- Sulfated polyborate-H2O assisted tunable activation of N-iodosuccinimide for expeditious mono and diiodination of arenes
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Owing to both Lewis and Bronsted acid active sites on sulfated polyborate under homogenous conditions, we were keen on developing iodination protocol of arenes that can meet the requirement of regioselectivity and higher yield. The sulfated polyborate activates N-iodosuccinimide for mono iodination of highly activated substrates viz. phenols, anilines under anhydrous condition. Water tunes sulfated polyborate to generate more Bronsted acid sites resulting in rapid activation of NIS for diiodination. The protocol was equally applicable to diiodination of 4-hydroxyphenylacetic acid to synthesize 4-hydroxy-3,5-diiodophenylacetic acid, an intermediate of tiratricol, a thyroid treatment drug. This protocol was further integrated via one-pot sequential iodination and Sonogashira coupling to synthesize aryl acetylenes, building blocks for the synthesis of a variety of specialty chemicals, API, and natural products.
- Misal, Balu,Palav, Amey,Ganwir, Prerna,Chaturbhuj, Ganesh
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supporting information
(2021/05/26)
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- NCBSI/KI: A Reagent System for Iodination of Aromatics through in Situ Generation of I-Cl
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In situ iodine monochloride (I-Cl) generation followed by iodination of aromatics using NCBSI/KI system has been developed. The NCBSI reagent requires no activation due to longer bond length, lower bond dissociation energy, and higher absolute charge density on nitrogen. The system is adequate for mono- and diiodination of a wide range of moderate to highly activated arenes with good yield and purity. Moreover, the precursor N-(benzenesulfonyl)benzenesulfonamide can be recovered and transformed to NCBSI, making the protocol eco-friendly and cost-effective.
- Palav, Amey,Misal, Balu,Chaturbhuj, Ganesh
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p. 12467 - 12474
(2021/08/24)
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- Synthesis and antibacterial activity of difluoromethyl cinnamoyl amides
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Series of novel amides of isoferulic acid, where the phenolic hydroxyl was replaced by a difluoromethyl group, were synthesized and their in vitro antibacterial activities assayed against fourteen bacterial strains (six Gram-positive and eight Gram-negati
- Martínez, Mario David,Riva, Diego Ariel,Garcia, Cybele,Durán, Fernando Javier,Burton, Gerardo
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- Protecting Group-Controlled Remote Regioselective Electrophilic Aromatic Halogenation Reactions
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Being able to utilize a protecting group to influence remote regiocontrol offers a simple alternative approach to direct late-stage functionalization of complex organic molecules. However, protecting groups that have the ability to influence reaction regi
- Brittain, William D. G.,Cobb, Steven L.
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p. 6862 - 6871
(2020/07/07)
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- Decarboxylative Suzuki-Miyaura coupling of (hetero)aromatic carboxylic acids using iodine as the terminal oxidant
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A novel methodology for the decarboxylative Suzuki-Miyaura-type coupling has been established. This process uses iodine or a bromine source as both the decarboxylation mediator and the terminal oxidant, thus avoiding the need for stoichiometric amounts of transition metal salts previously required. Our new protocol allows for the construction of valuable biaryl architectures through the coupling of (hetero)aromatic carboxylic acids with arylboronic acids. The scope of this decarboxylative Suzuki reaction has been greatly diversified, allowing for previously inaccessible non-ortho-substituted aromatic acids to undergo this transformation. The procedure also benefits from low catalyst loadings and the absence of stoichiometric transition metal additives.
- Quibell, Jacob M.,Duan, Guojian,Perry, Gregory J.P.,Larrosa, Igor
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supporting information
p. 6445 - 6448
(2019/06/07)
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- Transition-Metal-Free Decarboxylative Iodination: New Routes for Decarboxylative Oxidative Cross-Couplings
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Constructing products of high synthetic value from inexpensive and abundant starting materials is of great importance. Aryl iodides are essential building blocks for the synthesis of functional molecules, and efficient methods for their synthesis from chemical feedstocks are highly sought after. Here we report a low-cost decarboxylative iodination that occurs simply from readily available benzoic acids and I2. The reaction is scalable and the scope and robustness of the reaction is thoroughly examined. Mechanistic studies suggest that this reaction does not proceed via a radical mechanism, which is in contrast to classical Hunsdiecker-type decarboxylative halogenations. In addition, DFT studies allow comparisons to be made between our procedure and current transition-metal-catalyzed decarboxylations. The utility of this procedure is demonstrated in its application to oxidative cross-couplings of aromatics via decarboxylative/C-H or double decarboxylative activations that use I2 as the terminal oxidant. This strategy allows the preparation of biaryls previously inaccessible via decarboxylative methods and holds other advantages over existing decarboxylative oxidative couplings, as stoichiometric transition metals are avoided.
