- Regiospecific nitration of quinoline and isoquinoline through the Reissert compounds
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Regiospecific nitration of quinoline and isoquinoline was achieved via the Reissert compounds by treatment with acetyl nitrate. Nitration of 1-benzoyl-2-cyanoquinoline (3) afforded the 3-nitro derivative, which was converted to 3-nitroquinoline by hydrolysis with concentrated HCl. Meanwhile, 2-benzoyl-1-cyano-1,2-dihydroisoquinoline (4) was converted ultimately into 4-nitroisequinoline-1-carboxylic acid (10) via 4-nitro-1-cyanoisoquinoline by the same procedure. A novel method for introducing a nitro group at the β-position of a heterocyclic moiety has thus been developed. Crystal structure determinations and molecular orbital calculations of the Reissert compounds, are consistent with the regiospecific nitration.
- Sugiura,Hatano,Hirao,Mogi,Kurono,Tashiro,Usami,Hamada
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- Metal-free regioselective C-3 nitration of quinoline N-oxides with tert-butyl nitrite
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A direct and eco-friendly nitration methodology to synthesize 3-nitroquinoline N-oxides from quinoline N-oxides using tert-butyl nitrite as both the nitro source and oxidant has been developed. Although this reaction undergoes a free radical process, it exhibits high regioselectivity and can be smoothly scaled up to gram scale. This journal is
- Zhao, Jingjing,Li, Pan,Xia, Chungu,Li, Fuwei
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- Alkylation of Nitropyridines via Vicarious Nucleophilic Substitution
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Electrophilic nitropyridines react with sulfonyl-stabilized carbanions to give products of C-H alkylation via vicarious nucleophilic substitution. The process consists of formation of the Meisenheimer-type adduct followed by base-induced β-elimination of the sulfinic acid (e.g., PhSO2H). Mechanistic studies reveal that in the latter step alkyl substituent and adjacent nitro group tend to planarize for effective stabilization of benzyl anion, and thus, adduct of hindered isopropyl carbanion remains stable toward elimination for steric reasons.
- Antoniak, Damian,Barbasiewicz, Micha?
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supporting information
p. 516 - 519
(2022/01/20)
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- Bismuth nitrate as a source of nitro radical in ipso-nitration of carboxylic acids
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Aromatic nitro compounds are extensively used in synthetic chemistry. We disclose a new approach to obtain nitroarenes regioselectively starting from carboxylic acids under acid-free reaction conditions.
- Agasti, Soumitra,Maiti, Siddhartha,Maity, Soham,Anniyappan,Talawar,Maiti, Debabrata
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p. 120 - 124
(2019/05/22)
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- Method for nitrating aromatic compound by using nitrate under the action of auxiliary agent
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The invention discloses a method for nitrating an aromatic compound by using a nitrate under the action of an auxiliary agent, and provides an aromatic nitro compound preparation method, which comprises: in the presence of an external action and an auxiliary agent, carrying out a nitrating reaction on an aromatic compound and a metal nitrate or a hydrate thereof to obtain the aromatic nitro compound, wherein the external action can cause the physical and/or chemical property change of a substance, the auxiliary agent is a substance having water absorbing ability, the external action can be mechanical force or heating, and the mechanical force can be any one selected from compression, shearing, impacting, friction, stretching, bending and vibration. According to the present invention, the method does not require any solvents so as to avoid the generation of the waste liquid; the acidic substance is not used, such that the treatment is simple after the reaction is completed, and the equipment is not damaged; the added auxiliary agent can be theoretically recycled; and the method has extremely high conversion rate and extremely high selectivity, and can be used for the nitration of conventional aromatic compounds.
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Paragraph 0084; 0085
(2018/09/11)
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- Mechanical force under the action of the nitration of aromatic compounds of nitrate method (by machine translation)
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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 0079; 0080
(2018/09/11)
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- Ipso-nitration of arylboronic acids with bismuth nitrate and perdisulfate
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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.
- Manna, Srimanta,Maity, Soham,Rana, Sujoy,Agasti, Soumitra,Maiti, Debabrata
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supporting information; experimental part
p. 1736 - 1739
(2012/05/20)
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- Copper catalyzed ipso-nitration of iodoarenes, bromoarenes and heterocyclic haloarenes under ligand-free conditions
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A catalytic protocol for the conversion of haloarenes into the corresponding nitroarenes is presented using copper salts under ligand-free conditions. The method was effectively utilized for the ipso-nitration of a broad variety of haloarenes that includes iodoarenes, bromoarenes, and heterocyclic haloarenes.
- Amal Joseph,Priyadarshini,Lakshmi Kantam,Maheswaran
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supporting information; experimental part
p. 1511 - 1513
(2012/03/27)
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- Selective oxidation of aromatic amines to nitro derivatives using potassium iodide-tert-butyl hydroperoxide catalytic system
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The direct oxidation of aromatic primary amines to the corresponding nitro compounds selectively in 47-98% yields has been achieved by using potassium iodide as catalyst and tert-butyl hydroperoxide as the external oxidant. The present catalytic system works well for both electron-rich and electron-poor substrates.
