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Transition-Metal-Free Coupling of Polyfluorinated Arenes and Functionalized, Masked Aryl Nucleophiles
A chemoselective C(sp2)?C(sp2) coupling of sufficiently electron-deficient fluorinated arenes and functionalized N-aryl-N’-silyldiazenes as masked aryl nucleophiles is reported. The fluoride-promoted transformation involves the in situ generation of the aryl nucleophile decorated with various sensitive functional groups followed by a stepwise nucleophilic aromatic substitution (SNAr). These reactions typically proceed at room temperature within minutes. This catalytic process allows for the functionalization of both coupling partners, furnishing highly fluorinated biaryls in good yields.
Finck, Lucie,Oestreich, Martin
p. 11061 - 11064
(2021/06/12)

Orthogonal Stability and Reactivity of Aryl Germanes Enables Rapid and Selective (Multi)Halogenations
While halogenation is of key importance in synthesis and radioimaging, the currently available repertoire is largely designed to introduce a single halogen per molecule. This report makes the selective introduction of several different halogens accessible. Showcased here is the privileged stability of nontoxic aryl germanes under harsh fluorination conditions (that allow selective fluorination in their presence), while displaying superior reactivity and functional-group tolerance in electrophilic iodinations and brominations, outcompeting silanes or boronic esters under rapid and additive-free conditions. Mechanistic experiments and computational studies suggest a concerted electrophilic aromatic substitution as the underlying mechanism.
Deckers, Kristina,Fricke, Christoph,Schoenebeck, Franziska
supporting information
p. 18717 - 18722
(2020/08/25)

Boosting Low-Valent Aluminum(I) Reactivity with a Potassium Reagent
The reagent RK [R=CH(SiMe3)2 or N(SiMe3)2] was expected to react with the low-valent (DIPPBDI)Al (DIPPBDI=HC[C(Me)N(DIPP)]2, DIPP=2,6-iPr-phenyl) to give [(DIPPBDI)AlR]?K+. However, deprotonation of the Me group in the ligand backbone was observed and [H2C=C(N-DIPP)?C(H)=C(Me)?N?DIPP]Al?K+ (1) crystallized as a bright-yellow product (73 %). Like most anionic AlI complexes, 1 forms a dimer in which formally negatively charged Al centers are bridged by K+ ions, showing strong K+???DIPP interactions. The rather short Al–K bonds [3.499(1)–3.588(1) ?] indicate tight bonding of the dimer. According to DOSY NMR analysis, 1 is dimeric in C6H6 and monomeric in THF, but slowly reacts with both solvents. In reaction with C6H6, two C?H bond activations are observed and a product with a para-phenylene moiety was exclusively isolated. DFT calculations confirm that the Al center in 1 is more reactive than that in (DIPPBDI)Al. Calculations show that both AlI and K+ work in concert and determines the reactivity of 1.
Eyselein, Jonathan,F?rber, Christian,Grams, Samuel,Harder, Sjoerd,Langer, Jens
supporting information
p. 15982 - 15986
(2020/07/04)

Synthesis, structure, and synthetic potential of arenediazonium trifluoromethanesulfonates as stable and safe diazonium salts
Aromatic diazonium salts are valuable building blocks for organic synthesis; however, in most cases, they are unstable, unsafe, poorly soluble, and/or expensive. In this paper, we have shown that a variety of stable and safe arenediazonium triflates ArN2+ TfO– can be obtained easily and in high yields by diazotization of anilines with tert-butyl nitrite in the presence of trifluoromethanesulfonic acid. Arenediazonium triflates are relatively shelf-stable in the dry state. They dissolve well in water, as well as polar and even nonpolar organic solvents. Less than 800 J/g of energy is released during the thermal decomposition of these salts, which indicates their explosion safety. Arenediazonium triflates have a high reactivity in the known reactions of diazonium chemistry, and undergo an unusual metal-free chlorodediazonization reaction with chloroform and CCl4.
Filimonov, Victor D.,Krasnokutskaya, Elena A.,Kassanova, Assia Zh.,Fedorova, Valentina A.,Stankevich, Ksenia S.,Naumov, Nikolay G.,Bondarev, Alexander A.,Kataeva, Veronika A.
p. 665 - 674
(2018/09/14)