- Perry, Gregory J. P.,Quibell, Jacob M.,Panigrahi, Adyasha,Larrosa, Igor
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supporting information
p. 11527 - 11536
(2017/08/30)
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- A method of preparing alkoxyl monoiodo-benzene
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The invention relates to a method for preparing alkoxy iodobenzene. The method comprises the following steps: adding alkoxy benzene, I2, the catalyst nitrosonium tetrafluoroborate and an organic solvent into a reaction vessel, sealing the reaction vessel, performing a magnetic stirring reaction at the temperature of 20-60 DEG C under an airy condition, cooling to the room temperature after reaction, and performing purification on the mixture after reaction through column chromatography, so as to obtain the alkoxy iodobenzene. According to the method for preparing the alkoxy iodobenzene, any other auxiliary reagent is not added expect the catalyst and the solvent, used auxiliary material is less, the utilization rate of the iodine material under the optimum condition is high, the product purity is good, the reaction can be effectively performed at the room temperature, the production cost is remarkably reduced, and as acid is not added in the reaction system, the cost of production equipment can be lowered.
- -
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Paragraph 0045; 0046
(2016/10/31)
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- LAT-1 activity of meta-substituted phenylalanine and tyrosine analogs
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The transporter protein Large-neutral Amino Acid Transporter 1 (LAT-1, SLC7A5) is responsible for transporting amino acids such as tyrosine and phenylalanine as well as thyroid hormones, and it has been exploited as a drug delivery mechanism. Recently its role in cancer has become increasingly appreciated, as it has been found to be up-regulated in many different tumor types, and its expression levels have been correlated with prognosis. Substitution at the meta position of aromatic amino acids has been reported to increase affinity for LAT-1; however, the SAR for this position has not previously been explored. Guided by newly refined computational models of the binding site, we hypothesized that groups capable of filling a hydrophobic pocket would increase binding to LAT-1, resulting in improved substrates relative to parent amino acid. Tyrosine and phenylalanine analogs substituted at the meta position with halogens, alkyl and aryl groups were synthesized and tested in cis-inhibition and trans-stimulation cell assays to determine activity. Contrary to our initial hypothesis we found that lipophilicity was correlated with diminished substrate activity and increased inhibition of the transporter. The synthesis and SAR of meta-substituted phenylalanine and tyrosine analogs is described.
- Augustyn, Evan,Finke, Karissa,Zur, Arik A.,Hansen, Logan,Heeren, Nathan,Chien, Huan-Chieh,Lin, Lawrence,Giacomini, Kathleen M.,Colas, Claire,Schlessinger, Avner,Thomas, Allen A.
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supporting information
p. 2616 - 2621
(2016/05/09)
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- Selective Halogenation Using an Aniline Catalyst
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Electrophilic halogenation is used to produce a wide variety of halogenated compounds. Previously reported methods have been developed mainly using a reagent-based approach. Unfortunately, a suitable "catalytic" process for halogen transfer reactions has yet to be achieved. In this study, arylamines have been found to generate an N-halo arylamine intermediate, which acts as a highly reactive but selective catalytic electrophilic halogen source. A wide variety of heteroaromatic and aromatic compounds are halogenated using commercially available N-halosuccinimides, for example, NCS, NBS, and NIS, with good to excellent yields and with very high selectivity. In the case of unactivated double bonds, allylic chlorides are obtained under chlorination conditions, whereas bromocyclization occurs for polyolefin. The reactivity of the catalyst can be tuned by varying the electronic properties of the arene moiety of catalyst.
- Samanta, Ramesh C.,Yamamoto, Hisashi
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supporting information
p. 11976 - 11979
(2015/08/18)
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- Gold(I)-catalyzed iodination of arenes
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A wide variety of electron-rich arenes were efficiently converted into the corresponding iodinated compounds via a gold(I)-catalyzed reaction under mild conditions. Georg Thieme Verlag Stuttgart. New York.
- Leboeuf, David,Ciesielski, Jennifer,Frontier, Alison J.
