from 2-azido-aryl bromides. The scope of the reaction is illustrated using twenty-four examples with a variety of alkyl, alkoxy, perfluoroalkyl, and halogen substituents. We found that the directing effect of the azide group allows selective metal-halogen exchange in aryl azides containing several bromine atoms. Furthermore, (2-bromophenyl)diazomethane undergoes similar cyclization to give an indazole. Thus, cyclizations of aryl lithiums containing an ortho-X = Y = Z group emerge as a new general approach for the synthesis of aromatic heterocycles. DFT computations suggested that the observed endo-selectivity applies to the anionic cyclizations of other functionalities that undergo "1,1-additions" (i.e., azides, diazo compounds, and isonitriles). In contrast, cyclizations with the heteroatomic functionalities that follow the "1,2-addition" pattern (cyanates, thiocyanates, isocyanates, isothiocyanates, and nitriles) prefer the exo-cyclization path. Hence, such reactions expand the current understanding of stereoelectronic factors in anionic cyclizations.
- Ageshina, Alexandra A.,Chesnokov, Gleb A.,Topchiy, Maxim A.,Alabugin, Igor V.,Nechaev, Mikhail S.,Asachenko, Andrey F.
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p. 4523 - 4534
(2019/05/17)
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- Tert -Butyl nitrite mediated nitrogen transfer reactions: Synthesis of benzotriazoles and azides at room temperature
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A conversion of o-phenylenediamines into benzotriazoles was achieved at room temperature using tert-butyl nitrite. The optimized conditions are also well suited for the transformation of sulfonyl and acyl hydrazines into corresponding azides. This protocol does not require any catalyst or acidic medium. The desired products were obtained in excellent yields in a short span of time.
- Azeez, Sadaf,Chaudhary, Priyanka,Sureshbabu, Popuri,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
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supporting information
p. 6902 - 6907
(2018/10/02)
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- A 5 - chlorobenzene and triazole high efficient synthesis method
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The invention relates to a 5 - chlorobenzene and triazole high efficient synthesis method, the method comprises the following steps: (1) 2 - nitro - 4 - chloroaniline, water, catalyst of Raney nickel into reaction kettle reaction, crawls the board detected by complete reaction of the material; (2) the complete reaction of the material passes through the filter, and decompression dehydrating, shall be 4 - A [...] phenylenediamine materials and waste water; (3) 4 - [...] phenylenediamine material with sodium nitrite into medium-pressure reactor water, through the exothermic reaction shall be 5 - chlorobenzene and triazole sodium salt aqueous solution; (4) 5 - chlorobenzene and triazole sodium salt aqueous solution adds by drops of sulfuric acid, after [...] dry to obtain 5 - chlorobenzene and three nitrogen zuozuo thick and waste water B; (5) 5 - chlorobenzene and three nitrogen zuozuo thick washed, and dried to obtain the wash water and content ≥ 99% of the finished product 5 - chlorobenzene and triazole; (6) waste water and waste water A B after mixing and washing water, through the negative pressure distillation to obtain distilled water and residue; distilled water to return to the step (1) in the; residue dehydration be content ≥ 96% of the sodium sulfate by-product. The invention has low cost, low energy consumption and high yield.
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Paragraph 0011; 0013-0016; 0017; 0019-0022; 0023; 0025-0028
(2018/08/28)
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- Microwave-assisted solid phase diazotation: A method for the environmentally benign synthesis of benzotriazoles
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A novel environmentally benign approach based on microwave-assisted solid phase diazotation to convert o-phenylendiamines to substituted benzotriazoles is described. Excellent yields were obtained for a phenylenediamines proving the efficacy of the method. The reaction was carried out in the solid phase under microwave irradiation taking advantage of the strong microwave absorption capability of K-10 montmorillonite that acted as a catalyst and medium in one. The catalyst is recyclable, and the reaction occurs with high efficiency and does not produce any harmful waste.
