- Nitration method for aryl phenol or aryl ether derivative
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The invention relates to a nitration method for an aryl phenol or aryl ether derivative. The method comprises the steps of stirring an aryl phenol or aryl ether compound, nitrate, trimethylchlorosilane (TMSCl) and a copper salt in an acetonitrile solution in air at room temperature, simultaneously, monitoring extent of reaction through a TLC dot plate, removing a solvent from a mixture by a rotaryevaporator after a substrate is consumed completely, and carrying out purification through a silica-gel column, thereby obtaining a nitroolefin derivative. Meanwhile, the selective mono-nitration orbis-nitration of the substrate can be achieved through controlling equivalent weight of the nitrate. Compared with the prior art, the nitration method disclosed by the invention has the advantages that the consumption of strong-acid substances is avoided, the reaction conditions are mild, the yield is high, the applicable range of the substrate is wide, reaction activity is free of obvious attenuation after an amplified reaction, and an excellent yield is still obtained, so that the method has an obvious industrial application value.
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Paragraph 0119-0124
(2020/01/03)
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- 3-(Ethoxycarbonyl)-1-(5-methyl-5-(nitrosooxy)hexyl)pyridin-1-ium cation: A green alternative to tert-butyl nitrite for synthesis of nitro-group-containing arenes and drugs at room temperature
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Due to their remarkable properties, task-specific ionic liquids have turned out to be progressively popular over the last few years in the field of green organic synthesis. Herein, for the first time, we report that a new task-specific nitrite-based ionic liquid such as 3-(ethoxycarbonyl)-1-(5-methyl-5-(nitrosooxy)hexyl)pyridin-1-ium bis(trifluoromethanesulfonyl)imides (TS-N-IL) derived from biodegradable ethyl nicotinate indeed acted as an efficient and eco-friendly reagent for the synthesis of highly valuable nitroaromatic compounds and drugs including nitroxynil, tolcapone, niclofolan, flutamide, niclosamide and nitrazepam. The bridging of an ionic liquid with nitrite group not only increases the yield and rate of direct C[sbnd]N bond formation reaction but also allows easy product separation and recyclability of a byproduct. Nonvolatile nature, easy synthesis, merely stoichiometric need and mildness are a portion of the extra focal points of TS-N-IL while contrasted with tert-butyl nitrite an outstanding and highly-flammable reagent utilized largely in organic synthesis.
- Chaudhary, Renu,Natarajan, Palani,Rani, Neetu,Sakshi,Venugopalan, Paloth
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- Visible-Light-Induced Radical Polynitration of Arylboronic Acids: Synthesis of Polynitrophenols
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We report a visible light-assisted one-pot method for the synthesis of polynitrophenols through radical tandem hydroxylation and nitration of arylboronic acids by utilizing copper(II) nitrate tri-nitydrate as the nitro source. This method features mild conditions, a simple procedure, and good functional group tolerance. Compared to conventional methods, this work provides a straightforward approach for the polynitration of aromatic compounds.
- Zhang, Qi,Raveendra Babu, Kaki,Huang, Zhouliang,Song, Jinna,Bi, Xihe
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p. 2891 - 2896
(2018/06/20)
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- Nitration of phenolic compounds by antimony nitrate
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Antimony nitrate is new compound to be an efficient nitration reagent in the nitration of phenolic compounds with high yields. This producerworks efficiently onmost of the examples, as a grinding nitration reaction, proceed very fast (~1 min) and thermogenic. Copyright Taylor & Francis Group, LLC.
- Jirandehi, Hassan Fathinejad,Mirzaeian, Marjan
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experimental part
p. 284 - 286
(2011/07/08)
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- PEG-N2O4: An efficient nitrating agent for the selective mono- and dinitration of phenols under mild conditions
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N2O4 was easily impregnated on polyethyleneglycol to give a stable reagent. The polyethyleneglycol-N2O4 (PEG-N2O4) system was used as an effective nitrating agent for the nitration of phenols. Mono- and dinitrophenols can be obtained via direct nitration of phenols in the presence of PEG-N2O4 at room temperature in moderate to high yields. Copyright Taylor & Francis Group, LLC.
