The reactions of aromatic compounds with nitrogen dioxide
Degree GrantorUniversity of Canterbury
Degree NameDoctor of Philosophy
In the first part of this thesis the reactions of 3,4,5-trimethylphenol (58), 3,4-dimethylphenol (71) and 4-methylphenol (88) with nitrogen dioxide in benzene, and in dichloromethane, are investigated. These phenols are unsubstituted at C2 and C6. Typically the products of the reaction are 2,6-dinitrophenols, and 4-nitro or 4-hydroxy cyclohexa-2,5-dienones. The mode of formation of these compounds is described. In the second part of this thesis 3,4,5-trimethylbiphenyl (91) and 2,3,4- trimethylbiphenyl (92) were treated with nitrogen dioxide in benzene. Reaction of 3,4,5-trimethylbiphenyl (91) gave ring nitrated biphenyls [(97), (98) and (99)], nitromethylbiphenyl (100) and ring nitrated nitromethyl biphenyls [(101), (102) and (103)]. In contrast reaction of 2,3,4-trimethylbiphenyl (92) gave nitratomethylbiphenyls [(111), (112) and (113)] and ketones [(117) and (118)] in addition to the ring nitrated biphenyls [(114), (115) and (116)]. The mode of formation of these compounds is described. In the third part of this thesis the reaction of phenanthrene (130) with nitrogen dioxide in benzene was carried out. This reaction gave the novel isomeric nitro nitrates [(135) and (136)] in addition to the dimeric nitro nitrate (132) and nitrophenanthrenes [(131), (133) and (134)]. An overall mechanistic scheme for the formation of these compound is proposed. Throughout this thesis, extensive use is made of high field Fourier transform n.m.r. techniques and in three cases single crystal X-ray structure analyses were necessary for structure determinations.