- Nitration of Phenylboron Dichloride with Nitronium Tetrafluoroborate. Attempted Nitration of Iodobenzene and Phenylphosphorous Dichloride
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Electrophilic nitration of phenylboron dichloride with nitronium tetrafluoroborate and N-nitro-2,4,6-collidinium tetrafluoroborate was investigated in nitromethane solution.The reactions give 10 - 18 percent ortho, 67 - 69 percent meta, and 15 - 21 percent para isomer.NMR studies of the sytem als show the formation of PhBFCl and PhBF2 by fluoride exchange as well as their intermediate complexes with the BF4- anion.The high meta content is attributed to the nitration of uncomplexed phenylboron dihalides with the -BX2 group exhibiting an -I effect which directs the nitration significantly to the meta position.High para isomer content was obtained when phenylboron dihalides were mostly complexed by the BF4- anion, thereby reducing the -I effect of -BX2 group.The nitration of iodobenzene dichloride gave esentially only nitroiodobenzenes due to dissociation of PhICl2 and the much faster nitration of PhI as compared to PhICl2.Attempted nitration of PhPCl2 with NO2+BF4- in CH3NO2 led only to oxidation.The oxidation could not be prevented even when trimethyl phosphate was used as solvent or the milder nitrating agent MeONO2/BF3.
- Olah, George A.,Piteau, Mark,Laali, Khosrow,Rao, Chandra B.,Farooq, Omar
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Read Online
- Low-temperature and highly efficient liquid-phase catalytic nitration of chlorobenzene with NO2: Remarkably improving the para-selectivity in O2-Ac2O-Hβ composite system
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In this work, we developed a low-temperature and efficient approach for the highly selective preparation of valuable p-nitrochlorobenzene from the liquid-phase catalytic nitration of chlorobenzene with NO2 in O2-Ac2O-Hβ composite system. The results demonstrated that the introduction of molecular oxygen remarkably enhanced the chlorobenzene conversion and the cooperation catalysis of Hβ zeolite and Ac2O envidently improved the selectivity to para-nitro product. Under the optimized reaction conditions, 93.6 % of the selectivity to p-nitrochlorobenzene with 84.0 % of chlorobenzene conversion was obtained, and the ratio of p-nitrochlorobenzene to o-nitrochlorobenzene could reach up to 20.3. Furthermore, the selectivity distribution of nitration products was reasonably explained by the density functional theory (DFT) calculation. Finally, the possible nitration reaction pathway of chlorobenzene with NO2 was suggested in O2-Ac2O-Hβ composite catalytic system. The present work affords a new and mild nitration approach for highly selective preparation of valuable para-nitro products, and has potential industrial application prospects.
- Deng, Renjie,Liu, Pingle,Luo, He'an,Ni, Wenjin,You, Kuiyi,Zhao, Fangfang
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- Arene diazonium saccharin intermediates: A greener and cost-effective alternative method for the preparation of aryl iodide
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In the current protocol, the arene diazonium saccharin derivatives were initially produced from various substituted aromatic amines; subsequently, these intermediates were treated with a greener organic iodide for the preparation of the aryl iodide. We tried to choose low-cost, commercially available, biodegradable, recoverable, ecofriendly, and safe reagents and solvents. The arene diazonium saccharin intermediates could be stored in the liquid phase into a refrigerator for a long time with no significant loss activity. The outstanding merits of the current protocol (a) included the partial recovering of saccharin and tetraethylammonium salt, (b) reduce the use of solvents and the reaction steps due to eliminating separation and purification of intermediates, (c) good yield of the sterically hindered substrates, and (d) avoid the generation of heavy metal or corrosive waste.
- Ghaffari Khaligh, Nader,Rafie Johan, Mohd,Shahnavaz, Zohreh,Zaharani, Lia
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p. 535 - 542
(2020/06/01)
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- Two-Phase Electrochemical Generation of Aryldiazonium Salts: Application in Electrogenerated Copper-Catalyzed Sandmeyer Reactions
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The electrochemical generation of aryldiazonium salts from nitroarenes in a two-phase system (ethyl acetate/water) was reported for the first time. Some compounds including azo, azosulfone, and arylazides were prepared in good yields with good purity. Cathodically generated aryldiazoniums and anodically produced copper(Ι) ions were used to perform Sandmeyer reactions. To improve the method, an H-type self-driving cell equipped with a Zn rod as an anode was introduced and used for two-phase aryldiazonium production.
