cas 88-73-3, 2-Nitrochlorobenzene | Articles data

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Nitration of deactivated aromatic compounds via mechanochemical reaction
A variety of deactivated arenes were nitrated to their corresponding nitro derivatives in excellent yields under high-speed ball milling condition using Fe(NO3)3·9H2O/P2O5 as nitrating reagent. A radical involved mechanism was proposed for this facial, eco-friendly, safe, and effective nitration reaction.
Wu, Jian-Wei,Zhang, Pu,Guo, Zhi-Xin
supporting information

(2021/05/05)

Nitration of aromatics with dinitrogen pentoxide in a liquefied 1,1,1,2-tetrafluoroethane medium
Regardless of the sustainable development path, today, there are highly demanded chemical productions still operating that bear environmental and technological risks inherited from the previous century. The fabrication of nitro compounds, and nitroarenes in particular, is traditionally associated with acidic wastes formed in nitration reactions exploiting mixed acids. However, nitroarenes are indispensable for industrial and military applications. We faced the challenge and developed a greener, safer, and yet effective method for the production of nitroaromatics. The proposed approach comprises the application of an eco-friendly nitrating agent, namely dinitrogen pentoxide (DNP), in the medium of liquefied 1,1,1,2-tetrafluoroethane (TFE) - one of the most non-hazardous Freons. Importantly, the used TFE is not emitted into the atmosphere but is effortlessly recondensed and returned into the process. DNP is obtainedviathe oxidation of dinitrogen tetroxide with ozone. The elaborated method is characterized by high yields of the targeted nitro arenes, mild reaction conditions, and minimal amount of easy-to-utilize wastes.
Fauziev, Ruslan V.,Kharchenko, Alexandr K.,Kuchurov, Ilya V.,Zharkov, Mikhail N.,Zlotin, Sergei G.
p. 25841 - 25847
(2021/08/09)

Synthesis method of metolachlor intermediate
The synthesis method comprises the following steps: S1) nitration reaction of chlorobenzene in a nitration reagent to obtain a mixture of o-chloronitrobenzene and p-chloronitrobenzene without separation. S2) The mixture of o-chloronitrobenzene and p-chloronitrobenzene is subjected to catalytic hydrogenation reaction to obtain the mixture of o-chloroaniline and p-chloroaniline, and the product does not need to be separated. S3) The mixture of o-chloroaniline and chloroaniline is subjected to diazotization reaction to obtain the mixture of o-chlorophenylhydrazine and p-chlorophenylhydrazine, and the product does not need to be separated. S4) The mixture of o-chlorophenylhydrazine and p-chlorophenylhydrazine and aldehyde are subjected to a condensation reaction to obtain a triazole ring mixture of Formulae I through a and I through b. S5) The triazole ring mixture is subjected to chlorination reaction to obtain the metolachlor intermediate shown in the formula I. 2, 4 - Dichloroaniline is used as a raw material, the production cost of the metolachlor is reduced, and the supply limitation of the raw material is avoided.
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Paragraph 0078-0084; 0097-0103

(2021/09/21)

The graphite-catalyzed: ipso -functionalization of arylboronic acids in an aqueous medium: metal-free access to phenols, anilines, nitroarenes, and haloarenes
An efficient, metal-free, and sustainable strategy has been described for the ipso-functionalization of phenylboronic acids using air as an oxidant in an aqueous medium. A range of carbon materials has been tested as carbocatalysts. To our surprise, graphite was found to be the best catalyst in terms of the turnover frequency. A broad range of valuable substituted aromatic compounds, i.e., phenols, anilines, nitroarenes, and haloarenes, has been prepared via the functionalization of the C-B bond into C-N, C-O, and many other C-X bonds. The vital role of the aromatic π-conjugation system of graphite in this protocol has been established and was observed via numerous analytic techniques. The heterogeneous nature of graphite facilitates the high recyclability of the carbocatalyst. This effective and easy system provides a multipurpose approach for the production of valuable substituted aromatic compounds without using any metals, ligands, bases, or harsh oxidants.
Badgoti, Ranveer Singh,Dandia, Anshu,Parewa, Vijay,Rathore, Kuldeep S.,Saini, Pratibha,Sharma, Ruchi
p. 18040 - 18049
(2021/05/29)

The polyhedral nature of selenium-catalysed reactions: Se(iv) species instead of Se(vi) species make the difference in the on water selenium-mediated oxidation of arylamines
Selenium-catalysed oxidations are highly sought after in organic synthesis and biology. Herein, we report our studies on the on water selenium mediated oxidation of anilines. In the presence of diphenyl diselenide or benzeneseleninic acid, anilines react with hydrogen peroxide, providing direct and selective access to nitroarenes. On the other hand, the use of selenium dioxide or sodium selenite leads to azoxyarenes. Careful mechanistic analysis and 77Se NMR studies revealed that only Se(iv) species, such as benzeneperoxyseleninic acid, are the active oxidants involved in the catalytic cycle operating in water and leading to nitroarenes. While other selenium-catalysed oxidations occurring in organic solvents have been recently demonstrated to proceed through Se(vi) key intermediates, the on water oxidation of anilines to nitroarenes does not. These findings shed new light on the multifaceted nature of organoselenium-catalysed transformations and open new directions to exploit selenium-based catalysis.
Capperucci, Antonella,Dalia, Camilla,Tanini, Damiano
supporting information
p. 5680 - 5686
(2021/08/16)

