Chlorination Of Aromatic Compounds Research Articles

Mechanism and kinetics of ClO[rad]-mediated degradation of aromatic compounds in aqueous solution: DFT and QSAR studies

The action of ClO is more prominent than HO and Cl in the advanced oxidation degradation of some pollutants. However, studies on the pollutant degradation mechanism and kinetics by ClO are limited. In this study, 43 different kind of aromatic compounds which are important anthropogenic and natural water pollutants were selected as models to investigate their ClO oxidation mechanism and kinetics computationally. The results showed that radical adduct formation (RAF) rather than single electron transfer (SET) reaction was prominent in ClO-initiated reactions of aromatic compounds. In subsequent reactions of the ClO-adduct, the Cl end of the -OCl moiety shifted to the benzene ring, which was the key to hydroxylation and chlorination of aromatic compounds by ClO. The calculated ClO initiated reaction rate constants (kClO) of aromatic compounds were 102–1010 M−1 s−1. ClO was highly reactive to phenolates, anilines and alkoxy/hydroxyl aromatic compounds. Upon the deprotonation of phenol to phenolate, the kClO value increased by 4 orders of magnitude. The kClO values of alkoxybenzenes were higher for compounds with shorter alkyl side chains and more alkoxy substituents. The kClO increased for anilines with longer alkyl side chains. The kClO quantitative structure-activity relationships (QSARs) models were developed to predict the reactivity of ClO to complex aromatic compounds in aquatic systems.

Role of tertiary amines in enhancing trihalomethane and haloacetic acid formation during chlorination of aromatic compounds and a natural organic matter extract

Tertiary amines are prevalent in waters due to anthropogenic inputs and are known to enhance organic compound degradation while increasing disinfection by-product (DBP) formation,viathe strong chlorinating agent, R3N–Cl+.

Room temperature C(sp2)-H oxidative chlorination via photoredox catalysis.

Photoredox catalysis has been developed to achieve oxidative C-H chlorination of aromatic compounds using NaCl as the chlorine source and Na2S2O8 as the oxidant. The reactions occur at room temperature and exhibit exclusive selectivity for C(sp2)-H bonds over C(sp3)-H bonds. The method has been used for the chlorination of a diverse set of substrates, including the expedited synthesis of key intermediates to bioactive compounds and a drug.

ChemInform Abstract: An Efficient Chlorination of Aromatic Compounds Using a Catalytic Amount of Iodobenzene.

Abstract An efficient method was developed for chlorination of aromatic compounds with electron-donating groups using iodobenzene as the catalyst and m -chloroperbenzoic acid as the terminal oxidant in the presence of 4-methylbenzenesulfonic acid in THF at room temperature for 24 h, and a series of the monochlorinated compounds was obtained in good yields. In this protocol, the catalyst iodobenzene was first oxidized into the hypervalent iodine intermediate, which then treated with lithium chloride and finally reacted with aromatic compounds to form the chlorinated compounds.

Sodium Lauryl Sulfate–Catalyzed Oxidative Chlorination of Aromatic Compounds

Chlorination of commercially important aromatic compounds using sodium chloride as chlorine source and sodium periodate as oxidant in acidic medium catalyzed by sodium lauryl sulfate (SLS) led to the chloro-substituted aromatics in good yields and purity. Addition of sodium lauryl sulfate led to increased chlorination rate, better yield, excellent purity, and better quality of end product. The advantages of the present method are greater yield, excellent purity, and shorter reaction time at room temperature. Also dichlorinated product can be obtained by increasing the amount of sodium chloride and sodium periodate at slightly higher temperature (40 °C).

ChemInform Abstract: Silver‐Catalyzed Chlorination of Aromatic Compounds.

With the catalysis of AgOTf, a number of arenes underwent chlorination with tert-butyl hypochlorite to give the corresponding chrlorinated arenes in moderate yields.

Chlorination of aromatic compounds in micellar media: Regioselectivity

Chlorination of phenol and ortho-chlorophenol was studied in micellar media in order to observe the effect on regioselectivity. Hydrogen peroxide/hydrochloric acid–aqueous system, which is environmentally a safer route was employed for chlorination. Selectivity ratio was found to be dependent on the nature and concentration of the surfactant. Ortho/para selectivity ratio up to 12 was realized for the chlorination of phenol. 2,6-/2,4-dichlorophenol ratio up to 1.01 was realized for the chlorination of ortho-chlorophenol.

Chlorination of Aromatic Compounds with Chlorous Acid under Non-Aqueous Conditions

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 dichloromethane is 3HOClO→HOCl+2ClO2+H2O.