Metathesis-active ligands enable a catalytic functional group metathesis between aroyl chlorides and aryl iodides
Current methods for functional group interconversion have, for the most part, relied on relatively strong driving forces which often require highly reactive reagents to generate irreversibly a desired product in high yield and selectivity. These approaches generally prevent the use of the same catalytic strategy to perform the reverse reaction. Here we describe a catalytic functional group metathesis approach to interconvert, under CO-free conditions, two synthetically important classes of electrophiles that are often employed in the preparation of pharmaceuticals and agrochemicals—aroyl chlorides (ArCOCl) and aryl iodides (ArI). Our reaction design relies on the implementation of a key reversible ligand C–P bond cleavage event, which enables a non-innocent, metathesis-active phosphine ligand to mediate a rapid aryl group transfer between the two different electrophiles. Beyond enabling a practical and safer approach to the interconversion of ArCOCl and ArI, this type of ligand non-innocence provides a blueprint for the development of a broad range of functional group metathesis reactions employing synthetically relevant aryl electrophiles.
Lee, Yong Ho,Morandi, Bill
p. 1016 - 1022
(2018/09/06)

Functional Group Transposition: A Palladium-Catalyzed Metathesis of Ar-X σ-Bonds and Acid Chloride Synthesis
We describe the development of a new method to use palladium catalysis to form functionalized aromatics: via the metathesis of covalent σ-bonds between Ar-X fragments. This transformation demonstrates the dynamic nature of palladium-based oxidative addition/reductive elimination and offers a straightforward approach to incorporate reactive functional groups into aryl halides through exchange reactions. The reaction has been exploited to assemble acid chlorides without the use of high energy halogenating or toxic reagents and, instead, via the metathesis of aryl iodides with other acid chlorides.
De La Higuera Macias, Maximiliano,Arndtsen, Bruce A.
supporting information
p. 10140 - 10144
(2018/08/23)

An efficient gram scale synthesis of aryl iodides from aryl diazofluoroborates in water under mild conditions
Transition metal-free synthesis of synthetically valuable aryl iodides from aryl diazofluroborates in water under mild conditions has been described. Majority of synthesized aryl iodides are obtained in quantitative yields (>99%) under present reaction conditions. The structural effects due to the substituents present on aryl diazofluoroborates did not show any satisfactory effect on the yields of the aryl iodides. Hence, the methodology presented here was found to be adventitious for the quantitative production of synthetically valuable aryl iodides.
Gholap, Somnath S.
p. 594 - 599
(2018/06/26)

A general electrochemical strategy for the Sandmeyer reaction
Herein we report a general electrochemical strategy for the Sandmeyer reaction. Using electricity as the driving force, this protocol employs a simple and inexpensive halogen source, such as NBS, CBrCl3, CH2I2, CCl4, LiCl and NaBr for the halogenation of aryl diazonium salts. In addition, we found that these electrochemical reactions could be performed using anilines as the starting material in a one-pot fashion. Furthermore, the practicality of this process was demonstrated in the multigram scale synthesis of aryl halides using highly inexpensive graphite as the electrode. A series of detailed mechanism studies have been performed, including radical clock and radical scavenger study, cyclic voltammetry analysis and in situ electron paramagnetic resonance (EPR) analysis.
Liu, Qianyi,Sun, Beiqi,Liu, Zheng,Kao, Yi,Dong, Bo-Wei,Jiang, Shang-Da,Li, Feng,Liu, Guoquan,Yang, Yang,Mo, Fanyang
p. 8731 - 8737
(2018/12/10)

Visible-Light-Induced Decarboxylative Iodination of Aromatic Carboxylic Acids
A convenient, efficient and practical visible-light-induced decarboxylative iodination of aromatic carboxylic acids has been developed, and the corresponding aryl iodides were obtained in good yields. The method shows some advantages including the use of readily available aromatic carboxylic acids as the starting materials, simple and mild conditions, high efficiency, wide substrate scope and tolerance of various functional groups.
Jiang, Min,Yang, Haijun,Jin, Yunhe,Ou, Lunyu,Fu, Hua
supporting information
p. 1572 - 1577
(2018/06/26)

