- 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)
-
- Microwave-induced surface-mediated highly efficient regioselective nitration of aromatic compounds: Effects of penetration depth
-
Surface mediated highly regioselective nitration of aromatic compounds under diverse microwave-induced conditions was investigated in this work. The effects of the penetration depth of the surfaces were found to be more crucial than other dielectric parameters. Despite significant progress of microwave-induced reactions, no reports have examined the penetration depth of the surfaces used in these processes.
- BANIK, BIMAL K.,DAS, APARNA,YADAV, RAM NARESH
-
p. 2203 - 2206
(2021/08/24)
-
- Photoinduced Iron-Catalyzed ipso-Nitration of Aryl Halides via Single-Electron Transfer
-
A photoinduced iron-catalyzed ipso-nitration of aryl halides with KNO2 has been developed, in which aryl iodides, bromides, and some of aryl chlorides are feasible. The mechanism investigations show that the in situ formed iron complex by FeSO4, KNO2, and 1,10-phenanthroline acts as the light-harvesting photocatalyst with a longer lifetime of the excited state, and the reaction undergoes a photoinduced single-electron transfer (SET) process. This work represents an example for the photoinduced iron-catalyzed Ullmann-type couplings.
- Wu, Cunluo,Bian, Qilong,Ding, Tao,Tang, Mingming,Zhang, Wenkai,Xu, Yuanqing,Liu, Baoying,Xu, Hao,Li, Hai-Bei,Fu, Hua
-
p. 9561 - 9568
(2021/08/06)
-
- Ipso Nitration of Aryl Boronic Acids Using Fuming Nitric Acid
-
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.
-
supporting information
(2021/06/30)
-
- Selective preparation method of copper-catalyzed alpha-nitronaphthalene
-
The invention relates to a selective preparation method of copper-catalyzed alpha-nitronaphthalene, which comprises the following steps: dissolving naphthalene and nitric acid in an organic solvent toform a homogeneous solution, adding a copper catalyst, reacting at 0-50 DEG C for 0.5-10 hours, and carrying out after-treatment to obtain alpha-nitronaphthalene. According to the invention, copper is used as the catalyst, the synthesis process reduces the usage amount of acid, the operation is simple, the conditions are mild, the reaction time is short, the selectivity to alpha-nitronaphthaleneis very high, the supported copper catalyst can be recycled through centrifugal separation, the catalytic activity is high, the reaction raw materials are cheap and easily available. The method is a novel efficient preparation method.
- -
-
Paragraph 0030-0074
(2020/12/30)
-
- 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.
- -
-
Page/Page column 36; 46; 40; 57
(2020/05/28)
-
- Synthesis method of aromatic nitro-compound
-
The invention discloses a synthesis method of an aromatic nitro-compound. The synthesis method is characterized in that the aromatic nitro-compound is obtained by taking an aromatic amino-compound asa raw material and performing an oxidation reaction on the aromatic amino-compound and peroxytrifluoroacetic acid. The target aromatic nitro-compound is obtained by taking the aromatic amino-compoundas the raw material and performing the oxidation reaction on the aromatic amino-compound and peroxytrifluoroacetic acid; the synthesis method is high in yield, wide in application range, simple in operation and little in environmental pollution, therefore, the synthesis method is a good and ideal method for preparing the aromatic nitro-compound.
- -
-
Paragraph 0044; 0048
(2019/10/29)
-
- 2-Methyl-1,3-disulfoimidazolium polyoxometalate hybrid catalytic systems as equivalent safer alternatives to concentrated sulfuric acid in nitration of aromatic compounds
-
Ionic liquid-derived polyoxometalate salts [mdsim]3[PM12O40] (where M?=?W and Mo) of two heteropolyacids H3PW12O40.nH2O and H3PMo12O40.nH2O were synthesized using 2-methyl-1,3-disulfoimidazolium chloride ([mdsim][Cl]) ionic liquid and the corresponding heteropolyacids. Three equivalents of [mdsim][Cl] were treated with the respective Keggin-structured heteropolyacids (one equivalent) in aqueous medium at room temperature to afford the water-stable ionic polyoxometalates as acidic solids. They were completely characterized using spectroscopic and other analytical techniques including thermal analysis and Hammett acidity studies. The inherent Br?nsted acidic properties of ─SO3H group of these polyoxometalate salts were studied for the nitration of aromatic compounds with 69% HNO3 at normal temperature and 80°C without use of any external concentrated sulfuric acid. These strongly acidic polyoxometalates display good recyclability and efficient reusability.
