- Tetramethylammonium dichloroiodate: An efficient and environmentally friendly iodination reagent for iodination of aromatic compounds under mild and solvent-free conditions
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Tetramethylammonium dichloroiodate (1, TMADCI) as a mild and efficient iodination reagent was prepared. Iodination of different aromatic compounds with this reagent takes place fast and with high yields under solvent-free conditions.
- Hajipour, Abdol R.,Arbabian, Marty,Ruoho, Arnold E.
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- Chemoselective Hydrogenation of Nitroarenes Catalyzed by Molybdenum Sulphide Clusters
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Herein, we describe an atom efficient and general protocol for the chemoselective hydrogenation of nitroarenes to anilines catalyzed by well-defined diimino and diamino cubane-type Mo3S4 clusters. The novel diimino [Mo3S4Cl3(dnbpy)3]+ ([5]+) (dnbpy=4,4′-dinonyl-2,2′-dipyridyl, L1) trinuclear complex was synthesized in high yields by simple ligand substitution reactions starting from the thiourea (tu) [Mo3S4(tu)8(H2O)]Cl4?4 H2O (3) precursor. This strategy has also been successfully adapted for the isolation of the diamino [Mo3S4Cl3(dmen)3](BF4) ([6](BF4)), (dmen=N,N′-dimethylethylenediamine) salt. Applying these catalysts, high selectivity in the hydrogenation of functionalized nitroarenes has been accomplished. Over thirty anilines bearing synthetically functional groups have been synthesized in 70 to 99 % yield. Notably, the integrity of the cluster core is preserved during catalysis. Based on kinetic studies on the hydrogenation of nitrobenzene and other potential reaction intermediates, the direct reduction to aniline is the preferential route.
- Pedrajas, Elena,Sorribes, Iván,Gushchin, Artem L.,Laricheva, Yuliya A.,Junge, Kathrin,Beller, Matthias,Llusar, Rosa
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p. 1128 - 1134
(2017/03/27)
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- Nitrogen-doped graphene-activated iron-oxide-based nanocatalysts for selective transfer hydrogenation of nitroarenes
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Nanoscaled iron oxides on carbon were modified with nitrogen-doped graphene (NGr) and found to be excellent catalysts for the chemoselective transfer hydrogenation of nitroarenes to anilines. Under standard reaction conditions, a variety of functionalized and structurally diverse anilines, which serve as key building blocks and central intermediates for fine and bulk chemicals, were synthesized in good to excellent yields.
- Jagadeesh, Rajenahally V.,Natte, Kishore,Junge, Henrik,Beller, Matthias
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p. 1526 - 1529
(2015/03/14)
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- Highly selective transfer hydrogenation of functionalised nitroarenes using cobalt-based nanocatalysts
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Anilines are important feedstock for the synthesis of a variety of chemicals such as dyes, pigments, pharmaceuticals and agrochemicals. The chemoselective catalytic reduction of nitro compounds represents the most important and prevalent process for the manufacture of functionalized anilines. Consequently, the development of selective catalysts for the reduction of nitro compounds in the presence of other reducible groups is a major challenge and is crucial. In this regard, herein we show that the cobalt oxide (Co3O4-NGr@C) based nano-materials, prepared by the pyrolysis of cobalt-phenanthroline complexes on carbon constitute highly selective catalysts for the transfer hydrogenation of nitroarenes to anilines using formic acid as a hydrogen source. Applying these catalysts, a series of structurally diverse and functionalized nitroarenes have been reduced to anilines with unprecedented chemo-selectivity tolerating halides, olefins, aldehyde, ketone, ester, amide and nitrile functionalities.
- Jagadeesh, Rajenahally V.,Banerjee, Debasis,Arockiam, Percia Beatrice,Junge, Henrik,Junge, Kathrin,Pohl, Marga-Martina,Radnik, J?rg,Brückner, Angelika,Beller, Matthias
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supporting information
p. 898 - 902
(2015/03/04)
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- Greener iodination of arenes using sulphated ceria-zirconia catalysts in polyethylene glycol
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An environmentally benign method for the selective monoiodination of diverse aromatic compounds has been developed using reusable sulphated ceria-zirconia under mild conditions. The protocol provides moderate to good yields and selectively introduces iodine at the para/ortho position in monosubstituted arenes. SO42-/Ce0.07Zr 0.93O2 was found to be the best choice for the synthesis of aryl iodides in high yield, presumably due to the maximum number of acid sites (4.23 mmol g-1) among the various compositions of the catalyst system.
- Kahandal, Sandeep S.,Kale, Sandip R.,Gawande, Manoj B.,Zboril, Radek,Varma, Rajender S.,Jayaram, Radha V.
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p. 6267 - 6274
(2014/01/23)
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- Nanoscale Fe2O3-based catalysts for selective hydrogenation of nitroarenes to anilines
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Production of anilines - key intermediates for the fine chemical, agrochemical, and pharmaceutical industries - relies on precious metal catalysts that selectively hydrogenate aryl nitro groups in the presence of other easily reducible functionalities. Herein, we report convenient and stable iron oxide (Fe2O3) - based catalysts as a more earth-abundant alternative for this transformation. Pyrolysis of iron-phenanthroline complexes on carbon furnishes a unique structure in which the active Fe2O 3 particles are surrounded by a nitrogen-doped carbon layer. Highly selective hydrogenation of numerous structurally diverse nitroarenes (more than 80 examples) proceeded in good to excellent yield under industrially viable conditions.
