ISSN:
0947-3440
Keywords:
Kinetics
;
Azo couplings
;
Alkenes
;
Allylsilanes
;
Enthalpy relationships, linear-free
;
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The kinetics of the reactions of arenediazonium ions with arenes, alkenes, allylsilanes, allylstannanes, and silyl ketene acetals have been studied in acetonitrile solution. The reactions follow second-order kinetics, and in several cases rate-determining attack of the diazonium ion has been proven by kinetic isotope effect studies (1a + 2b), by the independence of the allylsilane reactivities of the rate of desilylation (1a + 10a, d) and by the independence of the rate constants of the diazonium counterion. A decrease of the rate constant with increasing solvent donor ability (correlation with Gutmann's donor number) was found. The reactions of diazonium ions with π-nucleophiles roughly follow the correlation lgk (20°C) = s (E + N), previously derived for the reactions of carbocations with nucleophiles. With the E parameters derived for diazonium ions, rate constants for azo couplings with aromatic and nonaromatic π-nucleophiles can be predicted with an accuracy of ≈102. On the basis of E, the electrophilic reactivities of diazonium ions can be compared with those of carbocations (Figure 9), and the combination with the nucleophilicity parameters N (Figure 10) gives a first clue on possible azo coupling reactions. Literature reports are discussed within this scheme.
Additional Material:
10 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/jlac.199719970111
Permalink
