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Durham E-Theses Durham E-Theses Halogen and interhalogen adducts of substituted amido-ions Britton, G.C. How to cite: Britton, G.C. (1979) Halogen and interhalogen adducts of substituted amido-ions, Durham theses, Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/8946/ Use policy The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that: • a full bibliographic reference is made to the original source • a link is made to the metadata record in Durham E-Theses • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders. Please consult the full Durham E-Theses policy for further details. Academic Support Oce, Durham University, University Oce, Old Elvet, Durham DH1 3HP e-mail: [email protected] Tel: +44 0191 334 6107 http://etheses.dur.ac.uk HALOGEN AND INTERHALOGEN ABDUCTS OF SUBSTITUTED AMI DO-IONS A THESIS PRESENTED BY G. C. BRITTON FOR THE DEGREE OF MASTER OF SCIENCE" OF THE UNIVERSITY OF DURHAM DEPARTMENT OF CHEMISTRY UNIVERSITY OF DURHAM The copyright of this thesis rests with the author. JUNE 1979 No quotation from it should be published without Unive. his prior written consent and information derived !*• SCIENCE "> 2 9 NOV V) from it should be acknowledged. SECTION LibraH ABSTRACT The reaction between N-dimethylchloramine and iodomethane - + which yields the species (CHj)4N (CH^)2N(lCl)2~ - has been investigated with a view to elucidating possible mechanisms, and a number of analagous and related compounds have been prepared. Variation of initial molar ratios gives rise to different products and ratios of products. A large excess of N-dimethyl• + chloramine yields a mixture of (CH^N.ICl and (CH5)4N (CH5)2N(lCl)2~ (1:1.55) whereas a one hundredfold excess of iodomethane yields iodine only. With nearly equal ratios of starting materials, (CHj)^N+l"" is formed. These results suggest a number of competing reactions which became more or less favourable depending on initial reactant concentrations. A proposed mechanism for the reaction leading to the formation of + (CH5)4N (CH5)2N(IC1)2~ has been suggested: (i) (CH5)2NC1 + CH^I » (CHINCH (ii) (CHJJJNCII > (CH^N + IC1 (iii) (CHJJJN + CHjI > (CHj) M+ i" XI (iv) (CH )2NC1 + IC1 » (CH )2N IC1 + + (v) (CH3)2M + (CH3)4N I" > (CH5)4N (CH^NdCl )g **IC1 The adduct (CH^gNCl.ICl is a proposed intermediate, and this substance has been prepared, together with two other previously unknown related compounds (CH^NCl.IBr and (CH^NCl.Br,,. The analagoua N-dibenzylchloramine compound (CgH^CH2)2NCl• IC1 has also been prepared. Various adducts of N-halami. es have been reacted with large cation halides. The reaction between (CH,)_NC1.IC1 and + (CH5)4N l" yields (CH^N* (CH^N (lCl)2" , and analagous + reactions have produced the now compounds Cs (CHj)2N(lCl)2~ , + (C6H5)2I (CFI5)2N(IC1)2~ and (CH^^CCH^N]^" . Attempts to synthesise these and related compounds from N-halamine adducts and large cation tri-iodides have yielded the novel + Tl (CH^)2N(lCl)2~ besides providing a faster route to + (CH3)4M (CK5)2N(IC1)2" and (CH^N^CH^NI^ A number of halide insertion reactions have been tried and have been shown to produce simple polyhalides or polyhalide mixtures in the majority of cases. Heaction of (CH^)2NC1.I2 t with (CH5)4N' 'Br" yielded the new substance (CH^N^CH^NIBrClg" while with (CH^N*!"" , the similarly novel (CH^N'^tCHj^NI^Cl"" is formed. Reaction of N-dimethyliodamine with iodoraethane gives + excellent yields of (GH^)/)N (CH^)?NI/1~ , but various attempts to alkylate !-!-halamines with allyl iodide failed. Benzyl iodide, on the other hand, produced complex mixtures or simple polyhalides + one such being (CHgH,-CH2)2 (CH^)2N I^~ which does not appear to have been previously reported. TO MY MOTHER. ACKNOWLEDGEMENTS The author would like to thank Professor T. C. Waddington and Dr. C. J. Ludman of the Chemistry Department, University of Durham, for their help and guidance during the completion of this work. Acknowledgement is also gratefully given to Mrs. N. Terry for typing the manuscript, often under somewhat trying circumstances. This work was carried out under a grant and year's leave of absence from Durham County Local Education Authority. TABLE OF CONTENTS CHAPTER 1 Introduction Page 1 CHAPTER 2 Experimental Techniques Page 2 CHAPTER 3 Alkylation of N~dimethylohloramine Page 21 CHAPTER 4 Reactions of N-dimethylchloramine Adducts with Large Cation Halides Page 32 CHAPTER 5 Further Reactions of N-halamines Page 39 •CHAPTER 6 Halide Insertion Reactions Page 49 CHAPTER 7 Reaction of N-dimethylchloramine CHAPTER 8 with Tetramethylammonium Iodide Page 57 Infra red Spectroscopy Page 60 Discussion and Conclusions Page 74 Suggestions for Further Work Page 80 References Page 84 CHAPTER ONE INTRODUCTION 1 INTRODUCTION N-halamines were discovered by Wurtz during his wider work on aminoalkanes (l). He found that addition of halogens to chilled solutions of free amines produced a variety of derivatives which in general possessed sharp odours and exhibited considerable reactivity; he suggested that