Abstract:
The work in this thesis deals mainly with nucleophilic substitution
of chloroanthraquinones as a route to various starting materials which
might rearrange, via aryne intermediates to afford fused-ring heterocy1ic
carboxylic acids.
1-Amino-5-chloroanthraquinone was successfully prepared by reacting
1,5-dichloroanthraquinone with sodium aZide in ref1uxing dimethylsulfoxide
(DMSO). It could also be prepared from the same starting material by
reaction with ammonia (gas) in DMSO in the presence of potassium fluoride.
Treatment of l-amino-5-chloroanthraquinone with potassium amide in liquid
ammonia or with potassium t-butoxide in t-butylbenzene returned mainly
starting material, although in the latter case some 1-amino-5-hydroxyanthraquinone
was also isolated.
1-Hydroxy-5-chloroanthraquinone was ultimately prepared by
diazotization of the amino-analog. It was recovered almost quantitatively
after treatmenu'with potassium amide in liquid ammonia. The reaction
with potassium t-butoxide in t-buty1benzene was anomalous and gave
1-hydroxyanthraquinone as the only iso1able product.
Acridines were successfully prepared by the action of 70% sulfuric
acid on 1,5-bis(p-toluidino)-anthraquinone and 1-p-toluidino-5-
ch10roanthraquinone, and in the latter case, cleavage to give an acridinecarboxylate
was attempted.
Substituted anthraquinones reacted with sodium azide in sulfuric
acid to give azepindiones by -NH insertion. Methods for separating and identifying isomeric mixtures of these compounds were examined.
Attempted decarbonylation of selected azepindiones to give acridones
gave mainly what were thought to be amino-benzophenone derivatives.
Chloroanthraquinones were found to react with hexamethylphosphoramide
(HMPA) to give mixtures of the dimethylamino- and methylaminoderivatives.
Under the same conditions halogeno-nitrobenzenes and
nitrophenols were substituted to give the appropriate dimethyl aminobenzenes,
except in two cases. 3-Chloronitrobenzene reacted anomalously
to give a small amount of 3,3'-dichloroazobenzene and a trace of
4-dimethylamino-nitrobenzene. Pentachlorophenol reacted to give a
pentachlorophenylphosphorodiamidate in good yield.