- Saikia, Susmita,Borah, Ruli
-
-
- On/Off O2 Switchable Photocatalytic Oxidative and Protodecarboxylation of Carboxylic Acids
-
Photoredox catalysis in recent years has manifested a powerful branch of science in organic synthesis. Although merging photoredox and metal catalysts has been a widely used method, switchable heterogeneous photoredox catalysis has rarely been considered. Herein, we open a new window to use a switchable heterogeneous photoredox catalyst which could be turned on/off by changing a simple stimulus (O2) for two opponent reactions, namely, oxidative and protodecarboxylation. Using this strategy, we demonstrate that Au@ZnO core-shell nanoparticles could be used as a switchable photocatalyst which has good catalytic activity to absorb visible light due to the localized surface plasmon resonance effect of gold, can decarboxylate a wide range of aromatic and aliphatic carboxylic acids, have multiple reusability, and are a reasonable candidate for synthesizing both aldehydes/ketones and alkane/arenes in a large-scale set up. Some biologically active molecules are also shown via examples of the direct oxidative and protodecarboxylation which widely provided pharmaceutical agents.
- Bazyar, Zahra,Hosseini-Sarvari, Mona
-
p. 13503 - 13515
(2019/10/11)
-
- Bismuth nitrate as a source of nitro radical in ipso-nitration of carboxylic acids
-
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
-
p. 120 - 124
(2019/05/22)
-
- 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)
-
- 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.
- -
-
Paragraph 0035-0036
(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.
- -
-
Paragraph 0039; 0040
(2018/06/16)
-
- Method for nitrating aromatic compound by using nitrate under the action of auxiliary agent
-
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.
- -
-
Paragraph 0080-0083
(2018/09/11)
-
- 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)
- -
-
Paragraph 0065; 0066
(2018/09/11)
-
- Superior Catalytic Performance of Hierarchically Micro-Meso-Macroporous CuAlPO-5 for the Oxidation of Aromatic Amines under Mild Conditions
-
Aromatic nitro compounds are versatile building blocks for organic synthesis because of easy transformation of the nitro group into other diverse functional groups. Herein, hierarchical mesoporous–macroporous CuAlPO-5 was prepared and found to exhibit excellent catalytic activity and stability for the oxidation of aromatic amines to nitroarenes. For the oxidation of bulky aromatic amine molecules (e.g., 1-naphthalenamine), hierarchical CuAlPO-5 exhibited higher selectivity to the product than homogeneous Cu catalysts and higher catalytic activity than traditional microporous CuAlPO-5; the former was attributed to shape selectivity to the product and the latter was attributed to improved diffusion of bulky molecules inside the meso- and macropores. After CuAlPO-5 was used five times in the oxidation of 4-bromoaniline, >98.6 % conversion and 98.1 % selectivity to the product were obtained. This shows the potential and attractiveness of this method for the preparation of nitroarenes by the selective oxidation of organic amines.
- Ke, Qingping,Wu, Mingzhou,Yu, Huizhen,Lu, Guanzhong
-
p. 733 - 737
(2017/03/14)
-
- 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)
-
- Highly efficient protocol for the aromatic compounds nitration catalyzed by magnetically recyclable core/shell nanocomposite
-
An efficient protocol for the nitration of aromatic compounds in the presence of a catalytic amount of sulfuric acid-functionalized silica-based magnetic core/shell nanocomposite was reported. The designed products were obtained in high yields in relatively short reaction times at room temperature under solvent-free conditions. The nanocatalyst was simply recovered from the reaction mixture by using an external magnet and efficiently reused for several times. The characterization of particle size, morphology and elemental analysis of the nanocatalyst were provided by scanning electron microscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy analyses, respectively.