- Goljani, Hamed,Tavakkoli, Zahra,Sadatnabi, Ali,Nematollahi, Davood
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supporting information
p. 5920 - 5924
(2020/08/12)
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- Dehydroxyalkylative halogenation of C(aryl)-C bonds of aryl alcohols
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We herein report Cu mediated side-directed dehydroxyalkylative halogenation of aryl alcohols. C(aryl)-C bonds of aryl alcohols were effectively cleaved, affording the corresponding aryl chlorides, bromides and iodides in excellent yields. Aryl alcohols could serve as both aromatic electrophilic and radical synthetic equivalents during the reaction.
- Liu, Mingyang,Zhang, Zhanrong,Liu, Huizhen,Wu, Tianbin,Han, Buxing
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supporting information
p. 7120 - 7123
(2020/07/14)
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- NITRATION
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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.
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Page/Page column 36; 41; 46; 64; 37; 43; 48; 69
(2020/05/28)
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- A new hypervalent iodine(iii/v) oxidant and its application to the synthesis of 2: H -azirines
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The reaction of o-nitroiodobenzene and mCPBA in acetic acid was found to afford a novel hypervalent iodine compound, in the structure of which both iodine(iii) and iodine(v) moieties coexist. The nitro groups at the ortho phenyl positions were found to be crucial in stabilizing this uncommon structure. This novel hypervalent iodine(iii/v) oxidant is proved to be effective in realizing the synthesis of 2-unsubstitued 2H-azirines via intramolecular oxidative azirination, which could not be efficiently achieved by the existing known hypervalent iodine reagents.
- Zhang, Guangtao,Wang, Yuanxun,Xu, Jun,Sun, Jiyun,Sun, Fengxia,Zhang, Yilin,Zhang, Chenglin,Du, Yunfei
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p. 947 - 953
(2020/02/11)
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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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- ipso-Bromination/iodination of arylboronic acids: Poly(4-vinylpyridine)-Br2/I2 complexes as safe and efficient reagents
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Poly(4-vinyl pyridine) supported bromine/iodine complexes were prepared and probed for ipso-bromination/iodination of arylboronic acids. These solid complexes with catalytic amount of additive are found to be safe and efficient reagent system for the ipso-bromination/iodination. The reaction occurs under mild conditions and tolerates various functional groups resulting in products with high selectivity and yields.
- Fu, Fang,Gurung, Laxman,Czaun, Miklos,Mathew, Thomas,Prakash, G.K. Surya
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supporting information
(2019/08/26)
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- Mechanism of Cu-catalyzed aryl boronic acid halodeboronation using electrophilic halogen: Development of a base-catalyzed iododeboronation for radiolabeling applications
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An investigation into the mechanism of Cu-catalyzed aryl boronic acid halodeboronation using electrophilic halogen reagents is reported. Evidence is provided to show that this takes place via a boronate-driven ipso-substitution pathway and that Cu is not required for these processes to operate: General Lewis base catalysis is operational. This in turn allows the rational development of a general, simple, and effective base-catalyzed halodeboronation that is amenable to the preparation of 125I-labeled products for SPECT applications.
- Molloy, John J.,O'rourke, Kerry M.,Frias, Carolina P.,Sloan, Nikki L.,West, Matthew J.,Pimlott, Sally L.,Sutherland, Andrew,Watson, Allan J. B.
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supporting information
p. 2488 - 2492
(2019/04/10)
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- An efficient gram scale synthesis of aryl iodides from aryl diazofluoroborates in water under mild conditions
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Transition metal-free synthesis of synthetically valuable aryl iodides from aryl diazofluroborates in water under mild conditions has been described. Majority of synthesized aryl iodides are obtained in quantitative yields (>99%) under present reaction conditions. The structural effects due to the substituents present on aryl diazofluoroborates did not show any satisfactory effect on the yields of the aryl iodides. Hence, the methodology presented here was found to be adventitious for the quantitative production of synthetically valuable aryl iodides.
- Gholap, Somnath S.
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p. 594 - 599
(2018/06/26)
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- A facile and sustainable protocol to the preparation of aryl iodides using stable arenediazonium bis(trifluoromethylsulfonyl)imide salts via the telescopic process
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The preparation of aryl iodides in a telescopic reaction using tert-butyl nitrite as a diazotization reagent and a mixture of bis(trifluoromethane) sulfonamide and glacial acetic acid as a mild acidic agent in ethanol followed by iododediazoniation with tetraethylammonium iodide in water was investigated. The current method has other advantages such as minimized waste by avoiding solvent for the purification of products in diazotization step, simple experimental procedure, and good yield of the sterically hindered aryl amines, metal and strong acid-free waste and environmentally benign conditions. The noteworthy features of this study are the preparation of stable arenediazonium bis(trifluoromethylsulfonyl)imide salts that can be used with no significant loss activity after 1?week and bis(trifluoromethane)sulfonamide was recovered in high yields from reactions.
