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Expedient synthesis and anticancer evaluation of dual-action 9-anilinoacridine methyl triazene chimeras
The efficient synthesis of molecular hybrids including a DNA-intercalating 9-anilinoacridine (9-AnA) core and a methyl triazene DNA-methylating moiety is described. Nucleophilic aromatic substitution (SNAr) and electrophilic aromatic substitution (EAS) reactions using readily accessible starting materials provide a quick entry to novel bifunctional anticancer molecules. The chimeras were evaluated for their anticancer activity. Chimera 7b presented the highest antitumor activity at low micromolar IC50 values in antiproliferative assays performed with various cancer cell lines. In comparison, compound 7b outperformed DNA-intercalating drugs like amsacrine and AHMA. Mechanistic studies of chimera 7b suggest a dual mechanism of action: methylation of the DNA-repairing protein MGMT associated with the triazene structural portion and Topo II inhibition by intercalation of the acridine core.
Walunj, Dipak,Egarmina, Katarina,Tuchinsky, Helena,Shpilberg, Ofer,Hershkovitz-Rokah, Oshrat,Grynszpan, Flavio,Gellerman, Gary
p. 237 - 252
(2020/08/21)

N-Aroylbenzotriazoles as Efficient Reagents for o-Aroylation in Absence of Organic Solvent
N-Aroylbenzotriazoles have been shown to be efficient reagents for esterification in the absence of organic solvent. Grinding of N-aroylbenzoytiazoles with twofold excess of alcohols for a couple of hours at room temperature gave corresponding esters in high percentage of yields.
Hahnvajanawong, Viwat,Phungpis, Baramee
p. 2671 - 2674
(2021/10/25)

A NaH-promoted N-detosylation reaction of diverse p-toluenesulfonamides
A NaH-mediated detosylation reaction of various Ts-protected indoles, azaheterocycles, anilines and dibenzylamine was reported. The method features cheap reagent, convenient operations, mild reaction conditions and broad substrate scope. Moreover, this study revealed that the loading of NaH in tosylation reactions of nitrogen-containing compounds with NaH as a base in DMA or DMF should be controlled due to the possibility of adverse detosylation.
Sun, Wanwan,Chen, Xiaobei,Hu, Ying,Geng, Huihui,Jiang, Yuanrui,Zhou, Yuxin,Zhu, Wenjing,Hu, Min,Hu, Haohua,Wang, Xingyi,Wang, Xinli,Zhang, Shilei,Hu, Yanwei
supporting information

(2020/10/05)

Transition-Metal-Free and Visible-Light-Mediated Desulfonylation and Dehalogenation Reactions: Hantzsch Ester Anion as Electron and Hydrogen Atom Donor
Novel approaches for N- and O-desulfonylation under room temperature (rt) and transition-metal-free conditions have been developed. The first methodology involves the transformation of a variety of N-sulfonyl heterocycles and phenyl benzenesulfonates to the corresponding desulfonylated products in good to excellent yields using only KOtBu in dimethyl sulfoxide (DMSO) at rt. Alternately, a visible light method has been used for deprotection of N-methyl-N-arylsulfonamides with Hantzsch ester (HE) anion serving as the visible-light-absorbing reagent and electron and hydrogen atom donor to promote the desulfonylation reaction. The HE anion can be easily prepared in situ by reaction of the corresponding HE with KOtBu in DMSO at rt. Both protocols were further explored in terms of synthetic scope as well as mechanistic aspects to rationalize key features of desulfonylation processes. Furthermore, the HE anion induces reductive dehalogenation reaction of aryl halides under visible light irradiation.
Heredia, Micaela D.,Guerra, Walter D.,Barolo, Silvia M.,Fornasier, Santiago J.,Rossi, Roberto A.,Budén, Mariá E.
supporting information
p. 13481 - 13494
(2020/12/15)

Method for synthesizing benzotriazole by one-step method
The invention belongs to the technical field of fine chemical synthesis, and provides a method for synthesizing benzotriazole by a one-step method. The method comprises: carrying out diazotization andcyclization one-step synthesis on o-phenylenediamine, glacial acetic acid and sodium nitrite, crystallizing, washing water, and drying to obtain benzotriazole. The method overcomes the problems of harsh reaction conditions and low yield.
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Paragraph 0018-0025

(2020/05/30)

