- Ipso Nitration of Aryl Boronic Acids Using Fuming Nitric Acid
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The ipso nitration of aryl boronic acid derivatives has been developed using fuming nitric acid as the nitrating agent. This facile procedure provides efficient and chemoselective access to a variety of aromatic nitro compounds. While several activating agents and nitro sources have been reported in the literature for this synthetically useful transformation, this report demonstrates that these processes likely generate a common active reagent, anhydrous HNO3. Kinetic and mechanistic studies have revealed that the reaction order in HNO3 is >2 and indicate that the ?NO2 radical is the active species.
- Baucom, Kyle D.,Brown, Derek B.,Caille, Seb,Murray, James I.,Quasdorf, Kyle,Silva Elipe, Maria V.
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supporting information
(2021/06/30)
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- Nitration of deactivated aromatic compounds via mechanochemical reaction
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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
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supporting information
(2021/05/05)
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- Weeding composition compounded by fine glufosinate-ammonium and diuron and preparation method and application thereof
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The invention provides a weeding composition compounded by fine glufosinate-ammonium and diuron. The weeding composition is characterized by comprising fine glufosinate-ammonium, diuron and other auxiliary agents, and the content of the fine glufosinate-ammonium is 1-60 parts by mass, the content of the diuron is 1-60 parts by mass, and the content of the auxiliary agents is 20-70 parts by mass. By reasonably proportioning the proportions of the fine glufosinate-ammonium and the diuron in the herbicide, the pesticide effect of the herbicide is enhanced, the control effect on weeds in uncultivated areas is superior to the activity of the singly applied components, meanwhile, the control spectrum of the weeds is expanded, the weeding effect is improved, the weeding composition has a prominent comprehensive control effect on gramineous weeds, cyperaceae weeds and broadleaf weeds, and has the advantages of fast effectiveness, long lasting period, delayed herbicide resistance, thorough weeding, low residue, low toxicity, safety, environmental protection and the like.
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Paragraph 0032
(2021/08/07)
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- Completely-continuous flow synthesis method of 3,4-dichloronitrobenzene under action of catalyst
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The invention discloses a completely-continuous flow synthesis method of 3,4-dichlonitrobenzene under the action of a catalyst. The completely-continuous flow synthesis method is carried out in an integrated completely-continuous flow reaction system, a reaction substrate and other raw materials are uninterruptedly added at a feed port, the product 3, 4-dichloronitrobenzene is uninterruptedly obtained at a discharge port, and the synthesis method is safe and efficient and has no amplification effect. Compared with a traditional production method, the method of the invention has the advantagesof shortening of the production time to be within 120 seconds, no amplification effect, stable product index and good reproducibility.
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Paragraph 0070-0082
(2020/05/30)
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- Environment-friendly preparation method of 2-chloro-4-nitro-6-bromoaniline
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A preparation method of 2-chloro-4-nitro-6-bromoaniline comprises the following steps: (a) carrying out mixed acid nitration on o-dichlorobenzene, and continuing to apply the generated waste acid to anext nitration reaction; (b) purifying the obtained nitration product in an alcohol solvent to obtain 3,4-dichloronitrobenzene, and continuously applying the recovered alcohol solvent to a next purification process; (c) carrying out ammonolysis on the 3,4-dichloronitrobenzene in a water phase by adopting a specific catalyst to prepare o-chloro-p-nitroaniline, and continuously applying the recycled liquid ammonia to a next ammonolysis reaction; and (d) brominating o-chloro-p-nitroaniline in a hydrogen bromide and oxidant system, and recycling brominated waste acid liquid and bromine for a nextbromination reaction. The product obtained by the method is good in yield, high in purity and high in quality; and two waste acids and bromine in the product are recycled, so that the amount of wastewater is reduced. Compared with traditional processes, the method has obvious quality and environmental protection advantages, and has high production safety.
