Investigations into the synthesis and properties of indenopyridines
Two novel routes have been investicated. Cyclisation of
enamidoindenes by the Vilsmeier-Haack formylation was
not possible because the condensation between ind8nones
and acetamide,under acidic conditions, did not afford
the desired monomer but instead two dimers,reported
previously, were observed.The two routes by which these
dimers maybe formed were thoroughly investigated and led
to the synthesis of three novel compounds and a known
Omission of an acid catalyst afforded 2-acetamidoindene but
Since commercial 2-indanone was found to be impure by TLC
and melting point,s sample was synthesised using e
literature method. Pure 2-indenone failed to react with
acetamide. It seemed that 2-acetamidoindene was produced
via an impurity in commercial 2-indanone and then only in
poor yield. Attempts to identify the impurity were
The thermolytic Wolff rearrangement of benz[h1r1uinoline-
5,6-diazoketone to benzyl 5H-indeno[1,2-b1pyridine-5-
carboxylate ini tially proved promising. L~any products were
observed but none were isolated in sufficient purity for
The photolytic Wolff rearrangement of 9-diazo- 10-phenanthrone
gave 9H-fluorene-911-tertbutylcarboxamide whose physical ....
properties, which "vere previously unknown, were recorded.
Rearrangement of the pyridyl analogue appeared promising.
0pectroscopic data indicated the desired products, but
isolation of pure compounds ~as not achieved.
UsinG a published synthesis, 5I1-indeno[1, 2-b)pyridin-5-one
was made and reduction,by two separate methods,afforded
the methylene compound.From these starting materials twentytwo
novel compounds were made.For example, reduction of the
ketone afforded the known alcohol (RS)5-hydroxy-511-indeno
1, 2-~:J pyridine. Gr"lc nara resc tl' on c'"ifforced the novel compound
5-hydroxy-5-phenylindeno [1, 2-~ pyridine.
The two substituted oximes, 5H-indeno[1,2-~pyridin-5-one
2-chlorobenzyloxime and 2,4-dichlorobenzyloxime were
prepared. Reduction of the known 5li-indeno[1, ?-b.} pyridin-5-one
oxime afforded 5-acetamido-5li-indeno[1, 2-bJ pyridine.
Substitution reactions afforded the known 7-bromo- and 7,9-
di bromo-5ll-indeno (1 , 2-b] pyridin-5-one. Di bromo- Bnd tri bromo-
5[-indeno (1 ,2-b) pyrillline were prepared, 8S confirme d by
mass spectrometry.The novel 6,7,8,9-tetrabromo-5li-indeno
[1,2-~pyridine was obtained pure and fully characterised.
The nitro- derivatives of the ketone and methylene compounds
were prepared. Reduction of these compounds afforded the
amino- derivatives which were diazotised to give the
corresponding hydroxy- derivatives.
Novel oximes of the 7-bromo- and 7-ni tro-5H--indeno[1, 2-~- pyridin-5-one derivatives were synthesized and then reduced
to the corresponding 5-acetamido- derivatives.
7-nitro-5li-indeno[1,2-~pyridin-5-one when reduced,gave the
unexpected 5,7-diacetamido- derivative. 7-acetamido-5Bindeno[
1,2-b)pyridin-5-one was also prepared.
The known N-oxides of the ketone and methylene compounds
were produced, as well as the novel N-oxides of the nitroderivatives
of 5li-indeno[1,2-b]pyridin-5-one and 5H-indeno
[1, 2-b] pyridine.
From fluorene,9-butyl, 9-propyl and 9-phenyl-9-hydroxyfluorene
were prepared by Grignard reaction.Reduction of
fluorenone using triethylsilane gave, unexpectedly, 9,9'bifluorenyl.
The structures of known and novel compounds were confirmed
by spectroscopic methods including 13C , 1H N~/lR , infrared
spectroscopy, mass spectrometry, melting point and TLC.