100-00-5Relevant articles and documents
Natural bentonite clay/dilute HNO3 (40%) - A mild, efficient, and reusable catalyst/reagent system for selective mono nitration and benzylic oxidations
Bahulayan, Damodaran,Narayan, Gopinathan,Sreekumar, Vellalath,Lalithambika, Malathy
, p. 3565 - 3574 (2002)
Selective mono nitration of Aromatic hydrocarbons and benzylic oxidations can be achieved in high yield using reusable catalyst/reagent system consisting of bentonite clay and dilute HNO3 under relatively mild experimental conditions. The dual behavior of the catalyst reagent system is utilized for the regioselective synthesis of a variety of industrially important compounds.
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Russell,Metcalfe
, p. 2359,2360 (1979)
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Paradigm confirmed: The first use of ionic liquids to dramatically influence the outcome of chemical reactions
Earle, Martyn J.,Katdare, Suhas P.,Seddon, Kenneth R.
, p. 707 - 710 (2004)
It has been an unproven paradigm that the choice of which ionic liquid to use in a chemical reaction can have a dramatic effect on the outcome of that chemical reaction. We demonstrate, for the first time, that the reaction of toluene and nitric acid in three different ionic liquids gives rise to three completely different products in high yield. Furthermore, ionic liquids can catalyze these reactions with the only byproduct being water.
Preparation of heteropoly acid based amphiphilic salts supported by nano oxides and their catalytic performance in the nitration of aromatics
Wang, Peng-Cheng,Yao, Kai,Lu, Ming
, p. 2197 - 2202 (2013)
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.
STIMULATION BY Sn(2+) OR ASCORBIC ACID ON DIAZONIUM SALTS REACTIONS
Galli, Carlo
, p. 4515 - 4516 (1980)
Use of a mild reducing agent and ligand transfer for the transformation of diazonium salts into aryl halides provides an alternative to the Sandmeyer procedure.
Reactions of Aryl Diazonium Salts and Arylazo Alkyl Ethers. 7. Kinetic Studies of the Decomposition of Z Ethers Derived from Some Substituted 2-Nitrobenzene Diazonium Salts
Broxton, Trevor J.,McLeish, Michael J.
, p. 3673 - 3679 (1982)
Rate constans for the decomposition of (Z)-syn ethers derived from some 4- or 5-substituted 2-nitrobenzenediazonium salts have been measured in both basic ethanol.For some compounds the rate of decomposition is independent of the base concetration while for others the rate is first order in base concetration.Solvent and substituent effects poit to the base-independent mechanism occuring on the free diazonium salt formed by ionization of the Z ether while the base-dependent mechanism occurs on the Z ether itself.Mechanisms are proposed for each of these reactions.
Electrophilic Aromatic Nitration Using a Mixed Catalyst of Lithium, Molybdenum, Ytterbium on Silica Gel
Shi, Min,Cui, Shi-Cong
, p. 1329 - 1333 (2003)
A novel mixed catalyst of LiClO4 (15% w/w), Yb(OPf)3 (15% w/w, Pf = perfluorooctanesulfonyl), MoO3 (15% w/w) on silica gel for electrophilic aromatic nitration reaction has been explored. The nitration reactions were accomplished by this mixed catalyst and nitric acid under solvent-free conditions. Moreover, the mixed catalyst can be easily recovered from the aqueous layer by heating in an oven and reused for the next nitration reaction.
Ipso-nitration of arylboronic acids with bismuth nitrate and perdisulfate
Manna, Srimanta,Maity, Soham,Rana, Sujoy,Agasti, Soumitra,Maiti, Debabrata
, p. 1736 - 1739 (2012)
An efficient and one pot synthetic method of ipso-nitration of arylboronic acids has been developed. The high efficiency, general applicability, and broader substrate scope including heterocycles and functional groups make this method advantageous. Due to its simplicity, we expect to find application of this method in synthesis.
AI203/MeS03H (AMA) as a novel heterogeneous system for the nitration of aromatic compounds by magnesium nitrate hexahydrate
Hosseini-Sarvari, Mona,Tavakolian, Mina
, p. 722 - 724 (2008)
Mg(NO3)2-6H2O was an efficient nitrating agent in the presence of a mixture of AI2O3/MeSO 3H (AMA) as a novel heterogeneous system for the nitration of aromatic compounds without use of any organic solvents and with high selectivity. The reaction proceeds at room temperature for the nitration of highly reactive aromatic compounds such as phenols and anilines.
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Newman,Fones
, p. 1221 (1947)
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Oxidation of aromatic amines into nitroarenes with m-CPBA
Liu, Jia,Li, Jue,Ren, Jiangmeng,Zeng, Bu-Bing
, p. 1581 - 1584 (2014)
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.