Low-temperature and highly efficient liquid-phase catalytic nitration of chlorobenzene with NO2: Remarkably improving the para-selectivity in O2-Ac2O-Hβ composite system
In this work, we developed a low-temperature and efficient approach for the highly selective preparation of valuable p-nitrochlorobenzene from the liquid-phase catalytic nitration of chlorobenzene with NO2 in O2-Ac2O-Hβ composite system. The results demonstrated that the introduction of molecular oxygen remarkably enhanced the chlorobenzene conversion and the cooperation catalysis of Hβ zeolite and Ac2O envidently improved the selectivity to para-nitro product. Under the optimized reaction conditions, 93.6 % of the selectivity to p-nitrochlorobenzene with 84.0 % of chlorobenzene conversion was obtained, and the ratio of p-nitrochlorobenzene to o-nitrochlorobenzene could reach up to 20.3. Furthermore, the selectivity distribution of nitration products was reasonably explained by the density functional theory (DFT) calculation. Finally, the possible nitration reaction pathway of chlorobenzene with NO2 was suggested in O2-Ac2O-Hβ composite catalytic system. The present work affords a new and mild nitration approach for highly selective preparation of valuable para-nitro products, and has potential industrial application prospects.
Deng, Renjie,Liu, Pingle,Luo, He'an,Ni, Wenjin,You, Kuiyi,Zhao, Fangfang
(2020/02/26)

Two-Phase Electrochemical Generation of Aryldiazonium Salts: Application in Electrogenerated Copper-Catalyzed Sandmeyer Reactions
The electrochemical generation of aryldiazonium salts from nitroarenes in a two-phase system (ethyl acetate/water) was reported for the first time. Some compounds including azo, azosulfone, and arylazides were prepared in good yields with good purity. Cathodically generated aryldiazoniums and anodically produced copper(Ι) ions were used to perform Sandmeyer reactions. To improve the method, an H-type self-driving cell equipped with a Zn rod as an anode was introduced and used for two-phase aryldiazonium production.
Goljani, Hamed,Tavakkoli, Zahra,Sadatnabi, Ali,Nematollahi, Davood
supporting information
p. 5920 - 5924
(2020/08/12)

Dehydroxyalkylative halogenation of C(aryl)-C bonds of aryl alcohols
We herein report Cu mediated side-directed dehydroxyalkylative halogenation of aryl alcohols. C(aryl)-C bonds of aryl alcohols were effectively cleaved, affording the corresponding aryl chlorides, bromides and iodides in excellent yields. Aryl alcohols could serve as both aromatic electrophilic and radical synthetic equivalents during the reaction.
Liu, Mingyang,Zhang, Zhanrong,Liu, Huizhen,Wu, Tianbin,Han, Buxing
supporting information
p. 7120 - 7123
(2020/07/14)

NITRATION
The present invention relates to a process for preparing a nitrated compound, comprising the step of reacting a compound (A) comprising at least one substituted or unsubstituted aromatic or heteroaromatic ring, wherein said heteroaromatic ring comprises at least one heteroatom selected from the group consisting of oxygen, sulfur, phosphor, selenium and nitrogen, with a compound of formula (I) wherein Y is selected from the group consisting of hydrogen and nitro.
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Page/Page column 36; 41; 46; 64; 37; 42; 48; 67

(2020/05/28)

A convenient room temperature ipso-nitration of arylboronic acid catalysed by molecular iodine using zirconium oxynitrate as nitrating species: An experimental and theoretical investigation
A simple and convenient protocol has been developed for ipso-nitration of arylboronic acid catalysed by molecular iodine at room temperature, using zirconium oxynitrate as the nitrating species. The protocol is applicable to electronically diverse aryl- and heteroarylboronic acid moieties under mild reaction conditions with good to excellent isolated yields. Furthermore, a theoretical investigation has been performed for the same reaction, and reaction profiles are modelled using modern density functional theory (DFT). DFT-based results support the experimentally observed results.
Mahanta, Abhijit,Gour, Nanda Kishor,Sarma, Plaban Jyoti,Borah, Raju Kumar,Raul, Prasanta Kumar,Deka, Ramesh Chandra,Thakur, Ashim Jyoti,Bora, Utpal
(2019/05/15)

Base promoted peroxide systems for the efficient synthesis of nitroarenes and benzamides
A useful and efficient approach for the synthesis of nitroarenes from several aromatic amines (including heterocycles) using peroxide and base has been developed. This oxidative reaction is very easy to handle and afforded the products in good yields. Formation of benzamides from benzylamine was also successfully carried out with this metal-free catalytic system in good to excellent yields.
Gupta, Sampa,Ansari, Alisha,Sashidhara, Koneni V.
supporting information

(2019/09/07)

Method for preparing nitro compound by using graphene to catalyze carbon dioxide
The invention discloses a method for preparing a nitro compound by using graphene to catalyze carbon dioxide. A graphene material is applied to catalysis of a reaction of carbon dioxide and a nitrification substrate such as an aromatic compound to prepare the nitro compound. The method is used for replacing a traditional nitric acid/sulfur acid method to prepare the nitro compound, so that the atom utilization rate of the reaction is increased, the energy is saved, and the emission is reduced; and the method has the characteristic of atom economy during industrial preparation of the nitro compound.
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Paragraph 0033-0034