Catalytic Reductions Without External Hydrogen Gas: Broad Scope Hydrogenations with Tetrahydroxydiboron and a Tertiary Amine
Facile reduction of aryl halides with a combination of 5% Pd/C, B2(OH)4, and 4-methylmorpholine is reported. Aryl bromides, iodides, and chlorides were efficiently reduced. Aryl dihalides containing two different halogen atoms underwent selective reduction: I over Br and Cl, and Br over Cl. Beyond these, aryl triflates were efficiently reduced. This combination was broadly general, effectuating reductions of benzylic halides and ethers, alkenes, alkynes, aldehydes, and azides, as well as for N-Cbz deprotection. A cyano group was unaffected, but a nitro group and a ketone underwent reduction to a low extent. When B2(OD)4 was used for aryl halide reduction, a significant amount of deuteriation occurred. However, H atom incorporation competed and increased in slower reactions. 4-Methylmorpholine was identified as a possible source of H atoms in this, but a combination of only 4-methylmorpholine and Pd/C did not result in reduction. Hydrogen gas has been observed to form with this reagent combination. Experiments aimed at understanding the chemistry led to the proposal of a plausible mechanism and to the identification of N,N-bis(methyl-d3)pyridin-4-amine (DMAP-d6) and B2(OD)4 as an effective combination for full aromatic deuteriation. (Figure presented.).
Korvinson, Kirill A.,Akula, Hari K.,Malinchak, Casina T.,Sebastian, Dellamol,Wei, Wei,Khandaker, Tashrique A.,Andrzejewska, Magdalena R.,Zajc, Barbara,Lakshman, Mahesh K.
supporting information
p. 166 - 176
(2020/01/02)

tert-Butyl nitrite catalyzed synthesis of benzimidazoles from o-phenylenediamine and aldehydes at room temperature
A simple and efficient method is demonstrated for the synthesis of benzimidazoles via cyclocondensation of o-phenylenediamine with aldehydes in the presence of catalytic amount of tert-butyl nitrite. All the reactions were carried out at room temperature while the desired products were obtained in good to excellent yields.
Azeez, Sadaf,Chaudhary, Priyanka,Kandasamy, Jeyakumar,Sabiah, Shahulhameed,Sureshbabu, Popuri
(2020/02/22)

Selective addition reactions of difluoromethyltriazoles to ketones and aldehydes without the formation of difluorocarbene
There has been great interest in the chemistry, syntheses and reactivities of heteroaryl-N-difluoromethane. The present work is based on the addition reaction of difluoromethyl anions, which are generated directly from difluoromethyl heterocycles, to benzophenone and benzaldehyde. As 1,2,3-triazoles and benzotriazoles can act as leaving groups, two reaction pathways are expected to exist: either the desired reaction route - deprotonation (formation of difluoromethyl anion) or the unfavored reaction route – the formation of difluorocarbene. We describe the chemistry for the selective addition reactions of difluoromethyltriazoles to ketones and aldehydes without the formation of difluorocarbene. Addition reactions of 1-(difluoromethyl)-1H-benzotriazole 1 to benzophenone 2 using potassium t-butoxide as a base were found to proceed smoothly at 0 °C for 5 min with high yields (80–88percent). A plausible mechanism for the addition reactions of 1-(difluoromethyl)-1H-benzotriazole 1 and 1-difluoromethyl-4-phenyltriazole 5 to benzophenones and benzaldehydes is proposed based on deuterium-quenching experiments.
Chai, Jin Young,Cha, Hyojin,Kim, Hyeong Baik,Chi, Dae Yoon
(2020/07/13)

Selective Synthesis of N-H and N-Aryl Benzotriazoles by the [3 + 2] Annulation of Sodium Azide with Arynes
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.
supporting information
p. 12692 - 12699
(2019/10/11)

Making endo-cyclizations favorable again: A conceptually new synthetic approach to benzotriazoles via azide group directed lithiation/cyclization of 2-azidoaryl bromides
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.
p. 4523 - 4534
(2019/05/17)

Method and device for continuous post-processing of benzotriazole synthetic fluid
The invention belongs to the technical field of petrochemical engineering, relates to a method for continuous post-processing of benzotriazole (BTA for short) synthetic fluid, and more specifically, relates to a method for synthesizing BTA through performing continuous post-processing steps such as acidification, washing, extraction, back extraction, dehydration and distillation on the BTA synthetic fluid. According to the method for continuous post-processing of the benzotriazole synthetic fluid, extraction separation is realized by utilizing the difference of solubility of the BTA in water under different PH (Potential of Hydrogen); a large quantity of evaporation energy does not need to be consumed; operation is simple; environmental pollution is little; the economical efficiency is strong; energy consumption is low, and industrialization is easy to realize.
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Paragraph 0023; 0032-0034

(2019/08/06)

Synthesis of Structurally Diverse Benzotriazoles via Rapid Diazotization and Intramolecular Cyclization of 1,2-Aryldiamines
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
p. 5344 - 5353
(2019/05/21)

