The uncatalysed autoxidation of aqueous solutions of tertiary aliphatic amines has been studied in order to obtain information concerning the mechanism of oxidation of Sirotherm resins. Oxidation occurs most rapidly in the free base, and the general correlation of rate with pK, or ionization potential suggests that electron transfer to form an aminium radical cation is rate-determining. The reaction is not initiated by free radical initiators, nor inhibited by radical traps. It is significantly catalysed by strong electron acceptors and by light and is moderately inhibited by the electron donor N-phenylanthranilic acid. Pyrrolidines and hexahydroazepines are oxidized faster than piperidines, and hydroxyl groups on /I-carbons increase the rate of oxidation, while those on y-carbons decrease it. The major products of autoxidation of alkyl pyrrolidines in water were found to be N-oxides. Various pyrrolidinones were isolated in smaller yield.I.C.I. Aust. Ltd., registered trade mark. Weiss, D. E., and Bolto, B. A,, Aust. Pat. 274,029 (1967).
The lithiation
of methoxy- and methylenedioxy-bemyl alcohols is
described; subsequent reactions with ethyl chloroformate
and carbon dioxide to form phthalides have been
investigated, and are compared with metallation-carboxylation
of alternative substrates. The preparation of phthalideisoquinoline
analogues by this method proceeds only in low yields due to the acidity of the
benzylic position in the benzylisoquinoline
precursor.
The synthetic potential for
the photolysis of alkylsuccinimides to give
6-substituted hexahydroazepine-2,5-diones is investigated. The reaction
generally proceeds poorly, particularly when phenyl, cyano
or ethoxycarbonyl groups are present. Fragmentation and
intramolecular disproportionation reactions are
identified as major side reactions.
The reactions of
isoquinoline and phthalazine Reissert
compounds with phthalaldehydic acids and their
derivatives have been investigated as a means of synthesizing 1-(3-phthalidyl)isoquinolines. Of a variety of conditions tried those
involving phase transfer were found, in general, to be the most suitable. The
products, which are analogues of the convulsant
alkaloid bicuculline, showed weak central nervous
system depressant activity.
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