- Zolfigol, Mohammad Ali,Madrakian, Elaheh,Ghaemi, Ezat,Niknam, Khodabakhsh
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p. 3366 - 3374
(2008/12/22)
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- Nitration of aromatic compounds by Zn(NO3)2· 2N2O4 and its charcoal-supported system
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Zn(NO3)2·N2O4 and its charcoal supported system were found to be efficient nitrating agents. Mononitration of aromatic compounds such as benzene, alkyl benzenes, halobenzenes, nitrobenzene, anisol, and the highly selective mono-, di-, and trinitration of phenol, and dinitraion of substituted phenols were also performed in the presence of these reagents.
- Iranpoor, Nasser,Firouzabadi, Habib,Heydari, Reza,Shiri, Morteza
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p. 263 - 270
(2007/10/03)
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- Nitration of phenolic compounds by metal-modified montmorillonite KSF
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The nitration of phenolic compounds with 60% nitric acid (1.2 equiv) has been carried out in the presence of metal-modified montmorillonite KSF, prepared from different metals (V, Mo, W; Sc, La, Yb, Eu, In, Bi, Ti, Zr, Hf) and KSF or nitric acid treated HKSF, as catalysts. These catalysts showed good stabilities and high catalytic activities in nitration process. In addition, these catalysts can be recovered easily and reused for many times in nitration. This process is an eco-safer and environment-benign way for clean synthesis of nitrated phenolic compounds.
- Yin, Wan-Po,Shi, Min
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p. 10861 - 10867
(2007/10/03)
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- Highly efficient catalytic nitration of phenolic compounds by nitric acid with a recoverable and reusable Zr or Hf oxychloride complex and KSF
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Phenolic compounds can be nitrated with 60% nitric acid (1.2 equiv.) in the presence of catalytic amounts of a Zr or Hf oxychloride complex and montmorillonite KSF to give the corresponding nitrated products in good yields in a heterogeneous catalytic system. The co-catalyst and montmorillon ite can be easily recovered and reused in the next batch of nitration. This is a practical process for the nitration of phenolic compounds in a clean way. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
- Shi, Min,Cui, Shi-Cong,Yin, Wan-Po
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p. 2379 - 2384
(2007/10/03)
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- Silica-acetate complex of N2O4: A heterogeneous reagent for the selective nitration of phenols and nitrosation of thiols
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Complexation of gaseous N2O4 with acylated silica gel affords an addition compound, which is an efficient heterogeneous reagent for the selective mono- and dinitration of phenol, substituted phenols and nitrosation of thiols.
- Iranpoor,Firouzabadi,Heydari
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p. 703 - 710
(2007/10/03)
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- Silica-polyethyleneglycols/N2O4 complexes as heterogeneous nitrating and nitrosating agents
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Silica-chloride was reacted with different quantities of H(OCH2CH2)nOH (n = 2-4) to furnish silica-based linear polyethylene glycols and cyclic polyethylene glycolic ethers. The N2O4 complex of silica-tetraethylene glycolic ether (III) was selected and used as a stable, cheap, and heterogeneous silica-based reagent for the selective mono- and dinitration of phenols and nitrosation of thiols.
- Iranpoor,Firouzabadi,Heydari
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p. 1027 - 1035
(2007/10/03)
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- Trichloroisocyanuric Acid/NaNO2/wet SiO2 as an Efficient System for the Selective Dinitration of Phenols under Solvent-free Conditions
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Dinitrophenols can be obtained via direct nitration of phenols with trichloroisocyanuric acid, NaNO2 and wet SiO2 at room temperature under solvent-free conditions with moderate to high yields.