Synthesis of benzotriazoles derivatives and their dual potential as α-amylase and α-glucosidase inhibitors in vitro: Structure-activity relationship, molecular docking, and kinetic studies
Benzotriazoles (4–6) were synthesized which were further reacted with different substituted benzoic acids and phenacyl bromides to synthesize benzotriazole derivatives (7–40). The synthetic compounds (7–40) were characterized via different spectroscopic techniques including EI-MS, HREI-MS, 1H-, and 13C NMR. These molecules were examined for their anti-hyperglycemic potential hence were evaluated for α-glucosidase and α-amylase inhibitory activities. All benzotriazoles displayed moderate to good inhibitory activity in the range of IC50 values of 2.00–5.6 and 2.04–5.72 μM against α-glucosidase and α-amylase enzymes, respectively. The synthetic compounds were divided into two categories “A” and “B”, in order to understand the structure-activity relationship. Compounds 25 (IC50 = 2.41 ± 1.31 μM), (IC50 = 2.5 ± 1.21 μM), 36 (IC50 = 2.12 ± 1.35 μM), (IC50 = 2.21 ± 1.08 μM), and 37 (IC50 = 2.00 ± 1.22 μM), (IC50 = 2.04 ± 1.4 μM) with chloro substitution/s at aryl ring were found to be most active against α-glucosidase and α-amylase enzymes. Molecular docking studies on all compounds were performed which revealed that chloro substitutions are playing a pivotal role in the binding interactions. The enzyme inhibition mode was also studied and the kinetic studies revealed that the synthetic molecules have shown competitive mode of inhibition against α-amylase and non-competitive mode of inhibition against α-glucosidase enzyme.
Hameed, Shehryar,Kanwal,Seraj, Faiza,Rafique, Rafaila,Chigurupati, Sridevi,Wadood, Abdul,Rehman, Ashfaq Ur,Venugopal, Vijayan,Salar, Uzma,Taha, Muhammad,Khan, Khalid Mohammed
(2019/09/10)

Benzotriazole preparation method
The invention provides a benzotriazole preparation method, which comprises: (1) mixing o-phenylenediamine, acetic acid and water to obtain a material A, and mixing sodium nitrite and water to obtain amaterial B; (2) carrying out a reaction on the material A and the material B obtained in the step (1) through a micro-channel reactor to obtain a reaction solution; and (3) freezing the reaction solution obtained in the step (2), and carrying out solid-liquid separation to obtain a solid phase, ie., benzotriazole. Compared with the preparation method based on the tank reactor in the prior art, the method of the invention has the following advantages that through the matching of the micro-channel reactor, the material ratio, the process steps and the parameters, the reaction rate of the raw materials and the process safety are remarkably improved, the reaction temperature and the reaction pressure are relatively low, the steps are simplified, the reaction time is greatly shortened and is shortened to within 2 min, the purity of the product can reach 90-96%, the yield is 90-95%, and the method is suitable for large-scale industrial production.
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Paragraph 0048-0109

(2020/01/03)

p-Toluenesulfonic acid-promoted autocatalytic hydrolyzation of 1-tosyl-1,2,3-triazoles
The first example of autocatalytic hydrolyzation of 4-aryl-1-tosyl-1,2,3-triazoles induced by p-toluenesulfonic acid was reported, providing an effective and metal-free synthetic approach to deliver a broad range of new 4-aryl-2H-1,2,3-triazoles in good yields. The kinetic profile of this hydrolyzation suggested that this reaction has exponential autocatalytic behavior.
Dong, Haohao,Zhang, Dongdong,Fang, Renjie,Du, Qingyang,Dong, Zhuoya,Wei, Hao,Shi, Min,Wang, Feijun
p. 1227 - 1234
(2018/04/05)

Tert -Butyl nitrite mediated nitrogen transfer reactions: Synthesis of benzotriazoles and azides at room temperature
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
supporting information
p. 6902 - 6907
(2018/10/02)

Molybdenum-Catalyzed Deoxygenation of Heteroaromatic N-Oxides and Hydroxides using Pinacol as Reducing Agent
A molybdenum-catalyzed deoxygenation of pyridine N-oxides and N-hydroxybenzotriazoles, as well as other azole N-oxides, has been developed using pinacol as an environmentally friendly oxo-acceptor. The only by-products are acetone and water making the process a convenient alternative to established protocols in terms of waste generation. The reaction is highly chemoselective and a variety of functional groups are tolerated. The processes are usually very clean allowing the isolation of the pure deoxygenated products after a simple extraction in most cases. (Figure presented.).
Rubio-Presa, Rubén,Fernández-Rodríguez, Manuel A.,Pedrosa, María R.,Arnáiz, Francisco J.,Sanz, Roberto
supporting information
p. 1752 - 1757
(2017/05/22)

Utilization method of waste alpha-1,2,3,5-tetra-O-acetyl-D-ribose in ribose crystalline residual liquid
The invention relates to a method for utilizing waste in ribose crystalline residual liquid. The method comprises the steps that crystalline residual liquid obtained after nucleoside pyrolysis serves as a raw material, an organic layer is extracted, an organic solvent is vaporized and eliminated, mixing is conducted with benzotriazole, under the action of a catalyst, on the condition that the temperature ranges from 100 DEG C to 160 DEG C, a condensation reaction is conducted for 0.33-5.0 h, after the reaction is completed, ethyl acetate is added for dissolving, washing is conducted with water, the solvent is dried out, recrystallization is conducted with diethyl ether, an intermediate product 1-(2,3,5-tri-O-acetyl-beta-D-furanribosyl)benzotriazole is obtained, under the faction of an aminomethanol solution or a sodium methylate methanol solution, acetyl is removed at room temperature, and 1-(2,3,5-tri-hydroxyl-beta-D-furanribosyl)benzotriazole is obtained. The method has the prominent advantages the waste is turned into wealth, at the same time of reducing beta-tetra-O-acetyl-D-ribose crystalline residual liquid, the original waste alpha-tetra-O-acetyl-D-ribose is utilized, and the method has the obvious implement value and social and economic benefits.
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Paragraph 0094; 0095; 0096

