- Generation of Dimethyl Sulfoxide Coordinated Thermally Stable Halogen Cation Pools for C?H Halogenation
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A method to generate halogen cation pools from the reaction of 1,2-dihaloethanes (hal=Br, I) and dimethyl sulfoxide (DMSO) for C?H halogenation of arenes and heteroarenes was reported. The initial reaction of DMSO and 1,2-dihaloethane generates the sulfur
- Dalai, Pallaba Ganjan,Palit, Kuntal,Panda, Niranjan
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supporting information
p. 1031 - 1038
(2022/02/02)
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- One-Pot Synthesis of N-Iodo Sulfoximines from Sulfides
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This is the first report on the synthesis and characterization of N-iodo sulfoximines. The synthesis was designed as a room temperature one-pot cascade reaction from readily available sulfides as starting compounds, converted into sulfoximines by reaction with ammonium carbonate and (diacetoxyiodo)benzene, followed by iodination with N-iodosuccinimide or iodine in situ, in up to 90% isolated yields, also at a multigram scale. Iodination of aryls with N-iodo sulfoximines, oxidation, and conversion to N-SCF3 congeners have been demonstrated.
- Zupanc, An?e,Jereb, Marjan
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p. 5991 - 6000
(2021/05/05)
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- Oxidative azidations of phenols and ketones using iodine azide after release from an ion exchange resin
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The oxidative oligoazidation of phenols and ketones using iodine azide (IN3) provided by its release from an ion exchange resin is reported. Preliminary mechanistic studies indicate a previously unknown reactivity of iodine azide toward phenols and ketones.
- K?sel, Teresa,Dr?ger, Gerald,Kirschning, Andreas
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supporting information
p. 2907 - 2911
(2021/04/14)
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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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- Iodination of industrially important aromatic compounds with aqueous potassium triiodide
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A new reagent system consisting of aqueous KI3in AcOH and NaIO4as oxidant has been found to be effective in iodinating a variety of commercially important aromatic substrates under ambient conditions. The presence of Na2SO3enhances the yield and the product purity. The procedure ensures high yields (72–98%) at room temperature in a short reaction time. A remarkable feature of this system is that even acidsensitive functionalities like anilines can be iodinated quantitatively.
- Sharma,Srivastava,Agarwal,Diwedi
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p. 433 - 436
(2016/06/13)
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- Synthesis of (-)-Piperitylmagnolol Featuring ortho-Selective Deiodination and Pd-Catalyzed Allylation
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A 1,4-addition strategy using an enone and a copper reagent was studied for the synthesis of (-)-piperitylmagnolol. A MOM-protected biphenol copper reagent was added to BF3·OEt2-activated 4-isopropylcyclohexenone, whereas 1,4-addition of protected monophenol reagents possessing an allyl group was found to be unsuccessful. The allyl group was later attached to the p-,p′-diiodo-biphenol ring by Pd-catalyzed coupling with allylborate. The aforementioned iodide was synthesized using a new method for ortho-selective deiodination of o-,p-diiodophenols.
- Ikoma, Atsushi,Ogawa, Narihito,Kondo, Daiki,Kawada, Hiroki,Kobayashi, Yuichi
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supporting information
p. 2074 - 2077
(2016/06/01)
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- Ultrasound-promoted rapid and efficient iodination of aromatic and heteroaromatic compounds in the presence of iodine and hydrogen peroxide in water
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A rapid and efficient ultrasound-promoted protocol for iodination of aromatic and heteroaromatic compounds, using molecular iodine in the presence of aqueous hydrogen peroxide in water without any cosolvent, has produced versatile iodinated organic molecules with potential application in organic synthesis and medicine in short reaction times and good to excellent yields. Copyright
- Ferreira, Irlon M.,Casagrande, Gleison A.,Pizzuti, Lucas,Raminelli, Cristiano
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supporting information
p. 2094 - 2102
(2014/07/07)
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- Fast halogenation of some N-heterocycles by means of N,N'-dihalo-5,5- dimethylhydantoin
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An instantaneous, selective and high-yielding halogenation process is reported. The method operates with imidazoles, pyrazoles, and indoles under benign reaction conditions. The developed process involves the use of N,N'-dihalo-5,5-dimethylhydantoins (halo=chlorine, bromine, iodine) as halogenation reagents that are activated by catalytic quantities of a strong Bronsted acid. Moreover, the halogenation process is switchable to produce either the mono- or di-halogenated products. Issues related to the reaction mechanism are investigated and a proposal for a reaction mechanism is disclosed.
- Sandtorv, Alexander H.,Bjorsvik, Hans-Rene
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p. 499 - 507
(2013/05/08)
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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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- Efficient and eco-friendly synthesis of iodinated aromatic building blocks promoted by iodine and hydrogen peroxide in water: A mechanistic investigation by mass spectrometry
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The reaction of aromatic and heteroaromatic compounds with molecular iodine in the presence of aqueous hydrogen peroxide using water without any co-solvent at 50 °C for 24 h produced versatile iodinated organic molecules with potential application in organic synthesis and medicine in very good yields. In addition, a mechanistic investigation for the iodination process was carried out by mass spectrometry.