(2018/06/16)

Method for preparing nitro compound by using graphene to catalyze nitric oxide
The invention discloses a method for preparing a nitro compound by using graphene to catalyze nitric oxide. A graphene oxide carbon material is used for catalysis of a reaction of nitric oxide and a nitrification substrate such as an aromatic compound to prepare the nitro compound. The method is used for replacing a traditional nitric acid/sulfur acid method to prepare the nitro compound, so thatthe atom utilization rate of the reaction is increased, the energy is saved, and the emission is reduced; and the method has the characteristic of atom economy during industrial preparation of the nitro compound.
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Paragraph 0037; 0038

(2018/06/16)

Silica-supported perchloric acid and potassium bisulfate as reusable green catalysts for nitration of aromatics under solvent-free microwave conditions
Silica-supported perchloric acid and bisulfate (SiO2/HClO4 and SiO2/KHSO4) have been developed as reusable green catalysts for nitration of aromatic compounds using NaNO2 in acetonitrile medium under conventional and solvent-free microwave conditions. The reaction times under microwave irradiation are significantly shorter than conventional method even though the yields obtained in microwave-assisted reactions are comparable with those obtained under reflux conditions.
Kumar, M. Satish,Sriram, Y. Hemanth,Venkateswarlu,Rajanna,Sudhakar, M. Sai,Venkanna, Purugula,Saiprakash
supporting information
p. 59 - 67
(2017/12/26)

HNO3/HFIP: A Nitrating System for Arenes with Direct Observation of π-Complex Intermediates
This report describes an efficient nitrating system for the nitration of arenes at room temperature by using an equivalent of nitric acid in HFIP (1,1,1,3,3,3-hexafluoroisopropanol). The π-complex intermediate of an arene with a nitronium ion stabilized by HFIP can be directly observed by UV-vis spectra and is supported by theoretical calculations.
Lu, Le,Liu, Huixin,Hua, Ruimao
supporting information
p. 3197 - 3201
(2018/06/11)

Mechanical force under the action of the nitration of aromatic compounds of nitrate method (by machine translation)
The invention discloses a mechanical force under the action of the nitration of aromatic compounds of nitrate method. The invention provides a method for preparing aromatic nitro compounds, comprising the following steps: under the action of mechanical force, aromatic compound with a metal nitrate or its hydrate by the nitration reaction, to obtain the aromatic nitro compound; the mechanical fastener is machinery offers can cause material physical and/or chemical nature of the change of the external force. The mechanical force can be compression, shear, impact, friction, tensile, bending and vibration of any kind. The invention has the following advantages: without the use of any solvent, thereby avoiding the waste liquid produced; and without the use of the acidic substance, the reaction is complete after treatment is simple, without any damage to the apparatus; a very high conversion and selectivity, can be applied to the nitration of conventional aromatic compound. (by machine translation)
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Paragraph 0050; 0051

(2018/09/11)

Inexpensive NaX (X = I, Br, Cl) as a halogen donor in the practical Ag/Cu-mediated decarboxylative halogenation of aryl carboxylic acids under aerobic conditions
Versatile and practical Ag/Cu-mediated decarboxylative halogenation between readily available aryl carboxylic acids and abundant NaX (X = I, Br, Cl) has been achieved under aerobic conditions in moderate to good yields. The halodecarboxylation is shown to be an effective strategy for S-containing heteroaromatic carboxylic acid and benzoic acids with nitro, chloro and methoxyl substituents at the ortho position. A gram-scale reaction and a three-step procedure to synthesize iniparib have been performed to evaluate the practicality of this protocol. A preliminary mechanistic investigation indicates that Cu plays a vital role and a radical pathway is involved in the transformation.
Fu, Zhengjiang,Jiang, Ligao,Zuo, Qianming,Li, Zhaojie,Liu, Yanzhu,Wei, Zhenhong,Cai, Hu
supporting information
p. 5416 - 5421
(2018/08/12)

Oxidation of Aniline to Nitrobenzene Catalysed by 1-Butyl-3-methyl imidazolium phosphotungstate Hybrid Material Using m-chloroperbenzoic Acid as an Oxidant
Abstract: Keggin ion based hybrid materials, [BmIm]3[PW12O40], [TBA]3PW12O40 and [BuPy]3PW12O40, were prepared by proton exchange with organic cations, 1-butyl-3-methyl imidazolium ion, tetrabutylammonium ion and butylpyridinium ion, respectively. The formation of hybrid materials was confirmed by FTIR, PXRD, SEM, TG-DTA, DSC analysis. These hybrid compounds are active for oxidation of aniline using m-chloroperbenzoic acid as an oxidant. Among the three hybrid compounds, 1-butyl-3-methyl imidazolium phosphotungstate was found to be the best and efficient catalyst for selective aniline oxidation to nitrobenzene. It is a recoverable and reusable catalytic system. The redox property of the phosphotungstate cluster in the hybrid material is involved in the catalytic activity. Graphical Abstract: [Figure not available: see fulltext.].
Meenakshi,Shakeela,Kutti Rani,Ranga Rao
p. 246 - 257
(2017/10/23)