(2017/05/27)

Microwave-assisted solid phase diazotation: A method for the environmentally benign synthesis of benzotriazoles
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
p. 2515 - 2519
(2017/07/17)

Visible-light-mediated C2-amination of thiophenes by using DDQ as an organophotocatalyst
In this work, a direct C-H activation of thiophenes was presented via an oxidation pathway under visible-light irradiation, in which the thiophene radical cation serves as the key intermediate. Various thiophenes and azoles could be transformed into the corresponding amination products well, and H2O was the only byproduct which is environmentally benign. Our results showed that tert-butyl nitrite (TBN) served as the electron transfer mediator and O2 as the terminal oxidant to regenerate the photocatalyst DDQ and revive the photocatalytic cycle.
Song, Chunlan,Yi, Hong,Dou, Bowen,Li, Yiying,Singh, Atul K.,Lei, Aiwen
supporting information
p. 3689 - 3692
(2017/04/03)

1,3,4-Oxadiazole derivatives as potential antitumor agents: Discovery, optimization and biological activity valuation
Recent studies have proved that focal adhesion kinase (FAK) is a new potential therapeutic target in cancer therapy. In this study, a virtual screening was conducted to discover potential candidates for FAK inhibitors. Based on the results, a series of novel oxadiazole derivatives (5a-5q) bearing the benzotriazole group were designed and synthesized for FAK inhibitory evaluation. Among the compounds, 5h, which has an ortho methoxy group on the benzene ring, exhibited the most potent inhibitory activity for cancer cell growth with an IC50 value of 11 μM and 0.250 μM against Hela cells and FAK, respectively. Further, the apoptosis assay indicated that compound 5h induced the apoptosis of HeLa cells, and docking simulation showed that 5h could bind to the FAK protein catalytic region. Taking these together, 5h could be a lead for discovering novel FAK inhibitors.
Luo, Yin,Liu, Zhi-Jun,Chen, Guo,Shi, Jing,Li, Jing-Ran,Zhu, Hai-Liang
p. 263 - 271
(2016/03/01)

Mild and general access to diverse 1H-benzotriazoles via diboron-mediated N-OH deoxygenation and palladium-catalyzed C-C and C -N bond formation
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.
p. 451 - 462
(2015/03/05)

Ambient benzotriazole ring opening through intermolecular radical addition to vinyltriazole
Radical addition to vinyltriazole was developed as a new approach to achieve 1,2,3-triazole ring opening under mild conditions. Through reagent control, excellent chemoselectivity was achieved, giving either nitrile under basic conditions or quinoxaline under neutral conditions. Reactivities made this method an attractive new reaction mode.
Su, Yijin,Petersen, Jeffrey L.,Gregg, Tesia L.,Shi, Xiaodong
supporting information
p. 1208 - 1211
(2015/03/14)

BICYCLIC HETEROARYL COMPOUNDS AND USES THEREOF FOR THE MODULATION OF HEMOGLOBIN
Provide herein are compounds and pharmaceutical compositions suitable as modulators of hemoglobin, methods and intermediates for their preparation, and methods for their use in treating disorders mediated by hemoglobin and disorders that would benefit from tissue and/or cellular oxygenation.
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(2015/10/06)

Biomimetic polymers responsive to a biological signaling molecule: Nitric oxide triggered reversible self-assembly of single macromolecular chains into nanoparticles
Novel nitric oxide (NO) responsive monomers (NAPMA and APUEMA) containing o-phenylenediamine functional groups have been polymerized to form NO-responsive macromolecular chains as truly biomimetic polymers. Upon exposure to NO - a ubiquitous cellular signaling molecule - the NAPMA- and APUEMA-labeled thermoresponsive copolymers exhibited substantial changes in solubility, clearly characterized by tuneable LCST behavior, thereby inducing self-assembly into nanoparticulate structures. Moreover, the NO-triggered self-assembly process in combination with environmentally sensitive fluorescence dyes could be employed to detect and image endogenous NO. NO problem: Polymerization of NO-responsive monomers containing o-phenylenediamine functional groups has led to the formation of NO-responsive macromolecular chains that act as truly biomimetic polymers. Exposure to NO results in the thermoresponsive copolymers undergoing self-assembly into micellar structures (see example). The NO-triggered self-assembly process with turn on fluorescence was further used to image endogenous NO.
Hu, Jinming,Whittaker, Michael R.,Duong, Hien,Li, Yang,Boyer, Cyrille,Davis, Thomas P.
supporting information
p. 7779 - 7784
(2014/08/05)