- Khaligh, Nader Ghaffari
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- Visible-Light-Induced Decarboxylative Iodination of Aromatic Carboxylic Acids
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A convenient, efficient and practical visible-light-induced decarboxylative iodination of aromatic carboxylic acids has been developed, and the corresponding aryl iodides were obtained in good yields. The method shows some advantages including the use of readily available aromatic carboxylic acids as the starting materials, simple and mild conditions, high efficiency, wide substrate scope and tolerance of various functional groups.
- Jiang, Min,Yang, Haijun,Jin, Yunhe,Ou, Lunyu,Fu, Hua
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supporting information
p. 1572 - 1577
(2018/06/26)
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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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- A new regiospecific synthesis method of 1H-pyrazolo[3,4-b]quinoxalines – Potential materials for organic optoelectronic devices, and a revision of an old scheme
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A series of 6-substituted-1,3-diphenyl-1H-pyrazolo[3,4-b]quinoxalines were prepared using a new synthetic pathway: reductive cyclization of appropriate 5-(o-nitrophenyl)-pyrazoles with ferrous oxalate or triphenylphosphine. The main advantage of this procedure is that, contrary to the older protocols of pyrazolo[3,4-b]quinoxaline synthesis, this method allows for a substituent to be introduced to the carbocyclic ring without the formation of isomers. The pyrazole ring can also be modified to some extent. Furthermore, we propose a new mechanism for the oldest reported pyrazolo[3,4-b]quinoxaline synthesis, based on the condensation between o-phenylenediamine and 3,4-pyrazolin-5-diones.
- Danel, Andrzej,Wojtasik, Katarzyna,Szlachcic, Pawe?,Gryl, Marlena,Stadnicka, Katarzyna
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p. 5072 - 5081
(2017/07/28)
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- Decarboxylative Halogenation and Cyanation of Electron-Deficient Aryl Carboxylic Acids via Cu Mediator as Well as Electron-Rich Ones through Pd Catalyst under Aerobic Conditions
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Simple strategies for decarboxylative functionalizations of electron-deficient benzoic acids via using Cu(I) as promoter and electron-rich ones by employing Pd(II) as catalyst under aerobic conditions have been established, which lead to smooth synthesis of aryl halides (-I, Br, and Cl) through the decarboxylative functionalization of benzoic acids with readily available halogen sources CuX (X = I, Br, Cl), and easy preparation of benzonitriles from decarboxylative cyanation of aryl carboxylic acids with nontoxic and low-cost K4Fe(CN)6 under an oxygen atmosphere for the first time.
- Fu, Zhengjiang,Li, Zhaojie,Song, Yuanyuan,Yang, Ruchun,Liu, Yanzhu,Cai, Hu
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p. 2794 - 2803
(2016/04/26)
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- Pyridine-promoted dediazoniation of aryldiazonium tetrafluoroborates: Application to the synthesis of SF5-substituted phenylboronic esters and iodobenzenes
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Pyridine promotes dediazoniation of aryldiazonium tetrafluoroborates. The formed aryl radicals were trapped with B2pin2, iodine, or tetrahydrofuran to afford boronic esters, iodobenzenes and benzenes, respectively. The application to the synthesis of (pentafluorosulfanyl) phenylboronic esters, iodo(pentafluorosulfanyl)benzenes and (pentafluorosulfanyl)benzene is shown.
- Iakobson, George,Du, Junyi,Slawin, Alexandra M. Z.,Beier, Petr
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supporting information
p. 1494 - 1502
(2016/04/09)
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- PROCESS FOR THE PREPARATION OF N-IODOAMIDES
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The present invention provides new stable crystalline N-iodoamides - 1-iodo- 3,5,5-trimethylhydantoin (1-ITMH) and 3-iodo-4,4-dimethyl-2-oxazolidinone (IDMO). The present invention further provides a process for the preparation of organic iodides using N-iodoamides of this invention and recovery of the amide co-products from waste water.