Convenient, metal-free ipso-nitration of arylboronic acids using nitric acid and trifluoroacetic acid
A feasible protocol for the direct ipso-nitration of arylboronic acids using trifluoroacetic acid and nitric acid as nitration reagent has been developed. Various aromatic nitro compounds are produced in moderate to good yields under the metal-free conditions. The method is operationally simple and regioselective, and might have potential application in industry.
Shen, Guodong,Zhao, Lingyu,Liu, Wanxing,Huang, Xianqiang,Song, Huina,Zhang, Tongxin
supporting information
p. 10 - 14
(2016/12/30)

Synthetic method of aryl halide taking aryl carboxylic acid as raw material
A synthetic method of an aryl halide taking aryl carboxylic acid as a raw material is characterized in that a corresponding aryl halide is formed by carrying out substitution reaction on an aryl carboxylic acid compound and haloid salt MX in an organic solvent under the condition that oxygen, a silver catalyst, a copper additive and a bidentate nitrogen ligand exist, wherein M in MX represents alkali metal or alkaline earth metal, and X represents F, Cl, Br or I. Compared with a conventional aryl halide synthetic method, the synthetic method disclosed by the invention has the obvious advantages that reaction raw materials (comprising aryl carboxylic acid and MX) are cheap and easy to obtain, the using amount of a metal catalyst is small, pollution to the environment when the oxygen is used as an oxidant is the smallest, good tolerance to various functional groups on an aromatic ring is obtained, the yield is high, and the like. The synthetic method disclosed by the invention can be widely applied to synthesis in the fields of medicine, materials, natural products and the like in industry and academia.
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Paragraph 0091

(2018/01/03)

Organocatalytic oxidation of substituted anilines to azoxybenzenes and nitro compounds: Mechanistic studies excluding the involvement of a dioxirane intermediate
An organocatalytic and environmentally friendly approach for the selective oxidation of substituted anilines was developed. Utilizing a 2,2,2-trifluoroacetophenone-mediated oxidation process, substituted anilines can be transformed into azoxybenzenes, while a simple treatment with MeCN and H2O2 leads to the corresponding nitro compounds, providing user-friendly protocols that can be easily scaled up. Various substitution patterns and functional groups were tolerated leading to products in high to excellent yields. Mechanistic studies utilizing HRMS provide clear evidence for the distinct mechanistic intermediates that are involved. This study constitutes an indirect proof excluding the involvement of a dioxirane intermediate in the green organocatalytic oxidation, utilizing 2,2,2-trifluoroacetophenone as the catalyst.
Voutyritsa, Errika,Theodorou, Alexis,Kokotou, Maroula G.,Kokotos, Christoforos G.
supporting information
p. 1291 - 1298
(2017/06/06)

Regioselective mononitration of aromatic compounds with N2O5 by acidic ionic liquids via continuous flow microreactor
We employed N2O5 as highly active nitrating reagents and a host of acidic ionic liquid as catalysts in these reactions which were conducted in a continuous flow microreactor. When we utilized PEG400-DAIL as catalysts, the conversion of toluene was increased to 95.5 % and the yield of mononitration product (o/p ratio reached 1.10) significantly improved to 99 %, meanwhile the reaction time was drastically shortened to 1/120 of the conventional reactor. Nitration in ionic liquids was surveyed using a host of aromatic substrates with similar reactivity. The ionic liquid recycling procedures had also been devised.
Liu, Jianhua,Li, Bindong,Wang, Huan
p. 513 - 516
(2016/01/20)

NITRATION OF AROMATIC COMPOUNDS
The present invention provides a process for nitrating aromatic compounds without the need for a solid catalyst and/or any organic solvents and/or any other additives. A typical process includes combining or admixing a nitric acid and an anhydride compound under conditions sufficient to produce a reactive intermediate. The aromatic compound to be nitrated is then added to this reactive intermediate to produce a nitroaromatic compound. The nitroaromatic compound can be substituted with one or more, typically, one to three, and often one or two nitrate (-NO2) groups.
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Paragraph 0051

(2016/08/17)

Decarboxylative Halogenation and Cyanation of Electron-Deficient Aryl Carboxylic Acids via Cu Mediator as Well as Electron-Rich Ones through Pd Catalyst under Aerobic Conditions
Simple strategies for decarboxylative functionalizations of electron-deficient benzoic acids via using Cu(I) as promoter and electron-rich ones by employing Pd(II) as catalyst under aerobic conditions have been established, which lead to smooth synthesis of aryl halides (-I, Br, and Cl) through the decarboxylative functionalization of benzoic acids with readily available halogen sources CuX (X = I, Br, Cl), and easy preparation of benzonitriles from decarboxylative cyanation of aryl carboxylic acids with nontoxic and low-cost K4Fe(CN)6 under an oxygen atmosphere for the first time.
Fu, Zhengjiang,Li, Zhaojie,Song, Yuanyuan,Yang, Ruchun,Liu, Yanzhu,Cai, Hu
p. 2794 - 2803
(2016/04/26)

