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Eliminations in Cyclic cis ‐ trans ‐Isomers
Author(s) -
Hückel W.,
Hanack M.
Publication year - 1967
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.196705341
Subject(s) - solvolysis , chemistry , alkylation , primary (astronomy) , medicinal chemistry , deamination , cis–trans isomerism , hydrogen , organic chemistry , hydrolysis , catalysis , physics , astronomy , enzyme
Solvolytic El eliminations from cis‐alkylated p‐toluenesulfonates of cycloalkanols (particularly menthols and decalols) lead almost exclusively to “Saytzeff hydrocarbons”; this fact is accounted for by the increase in the rate of solvolysis that results from the participation of the tertiary trans‐hydrogen. The corresponding trans‐alkylated compounds give mixtures. The solvolysis of these compounds is compared with the deamination of stereoisomeric primary amines and with the proton‐catalysed dehydration of tertiary alcohols. E2 reaction of vicinally alkylated cycloalkane derivatives involves attack on the secondary hydrogen, and in the case of the trans isomers leads to pure “Hofmann hydrocarbon”; with the cis‐isomers, competition occurs between the E1 and E2 reactions. The fact that the tertiary hydrogen is not attacked is explained by its anionic character. Reference is made to the competition of E1 and E2 reactions in exhaustive methylation.