Copper-catalysed aromatic-Finkelstein reactions with amine-based ligand systems
A new efficient and low-cost ligand, diethylenetriamine, has been utilised to promote the iodination of 16 different bromo-substrates via the copper catalysed Finkelstein halogen exchange reaction under mild conditions. In contrast to earlier methods, the use of inert atmosphere conditions was not required to obtain high yields and purity. Studies on the speciation of the catalyst in solution indicate rapid disproportionation of copper(i) in the presence of diethylenetriamine to give copper(0) and a bis-ligated copper(ii) complex which is characterised by X-ray diffraction. This copper(ii) complex was also shown to be catalytically active in the halogen exchange reaction. In contrast, no significant disproportionation was observed using dimethylethylenediamine as the ligand, and the solid-state structures of a copper(i) dimeric complex and a 2D polymeric network of copper(i) iodide tetramers are reported. The catalytic activity of diethylenetriamine and dimethylethylenediamine with both copper(i) and copper(ii) salts are compared, and possible mechanistic implications discussed.
Jin, Xiaodong,Davies, Robert P.
p. 2110 - 2117
(2017/07/22)

Oligo p-Phenylenevinylene Derivatives as Electron Transfer Matrices for UV-MALDI
Phenylenevinylene oligomers (PVs) have outstanding photophysical characteristics for applications in the growing field of organic electronics. Yet, PVs are also versatile molecules, the optical and physicochemical properties of which can be tuned by manipulation of their structure. We report the synthesis, photophysical, and MS characterization of eight PV derivatives with potential value as electron transfer (ET) matrices for UV-MALDI. UV-vis analysis show the presence of strong characteristic absorption bands in the UV region and molar absorptivities at 355 nm similar or higher than those of traditional proton (CHCA) and ET (DCTB) MALDI matrices. Most of the PVs exhibit non-radiative quantum yields (φ) above 0.5, indicating favorable thermal decay. Ionization potential values (IP) for PVs, calculated by the Electron Propagator Theory (EPT), range from 6.88 to 7.96 eV, making these oligomers good candidates as matrices for ET ionization. LDI analysis of PVs shows only the presence of radical cations (M+.) in positive ion mode and absence of clusters, adducts, or protonated species; in addition, M+. threshold energies for PVs are lower than for DCTB. We also tested the performance of four selected PVs as ET MALDI matrices for analytes ranging from porphyrins and phthalocyanines to polyaromatic compounds. Two of the four PVs show S/N enhancement of 1961% to 304% in comparison to LDI, and laser energy thresholds from 0.17 μJ to 0.47 μJ compared to 0.58 μJ for DCTB. The use of PV matrices also results in lower LODs (low fmol range) whereas LDI LODs range from pmol to nmol. [Figure not available: see fulltext.].
Castellanos-García, Laura J.,Agudelo, Brian Castro,Rosales, Hernando F.,Cely, Melissa,Ochoa-Puentes, Christian,Blanco-Tirado, Cristian,Sierra, Cesar A.,Combariza, Marianny Y.
p. 2548 - 2560
(2017/12/12)

Simple and Efficient Generation of Aryl Radicals from Aryl Triflates: Synthesis of Aryl Boronates and Aryl Iodides at Room Temperature
Despite the wide use of aryl radicals in organic synthesis, current methods to prepare them from aryl halides, carboxylic acids, boronic acids, and diazonium salts suffer from limitations. Aryl triflates, easily obtained from phenols, are promising aryl radical progenitors but remain elusive in this regard. Inspired by the single electron transfer process for aryl halides to access aryl radicals, we developed a simple and efficient protocol to convert aryl triflates to aryl radicals. Our success lies in exploiting sodium iodide as the soft electron donor assisted by light. This strategy enables the scalable synthesis of two types of important organic molecules, i.e., aryl boronates and aryl iodides, in good to high yields, with broad functional group compatibility in a transition-metal-free manner at room temperature. This protocol is anticipated to find potential applications in other aryl-radical-involved reactions by using aryl triflates as aryl radical precursors.
Liu, Wenbo,Yang, Xiaobo,Gao, Yang,Li, Chao-Jun
supporting information
p. 8621 - 8627
(2017/07/06)