Method for synthesizing pyraclostrobin intermediate
The invention discloses a method for synthesizing a pyraclostrobin intermediate. The synthetic method comprises the following steps: preparing an intermediate 1-(4-chlorophenyl)-3-hydroxy-1-h-pyrazole from 4-chlorophenylhydrazine hydrochloride prepared with p-bromochlorobenzene and hydrazine hydrate as reaction raw materials; reacting o-nitrotoluene with chlorine in the presence of a catalyst so as to prepare o-nitrobenzyl chloride; and subjecting 1-(4-chlorophenyl)-3-hydroxy-1-h-pyrazole and o-nitrobenzyl chloride to an etherification reaction so as to obtain the pyraclostrobin intermediate, i.e., an etherification product 2[(N-4-chlorophenyl)-3-pyrazolyl-oxymethyl]nitrobenzene. The synthetic method provided by the invention can greatly reduce the amount of waste water produced in the synthesis process of 4-chlorophenylhydrazine hydrochloride; with 4-chlorophenylhydrazine hydrochloride as a raw material, the produced intermediate 1-(4-chlorophenyl)-3-hydroxy-1-h-pyrazole has HPLC content of no less than 98% and yield of no less than 90%; since chlorine is used for replacing bromine or hydrobromic acid to prepare o-nitrobenzyl bromide, production cost and environmental protection burden are controlled; and the etherification product with a content of no less than 98% and yield of no less than 90% is obtained.
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Paragraph 0119; 0120

(2017/01/17)

A cuprous ion exchange treatment 13X molecular sieve is applied to the aromatic hydrocarbon chloride aminolysis method for the synthesis of aniline compounds
The invention discloses a method for application of 13X molecular sieve produced by exchange treatment of cuprous ions to synthesis of anilines through ammonolysis of aromatic chlorides. According to the method, a porous molecular sieve is in organic combination with cuprous ions, and the characteristics of high activity and high selectivity of the porous molecular sieve catalyst are utilized, and the 13 X porous molecular sieve is taken as the parent body; the high catalytic activity of cuprous ions is utilized, and 13X is modified through adopting the cuprous ions so as to obtain the Cu-13X solid catalyst; the activity of the Cu-13X solid catalyst is not changed after the Cu-13X solid catalyst is reused for more than 300 times, so that the use cost of the catalyst is effectively lowered; the ammonolysis conversion rate of the aromatic chlorides is increased to more than 98% under the catalysis of the Cu-13X, and the side reaction is effectively reduced.
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Paragraph 0023; 0024; 0025

(2016/10/07)

Poly(4-vinylpyridine)-nitrating mixture complex (PVP-NM): Solid nitrating mixture equivalent for safe and efficient aromatic nitration
Friedel-Crafts type aromatic nitration has served as an indispensable reaction within both industrial and academic applications. However, growing concern over the use of copious amounts of strong acids has prompted the search for more environmentally friendly alternatives. Polymer-bound Bronsted acids, on the other hand, have been shown useful as convenient alternatives to liquid acids. Nitric acid and sulfuric acids have, therefore, been combined, both individually and as a mixture, with poly(4-vinylpyridine). The new solid acid systems have been used to nitrate both activated and deactivated arenes under mild conditions and proved to be effective nitrating agent.
Surya Prakash,Gurung, Laxman,Glinton, Kevin E.,Belligund, Kavita,Mathew, Thomas,Olah, George A.
supporting information
p. 3446 - 3451
(2015/06/25)

Glycinatocopper(II) complex as an efficient heterogeneous catalyst for aromatic Finkelstein reaction of aryl and heteroaryl bromides to chlorides
Glycinatocopper(II) complex 1, readily synthesized from copper chloride and glycine was characterized by various techniques including FTIR, XRD, TGA and SEM analysis. The as-synthesized copper complex was found to be a simple and efficient catalyst for the synthesis of aryl and heteroaryl chlorides via aromatic Finkelstein reaction of aryl and heteroaryl bromides in high to excellent yields. The developed glycinatocopper(II) catalyst could easily be recovered from the reaction mixture and reused successfully for several runs without any loss in catalytic efficiency. The developed methodology represents the first example of the use of heterogeneous catalyst for the synthesis of aryl and heteroaryl chlorides via aromatic Finkelstein reaction.
Verma, Sanny,Saran, Sandeep,Jain, Suman L.
p. 178 - 183
(2014/02/14)

Eco-friendly nitration of benzenes over zeolite-β-SBA-15 composite catalyst
Direct synthesis of microporous-mesoporous zeolite-β-SBA-15 (ZBS-15) composite catalyst from the synthetic precursors of SBA-15and zeolite-β seeds under acidic hydrothermal conditions through the simultaneous self-assembly of mesoporous silica SBA-15 and zeolite-β has been accomplished and characterized the ZBS-15 catalyst by XRD, N2 sorption, FT-IR, TPD of ammonia and SEM techniques. The activity of the ZBS-15 composite catalyst for the nitration of benzenes under solvent-free conditions has been investigated, which revealed that there is a significant synergistic influence of both zeolite-β and SBA-15 materials on the activity of the ZBS-15 catalyst.
Ganjala, Venkata Siva Prasad,Neeli, Chinna Krishna Prasad,Pramod, Chodimella Venkata,Khagga, Mukkanti,Rao, Kamaraju Seetha Rama,Burri, David Raju
p. 82 - 86
(2014/03/21)

Bismuth triflate catalyzed mononitration of aromatic compounds with N 2O5
This page isvestigated that bismuth triflate catalysed the nitration of a range of simple aromatic compounds in good to excellent yields at 0-30 °C within 2 h using N2O5 and the catalyst can be recycled without apparent loss of activity. Mechanistic insights demonstrate that triflic acid is generated and that, at least, when two competing catalytic cycles are operating at the same time: a rapid one involving triflic acid and a slower one involving the bismuth triflate.
Qian, Hua,Wang, Ya,Liu, Dabin,Lv, Chunxu
p. 509 - 512
(2014/05/20)