A convenient room temperature ipso-nitration of arylboronic acid catalysed by molecular iodine using zirconium oxynitrate as nitrating species: An experimental and theoretical investigation
Mahanta, Abhijit,Gour, Nanda Kishor,Sarma, Plaban Jyoti,Borah, Raju Kumar,Raul, Prasanta Kumar,Deka, Ramesh Chandra,Thakur, Ashim Jyoti,Bora, Utpal
, (2019)
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.
An efficient and eco-friendly MoO3-SiO2 solid acid catalyst for electrophilic aromatic nitration with N2O5
Ma, Xiaoming,Li, Bindong,Lv, Chunxu,Lu, Ming,Wu, Jian,Liang, Linjie
, p. 1814 - 1820 (2011)
Electrophilic aromatic nitration using N2O5 as a green nitrating agent catalyzed by MoO3-SiO2 under mild conditions has been described. A series of MoO3-SiO2 catalysts with varying MoO3 loadings (5-20 mol%) were prepared by sol-gel technique and characterized using FTIR, XRD, SEM, BET and NH 3-TPD to study its surface properties. MoO3-SiO 2 shows good catalytic activity and reusability for the nitration of alkyl and halogen aromatics giving high conversions, but less efficiency for the deactivated aromatics. Reactions conducted under non-acidic conditions using N2O5 makes the process safe and environmentally friendly. Graphical Abstract: [Figure not available: see fulltext.]
Selective nitration of aromatic compounds by solid acid catalysts
Choudary,Sateesh,Lakshmi Kantam,Koteswara Rao,Ram Prasad,Raghavan,Sarma
, p. 25 - 26 (2000)
High activity and para-selectivity in the nitration of aromatic compounds is achieved by a high density of acidic sites and ready formation of the para-isomer in the pores of zeolite beta with low Si/Al ratio as revealed by molecular modeling studies.
para-Selective nitration of halogenobenzenes using a nitrogen dioxide-oxygen-zeolite system
Smith,Almeer,Black
, p. 1571 - 1572 (2000)
The nitration of halogenobenzenes using zeolite Hβ or zeolite HY as a solid inorganic catalyst and a combination of liquid nitrogen dioxide and gaseous oxygen as the nitrating reagent leads to high yields and significant para-selectivities in a relatively clean process for aromatic nitration.
Synthesis, structure, and synthetic potential of arenediazonium trifluoromethanesulfonates as stable and safe diazonium salts
Filimonov, Victor D.,Krasnokutskaya, Elena A.,Kassanova, Assia Zh.,Fedorova, Valentina A.,Stankevich, Ksenia S.,Naumov, Nikolay G.,Bondarev, Alexander A.,Kataeva, Veronika A.
, p. 665 - 674 (2019)
Aromatic diazonium salts are valuable building blocks for organic synthesis; however, in most cases, they are unstable, unsafe, poorly soluble, and/or expensive. In this paper, we have shown that a variety of stable and safe arenediazonium triflates ArN2+ TfO– can be obtained easily and in high yields by diazotization of anilines with tert-butyl nitrite in the presence of trifluoromethanesulfonic acid. Arenediazonium triflates are relatively shelf-stable in the dry state. They dissolve well in water, as well as polar and even nonpolar organic solvents. Less than 800 J/g of energy is released during the thermal decomposition of these salts, which indicates their explosion safety. Arenediazonium triflates have a high reactivity in the known reactions of diazonium chemistry, and undergo an unusual metal-free chlorodediazonization reaction with chloroform and CCl4.
Iron(III)-mediated photocatalytic selective substitution of aryl bromine by chlorine with high chloride utilization efficiency
Wang, Ying,Li, Lina,Ji, Hongwei,Ma, Wanhong,Chen, Chuncheng,Zhao, Jincai
, p. 2344 - 2346 (2014)
An iron(III)-mediated photocatalytic method for the conversion of aryl, heteroaryl and polycyclic aromatic bromides to the corresponding chlorides with high selectivity has been achieved successfully. The mild reaction conditions and high chloride utilization efficiency promise a bright future for chlorination reactions. The Royal Society of Chemistry 2014.
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Roberts et al.
, p. 4525,4533 (1954)
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Regioselective mononitration of aromatic compounds with N2O5 by acidic ionic liquids via continuous flow microreactor
Liu, Jianhua,Li, Bindong,Wang, Huan
, p. 513 - 516 (2016)
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.
ipso-nitration of arylboronic acids with chlorotrimethylsilane-nitrate salts
Surya Prakash,Panja, Chiradeep,Mathew, Thomas,Surampudi, Vijayalakshmi,Petasis, Nicos A.,Olah, George A.
, p. 2205 - 2207 (2004)
A mixture of nitrate salt and chlorotrimethylsilane is found to be an efficient regioselective nitrating agent for the ipso-nitration of arylboronic acids to produce the corresponding nitroarenes in moderate to excellent yields. High selectivity, simplicity, and convenience are the key features of the reaction.