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Paragraph 00234-00235
(2015/05/26)
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- Magnesium complexes containing biphenyl-based tridentate imino-phenolate ligands for ring-opening polymerization of rac-lactide and α- methyltrimethylene carbonate
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A series of racemic 2-[(2′-(dimethylamino)biphenyl-2-ylimino)methyl]- 4-R2-6-R1-phenols (L1H-L4H) were reacted with {Mg[N(SiMe3)2]2}2 to provide four heteroleptic magnesium complexes (L1-4)MgN(SiMe 3)2·(THF)n (1, R1 = tBu, R2 = Me, n = 1; 2, R1 = R2 = CMe2Ph, n = 0; 3, R1 = CPh3, R2 = tBu, n = 1; 4, R1 = Br, R2 = tBu, n = 0), which have been fully characterized. X-ray structural determination shows that complex 1 possesses a monomeric structure, but complex 4 is dimeric with C2-symmetry where the two metal centers are bridged by two phenolate oxygen atoms of the ligands. The coordination geometry around the magnesium center in these complexes can be best described as a distorted tetrahedral geometry. The heteroleptic complexes 1-4 efficiently initiate the ring-opening polymerization of rac-lactide and α-methyltrimethylene carbonate (α-MeTMC) and the polymerizations are better controlled in the presence of 2-propanol. In general, the introduction of a bulky ortho-substituent on the phenoxy unit results in increases of both the catalytic activity and the stereo- or regioselectivity of the corresponding magnesium complex. Microstructure analyses of the resulting PLAs revealed that Pr values range from 0.46 to 0.81, depending on the catalyst and the polymerization conditions. For racemic α-MeTMC, detailed analyses using 1H and 13C NMR spectroscopy indicated the preferential ring-opening of α-MeTMC at the most hindered oxygen-acyl bond (Xreg = 0.65-0.86).
- Yi, Wei,Ma, Haiyan
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p. 5200 - 5210
(2014/04/03)
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- A highly regioselective synthesis of N-acyl-2-acyl(aroyl)indolium Chloride through Palladium-Copper Catalysis Followed by Friedel-Crafts Reaction
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2-Trimethylsilylethynyl acetanilides, obtained from the palladium-catalyzed reactions of 2-iodoacetanilides with trimethylsilylacetylene, underwent Friedel-Crafts acylation reactions yielding the N-acyl-2-acyl(aroyl)indolium chlorides in good yields. Georg Thieme Verlag Stuttgart New York.
- Khan, Md. Wahab,Akther, Arifa,Alam, Md. Shariful
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supporting information
p. 831 - 834
(2014/04/17)
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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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- Nitrite ionic liquid as a new reagent for in situ synthesis of aryl iodides and azides
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A new ionic liquid, 1-methyl-3-(2-[2-(1-methyl-1H-imidazol-3-ium-3-yl)ethyloxy] ethyl)-1H-imidazol-3-ium dinitrite, was synthesized. This ionic liquid was used as a convenient nitrosonium source in diazotization of aryl amines into their corresponding diazonium salts, which were converted into aryl iodides and aryl azides using potassium iodide or sodium azide, respectively. Various aryl amines possessing electron-withdrawing groups or electron-donating groups were converted into the corresponding aryl iodides and aryl azides in excellent yields. Advantages of this methodology are the use of mild reaction conditions, short reaction times, and avoiding the use of toxic solvents.
- Eshghi, Hossein,Bakavoli, Mehdi,Ghasemzadeh, Marjan
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p. 3999 - 4007
(2015/06/08)
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- Halogenation and DNA cleavage via thermally stable arenediazonium camphorsulfonate salts
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A series of stable arenediazonium camphorsulfonate salts (2a-2j) were synthesized by simple diazotization of several aromatic amines in the presence of sodium nitrite and camphorsulfonic acid. All the new arenediazonium camphorsulfonates, which were characterized by multinuclear (1H and 13C) NMR, IR, DSC, and X-ray diffraction analysis (2e and 2f) provide unambiguous proof for the molecular structures of 2e and 2f. The efficient application of these salts in halogenation reactions was studied in solvent and solvent-free conditions and the DNA cleavage activity was also assessed. These arenediazonium camphorsulfonate salts are noticed as efficient DNA cleaving agents.