Green preparation technique of 1,4-diiodo-benzene
The invention relates to a green preparation technique of 1,4-diiodo-benzene. The technique comprises the following steps: carrying out electrophilic substitution reaction on a simple substance iodine and aniline in a weakly alkaline medium solution, separating, and drying to obtain a paraiodoaniline crude product; carrying out diazo-reaction on the paraiodoaniline crude product and a sodium nitrate solution to prepare a diazonium salt, and removing excess sodium nitrate in the system; adding chloroform and a potassium iodide solution into the reaction system, reacting for 3-6 hours while keeping the temperature at -5 to -10 DEG C, slowly heating to room temperature, continuing reacting for 2-6 hours, and carrying out separation and purification on the reaction product to obtain the 1,4-diiodo-benzene. The technique has the advantage of high product purity, and obviously lowers the production cost. The technique implements comprehensive utilization of the potassium iodide waste solution resources, thereby lowering the production cost. The technique simplifies the operation engineering, and enhances the yield of the product.
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Paragraph 0032; 0034

(2016/10/24)

Facile Separation of Regioisomeric Compounds by a Heteronuclear Organometallic Capsule
Owing to the often-similar physical and chemical properties of structural isomers of organic molecules, large efforts have been made to develop efficient strategies to isolate specific isomers. However, facile separation of regioisomeric compounds remains difficult. Here we demonstrate a universal organometallic capsule in which two silver centers are rigidly separated from each other by two tetranuclear [Rh4] pyramidal frustums, which selectively encapsulate a specific isomer from mixtures. Not only is the present heterometallic capsule suitable as a host for the encapsulation of a series of aromatic compounds, but also the receptor shows widely differing specificity for the various isomers. Direct experimental evidence is provided for the selective encapsulation of a series of para (p)-disubstituted benzene derivatives, such as p-xylene, p-dichlorobenzene, p-dibromobenzene, and p-diiodobenzene. The size and shape matching, as well as the Ag-π interactions, are the main forces governing the extent of molecular recognition. The encapsulated guest p-xylene can be released by using the solid-liquid solvent washing strategy, and the other guest molecules are easily liberated by using light stimulus.
Zhang, Wen-Ying,Lin, Yue-Jian,Han, Ying-Feng,Jin, Guo-Xin
p. 10700 - 10707
(2016/09/04)

Photo-induced Metal-Catalyst-Free Aromatic Finkelstein Reaction
The facile iodination of aromatic compounds under mild conditions is a great challenge for both organic and medicinal chemistry. Particularly, the synthesis of functionalized aryl iodides by light has long been considered impossible due to their photo-lability, which actually makes aryl iodides popular starting materials in many photo-substitution reactions. Herein, a photo-induced halogen exchange in aryl or vinyl halides has been discovered for the first time. A broad scope of aryl iodides can be prepared in high yields at room temperature under exceptionally mild conditions without any metal or photo-redox catalysts. The presence of a catalytic amount of elemental iodine could promote the reaction significantly.
Li, Lu,Liu, Wenbo,Zeng, Huiying,Mu, Xiaoyue,Cosa, Gonzalo,Mi, Zetian,Li, Chao-Jun
supporting information
p. 8328 - 8331
(2015/07/15)

Method of preparing aromatic iodide compounds
The present invention is able to minimize unreacted iodine and aromatic compounds while increasing the productivity of diiodine compounds and the selectivity of para diiodine compounds by manufacturing iodinated aromatic compounds by using aromatic compounds and iodine ingredients as raw materials, passing the aromatic compounds and iodine ingredients to a zeolite catalyst layer in a gas phase and dividing and inserting the iodine ingredients and mono-iodine aromatic compounds into a middle layer of the zeolite catalyst layer.
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Paragraph 0037-0039; 0042