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Paragraph 0040-0042; 0046-0048; 0051-0053; 0056-0058
(2020/05/02)
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- Environment-friendly 2, 6-dichloro-4-nitroaniline preparation method
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The invention discloses an environment-friendly 2, 6-dichloro-4-nitroaniline preparation method, and belongs to the field of environmental protection. The environment-friendly 2, 6-dichloro-4-nitroaniline preparation method comprises the following steps: step 1, adding o-dichlorobenzene, namely a component shown as a formula (I), into a nitric acid and sulfuric acid solution for reaction to obtainm-nitro-1, 2-dichlorobenzene, namely a component shown as a formula (II); step 2, adding the m-nitro-1, 2-dichlorobenzene obtained in the step 1 into an ammonia water solution for reaction to obtain2-chloro-4-nitroaniline, namely a component shown as a formula (III); step 3, dropwise adding hydrochloric acid and a hydrogen peroxide solution into the 2-chloro-4-nitroaniline obtained in the step 2. According to the new preparation method, the generation of polychlorophenol during the 2, 6-dichloro-4-nitroaniline preparation process is effectively reduced, the environmental protection meets therequirements of OECO-Textile 100, and a dye obtained after the actual production of the preparation method directly meets the requirements of OECO-Textile 100.
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Paragraph 0037-0057
(2020/08/27)
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- Preparation method of 1,2-dichloro-4-nitrobenzene
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The invention discloses a preparation method of 1,2-dichloro-4-nitrobenzene. The preparation method comprises the following steps: adding p-nitrochlorobenzene into a sulfuric acid solution with a massfraction of 65%, carrying out stirring for dissolving of the p-nitrochlorobenzene, conducting heating to 55 DEG C, then adding potassium chlorate, carrying out a stirring and heat-preserved reactionfor 8 h, performing cooling with ice water after the reaction is completed, extracting a reaction solution with a carbon tetrachloride solution, conducting liquid separation, subjecting an organic phase to washing by an aqueous sulphurous acid solution with a mass fraction of 6%, an aqueous sodium hydroxide solution with a mass fraction of 12% and water in sequence, carrying out drying, evaporating an organic solution to dryness, and performing recrystallizing to obtain a yellow acicular crystal, namely the product 1,2-dichloro-4-nitrobenzene. The preparation method is simple in synthesis process, improved in product yield and mild in reaction conditions, and has practical application and promotion values.
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Paragraph 0007
(2020/04/17)
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- Base promoted peroxide systems for the efficient synthesis of nitroarenes and benzamides
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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.
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supporting information
(2019/09/07)
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- meta-Nitration of Arenes Bearing ortho/para Directing Group(s) Using C?H Borylation
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Herein, we report the meta-nitration of arenes bearing ortho/para directing group(s) using the iridium-catalyzed C?H borylation reaction followed by a newly developed copper(II)-catalyzed transformation of the crude aryl pinacol boronate esters into the corresponding nitroarenes in a one-pot fashion. This protocol allows the synthesis of meta-nitrated arenes that are tedious to prepare or require multistep synthesis using the existing methods. The reaction tolerates a wide array of ortho/para-directing groups, such as ?F, ?Cl, ?Br, ?CH3, ?Et, ?iPr ?OCH3, and ?OCF3. It also provides regioselective access to the nitro derivatives of π-electron-deficient heterocycles, such as pyridine and quinoline derivatives. The application of this method is demonstrated in the late-stage modification of complex molecules and also in the gram-scale preparation of an intermediate en route to the FDA-approved drug Nilotinib. Finally, we have shown that the nitro product obtained by this strategy can also be directly converted to the aniline or hindered amine through Baran's amination protocol.
- Li, Xuejing,Deng, Xingwang,Coyne, Anthony G.,Srinivasan, Rajavel
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supporting information
p. 8018 - 8023
(2019/05/29)
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- 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
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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
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supporting information
p. 5416 - 5421
(2018/08/12)
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- Method for synthesizing 3,4-dichloroaniline by using micro-channel reactor
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The invention provides a method for synthesizing 3,4-dichloroaniline by using a micro-channel reactor. The micro-channel reactor is used for nitration and catalytic hydrogenation. The method comprisesthe following steps: nitration: preheating o-dichlorobenzene, mixing and preheating concentrated nitric acid and concentrated sulfuric acid, allowing the preheated materials to enter a reaction module group for a reaction and carrying out refining so as to obtain an intermediate 3,4-dichloronitrobenzene; and catalytic hydrogenation: dissolving 3,4-dichloronitrobenzene in a solvent, adding a Pd-loaded active carbon catalyst, adding a dechlorination inhibitor, then carrying out preheating, allowing a preheated product and hydrogen to enter a reaction module group for a reaction and carrying outpost-treatment so as to obtain 3,4-dichloroaniline. The method provided by the invention is good in material mixing effect, accurate in material proportion control, capable of improving reaction yield and product purity, safe and stable in reactions, short in synthesis time and free of amplification effect, and has good application prospects in industrial production.