METHODS FOR TRIAZOLE SYNTHESIS
Disclosed are methods of synthesizing triazoles that avoids the use of concentrated acids in favor of carbonic acid generated from CO2 that can be practiced at ambient and/or elevated temperature and/or atmospheric and/or elevated pressures. The disclosed methods also provide a way of synthesizing triazole products that are sufficiently pure and/or of sufficient concentration whereby the reaction product(s) may not require purification or other treatment before being used in, for example, formulating water treatment compositions that will tend to suppress corrosion or as an intermediate product in a more complex synthesis.
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Paragraph 0017

(2014/06/25)

Mixed oxides as highly selective catalysts for the flash pyrolysis of phenacyl benzotriazole: One-pot synthesis of dibenzazepin-7-one
The one-pot synthesis of dibenzo[b,d]azepin-7-one (3) was selectively achieved from 1-phenacyl-1,2,3-benzotriazole (1) using the catalytic flash vacuum pyrolysis (cfvp) methodology. Catalysts with the scheelite structure ABO4 (A = Ca2+, Sr2+, Ba2+ and B = Mo6+, W6+) and fergusonite BiVO4 were explored in this new catalytic reaction. These oxides promoted high conversion of starting material at lower temperatures than those observed for noncatalytic reactions. The chemical nature of A and B cations in the scheelite structure showed a strong influence on the formation toward the desired azepinone. In addition, the catalyst's morphology had a significant influence on the course of the cfvp reaction.
Lener, German,Carbonio, Raul E.,Moyano, E. Laura
p. 1020 - 1025
(2013/07/25)

A N-(2-aminophenyl)-5-(dimethylamino)-1-naphthalenesulfonic amide (Ds-DAB) based fluorescent chemosensor for peroxynitrite
A dansyl derivative (Ds-DAB) was prepared and used as a fluorescent probe for peroxynitrite (ONOO-) detection. The results showed that the addition of peroxynitrite to the aqueous solution of Ds-DAB would result in obvious fluorescence enhancement. This probe is highly specific for peroxynitrite in aqueous solution, avoiding interference from other reactive oxygen species (ROS) and nitrogen species (RNS). The advantages of high selectivity, fast reaction rate, and peroxynitrite bioimaging render Ds-DAB suitable for peroxynitrite detection.
Lin, Ku-Kuei,Wu, Shou-Cheng,Hsu, Kuang-Mei,Hung, Chen-Hsiung,Liaw, Wen-Feng,Wang, Yun-Ming
supporting information
p. 4242 - 4245
(2013/09/12)

Facile synthesis of benzotriazole derivatives using nanoparticles of organosilane-based nitrite ionic liquid immobilized on silica and two room-temperature nitrite ionic liquids
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
p. 2801 - 2808
(2013/08/15)

Heterobimetallic Ir-Sn catalysis: Aza-Friedel-Crafts reaction of N-sulfonyl aldimines
The heterobimetallic complex [Ir(COD)(SnCl3)Cl(μ-Cl)] 2 catalyzes the aza-Friedel-Crafts reaction of 1,3,5- trimethoxybenzene, as well as substituted indoles with N-sulfonyl aldimines leading to the formation of diarylamines and triarylmethanes in good yields. The symmetrical triarylmethanes were also obtained from diarylamines and suitable nucleophiles via simultaneous cleavage of sp3 C-N bond and elimination of 1,3,5-trimethoxybenzene.
Chatterjee, Paresh Nath,Maity, Arnab Kumar,Mohapatra, Swapna Sarita,Roy, Sujit
supporting information
p. 2816 - 2826
(2013/04/10)

Spectrofluorimetric determination of trace nitrite with o-phenylenediamine enhanced by hydroxypropyl-β-cyclodextrin
A simple and sensitive spectrofluorimetric method was developed for the determination of nitrite in environmental and food samples. The method was based on the selective reaction of o-phenylenediamine with nitrite in acidic medium to form benzotriazole, which exhibited strong fluorescence at 568 nm with excitation at 420 nm in alkaline medium. The detection limit and sensitivity of the proposed method were improved by hydroxypropyl-β-cyclodextrin through complexation. The linear calibration range for nitrite was 0.04-0.8 μg mL-1 with a detection limit of 13.6 ng mL-1 (S/N = 3.29). The relative standard deviation for ten determinations of 0.1 and 0.4 μg mL-1 nitrite were 1.38% and 2.01%, respectively. Twenty-eight coexistent ions were examined, and no serious interference for most of ions was observed. The proposed method was successfully applied for the determination of nitrite in the water, sausage and soil samples with recoveries of 95.5-108.5%. The results were in good agreement with the recommended AOAC method.
Guo, Yu-Xian,Zhang, Qing-Feng,Shangguang, Xincheng,Zhen, Guodong
p. 107 - 111
(2013/02/22)

