Abstract:
This research was directed mainly towards the investigation
of the reacti.ons of· substituted chlorobenziophenones under strongly
basi,c conditions. The work 'can be divided into two main sections.
The Introduction deals mainly with historical studies on
aryne chemistry and the Haller-Bauer reaction.
Secti.on I i.s concerned with syntheses of 2-benzamido-2'chlorobenzophenone
and 2-benzamido~3'-chlorobenzophenone,and with
thei,r respective reactions wi.th potassium amide in ammonia.
o-Chlorophenylacetic acid was converted to the acid chloride and then
by Friedel-Craftsreaction with benzene to w-(o-chlorophenyl)acetophenone.
Reaction wi.th phenylhydrazine and Fischer cyclization gave 3- (0chlorophenyl)-
2-phenylindole, which was ozonized to 2-benzamido-2'chlorobenzophenone.
The isomeric 3' -chlor,..o ke: tone was similarly
synthesised from m-chlorophenylacetic acid. Both the 2'- and
3' -ch.loroketones gave N-benzoylacridone on treatment with potassium
amide in ammonia; an aryne mechanism is involved for the 3'-chloroketone
but aryne and nucleophilic substitution mechanisms are possible for
the 2'-chloroketone.
Hydrolysis of the 2'- and 3'-chloroketones gave 2-amino-2'chlorobenzophenone
and 2-amino-3'-chlorobenzophenone respectively. A
second new acridone synthesis is given in the Appendix involving reactions
of these two ketones with potassium t-butoxide in t-butylbenzene.
i
Section 2 deals with the investigation of the reaction of
some tricyclic ch1orobenzophenones with potassium amide in liquid
ammonia. These were 1-ch1orof1uorenone; which was pr~pared in several
steps from f1uoranthene, and 1- and 2-ch1oroanthraquinones. 1-Ch1orof1uorenone
gave 1-aminof1uorenone ; 1-ch1oroanthraquinone gave 1- and
2-aminoanthraquinones; 2-ch1oroanthraquinone was largely recovered
from the attempted reaction.