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Paragraph 0022; 0038-0040; 0035; 0050-0052; 0059
(2018/05/16)
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- O-dichlorobenzene with a quinolone drugs for coproduction method of key intermediate
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The invention relates to the field of methods for preparing medicinal intermediates, in particular to the field of methods for preparing key intermediates of quinolone medicines, and develops a method for coproducing the key intermediates of the quinolone medicines by using o-dichlorobenzene as a raw material. The method comprises the following steps of: nitrifying the o-dichlorobenzene serving as the raw material, and performing distillation, purification and stepwise crystallization to obtain 2,3-dichloronitrobenzene and 3,4-dichloronitrobenzene; performing fluoridation on the 2,3-dichloronitrobenzene to obtain 3-chloro-2-fluoronitrobenzene, performing chlorination to obtain 2,6-dichlorofluorobenzene, performing nitration to obtain 1,3-dichloro-2-fluoro-4-nitrobenzene, and finally performing fluoridation to obtain 2,3,4-trifluoronitrobenzene; and performing fluoridation on the 2,3,4-trifluoronitrobenzene to obtain 3-chloro-4-fluoronitrobenzene, performing chlorination to obtain 1,3-dichloro-4-fluorobenzene, and finally performing acylation reaction on the 1,3-dichloro-4-fluorobenzene and acetylchloride to obtain 2,4-dichloro-5-fluoroacetophenone.
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Paragraph 0009; 0034-0035
(2017/01/19)
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- Method and device for producing 3,4-dichloronitrobenzene through continuous kettle type reaction
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The invention relates to the field of chemical production and particularly discloses a method and device for producing 3,4-dichloronitrobenzene through a continuous kettle type reaction. According to the method, parachloronitrobenzene serves as a raw material. The method is characterized in that parachloronitrobenzene and ferric trichloride are prepared into mixed liquor, the mixed liquor enters reaction kettles continuously through a nitro compound pump, and meanwhile chlorine enters the bottom of a chlorination kettle; under the catalyst effect, parachloronitrobenzene and chlorine react to generate 3,4-dichloronitrobenzene; later, by the utilization of the high-order difference among all the reaction kettles, the materials overflow sequentially to enter the reaction kettles connected in series, enter a storage tank finally, and then enter a static mixer through a mixing pump to be mixed with water, multiple washing kettles are connected in series, and qualified materials enter a crude product tank. The process is easy to operate, high in automatic control level, low in production cost, high in stability, safe to operate and suitable for large-scale industrial production, and effectively saves labor, and the purpose of continuously chlorinating and washing 3,4-dichloronitrobenzene is achieved.
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Paragraph 0015
(2016/10/31)
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- Diuron-intermediate production waste residue treatment technology
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A provided diuron-intermediate production waste residue treatment technology comprises the following steps: firstly crushing a catalyst anhydrous ferric chloride into a micro powder, and transferring into a reaction kettle; dropwise adding p-chloronitrobenzene in a fusion state into the above mentioned reaction kettle, and introducing chlorine into the reaction kettle at the same time; then introducing nitrogen into the above mentioned reaction kettle for first gas expelling; then transferring the above mentioned material subjected to gas expelling into a reduction kettle, and dropwise adding formic acid into the reduction kettle; then adding iron powder and water into the above mentioned reduction kettle, and slowly stirring; performing nitrogen secondary gas expelling on the above mentioned material; and cooling the material subjected to secondary gas expelling. By employing the above mentioned production technology, solid byproducts can be thoroughly filtered and separated, the purity of 3,4-dichloroaniline is guaranteed, and also resource waste is avoided, and also reaction efficiency is improved, reaction time is reduced, and the recovery yield is relatively high.