- Vajpayee, Vaishali,Moon, Mi Eun,Lee, Sunmi,Ravikumar, Sambandam,Kim, Hyunuk,Ahn, Byungchan,Choi, Seoyoon,Hong, Soon Ho,Chi, Ki-Whan
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p. 3511 - 3517
(2013/04/23)
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- Magnesium and calcium complexes containing biphenyl-based tridentate iminophenolate ligands for ring-opening polymerization of rac -lactide
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A series of racemic 2-[(2′-methoxybiphenyl-2-ylimino)methyl]-4-R 2-6-R1-phenols (L1H-L8H) were reacted with {Mg[N(SiMe3)2]2}2 and Ca[N(SiMe3)2]2·2THF (THF = tetrahydrofuran), respectively, to provide nine heteroleptic magnesium complexes L1-8MgN(SiMe3)2 [R1 = iPr, R2 = H (1a); R1 = tBu, R 2 = Me (2a and 2a·THF); R1 = R2 = tBu (3a); R1 = R2 = CMe2Ph (4a); R1 = CPh3, R2 = tBu (5a); R 1 = 1-piperidinylmethyl, R2 = tBu (6a); R 1 = Cl, R2 = tBu (7a); R1 = Br, R2 = tBu (8a)], two homoleptic calcium complexes (L 2,5)2Ca (2b and 5b), and one heteroleptic calcium complex [(L4)CaN(SiMe3)2·THF] (4b), which have been fully characterized. In the solid state, magnesium complexes 2a and 6a are isostructural, and each possesses a monomeric structure, while magnesium complexes 7a and 8a are dimeric, where the two metal centers are bridged by two phenolate oxygen atoms of the ligands. The coordination geometry around the magnesium center in these complexes can be best described as a distorted tetrahedral geometry. Although bearing the same iminophenoloate ligand, the molecular structures of complexes 2a and 2a·THF are different from each other. In complex 2a·THF, the coordination of one molecule of THF to the magnesium atom leads to dissociation of the methoxy group of the ligand from the metal center. The homoleptic calcium complex 2b has a six-coordinate metal core ligated by all six donor atoms of two iminophenolate ligands. The heteroleptic magnesium complexes 1a-8a and calcium complex 4b proved to be efficient initiators for the ring-opening polymerization of rac-lactide at ambient temperature in THF or at 70 C in toluene, and the polymerizations were better controlled in the presence of 2-propanol. The introduction of a bulky ortho substituent on the phenoxy unit of the ligand resulted in an increase of the catalytic activity of the corresponding metal complex. Microstructure analysis of the resultant poly(rac-lactide) samples via homonuclear-decoupled 1H NMR spectroscopy revealed Pr values ranging from 0.60 to 0.81, which closely depended on the employed catalyst and polymerization conditions.
- Yi, Wei,Ma, Haiyan
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p. 11821 - 11835
(2013/11/19)
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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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- A green procedure for the diazotization-iodination of aromatic amines under aqueous, strong-acid-free conditions
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A convenient and mild one-pot method for the synthesis of iodoarenes in high yields by the sequential diazotization-iodination of aromatic amines with a reusable polymeric diazotization agent in the presence of p-toluenesulfonic acid at room temperature in water was developed. The method is general and is the greenest alternative of the known diazotization-iodination methods. The method is also effective for the preparation of 1H-benzo[d][1,2,3]triazole and benzo[d][1,2,3]thiadiazole. Georg Thieme Verlag Stuttgart ? New York.
- Trusova, Marina E.,Krasnokutskaya, Elena A.,Postnikov, Pavel S.,Choi, Younghwa,Chi, Ki-Whan,Filimonov, Victor D.
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experimental part
p. 2154 - 2158
(2011/08/05)
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- Nitration of aromatic compounds under neutral conditions using the Ph 2PCl/I2/AgNO3 reagent system
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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
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experimental part
p. 5081 - 5082
(2011/10/09)
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- PROCESS FOR THE PREPARATION OF IODIDES
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This invention is directed to a process for the preparation of high yield alkyl or aryl iodide from its corresponding carboxylic acid using N-iodo amides.
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Page/Page column 34
(2012/01/05)
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- A novel mode of reactivity for gold(I): The decarboxylative activation of (hetero)aromatic carboxylic acids
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Gold(I) salts are found to mediate the decarboxylation of a variety of aromatic and heteroaromatic carboxylic acids at significatively lower temperatures (as low as 60°C) than the currently used copper(I) (180-190°C) and silver(I) (80-140°C) systems. In contrast to silver(I)- and copper(I)-mediated decarboxylations, the resulting aryl-gold(I) complexes are stable towards protodemetallation and can be readily isolated.
- Cornella, Josep,Rosillo-Lopez, Martin,Larrosa, Igor
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supporting information; experimental part
p. 1359 - 1366
(2011/06/26)
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- Copper-catalyzed halogenation of arylboronic acids
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In this Letter, a copper-catalyzed halogenation of arylboronic acids was described. This reaction tolerates a variety of functional groups, providing aromatic halides with good yields. It represents a facile and mild procedure to aryl halides.