- Zolfigol, Mohammad Ali,Madrakian, Elaheh,Ghaemi, Ezat
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p. 2222 - 2224
(2007/10/03)
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- Selective nitration of aromatic compounds with bismuth subnitrate and thionyl chloride
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Bismuth subnitrate/thionyl chloride have been found to be an efficient combination of reagents for nitration of a wide range of aromatic compounds in dichloromethane. Phenols, in particular, were easily mononitrated and dinitrated with the reagents by controlling the stoichiometry.
- Muathen, Hussni A.
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p. 593 - 598
(2007/10/03)
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- A New Method for Nitration of Phenolic Compounds
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Phenolic compounds can be nitrated by 65% nitric acid in the presence of catalytic amounts of montmorillonite KSF and bismuth(III) nitrate to give the corresponding nitrated products in good yields in a heterogeneous phase. The co-catalyst of KSF and Bi(NO3)3 can be easily recovered and reused in the next batch of nitration.
- Shi, Min,Cui, Shi-Cong
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p. 1197 - 1202
(2007/10/03)
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- The NO3 radical-mediated liquid phase nitration of phenols with nitrogen dioxide
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Analysis of Kyodai nitration, which refers to the mixture of NO2 and O3 in nonprotic solvents, may contribute to an understanding of the atmosphere because it can be used in the study of the nitration of aromatic compounds with NOsu
- Rindone,Barletta,Bolzacchini,Meinardi,Orlandi
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p. 2224 - 2230
(2007/10/03)
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- Ionic complex of N2O4 with 18-crown-6: A highly efficient and selective reagent for nitration of phenols
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Interaction of gaseous N2O4 with 18-crown-6 affords the stable crystalline complex of NO+ · 18-crown-6 · H(NO3)2· This ionic complex is an efficient nitrating agent for the selective mono-, di-, and trinitration of phenol and also for the selective mono-, and dinitration of substituted phenols.
- Iranpoor,Firouzabadi,Heydari
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p. 3295 - 3302
(2007/10/03)
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- Nighttime tropospheric chemistry: Kinetics and product studies in the reaction of 4-Alkyl- and 4-Alkoxytoluenes with NO3 in gas phase
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Alkylbenzenes are important constituents of gasoline and industrial solvents and contribute to the formation of tropospheric ozone. The removal of these compounds from the troposphere is due to reaction with OH during the day and with NO3 during the night. Five para-substituted toluenes are reacted with the nitrate radical in gas phase. Samples to be used for product analysis were preconcentrated and analyzed by GC-MSD analysis with the use of a reference curve. The yields of methanol, ethanol, and formaldehyde were determined by FTIR analysis of the reaction mixture in the chamber. Carbonyl compounds, benzyl alcohols, and nitroderivatives were formed. In the case of the alkoxytoluenes, products were also an alkanol, benzyl alcohols, and nitrophenols. Indirect rate constants measurements were performed by comparing by FTIR measurements the decay of the aromatic compound under investigation to that of a reference compound, with a known rate constant for the reaction with NO3 added to the gas mixture. Wall loss constants were evaluated by FTIR. A Hammett correlation with ρ = - 4.3 ± 0.6; r2-= 0.87 was obtained. This and the kinetic isotope effect of 1.5-1.8 suggest a reaction mechanism occurring via an addition-elimination pathway.
- Bolzacchini, Ezio,Meinardi, Simone,Orlandi, Marco,Rindone, Bruno,Hjorth, Jens,Restelli, Gianbattista
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p. 461 - 468
(2007/10/03)
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- Efficient and selective mono and dinitration of phenols with Cr(No3)3. 2N2O4 as a new nitrating agent
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Cr(NO3)3.2N2O4 is easily prepared reagent for the efficient and selective mono or dinitration of phenolic compounds. High selectivity ratio of p-nitrophenol formation vs o-nitrophenol is also observed.
