| dc.description.abstract | This research was directed mainly towards the investigation
of the reactions of allylic amineimides. The work can be divided into
two main sections.
Section 1 of the thesis deals mainly with thermolysis studies
of amineimides. Sections 1a and 1b represent a comprehensive survey
of amineimide literature up to 1971.
N-A1ly1-N,N-dirnethylarnine-benzirnide was prepared and rearranged
at 1400 to l-allyl-1-benzoyl-2,2-dimethylhydrazine. A tentative mechanism
involving an initial migration to the carbonyl oxygen was disproved
by incorporating the amineimide system into a five-membered ring.
N,N~Dimethyl-N-propargylamine-benzimidedid not rearrange
on heating; but the hydrobromide, on heating, disproportionated to
give 1-benzoyl~2,2,2-trimethylhydraziniumbromide and I-benzoyl-2,2~
dimethylhydrazine. l-Ally'l--l, I-dimethyl-2-benzoy-lhydrazinium bromide
and 1~benzoy-1-2,2, 2-trimethy-lhydrazinium iodide both disproportionated
to give l~benzoyl-2,2-dimethylhydrazine.
Section 1 concludes with a discussion of the mechanisms of
ally'lic migrations in amineimides proposed by J. E. Baldwin.
Section 2 deals with the formation of five-membered heterocyclic
compounds from amineimides by bromination. 1,1-Dimethyl-2benzoyl-
4-bromopyrazolidinium bromide was formed from N-allyl-N,Ndime
thy-lamtne-benzimide , 1,1-dimethyl-2-benzoyl-4-bromopyrazol-3enium
bromide from N,N~dimethyl-N-propargylamine~benzimidevia the unusual acetylenic "bromonium" ion. Hydrogenolysis of both heterocyclic
compounds gave the same product. The preparation was extended
by forming 2,2-dimethyl-4-bromoisoxazolinium bromide from N-allylN,
N-dimethylamine-N-oxide.
Sections 3 and 4 cover a number of unsuccessful attempts to
synthesise other amineimides and l,2-dipolar species. | en_US |