Nitration of aromatics with dinitrogen pentoxide in a liquefied 1,1,1,2-tetrafluoroethane medium
Fauziev, Ruslan V.,Kharchenko, Alexandr K.,Kuchurov, Ilya V.,Zharkov, Mikhail N.,Zlotin, Sergei G.
, p. 25841 - 25847 (2021)
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.
Electrophilic Aromatic Nitration in the Gas Phase
Attina, Marina,Cacace, Fulvio,Yanez, Manuel
, p. 5092 - 5097 (1987)
Aromatic nitration by MeO+(H)NO2, in essence nitronium ion solvated by one methanol molecule, has been studied in the gas phase by using an integrated approach, based on the coordinate application of ICR, Cl, and CID mass spetrometric methods with a highly complementary radiolytic technique.The latter can be used in gases at atmospheric pressure and allows direct evaluation of key mechanistic features, in particular of substrate and positional selectivity.The results resolve early discrepancies between gas-phase and liquid-phase studies, characterizing the reaction as a typical, well-behaved electrophilic substitution of moderate selectivity.The date from the gas-phase nitration of ten monosubstituted benzenes fit a Hammett's type linear plot, characterized by a ρ value of -3.87.The correlation does not extend to highly activated substrates, such as anisole and mesitylene, since the nitration rate tends to a limiting value that cannot be increased by further enhancing the activation of the substrate, exactly as in "encounter-rate" nitrations occurring in solution.The mechanism and the energetics of the gas-phase nitration have been investigated, and the relative stability of the charged intermediates involved, in particular of the isomeric protonated nitrobenzenes, has been estimated by theoretical approaches at two different levels, using STO-3G minimal basis and 4-31G split-valence basis sets.
PALLADIUM CATALYZED DECARBONYLATION OF AROMATIC ACYL CHLORIDES
Verbicky, John W.,Dellacoletta, Brent A.,Williams, Louella
, p. 371 - 372 (1982)
A variety of palladium catalysts have been found to effectively promote the decarbonylation of aromatic acyl chlorides at elevated temperatures.
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
Jacoway, Jonathan,Kumar, G. G. K. S. Narayana,Laali, Kenneth K.
, p. 6782 - 6785,4 (2012)
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.
Relative Electron Affinities of Substituted Nitrobenzenes in the Gas Phase
Fukuda, Elaine K.,McIver, Robert T.
, p. 2993 - 2995 (1983)
Using pulsed ion cyclotron resonance mass spectrometry, we have determined the relative electron affinities of 12 substituted nitrobenzenes in the gas phase by measuring equilibrium constants for electron transfer reactions of the type C6H5NO2- + X-C6H4NO2 = X-C6H4NO2- + C6H5NO2, where X is a substituent group.An excellent correlation is found between the relative electron affinities of the substituted nitrobenzenes and the relative gas-phase acidities of substituted anilines and phenols.
Nitration of deactivated aromatic compounds via mechanochemical reaction
Wu, Jian-Wei,Zhang, Pu,Guo, Zhi-Xin
supporting information, (2021/05/05)
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.
Selective Mild Oxidation of Anilines into Nitroarenes by Catalytic Activation of Mesoporous Frameworks Linked with Gold-Loaded Mn3O4 Nanoparticles
Armatas, Gerasimos S.,Daikopoulou, Vassiliki,Koutsouroubi, Eirini D.,Lykakis, Ioannis N.,Skliri, Euaggelia
, (2021/11/01)
This work reports the synthesis and catalytic application of mesoporous Au-loaded Mn3O4 nanoparticle assemblies (MNAs) with different Au contents, i. e., 0.2, 0.5 and 1 wt %, towards the selective oxidation of anilines into the corresponding nitroarenes. Among common oxidants, as well as several supported gold nanoparticle platforms, Au/Mn3O4 MNAs containing 0.5 wt % Au with an average particle size of 3–4 nm show the best catalytic performance in the presence of tert-butyl hydroperoxide (TBHP) as a mild oxidant. In all cases, the corresponding nitroarenes were isolated in high to excellent yields (85–97 %) and selectivity (>98 %) from acetonitrile or greener solvents, such as ethyl acetate, after simple flash chromatography purification. The 0.5 % Au/Mn3O4 catalyst can be isolated and reused four times without a significant loss of its activity and can be applied successfully to a lab-scale reaction of p-toluidine (1 mmol) leading to the p-nitrotulene in 83 % yield. The presence of AuNPs on the Mn3O4 surface enhances the catalytic activity for the formation of the desired nitroarene. A reasonable mechanism was proposed including the plausible formation of two intermediates, the corresponding N-aryl hydroxylamine and the nitrosoarene.