Zinc phthalocyanine with PEG-400 as a recyclable catalytic system for selective reduction of aromatic nitro compounds
Zinc phthalocyanine with PEG-400 was established as a catalytic system for chemo and regioselective reduction of aromatic nitro compounds to corresponding amines. A large range of reducible functional groups such as acid, amide, ester, halogen, lactone, nitrile, N-benzyl, O-benzyl, hydroxy and heterocycles were well tolerated. Direct synthesis of benzotriazole from O-dinitrobenzene was achieved for the first time. The present catalytic system was successfully employed for the reduction of carbonyl and ester compounds to corresponding alcohols and reductive amination of benzaldehydes with primary amines to form corresponding secondary amines. Remarkable advantages of the present catalytic method include low loading of metal, avoidance of toxic ligands and high isolated yields. The catalyst was recyclable up to four times without any loss of selectivity and activity.
Sharma, Upendra,Kumar, Neeraj,Verma, Praveen Kumar,Kumar, Vishal,Singh, Bikram
supporting information; experimental part
p. 2289 - 2293
(2012/09/10)

A new class of bioactivable self-immolative N,O-ligands
A hexadentate ligand built on an amine-bis(phenol) skeleton with an aminal, self-immolative moiety is presented. Synthesis of the ligand is convenient and relatively high yielded. Moreover, it enables synthesis of many derivatives, both in the amino-phenol and aminal fragment (various heterocycles). Once the final hexadentate ligand is synthesized via the Katritzky reaction, it becomes prone to hydrolysis. Bioactivation by β-galactosidase cleaves the glycosylic bond and a spontaneous collapse of the aminal fragment occurs, thus leading to a pentadentate chelate. This bioactivation has been shown for pyrazole, 1,2,4-triazole and benzotriazole derivatives.
Ku?nik, Nikodem,Chrobaczyński, Arkadiusz,Mika, Ma?gorzata,Miler, Patrycja,Komor, Roman,Kubicki, MacIej
supporting information; experimental part
p. 184 - 192
(2012/07/28)

Fe(HSO4)3 as an Efficient Catalyst for Diazotization and Diazo Coupling Reactions
Diazo coupling reactions of aromatic amines with 2-naphthol in a green, efficient and easy procedure is described. Ferric hydrogensulfate catalyses this reaction in water at room temperature and short reaction time with high yields. The antibacterial activities of the synthesized compounds against four pathogenic bacteria are also investigated.
Rahimizadeh, Mohammad,Eshghi, Hossein,Shiri, Ali,Ghadamyari, Zohreh,Matin, Maryam M.,Oroojalian, Fatemeh,Pordeli, Parvaneh
p. 716 - 719
(2013/05/08)

Oxidative dehydrocoupling of N-H bonds using a redox-active main group superbase
Reaction of the redox-active base Sn(NMe2)2/ nBuLi with o-phenylene diamine leads to oxidative dehydrocoupling and rearrangement into the triazolyl anion.
Less, Robert J.,Naseri, Vesal,McPartlin, Mary,Wright, Dominic S.
experimental part
p. 6129 - 6131
(2011/08/02)

Preparation and evaluation of 2-azinyl-2H-benzotriazoles as bidentate ligands: Synthesis and characterization of [2-(2-pyridynyl)-2H-benzotriazole] (bpy)2Ru2+
Five 2-azinyl-2H-benzotriazoles (azinyl = 2-pyridinyl, 2-pyrazinyl, 2-pyrimidinyl, 6-methoxy-3-pyridazinyl, 5-methyl-2-pyridinyl were prepared and characterized as bidentate ligands. The electronic structure of these and related heterocycles was investigated spectroscopically and computationally (TD-DFT). They were tested at the B3LYP/6-31++G(d, p)//B3LYP/6-31G(d, p) level of theory as ligands for MgH2, which permitted the elucidation of trends in complex formation, its geometry as a function of the ring structure, and the number and position of the nitrogen atoms in the azine ring. A Ru 2+ complex 7a-Ru with 2-pyridinyl-2H-benzotriazole (7a) and two bpy ligands was prepared and characterized structurally, spectroscopically and electrochemically. The results were compared to those for similar complexes and discussed in the context of computational results for MgH2 complexes.
Obijalska, Emilia,Kaszynski, Piotr,Jankowiak, Aleksandra,Young, Victor G.
p. 1339 - 1348
(2011/06/26)

A green procedure for the diazotization-iodination of aromatic amines under aqueous, strong-acid-free conditions
A convenient and mild one-pot method for the synthesis of iodoarenes in high yields by the sequential diazotization-iodination of aromatic amines with a reusable polymeric diazotization agent in the presence of p-toluenesulfonic acid at room temperature in water was developed. The method is general and is the greenest alternative of the known diazotization-iodination methods. The method is also effective for the preparation of 1H-benzo[d][1,2,3]triazole and benzo[d][1,2,3]thiadiazole. Georg Thieme Verlag Stuttgart ? New York.
Trusova, Marina E.,Krasnokutskaya, Elena A.,Postnikov, Pavel S.,Choi, Younghwa,Chi, Ki-Whan,Filimonov, Victor D.
experimental part
p. 2154 - 2158
(2011/08/05)