- Zhang, Guangyou,Lv, Guanglei,Li, Liping,Chen, Fan,Cheng, Jiang
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experimental part
p. 1993 - 1995
(2011/04/25)
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- Highly stereoselective 7-endo-trig /ring contraction cascade to construct pyrrolo[1,2- a ]quinoline derivatives
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With the cooperation of Cram's phenonium ion, a novel cascade reaction was illustrated to construct pyrrolo[1,2-a]quinolines as a sole diastereoisomer in good to excellent yields. Preliminary mechanistic studies revealed that the γ-lactam ring and electron-rich arene are important driving forces for ring contraction.
- Li, Xinyu,Li, Cheng,Zhang, Wenjing,Lu, Xiang,Han, Shiqing,Hong, Ran
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supporting information; experimental part
p. 1696 - 1699
(2010/09/05)
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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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- Synthesis and antiplasmodial activity of new indolone N-Oxide derivatives
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A series of 66 new indolone-N-oxide derivatives was synthesized with three different methods. Compounds were evaluated for in vitro activity against CQ-sensitive (3D7), CQ-resistant (FcB1), and CQ and pyrimethamine cross-resistant (K1) strains of Plasmodium falciparum (P.f.), aswell as for cytotoxic concentration (CC50) on MCF7 and KB human tumor cell lines. Compound 26 (5-methoxy-indolone-N-oxide analogue) had the most potent antiplasmodial activity in vitro (50 MCF7/IC50 FcB1: 14623; CC50 KB/IC50 3D7: 198823). In in vivo experiments, compound 1 (dioxymethylene derivatives of the indolone-N-oxide) showed the best antiplasmodial activity against Plasmodium berghei, 62% inhibition of the parasitaemia at 30 mg/kg/day. 2009 American Chemical Society.
- Nepveu, Fran?oise,Kim, Sothea,Boyer, Jeremie,Chatriant, Olivier,Ibrahim, Hany,Reybier, Karine,Monje, Marie-Carmen,Chevalley, Severine,Perio, Pierre,Lajoie, Barbora H.,Bouajila, Jalloul,Deharo, Eric,Sauvain, Michel,Tahar, Rachida,Basco, Leonardo,Pantaleo, Antonella,Turini, Francesco,Arese, Paolo,Valentin, Alexis,Thompson, Eloise,Vivas, Livia,Petit, Serge,Nallet, Jean-Pierre
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scheme or table
p. 699 - 714
(2010/07/09)
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- A one-pot method for the iodination of aryl amines via stable aryl diazonium silica sulfates under solvent-free conditions
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A convenient and rapid one-pot method for the synthesis of iodoarenes is developed which involves the sequential diazotization-iodination of aromatic amines with sodium nitrite, silica sulfuric acid and potassium iodide under solvent-free conditions at room temperature. Various aromatic amines possessing electron-withdrawing groups or electron-donating groups are converted into the corresponding aryl iodides in good yields. Georg Thieme Verlag Stuttgart.
- Zarei, Amin,Hajipour, Abdol R.,Khazdoozd, Leila
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experimental part
p. 941 - 944
(2009/12/02)
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- Synthetic study on tetrapetalones: Stereoselective cyclization of N-acyliminium ion to construct substituted 1-benzazepines
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The synthesis of the tetracyclic core of complex antibiotic tetrapetalones has been achieved In three steps starting from the simple Intermediate γ-hydroxy amide, which can be accessed through a high-yielding six-step sequence. The successful synthesis relies on a novel strategy based on the N-acyliminium ion cyclizatlon.
- Cheng, Li,Xlnyu, L.I. And,Ran, Hong
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supporting information; experimental part
p. 4036 - 4039
(2009/12/09)
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- Lanthanide Bis[(trifluoromethyl)sulfonyl]imides as reusable catalysts for mononitration of substituted benzenes in ionic liquids
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Lanthanide bis[(trifluoromethyl)sulfonyl]imides as a kind of effective catalyst were used in quaternary ammonium ionic liquids to afford a useful new method for the nitration of substituted benzenes with concentrated nitric acid (95%) as nitrating agent. The less expensive lanthanum bis[(trifluoromethyl) sulfonyl]imide was found to be the most effective catalyst employed in the ionic liquid tributylammonium bis[(trifluoromethyl)sulfonyl]imide. The lanthanum bis[(trifluoromethyl)sulfonyl]-imide/tributylammonium bis[(trifluoromethyl) sulfonyl]imide system demonstrated high catalytic activity for the nitration of halobenzenes and rendered good to excellent yields. This catalyst/ionic liquid system could be recovered by simple procedures and recycled for at least 5 times.
