Reactions of Chloramines with Ag(0) and Ag(I) States

Edwards, O. E.; Vocelle, D.; ApSimon, John W.

doi:10.1139/v72-184

Cited by 25 publications

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“…It is noteworthy that the compounds studied by Gassman generally involved cyclic structures.11'25 •26 In the conversion of fV-chloroazacyclooctane and A7-chloroazacyclononane to bicyclic amines by exposure to silver ion, apparently homolytic processes are involved, rather than formation of discrete nitrenium ions. 27 In summary, the low relative migratory aptitudes, the lack of any convincing evidence for singlet-triplet conversion, and the pronounced steric requirements weaken the case for an intermediate nitrenium ion, but are in accord with concerted loss of chloride with alkyl migration, involving a somewhat electron-deficient nitrogen in the transition state.…”

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Chemistry of N-haloamines. XX. Relative migratory aptitudes in the rearrangement of N,N-dichlorocarbinamines by aluminum chloride

White¹,

Nazareno²,

Gleissner³

et al. 1973

J. Org. Chem.

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Rearrangement of a series of iV,iV-dichlorocarbinamines (RWR'CNCU) at low temperatures with aluminum chloride in methylene chloride, followed by acid hydrolysis, produced carbonyl and amine products in moderate to high yields. The following relative migratory aptitudes were determined: phenyl, 18; sec-butyl, 2.4; benzyl, 1.8; «-butyl, 1.0; hydrogen, 0.09; methyl, 0.05. These values compare reasonably well with migratory aptitudes observed in the Schmidt and Baeyer-Villiger rearrangements which appear to proceed by concerted processes. Further support for synchronous loss of chloride ion and 1,2 alkyl shift is provided by the low degree of hydrogen migration, indicating the importance of a trans migratory requirement.Most of the previous work on rearrangement of N,Ndihaloamines by aluminum chloride comprised bi-5 or tricyclic systems.6•7 We recently reported8 the rearrangement of IV , -dichIor otri-n-butylcarbinamine, which yielded, after acid hydrolysis, di-n-butyl ketone and n-butylamine. Migration appeared to involve electron-deficient nitrogen. The present study was concerned with obtaining relative migratory aptitudes for various types of alkyl groups, hydrogen, and phenyl, with the aim of elucidating additional aspects of the reaction mechanism. Useful comparisons are made with related systems entailing 1,2 shifts from carbon to nitrogen, carbon to oxygen, and carbon to carbon. Results and DiscussionPreparation of Starting Materials.-All the amines except di-n-butylcarbinamine were prepared by means of the Ritter reaction or Hofmann degradation as described in the earlier paper.8 (n-Bu)2CHNH2 was obtained from reduction of di-n-butylketoxime with sodium in ethanol. Acetylation of tri-n-butylcarbinamine, followed by LiAlH4 reduction, provided jV-ethyltri-n-butylcarbinamine. N ,N-Dichloroamines 2-8 were synthesized by the previous procedure.8 Treatment of the amine with iV-chlorosuccinimide was used to generate A-chloro-N-ethyltri-n-butylcarbinamine. Yields of products are calculated8 on the basis of N-monochloroamine as the impurity in crude N,AT-dichloroamine.Rearrangement.-Rearrangement of the N,N-dichlorocarbinamines by aluminum chloride, followed by acid hydrolysis, generally yielded a mixture of two carbonyl compounds, two alkyl amines, recovered parent amine, and intractable material (Table I). The best procedure developed in the previous work8 was employed in the majority of runs.Rearrangement of (n-Bu)2(sec-Bu) CNCl2 (2) was studied under a variety of conditions. Little change in yield was noted for (1) Paper XX. Chemistry of .V-Haloamines.

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