- Kokel, Anne,T?r?k, Béla
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p. 2515 - 2519
(2017/07/17)
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- Mild and general access to diverse 1H-benzotriazoles via diboron-mediated N-OH deoxygenation and palladium-catalyzed C-C and C -N bond formation
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Benzotriazoles are a highly important class of compounds with broad-ranging applications in such diverse areas as medicinal chemistry, as auxiliaries in organic synthesis, in metallurgical applications, in aircraft deicing and brake fluids, and as antifog agents in photography. Although there are numerous approaches to N-substituted benzotriazoles, the essentially one general method to N-unsubstituted benzotriazoles is via diazotization of ortho -phenylenediamines, which can be limited by the availability of suitable precursors. Other methods to N-unsubstitued benzotriazoles are quite specialized. Although reduction of 1-hydroxy-1 H-benzotriazoles is known, the reactions are not particularly convenient or broadly applicable. This presents a limitation for easy access to and availability of diverse benzotri-ACHTUNGTRENUNGazoles. Herein, we demonstrate a new, broadly applicable method to diverse 1H-benzotriazoles via a mild diboron reagent-mediated deoxygenation of 1-hydroxy-1H-benzotriazoles. We have also evaluated sequential deoxygenation and Pd-mediated C-C and C-N bond formation as a one-pot process for further diversification of the benzotriazole moiety. However, the results indicated that purification of the deoxygenation product prior to the Pd-mediated reaction is critical to the success of such reactions. The overall chemistry allows for facile access to a variety of new benzotriazoles. Along with the several examples presented, a discussion of the advantages of the approaches is described, as is also a possible mechanism for the deoxygenation process.
- Gurram, Venkateshwarlu,Akula, Hari K.,Garlapati, Ramesh,Pottabathini, Narender,Lakshman, Mahesh K.
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p. 451 - 462
(2015/03/05)
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- Facile synthesis of benzotriazole derivatives using nanoparticles of organosilane-based nitrite ionic liquid immobilized on silica and two room-temperature nitrite ionic liquids
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Nanoparticles of organosilane-based nitrite ionic liquid immobilized on silica, 1-butyl-3-methylimidazolium nitrite, and 1-(3-trimethoxysilylpropyl)-3- methylimidazolium nitrite were used as effective reagents for the preparation of benzotriazole derivatives from 1,2-diaminobenzenes at room temperature under mild solvent-free conditions. These ionic liquids play as nitrosonium sources in this procedure.1,2-Diaminobenzene derivatives have been treated with ionic liquids to give the related diaminobenzenes in very good to excellent yields in short reaction times. Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for the full experimental and spectral details.
- Valizadeh, Hassan,Gholipour, Hamid,Mahmoodian, Manzar
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p. 2801 - 2808
(2013/08/15)
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- Benzoxazolone-5-sulphonanilides, 1-(benzoxazolone-5'-sulphonyl)-benzotriazoles and 4-hydroxy-3,2'-diaminobenzenesulphonanilides with antiviral activity
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Benzoxazolone-5-(2'-nitro)-sulphonanilides were synthesized by acylation of o-nitroanilines with benzoxazolone-5-sulphochloride or 3-methylbenzoxazolone-5-sulphochloride. The nitro group in these compounds was subjected to reduction and the resulting amino derivatives were cyclysed to yield the corresponding 1-(benzoxazolone-5'-sulphonyl)-benzotriazoles. Decyclization of the oxazolone cycle of benzoxazolone-5-(2'-amino)-sulphonanilides resulted in 4-hydroxy-3,2'-diaminobenzenesulphonanilides. In vitro testing of the antiviral activity of the compounds obtained during successive synthetic steps revealed that some of them exhibited marked antiviral effect against toga, orthomixo, oncorna and herpes viruses.
- Neykova,Simov,Galunska,Velichkova,Galabov,Karparov
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p. 747 - 752
(2007/10/02)
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- The Photolysis of the 1-Cycloalkoxy-5-chloro-1,2,3-benzotriazole System
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Three 1-cycloalkoxy-5-chloro-1,2,3-benzotriazoles were photolyzed at 254 nm.The major photolytic pathway yielded the corresponding cyclic ketone and 4,4'-dichloroazobenzene.
- Feld, W. A.,Serve, M. P.
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p. 825 - 827
(2007/10/02)
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