- Wang, Shuojin,Jiang, Shaojie,Nie, Jin
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experimental part
p. 1939 - 1945
(2011/02/28)
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- Sulfonic acid based cation-exchange resin: A novel proton source for one-pot diazotization-iodination of aromatic amines in water
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A convenient and simple one-pot method for the preparation of iodoarenes at room temperature has been developed, by sequential diazotization-iodination of aromatic amines with NaNO2/KI in the presence of a sulfonic acid based cation-exchange resin in water. This inexpensive, noncorrosive and eco-friendly synthetic route is general in nature and allows for the preparation of iodoarenes with an electron-donating or -withdrawing group in various positions from the corresponding amines in 50-98% yields. Georg Thieme Verlag Stuttgart.
- Filimonov, Victor D.,Semenischeva, Nadya I.,Krasnokutskaya, Elena A.,Tretyakov, Alexei N.,Ho, Yun Hwang,Chi, Ki-Whan
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p. 185 - 187
(2008/12/20)
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- Unusually stable, versatile, and pure arenediazonium tosylates: Their preparation, structures, and synthetic applicability
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(Graph Presented) A new, simple, and effective method for the diazotization of a wide range of arylamines has been developed by using a polymer-supported diazotization agent in the presence of p-toluenesulfonic acid. Various pure arenediazonium tosylates with unusual stabilities can be easily prepared by this method. As a result, these salts are useful and versatile substrates for subsequent transformations, such as halogenation and Heck-type reactions. The unusual stabilities of arenediazonium tosylates are also preliminarily discussed with their X-ray structures.
- Filimonov, Victor D.,Trusova, Marina,Postnikov, Pavel,Krasnokutskaya, Elena A.,Lee, Young Min,Hwang, Ho Yun,Kim, Hyunuk,Chi, Ki-Whan
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supporting information; experimental part
p. 3961 - 3964
(2009/05/30)
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- Iodination of aryl amines in a water-paste form via stable aryl diazonium tosylates
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The diazotization of aryl amines at room temperature in paste form with NaNO2, p-TsOH and a small amount of water, followed by treatment with KI provides a new, simple, and effective route for the preparation of various aryl iodides. The water-paste and strong acid-free reaction conditions are environmentally friendly and compatible with acid-sensitive functional groups.
- Gorlushko, Dmitry A.,Filimonov, Victor D.,Krasnokutskaya, Elena A.,Semenischeva, Nadya I.,Go, Bong Seong,Hwang, Ho Yun,Cha, Eun Hye,Chi, Ki-Whan
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p. 1080 - 1082
(2008/09/18)
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- A new, one-step, effective protocol for the iodination of aromatic and heterocyclic compounds via aprotic diazotization of amines
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We have developed a convenient one-step preparation of aromatic and some heterocyclic iodides by the sequential diazotization-iodination of the aromatic amines with a KI/NaNO2/p-TsOH system in acetonitrile at room temperature. This method has general character and allows aryl iodides with either donor or acceptor substituents in various positions to be obtained from the corresponding amines in 50-90% yield. Georg Thieme Verlag Stuttgart.
- Krasnokutskaya, Elena A.,Semenischeva, Nadya I.,Filimonov, Victor D.,Knochel, Paul
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- Nitration of aromatic compounds catalyzed by divanadium-substituted molybdophosphoric acid, H5[PMo10V2O 40]
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The nitration of aromatic compounds was carried out in the presence of divanadium-substituted molybdophosphoric acid, H5PMo 10V2O40, as catalyst and a mixture of nitric acid and acetic anhydride as nitrating agent. In the presence of this heteropolyacid the ortho- and para-nitro compounds were obtained in good to excellent yields under mild reaction conditions. Springer-Verlag 2007.
- Heravi, Majid M.,Bakhtiari, Khadijeh,Benmorad, Tina,Bamoharram, Fatemeh F.,Oskooie, Hossein A.,Tehrani, Maryam H.
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p. 449 - 452
(2008/02/02)
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- Efficient one-pot transformation of aminoarenes to haloarenes using halodimethylisulfonium halides generated in situ
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Halodimethylsulfonium halide 1, which is readily formed in situ from hydrohaloic acid and DMSO, is a good nucleophilic halide. This activated nucleophilic halide rapidly converts aryldiazonium salt prepared in situ by the same hydrohaloic acid and nitrite ion to aryl chlorides, bromides, or iodides in good yield. The combined action of nitrite ion and hydrohaloic acid in DMSO is required for the direct transformation of aromatic amines, which results in the production of aryl halides within 1 h. Substituted compounds with electron-donating or -withdrawing groups or sterically hindered aromatic amines are also smoothly transformed to the corresponding aromatic halides. The only observed by-product is the deaminated arene (usually 7%). The isolated aryldiazonium salts can also be converted to the corresponding aryl halides using 1. The present method offers a facile, one-step procedure for transforming aminoarenes to haloarenes and lacks the environmental pollutants that usually accompany the Sandmeyer reaction using copper halides.