Synthesis and cytotoxic evaluation of benzimidazoles and benzotriazoles with dithiocarbamate side chain
Some new benzimidazolyl and benzotriazolyl dithiocarbamates (4a-e & 5a-e) were prepared by reacting corresponding benzimidazoles and benzotriazoles with carbon disulfide and various alkylhalides in dimethylformamide. The newly synthesized compounds were characterized by 1H NMR, MS and elemental analysis. All the compounds have been screened for cytotoxic activity using Trigonella seeds.
Madhu,Tangeda, Saritha Jyostna,Qarlapati, Achaiah
p. 173 - 176
(2013/09/24)

Caste-specific tyramides from Myrmicine ants
Analysis of the extracts of male ants of Monomorium minimum and Monomorium ebeninum by GC-MS and GC-FTIR revealed the presence of tyramides 2 and 4c, for which the structures were established by comparison with synthetic samples. These compounds and their analogues 1 and 3 were also found in males of other Monomorium species, males of Myrmicaria opaciventris, and males of several Solenopsis (Diplorhoptrum) species. Vapor-phase FTIR spectra revealed critically important structural clues to two of the tyramides, which had methyl branching in the tyramide acyl moiety. Tyramide 4c exhibited a strong intramolecular amide NH hydrogen bond where an α-keto group was deduced to be present in the acyl moiety and also showed the overlap of this ketone group frecquency with that of the amide vc-o The biological function of these compounds is uncertain; however, their role in ant-mating behavior may be suggested by a large body of evidence.
Jones, Tappey H.,Martin Garraffo,Spande, Thomas F.,Andriamaharavo, Nirina R.,Gorman, Jeffrey S. T.,Snyder, Alexander J.,Jeter, Andrew W.,Torres, Juan A.,Snelling, Roy R.,Daly, John W.
experimental part
p. 313 - 316
(2010/07/06)

Discovery of 1H-benzo[d][1,2,3]triazol-1-yl 3,4,5-trimethoxybenzoate as a potential antiproliferative agent by inhibiting histone deacetylase
Twenty-one benzotriazoles (3-16 and 18-24) were synthesized and half of them (5, 8-16, 20, and 21) were reported for the first time. Their antiproliferative activities against three human cancer cells were assayed. It revealed that 1H-benzo[d][1,2,3]triazol-1-yl 3,4,5-trimethoxybenzoate (9) showed considerable activity against three human cancer cell lines with the half maximal inhibitory concentration (IC50) values of 1.2-2.4 nM, which were close to the value of the positive control, doxorubicin. Further investigation indicated compound 9 was a potential histone deacetylase inhibitor (IC50 = 9.4 μM) and its binding mode was simulated using docking method.
Fu, Jie,Yang, Ying,Zhang, Xue-Wei,Mao, Wen-Jun,Zhang, Zhi-Ming,Zhu, Hai-Liang
experimental part
p. 8457 - 8462
(2011/02/26)

Boiling water-catalyzed neutral and selective N-Boc deprotection
A general protocol for removing Boc groups from various types of nitrogen is reported and a preliminary investigation of the reaction mechanism indicates that water acts as a dual acid/base catalyst at elevated temperature. The Royal Society of Chemistry 2009.
Wang, Jia,Liang, Yan-Liang,Qu, Jin
supporting information; experimental part
p. 5144 - 5146
(2009/12/08)

Reactions of monoaryl-substituted methylenecyclobutanes and methylenecyclopropanes with 1-hydroxybenzotriazole (HOBt), 1-hydroxy-7- azabenzotriazole (HOAt), and 1-hydroxysuccinimide (HOSu)
Monoaryl-substituted methylenecyclobutanes (MCBs) and methylenecyclopropanes (MCPs) react with 1-hydroxybenzotriazole (HOBt), 1-hydroxy-7-azabenzotriazole (HOAt), and 1-hydroxysuccinimide (HOSu) smoothly to produce the corresponding cyclobutylmethanone an
Jiang, Min,Shi, Min
experimental part
p. 2516 - 2520
(2009/07/25)

PROCESS FOR THE PREPARATION OF ε-ALKOXYCARBONYLLYSINES AND THEIR ANALOGUES
A process for the preparation of ω-alkoxycarbonylamino-α-aminoacids and α,ω orthogonally diprotected diaminoacids from α,ω-diaminoacids using 1- alkoxycarbonylbenzotriazoles as protecting agents is disclosed. In an alternative embodiment, carbamoylating agents in the presence of benzotriazoles are used instead of 1-alkoxycarbonylbenzotriazoles. This reaction is preferably applied to the preparation of ε- alkoxycarbonyllysines from lysine. A process for the preparation of t-butoxycarbonylbenzotriazoles and novel complexes of ω-alkoxycarbonylamino-α-aminoacids with benzotriazoles are also disclosed.
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Page/Page column 13-14

