The alkylation of 2-methylcyclohexanone imines using methyl acrylate has
been investigated with a view to optimising the reaction conditions.
The mechanism of this alkylation reaction has been investigated and it has
been shown that the alkylation does not proceed via a 2,6-intermediate
which subsequently undergoes a rearrangement to the 2,2-product, but
rather proceeds directly to the 2,2-product.
As it had been shown that the alkylation of 2-substituted cyclohexanone
imines in dry methanol occurred at the more substituted position, it was
decided, in the light of certain apparently anomolous patent work, to
investigate the alkylation of unsubstituted cyclohexanone imines using a
variety of electrophilic alkenes. The results show that in certain instances,
2,2-bis-alkylation occurs and in others, mono-alkylation and that it is the
strength of the electron-withdrawing group attached to the alkene which
determines whether 2,2-bis-alkylation occurs or not. The reasons for this
are discussed in the text. The preparation of a number of novel
2,2-bis-eyclohexanones and an octahydroquinoline are described.
The reaction of I-phenyl-2-propen-l-one (phenyl vinyl ketone) with the
benzylaluine imines of 2-butanone and I-phenyl-2-propanone in methanol
gave gave two novel bicyclic diones, whereas the reaction between the
benzylamine imine of 3-pentanone with I-phenyl-2-propen-l-one gave
only mono-eyclic products only even though there appeared to be no
impediment to the formation of the bicyclic compound. The structures were
determined using nuclear magnetic resonance and confirmed by X-ray
crystallography. The reaction between I-phenyl-2-propen-l-one and
N-(l-phenyl-l-ethylidene)benzylamine gave after hydrolysis only the
mono-substituted product, 1,5-diphenyl-l ,5-pentandione. / Thesis (Ph.D.)-University of Natal, Durban, 1990.
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:ukzn/oai:http://researchspace.ukzn.ac.za:10413/5650 |
| Date | January 1990 |
| Creators | Rae, Bruce. |
| Contributors | Hickmott, P. W. |
| Source Sets | South African National ETD Portal |
| Language | en_ZA |
| Detected Language | English |
| Type | Thesis |
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