100-44-7Relevant articles and documents
Photocatalytic oxidation of alkanes with dioxygen by visible light and copper(II) and iron(III) chlorides: Preference oxidation of alkanes over alcohols and ketones
Takaki, Ken,Yamamoto, Jun,Komeyama, Kimihiro,Kawabata, Tomonori,Takehira, Katsuomi
, p. 2251 - 2255 (2004)
Visible light irradiation of alkanes in acetonitrile with CuCl2 and FeCl3 catalysts under atmospheric dioxygen gave the corresponding alcohols and ketones effectively; in these reactions, the total selectivity of the products did not decrease so much with increase of alkane conversion. For example, cyclohexanol and cyclohexanone were formed with ca. 70% selectivity at 50% conversion, because overoxidation of the products took place more slowly than cyclohexane oxidation. The relative reactivity values of cycloalkanes increased as their ring-sizes decreased. In the oxidation of hexane, the reactivity ratio of C1-/C2-/C3-H was found to be 1.0/1.4/1.8 with CuCl2 and 1.0/4.6/6.6 with FeCl3, respectively. Toluene and diphenylmethane were more reactive than cyclohexane with FeCl3, as expected, whereas the alkane was oxidized faster than the benzylic compounds in the separate reaction with CuCl2. Moreover, the alkane oxidation could be comparably performed by sunlight instead of an artificial lamp.
An experimental and theoretical study on imidazolium-based ionic liquid promoted chloromethylation of aromatic hydrocarbons
Wang, Yun,Xi, Yanli
, p. 2196 - 2199 (2013)
The chloromethylation of aromatic hydrocarbons proceeded efficiently using the reusable imidazolium-based ionic liquid as promoter. Mild reaction conditions, enhanced rates, improved yields, recyclability of ionic liquids, and reagents' reactivity which is different from that in conventional organic solvents are the remarkable features observed in ionic liquids. The ionic liquids were recycled in three subsequent runs with no decrease in activity. In addition, the results of calculations with the Gaussian 98 suite of program are in good accordance with the experimental outcomes.
Trichloroisocynuric acid/DMF as efficient reagent for chlorodehydration of alcohols under conventional and ultrasonic conditions
Venkana, Purugula,Kumar, Mukka Satish,Rajanna, Kamatala Chinna,Ali, Mir Moazzam
, p. 97 - 103 (2015)
A new and efficient method for the chlorodehydration of alcohols utilizing TCCA/DMF is described. Various alcohols can be converted smoothly into their corresponding alkyl chlorides in high yields under mild conditions with short reaction times. Taylor & Francis Group, LLC.
Vitamin B12 Catalyzed Atom Transfer Radical Addition
Proinsias, Keith O.,Jackowska, Agnieszka,Radzewicz, Katarzyna,Giedyk, MacIej,Gryko, Dorota
, p. 296 - 299 (2018)
Vitamin B12, a natural Co-complex, catalyzes atom transfer radical addition (ATRA) of organic halides to olefins. The established conditions were found to be very selective, with atom transfer radical polymerization (ATRP) occurring only in the case of acrylates.
Chloroalkylation of aryl aldehydes using alkylboron dichlorides in the presence of oxygen
Kabalka, George W,Wu, Zhongzhi,Ju, Yuhong
, p. 6239 - 6241 (2001)
Reactions of aryl aldehydes with alkylboron dichlorides in the presence of oxygen at room temperature produces arylalkyl chlorides in good to excellent yields.
