ISSN:
0894-3230
Schlagwort(e):
Organic Chemistry
;
Physical Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
,
Physik
Notizen:
The rates of elimination of several alkyl methanesulphonates were determined in a seasoned, static reaction vessel over the temperature range 300-420°C and the pressure range 28-163 Torr. The reactions are homogeneous, unimolecular and follow a first-order rate law. The overall rate coefficients are given by the following equations: for isobutyl methanesulphonate, log k1 (s-1) = (12·51 ± 0·38) - (177·0 ± 2·1) kJ mol-1 (2·303RT)-1; for 2-phenyl-1-propyl methanesulphonate, log k1(s-1) = (12·62 ± 0·04) - (176·2 ± 0·5) kJ mol-1 (2·303RT)-1; for neopentyl methane-sulphonate, log k1(s-1) = (13·35 ± 0·42) - (198·2 ± 5·2) kJ mol-1 (2·303RT)-1; and for 3-chloro-2,2-dimethyl-1-propyl methanesulphonate, log k1(s-1) = (13·87 ± 0·42) - (218·2 ± 5·4) kJ mol-1 (2·303RT)-1. Rearrangements in these methanesulphonate pyrolyses may proceed via an intimate ion-pair type of mechanism. Consequently, the results appear to confirm that intramolecular migration through autosolvation is possible in gas-phase elimination reactions of certain types of organic molecules.
Zusätzliches Material:
11 Tab.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/poc.610060204
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