- Structure-activity considerations in kinetics and mechanism of chlorine exchange between chloramine-T and secondary amines
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To study the mechanism of N-chlorination of secondary amines by chloramine-T, the kinetics of the reactions of some aromatic-substituted analogues of N-chlorobenzenesulfonamide with various secondary amines were determined. The importance of amine basicity and reactivity of the N-Cl bond of the N-chlorobenzenesulfonamide was also assessed. The results indicate that a mechanism involving the un-ionized species of both reactants (i.e., a molecular mechanism), rather than an ionic mechanism, is operating and that the reaction most likely proceeds via a six-membered-ring transition state that incorporates a water molecule.
- Dannan,Hussain,Crooks,Dittert
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p. 657 - 660
(2007/10/02)
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- Reaction of Cyclopropanamines with Hypochlorite
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Ethylene was formed in 65percent yield when 1-(1-piperidino)cyclopropanol 6, was treated with hypochlorite.This observation raised the possibility that 1-aminocyclopropanecarboxylic acids (ACCs) could yield ethylene by a mechanism that involves (1) decarboxylation to a 1-aminocyclopropanol, followed by (2) a fragmentation of the carbinolamine to ethylene induced by a hypochlorite equivalent.Although this mechanism could be ruled out only for 1e, no evidence could be found for it in the reactions of other ACCs, 1a-f, with hypochlorite.The fact that 1b-cis-2,3-d2 yieldedonly ethylene-cis-1,2-d2 is consistent with either the mechanism described above or a nitrenium ion mechanism.In the reaction of cyclopropanamines with neutral hypochlorite, ethylene is not the major product.From the primary and secondary amino acids 1a-c, a 3-hydroxypropanenitrile or propanamide, 2a-c, probably the product of a nucleophilic ring-opening step followed by decarboxylation, is formed.Similar products are formed from other cyclopropanamines: 2a from 1g, 2d from 1h, 2e and 2f from 1i, and lactone 5 from 1j.
- Vaidyanathan, Ganesan,Wilson, Joseph W.
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p. 1815 - 1820
(2007/10/02)
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