(2017/01/02)

A practical and general ipso iodination of arylboronic acids using N-iodomorpholinium iodide (NIMI) as a novel iodinating agent: mild and regioselective synthesis of aryliodides
A mild and efficient protocol for the ipso-iodination of aryl boronic acids using N-iodomorpholinium iodide (NIMI) generated in situ from morpholine and molecular iodine as a novel iodinating agent has been developed. The addition of a catalytic amount of copper iodide found to promote rate enhancement of the iodination reaction and dramatic increase in the yield depending upon the nature of the boronic acid was observed. The mechanistic study revealed that depending upon the nature of the substrate, either the classical ipso substitution or copper catalysed iododeborylation pathway overall dominates the present iodination reaction. The features such as mild reaction conditions, operational simplicity, high to excellent yields, excellent functional group compatibility and low catalyst loading make this method potentially useful in organic synthesis.
Tale,Toradmal,Gopula
p. 84910 - 84919
(2015/10/28)

Halogenation and DNA cleavage via thermally stable arenediazonium camphorsulfonate salts
A series of stable arenediazonium camphorsulfonate salts (2a-2j) were synthesized by simple diazotization of several aromatic amines in the presence of sodium nitrite and camphorsulfonic acid. All the new arenediazonium camphorsulfonates, which were characterized by multinuclear (1H and 13C) NMR, IR, DSC, and X-ray diffraction analysis (2e and 2f) provide unambiguous proof for the molecular structures of 2e and 2f. The efficient application of these salts in halogenation reactions was studied in solvent and solvent-free conditions and the DNA cleavage activity was also assessed. These arenediazonium camphorsulfonate salts are noticed as efficient DNA cleaving agents.
Vajpayee, Vaishali,Moon, Mi Eun,Lee, Sunmi,Ravikumar, Sambandam,Kim, Hyunuk,Ahn, Byungchan,Choi, Seoyoon,Hong, Soon Ho,Chi, Ki-Whan
p. 3511 - 3517
(2013/04/23)

Photochemical reactions of acyl iodides with aryl halides
Photochemical reactions of acyl iodides RC(O)I (R = Me, Ph) with aryl halides, fluoro-, chloro-, and bromobenzenes, 1,4-dibromobenzene, 2- and 3-bromotoluenes, and 4-bromo-1,2-dimethylbenzene, were studied. Acetyl iodide reacted with chloro- and bromobenzenes and 1,4-dibromobenzene according to the exchange pattern to give iodobenzene and 1,4-diiodobenzene, respectively. No halogen exchange was observed in the reactions of acetyl iodide with fluorobenzene and hexafluorobenzene. Benzoyl iodide failed to react with chloro- and brombenzene under UV irradiation but underwent polycondensation with formation of black nonfusible oligomers which were found to possess paramagnetic and semiconducting properties. Ultraviolet irradiation of a mixture of MeCOI with 2- or 3-bromotoluene, as well as with 4-bromo-1,2-dimethylbenzene, also led to the formation of polymeric products as a result of polycondensation of aryl iodides formed initially via replacement of bromine by iodine. Irradiation of benzoyl iodide in 2- or 3-bromotoluene involved recombination of benzoyl radicals to give benzil as the only product.
Voronkov,Vlasova,Belousova,Vlasov,Vakul'Skaya,Prozorova,Khutsishvili
p. 17 - 21
(2013/03/29)

Regioselective bromination and iodination of aromatic substrates promoted by trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane
Selective and efficient bromination and iodination of aromatic compounds by ammonium bromide and ammonium iodide, respectively, under promotion of trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane have been explored. Mild reaction conditions, high selectivity and yield, and high reaction rate are some of the major advantages of this synthetic method.
Azarifar, Davood,Khosravi, Kaveh,Najminejad, Zohreh,Soleimani, Khadijeh
experimental part
p. 321 - 326
(2012/08/14)

