- An Efficient and Selective Method for the Preparation of Iodophenols
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Direct iodination of a wide range of phenols may be achieved with unprecedented selectivity in aqueous alcohol solvents by the action of a reagent preparated in situ from sodium hypochlorite and sodium iodide.Para-substituted phenols (or ortho-substituted, when the para-position is already occupied) are obtained in fair to excellent yields by simple isolation techniques.The extent of iodination is easily controlled by stoichiometry.The technique is also useful with some anilines.
- Edgar, Kevin J.,Falling, Stephen N.
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- A green catalytic method for selective synthesis of iodophenols via aerobic oxyiodination under organic solvent-free conditions
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A highly efficient catalytic method for aerobic oxyiodination of various phenols catalysed by copper(II) nitrate was achieved under mild conditions using I2as an iodinating reagent, molecular oxygen as an oxidant, and water as a solvent. The catalyst shows not only high activity for phenols with either electron-donating or electron-withdrawing groups, but also a remarkable selectivity for the formation of para-iodo substituted phenols. This study offers a green method for iodination of aromatic phenols with high atom economy.
- Xin, Hongchuan,Hu, Liangning,Yu, Jianqiang,Sun, Wenshou,An, Zengjian
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- Oxidative and non-oxidative metabolism of 4-iodoanisole by rat liver microsomes
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1. The oxidative metabolism of 4-iodoanisole (1) by liver microsomes from β-naphthoflavone-treated rats yields 4-iodophenol (2) 2-iodo-5-methoxyphenol (3), 2-methoxy-5-iodophenol (4), 4-methoxyphenol (5), and 3-methoxyphenol (6) in relative yields of 5:2:
- Rizk,Hanzlik
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- Iodine(III)-Mediated, Controlled Di- or Monoiodination of Phenols
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An oxidative procedure for the electrophilic iodination of phenols was developed by using iodosylbenzene as a nontoxic iodine(III)-based oxidant and ammonium iodide as a cheap iodine atom source. A totally controlled monoiodination was achieved by buffering the reaction medium with K3PO4. This protocol proceeds with short reaction times, at mild temperatures, in an open flask, and generally with high yields. Gram-scale reactions, as well as the scope of this protocol, were explored with electron-rich and electron-poor phenols as well as heterocycles. Quantum chemistry calculations revealed PhII(OH)·NH3 to be the most plausible iodinating active species as a reactive "I+" synthon. In light of the relevance of the iodoarene moiety, we present herein a practical, efficient, and simple procedure with a broad functional group scope that allows access to the iodoarene core unit.
- Satkar, Yuvraj,Yera-Ledesma, Luisa F.,Mali, Narendra,Patil, Dipak,Segura-Quezada, Luis A.,Ramírez-Morales, Perla I.,Solorio-Alvarado, César R.,Navarro-Santos, Pedro
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p. 4149 - 4164
(2019/04/30)
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- 4,5-Dimethyl-2-Iodoxybenzenesulfonic Acid Catalyzed Site-Selective Oxidation of 2-Substituted Phenols to 1,2-Quinols
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A site-selective hydroxylative dearomatization of 2-substituted phenols to either 1,2-benzoquinols or their cyclodimers, catalyzed by 4,5-dimethyl-2-iodoxybenzenesulfonic acid with Oxone, has been developed. Natural products such as biscarvacrol and lacinilene C methyl ether could be synthesized efficiently under mild reaction conditions. Furthermore, both the reaction rate and site selectivity could be further improved by the introduction of a trialkylsilylmethyl substituent at the 2-position of phenols. The corresponding 1,2-quinols could be transformed into various useful structural motifs by [4+2] cycloaddition cascade reactions.
- Uyanik, Muhammet,Mutsuga, Tatsuya,Ishihara, Kazuaki
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supporting information
p. 3956 - 3960
(2017/03/27)
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- Iodide/tert-Butyl Hydroperoxide-Mediated Benzylic C–H Sulfonylation and Peroxidation of Phenol Derivatives
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We disclose here the first iodine/tert-butyl hydroperoxide (I2/TBHP)-mediated benzylic C–H sulfonylation of phenol derivatives. This new methodology provides an economic, operationally simple and metal-free approach toward C(sp3)–S bond formation with medium to excellent yields at room temperature. Moreover, a novel sulfonylative and peroxidative bifunctionalization of phenol derivatives was also achieved by changing the amount of the oxidant. The reaction mechanism is exemplified via a radical pathway. (Figure presented.).