- Maleki, Ali,Aghaei, Morteza,Paydar, Reza
-
p. 485 - 490
(2017/01/10)
-
- Nitration of arenes by 1-sulfopyridinium nitrate as an ionic liquid and reagent by in situ generation of NO2
-
1-Sulfopyridinium nitrate was synthesized as a potent nitrating agent for the nitration of arenes without the need for any co-catalysts. A variety of nitro compounds were synthesized and fully characterized by IR, 1H NMR, 13C NMR, thermal gravimetric analysis (TGA), differential thermal gravimetry (DTG), CHN analysis and mass spectroscopy. Mechanistically, in situ generated nitrogen dioxide as a radical from the reagent is proposed for the presented nitration protocol.
- Moosavi-Zare, Ahmad Reza,Zolfigol, Mohammad Ali,Zarei, Mahmoud,Noroozizadeh, Ehsan,Beyzavi, M. Hassan
-
p. 89572 - 89577
(2016/10/03)
-
- One-Pot C?H Functionalization of Arenes by Diaryliodonium Salts
-
A transition-metal-free, mild, and highly regioselective synthesis of nitroarenes from arenes has been developed. The products are obtained in a sequential one-pot reaction by nitration of iodine(III) reagents with two carbon ligands, which are formed in situ from iodine(I). This novel concept has been extended to formation of aryl azides, and constitutes an important step towards catalytic reactions with these hypervalent iodine reagents. An efficient nitration of isolated diaryliodonium salts has also been developed, and the mechanism is proposed to proceed by a [2,2] ligand coupling pathway.
- Reitti, Marcus,Villo, Piret,Olofsson, Berit
-
supporting information
p. 8928 - 8932
(2016/07/26)
-
- Nucleophilic Nitration of Arynes by Sodium Nitrite and its Multicomponent Reaction Leading to Double-Functionalized Arenes
-
An unusual nucleophilic nitration of arynes by NaNO2 in the presence of water has been developed, and the concept was further demonstrated to accomplish a double functionalization of arynes using a multicomponent reaction protocol to synthesize pharmaceutically important (2-nitrophenyl)methanol derivatives. Such substitution ortho to -NO2 is difficult by other means. The reaction conditions are mild and avoid the use of strong acids, expensive transition metal catalysts, and additives.
- Dhokale, Ranjeet A.,Mhaske, Santosh B.
-
supporting information
p. 3010 - 3013
(2016/07/06)
-
- 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)
-
- A simple approach for preparation of dinitronaphthalene compounds from the nitration reaction of 1-nitronaphthalene with NO2 as nitration reagent
-
A simple method for the preparation of dinitronaphthalene from the nitration reaction of 1-nitronaphthalene with NO2 as nitration reagent under the mild conditions has been successfully developed in this work. The results indicated that Ni(CH3COO)2·4H2O catalyst shows better catalytic performances, and the conversion of 1-nitronaphthalene is 33.10 % with 34.10, 23.56, 19.30, and 3.56 % of the selectivity to 1,5-DNN, 1,3-DNN, 1,4-DNN, and 1,8-DNN, respectively, under the optimal reaction conditions. This is a mild, environmentally benign, and economical method for the preparation of dinitronaphthalene.
- You, Kuiyi,Zhou, Zhongcang,Jian, Jian,Deng, Renjie,Liu, Pingle,Ai, Qiuhong,Luo, He'An
-
p. 8307 - 8315
(2015/03/05)
-
- Regioselective nitration of naphthalene over HZSM-5-supported phosphotungstic acid
-
HZSM-5-supported phosphotungstic acid (PW) has been prepared and characterized. The results indicate that 5 wt% PW/HZSM-5 calcined at 773 K has the largest surface area and high dispersion of PW. It was confirmed that Keggin units are present inside the catalyst and that the proton of PW and the silanol of HZSM-5 interact via bridging structure. The catalytic properties of PW/HZSM-5 in the regioselective nitration of naphthalene to dinitronaphthalene were investigated. The best results, i.e. 48.5 % yield of 1,5-dinitronaphthalene, 49.2 % yield of 1,8-dinitronaphthalene, and the highest ratio of 1,5-dinitronaphthalene to 1,8-dinitronaphthalene, were obtained by use of 5 wt% PW/HZSM-5.