- Iranpoor, Nasser,Firouzabadi, Habib,Zolfigol, Mohammad Ali
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p. 2773 - 2781
(2007/10/03)
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- Transformations of arylcyclopropanes under the action of dinitrogen tetroxide
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p-Bromophenylcyclopropane, 1- and 2-methylphenylcyclopropanes, and 1,2-di-p-tolyl- and l,2-bis(p-methoxyphenyl)cyclopropanes react with N2O4with opening of the three-membered ring. Reactions of p-methoxyphenylcyclopropane, 6-cyclopropyl-l,4-benzodioxane, and 2-cyclopropylfluorene yield the corresponding nitroaromatic derivatives with conservation of the cyclopropane ring. The nitration of p-methoxyphenylcyclopropane is accompanied by demethylation. 2-Nitro- and 4-nitrophenylcyclopropanes, as well as l-chloro-2-phenylcyclopropane, do not react with N2O4 under the same conditions. The differences in the behavior of arylcyclopropanes in reactions with N2O4 are explained by the different action of nitrosonium ion in the first reaction step: It acts as either electrophilic species capable of initiating opening of the cyclopropane ring or one-electron oxidant converting the initial arylcyclopropanes into the corresponding radical cations which are precursors of Wheland σ complexes responsible for aromatic nitration. copy;1998 MAHK "Hayka/Interperiodica".
- Mochalov,Kuz'min,Fedotov,Trofimova,Gazzaeva,Shabarov,Zefirov
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p. 1322 - 1330
(2007/10/03)
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- Dinitrogen tetroxide complexes of iron and coppernitrates as new reagents for selective mono- and dinitration of phenolic compounds
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Fe(NO3)3.1.5 N2O4 and Cu(NO3)2.N2O4 are easily prepared reagents for the efficient and selective mono- or dinitration of phenolic compounds. In comparison with metal nitrates, these complexes resemble a synergetic effect on the rates and the yields of the reactions. High ratio of p-nitrophenol formation vs o-nitrophenol is also observed in the mononitration reactions.
- Firouzabadi,Iranpoor,Zolfigol
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p. 3301 - 3311
(2007/10/03)
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- Photochemical nitration by tetranitromethane. Part XXVII. Adduct formation in the photochemical reaction of 4-methylanisole. Solvent and temperature effects on the regiochemistry of reaction of the radical cation of 4-methylanisole
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The photolysis of the charge-transfer complex of 4-methylanisole and tetranitroroethane in dichloromethane gives four isomcnc nitro-triniromethyl adducts, including the epimeric 1-methoxy-4-methyl-3-nitro-6-trinitromethylcyclohexa-1,4-dienes 3 and 4 and the epimeric 1-methoxy-4-methyl-6-nitro-3-trinitromethylcyclohexa-1,4-dienes 5 and 6, 4-methyl-2-trinitromethylanisole 1, 4-methyl-2-nitroanisole 2, nitrophenols 7 and 9, and 4-methyl-4-nitrocyclohexa-2,5-dienone 8. Similar reaction in acetonitrile also gives these products, with the exception of two of the adducts (3 and 4). The effect of reaction temperature on the yields of the various products indicates that they are formed either by attack of trinrtromethanide ion on the radical cation of 4-methylanisole vicinal to the methoxy group at C2 (1, 3 and 4), or by attack of trinitromethanide ipso to the methoxy group (2, 5, 6 and 8). By conducting the photolysis in dichloromethane with trifluoroacetic acid present, the trinitromethanide pathway is eliminated, and the products formed are derived from reaction between 4-methylanisole and or its radical cation and NO2. The effects of added salts Bu4N+ClO4- (TBAP) or Bu4N+C(NO2)3- (TBAT) to reactions on dichloromethane are seen as the consequences of changes in the polarity of the solvent and not to competition between ion-pair and radical-pair collapse during the reactions. By analogy with adducts 3 and 4, two adducts 16 and 17 derived from similar photolysis reactions of 4-chloroanisole are shown to be the epimeric 4-chloro-1-methoxy-3-nitro-6-trinitromethyleyclohexa-1,4-dienes It and 17 rather than nitrit(or hydroxy)-trinitromethyl adducts. The X-ray crystal Structure of 1-methoxy-4-methyl-r-3-nitro-c-6-trinitromethylcyclohexa-1,4-. diene 3 is reported. Acta Chemica Scandinavica 1996.