Reactivity of [WCl6] with Ethers: A Joint Computational, Spectroscopic and Crystallographic Study
Bortoluzzi, Marco,Marchetti, Fabio,Pampaloni, Guido,Zacchini, Stefano
, p. 3169 - 3177 (2016)
The reactions of [WCl6] with a series of ethers have been performed in chlorinated solvent and elucidated by means of analytical, spectroscopic and DFT methods. The addition of tetrahydropyran (thp) or 1,4-dioxane to [WCl6] resulted in the reversible formation of the adducts WCl6···L [L = thp (1a), 1,4-dioxane (1b)], detected in solution by NMR spectroscopy. The reaction of [WCl6] with thp in a molar ratio of 1:2 in chloroform at reflux afforded [WOCl4(thp)] (2a), which was isolated in 51 % yield. [WOCl4(OMe2)] (2b) and [WOCl3(OMe2)2] (3a) were isolated in yields of 53 and 18 %, respectively, from the reaction of [WCl6] with an excess of dimethyl ether. [WOCl3(OEt2)2] (3b) was the only identified metal compound produced from the reaction of [WCl6] and OEt2(1:2 molar ratio). According to NMR studies, the oxide ligand in 2a,b and 3a,b was generated by double C–O bond cleavage involving one equivalent of organic reactant. The 1:1 reaction of [WCl6] with 1,2-diethoxyethane led to [WCl5(κ1-OCH2CH2OEt)] (4) and a minor amount of [WCl4(κ2-EtOCH2CH2OEt)] (5). The aryl oxide compound [WCl5(OPh)] (6) was prepared in 62 % yield from the reaction of [WCl6] and anisole by selective Csp3–O bond activation. The prolonged heating of a mixture of [WCl6] and diphenyl ether in 1,2-dichloroethane led to the isolation of the WVcomplex [WCl5(OPh2)] (7). The molecular structures of 2a and 3a were ascertained by X-ray diffraction.
Chlorination of aromatic compounds with chlorous acid under non-aqueous conditions
Muathen, Hussni A.
, p. 1493 - 1497 (1999)
The non-aqueous solution of chlorous acid is a versatile chlorinating agent for aromatic compounds, e.g. alkylbenzenes, anisoles, and acetanililides. It is also an effective chlorine-substitute for the conversion of aryl bromides into aryl chlorides under mild conditions. The stoichiometry of the chlorination reaction is ArH+3HOClO→ArCl+2ClO2+2H2O, and the mode of dissociation of chlorous acid in dichloromethanc is 3HOClO→HOCl+2ClO2+H2O.
Diphenylphosphinated Ethylene Oligomers as polymeric Reagents for Synthesis of Alkyl Chlorides from Alcohols
Bergbreiter, David E.,Blanton, James R.
, p. 337 - 338 (1985)
Diphenylphosphinated ethylene oligomers can be used as homogeneous polymeric reagents at 90 deg C in carbon tetrachloride to form alkyl chlorides from alcohols and since these funcionalized ethylene oligomers precipitate quantitatively from solution at 25 deg C, they can be easily recovered and separated from the reaction products and can be partially recycled.
The Hexachlorocerate(III) Anion: A Potent, Benchtop Stable, and Readily Available Ultraviolet A Photosensitizer for Aryl Chlorides
Yin, Haolin,Jin, Yi,Hertzog, Jerald E.,Mullane, Kimberly C.,Carroll, Patrick J.,Manor, Brian C.,Anna, Jessica M.,Schelter, Eric J.
, p. 16266 - 16273 (2016)
The hexachlorocerate(III) anion, [CeIIICl6]3-, was found to be a potent photoreductant in acetonitrile solution with an estimated excited-state reduction potential of - 3.45 V versus Cp2Fe0/+. Despite a short lifetime of 22.1(1) ns, the anion exhibited a photoluminescence quantum yield of 0.61(4) and fast quenching kinetics toward organohalogens allowing for its application in the photocatalytic reduction of aryl chloride substrates.
The selective functionalization of saturated hydrocarbons. Part 47, investigation of the size of the reagent involved in the Fe(II)-Fe(IV) manifold
Barton, Derek H.R.,Launay, Franck
, p. 12699 - 12706 (1998)
Competition experiments between cyclohexane and various aromatic substrates have been carried out in pyridine-acetonitrile in order to ascertain the steric requirements of the Fe(II)-H2O2 reagent in comparison with the Fe(III)-H2O2 reagent already studied. The latter is distinctly larger and much less reactive than the former. Although these results might indicate that the Fe(II)H2O2 reagent is simply the hydroxyl radical, the chemistry observed is strictly dependent on the presence of picolinic acid. Without the latter, no significant oxidation of any substrate is observed. Hydroxyl radical formation (Fenton Chemistry) is not considered to be ligand dependent in preceding investigations.