(2008/06/13)

A green N-detosylation of indoles and related heterocycles using phase transfer catalysis
A practical method for the N-detosylation of indoles and related heterocycles with KOH in THF and water in the presence of a phase transfer catalyst is described. Using a nonalcoholic solvent, this method prevents the formation of toxic alkyl p-toluene-sulfonate and consequently eliminates the formation of even traces of N-alkyl byproduct. This green method is particularly useful for indoles bearing electron-withdrawing groups and for azaindoles.
Liu, Yugang,Shen, Lichun,Prashad, Mahavir,Tibbatts, Jessica,Repic, Oljan,Blacklock, Thomas J.
p. 778 - 780
(2013/01/03)

Fluorogenic and chromogenic rhodamine spirolactam based probe for nitric oxide by spiro ring opening reaction
(Chemical Equation Presented) A new fluorogenic and chromogenic probe rhodamine B spirolactam (1) was developed that in aqueous solutions exhibited a highly selective and sensitive turn-on type spectral response toward NO detection following a NO-induced spiro-ring opening reaction in 1.
Zheng, Hong,Shang, Gui-Qin,Yang, Shi-Yao,Gao, Xia,Xu, Jin-Gou
supporting information; body text
p. 2357 - 2360
(2009/05/27)

Novel N,S-phenacyl protecting group and its application for peptide synthesis
The phenacyl group can be introduced onto amino and thio groups by N,S-alkylation reactions. Conversely, these groups are removed rapidly by employing magnesium in acetic acid. This protecting group was successfully applied to a short peptide synthesis of Boc-L-Cys-Gly-OMe. Georg Thieme Verlag Stuttgart.
Tang, Guo,Ji, Tao,Hu, An-Fu,Zhao, Yu-Fen
experimental part
p. 1907 - 1909
(2009/04/11)

Synthesis, structure, and isomerism of N-2,4-dinitrophenylbenzotriazoles
Both isomers of N-(2′,4′-dinitrophenyl)benzotriazole, the 1(3)- and the 2-substituted, have been characterized and their reciprocal isomerism was studied. Cross-experiments in the presence of 5(6)-nitro-1H-benzotriazole proved that the isomerization of 2-(2′,4′-dinitrophenyl)-2H-benzotriazole into the 1-isomer occurs by an intermolecular mechanism. The reported reaction of 5(6)-nitro-1H-benzotriazole with 1-chloro-2,4-dinitrobenzene has been reexamined discovering that there is an error in the proportions of N-substituted isomers. A possible explanation for the observed isomerizations was proposed. Identification of all compounds by multinuclear magnetic resonance, including solid-state studies, has been achieved.
Santa María, M. Dolores,Claramunt, Rosa M.,García, M. ángeles,Elguero, José
p. 3737 - 3744
(2007/10/03)

Photochemical study of tris(benzotriazol-1-yl)methane
(Chemical Equation Presented) Photodecomposition of tris(benzotrizol-1-yl) methane (1) in benzene gives [1-benzotryazol-1-yl-methylidene]-biphenyl-2- ylamine (2) resulting from the loss of the benzotriazolyl radical and nitrogen followed by addition of benzene. Elimination of the second benzotriazolyl radical from 2 provides the biphenyl-2-ylmethyleneamine radical, which affords phenantridine (3) after ring closure. In contrast, the photolysis of 1 in methanol gives a high yield of benzotriazole (4).
Androsov, Dmitry A.,Neckers, Douglas C.
p. 1148 - 1152
(2007/10/03)

Pd0/SnII promoted Barbier-type allylation and crotylation of sulfonimines
A one-pot Barbier protocol is described for the facile formation of homoallyl sulfonamides from sulfonimines and allyl or crotyl bromide in the presence of SnCl2, and catalytic Pd2(dba)3·CHCl3 at room temperature.
Roy, Ujjal Kanti,Roy, Sujit
p. 7177 - 7180
(2008/03/11)

Docking studies and development of novel 5-heteroarylamino-2,4-diamino-8-chloropyrimido-[4,5-b]quinolines as potential antimalarials
MOE-Dock (Docking software) was used to predict the binding modes of 10 novel and potent 5-substituted amino-2,4-diamino-8-chloropyrimido-[4,5-b]quinolines (compounds I-X) as part of our antimalarial drug development programme. This was done by analyzing the interaction of these compounds with the active sites of 11 enzymes present in Plasmodium falciparum and based on this, effective binding was observed to enzyme P. falciparum glutathione reductase (PfGR). The binding scores for compounds I-X with PfGR were also congruent with their antimalarial activity. Three additional analogs were then designed and synthesized based on the above docking study and the pharmacophoric requirements for this class.
Joshi, Advait A.,Viswanathan
p. 2613 - 2617
(2007/10/03)