Oxidative chlorination of aromatic compounds in the presence of sulphuric acid

Oxidative chlorination of aromatic compounds in the presence of sulphuric acid

Chlorination of toluene by two-phase electrolysis

The electrochemical chlorination of aromatic compounds is of interest from two standpoints; the development of new practical processes and understanding the mechanism of many electrochemical oxidations. The electro-chlorination of toluene has been attempted by many workers. Gourcy et al. [1], for instance, carried out the anodic chlorination of toluene in CH3CN containing some Lewis acids and obtained oand p-chlorotoluenes. We [2] have also obtained chlorotoluenes with high yields through the electrolysis of toluene in CH3OH/LiC1. However, no chloroderivatives substituted in the methyl group have been reported as formed by electrochemical methods. Forsyth and Pletcher [3] have discussed Xwo-phase electrolysis' as an advantageous technology in practical organic electrosynthesis. However, we wish to show that two-phase electrolysis can yield different products from conventional homogeneous electrolysis. In the present work, we have obtained benzyl chloride as well as chlorotoluenes by the electrolysis of toluene in immiscible two-phase systems (Scheme 1).

Selective functionalisation-7: Chlorination of aromatic compounds in the presence of tentacle molecules with pyridinium head groups

tris-Pyridiniumalkyl triesters of benzene-1, 3, 5-tricarboxylic acid with 3, 6 and 11 carbon atoms in the alkyl chain interact with aromatic substrates, phenol, anisole, diphenyl ether and naphthalene in a manner dependent upon the structure of the substrate. Thus all three tentacle molecules interact with phenol through the pyridinium head group as shown by 1H NMR (250 MHz) and confirmed by inhibition of chlorination of the bound phenol. The remaining substrates interact but away from the head group; chlorination is also inhibited. In these cases, a contributor to the low reactivity of the substrates to chlorination in the presence of the tentacle molecules is shown to be the unexpected inactivation of the chlorinating agent, t-butyl hypochlorite, by the tentacle molecules.

Anodic chlorination of aromatic compounds in acetic acid. Part II

Anodic chlorination of aromatic compounds in acetic acid. Part II

Anodic chlorination of aromatic compounds in acetic acid

Summary The electrochemical chlorination of some aromatic compounds at the oxidation potential of Cl − ion has been studied by several electrochemical techniques in anhydrous acetic acid. The species Cl − 2 was evidentiated to be the chlorinating agent under the experimental conditions considered.

Potential-Energy Diagram for the Electrophilic Chlorination of Aromatic Compounds

Potential-Energy Diagram for the Electrophilic Chlorination of Aromatic Compounds

Substitution electrophile aromatique: Nature de l'etape lente dans les reactions de bromation et de chloration catalysees par AlCl 3

Subsequent to the work of Olah et al., the direct and competitive kinetics of bromination and chlorination of aromatic compounds, catalysed by AlCl 3 has been studied. The rate equation for the bromination of benzene and toluene was determined with great care and the ratio k tol./ k benz., measured by two kinetic methods, is very superior to that given by Olah et al. The chlorination of other aromatic compounds has been discussed along similar lines to benzene and toluene. The observed differences between the two methods have been explained and the selectivity determination by the competitive kinetic method within the limits given has been discussed. These results show that the small selectivities observed by Olah et at. cannot be generalized, as having an effect on the diffusion of the reactants. Therefore, it is not necessary to have a π complex in the rate determining step of the aromatic electrophilic substitution.

Chlorination of Aromatic Compounds by Antimony Pentachloride1,2

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTChlorination of Aromatic Compounds by Antimony Pentachloride1,2Peter Kovacic and Allen K. SparksCite this: J. Am. Chem. Soc. 1960, 82, 21, 5740–5743Publication Date (Print):November 1, 1960Publication History Published online1 May 2002Published inissue 1 November 1960https://doi.org/10.1021/ja01506a044RIGHTS & PERMISSIONSArticle Views324Altmetric-Citations38LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (523 KB) Get e-Alerts Get e-Alerts

The Chlorinium Ion as an Intermediate in Chlorination of Aromatic Compounds by Hypochlorous Acid

The Chlorinium Ion as an Intermediate in Chlorination of Aromatic Compounds by Hypochlorous Acid

Chlorination of Aromatic Compounds with Metal Chlorides

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTChlorination of Aromatic Compounds with Metal ChloridesPeter Kovacic and Neal O. BraceCite this: J. Am. Chem. Soc. 1954, 76, 21, 5491–5494Publication Date (Print):November 1, 1954Publication History Published online1 May 2002Published inissue 1 November 1954https://doi.org/10.1021/ja01650a069RIGHTS & PERMISSIONSArticle Views1121Altmetric-Citations44LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (526 KB) Get e-Alerts Get e-Alerts