- Gallo, Rafael D.C.,Ferreira, Irlon M.,Casagrande, Gleison A.,Pizzuti, Lucas,Oliveira-Silva, Diogo,Raminelli, Cristiano
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p. 5372 - 5375
(2012/10/29)
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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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- 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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- Direct green iodination of phenol over solid acids
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Examination of several solid acid catalysts of different nature (acid resins, zeolites, mixed oxides, Nb-oxide, and Nb-phosphate) was performed for the direct iodination reaction of phenol by using molecular iodine. The experiments were carried out in mil
- Carniti, Paolo,Colonna, Stefano,Gervasini, Antonella
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scheme or table
p. 55 - 62
(2010/09/05)
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- Ecofriendly iodination of activated aromatics and coumarins using potassium iodide and ammonium peroxodisulfate
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An environmentally benign protocol for the iodination of activated aromatics, such as phenols, anilines, and hydroxycou-marins, using inexpensive commercially available potassium iodide and ammonium peroxodisulfate (1:2.5 molar equivalents per mole of substrate) in aqueous methanol (MeOH-H 2O, 6:1) at room temperature has been developed. The protocol provides for ortho-selective monoiodination as the predominant product without added acid and it is compatible with a number of common oxidizible functional groups, such as formyl, benzylic C-H, aromatic amines and hydroxymethyl. Good to acceptable yields of monoiodinated products in acceptable reaction times and exclusive ortho-iodination for 7-hydroxycoumarins, despite the presence of vinylogous electronrich C3, are some of the key advantageous features of the method. Georg Thieme Verlag Stuttgart.
- Ganguly, Nemai C.,Barik, Sujoy Kumar,Dutta, Sanjoy
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experimental part
p. 1467 - 1472
(2010/09/16)
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- Regioselective synthesis of phenols and halophenols from arylboronie acids using solid poly(N-vinylpyrrolidone)/hydrogen peroxide and poly(4-vinylpyridine) /hydrogen peroxide complexes
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Solid hydrogen peroxide complexes based on poly(N-vinylpyrrolidone) and poly(4-vinylpyridine) were prepared and used as solid hydroxylating reagents. These solid hydrogen peroxide equivalents are found to be much safer, convenient and efficient reagent systems for the ipso-hydroxylation of arylboronie acids to the corresponding phenols in high yields at a faster rate. The versatility of the reagents has been further expanded for the one-pot synthesis of halophenols. Density functional theory calculations were carried out on hydrogen peroxide complexes of N-ethylpyrrolidone and 4-ethylpyridine as models to get a better understanding of structure and behavior of hydrogen peroxide complexes of the polymers poly(N-vinylpyrrolidone) and poly(4-vinylpyridine) compared to aqueous hydrogen peroxide.
- Prakash, G. K. Surya,Chacko, Sujith,Panja, Chiradeep,Thomas, Tisa Elizabeth,Gurung, Laxman,Rasul, Golam,Mathew, Thomas,Olah, George A.
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experimental part
p. 1567 - 1574
(2011/02/25)
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- Process for the iodination of aromatic compounds
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The present invention relates to a process for the preparation of iodinated phenols; in particular, it relates to a process including the electrochemical iodination of 3,5-disubstituted phenols of formula (1) to the corresponding 3,5-disubstituted-2,4,6-triiodophenols of formula (2), which are useful intermediates for the synthesis of x-ray contrast media, and to the preparation of the contrast media themselves.
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Page/Page column 10
(2009/09/07)
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- Regioselective iodination of phenol and analogues using N-iodosuccinimide and p-toluenesulfonic acid
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Mild and highly regioselective monoiodination of phenol and analogues is achieved in high to excellent yields at room temperature with a combination of stoichiometric p-toluenesulfonic acid and N-iodosuccinimide.
- Bovonsombat, Pakorn,Leykajarakul, Juthamard,Khan, Chiraphorn,Pla-on, Kawin,Krause, Michael M.,Khanthapura, Pratheep,Ali, Rameez,Doowa, Niran
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scheme or table
p. 2664 - 2667
(2009/08/09)
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- IBX-I2 redox couple for facile generation of IOH and I +: Expedient protocol for iodohydroxylation of olefins and iodination of aromatics
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(Chemical Equation Presented) IBX is readily reduced to IBAin the presence of molecular iodine in DMSO to generate hypoiodous acid (IOH), which reacts with a variety of olefins as well as R, β-unsaturated ketones leading to their respective iodohydrins with anti stereochemistry. The same redox chemistry in acetonitrile containing TFA produces iodonium ions for facile iodination of a variety of aromatic compounds in respectable isolated yields.
