ISSN:
0894-3230
Schlagwort(e):
Chemistry
;
Theoretical, Physical and Computational Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
,
Physik
Notizen:
3-Chloro-2,2-dimethylpropan-1-ol was pyrolysed in a static system at 410·0-459·1 °C and 62-179 Torr. The reaction, in a seasoned vessel and in the presence of the free radical suppressor propene, is homogeneous, unimolecular, and follows a first-order rate law. The rate coefficient follows the Arrhenius equation: log k1 (s-1) = (13·14±0·15) - (218·8 ± 2.1) kJ mol-1 (2·303RT)-1. The products are isobutene, formaldehyde and HCl gas. The exclusive intramolecular migration of the CH2OH group to the positively charged carbon atom, from the C(SINGLE BOND)Cl bond polarisation, appears to proceed by way of an intimate ion-pair type of mechanism. The intermediate 3-methylbut-3-en-1-ol, under the reaction conditions, undergoes a six-centered decomposition characteristic of β-hydroxyalkenes to produce isobutene, formaldehyde and HCl. The pyrolysis of the deuterated substrate, 3-chloro-2,2-dimethylpropan-1-[2H]ol, serves to support the mechanistic consideration assumed above.
Zusätzliches Material:
7 Tab.
Materialart:
Digitale Medien
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