- Liu, Pingle,Xiong, Wei,Wang, Xiaofei,Huang, Kun,Hao, Fang,Wang, Liangjie,Luo, He'An
-
p. 4533 - 4543
(2015/06/30)
-
- A novel transition metal free [bis-(trifluoroacetoxy)iodo]benzene (PIFA) mediated oxidative ipso nitration of organoboronic acids
-
A mild, convenient and transition metal free methodology for oxidative ipso nitration of diversely functionalized organoboronic acids, including heteroaryl- and alkylboronic acids, has been developed at ambient temperature using a combination of [bis-(trifluoroacetoxy)]iodobenzene (PIFA) - N-bromosuccinimide (NBS) and sodium nitrite as the nitro source. It is anticipated that the reaction proceeds through in situ generation of NO2 and O-centred organoboronic acid radicals followed by the formation of an O-N bond via combination of the said radicals. Finally transfer of the NO2 group to the aryl moiety occurs through 1,3-aryl migration to provide the nitroarenes.
- Chatterjee, Nachiketa,Bhatt, Divya,Goswami, Avijit
-
supporting information
p. 4828 - 4832
(2015/05/05)
-
- 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)
-
- Zeolite-assisted regioselective synthesis of dinitronaphthalene
-
The nitration selectivity of naphthalene was studied in different organic solvents with 95 % fuming nitric acid as nitration reagent. The yield of dinitronaphthalene can achieve 78 % in hexane. With nitrogen dioxide as nitration reagent in oxygen, the selectivity of dinitronaphthalene in different types of molecular sieve catalyst was studied. When HBEA zeolite catalyst was used, the yield of dinitronaphthalene was up to 61 %. This method is easy to carry out, environmentally benign, and economical.
- Wang, Haocai,Peng, Xinhua,Shi, Chunjie,Dong, Xiongzi,Tai, Yanfang,Liu, Hongtao
-
p. 1495 - 1500
(2014/05/06)
-
- Zeolite-assisted regioselective mononitration of naphthalene with nitrogen dioxide/molecular oxygen
-
The nitration process using nitrogen dioxide and oxygen instead of the classical nitric acid-sulfuric acid system appears to be attractive and promising in the selective preparation of nitro compounds. The ratio of 1-nitronaphthalene isomer to 2-nitronaphthalene can reach 11 in a moderate yield of 60 % when the reaction is carried out in acetonitrile with 5.0 mmol naphthalene, 10 mmol nitrogen dioxide, and 0.13 g HZSM-5 under molecular oxygen atmosphere at -15 C. The isomeric distribution of the product nitro-naphthalene was found to be superior to traditional methods. The zeolite could be easily regenerated and recycled and reused by simple work-up to give results similar to those obtained with the fresh catalyst.
- Shi, Chunjie,Peng, Xinhua,Tai, Yanfang,Dong, Xiongzi,Wang, Haocai
-
p. 3151 - 3156
(2013/09/23)
-
- 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)
-
- Design of ionic liquid 3-methyl-1-sulfonic acid imidazolium nitrate as reagent for the nitration of aromatic compounds by in situ generation of NO 2 in acidic media
-
3-Methyl-1-sulfonic acid imidazolium nitrate ([Msim]NO3) as a new Bronsted acidic ionic liquid and nitrating agent was prepared and used for the efficient nitration of aromatic compounds (even aniline derivatives). The dramatic effect of this reagent by in situ generation of nitrogen dioxide as a radical on aromatic compounds to give nitroarenes has been studied.