- Moorthy, Jarugu Narasimha,Senapati, Kalyan,Kumar, Sarvesh
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supporting information; experimental part
p. 6287 - 6290
(2009/12/08)
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- Mild and efficient iodination of aromatic and heterocyclic compounds with the NaClO2/NaI/HCl system
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NaClO2/NaI in the presence of HCl is a mild, cheap, and non-toxic reagent for the iodination of phenols, including estradiol and naphthol, aromatic amines, and heterocyclic substrates, e.g., indoles, 8-hydroxyquinoline, imidazole, in fair to excellent yields by a very simple isolation protocol. The scope of the procedure is exemplified by the first iodination of 5-nitroindole to 3-iodo-5-nitroindole in 75% yield.
- Lista, Liliana,Pezzella, Alessandro,Napolitano, Alessandra,d'Ischia, Marco
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p. 234 - 239
(2008/09/16)
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- 1,3-Diiodo-5,5-dimethylhydantoin-An efficient reagent for iodination of aromatic compounds
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1,3-Diiodo-5,5-dimethylhydantoin in organic solvents successfully iodinates alkylbenzenes, aromatic amines, and phenyl ethers. The reactivity of electrophilic iodine is controlled by acidity of the medium. Superelectrophilic iodine generated upon dissolution of 1,3-diiodo-5,5-dimethylhydantoin in sulfuric acid readily reacts with electron-deficient arenes at 0 to 20°C with formation of the corresponding iodo derivatives in good yields. The structure of electrophilic iodine species generated from 1,3-diiodo-5,5- dimethylhydantoin in sulfuric acid is discussed.
- Chaikovskii,Filimonov,Funk,Skorokhodov,Ogorodnikov
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p. 1291 - 1296
(2008/03/27)
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- NaIO4/KI/NaCl: a new reagent system for iodination of activated aromatics through in situ generation of iodine monochloride
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A new reagent system consisting of NaIO4/KI/NaCl in aq AcOH has been found to be effective in iodinating a variety of activated aromatic substrates via in situ-generated iodine monochloride, to furnish iodoaromatics in excellent yields. This iodination procedure has been applied successfully for a cost-effective synthesis of 3,3′-diaminobenzidine, a key intermediate for preparing proton conducting membranes for fuel cell applications, with high yield and a purity of 99.7%.
- Emmanuvel, Lourdusamy,Shukla, Ravi Kant,Sudalai, Arumugam,Gurunath, Suryavanshi,Sivaram, Swaminathan
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p. 4793 - 4796
(2007/10/03)
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- Catalysis and regioselectivity of the aqueous Heck reaction by Pd(0) nanoparticles under ultrasonic irradiation
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An aqueous Heck reaction carried out under ultrasonic irradiation at the ambient temperature (25 °C) has been shown in this study to afford high yields of corresponding products. It was found that as a catalyst for the reaction palladium forms nanoparticles in-situ, characterized by transmission electron microscopy (TEM) and X-ray powder diffraction (XRD) analyses, and can be recycled. Furthermore, the Heck reaction under such mild and environmentally friendly conditions offers excellent regioselectivity of para-over ortho-substitution in phenyl iodides especially with electron-donating groups.
- Zhang, Zuhui,Zha, Zhenggen,Gan, Changsheng,Pan, Chongfeng,Zhou, Yuqing,Wang, Zhiyong,Zhou, Ming-Ming
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p. 4339 - 4342
(2007/10/03)
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- Comparative study of the reactivity of iodinating agents in solution and solid phase
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The results of reactions of a series of aromatic substrates with iodine, iodine(I) chloride, and N-iodosuccinimide in solution and solid phase were compared for the first time. In all cases, the general relations holding in the iodination process were similar. Iodine(I) chloride was found to chlorinate anthracene. A high efficiency of solid-phase iodination of β-diketones was demonstrated using dibenzoylmethane as an example.
- Krasnokutskaya,Lesina,Gorlushko,Filimonov
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p. 855 - 859
(2007/10/03)
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- A new, environment friendly protocol for iodination of electron-rich aromatic compounds
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A new environment friendly procedure for effective aromatic iodination is presented. A mixture of potassium iodide and potassium iodate is used in the presence of an acid for in situ iodination of aromatic compounds.
- Adimurthy, Subbarayappa,Ramachandraiah, Gadde,Ghosh, Pushpito K.,Bedekar, Ashutosh V.
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p. 5099 - 5101
(2007/10/03)
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- 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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p. 5287 - 5291
(2007/10/02)
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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 by Use of Benzyltrimethylammonium Dichloroiodate(1-)
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The reaction of phenols with benzyltrimethylammonium dichloroiodate(1-) in dichloromethane-methanol in the presence of CaCO3 or NaHCO3 for several hours at room temperature gave iodophenols in good yields.
- Kajigaeshi, Shoji,Kakinami, Takaaki,Yamasaki, Hiromichi,Fujisaki, Shizuo,Kondo, Manabu,Okamoto, Tsuyoshi
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p. 2109 - 2112
(2007/10/02)
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- Process for preparing and therapeutical applications of the "2,4,6-triiodophenol"
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Pharmaceutical compositions containing 2,4,6-triiodophenol are useful for treating a variety of medical conditions, for example, atherosclerosis.
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