- Generation of Organozinc Reagents from Arylsulfonium Salts Using a Nickel Catalyst and Zinc Dust
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Readily available aryldimethylsulfonium triflates react with zinc powder under nickel catalysis via the selective cleavage of the sp2-hybridized carbon-sulfur bond to produce salt-free arylzinc triflates under mild conditions. This zincation displays superb chemoselectivity and thus represents a protocol that is complementary or orthogonal to existing methods. The generated arylzinc reagents show both high reactivity and chemoselectivity in palladium-catalyzed and copper-mediated cross-coupling reactions.
- Yamada, Kodai,Yanagi, Tomoyuki,Yorimitsu, Hideki
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p. 9712 - 9718
(2021/01/09)
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- Selective Vicinal Diiodination of Polycyclic Aromatic Hydrocarbons
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Vicinally diiodinated polycyclic aromatic hydrocarbons (I2-PAHs) are accessible from the corresponding diborylated B2-PAHs through boron/iodine exchange. The B2-PAHs have been prepared via twofold electrophilic borylation reactions templated by a vicinally disilylated benzene. Our protocol is applicable to fluorenes, acenes, annulated acenes, oligoaryls, and even [5]helicene. Using B2-naphthalene as the example, we have shown that the reaction scope can, in principle, be expanded to include the synthesis of vicinally dibrominated and dihydroxylated PAHs. The usefulness of the building blocks provided by our method in the field of optoelectronic materials was demonstrated by the successful conversion of I2-fluoranthene to the analogous doubly alkynylated fluoranthene emitter.
- Bolte, Michael,Jin, Tao,John, Alexandra,Kaehler, Tanja,Lerner, Hans-Wolfram,Wagner, Matthias
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supporting information
p. 5847 - 5851
(2020/09/09)
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- Direct Transformation of Arylamines to Aryl Halides via Sodium Nitrite and N-Halosuccinimide
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A one-pot universal approach for transforming arylamines to aryl halides via reaction with sodium nitrite (NaNO2) and N-halosuccinimide (NXS) in DMF at room temperature under metal- and acid-free condition is described. This new protocol that is complementary to the Sandmeyer reaction, is suggested to involve the in situ generation of nitryl halide induce nitrosylation of aryl amine to form the diazo intermediate which is halogenated to furnish the aryl halide.
- Mukhopadhyay, Sushobhan,Batra, Sanjay
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supporting information
p. 14622 - 14626
(2018/09/21)
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- Tetraflic acid (1,1,2,2-Tetrafluoroethanesulfonic acid, HC 2F4SO3H) and gallium tetraflate as effective catalysts in organic synthesis
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Tetraflic acid offers ample acidity for various organic reactions that require high acidity. Its gallium(III) salt is an efficient catalyst under mild condtions for synthetic transformations such as the ketonic Strecker reaction for the synthesis of fluorinated α-amino nitriles and condensation- cyclzation reactions using suitable fluoro ketones and 1,2-disubstituted benzenes for the direct preparation of 5-membered or 6-membered fluorinated heterocycles. Copyright
- Prakash, G. K. Surya,Mathew, Thomas,Panja, Chiradeep,Kulkarni, Aditya,Olah, George A.,Harmer, Mark A.
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p. 2163 - 2171
(2012/11/07)
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- Aryne Insertion into I-I σ-Bonds
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A new protocol for the efficient synthesis of o-diiodoarenes has been developed. This method allows the synthesis of substituted and polycyclic o-diiodoarenes, which are difficult to obtain by classical methods. This diiodination process involves the formal insertion of arynes into the I-I σ-bond.
- Rodriguez-Lojo, Diego,Cobas, Agustin,Pena, Diego,Perez, Dolores,Guitian, Enrique
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supporting information; experimental part
p. 1363 - 1365
(2012/05/20)
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- Superelectrophilic iodination of deactivated arenes with triiodoisocyanuric acid
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The reaction of triiodoisocyanuric acid (TICA) with deactivated arenes in acidic medium led to the efficient and regioselective formation of the corresponding iodoarenes, in 55-88% isolated yield. The acidity of the medium was found to be the most important factor influencing the electrophilic iodination of weakly nucleophilic substrates by TICA. Georg Thieme Verlag Stuttgart New York.