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Paragraph 0028; 0029; 0030; 0031
(2016/11/28)
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- A production method for producing 3,4-dichloroaniline to aminochlorobenzene process and (by machine translation)
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The invention relates to a process for producing 3, 4-dichloroaniline and parachloroaniline based on a combined production method. The process comprises the following steps: chloridizing parachloronitrobenzene, and directly hydrotreating in a hydrogenated kettle in the absence of solvents at the temperature of 80+/-5 DEG C and the pressure of 0.5-0.6 Mpa to generate a mixed solution of parachloroaniline accounting for 20-35 percent of the mixed solution and 3, 4-dichloroaniline, then carrying out continuous rectification to produce parachloroaniline from the top of the tower and a mixed solution containing no parachloroaniline from the bottom of the tower, and rectifying the mixed solution to obtain 3, 4-dichloroaniline. The process for producing 3, 4-dichloroaniline and parachloroaniline based on a combined production method is suitable for production of large-output products, especially for temperature-sensitive chemical reaction, is labor-saving, easily and automatically controlled and simply and safely operated, has good stability, and is suitable for wide popularization and application.
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Paragraph 0020-0022
(2017/03/25)
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- Preparation of heteropoly acid based amphiphilic salts supported by nano oxides and their catalytic performance in the nitration of aromatics
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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
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p. 2197 - 2202
(2013/03/14)
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- Preparation, catalytic performance and theoretical study of porous sulfated binary metal oxides shell (SO42 -/M1xO y-M2xOy) using pollen grain templates
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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
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- Regioselective nitration of aromatics with nanomagnetic solid superacid SO42-/ZrO2-MxOy-Fe 3O4 and its theoretical studies
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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
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p. 310 - 317
(2013/08/23)
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- Green route for the chlorination of nitrobenzene
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A new green chlorination process of deactivated aromatics has been developed, being environmental-friendly and allowing the continuous chlorination of 1.7 kg nitrobenzene/kg catalyst per day. The triple novelty consists of using a non-conventional chlorination agent, the trichloroisocyanuric acid (TCCA, C3N3O3Cl3), along with solid acid catalysts (mainly zeolites) in a continuous flow reactor system. Different zeolites and solid acids have been tested in the chlorination of nitrobenzene, chosen as a model deactivated aromatic substrate. HUSY zeolite was found as the more promising catalyst for performing the chlorination of nitrobenzene, with good conversions (39-64%) at high selectivity toward monochlorinated products (90-99%). Finally, it is worthy to note that HUSY zeolite could be reused for at least five successive runs.
- Boltz, Marilyne,De Mattos, Márcio C.S.,Esteves, Pierre M.,Pale, Patrick,Louis, Benoit
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- Regioselective nitration of aromatics under phase-transfer catalysis conditions
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Mononitration of aromatics was performed in a two-phase system using phase-transfer catalyst. The most advantageous conditions for the nitration were determined (temperature, reaction time, the type and amount of phase transfer catalyst, nitrification strength of the nitro-sulfuric acid). From the results, a significant improvement in the selectivity and conversion of the nitration of xylene was observed: the ratio of 4-nitro-m-xylene to 2-nitro-m-xylene was unprecedented increased up to 91.3%:7.7%, the ratio of 4-nitro-o-xylene to 3-nitro-o-xylene was also increased to 71.1%:27.2%; both the conversions were over 96%.
- Wang, Peng-Cheng,Lu, Ming,Zhu, Jie,Song, Yan-Ming,Xiong, Xian-Feng
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experimental part
p. 42 - 47
(2012/01/15)
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- Trichloroisocyanuric acid in 98% sulfuric acid: A superelectrophilic medium for chlorination of deactivated arenes
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Trichloroisocyanuric acid (TCCA) reacts with arenes and its reactivity is highly affected by the acid strength of the reaction medium. Deactivated arenes are efficiently chlorinated by TCCA in H2SO4. Our results, along with DFT calculations and 13C NMR spectrometry suggest the formation of a monoprotonated TCCA superelectrophile as the reactive species that can efficiently transfer electrophilic Cl+ to even very weak nucleophiles, such as m-dinitrobenzene.