- Reddy, K. Rajender,Maheswari, C. Uma,Venkateshwar,Kantam, M. Lakshmi
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supporting information; body text
p. 93 - 96
(2009/08/07)
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- An Investigation of the Reaction of 2-Aminobenzaldehyde Derivatives with Conjugated Nitro-olefins: An Easy and Efficient Synthesis of 3-Nitro-1,2-dihydroquinolines and 3-Nitroquinolines
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2-Aryl-3-nitro-1,2-dihydroquinolines 3 were prepared from the reaction of β-nitrostyrenes 2 and 2-aminobenzaldehyde 1 in the presence of DABCO. Not only β-nitrostyrenes but other alkyl nitro olefins also can be used in this reaction as well. When DDQ or silica gel was added to a solution of 3-nitro-1,2-dihydroquinolines 3, 3-nitro-2-substituted-quinolines 4 were obtained. When 2-aminobenzaldehyde derivatives 7 and 12 were reacted with β-nitrostyrenes 2, unique rearrangement products were produced.
- Yan, Ming-Chung,Tu, Zhijay,Lin, Chunchi,Ko, Shengkai,Hsu, Jianming,Yao, Ching-Fa
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p. 1565 - 1570
(2007/10/03)
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- Preparation of novel heteroisoindoles from nitropyridines and nitropyridones
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The reaction of nitropyridine derivatives with ethyl isocyanoacetate in the presence of 1,8-diazabicyclo[5.4.0]undecene proceeded tandem cyclization to give polycyclic pyrrolopyridines or imidazopyridines. On the other hand, N-protected 3-nitro- and 5-nitropyridones and N,N-diprotected 5-nitrouracil gave corresponding bicyclic pyrroles in good yields under the similar conditions.
- Murashima, Takashi,Nishi, Keiji,Nakamoto, Ken-ichi,Kato, Atsushi,Tamai, Ryuji,Uno, Hidemitsu,Ono, Noboru
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p. 301 - 310
(2007/10/03)
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- Investigation on the photoreactions of nitrate and nitrite ions with selected azaarenes in water
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The photoreactions of selected azaarenes with nitrate and nitrite ions were investigated under irradiation at λ = 313 nm. The excitation of both anions leads to several photochemical reactions forming mainly hydroxyl radicals and nitrogen oxides. The purification capability of natural waters i.e. the oxidation of inorganic and organic substances results from the formation of hydroxyl radicals. Nitrated isomers of azaarenes were found among the main products of the investigated photoreactions. The nitrogen oxides were responsible for the production of nitrated derivatives which possess a high toxic potential. Their formation was explained by the parallel occurance of two mechanism, a molecular and a radical one. The molecular mechanism became more important with increasing ionisation potentials of the azaarenes. The spectrum of oxidized products corresponded to the one got in the photoreactions of azaarenes with hydrogen peroxide. The formation of several oxidation and nitration products of the pyridine ring with its low electron density was explained by the reaction of excited states of azaarenes. The photoreactions with nitrite ions only led to the formation of oxidized and nitrated products. Nitroso products were not formed. The reactivity of nitrogen monoxide is too low for its reaction with the azaarenes.
- Beitz, Toralf,Bechmann, Wolfgang,Mitzner, Rolf
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p. 351 - 361
(2007/10/03)
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- The synthesis of β-nitropyridine compounds
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Pyridine and a number of substituted pyridines have been nitrated by reaction with N2O5 followed by reaction with an aqueous solution of SO2xH2O or NaHSO3. The dependence of the yields on the pH of the aqueous reaction medium, on the concentration of SO2xH2O-HSO3-, on addition of methanol to the aqueous phase, and on the reaction temperature were investigated. The yields obtained with NaHSO3 were: 3-nitropyridine 77%, 2-methyl-5-nitro-pyridine 36%, 3-methyl-5-nitropyridinc 24%, 3-acetyl-5-nitropyridine 18%, 5-nitropyridine-3-carboxylic acid 15%, 3-chloro-5-nitropyridine 11%, 4-methyl-3-nitropyridine 39%, 4-acetyl-3-nitropyridine 67%, 4-cyano-3-nitropyridine 45%, 4-phenyl-3-nitropyridine 68%, 4-formyl-3-nitropyridine 62% (from reaction in liquid SO2), 3-nitropyridine-4-carboxylic acid 48%, methyl 3-nitropyridine-4-carboxylate 75%, 2,3-dimethyl-5-nitropyridine 37%, 2,4-dimethyl-5-nitropyridine 64%, 3-nitroquinoline 10% and 4-nitroisoquinoline 42%.
- Bakke, Jan M.,Ranes, Eli,Riha, Jaroslav,Svensen, Harald
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p. 141 - 144
(2007/10/03)
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- Selective deoxygenation of heteroaromatic N-oxides with olefins catalyzed by ruthenium porphyrin
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A new convenient method of deoxygenation of heteroaromatic N-oxides is described. Ruthenium porphyrin was used as a catalyst and this method expressed high yields for o-substituted pyridine N-oxides, quinoline N-oxide derivatives, acridine N-oxide, etc. under mild conditions. Moreover, nitro-, benzyloxy-, and ketone carbonyl groups, which can be affected by the usual deoxygenation methods such as catalytic hydrogenation or borane reduction, were retained.
- Nakagawa, Hiroshi,Higuchi, Tsunehiko,Kikuchi, Kazuya,Urano, Yasuteru,Nagano, Tetsuo
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p. 1656 - 1657
(2007/10/03)
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- A new efficient synthesis of 3-nitropyridine and substituted derivatives
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Pyridine and pyridine derivatives have been nitrated in the β-position by reaction with N2O5 or NO2·BF4 in MeNO2, THF or MeCN to form the N-nitropyridinium salt. This was then reacted with an aqueous solution of a nucleophile to give the β-nitro compound in moderate to good yield.
- Bakke, Jan M.,Ranes, Eli
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p. 281 - 283
(2007/10/03)
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