Hydroxyl radical promotes the direct iodination of aromatic compounds with iodine in water: A combined experimental and theoretical study
It is still a challenge to develop green, simple and effective approaches to prepare aromatic iodides. Herein, a novel and green strategy for the direct mono-iodination of aromatic compounds starting with molecular iodine has been developed. The strategy uses ceria nanocrystals to decompose hydrogen peroxide, giving hydroxyl radicals which are demonstrated experimentally and computationally to be crucial to promote the iodinations. Copyright
Zhang, Peng,Sun, Dongqing,Wen, Mingwei,Yang, Jingkui,Zhou, Kebin,Wang, Zhixiang
experimental part
p. 720 - 729
(2012/05/04)

Tetraflic acid (1,1,2,2-Tetrafluoroethanesulfonic acid, HC 2F4SO3H) and gallium tetraflate as effective catalysts in organic synthesis
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.
p. 2163 - 2171
(2012/11/07)

Synthesis and biological evaluation of 3-aryltyramines as fragments binding to BACE-1 and BACE-2
3-Aryltyramines were prepared in one single step from tyramine and various arenediazonium salts by radical arylation. Binding as well as enzyme inhibition data of the 14 compounds do not prove true interaction with BACE-1. In contrast, with BACE-2 inhibition and binding could be confirmed indicating that 3-aryltyramines are potential starting points for a drug discovery effort.
Fehler, Stefanie K.,Pratsch, Gerald,Huber, Walter,Gast, Alain,Hochstrasser, Remo,Hennig, Michael,Heinrich, Markus R.
supporting information; experimental part
p. 2189 - 2194
(2012/05/20)

Application of [Hcpy]HSO4 Broensted acidic ionic liquid for the synthesis of aryl iodides from aromatic amines
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Hajipour, Abdol Reza,Seddighi, Mohadeseh
experimental part
p. 292 - 296
(2011/07/31)

Superelectrophilic iodination of deactivated arenes with triiodoisocyanuric acid
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.
experimental part
p. 739 - 744
(2011/04/24)

Photochemical reactions of acyl iodides with haloarenes
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Vlasova,Belousova,Vlasov,Vakul'Skaya,Khutsishvili,Voronkov
scheme or table
p. 164 - 166
(2011/12/15)

PROCESS FOR PREPARING IODINATED AROMATIC COMPOUNDS
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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(2011/10/13)

Metal-free efficient, general and facile iododecarboxylation method with biodegradable co-products
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
supporting information; experimental part
p. 1438 - 1442
(2011/07/30)

PROCESS FOR PREPARING AROMATIC IODINE COMPOUNDS
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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(2011/10/19)

METHOD OF PRODUCING IODIZING AGENT, AND METHOD OF PRODUCING AROMATIC IODINE COMPOUND
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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(2010/05/13)

MANUFACTURING PROCESS FOR IODINATED AROMATIC COMPOUNDS
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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(2010/08/07)

A one-pot method for the iodination of aryl amines via stable aryl diazonium silica sulfates under solvent-free conditions
A convenient and rapid one-pot method for the synthesis of iodoarenes is developed which involves the sequential diazotization-iodination of aromatic amines with sodium nitrite, silica sulfuric acid and potassium iodide under solvent-free conditions at room temperature. Various aromatic amines possessing electron-withdrawing groups or electron-donating groups are converted into the corresponding aryl iodides in good yields. Georg Thieme Verlag Stuttgart.
Zarei, Amin,Hajipour, Abdol R.,Khazdoozd, Leila
experimental part
p. 941 - 944
(2009/12/02)

METHOD OF PREPARING IODINATED AROMATIC COMPOUNDS
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)

MANUFACTURING PROCESS FOR IODINATED AROMATIC COMPOUNDS
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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(2009/05/30)

A simple and efficient procedure for diazotization-iodination of aromatic amines in aqueous pastes by the action of sodium nitrite and sodium hydrogen sulfate
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Gorlushko,Filimonov,Semenishcheva,Krasnokutskaya,Tret'yakov,Go, Bong Seong,Hwang, Ho Yun,Cha, Eun Hye,Chi, Ki-Whan
body text
p. 1243 - 1244
(2009/08/07)