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supporting information
p. 399 - 402
(2014/03/21)
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- Selective reductive cleavage of inert aryl C-O bonds by an iron catalyst
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Breaking point: An effective reductive cleavage of inert aryl C-O bonds with an inexpensive iron catalyst has been developed. During this process, the reduction of the arene rings was not observed. This catalytic system also enabled the selective cleavage of the β-O-4 linkage of lignin model compounds under an atmosphere of hydrogen, thus offering an opportunity for the depolymerization of lignin. Copyright
- Ren, Yunlai,Yan, Mengjie,Wang, Jianji,Zhang, Z. Conrad,Yao, Kaisheng
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supporting information
p. 12674 - 12678
(2013/12/04)
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- Nitrogen dioxide-catalyzed electrophilic iodination of arenes
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Nitrogen dioxide is demonstrated to be an effective catalyst precursor for the iodination of alkoxy-substituted benzenes and naphthalenes. Different from the transition metal catalysts, nitrogen dioxide can be easily separated from the final products, and is free of heavy metal waste. Although the present catalyst precursor is toxic, it does not stain the final products due to its low-boiling character. No other reagents apart from 0.5 equiv. of iodine (I 2), 6.5 mol% nitrogen dioxide and acetonitrile solvent were used in the iodination, and basically all the iodine atoms in the iodine source were transferred to the iodination products, showing that the presented protocol is highly atom-economic and practical. Copyright
- Ren, Yun-Lai,Shang, Huantao,Wang, Jianji,Tian, Xinzhe,Zhao, Shuang,Wang, Qian,Li, Fuwei
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supporting information
p. 3437 - 3442
(2013/12/04)
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- Regioselective iodination of aromatic compounds with potassium iodide in the presence of benzyltriphenylphosphonium perchlorate
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A simple and efficient method for the selective iodination of various aromatic compounds by using potassium iodide in the presence of benzyltriphenylphosphonium perchlorate, is reported. This method provides several advantages such as good selectivity between ortho and para positions of aromatic compounds and high yields of the products.
- Albadi, Jalal,Abedini, Masoumeh,Iravani, Nasir
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experimental part
p. 261 - 264
(2012/05/07)
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- Palladium-catalyzed intermolecular C(sp3)-H amidation
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Dual capacity: A new palladium-catalyzed intermolecular sequence consisting of the C-H activation and amidation of methyl groups relies on N-fluorobis(phenylsulfonyl)imide (NFSI) as both the oxidant and the nitrogen source. The reaction provides the corresponding arylamines as bissulfonimides along with HF as the only by-product. Both experimental and computational results suggest the involvement of a monomeric palladium(IV) intermediate. Copyright
- Iglesias, Alvaro,Alvarez, Rosana,De-Lera, Angel R.,Muniz, Kilian
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supporting information; experimental part
p. 2225 - 2228
(2012/04/10)
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- Environmental friendly method for the iodination of moderately active arenes
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An effective and environmental friendly method for the iodination of various moderately active methoxy arenes, phenols and anilines using hydrogen peroxide and acidified sodium periodate in aqueous ethanol medium is reported. The extent of iodination is e
- Sathiyapriya
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experimental part
p. 41 - 43
(2011/11/13)
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- METHOD OF PRODUCING IODIZING AGENT, AND METHOD OF PRODUCING AROMATIC IODINE COMPOUND
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A method of the present invention, for producing an iodizing agent, includes the step of electrolyzing iodine molecules in a solution by using an acid as a supporting electrolyte. This realizes (i) a method of producing an iodine cation suitable for use as an iodizing agent that does not require a sophisticated separation operation after iodizing reaction is completed, and (ii) an electrolyte used in the method. Further, a method of the present invention, for producing an aromatic iodine compound, includes the step of causing an iodizing agent, and an aromatic compound whose nucleus has one or more substituent groups and two or more hydrogen atoms, to react with each other under the presence of a certain ether compound. This realizes such a method of producing an aromatic iodine compound that position selectivity in iodizing reaction of an aromatic compound is improved.
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Page/Page column 12
(2010/05/13)
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- Practical electrochemical iodination of aromatic compounds
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A practical method for electrochemical iodination of aromatic compounds was developed. The method involves the generation of I+ by electrochemical oxidation of I2 in CH3CN using H 2SO4 as supporting electrolyte followed by the reaction with aromatic compounds. The para/ortho selectivity for the reaction of mono-substituted benzenes was significantly improved using dimethoxyethane as cosolvent in the second step. The reaction with highly reactive aromatic compounds led to the formation of significant amounts of diiodo compounds in a macrobatch reactor. This problem was solved by fast 1:1 mixing of I+ with an aromatic compound using a microflow system consisting of a T-shaped micromixer and a microtube reactor.
- Kataoka, Kazuhide,Hagiwara, Yuji,Midorikawa, Koji,Suga, Seiji,Yoshida, Jun-Ichi
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p. 1130 - 1136
(2013/01/03)
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- One-pot preparation of arylalkynes by a tandem catalytic iodination of arenes and palladium-catalyzed coupling of iodoarenes with terminal alkynes
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Iodination of activated arenes by air-oxidation is carried out in the presence of catalytic bismuth salts at room temperature. Subsequently, the formed iodoarenes react with terminal alkynes to give arylalkynes under a selected palladium-catalyzed coupling condition in the same pot.