Phosphoric acid modified montmorillonite clay: A new heterogeneous catalyst for nitration of arenes
The easily available montmorillonite clay is treated with phosphoric acid and 10 wt.% is found to be the optimum concentration of phosphoric acid that can be adsorbed chemically on the surface of the clay. Acidity of this phosphoric acid treated montmorillonite clay (PAM) is determined by volumetric as well as potentiometric titration and characterized. Catalytic efficacy of PAM in nitration of various aromatic compounds is reported.
Bharadwaj, Saitanya K.,Boruah, Purna K.,Gogoi, Pradip K.
p. 124 - 128
(2014/12/11)

Oxidation of aromatic amines into nitroarenes with m-CPBA
A versatile and highly efficient approach for the synthesis of nitroarenes from aromatic amine using m-CPBA has been developed. This oxidation reaction was operationally straightforward and proceeded to afford products in good isolated yields.
Liu, Jia,Li, Jue,Ren, Jiangmeng,Zeng, Bu-Bing
p. 1581 - 1584
(2014/03/21)

Click chemistry inspired facile synthesis and bioevaluation of novel triazolyl analogs of Ludartin
A convenient and modular synthesis involving diastereoselective Michael addition followed by regioselective Huisgen 1,3-dipolar cycloaddition reaction was carried out to furnish 1,4-disubstituted-1,2,3-triazoles of Ludartin. This reaction scheme involving Michael addition followed by regioselective Huisgen 1,3-dipolar cycloaddition reaction leading to the formation of triazolyl analogs is being reported for the first time. All the triazolyl products were characterised using spectral data analysis. Sulphorhodamine B cytotoxicity screening of the resulting products against a panel of five human cancerous cell-lines revealed that few of the analogs display promising broad spectrum cytotoxic effect. Among all the synthesized compounds, only 3q displayed the best cytotoxic effect with IC50 values of 12, 11, 38, 39 and 8.5 μM but less than the standard Ludartin (1) with IC50 values of 6.3, 7.4, 7.5, 6.9 and 0.5 μM against human neuroblastoma (T98G), lung (A-549), prostate (PC-3), colon (HCT-116) and breast (MCF-7) cancer cell lines, respectively. The present synthesis was designed based on the previous literature reports of Ludartin as an aromatase inhibitor. Our work provides an initial study on structure-activity relationship of triazolyl analogs of sesquiterpene lactones in general and Ludartin (1) in particular.
Lone, Shabir H.,Bhat, Khursheed A.,Majeed, Rabiya,Hamid, Abid,Khuroo, Mohd A.
p. 1047 - 1051
(2014/03/21)

Regioselective mononitration of chlorobenzene using caprolactam-based Br?nsted acidic ionic liquids
Three kinds of Br?nsted acidic ionic liquids caprolactam benzenesulfonate ([CP]BSA), caprolactam hydrosulfate ([CP]HSO4) and caprolactam p-toluenesulfonate ([CP]pTSA) were synthesized. The structures of the ILs were confirmed by 1HNM
Zhang, Cun,Yu, Mei-Jing,Pan, Xiao-Yu,Wu, Guo,Jin, Liang,Gao, Wei-Dan,Du, Meng,Zhang, Jun-Chao
p. 101 - 105
(2014/01/06)

Regioselective nitration of aromatics with nanomagnetic solid superacid SO42-/ZrO2-MxOy-Fe 3O4 and its theoretical studies
A series of micro- and nanosulfated zirconia loaded on Fe3O 4 or other metal oxides (SO42-/ZrO 2-MxOy-Fe3O4 (M=Ti 4+, V5+, and Zn2+)) was prepared, characterized, and used in nitration. The nitration conditions with these solid superacids were then optimized to achieve the best regioselectivity and improve the performances of the catalysts as well. In the experimental results, SZTF (SO42-/ZrO2-TiO2-Fe 3O4) showed excellent catalytic activity and it increased the surface area of SO42-/ZrO2 by up to 15 %. The increase not only facilitated the generation of NO2+, but also provided more opportunities for metal ions to interact with aromatic compounds. With chlorobenzene as substrate, theoretical research on its geometric parameters, electron clouds, and electron spin density was used to investigate the interaction between transition metals and chlorobenzene.
Wang, Peng Cheng,Zhu, Jie,Liu, Xiang,Lu, Ting Ting,Lu, Ming
p. 310 - 317
(2013/08/23)