Sulfonic acid based cation-exchange resin: A novel proton source for one-pot diazotization-iodination of aromatic amines in water
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
p. 185 - 187
(2008/12/20)

NANOPARTICLES FOR TWO-PHOTON ACTIVATED PHOTODYNAMIC THERAPY AND IMAGING
The present invention provides organically modified silica (ORMOSIL) nanoparticles into which have been incorporated two-photon absorption dye molecules. The two photon absorption dye displays a unique aggregation induced fluorescence enhancement behavior. As a result ORMOSIL nanoparticles with high amounts of the dye can be prepared. These particles can be used for imaging. In one embodiment, the nanoparticles can additionally have incorporated therein a photosensitizer. The photosensitizer can be activated by intraparticle fluorescence resonance energy transfer (FRET) from the dye aggregates resulting in enhanced fluorescence and singlet oxygen generation from photosensitizer under two-photon excitation conditions. Such nanoparticles can be used for photodynamic therapy applications.
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(2008/06/13)

Direct synthesis of iodoarenes from aromatic substrates using molecular iodine
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
p. 690 - 692
(2008/09/21)

Iodination of aryl amines in a water-paste form via stable aryl diazonium tosylates
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
p. 1080 - 1082
(2008/09/18)

A new, one-step, effective protocol for the iodination of aromatic and heterocyclic compounds via aprotic diazotization of amines
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
p. 81 - 84
(2008/01/03)

Eco-friendly oxidative iodination of various arenes with sodium percarbonate as the oxidant http://www.mdpi.org
Six easy laboratory procedures are presented for the oxidative iodination of various aromatics, mostly arenes, with either molecular iodine or potassium iodide (used as the sources of iodinating species, I+ or I 3+), in the presence of sodium percarbonate (SPC), a stable, cheap, easy to handle, and eco-friendly commercial oxidant.
Zielinska, Agnieszka,Skulski, Lech
p. 1307 - 1317
(2007/10/03)

An aromatic iodination method, with iodic acid used as the only iodinating reagent
Benzene, halobenzenes, and a number of more or less deactivated arenes, including nitrobenzene, readily reacted in anhydrous HIO3/AcOH/ Ac2O/conc. H2SO4 mixtures to probably give ArIO2 intermediates or other hypervalent species (not isolated). The final reaction mixtures were poured into excess aq. Na2SO3 solution (a reductant) to give the purified iodinated products in 39-83% yields.
Krassowska-Swiebocka, Barbara,Prokopienko, Grazyna,Skulski, Lech
p. 394 - 400
(2007/10/03)

A Novel Aromatic Iodination Method, with Sodium Periodate Used as the Only Iodinating Reagent
Benzene, halobenzenes and some deactivated arenes readily reacted in anhydrous NaIO4/AcOH/Ac2O/concd. H2SO4 mixtures to afford, after quenching with excess aqueous Na2SO3 solution (a reducing agent), purified iodinated products in 27-88 percent yields. This novel method of aromatic iodination is simple, fairly effective and environmentally safe.
Lulinski, Piotr,Sosnowski, Maciej,Skulski, Lech
p. 671 - 675
(2007/10/03)

Eco-friendly Oxidative Iodination of Various Arenes with a Urea-Hydrogen Peroxide Adduct (UHP) as the Oxidant
Three easy eco-friendly laboratory procedures are presented for the oxidative iodination of various activated and deactivated arenes with molecular iodine, in the presence of UHP (percarbamide), a stable, strongly H-bonded, solid urea-hydrogen peroxide adduct as the oxidant.
Lulinski, Piotr,Kryska, Anna,Sosnowski, Maciej,Skulski, Lech
p. 441 - 445
(2007/10/03)

Chemical Manganese Dioxide (CMD): Its application to the oxidative iodination of benzene, halobenzenes and some deactivated arenes
After comparing our previous and newer results for numerous oxidative aromatic iodination experiments using various brands (of active MnO2 as the oxidants, we recommend the use of a Chemical Manganese Dioxide (Aldrich CMD; 90+% (MnO2) as the oxidant of choice, since it is satisfactorily pure and chemically active, and is notably less costly than other options.
Lulinski, Piotr,Krassowska-Swiebocka, Barbara,Skulski, Lech
p. 595 - 601
(2007/10/03)