- Butts, Craig P.,Eberson, Lennart,Hartshorn, Michael P.,Robinson, Ward T.
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p. 122 - 131
(2007/10/03)
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- Mild and Selective Nitration by "Claycop"
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A one-pot nitration of aromatic compounds by "claycop", a reagent consisting of an acidic montmorillonite clay impregnated with anhydrous cupric nitrate, is reported.Simply by varying the conditions, it is possible to drive the reaction at will toward either mono- or polynitration.Both the yields and selectivities are superior to those obtained under homogeneous reaction conditions.
- Gigante, Barbara,Prazeres, Angela O.,Marcelo-Curto, Maria J.,Cornelis, Andre,Laszlo, Pierre
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p. 3445 - 3447
(2007/10/02)
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- 15N Nuclear Polarisation in Nitration and Related Reactions. Part 7. The Mechanisms of Rearrangement of 4-Methyl-4-nitrocyclohexa-2,5-dienones
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The rearrangement of 4-methyl-4-nitrocyclohexa-2,5-dienone to 4-methyl-2-nitrophenol has been studied in acetic anhydride at 22-37.5 deg C in the presence of varying concentrations of sulfuric acid.Similar studies have been carried out on the 15N labelled compound and on the effects of some substituents (2-Me, 3-Me, 2-NO2).During reaction, the thermal rearrangement of the labelled compound gives very strongly enhanced 15N NMR absorption signals (enhancement coefficient ca. 1000) for both the substrate and the product.For acid catalysed reaction, the enhancement coefficient of the signals is less (ca. 130) but still sufficient to indicate a homolytic reaction path.This interpretation is shown to be consistent with the properties of the radicals involved and with the substituent effects observed.
- Ridd, John H.,Trevellick, Susan,Sandall, John P. B.
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p. 1535 - 1540
(2007/10/02)
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- The Rearrangement of Aromatic Nitro Compounds. Part 2. The Rearrangement os Substituted Nitrophenols in Trifluoromethanesulphonic Acid
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o-Nitrophenols with an additional substituent (Y = NO2, Cl, or Me) in the 3-position rearrange in trifluoromethanesulphonic acid at 100 deg C to give mainly the product with the nitro group in the opposite ortho position; no more than 1-4percent of other products are formed.The reactions give first-order kinetics, are acid-catalysed and (at least when Y = NO2) are intramolecular.The rate of rearrangement varies with the 3-substituent in the order Me > Cl > NO2.The results are discussed in terms of a rate-determining migration of the nitro group in the Wheland intermediate formed by protonation at the 2-position.A much slower rearrangement occurs with 3,4-dinitrophenol under the same conditions to give a small yield of 2,5-dinitrophenol accompanied by decomposition of the substrate.
- Bullen, John V.,Ridd, John H.
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p. 1675 - 1679
(2007/10/02)
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- The Nitration of 4-Methylphenol, 3,4-Dimethylphenol and 3,4,5-Trimethylphenol with Nitrogen Dioxide
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Reaction of 4-methylphenol (1a) with excess nitrogen dioxide in either benzene or dichloromethane gives the 4-nitro dienone (2a) and the 2,6-dinitrophenol (5).Similar reactions of 3,4-dimethylphenol (1b) yields the 4-nitro dienone (2b), the 2,6-dinitrophe
- Hartshorn, Michael P.,Judd, Maurice C.,Vannoort, Richard W.,Wright, Graeme J.
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p. 689 - 697
(2007/10/02)
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