- Solvent-Free and Liquid-Phase Iodination of Thiophene Derivatives with Potassium Dichloroiodate Monohydrate
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Iodination of a series of benzene and thiophene derivatives by potassium dichloroiodate monohydrate was studied with and without a solvent. The liquid substrates tend to be more reactive in water while the solid substrates afford better yields in dichloromethane or under the solvent-free conditions. The 2-substituted thiophenes show good to excellent yields whereas the yield for 3-substituted and 3,4- or 2,4-disubstituted thiophenes and benzene derivatives are significantly lower. The mechanochemical reaction of 5-carbaldehyde-2,2′-bithiophene shows excellent yields, while 2,2′-bithiophene gives practical yields only in dichloromethane. In the case of thiophene and N -acetyl- p -toluidine, electrophilic iodination is accompanied by a small extent of chlorination.
- Hussain, Anwar,Sarkar, Akash Mamon,Sereda, Grigoriy,Zefirov, Nikolai
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p. 1140 - 1146
(2020/04/01)
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- Clean and Efficient Iodination of Thiophene Derivatives
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Iodination of thiophene derivatives is realized using a simple, fast, and efficient methodology. Iodination of thiophene and 2- or 3-substituted or 3,4-disubstituted thiophenes with N-iodosuccinimide (NIS) activated with 4-toluenesulfonic acid in ethanol gives pure iodinated products that require no further purification.
- Grolleau, Jérémie,Frère, Pierre,Gohier, Frédéric
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p. 3901 - 3906
(2015/12/18)
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- New approach to electrochemical iodination of arenes exemplified by the synthesis of 4-iodopyrazoles of different structures
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The two-stage electrosynthesis of 4-iodosubstituted pyrazole derivatives was performed. At the first stage, KIO3 was obtained at the Ni anode under the undivided galvanostatic conditions of electrolysis of an aqueous alkaline solution of KI (or I2) at the Ni anode. At the second stage, pyrazole and its derivatives were iodinated in the heterophase (H2O-CHCl3 (CCl4)) medium by the KIO3-KI (or KIO3-I2) system in the presence of H2SO4. The yields of iodopyrazoles were 74-92%. The electrochemical iodination of anisole, 2-methylpyrazole, and thiophene was carried out to form 4-iodoanisole (88% yield), 4,5-diiodo-2-methylimidazole (54% yield), and a mixture of 2-iodothiophene (60% yield) and 2,5-diiodothiophene (4% yield).
- Lyalin,Petrosyan
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p. 360 - 367
(2015/02/05)
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- Potassium-alkyl magnesiates: Synthesis, structures and Mg-H exchange applications of aromatic and heterocyclic substrates
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Using structurally well-defined dipotassium-tetra(alkyl)magnesiates, a new straightforward methodology to promote regioselective Mg-H exchange reactions of a wide range of aromatic and heteroaromatic substrates is disclosed. Contacted ion pair intermediates are likely to be involved, with K being the key to facilitate the magnesiation processes. This journal is
- Baillie, Sharon E.,Bluemke, Tobias D.,Clegg, William,Kennedy, Alan R.,Klett, Jan,Russo, Luca,De Tullio, Marco,Hevia, Eva
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supporting information
p. 12859 - 12862
(2014/12/11)
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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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- 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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- 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.
- -
-
Page/Page column 10
(2010/05/13)
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- Deprotonative metalation of substituted benzenes and heteroaromatics using amino/alkyl mixed lithium-zinc combinations
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Different homoleptic and heteroleptic lithium-zinc combinations were prepared, and structural elements obtained on the basis of NMR spectroscopic experiments and DFT calculations. In light of their ability to metalate anisole, pathways were proposed to justify the synergy observed for some mixtures. The best basic mixtures were obtained either by combining ZnCl 2·TMEDA (TMEDA = N,N,N',N'tetramethylethylenediamine) with [Li(tmp)] (tmp = 2,2,6,6-tetramethylpiperidino; 3 equiv) or by replacing one of the tmp in the precedent mixture with an alkyl group. The reactivity of the aromatic lithium zincates supposedly formed was next studied, and proved to be substrate-, base-, and electrophile-dependent. The aromatic lithium zincates were finally involved in palladium-catalyzed cross-coupling reactions with aromatic chlorides and bromides.
- Snegaroff, Katia,Komagawa, Shinsuke,Chevallier, Floris,Gros, Philippe C.,Golhen, Stephane,Roisnel, Thierry,Uchiyama, Masanobu,Mongin, Florence
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experimental part
p. 8191 - 8201
(2010/09/11)
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- Co-thermolysis: A one-pot synthetic method for novel 2-substituted-5- (trifluoromethoxy)thiophenes
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A new 'green' process to obtain trifluoromethoxylated compounds by a gas-phase method has been accomplished. Through it, new 2-substituted-5- (trifluoromethoxy)thiophenes have been obtained in moderate to good yields. Though the reaction occurs in the gas-phase and radicals are involved, an electron transfer mechanism is also postulated to explain the appearance of all detected products.