Easy, inexpensive and effective oxidative iodination of deactivated arenes in sulfuric acid
Two 'model' deactivated arenes, benzoic acid and nitrobenzene, were effectively monoiodinated within 1 h at 25-30 °C, with strongly electrophilic I+ reagents, prior prepared from diiodine and various oxidants (CrO3, KMnO4, active MnO2, HIO 3, NaIO3, or NaIO4) in 90% (v/v) concd sulfuric acid (ca. 75 mol% H2SO4). Next, an I2/ NaIO3/90% (v/v) concd H2SO4 exemplary system was used to effectively mono- or diiodinate a number of deactivated arenes. All former papers dealing with the direct iodination of deactivated arenes are briefly reviewed.
Kraszkiewicz, Lukasz,Sosnowski, MacIej,Skulski, Lech
p. 9113 - 9119
(2007/10/03)

N-halosuccinimide/BF3-H2O, efficient electrophilic halogenating systems for aromatics
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.
p. 15770 - 15776
(2007/10/03)

Synthesis of 4-[18F]fluoroiodobenzene and its application in Sonogashira cross-coupling reactions
The first application of a Sonogashira cross-coupling reaction in 18F chemistry has been developed. The reaction was exemplified by the cross-coupling of terminal alkynes (ethynylcyclopentyl carbinol 6, 17α-ethynyl-3,17β-estradiol 7 and 17α-ethynyl-3-methoxy-3,17β-estradiol 8) with 4-[18F]fluoroiodobenzene. 4,4′-Diiododiaryliodonium salts were used as precursors for the synthesis of 4-[18F]fluoroiodobenzene, enabling the convenient access to 4-[18F]fluoroiodobenzene in 13-70% yield using conventional heating or microwave activation. The Sonogashira cross-coupling of 4-[18F]fluoroiodobenzene with terminal alkynes gave the corresponding 4-[18F]fluorophenylethynyl-substituted compounds [18F]-9, [18F]-10 and [18F]-13 in yields up to 88% within 20min of starting from 4-[18F]fluoroiodobenzene. Copyright
Wuest, Frank R.,Kniess, Torsten
p. 699 - 713
(2007/10/03)

Combinatorial synthesis of oligo(phenylene ethynylene)s
The combinatorial synthesis of oligo(phenylene ethynylene) tetramers, both in solution and on solid support, is described. These products are of interest for molecular electronics applications. An iterative sequence, coupling of aryl halides to alkynes under Sonogashira conditions, was used. Five monomers functionalized with electron-donating or electron-withdrawing groups were synthesized, and used to generate a library of 25 trimers in a solution-phase based process. A library of 24 tetramers was prepared by subsequent protodesilylation and coupling with the alligator clip 4-iodo-1-thioacetylbenzene. The solution-phase based sequence was successfully adapted to a higher yielding directed split-and-pool solid-phase process, with average yields of 78-86% for each step over seven steps. A triazene linker group was used to attach the starting monomer to the polymer beads. At the completion of the solid-phase-based process, traceless cleavage of trimers from the resin was achieved by sonication of the resin in 10% HCl/THF solution. The released products were then poised for the final step in the sequence, attachment of the alligator clip.
Hwang, Jiunn-Jye,Tour, James M.
p. 10387 - 10405
(2007/10/03)

2,4,6,8-tetraiodo-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione as a mild and convenient reagent for iodination of aromatic compounds
2,4,6,8-Tetraiodo-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione (tetraiodoglycoluril) is a convenient reagent for preparative iodination of benzene, alkylbenzenes, polycyclic hydrocarbons, aromatic amines, and phenol ethers in organic solvents under mild conditions.
Chaikovski,Filimonov,Yagovkin,Ogorodnikov
p. 2411 - 2415
(2007/10/03)