- Baik, Woonphil,Luan, Wanqiang,Lee, Hyun Joo,Yoon, Cheol Hun,Koo, Sangho,Kim, Byeong Hyo
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p. 213 - 219
(2007/10/03)
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- 2-Methoxy-4-nitrobenzenediazonium salt as a practical diazonium-transfer agent for primary arylamines via tautomerism of 1,3-diaryltriazenes: Deaminative iodination and arylation of arylamines without direct diazotization
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1,3-Diaryltriazenes, prepared from a 2-methoxy-4-nitrobenzenediazonium salt and primary arylamines, exist as "azo-transfer" tautomers in which the 2-methoxy-4-nitrophenyl group is present on the saturated nitrogen atom and forms a hydrogen bond between the 2-methoxy group and the N-H moiety. The synthetic utility of the diazonium salt as a practical diazonium-transfer agent for primary arylamines via tautomerism of the 1,3-diaryltriazenes has been demonstrated by the deaminative iodination and arylation of the arylamines without direct diazotization. The starting 2-methoxy-4-nitrophenylamine can be easily recovered after the reactions.
- Saeki, Tomoyuki,Son, Eun-Cheol,Tamao, Kohei
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p. 1654 - 1658
(2007/10/03)
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- Clay supported ammonium nitrate "clayan": A new reagent for selective nitration of arenes
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The nitration of activated, deactivated and highly functionalized arenes is described using clay-supported ammonium nitrate in the presence of perchloric acid.
- Meshram,Ganesh,Madhavi,Eshwaraiah,Yadav,Gunasekar
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p. 2497 - 2503
(2007/10/03)
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- Zinc(II) promoted conversion of aryltriazenes to aryl iodides and aryl nitriles
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Aryltriazenes react with zinc perchlorate/zinc cyanide to produces arylnitriles and react with zinc iodide to produce aryliodides. The reaction mechanism involves aryl radicals that have been trapped by addition to propenenitriles in a good preparative Meerwein arylation process.
- Patrick, Timothy B.,Juehne, Thomas,Reeb, Elmer,Hennessy, Daniel
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p. 3553 - 3554
(2007/10/03)
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- para-Selective nitration of halogenobenzenes using a nitrogen dioxide-oxygen-zeolite system
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The nitration of halogenobenzenes using zeolite Hβ or zeolite HY as a solid inorganic catalyst and a combination of liquid nitrogen dioxide and gaseous oxygen as the nitrating reagent leads to high yields and significant para-selectivities in a relatively clean process for aromatic nitration.
- Smith,Almeer,Black
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p. 1571 - 1572
(2007/10/03)
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- Selective nitration of aromatic compounds by solid acid catalysts
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High activity and para-selectivity in the nitration of aromatic compounds is achieved by a high density of acidic sites and ready formation of the para-isomer in the pores of zeolite beta with low Si/Al ratio as revealed by molecular modeling studies.
- Choudary,Sateesh,Lakshmi Kantam,Koteswara Rao,Ram Prasad,Raghavan,Sarma
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- Halodediazoniations of dry arenediazonium o-benzenedisulfonimides in the presence or absence of an electron transfer catalyst. Easy general procedures to prepare aryl chlorides, bromides, and iodides
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The paper reports the results of a wide study aimed at preparing aryl chlorides 3 (19 examples), bromides 4 (19 examples), and iodides 5 (9 examples) by halodediazoniation of dry arenediazonium o-benzenedisulfonimides 1 with tetraalkylammonium halides 2. The reactions were carried out in anhydrous acetonitrile at room temperature (~20 °C) in the presence of copper powder and at 60 °C or room temperature without the catalyst. In optimal conditions the yields were from good to excellent (60 reactions, 61- 94% yield), with only a few exceptions (8 reactions, 51-55% yield). A good amount of the o-benzenedisulfonimide (7) was always recovered from the reactions and could then be reused to prepare salts 1. An interesting aspect of this research is the surprising role of the anion of o- benzenedisulfonimide (9) as an electron transfer agent.
- Barbero,Degani,Dughera,Fochi
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p. 3448 - 3453
(2007/10/03)
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