- Peláez,Argüello
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scheme or table
p. 5242 - 5245
(2010/11/03)
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- Deprotonative metalation of functionalized aromatics using mixed lithium-cadmium, lithium-indium, and lithium-zinc species
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In situ mixtures of CdCl2TMEDA (0.5 equiv; TMEDA = N,N,N',N'-tetramethylethylenediamine) or InCl3 (0.33 equiv) with [Li(tmp)] (tmp = 2,2,6,6-tetramethylpiperidino; 1.5 or 1.3 equiv, respectively) were compared with the previously described mixture of ZnCl2-TMEDA (0.5 equiv) and [Li(tmp)] (1.5 equiv) for their ability to deprotonate anisole, benzothiazole, and pyrimidine. [(tmp)3CdLi] proved to be the best base when used in tetrahydrofuran at room temperature, as demonstrated by subsequent trapping with iodine. The Cd-Li base then proved suitable for the metalation of a large range of aromatics including benzenes bearing reactive functional groups (CONEt2, CO2Me, CN, COPh) or heavy halogens (Br, I), and heterocycles (from the furan, thiophene, pyrrole, oxazole, thiazole, pyridine, and diazine series). Fivemembered heterocycles benefiting from doubly activated positions were similarly dideprotonated at room temperature. The aromatic lithium cadmates thus obtained were involved in palladium-catalyzed cross-coupling reactions or simply quenched with acid chlorides.
- Snegaroff, Katia,L'Helgoual'ch, Jean-Martial,Bentabed-Ababsa, Ghenia,Nguyen, Tan Tai,Chevallier, Floris,Yonehara, Mitsuhiro,Uchiyama, Masanobu,Derdour, Aicha,Mongin, Florence
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experimental part
p. 10280 - 10290
(2010/04/24)
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- Deprotonative cadmation of functionalized aromatics
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This communication describes the deproto-metalation of a large range of aromatics including heterocycles using a newly developed lithium-cadmium base; the reaction proceeds at room temperature with an excellent chemoselectivity and efficiency, and proved to be regioselective in most cases. The Royal Society of Chemistry.
- L'Helgoual'ch, Jean-Martial,Bentabed-Ababsa, Ghenia,Chevallier, Floris,Yonehara, Mitsuhiro,Uchiyama, Masanobu,Derdour, Aicha,Mongin, Florence
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supporting information; experimental part
p. 5375 - 5377
(2009/03/11)
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- A comparison of microwave-accelerated and conventionally heated iodination reactions of some arenes and heteroarenes, using ortho-periodic acid as the oxidant
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A fast and simple method for the oxidative iodination of some activated arenes and heteroarenes, either under microwave irradiation or by conventional heating, is reported, using diiodine and ortho-periodic acid as the oxidant. The reactions were carried out in hot 95% ethanol under a reflux condenser. For the microwave assisted reactions, the reaction times were always notably shortened, but the yields were nearly the same as those afforded by the conventional method.
- Sosnowski, Maciej,Skulski, Lech
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p. 401 - 406
(2007/10/03)
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- An Efficient, Catalytic, Aerobic, Oxidative Iodination of Arenes Using the H5PV2Mo10O40 Polyoxometalate as Catalyst
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Iodination of arenes was carried out by reacting 1 equiv of arene substrate with 0.5 equiv of iodine under an oxygen atmosphere with H 5PV2Mo10O40 as oxidation catalyst. The synthesis is an inherently waste-free method for the preparation of iodoarenes.
- Branytska, Olena V.,Neumann, Ronny
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p. 9510 - 9512
(2007/10/03)
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- Exclusive CIS-1,4-addition reaction in the bromination of 2,5-bis(trimethylsilyl)thiophene monooxide
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2,5-Bis(trimethylsilyl)thiophene monooxide (1) underwent a 1,4-addition reaction with Br2 to give stereospecifically 2,5-bis(trimethylsilyl)-2,5-cis-dibromothiolene monooxide (2) in quantitative yield.
- Zhang, Shao-Zhong,Sato, Soichi,Horn, Ernst,Furukawa, Naomichi
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p. 227 - 234
(2007/10/03)
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- Reevaluation of benzyltrimethylammonium dichloroiodide, previously reported to be a selective iodinating agent
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Benzyltrimethylammonium dichloroiodate, previously reported as an iodinating agent of thiophenes, appears to be a selective chlorinating agent of both thienyl and furyl derivatives containing a carbonyl group.
- D'Auria,Mauriello
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p. 248 - 250
(2007/10/02)
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- Bis-(trifluoroacetoxy)iodobenzene-iodine system: An efficient and selective reagent for iodination of thiophene derivatives
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Bis-(trifluoroacetoxy)iodobenzene-iodine system is a good iodinating reagent of thiophene derivatives giving products with iodine atom in α-position on the thiophene ring.