- Yang, Wen-Chao,Dai, Peng,Luo, Kai,Wu, Lei
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p. 3184 - 3190
(2016/10/20)
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- Efficient and Practical Oxidative Bromination and Iodination of Arenes and Heteroarenes with DMSO and Hydrogen Halide: A Mild Protocol for Late-Stage Functionalization
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An efficient and practical system for inexpensive bromination and iodination of arenes as well as heteroarenes by using readily available dimethyl sulfoxide (DMSO) and HX (X = Br, I) reagents is reported. This mild oxidative system demonstrates a versatile protocol for the synthesis of aryl halides. HX (X = Br, I) are employed as halogenating reagents when combined with DMSO which participates in the present chemistry as a mild and inexpensive oxidant. This oxidative system is amenable to late-stage bromination of natural products. The kilogram-scale experiment (>95% yield) shows great potential for industrial application.
- Song, Song,Sun, Xiang,Li, Xinwei,Yuan, Yizhi,Jiao, Ning
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supporting information
p. 2886 - 2889
(2015/06/30)
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- Synthesis, optical power limiting, and DFT calculations of triplet-triplet absorption of three novel Pt(II)-diacetylide chromophores
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Three novel rod-like Pt(II)-diacetylides have been synthesized. When subjected to intense laser light, all three compounds showed strong optical power limiting at 532 and 600 nm. DFT calculated triplet-triplet electronic excitations were found to correlate with the nonlinear absorption.
- Kindahl, Tomas,?hgren, Johan,Lopes, Cesar,Eliasson, Bertil
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supporting information
p. 2403 - 2408
(2013/06/26)
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- Gas-Chromatographic identifi cation of products formed in iodination of methyl phenols by retention indices
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Iodination reaction followed by conversion of iodine-substituted methylphenols to the corresponding trifl uoroacetates was suggested for improving the sensitivity of the gas-chromatographic determination of phenol and its methyl-substituted derivatives (al isomers of mono- and diethylphenols, 2,3,5-, 2,3,6-, and 3,4,5-trimethylphenols) in aqueous media. Acylation products of iodo methylphenols (104 compounds) were identifi ed by linear-logarithmic retention indices on a standard nonpolar polydimethylsiloxane stationary phase, and the pattern of their variation with the number and nature of substituents were characterized. A procedure for identifi cation of methyl-substituted phenols in water in their gas-chromatographic determination with an electron-capture detector was developed. Pleiades Publishing, Ltd., 2012.
- Gruzdev,Kuzivanov,Zenkevich,Kondratenok
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p. 1355 - 1365
(2013/01/15)
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- Synthesis, characterization, X-ray structural analysis, and iodination ability of benzyl(triphenyl)phosphonium dichloroiodate
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Benzyl(triphenyl)phosphonium dichloroiodate (BTPPICl2), BnPh3P+(ICl2)-, is easily synthesized in a nearly quantitative yield by the addition of BnPh 3P+Cl- to a CH2Cl2 solution of iodine monochloride (ICl). BnPh3P+Cl - can be prepared by the reaction of Ph3P and BnCl. The compound was characterized by physicochemical and spectroscopic methods (elemental analysis, FT-IR, and 1H-NMR). The use of phosphonium counterion improves the quality of the BTPPICl2 crystals. BTPPICl2 crystallizes in the monoclinic system, and its crystal and molecular structure has been determined at 100(1) K by X-ray diffraction. The structure was solved by the direct method and had refined R value of 0.0637 for 699 reflections (I>2σ(I)), space group P21/n with a=12.4700(3), b=13.2196(3), c=14.4580(3) A, β=102.6340(10)°, V=2325.67(9) A3, and Z=4. The I-atom is coordinated by two Cl-atoms as ligands in a linear geometry. This compound is a versatile reagent for the efficient and selective iodination of organic substrates, in particular of aromatic phenols to the corresponding iodo compounds, under mild conditions. To assess the generality of method, a wide variety of phenols with electron-donating and electron-withdrawing substituents were studied. BTPPICl2 is a mild iodination reagent, which offers a new avenue for an expeditious iodination of phenols. The inexpensive, relatively non-toxic reagent, and mild conditions are the positive features of the procedure and reagent. Copyright
- Imanieh, Hossein,Ghammamy, Shahriar,Nikje, Mir Mohammad Alavi,Hosseini, Farhang,Aghbolagh, Zahra Shokri,Fun, Hoong-Kun,Khavasi, Hamid Reza,Kia, Reza
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experimental part
p. 2248 - 2255
(2012/01/12)
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- Iodination of anilines and phenols with 18-crown-6 supported ICl 2-
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A highly crystalline iodinating reagent, {[K·18-C-6]ICl 2}n, was synthesized in high yield (93%). The trihalide is supported by an 18-crown-6 macrocycle and forms a coordination polymer in the solid state. This reagent iodinates anilines and phenols efficiently under mild conditions. Controlled mono-iodination with anilines was easily achieved while poly-iodination was observed with phenols.
