ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The aminolysis and hydrolysis of several sulphamate esters, RNHSO2ONp (R = PhCH2, Ph, 4-MeC6H44, 3-MeC6H4, 4-FC6H4, 4-ClC6H4, 3-ClC6H4, H; Np = 4-NO2C6H4) were been studied in 50% (v/v) aqueous acetonitrile at various temperatures. Reaction of the esters with an amine (R1NH2) gives -ONp and both sulphamide, (RNHSO2NHR1) and sulphamate (RNHSO2O-R1NH3+) products. First-order rates were determined by the appearance of -ONp and sometimes also by the disapperance of ester. The reaction was found to be independent of amine type and concentration and at the high pHs that obtain the substrate esters are fully ionized. A Hammett ρacyl of -;1·8 was obtained for the decomposition of the sulphamate anions and this is consistent with substantial N=S bonding in the transition state leading to N-sulphonylamine, RN=SO2. This intermediate then partitions very rapidly, reacting with R1NH2 and H2O respectively. ΔH
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610080907
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