- D'Auria,Mauriello
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p. 4883 - 4884
(2007/10/02)
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- STRUCTURE AND SYNTHESIS OF 1,3,5,7-TETRAMETHOXYDITHIENO-DITHIIN
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Starting from thiophene (6), the sequence 2,5-diiodothiophene (7), 2,5-bismethoxythiophene (8), 3,4-dibromo-2,5-bismethoxythiophene (9) finally leads to the title compound 5.The 1H- and 13C-NMR, the MS and IR data and the structure of 5 are reported. - Key words: Dithieno-1,4-dithiin, X-ray structure.
- Friederichs, Stephan,Link, Thorsten,Klar, Guenter
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p. 279 - 284
(2007/10/03)
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- Halogenation Using Quaternary Ammonium Polyhalides. XXXI. Halogenation of Thiophene Derivatives with Benzyltrimethylammonium Polyhalides
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The reactions of thiophene derivatives with benzyltrimethylammonium tetrachloroiodate, benzyltrimethylammonium tribromide, and benzyltrimethylammonium dichloroiodate in acetic acid or in acetic acid-zinc chloride under mild conditions gave chloro-, bromo-, and iodo-substituted thiophene derivatives, respectively, in satifactory yields.
- Okamoto, Tsuyoshi,Kakinami, Takaaki,Fujimoto, Hiroshi,Kajigaeshi, Shoji
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p. 2566 - 2568
(2007/10/02)
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- Lower Nitrogen Oxide Species as Catalysts in a Convenient Procedure for the Iodination of Aromatic Compounds
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A simple method for the iodination of aromatic compounds, using I- as the iodine source and the O2 and catalytic amounts of NO+BF4- as the oxidant, is presented.The reactions are performed at 25 deg C in CF3COOH/CH2Cl2 or CF3COOH/CH3COOH mixtures and compounds with as different reactivities as the halobenzenes and 1-methoxynaphthalene can be iodinated in very good yields.A set of relative rates, isotope effects, and isomer distributions in accordance with the electrophilic action of an "I+" species are presented.The formation of "I+" is discussed in terms of possible outer-sphere and inner-sphere electron-transfer steps.Aromatic bromination and to a lesser extent chlorination can be performed by using similar methods.
- Radner, Finn
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p. 3548 - 3553
(2007/10/02)
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- Photochemical Synthesis of Phenyl-2-thienyl Derivatives
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The irradiation (in benzene solution) of 5-bromo- and 5-iodo-thiophene-2-carbaldehyde or the corresponding methyl ketones furnishes the corresponding 5-phenyl derivatives.The same reactivity for other halogenothiophenes is reported: 3,5-dibromothiophene-2-carbaldehyde furnishes the 3-bromo-5-phenyl-2-thienyl derivative while the corresponding di-iodo compound yields 3,5-diphenylthiophene-2-carbaldehyde.In contrast, 5-acetyl-2,3-di-iodothiophene furnishes only the photosubstitution pruduct at C-5.Generally the iodine-containing compounds are more reactive and more stable under the reaction conditions than ones bearing bromine, in agreement with previous reports on the corresponding furan photochemistry.
- Antonioletti, Roberto,Auria, Maurizio D',Onofrio, Franco D',Piancatelli, Giovanni,Scettri, Arrigo
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p. 1755 - 1758
(2007/10/02)
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- SYNTHESIS AND REACTIVITY OF THE 2,5-BIS(TRIMETHYLSTANNYL) DERIVATIVES OF THIOPHENE AND FURAN
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The synthesis of the 2,5-bis(trimethylstannyl) derivatives of thiophene and furan is reported.Conditions for monotransmetalation and electrophilic destannylation are described.
- Seitz, David E.,Lee, Shi-Hung,Hanson, Robert N.,Bottaro, Jeffrey C.
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p. 121 - 128
(2007/10/02)
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- Disproportionation of 2-Iodothiophene in Hexamethylphosphoric triamide/18-Crown-6
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2,5-Diiodothiophene has been obtained in 46percent yield by the disproportionation of 2-iodothiophene in the presence of potassium t-butoxide in hexamethylphosphoric triamide/18-crown-6.
- Woo, H. G.
-
-
- Kinetics of Iodination of Thiophene and 2-Halothiophenes
-
The effect of substituents (Cl, Br and I) at the 2-position upon the rate of iodination with iodine monochloride in hydrochloric acid of thiophene at the 5-position, in 50percent aqueous acetic acid, had been studied at different temperatures.The rates and activation parameters for the 2-iodothiophene indicate an inductomeric mode of electron release by the iodine atom.
- Nair, M. R.
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p. 417 - 418
(2007/10/02)
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- benzene, a Versatile Reagent for the Mild Oxidation of Aryl Iodides at the Iodine Atom by Ligand Transfer
-
Treatment of a variety of aryl iodides with benzene (1) under mild conditions resulted in ligand transfer, and new arenes were obtained.However, with some substrates containing proximate functional groups cyclic iodonium salts and iodinanes resulted.The reaction between 1 and 2-iodothiophene took a distinctly different course.
- Koser, Gerald F.,Wettach, Richard H.
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p. 1542 - 1543
(2007/10/02)
-