- Zolfigol, Mohammad A.,Khazaei, Ardeshir,Moosavi-Zare, Ahmad R.,Zare, Abdolkarim,Kruger, Hendrik G.,Asgari, Zhila,Khakyzadeh, Vahid,Kazem-Rostami, Masoud
-
experimental part
p. 3640 - 3645
(2012/06/15)
-
- Aromatic nitration under neutral conditions using N-bromosuccinimide/ silver(I) nitrate
-
The use of N-bromosuccinimide and silver nitrate as a convenient reagent system for the nitration of aromatic compounds under neutral and environmentally safer reaction conditions is described.
- Nowrouzi, Najmeh,Mehranpour, Abdol Mohammad,Bashiri, Elham,Shayan, Zohre
-
experimental part
p. 4841 - 4842
(2012/09/22)
-
- 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.
- -
-
Page/Page column 24-25
(2012/12/13)
-
- Zeolite-assisted regioselective synthesis of dinitronaphthalene
-
Efficient methods of nitration of naphthalene or 1-nitronaphthalane with fuming nitric acid (wt. 95 %) in organic solvent over zeolite were investigated, where the regioselection of nitration can be improved and in certain cases the isomer ratio of nitration products can be reversed. The recovered zeolite was reused three times without appreciable loss of catalytic activity.
- Shi, Wenwen,Peng, Xinhua,Dong, Xiongzi,Wang, Haocai,Shi, Chunjie
-
experimental part
p. 4975 - 4978
(2012/10/08)
-
- Ipso-nitration of arylboronic acids with bismuth nitrate and perdisulfate
-
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
-
supporting information; experimental part
p. 1736 - 1739
(2012/05/20)
-
- Copper catalyzed ipso-nitration of iodoarenes, bromoarenes and heterocyclic haloarenes under ligand-free conditions
-
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
-
supporting information; experimental part
p. 1511 - 1513
(2012/03/27)
-
- Mild and efficient nitration of aromatic compounds mediated by transitionmetal complexes
-
Aromatic compounds were efficiently nitrated under facile reaction conditions by employing 69% nitric acid catalyzed by transition-metal complexes such as [Co(NH3)5Cl]Cl2, [Cu(NH 3)4]SO4, Mn(acac)3, [Ni(NH 3)6]Cl2, [Ni(en)3]S 2O3, and Hg[Co(SCN)4]. The reaction was completed smoothly at room temperature and afforded corresponding mono-nitro derivatives in quantitative yield. This new method offers efficient and facile regioselective mononitration of aromatic compounds. Taylor & Francis Group, LLC.
- Abdulla,Amina,Kumar, Y. Arun,Arifuddin,Rajanna
-
experimental part
p. 2946 - 2951
(2011/09/12)
-
- Nitration of aromatic compounds under neutral conditions using the Ph 2PCl/I2/AgNO3 reagent system
-
Aromatic compounds were nitrated efficiently under essentially neutral conditions by employing Ph2PCl in the presence of I2 and AgNO3. This method minimizes waste products compared to traditional methods and gives the corresponding mononitro derivatives in good to excellent yields in dichloromethane at room temperature.
- Nowrouzi, Najmeh,Zareh Jonaghani, Mohammad
-
experimental part
p. 5081 - 5082
(2011/10/09)
-
- Convenient and mild synthesis of nitroarenes by metal-free nitration of arylboronic acids
-
A novel methodology for the direct nitration of arylboronic acids has been developed. By using inexpensive tert-butyl nitrite various aromatic nitro compounds are produced in moderate to good yields (45-87%) without the need of any catalyst.
- Wu, Xiao-Feng,Schranck, Johannes,Neumann, Helfried,Beller, Matthias
-
supporting information; experimental part
p. 12462+12463
(2012/02/03)
-
- Nitration of aromatic hydrocarbons and halobenzenes using NOx catalyzed by solid acid catalysts
-
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.
