DOWNLOAD CHLOROSULFONIC ACID A VERSATILE REAGENT PDF

Apart from any fair dealing for the purpose of research or private study, or criticism or review as permitted under the terms of the UK Copyright, Designs and Patents Act, , this publication may not be reproduced, stored or transmitted, in any form or by any means, without the prior permission in writing of The Royal Society of Chemistry, or in the case of reprographic reproduction only in accordance with the terms of the licences issued by the Copyright Licensing Agency in the UK, or in accordance with the terms of the licences issued by the appropriate Reproduction Rights Organization outside the UK. In sulfonation, the sulfonic acid group is very bulky so that in the sE2 reaction k-' becomes large in comparison with k2 which results in a kinetic isotope effect. Stewart' lo successfully reacted cinnamic, salicylic and phenylacetic acid with excess chlorosulfonic acid to obtain the corresponding sulfonyl chlorides. Giles, US ; Chem. Reactions of chlorosulfonic acid with heterocyclic compounds R. In the dialkyl diaryltins, e.

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However, under forcing conditions, alkyl halides can react with the reagent; the reaction involving replacement of one or more halogen atoms by the chlorosulfonate group.

B, Solvolyses of electron-rich arylsulfonyl chlorides, under neutral or acidic conditions, exhibited surprising maxima in solvent-dependent S values as defined versatild Equation Overall, the approximate breakdown of the commercial applications of chlorosulfonic acid is as follows: CHAPTER 5 The Reaction of Chlorosulfonic Acid with Aliphatic Compounds The early work on the sulfonation of aliphatic compounds is described in Suter's book;' there are also several general references2d which include the use of chlorosulfonic acid in the sulfonation of aliphatic compounds.

Prates, Phosphorus, Sulful; Silicon,79, In contrast, when glycerol was heated with chlorosulfonic acid at "C, the product was a glyptal resin.

The sulfonylamino acids were coupled with the appropriate amino acid methyl ester hydrochloride in THF-water-triethylamine mixture using DCC as the coupling reagent to yield the corresponding sulfonylamino dipeptide methyl esters Scheme Hussain, Indian J Chem. In the nucleophilic versatlie reactions of isopropyl p-substituted benzenesulfonates with amines in acetonitrile an SN1-type mechanism was favoured. Raecke, Henkel and Cie. In the majority of cases, the aryl halides were converted into the corresponding scid chlorides in good yields and these were subsequently treated with ammonium hydroxide to give the sulfonamides, the melting points of which were used in organic qualitative analysis to identifl the original aryl halides.

Ban, T, Shimizu, K. It fumes in moist air producing pungent clouds of hydrogen chloride and sulfuric acid Equation 1.

Chemical Forums: Chlorosulfonic Acid : A Versatile Reagent [E-book]

The most effective catalyst for chlorination was found to be a mixture of 0. A reaction mechanism for the sulfonation of phenols was postulated2" in which the first step is esterification sulfation of the hydroxyl group step 1 followed by rearrangement of the sulfate ester into the arylsulfonic acid step 2. Other arylidenecamphor derivatives reacted similarly with chlorosulfonic acid, giving exclusive sulfonation of the aryl ring see Chapter 4, p For instance, 2-methylnitrobenzenesulfonylchloride 92 by condensation with imidazole afforded the sulfonylimidazole 93, which controlled Phytophthora infestans, an important fungal pathogen on tomato.

Gilbert, US ; Chem. For instance, 2-methylpropane or tertiary butane 1 is readily converted into the sulfonic acid 2 by treatment with sulhr tioxide or chlorosulfonic acid in cold chloroform Equation 1.

Chlorosulfonic Acid

Chlorosulfonic acid is an oxidizing and Chapter 1 6 dehydrating agent and functions as a catalyst in the esterification of aliphatic alcohols, alkylation of alkenes, and synthesis of alkyl halides from alkenic halides and isoalkanes containing tertiary hydrogen. News,55, 91;57, 8.

The complexes are prepared by dropwise addition of chlorosulfonic acid to a slight excess approx. It was originally anticipated that the chlorosulfonation of benzil would demand forcing conditions, rather similar to those required for chlorosulfonation of benzophenone, namely prolonged reaction with a large excess of reagent at "C see p In the dialkyl diaryltins, e.

Chlorosulfonic Acid - PDF Free Download

However, the literature is confusing: Further details of the preparation of chlorosulfonic acid are given in Chapter 10, p The structure proposed"' for the product from the action of chlorosulfonic acid on methyl malondiarylamides is also unlikely since at least one of the sulfonic acid groups probably enters the aryl ring. Sulfonation and Chlotosulfonic of Aromatic Compounds using ChlorosulfonicAcid 71 Me In the carbethoxy derivativethe electron-donating power of the original hydroxyl group has been reduced by the attached carbethoxy group hence facilitating selective monochlorosulfonation, and research showed that other protective groups did not versaile to the same selective monochlorosulfonation of phenols.

In this reaction, there was surprisingly no apparent attack by the reagent on the camphor ring see p Under these conditions, the sulfonyl chloride appears directly in the rate equations and for benzenesulfonylation in nitrobenzene solvent, the greater polarity of the solvent should enhance ionization of the sulfonyl chloride-catalyst complex Equation However, it is possible that the sulfonic acid groups may be specially stabilized in this compound by intramolecular H- hydrogen bonding between the hydroxyl and sulfonic acid groups.

Experiments on the hydrolysis fersatile related nucleophilic substitution reactions of alkylsulfonyl chlorides showed the mechanisms were dependent on pH and deuterium substitution patterns. The action of excess chlorosulfonic acid at room temperature on 2,3- 2,4- 2,5- 2,6- 3,4- and 3,5-dichlorophenols afforded the chlogosulfonic substituted benzenesulfonyl chlorides: It was expected that this substrate would yield benzylidenepinacolonesulfonylchloride.

In alkylbenzenes, sulfonation occurs ortholpara to the alkyl group with a predominance of the p sulfonic acid being formed.

The chlorosulfonation of higher alkylphenols has been reported using chlorosulfonic and sulhric acid.