- Wan, Shun,Wang, Sunewang R.,Lu, Wenjun
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p. 4349 - 4352
(2007/10/03)
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- Regioselective iodination of activated arenes using phenyl trimethylammonium dichloroiodate in ionic liquid under microwave irradiation
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The regioselective iodination of activated arenes has been achieved in the presence of phenyltrimethylammonium dichloroiodate and ionic liquid. The reaction has been carried out by both conventional heating as well as by microwave irradiation. Copyright Taylor & Francis, Inc.
- Tilve, Rutuja D.,Kanetkar, Vinod R.
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p. 1313 - 1318
(2007/10/03)
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- Effective and regioselective iodination of arenes using iron(III) nitrate in the presence of tungstophosphoric acid
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An easy, cheap, and effective method for iodination of various aromatic compounds takes place with molecular iodine and iron nitrate nonahydrate as the oxidant in the presence of a catalytic amount of tungstophosphoric acid in dichloromethane, with good yield and high regioselectivity under very mild conditions.
- Jafarzadeh, Mohammad,Amani, Kamal,Nikpour, Farzad
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p. 1808 - 1811
(2007/10/03)
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- Selective para-iodination of methoxyarenes, phenols, and anilines with iodine in the presence of poly (4-vinylpyridine)-supported peroxodisulfate
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A mild and efficient method for the direct iodination of methoxyarenes, phenols, and anilines using iodine and poly (4-vinylpyridine)-supported peroxodisulfate in acetonitrile solution, is presented. Selective para-substitution and also, the rather general applicability of this system is the advantage of the method.
- Tajik, Hassan,Mohammadpoor-Baltork, Iraj,Rasht-Abadi, Hassan Rafiee
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p. 3579 - 3585
(2007/10/03)
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- Iodination of aromatic compounds with iodine and n-butyltriphenylphosphonium peroxodisulfate
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Iodine and n-butyltriphenylphosphonium peroxodisulfate can be successfully used for the iodination of some aromatic compounds in acetonitrile as solvent. The yields obtained are good to excellent.
- Tajik,Esmaeili,Mohammadpoor-Baltork,Ershadi,Tajmehri
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p. 1319 - 1323
(2007/10/03)
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- Direct and regioselective iodination and bromination of benzene, naphthalene and other activated aromatic compounds using iodine and bromine
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Direct and regioselective iodination and bromination of benzene, naphthalene and other activated aromatic compounds with iodine and bromine or their sodium salts proceed well in the presence of Fe(NO3) 3·1.5N2O4/charcoal in CH 2Cl2 at room temperature.
- Firouzabadi,Iranpoor,Shiri
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p. 8781 - 8785
(2007/10/03)
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- Solvent-Free Iodination of Arenes at Room Temperature
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Silica supported bismuth(III)nitrate pentahydrate [BNP-SiO2] was prepared under simple co-grinding condition. The iodination of aromatic compounds using BNP-SiO2 and molecular iodine under solvent-free conditions is described. The reaction occurred in the solid state at room temperature, yielding the corresponding mono-iodo derivative in good yields. However, less activated aromatics required longer reaction time with comparatively less yield.
- Alexander, Varughese M.,Khandekar, Amit C.,Samant, Shriniwas D.
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p. 1895 - 1897
(2007/10/03)
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- Iodination of activated arenes using silfen: An improved protocol
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A simple and direct method for the iodination of activated arenes, using molecular iodine and silfen (silica supported ferric nitrate nonahydrate) as an oxidant, is presented. The reactions are performed at 20°C in dichloromethane. The method provides an easy access to the corresponding iodinated products in good yields. The observed orientation effects are in agreement with those based on general aromatic electrophilic substitution theory.
- Tilve, Rutuja D.,Alexander, Varughese M.,Khadilkar, Bhushan M.
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p. 9457 - 9459
(2007/10/03)
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- Mild and regioselective iodination of electron-rich aromatics with N-iodosuccinimide and catalytic trifluoroacetic acid
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A variety of aromatics compounds substituted with methoxy or methyl groups were regioselectively iodinated with N-iodosuccinimide and catalytic trifluoroacetic acid with excellent yields under mild conditions and short reaction times.