these new substances were effectively amines with their original hydrogen atoms replaced by halogens, e.g. 3CH,NH0 + 2C1„ * CH,NC10 + 2CH,NH0.HC1 Tscherniak disovered another route to these compounds which employed the reaction between alky1ammonium chlorides and chlorates(l) e.g. (C2H5)2NH2C1 + NaCIO > (C^^NCl + HgO + NaC1 and this method of preparation (2) is still widely used. It was modified and greatly extended in 1894 by Berg (3) who described the preparation and properties of nineteen N-halamines in sufficient detail for the results to be reproduceable, and his methods have become more or less standard since. N-halamines are in general highly reactive substances. They possess two active centres - a nitrogen atom and a halogen atom which together provide the basis of an extensive and diverse chemistry. The nitrogen atom plays a dominant role in various bicyclic re-arrangements and hydrazine formation and acts as a base (in nucleophilic substitution), a radical cation (in the Hoffman- Loffler reaction) and a radical (in a number of addition and photolytic reactions). 2 The halogen can act as a cation in halogenation reactions and as an anion in Grignard reactions. Reaction of N-halamines with Grignard reagents was extensively investigated by Coleman (4) who showed the former's valuable potential as synthetic reagents, a potential which has been well exploited since (5)« There is as yet no complete review of the chemistry of N-halamines, but an important step towards this has been undertaken by Kovaeic et al (6). N-halamine chemistry covers such a wide field that it would clearly be neither possible or desirable to cover it - even superficially - here. In any case, much of it although extremely interesting is not strictly relevant to the brief provided by the title, so it is perhaps more appropriate to concentrate on an aspect which has a more direct bearing on the subject matter of the thesis - the reaction of N-halamines with haloalkanes, which can produce a variety of unusual and unexpected substances. 1. The formation of trialkylhalammonium cations. For many years studies of both amine-halogen addition compounds and the reaction between tri-alkylamines and chlorates (i) have suggested the existence of tri-alkylhalammonium ions. For example, Hantzch (7) reacted aqueous trimethylamine with chloric (i) acid and obtained N-dimethylchloraraine and methanol as products. He proposed that an intermediate species was formed, which in modem terms would be (CH^N + H0C1 > (CH^NCIOH * (CH^NCI + CH,OH 3 formulated (CHj)^NCl OH. Ellis (8) adduced kinetic, spectroscopic and colligative evidence for this or similar species but no solid products were obtained until Cowan (9) isolated salts by precipitating the trialkylhalammonium ions with large, stabilising anions such as BFj or CIO^. These salts were prepared via three routes: (i) by reaction of aqueous trimethylammonium-chlorine complex with sodium tetrafluoborate (ill) or chlorate (VII) + - BP" + 4 (CH5)3NC12 (aq) > (CH^NCl CI (aq) > (C^) BC1 BF^'o) (ii) by reaction of trimethylamine-chlorine complex with Lewis acids in a sealed tube, e.g: + (CH,),NC10 + BC1, } (CHj^NCl BC1. 3 5 2 3 5 3 4 (iii) by reaction of dimethylhalamines with alkylating agents, e.g. + - (CH^NCl + CH^O C105 > (CH^NCI C104 This last method was extensively investigated and the following results were obtained: (a) N-Mmethylchloramine reacts with dimethyl sulphate, methyl fluo- sulphonate and methyl perchlorate producing, respectively, + - + + - (CIL^NCl 05SOCH5 , (CH^NCl SO^P , (CH^NCl C104 The reactions were performed simply by condensing an appropriate amount of N—dimethylehloramine on to a. solution of the alkylating, agent in diethyl ether or carbon tetrachloride on the vacuum line at liquid nitrogen temperature (-196°C). The mixture was allowed to warm up in a refrigerator to -5°C and the solid salt isolated either by filtration in a glove box or by pumping away all volatile material. 4 Methyl nitrate did not react, but iodomethane gave an unexpected and most interesting product which is discussed below. (b) N-dimethylbromamine reacts with methyl fluosulphonate to give + highly water soluble (CH^)jNBr SO^P which can be precipitated by aqueous sodium chlorate (VII) as (CHj)^NBr CIO^. The bromo- compounds are much less stable than their chloro-equivalents, samples changing rapidly from white to red at room temperature. 2. Reaction of N-halamines with alkylhalides. Reaction of aminoalkanes with haloalkanes produces successively dialkyl and trialkylamines and finally quaternary ammonium salts thus: + - CH5NH2 + CHZI ^ (CH5)2NH:+ EL ^ {CR^)^SE^I + - (CH5)2NH + CHjI > (CH^N + HI > (CH2)TNH I + - (CH-.)2N + CH3I > (CH,).N I 3 3 3 3 4 The reactions proceed via nucleophilic attack of the haloalkane by the basic amine: (CH3)3N:,N:' *GH,—«GH5—— I >> (CH^NI which is exactly parallelled by the reaction of N-dimethylchloramine with methyl perchlorate mentioned previously (CH,)_C1N:: «CH«CI,L 00- CIO, > (CH2),NC1 CIO.
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