The Smiles rearrangement in hydrazidic systems and related syntheses /|nG. A. Pawelchak. -- 260 St. Catharines, Ont. : [s. n.],

This research was directed towards the investigation of the Smiles rearrangement in hydrazidic systems and the synthesis of related heterocyclic compounds. The work can be conveniently divided into two main sections. Section 1 of the thesis relates to the synthesis and examination of the O+N migration of phenoxy- derivatives of hydrazidic halides. In general, hydrazidic halides were found to react with 2-nitrophenol and 4-nitrophenol to give corresponding a-nitrophenoxy- compounds. These a-nitrophenoxy- compounds were found to rearrange in warm base to give the corresponding N-benzoyl compounds via a proposed five-membered transition state. Experiments conducted in styrene revealed no radical contribution to the rearrangement. Cross-over product analysis indicated the rearrangement as intramolecular and consistent with the Smiles rearrangement. The preparation of N-a-chlorobenzylidene-N'-2-nitrophenyl- -N'-(2,4-dibromophenyl)hydrazine from N-benzoyl-N'-2-nitrophenyl- N'-(2,4-dibromophenyl)hydrazine was accomplished using phosphorus oxychloride. Examination of this hydrazidic chloride indicated a marked decrease .in reactivity as compared to the N-a-chlorobenzylidene-N'-phenylhydrazine case. Section 2 concerns itself with the preparation of heterocyclic compounds using an analogy of the five-membered transition state present in the Smiles rearrangement of a substituted benzylidene derivatives A new preparation of 2,4-phenyl1,3,4- oxadiazol-S-one using N-benzoyl-N'-phenylhydrazine and ethyl thiochloroformate is reported. Two new preparations of N-a-thiobenzoyl-N'-(2,4-dibromophenylhydrazine are reported using sodium hydrosulfide in conjunction with N-a-bromobenzylidene-N'-(2,4-dibromophenyl)hydrazine in the first, and phosphorus pentasulfide with N-benzoylN'-( 2,4-dibromophenyl)hydrazine in the second. The latter is preferred due to the formation of a sulfide co-product in the former. Two preparations of 2-phenyl-4-(2,4-dibromophenyl)-1,3,4- thiadiazol-S-one are reported using N-thiobenzoyl-N'-(2,4-dibromophenyl) hydrazine and ethyl chloroformate and ethyl thiochloroformate Two rapid and easy preparations of 2-phenyl-4-(2,4-dibromophenyl)- 1,3,4-triazol-S-one are reported using ethyl chloroformate and ethyl thiochloroformate. Sodium cyanate in conjunction with a-aminobenzylidene-N'-(2,4-dibromophenyl)hydrazine also provided 2-phenyl-4-(2,4-dibromophenyl)-1,3,4-triazol-S-one Section 2 concludes with an examination of two possible mechanistic routes to the prepared heterocycles.

The neo-liberal state and the crisis of public service broadcasting in the Anglo-American democracies /

The NeO'liberal State and the Crisis ofPublic Service Broadcasting in the Anglo-American Democracies The purpose ofthis analysis ofthe present condition ofpublic service broadcasting in the Anglo- American democracies was to investigate whether such media can still be regarded as the primarypublic spherefor a dialogue between each nation 's civil society and the State. The motivationfor this thesis was based on a presumption that such fora for public discussion on the central issues of each society have become viewed as less relevant bypoliticians andpolicy-makers and thepublics they were intended to serve in the Anglo-American democracies over thepast two decades. It is speculated that this is the case because ofa beliefthat the post-war consensus between the respective States andpublics that led to the construction of the Keynesian Welfare State and the notion ofpublic service broadcasting has been displaced by an individualistic, neo-liberal, laissez-faire ideology. In other words, broadcasting as a consumer-oriented, commercial commodity has superseded concerns pertaining to the importance ofthe public interest. The methodology employed in this thesis is a comparative analysisfrom a criticalpolitical economy perspective. It was considered appropriate to focus on the United Kingdom, Australia, Canada and the\ United States because they comprise the four largest Anglo-American nations with democratic political systems andprimarily market economies. Justificationfor this particular sample is reinforced by thefact that case study countries also share a common socio-political and economic tradition. The evidence assembledfor this thesis consisted almost exclusively ofexisting literature on the subjects ofpublic service broadcasting, global economic andpolitical integration, and the ascendance ofthe 'free-market ' ethos in Western democracies since the late mid- to late-1970s. In essence, this thesis could be considered as a reinterpretation ofthe existing literature relevant to these issues. Several important common features werefound among the political, economic and broadcasting systems of the four case study nations. It is proposed that the prevalence of the neo-liberal world view throughout the political and policy environments of the four countries has undermined the stability and credibility of each nation 's national public service broadcasting organization, although with varying intensity and effect,. Deregulation ofeach nation 's broadcasting system and the supremacy ofthe notion of 'consumer sovereignty' have marginalized the view of broadcasting on any basis other than strictly economic criteria in thefour case study countries. This thesis concludes that,for a reconstruction ofa trulyparticipatory anddemocraticpublicsphere to be realized in the present as well as thefuture, a reassessment ofthe conventional concept ofthe 'public sphere ' is necessary. Therefore, it is recommended that thefocus ofpolicy-makers in each Anglo-American democracy be redirectedfrom that which conceived ofan all-encompassing, large, state-ownedand operated public broadcasting service toward a view which considers alternativeforms ofpublic communication, such as local community and ethnic broadcasting operations, that are likely to be more responsive to the needs of the increasingly diverse and heterogeneous populations that comprise the modem Anglo-American democracies. The traditional conception of public broadcasters must change in accordance with its contemporary environment if the fundamental principles of the public sphere and public service broadcasting are to be realized.

Bis-and tris (amidine) fluoroboron cations and related systems studies by Multinuclear NMR and fast atom bombardment mass spectometry

The formation and the isolation of fluoroboron salts, (D2BF2+)(PF6-), (DD'BF2+)(PF6-) and (D3BF2+)(PF6-)2, have been carried out. 1,8-Diazabicyclo [5,4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4,3,O]non-5-ene (DBN), extremely strong organic bases, were introduced into the fluoroboron cation systems and induced a complicated redistribution reaction in the D/BF3/BC13 systems. The result was the formation of all BFnCI4-n-, D.BFnCI3-n and fluoroboron cation species which were detected by 19p and 11B NMR spectrometry. The displacement reaction of CI- from these D.BFnCI3-n (n = 1 and 2) species by the second entering ligand is much faster than in other nitrogen donor containing systems which have been previously studied. Tetramethylguanidine, oxazolines and thiazolines can also produce similar reactions in D/BF3/BCI3 systems, but no significant BFnC4-n- species were observed. As well as influences of their basicity and their steric hindrance, N=C-R(X) (X = N, 0 or S) and N=C( X)2 (X = N or S) structures of ligands have significant effects on the fonnationof fluoroboron cations and the related NMR parameters. D3BF2+ and some D2BF2+ show the expected inertness, but (DBU)2BF2+ shows an interestingly high reactivity. (D2BF2+)(X-) formed from weak organic bases such as pyridine can react with stronger organic bases and form DD'BF2+ and D'2BF2+ in acetone or nitromethane. Fast atom bombardment mass spectrometry is doubly meaningful to this work. Firstly, FABMS can be directly applied to the complicated fluoroboron cation containing solution systems as an excellent complementary technique to multinuclear NMR. Secondly, the gas-phase ion substitution reaction of (D2BF2+)(PF6-) with the strong organic bases is successfully observed in a FABMS ion source when the B-N bond is not too strong in these cations.