-
experimental part
p. 3734 - 3738
(2011/02/16)
-
- Efficient and facile method for the nitration of aromatic compounds by nitric acid in micellar media
-
Aromatic compounds were efficiently nitrated under mild reaction conditions by employing HNO3 in the presence of anionic (sodium dodecyl sulfate, SDS), cationic (cetyl trimethyl ammonium bromide, CTAB), and nonionic (Triton-X 100) micelles. The reaction rapidly afforded corresponding mononitro derivatives in fair to good yields with high regioselectivity. This new method offers an environmentally safe reaction condition to minimize the waste products.
- Sana,Tasneem,Ali, M. Moazzam,Rajanna,Saiprakash
-
experimental part
p. 2949 - 2953
(2009/12/03)
-
- Ceric ammonium nitrate (CAN) as oxidizing or nitrating reagent for organic reactions in ionic liquids
-
The reaction of ceric ammonium nitrate, (NH4)2[Ce(NO3)6] or CAN, with naphthalene and 2-methylnaphthalene in the ionic liquid 1-ethyl-3-methylimidazolium triflate showed that the reaction products are strongly d
- Deleersnyder, Karen,Schaltin, Stijn,Fransaer, Jan,Binnemans, Koen,Parac-Vogt, Tatjana N.
-
scheme or table
p. 4582 - 4586
(2009/10/11)
-
- Aromatic nitration in liquid Ag0.51K0.42Na 0.07NO3
-
(Figure Presented) Aromatic molecules have a strong affinity for silver(I) and dissolve to a limited extent in Ag0.51K0.42Na 0.07NO3, a low-melting eutectic mixture of silver, potassium, and sodium nitrates. Aromatic nitration in this inorganic ionic liquid leads to products which arise from nonelectrophilic substitution pathways.
- Mascal, Mark,Yin, Lunxiang,Edwards, Ross,Jarosh, Michael
-
p. 6148 - 6151
(2008/12/22)
-
- Imidazolium ionic liquids as solvents for cerium(IV)-mediated oxidation reactions
-
Use of imidazolium ionic liquids as solvents for organic transformations with tetravalent cerium salts as oxidizing agents was evaluated. Good solubility was found for ammonium hexanitratocerate(IV) (ceric ammonium nitrate, CAN) and cerium(IV) triflate in 1-alkyl-3-methylimidazolium triflate ionic liquids. Oxidation of benzyl alcohol to benzaldehyde in 1-ethyl-3-methylimidazolium triflate was studied by in-situ FTIR spectroscopy and 13C NMR spectroscopy on carbon-13-labeled benzyl alcohol. Careful control of the reaction conditions is necessary because ammonium hexanitratocerate(IV) dissolved in an ionic liquid can transform benzyl alcohol not only into benzaldehyde but also into benzyl nitrate or benzoic acid. The selectivity of the reaction of cerium(IV) triflate with benzyl alcohol in dry ionic liquids depends on the degree of hydration of cerium(IV) triflate: anhydrous cerium(IV) triflate transforms benzyl alcohol into dibenzyl ether, whereas hydrated cerium(IV) triflate affords benzaldehyde as the main reaction product. Reactions of ammonium hexanitratocerate(IV) with organic substrates other than benzyl alcohol have been explored. 1,4-Hydroquinone is quantitatively transformed into 1,4-quinone. Anisole and naphthalene are nitrated. For the cerium-mediated oxidation reactions in ionic liquids, high reaction temperatures are an advantage because under these conditions smaller amounts of byproducts are formed.
- Mehdi, Hasan,Bodor, Andrea,Lantos, Diana,Horvath, Istvan T.,De Vos, Dirk E.,Binnemans, Koen
-
p. 517 - 524
(2007/10/03)
-
- Indium triflate as a recyclable catalyst for the nitration of aromatic compounds without a halogenated solvent
-
Indium triflate [In(OTf)3] was found to be excellent catalyst (0.5 or 2.0 mol%) for the mononitration of aromatic compounds using a single equivalent of nitric acid (60 or 90%, 1.0 equiv.) without using a halogenated solvent. The side product is water and the indium triflate catalyst can be readily recovered from the aqueous phase and reused.