- Da Ribeiro, Rodrigo S.,Esteves, Pierre M.,De Mattos, Marcio C. S.
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experimental part
p. 739 - 744
(2011/04/24)
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- PROCESS FOR PREPARING IODINATED AROMATIC COMPOUNDS
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The present invention relates to a process for preparing iodinated aromatic compounds. Particularly, the present invention comprises the step of performing the iodination of a non-halogenated aromatic compound, a monoiodo aromatic compound, a diiodo aromatic compound, and iodine in the presence of a zeolite catalyst under oxygen atmosphere. In the process for preparing iodinated aromatic compounds according to the present invention, an iodination and an iodine conversion simultaneously occur, and then prevent side-reactions. Also, the lifetime of an iodination catalyst used therein can be extended by controlling the reaction temperature stably. Therefore, the process can be used for mass production of diiodo compound.
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Page/Page column 5
(2011/10/13)
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- Metal-free efficient, general and facile iododecarboxylation method with biodegradable co-products
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The development of a novel, efficient and robust method for the general conversion of aliphatic and aromatic carboxylic acids to organic iodides without the use of heavy metals or strong oxidizing agents is reported. Commercially available N-iodoamides were used for both initiation and halogen donation under irradiative conditions. Isolation of the product is extremely simple and the major co-product is removed as a water-soluble biodegradable material. Copyright
- Kulbitski, Kseniya,Nisnevich, Gennady,Gandelman, Mark
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supporting information; experimental part
p. 1438 - 1442
(2011/07/30)
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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 11
(2010/05/13)
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- METHOD OF PREPARING IODINATED AROMATIC COMPOUNDS
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The present invention relates to a method of preparing iodinated aromatic compounds, and more preferably a method of preparing iodinated aromatic compounds comprising a step of iodinating a react ant including an aromatic compound, a di-iodo aromatic compound or water, and iodine (I2) in the presence of a zeolite catalyst and oxygen. The method of the present invention has an advantage that by iodination of a reactant including the aromatic compound, and the di~ iodo aromatic compound or water in the presence of the zeolite catalyst and oxygen, the temperature of the iodinating reactor can be controlled reliably and constantly, thereby resulting in improved productivity per unit weight of catalyst and inhibition of a side reaction in accordance with suppression of producing impurities. In addition, the productivity of the iodinated aromatic compound, preferably the di-iodo aromatic compound, more preferably a p-di-iodo aromatic compound can be improved, and thus can be widely used in the preparation of a di-iodo aromatic compound such as a p-di-iodo aromatic compound.
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Page/Page column 17-18; 19
(2009/07/18)
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- MANUFACTURING PROCESS FOR IODINATED AROMATIC COMPOUNDS
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Disclosed is a method for preparing an iodinated aromatic compound. More specifically, disclosed is a method of preparing an iodinated aromatic compound by iodinating an aromatic compound in the presence of oxygen over a zeolite catalyst, in which the aromatic compound and its monoiodo compound, as raw materials, are allowed to react with iodine. In comparison with a method in which only the aromatic compound is used as a raw material without adding the monoiodo compound, the disclosed method can increase the productivity of diiodo compounds and the selectivity to a p-diiodo compound and, at the same time, suppress side reactions, thus lengthening the life span of the catalyst.
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Page/Page column 9
(2009/05/30)
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- A concise synthesis of ortho-iodobenzyl alcohols via addition of ortho-Iodophenyl grignard reagent to aldehydes and ketones
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A wide range of both secondary and tertiary ortho-iodobenzyl alcohols was synthesized via addition of ortho-iodophenyl Grignard reagents to aldehydes and ketones. Significant improvements in terms of yields were observed with ketones upon addition of CeCl3. The potential application of the target compounds as precursors for novel electrophilic trifluoromethylating reagents based on hypervalent iodine derivatives was demonstrated. Georg Thieme Verlag Stuttgart.