Synthesis and in vitro antibacterial activity of 5-halogenomethylsulfonyl- benzimidazole and benzotriazole derivatives
A series of 5-halogenomethylsulfonylbenzimidazole and benzotriazole derivatives was synthesized as potential antibacterial agents. A new method of synthesis of benzimidazoles was developed. The antimicrobial activities of these compounds were tested against a series of reference and clinical strains. The reference strains include Gram-positive bacteria (S. aureus, S. epidermidis, B. subtilis, B. cereus, E. hirae, M. luteus) and Gram-negative rods (E. coli, P. vulgaris, P. aeruginosa, B. bronchiseptica). The clinical strains include six methicillin-resistant (MRSA) and two methicillin-sensitive (MSSA) S. aureus strains, one methicillin-resistant S. epidermidis, three E. faecalis and two E. faecium strains. Compound with trifluoromethyl- substituent at C-2 position (4) displayed significant antibacterial activities comparable with nitrofurantoin against four strains, and higher against Micrococcus luteus. MIC values for clinical Staphylococci strains (MRSA) were 12.5-25 μg/mL; for Enterococcus strains these values were 50-100 μg/mL. MIC values for reference and clinical strains of Staphylococcus and Enterococcus group were similar, respectively.
Ochal, Zbigniew,Bretner, Maria,Wolinowska, Renata,Tyski, Stefan
p. 1129 - 1136
(2014/01/06)

Preparation of heteropoly acid based amphiphilic salts supported by nano oxides and their catalytic performance in the nitration of aromatics
A series of Keggin heteropoly acid anion based amphiphilic salts supported by nano oxides were synthesized and used as catalysts in the nitration of aromatic compounds with HNO3. The reaction conditions in the nitration of toluene were optimized and both 92.6% conversion and good para selectivity (ortho:para = 1.09) were obtained.
Wang, Peng-Cheng,Yao, Kai,Lu, Ming
p. 2197 - 2202
(2013/03/14)

Preparation, catalytic performance and theoretical study of porous sulfated binary metal oxides shell (SO42 -/M1xO y-M2xOy) using pollen grain templates
Porous micro-sized particles of binary metal oxide (SO4 2 -/M1xOy-M2xOy) shell were prepared by template-directed synthesis method employing HCl-treated pollen grains. With 150 m2/g high surface area, these solid acids could provide more acid sites and thus obtain better catalytic activity. Using aromatic nitration as the typical reaction, their catalytic performances were evaluated and showed a significant improvement in both conversion and regioselectivity. Then, with chlorobenzene as substrate, theoretical studies were performed to investigate the interaction between transition metals and chlorobenzene. The results showed that the excellent para-selectivity was closely relative to the metal ion in these solid acids.
Wang, Peng Cheng,Yao, Kai,Zhu, Jie,Liu, Xiang,Lu, Ting Ting,Lu, Ming
p. 90 - 95
(2013/07/26)

Halogenation and DNA cleavage via thermally stable arenediazonium camphorsulfonate salts
A series of stable arenediazonium camphorsulfonate salts (2a-2j) were synthesized by simple diazotization of several aromatic amines in the presence of sodium nitrite and camphorsulfonic acid. All the new arenediazonium camphorsulfonates, which were characterized by multinuclear (1H and 13C) NMR, IR, DSC, and X-ray diffraction analysis (2e and 2f) provide unambiguous proof for the molecular structures of 2e and 2f. The efficient application of these salts in halogenation reactions was studied in solvent and solvent-free conditions and the DNA cleavage activity was also assessed. These arenediazonium camphorsulfonate salts are noticed as efficient DNA cleaving agents.
Vajpayee, Vaishali,Moon, Mi Eun,Lee, Sunmi,Ravikumar, Sambandam,Kim, Hyunuk,Ahn, Byungchan,Choi, Seoyoon,Hong, Soon Ho,Chi, Ki-Whan
p. 3511 - 3517
(2013/04/23)

Efficient ipso-nitration of arylboronic acids with iron nitrate as the nitro source
A novel, simple and efficient ipso-nitration of arylboronic acids with iron nitrate has been developed. The protocol uses readily available arylboronic acids as the starting materials, inexpensive iron nitrate (0.5 equiv.) as the nitro source without addition of an additive, and the corresponding nitroarenes were obtained in good to excellent yields.
Jiang, Min,Yang, Haijun,Li, Yong,Jia, Zhiying,Fu, Hua
p. 25602 - 25604
(2013/12/04)

Rare earth metal triflates catalyzed electrophilic nitration using N 2O5
A mild, efficient and eco-friendly process for the electrophilic nitration is described using N2O5 as a green nitrating agent in the presence of rare earth metal triflates [RE(OTf)3] under mild conditions.
Ma, Xiao Ming,Li, Bin Dong,Lu, Ming,Lv, Chun Xu
experimental part
p. 73 - 76
(2012/03/26)

Selective nitration of aromatic compounds catalyzed by Hβ zeolite using N2O5
A selective and efficient process for the electrophilic nitration is described using N2O5 as a green nitrating agent, Hβ zeolite as a solid acid catalyst and shape controlling agent under mild conditions.
Ma, Xiao Ming,Li, Bin Dong,Chen, Lei,Lu, Ming,Lv, Chun Xu
scheme or table
p. 809 - 812
(2012/08/08)

Regioselective nitration of aromatic hydrocarbons with bentonite supported metallic nitrates in the presence of solid acids catalysts
Toluene and chlorobenzene are mononitrated of good regioselectivities using metallic nitrates as nitrating reagents in the presence of solid acid catalysts. Para selectivities are much improved, up to para-to-ortho ratios of 1.2 for toluene and 5.6 for chlorobenzene respectively.
Zhang,Peng,Yuan
experimental part
p. 3927 - 3928
(2012/09/10)