- Castanet, Anne-Sophie,Colobert, Fran?oise,Broutin, Pierre-Emmanuel
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p. 5047 - 5048
(2007/10/03)
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- Mild and regiospecific nuclear iodination of methoxybenzenes and naphthalenes with N-iodosuccinimide in acetonitrile
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A wide range of methoxy substituted benzenes and naphthalenes were regiospecifically iodinated at para position with N-iodosuccinimide in acetonitrile under mild conditions in excellent yields. Methylanisoles afforded only nuclear iodination products.
- Carreno, M. Carmen,Garcia Ruano, Jose L.,Sanz, Gema,Toledo, Miguel A.,Urbano, Antonio
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p. 4081 - 4084
(2007/10/03)
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- Iodination of Methylated Anisoles: Unusual Aryl Methyl Replacement and Oxidations
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The treatment of methylated anisoles with iodine, periodic acid, sulfuric acid, and aqueous acetic acid has resulted in iododemethylations and/or aryl methyl oxidations in addition to the expected mono- and diiodinations of the aromatic ring.Four dimethylanisoles and o-methylanisole were treated under identical conditions.Iododemethylations were observed in three of the four dimethylanisoles and aryl methyl oxidations to benzaldehydes occured with o-methylanisole and two of the dimethylanisoles.No precedence could be found for either of these reactions under the experimental conditions employed.Several possible mechanisms are discussed for these transformations.Some experimental evidence suggests that methyl oxidation to a benzaldehyde could be a prerequisite for an iododemethylation via an iodonium ion-assisted reverse Gatterman-Koch reaction; single-electron-transfer or classical electrophilic mechanisms are also consistent with the iododemethylations.
- Panetta, Charles A.,Fang, Zheng,Mattern, Daniell L.
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p. 7953 - 7958
(2007/10/03)
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- Iodination of alkyl aryl ethers by mercury(II) oxide-iodine reagent in dichloromethane
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A convenient method for selective mono- and diiodination of alkyl aryl ethers by mercury(II) oxide-iodine reagent in dichloromethane is reported.
- Orito,Hatakeyama,Takeo,Suginome
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p. 1273 - 1277
(2007/10/02)
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- Direct Iodination of Aromatic Compounds with Iodine and Alumina-Suppored Copper(II) Chloride or Sulfate
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The iodination of aromatic compounds (polymethylbenzenes, alkyl phenyl ethers, and polynuclear aromatic hydrocarbons) with iodine in combination with copper(II) chloride or sulfate supported on alumina proceeds well under mild conditions to selectively gi
- Kodomari, Mitsuo,Amanokura, Natsuki,Takeuchi, Kiyoshi,Yoshitomi, Suehiko
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p. 306 - 308
(2007/10/02)
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- Iodination of Aromatic Ethers by Use of Benzyltrimethylammonium Dichloroiodate and Zinc Chloride
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The reaction of aromatic ethers with benzyltrimethylammonium dichloroiodate(1-) in acetic acid in the presence of zinc chloride at room temperature gave iodo-substituted aromatic ethers in good yields.
- Kajigaeshi, Shoji,Kakinami, Takaaki,Moriwaki, Masayuki,Watanabe, Masakazu,Fujisaki, Shizuo,Okamoto, Tsuyoshi
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p. 795 - 798
(2007/10/02)
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- Electron Transfer Mechanism for Periodic Acid Oxidation of Aromatic Substrates
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Evidence for the involvement of cation radicals during the periodic acid oxidation of aromatic substrates like hydrocarbons, phenolic ethers, phenols etc. has been presented.
- Bhatt, M. V.,Hosur, B. M.
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p. 1004 - 1005
(2007/10/02)
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- Ambident Reactivity of Anisole and p-Iodoanisole toward Phenylium Cations and Evidence for ipso-Attack in Cationic Phenylation
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The phenylation of p-iodoanisole from the thermolysis of benzenediazonium tetrafluoroborate affords, among other products, 4-methoxybiphenyl and 4-iododiphenyl ether, providing evidence for the occurrence of ipso-attack and attack on oxygen by C6H5+.In the case of anisole, the oxygen atom of the methoxy-substituent is also attacked by C6H5+ giving rise to diphenyl ether via the initial formation of diphenylmethyloxonium ion followed by intermolecular demethylation.We have demonstrated that no intramolecular rearrangement occurs with the oxonium ion.The results are consistent with a mechanism involving kinetically predominant C-phenylation of both substrates.Boron trifluoride (a Schiemann reaction product) promotes deiodination of p-iodoanisole and its phenylated isomers.This deiodination invalidates the conclusions drawn from isomeric distributions; therefore the presence of BF3 must be carafully controlled in a mechanistic study.
- Eustathopoulos, Helene,Court, Jean,Bonnier, Jane-Marie
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p. 803 - 808
(2007/10/02)
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