- Cvengro, Alcohols Jan,Stolz, Daniel,Togni, Antonio
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experimental part
p. 2818 - 2824
(2010/01/21)
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- Direct synthesis of iodoarenes from aromatic substrates using molecular iodine
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Easy laboratory procedures for oxidative iodination of aromatic substrates are presented. One procedure includes the iodination using molecular iodine, concentrated sulfuric acid, and potassium peroxodisulfate, and another uses a reagent system containing molecular iodine, potassium peroxodisulfate, and trifluoroacetic acid. These procedures are especially effective for benzene and less deactivated aromatic substrates, such as halobenzenes, trifluoromethylbenzene, and benzoic acid. Georg Thieme Verlag Stuttgart.
- Hossain, Md. Delwar,Oyamada, Juzo,Kitamura, Tsugio
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p. 690 - 692
(2008/09/21)
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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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- 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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- N-halosuccinimide/BF3-H2O, efficient electrophilic halogenating systems for aromatics
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N-Halosuccinimides (NXS, 1) are efficiently activated in trifluoromethanesulfonic acid and BF3-H2O, allowing the halogenations of deactivated aromatics. Because BF3-H2O is more economic, easy to prepare, nonoxidizing, and offers sufficiently high acidity (-H0 ≈ 12, only slightly lower than that of trifluoromethanesulfonic acid), an efficient new electrophilic reagent combination of NXS/BF3-H2O has been developed. DFT calculations at the B3LYP/6-311++G**//B3LYP/6-31G* level suggest that protonated N-halosuccinimides undergo further protosolvation at higher acidities to reactive superelectrophilic species capable either in the transfer of X+ from the protonated forms of NXS to the aromatic substrate or in forming a highly reactive and solvated X+ which would readily react with the aromatic substrates. Structural aspects of the BF 3-H2O complex have also been investigated.
- Prakash, G. K. Surya,Mathew, Thomas,Hoole, Dushyanthi,Esteves, Pierre M.,Wang, Qi,Rasul, Golam,Olah, George A.
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p. 15770 - 15776
(2007/10/03)
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- One-pot oxidation of azomethine compounds into arenecarboxylic acids
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Aromatic azomethine compounds, such as aldazines 1, aldoximes 7 and tosylhydrazones 8 oxidized with 30% hydrogen peroxide in the presence of poly(bis-1,2-phenylene) diselenide (6) as catalyst produce arenecarboxylic acids 2 mostly in high to excellent yields. The presented one-pot procedure has a synthetic value.
- Giurg,Said,Syper,Mlochowski
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p. 3151 - 3159
(2007/10/03)
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- A new approach to dihydrobenzofurans and dihydrobenzopyrans (chromans) based on the intramolecular trapping by alcohols of benzynes generated from 7-substituted-1-aminobenzotriazoles
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1-Aminobenzotriazoles 9 having 7-hydroxyalkyl substituents are efficiently convened into the corresponding benzynes 4 when treated with N- iodosuccinimide which then undergo highly efficient intramolecular trapping by the pendant hydroxyl groups leading to dihydrobenzofurans 24-26 and dihydrobenzopyrans (chromans) 27, with incorporation of a synthetically useful iodine atom adjacent to the new ether bond, which allows subsequent and high-yielding homologations using Stille, Sonogashira and Heck couplings. (C) 2000 Elsevier Science Ltd.
- Birkett, Michael A.,Knight, David W.,Little, Paul B.,Mitchell, Michael B.
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p. 1013 - 1023
(2007/10/03)
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- Consecutive cross-coupling of o-phenylenedizinc compound with acyl and/or aryl halides in the presence of Pd(0)-tris(2,4,6- trimethoxyphenyl)phosphine
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Consecutive cross-coupling of an o-phenylenedizinc compound 1 with two different acyl or aryl halides or acyl and aryl halides was accomplished in one pot by the catalysis of Pd(0)-tris(2,4,6-trimethoxyphenyl)phosphine to yield a variety of functionalized unsymmetrical 1,2-disubstituted benzenes in good yields. (C) 2000 Elsevier Science Ltd.