Aromatic nitration with bismuth nitrate in ionic liquids and in molecular solvents: A comparative study of Bi(NO3)3·5H 2O/[bmim][PF6] and Bi(NO3)3· 5H2O/1,2-DCE systems
A suspension of bismuth nitrate pentahydrate (BN) in [bmim][PF6] or [bmim][BF4] imidazolium ionic liquid (IL) is an effective reagent for ring nitration of activated aromatics under mild conditions without the need for external promoters. Nitration can also be effected in 1,2-DCE, MeCN, or MeNO2 without additives. Nitration of activated arenes (anisole, toluene, ethylbenzene, cumene, p-xylene, mesitylene, durene, and 1,3-dimethoxybenzene) is considerably faster (time to completion) in BN/[bmim][PF6] relative to BN/1,2-DCE and there are also differences in isomer distributions (for anisole, toluene, and ethylbenzene). With introduction of strongly deactivating substituents (-CHO; -MeCO; -NO 2) the BN/IL system is no longer active but reactions still proceed with BN/1,2-DCE in reasonable yields. The ready availability and low cost of BN, simple operation, and absence of promoters, coupled to recycling and reuse of the IL, provide an attractive alternative to classical nitration methods for activated arenes. Switching from Bi(NO3)3·5H 2O/[bmim][PF6] to Bi(NO3)3· 5H2O/1,2-DCE increases the scope of the substrates that can be nitrated.
Jacoway, Jonathan,Kumar, G. G. K. S. Narayana,Laali, Kenneth K.
p. 6782 - 6785,4
(2012/12/12)

METHOD FOR PREPARATION OF MONONITRATED AROMATIC COMPOUNDS
The invention discloses a method for preparation of mononitrated aromatic compounds in a liquid-liquid biphasic solvent system with aqueous nitric acid as one phase and ionic liquids (ILs) as the second phase, wherein the nitric acid is continuously exchanged during the reaction, or the water, that is generated during the reaction, is removed by addition of NO2 and an oxidizing agent during the reaction.
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Page/Page column 23

(2012/12/13)

The first example of the copper-free chloro- and hydrodediazoniation of aromatic amines using sodium nitrite, CCl4, and CHCl3
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Kutonova, K. V.,Trusova, M. E.,Postnikov, P. S.,Filimonov, V. D.
p. 206 - 208,3
(2020/09/16)

Reusable and efficient polystryrene-supported acidic ionic liquid catalyst for mononitration of aromatic compounds
A series of polystyrene-supported 1-(propyl-3-sulfonate)-3-methyl- imidazolium hydrosulfate acidic ionic liquid (PS-[SO3H-PMIM][HSO 4]) catalysts were prepared and tested for mononitration of simple aromatics compounds with nitric acid. It was found that the reactivity of the catalysts increased with increasing [SO3HPMIM][ HSO4] content. The para-selectivity was not only related to the [SO 3H-PMIM][HSO4] content but also the substituent groups in aromatics. A reaction mechanism of nitration over this new catalyst was proposed. The catalytic activity of this catalyst decreased slightly after fifth runs in the synthesis of nitrotoluene.
Li, Li Xia,Ling, Qi Long,Liu, Zu Liang,Xing, Xiao Dong,Zhu, Xiao Qin,Meng, Xiao
p. 3373 - 3377
(2013/01/15)

The palladium-catalyzed desulfitative cyanation of arenesulfonyl chlorides and sodium sulfinates
A palladium-catalyzed desulfitative cyanation of arenesulfonyl chlorides and sodium sulfinates has been developed, providing aryl nitriles in moderate to excellent yields. It represents a facile procedure to access aryl nitriles.
Chen, Jianbin,Sun, Yang,Liu, Bin,Liu, Dongfang,Cheng, Jiang
experimental part
p. 449 - 451
(2012/01/05)

Ethylammonium nitrate (EAN)/Tf2O and EAN/TFAA: Ionic liquid based systems for aromatic nitration
Acting as in situ sources of triflyl nitrate (TfONO2) and trifluoroacetyl nitrate (CF3COONO2), the EAN/Tf 2O and EAN/TFAA systems, generated via metathesis in the readily available ethylammonium nitrate (EAN) ionic liquid as solvent, are powerful electrophilic nitrating reagents for a wide variety of aromatic and heteroaromatic compounds. Comparative nitration experiments indicate that EAN/Tf2O is superior to EAN/TFAA for nitration of strongly deactivated systems. Both systems exhibit low substrate selectivity (K T/KB = 5-10) in (Figure presented) between values reported for covalent nitrates and preformed nitronium salts.
Aridoss, Gopalakrishnan,Laali, Kenneth K.
experimental part
p. 8088 - 8094
(2011/11/13)

Regioselectivity nitration of aromatics with N2O5 in PEG-based dicationic ionic liquid
Regioselective mononitration of simple aromatic compounds has been investigated with N2O5 as nitrating agent and a new PEG200-based dicationic acidic ionic liquid (PEG200-DAIL) as catalyst. The results of experiments show that this nitration system can significantly improve the para-selectivity of alkyl-benzenes and the ortho-selectivity of halogenated-benzenes. The PEG200-DAIL exhibits recyclable temperature-dependant phase behavior in CCl4 solvent, and it can be recycled without apparent loss of catalytic activity, and only 5% loss of weight is observed after six times recycling.
Wang, Peng-Cheng,Lu, Ming
supporting information; experimental part
p. 1452 - 1455
(2011/05/16)