ISSN:
0009-2940
Keywords:
Alkylation
;
Allylation
;
Carbenium ions
;
Friedel-Crafts reactions
;
Linear free energy relationships
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Competition experiments have been performed to determine the relative reactivities of 23 alkyl chlorides toward allyltrimethylsilane in the presence of catalytic amounts of ZnCl2.The krel scale spans over 11 orders of magnitude from 1-adamantyl chloride (least reactive) to bis(p-methoxyphenyl)methyl chloride (most reactive compound). A fair correlation between the alkylating ability and the SN1 reactivity in solvolysis reactions is found, thus providing a quantitative basis for our long-standing working hypothesis that Lewis acid-catalyzed additions of alkyl halides to CC multiple bonds only yield 1:1 products if the reactants ionize faster than the products. Trityl chlorides do not follow this correlation and are 105 times less reactive than predicted from their SN1 reactivities.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19941270129
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