- Saiga, Akihiro,Hossain, Kabir M.,Takagi, Kentaro
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p. 4629 - 4632
(2007/10/03)
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- Kinetics of aromatic iodination reactions using iodine, diiodine pentoxide and sulfuric acid in acetic acid
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Kinetic studies of an aromatic iodination reaction using benzene or acetanilide, iodine, diiodine pentoxide and sulfuric acid in glacial acetic acid have been carried out. The reaction, followed using FT-Raman spectroscopy to monitor the disappearance of the aromatic over time, exhibits fractional order dependence in benzene but first order dependence in acetanilide. The difference in order between the two aromatics indicates that benzene participates in an equilibrium reaction before the rate limiting step of the reaction. This reversible step is proposed to be the reversible formation of a π-complex between adsorbed I2 and benzene as it adsorbs onto I2O5. Based on the calculated order, acetanilide most likely does not form a π-complex with adsorbed I2, rather it reacts from solution to form a σ-complex with activated I2 on the I2O5 surface. In both reactions, it is proposed that the rate limiting step is the formation of the σ-complex.
- Brazdil, Linda C.,Fitch, Jill L.,Cutler, Carlo J.,Haynik, Denise M.,Ace, Eryn R.
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p. 933 - 936
(2007/10/03)
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- Polyiodination on benzene at room temperature. A regioselective synthesis of derivatives
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Reaction of IPy2BF4 with benzene and CF3SO3H in CH2Cl2 gives regioselectively polyiodinated compounds at room temperature, providing a definitely easy synthetic entry to those rarely accessible benzene derivatives.
- Barluenga,Gonzalez,Garcia-Martin,Campos
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p. 3893 - 3896
(2007/10/02)
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- A Novel Aromatic Iodination Method Using F2
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A new method for direct aromatic iodination with IF, made in situ from the corresponding elements, is described.Depending on the reaction time and temperature, mono- or polyiodination can be achieved.Even deactivated aromatic rings can be directly iodinated without the presence of any Friedel-Crafts catalyst.Sensitive groups such as aromatic aldehydes are not affected by the reagent.
- Rozen, Shlomo,Zamir, Dov
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p. 3552 - 3555
(2007/10/02)
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- STOICHIOMETRIC AND CATALYTIC OXIDATIVE IODINATION OF AROMATIC COMPOUNDS IN THE PRESENCE OF NITROGEN-CONTAINING OXIDIZING AGENTS IN AQUEOUS TRIFLUOROACETIC ACID
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The conditions for oxidative monoiodination of benzene, halogenobenzenes, toluene, halogenotoluenes, and p-toluic acid in solvents based on trifluoroacetic acid were studied.Yields of the respective iodoarenes close to quantitative were obtained in systems containing 10-20 vol. percent of water in the solvent with equimolar amounts of alkali-metal metal iodides in relation to the substrate in the presence of stoichiometric (under anaerobic conditions) or catalytic (in the presence of oxygen or air) amounts of alkali-metal nitrates.The analogous reactions with nitrites can only be conducted under aerobic conditions.These iodinating systems are compared with systems based on acetic acid containing iodine and mixtures of sulfuric and nitric acids.The conditions for the iodination of toluene and for the transformations of the obtained iodotoluenes in the presence of nitrogen-containing oxidizing agents in trifluoroacetic acid solutions were studied in detail.It was shown that p-iodotoluene undergoes ipso-nitrodeiodination to a significant degree under these conditions.It is supposed that the iodinating agent in the investigated systems is trifluoroacetyl hypoiodite.Data on the assignment of the PMR spectra of the synthesized isomeric nitroiodotoluenes and chloroiodotoluenes by a simple additive method are given.