- Mbatia, Hannah W.,Ulloa, Olbelina A.,Kennedy, Daniel P.,Incarvito, Christopher D.,Burdette, Shawn C.
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experimental part
p. 2987 - 2991
(2011/06/16)
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- HIO4/Al2O3 as a new system for iodination of activated aromatics and 1,3-dicarbonyl compounds
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The use of a periodic acid/alumina system for the iodination of activated aromatics and 1,3-dicarbonyl compounds is described.
- Khalilzadeh, Mohammad A.,Hosseini, Abolfazl,Shokrollahzadeh, Mojtaba,Halvagar, Mohammad R.,Ahmadi, Daryoush,Mohannazadeh, Farajollah,Tajbakhsh, Mahmoud
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p. 3525 - 3528
(2007/10/03)
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- Replacement of the N-terminal tyrosine residue in opioid peptides with 3-(2,6-dimethyl-4-carbamoylphenyl)propanoic acid (Dcp) results in novel opioid antagonists
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3-(2,6-Dimethyl-4-carbamoylphenyl)propanoic acid (Dcp), a 2′,6′-dimethyltyrosine analogue containing a carbamoyl group in place of the hydroxyl function and lacking the amino group, was synthesized. The replacement of Tyr1 in an enkephalin analogue and in dynorphin A(1-11)-NH2 with Dcp resulted in the first opioid peptide-derived antagonists that do not contain a phenolic hydroxyl group at the 1-position residue. The cyclic peptide Dcp-c[D-Cys-Gly-Phe(pNO2)-D-Cys]NH 2 represents a novel, potent μ opioid antagonist.
- Lu, Yixin,Lum, Tze Keong,Augustine, Yoon Wui Leow,Weltrowska, Grazyna,Nguyen, Thi M.-D.,Lemieux, Carole,Chung, Nga N.,Schiller, Peter W.
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p. 5382 - 5385
(2007/10/03)
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- Highly selective iodination of phenols using potassium iodide and benzyltriphenylphosphonium peroxymonosulfate
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An easy and selective method for monoiodination of phenols using potassium iodide in the presence of benzyltriphenylphosphonium peroxymonosulfate is presented. The reactions have been carried out in acetonitrile to afford the corresponding iodophenols in
- Hajipour, Abdol Reza,Adibi, Hadi
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p. 294 - 295
(2007/10/03)
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- Influence de la complexation sur la reactivite de nitrates d'halogenes
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Iodine nitrate or bromine nitrate in acetonitrile or in chloroform react with a variety of phenolic substrates to form both halogenated and nitrated products.In the presence of strong complexing agents of halonium ions, no reacting occurs, while in the presence of pyridine or triethylamine, only halogenated phenols exhibiting a strong ortho-directing effect of the phenolic function are produced. Keywords: phenols, iodine nitrate, bromine nitrate, halogenation, nitration.
- Gaude, Didier,Gellon, Gisele,Goaller, Raymond Le,Pierre, Jean-Louis
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p. 104 - 108
(2007/10/02)
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- IODINATION OF PHENOLS USING CHLORAMINE T AND SODIUM IODIDE
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A convenient procedure for the iodination of many substituted phenols uses chloramine T and sodium iodide in DMF, DMSO, or acetonitrile.
- Kometani, Tadashi,Watt, David S.,Ji, Tae
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p. 2043 - 2046
(2007/10/02)
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- Experiments Directed Towards the Synthesis of Anthracyclinones. VII. Model Studies with Allyl Naphthalenyl Ethers
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The Claisen rearrangement of some allyl naphthalen-1-yl ethers has been examined, together with methods for modification of the resulting 2-allyl side chain.Isomerisation of the C-allyl substituent to a prop-1-enyl group followed by ozonolysis gives a formyl derivative, while ozonolysis of a 2-(2-methylprop-2-enyl) moiety or mercuriation of a 2-(-2-chloroprop-2-enyl) substituent leads to an acetonyl derivative.Treatment of phenols with iodine(I) acetate and an excess of silver(I) acetate gives 4-hydroxyaryl acetates, probably via dienone intermediates.
- Boddy, Ian K.,Cambie, Richard C.,Dixon, Graham,Rutledge, Peter S.,Woodgate, Paul D.
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p. 803 - 813
(2007/10/02)
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