- Mendo?a, Gabriela Fonseca,Senra, M?nica Rufino,Esteves, Pierre M.,De Mattos, Marcio C.S.
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experimental part
p. 176 - 181
(2012/04/04)
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- Nitration of aromatic hydrocarbons and halobenzenes using NOx catalyzed by solid acid catalysts
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The nitration of aromatics using zeolite as a solid inorganic catalyst and nitric oxides as nitrating agents is a relatively clean process for aromatic nitration. Copyright
- Pande, Manoj A.,Samant, Shriniwas D.
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experimental part
p. 3734 - 3738
(2011/02/16)
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- Ozone-mediated reaction of polychlorobenzenes and some related halogeno compounds with nitrogen dioxide: A novel non-acid methodology for the selective mononitration of moderately deactivated aromatic systems
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In the presence of ozone and preferably methanesulfonic acid as catalyst, polychlorobenzenes undergo selective mononitration with nitrogen dioxide at low temperatures, giving the corresponding polychloronitrobenzenes, in most cases in nearly quantitative yields.
- Suzuki,Mori,Maeda
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p. 841 - 845
(2007/10/02)
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- Electrophilic Aromatic Substitution. Part 35. Chlorination of 1,3-Dinitrobenzene, 1-Chloro-2,4-dinitrobenzene, and 2,4-Dinitrotoluene with Nitric Acid and Hydrogen Chloride or Chlorine in Sulphuric Acid or Oleum
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Solutions of sulphuric acid or oleum containing HCl or Cl2 and nitric acid have been found both to chlorinate and nitrate deactivated aromatic compounds.The kinetics and products of the chlorination of 1,3-dinitrobenzene and 1-chloro-2,4-dinitrobenzene in sulphuric acid or oleum containing HCl and nitric acid at 130 deg C, and the kinetics and products of the chlorination of 2,4-dinitrotoluene at 90 deg C in sulphuric acid or oleum containing Cl2 and nitric acid, are reported. 1,3-Dinitrobenzene and 1-chloro-2,4-dinitrobenzene were predominantly chlorinated. 2,4-Dinitrotoluene gave approximately equal amounts of 6-chloro-2,4-dinitrotoluene and 2,4,6-trinitrotoluene.The results show that under these conditions, chlorination and nitration are competing electrophilic reactions, and that chlorination is less selective than nitration.Possible mechanisms for chlorination are discussed.
- Melhuish, Martin W.,Moodie, Roy B.
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p. 667 - 674
(2007/10/02)
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- Novel 4'(benzisothiazo-5-yloxy)-phenylurea derivatives, their preparation and their use as herbicides
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A 4'-(Benzisothiazol-5-yloxy)-phenylureas of the formula STR1 where R1 and R2 are each a saturated straight-chain or branched aliphatic radical of 1 to 10 carbon atoms, an unsaturated straight-chain or branched aliphatic radical of 3 to 10 carbon atoms, or an araliphatic or aromatic radical which may be substituted by 1, 2 or 3 C1 -C4 -alkyl, C1 -C4 -alkoxy, cyano, halogen, nitro, monofluoromethyl or trifluoromethyl groups, or are each alkoxy of 1 to 6 carbon atoms, R2 may furthermore be hydrogen, or R1 and R2, together with the nitrogen atom, may be members of a 5-membered or 6-membered ring which may contain further nitrogen and/or oxygen atoms as heteroatoms, and X is hydrogen, trifluoromethyl or chlorine, processes for their preparation, and herbicides containing ureas of the formula I as active ingredients.
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- Rate Constants of Series-Parallel Reactions in the Catalytic Chlorination of Nitrobenzene
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We have determined the relative rate constants of series-parallel reactions in the catalytic chlorination of nitrobenzene in the presence of ferric chloride at 60-120 deg C up to the trichloro derivative stage.
- Lebedev, V. V.,Emel'yanov, V. I.,Zetkin, V. I.
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p. 415 - 416
(2007/10/02)
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