- Makhon'kov, D. I.,Cheprakov, A. V.,Beletskaya, I. P.
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p. 2029 - 2035
(2007/10/02)
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- Vapour-phase Chemistry of Arenes. Part 13. Reactivity and Selectivity in the Gas-phase Reactions of Hydroxyl Radicals with Monosubstituted Benzenes at 563 K
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The reactions of hydroxyl radicals with benzene derivates C6H5Z (Z = H, Me, F, Cl, Br, I, CF3, or CN) have been studied in a flow reactor at 563 K in nitrogen, using the thermolysis of ButOOH as a source of .OH.Under these conditions there are two product-forming pathways.The major one involves hydrogen abstraction to give aryl radicals ZC6H4. (II) as the first step; depending on Z, its displacement to form phenol may also occur.Relative rates for hydrogen abstraction were determined in competition experiments using side-chain hydrogen abstraction from added toluene as a reference.This resulted in the order (for Z =): 1,8(Me), 1.0(H), 0.47(F), 0.29(Cl), 0.34(CF3), 0.20(CN), consonant with the electrophilic nature of .OH.The site selectivity of hydrogen abstractions was determined by scavenging part of the aryl radicals (II) with iodine.A Hammett plot, using ? constants for meta and para positions, led to ρ -1.0.The features of hydrogen abstraction by .OH are discussed and compared with those for the analogous reaction of Cl.The formation of phenol was found to decrease in importance in the order F, Cl, Br, and I.This result is rationalized on a thermochemical kinetic basis.
- Mulder, Peter,Louw, Robert
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p. 1167 - 1174
(2007/10/02)
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- OXIDATION BY THE SALTS OF METALS. VI. OXIDATIVE IODINATION OF AROMATIC SUBSTRATES, PROMOTED BY Co(III), Mn(III), AND Ce(IV) COMPOUNDS IN AQUEOUS TRIFLUOROACETIC ACID
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The direct iodination of benzene, halogenobenzenes, and p-methoxycarbonyltoluene in trifluoroacetic acid and its aqueous solutions with iodine or alkali-metal iodides was studied in the presence of Co(III) and Mn(III) acetates and ammonium cerium(IV) sulfate, which make it possible to obtain the respective iodoarenes with high yields under mild conditions.In the case of toluene the reaction is complicated by the formation of α-oxidation products.It is assumed that the iodinating agent is trifluoroacetyl hypoiodite, formed as a result of the oxidation of the iodine by the salt of the metal having variable valence.The highest yields of the iodoarenes were obtained with 90percent aqueous trifluoroacetic acid.
- Makhon'kov, D. I.,Cheprakov, A. V.,Rodkin, M. A.,Beletskaya, I. P.
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p. 1003 - 1006
(2007/10/02)
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- Iodination of Benzene with Iodine and Metal Salts in Acidic Solvents
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Iodobenzene was obtained by a reaction of benzene with molecular iodine in trifluoromethanesulfonic acid in oxygen atmosphere in the presence of vanadium salt as a catalyst.The method affords a new aromatic iodination process in which benzene is iodinated directly with molecular iodine.
- Shimizu, Atsushi,Yamataka, Kazunori,Isoya, Toshiro
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p. 1611 - 1612
(2007/10/02)
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- AROMATIC IODINATION WITH ALUMINUM AND COPPER (II) CHLORIDES AND IODINE
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Aryl iodides have been synthesized by a simple reaction of aromatic compounds with iodine and an equimolecular mixture of aluminum and copper(II) chlorides.The reaction is widely capable of application, especially to liquid aromatic substrates, with fair to excellent yields.
- Sugita, Toshio,Idei, Mitsushige,Ishibashi, Yoshiyuki,Takegami, Yoshinobu
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p. 1481 - 1484
(2007/10/02)
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- Iodination process
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A decarboxylation process for substituting iodine atoms for silver carboxylate radicals which comprises reacting the silver salts of carboxylic acids with iodine under decarboxylation conditions.
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