- Jagadeesh, Rajenahally V.,Surkus, Annette-Enrica,Junge, Henrik,Pohl, Marga-Martina,Radnik, Joerg,Rabeah, Jabor,Huan, Heming,Schunemann, Volker,Brueckner, Angelika,Beller, Matthias
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p. 1073 - 1076
(2014/01/06)
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- Remarkable switch in the regiochemistry of the iodination of anilines by N-iodosuccinimide: Synthesis of 1,2-dichloro-3,4-diiodobenzene
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Direct iodination of anilines by NIS in polar solvents (such as DMSO) affords p-iodinated products with up to >99% regioselectivity. Switching to less polar solvents (such as benzene) in the presence of AcOH inverts this outcome toward dramatically increased or preferential generation of the o-isomers, also with up to >99% regioselectivity. This finding was exploited in the synthesis of 1,2-dichloro-3,4-diiodobenzene. Georg Thieme Verlag Stuttgart - New York.
- Shen, Hao,Vollhardt, K. Peter C.
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supporting information; experimental part
p. 208 - 214
(2012/03/11)
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- Environmental friendly method for the iodination of moderately active arenes
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An effective and environmental friendly method for the iodination of various moderately active methoxy arenes, phenols and anilines using hydrogen peroxide and acidified sodium periodate in aqueous ethanol medium is reported. The extent of iodination is e
- Sathiyapriya
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experimental part
p. 41 - 43
(2011/11/13)
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- A practical iodination of aromatic compounds by using iodine and iodic acid
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This article describes simple and efficient method for the iodination of different aromatic amines, hydroxy aromatic aldehydes, hydroxy acetophenones and phenols using iodine and iodic acid in ethanol as a solvent. Notable advantages include mild reaction condition, no need of catalyst, short reaction time, simple practical procedure, giving excellent yield of the product. Copyright Taylor & Francis Group, LLC.
- Shinde, Avinash T.,Zangade, Sainath B.,Chavan, Shivaji B.,Vibhute, Archana Y.,Nalwar, Yogesh S.,Vibhute, Yeshwant B.
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experimental part
p. 3506 - 3513
(2011/02/22)
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- Eco-friendly oxyiodination of aromatic compounds using ammonium iodide and hydrogen peroxide
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A new eco-friendly procedure for the oxyiodination of aromatic compounds with NH4I as an iodine source and H2O2 as an oxidant without any catalyst is presented.
- Narender,Reddy, K. Suresh Kumar,Mohan, K.V.V. Krishna,Kulkarni
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p. 6124 - 6128
(2008/03/12)
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- Preparation of annulated nitrogen-containing heterocycles via a one-pot palladium-catalyzed alkylation/direct arylation sequence
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A palladium-catalyzed/norbornene-mediated sequential coupling reaction involving an aromatic sp2 C-H functionalization as the key step is described, in which an alkyl-aryl bond and an aryl-heteroaryl bond are formed in one pot. A variety of hig
- Blaszykowski, Christophe,Aktoudianakis, Evangelos,Bressy, Cyril,Alberico, Dino,Lautens, Mark
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p. 2043 - 2045
(2007/10/03)
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- Microwave-accelerated or conventionally heated iodination reactions of some aromatic amines, using ortho-periodic acid as the oxidant
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A fast and simple method for the oxidative iodination of some aromatic amines, either under microwave irradiation or conventional heating, is reported, using diiodine and ortho-periodic acid as the oxidant. The reactions were carried out in boiling CH2Cl2 solutions under a reflux condenser. For the microwave assisted reactions, the reaction times were always notably shortened, but the yields were usually less influenced as compared with the conventional method.
- Sosnowski, Maciej,Skulski, Lech,Wolowik, Katarzyna
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p. 617 - 621
(2007/10/03)
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- Microwave-accelerated iodination of some aromatic amines, using urea-hydrogen peroxide addition compound (UHP) as the oxidant
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A fast and simple method for the oxidative iodination of some aromatic amines, under microwave irradiation, is reported, using diiodine and the the strongly H-bonded urea-hydrogen peroxide addition compound (H 2NCONH)2...H2O2, UHP) as the oxidant. The reactions were carried out in boiling CHCl3 under a reflux condenser to afford, within 10 minutes, the purified monoiodinated products in 40-80% yields.
- Sosnowski, Maciej,Skulski, Lech
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p. 867 - 870
(2007/10/03)
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- Benzyltriethylammonium dichloroiodate/sodium bicarbonate combination as an inexpensive, environmentally friendly, and mild iodinating reagent for anilines
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(matrix presented) Monoiodinated anilines were prepared in good to excellent yields by the action of benzyltriethylammonium dichloroioadate on anilines in the presence of sodium bicarbonate and methanol. The iodinating reagent was prepared in an environmentally friendly fashion without the use of organic solvents.
- Kosynkin, Dmitry V.,Tour, James M.
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p. 991 - 992
(2007/10/03)
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- Aromatic iodination with the I2-HgX2 combination
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The reaction of differnt aromatic compounds 1a-1t with iodine and a mercury(II)-salt 2 [mercury(II) chloride, nitrate or triflate] (1:1:1 molar ratio) in dichloromethane at room temperature leads to the corresponding iodoarene 3, the obtained regiochemistry being the expected. Concerning the mercury(II) salt, the observed reactivity decreased in the series triflate > nitrate > chloride according to their ionic character. An activation of the iodine molecule by the mercury(II) salt followed by a S(E) reaction with the aromatic compounds is postulated as the possible mechanism.
- Bachki, Abderrazak,Foubelo, Francisco,Yus, Miguel
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p. 5139 - 5146
(2007/10/02)
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