- Yin, Wan-Po,Shi, Min
-
p. 549 - 551
(2007/10/03)
-
- Ortho effect in the Bergman cyclization: Comparison of experimental approaches and dissection of cycloaromatization kinetics
-
Four different experimental sources of kinetic information were combined to study the effect of ortho substituents on the rate of Bergman cycloaromatization. All methods confirm that the cyclization barrier is highly sensitive to the nature of the ortho substituents. However, the measured activation energies strongly depend on the choice of experimental technique: even the relative trends provided by the different methods agree with each other only in the case of acceptor substituents. Both the onset peaks and the activation energies determined by differential scanning calorimetry (DSC; either in neat enediynes or in their solutions in 10.6 M 1,4-cyclohexadiene (1,4-CHD)) strongly overestimate the reactivity of 1,2-diethynylbenzene, suggesting that DSC cannot be taken as a reliable indicator of enediyne reactivity. This discrepancy is likely to stem from the presence of side reactions with low activation barriers, especially important when the reaction is conducted in neat enediyne. On the other hand, kinetic measurements based on monitoring the concentrations of enediyne reactants and naphthalene products provide reliable general trends that include the parent benzannelated enediyne. These measurements confirm that both ortho-NO2 and ortho-CHO substituents substantially decrease activation energies for the Bergman cyclization, supporting earlier computational predictions. A comparison of theory and experiment suggests that computations at the Moeller-Plesset second-order perturbation theory (MP2)/6-31G** level provide an excellent alternative to DFT when an accurate description of the contribution of noncovalent interactions to the activation energy is needed. Activation energies derived from keff, the effective rate constant under the pseudo-first-order approximation, depend on the 1,4-CHD concentrations. The true rate constant, k-1, for the cyclization step and the ratio of constants for the retro-Bergman ring opening, k-1, and the intermolecular H-atom abstraction, k2, were determined from the dependence of cycloaromatization kinetics of ortho- and para-NO2 substituted enediynes on the concentration of 1,4-CHD.
- Zeidan, Tarek A.,Kovalenko, Serguei V.,Manoharan, Mariappan,Alabugin, Igor V.
-
p. 962 - 975
(2007/10/03)
-
- Supported bismuth(III) nitrate on silica sulfuric acid as useful reagent for nitration of aromatic compounds under solvent-free conditions
-
A number of aromatic compounds were nitrated to the corresponding nitroaromatic derivatives with the use of supported bismuth(III) nitrate on silica sulfuric acid under solvent-free conditions.
- Hajipour,Zarei,Ruoho
-
p. 1493 - 1495
(2007/10/03)
-
- Nitric acid in the presence of P2O5 supported on silica gel - A useful reagent for nitration of aromatic compounds under solvent-free conditions
-
A variety of aromatic compounds are nitrated to parent nitro aromatic compounds under solvent-free conditions using 65% nitric acid in the presence of P2O5 supported on silica gel is described. This methodology is useful for nitration of activated and deactivated aromatic rings.
- Hajipour, Abdol Reza,Ruoho, Arnold E.
-
p. 8307 - 8310
(2007/10/03)
-
- Supported tetramethylamonium nitrate/silicasulfuric acid as a useful reagent for nitration aromatic compounds under solvent-free conditions
-
A variety of aromatic compounds are nitrated to the parent nitro aromatic compounds under solvent-free conditions using supported tetramethylammonium nitrate/silicasulfuric acid as a useful reagent. This methodology is useful for nitration of activated and deactivated aromatic rings. Copyright Taylor & Francis, Inc.
- Hajipour, Abdol R.,Zarei, Amin,Khazdooz, Leila,Ruoho
-
p. 2237 - 2241
(2007/10/03)
-
- Nitration of aromatic compounds by Zn(NO3)2· 2N2O4 and its charcoal-supported system
-
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
-
p. 263 - 270
(2007/10/03)
-
