- 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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- Sulfated polyborate-H2O assisted tunable activation of N-iodosuccinimide for expeditious mono and diiodination of arenes
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Owing to both Lewis and Bronsted acid active sites on sulfated polyborate under homogenous conditions, we were keen on developing iodination protocol of arenes that can meet the requirement of regioselectivity and higher yield. The sulfated polyborate activates N-iodosuccinimide for mono iodination of highly activated substrates viz. phenols, anilines under anhydrous condition. Water tunes sulfated polyborate to generate more Bronsted acid sites resulting in rapid activation of NIS for diiodination. The protocol was equally applicable to diiodination of 4-hydroxyphenylacetic acid to synthesize 4-hydroxy-3,5-diiodophenylacetic acid, an intermediate of tiratricol, a thyroid treatment drug. This protocol was further integrated via one-pot sequential iodination and Sonogashira coupling to synthesize aryl acetylenes, building blocks for the synthesis of a variety of specialty chemicals, API, and natural products.
- Misal, Balu,Palav, Amey,Ganwir, Prerna,Chaturbhuj, Ganesh
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supporting information
(2021/05/26)
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- NCBSI/KI: A Reagent System for Iodination of Aromatics through in Situ Generation of I-Cl
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In situ iodine monochloride (I-Cl) generation followed by iodination of aromatics using NCBSI/KI system has been developed. The NCBSI reagent requires no activation due to longer bond length, lower bond dissociation energy, and higher absolute charge density on nitrogen. The system is adequate for mono- and diiodination of a wide range of moderate to highly activated arenes with good yield and purity. Moreover, the precursor N-(benzenesulfonyl)benzenesulfonamide can be recovered and transformed to NCBSI, making the protocol eco-friendly and cost-effective.
- Palav, Amey,Misal, Balu,Chaturbhuj, Ganesh
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p. 12467 - 12474
(2021/08/24)
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- A convenient and efficient H2SO4-promoted regioselective monobromination of phenol derivatives using N-bromosuccinimide
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A convenient, rapid H2SO4-promoted regioselective monobromination reaction with N-bromosuccinimide was developed. The desired para-monobrominated or ortho-monobrominated products of phenol derivatives were obtained in good to excellent yields with high selectivity. Regioselective chlorination and iodination were also achieved in the presence of H2SO4 using N-chlorosuccinimide and N-iodosuccinimide, respectively.
- Wu, Yong-Qi,Lu, Hai-Jia,Zhao, Wen-Ting,Zhao, Hong-Yi,Lin, Zi-Yun,Zhang, Dong-Feng,Huang, Hai-Hong
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supporting information
p. 813 - 822
(2020/02/15)
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- Method for the synthesis of many halo benzoic acid
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The invention provides a poly-halogenated benzoic acid synthesizing method. The method comprises the following steps: dissolving substituted benzoic acid, halogen and organic strong acid in a polar solvent for increasing temperature, after oxidation at a temperature of 50-70 DEG C, performing heat preservation at the temperature of 60-80 DEG C for 2-6 h, adding a right amount of water, and cooling to a room temperature, so as to obtain poly-halogenated benzoic acid. According to the invention, synthetic reaction is performed in an alcohols solvent, the halogen simple substance is used as a halogenating reagent, a small amount of organic strong acid is added, used as a catalyst, and used for catalyzing the electrophilic substitution reaction of the halogen to benzene rings, and hydrogen peroxide is dropwise added during the reaction to enable the halogen simple substance in the reaction system to be oxidized into halide ions so as to improve the utilization rate of the halogen and achieve the effect of atom economy.
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Paragraph 0040
(2017/04/03)
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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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- Synthesis of Linear and Tripoidal Oligo(phenylene ethynylene)-Based Building Blocks for Application in Modular DNA-Programmed Assembly
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Rigid linear and tripoidal organic modules based on the oligo(phenylene ethynylene) backbone having salicylaldehyde-derived termini are synthesized. A highly functionalized 5-iodosalicyl aldehyde was prepared and coupled to each ethynyl group of 1,4-diethynylbenzene or 1,3,5-triethynylbenzene in Sonogashira couplings. The two or three termini of the compounds are functionalized for incorporation in linear and branched oligonucleotide strands. For the linear module (LM), the two termini are equipped with amide spacers, and one of these was functionalized with a DMTr (dimethoxytrityl)-protected hydroxy group and the other with a phosphoramidite. One of the tripoidal modules is prepared with DMTr groups in two of its three termini. A tripoidal module is also synthesized with three different groups on its hydroxy termini: a phosphoramidite, a DMTr group, and an Fmoc group. Extended studies have shown that these rigid linear and tripoidal organic modules can be incorporated into short oligonucleotides. Several of these modules can be applied for DNA-directed assembly and covalent coupling into structures of predetermined connectivity. Such structures have potential application for molecular electronics and nanotechnology.
- Nielsen, Morten,Thomsen, Anne H.,Clo, Emiliano,Kirpekar, Finn,Gothelf, Kurt V.
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p. 2240 - 2250
(2007/10/03)
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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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