The synthesis of novel fungicidal phosphoramidates was the main objective of the present work. Various fungitoxic substituents were included in their structure together with a trichloromethyl group which has been shown to enhance fungicidal activity in other compounds. Fourteen compounds containing the 1,1,1-trichloro-2-(diethoxyphosphinylamino)ethyl group were synthesised from the condensation product of chloral and diethyl phosphoramidate. These included one derivative which also contained the 1,1,1-trichloro-2-(bisdimethylaminophosphinyl- amino)ethyl group. Other fungitoxic substituents introduced into the molecular structure of the compounds include imidazole 1,2,4-triazole, morpholine, piperazine, dimethyldithiocarbamate, diethyldithiocarbamate, xanthate and 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxylate. Preliminary investigations were carried out into the synthesis of compounds containing the 1,1,1-trichloro-2-(bisdimethylaminophosphinyl- amino)ethyl group via the condensation of chloral with N,N,N',N'-tetramethyIphosphoric triamide but these proved to be unfruitful due to side reactions. Similar side reactions occurred, but to a lesser extent, when chloral was condensed with 0-ethyl N, N-dimethylphosphorodiamidate, and one derivative was prepared containing the 1,1,1-trichloro-2-(ethoxydimethylaminophosphinylamino)ethyl group. The fifteen potential fungicides were characterised by elemental analysis, nuclear magnetic resonance spectrometry, mass spectrometry, and infra-red spectroscopy. Their fungicidal activity was assessed in vitro against spores of Fusarium culmorum, Fusarium oxysporum, Helminthosporium sativum, Helminthosporium avenge, Septoria nodorum, Ophiobolus graminis, Piricularia oryzoe and Rhizoctania solani and in vivo against Dreschlera teres and Septoria nodorum. These pathogens were chosen because they affect economically important crops, mainly wheat and barley or, in the case of P. oryzae, rice. All the compounds showed some fungicidal activity, the best results being shown by 0,0-diethyl-N-2,2,2-trlchloro-1-(dimethylthiocarbamoylthio)ethyl phosphoramidate against Fusarium culmorum.

The preparations of quadridentate macrocyclic ligands with N4-, O2N2- and S2N2-donor-sets are described.

A range of organophosphorus compounds with bicyclic and tricyclic cage structures has been prepared and studied by n.m.r. spectroscopy.

Several complexes of lithium derived from 1,2-naphthoquinone 1-oxime and 1,2-naphthoquinone 2-oxime have been prepared and characterised using analytical, spectroscopic and thermal gravimetric techniques. I.r. studies indicate that the ligands in these complexes are essentially quinoneoximic in character. For the complex Li(1-nqo)(1-nqoH).Eton the quinoneoximic character has been confirmed by X-ray crystallography. All the lithium complexes were found to be stable towards atmospheric oxygen and water. Their reactivity towards dimethylacetylene dicarboxylate was investigated and compared to that of the copper quinoneoximato complexes. Each of the lithium complexes reacted readily with the acetylene dicarboxylate to give a novel nucleophilic addition product isomeric to the Diels-Alder adduct (1,4-oxazine) obtained from the copper complexes. Re-examination of the behaviour of the copper quinoneoximato complexes towards dimethylacetylene dicarboxylate has given an insight to the mechanism of the reaction and has shown that the copper complexes also act as catalysts in the conversion of 1,4-oxazine derivatives to 1,3-oxazoles. Several lithium carboxylato and dithiocarbamato complexes have been prepared. For the dithiocarbamato complexes a new synthetic method involving the reaction of carbon disulphide and the amine with lithium chloride was developed during this study. Solubility studies were carried out on several complexes of types Li(RCO,), Li(R-NCS,)(R-NCSSH), Ll(nqo) and M(qo) (M = Li, Na2 K, Ni, Co) in polar and non-polar solvents. Maximum solubility was observed in pyridine, dimethylsulphoxlde and ethanol. The scintillation efficiency of pyridine, dimethylsulphoxide and ethanol was examined in commercially available scintillator mixtures and in scintillator mixtures developed during this study. The scintillation efficiency of the lithium complexes derived from the mono-oximes of 1,2-naphthoqulnone, carboxylic and dlthlocarbamlc acids was also investigated. The latter two set of complexes proved promising for loading liquid scintillation counters, when present as 'solid' in the scintillator mixture.

The complexlng behaviour of chloroglyoxine (cgH2), dichloroglyozime (dcgH2), and diaminoglyoxime (dagH2) towards copper and nickel has been studied.

The synthesis and structure of amine adducts of Cu(qo), where qoH = 1,2-naphthoquinone 1-oxime (1-nqoH), 1,2 naphthoquinone 2-oxime (2-nqoH), 4-chloro-1, 2-benzoquinone 2-oxime (4-ClqoH), 4-methyl-1, 2-benzoquinone 2-oxime (4-MeqoH) have been examined.

A selection of metal complexes including ligands of the type R3Xn-3M (where X = halide, M = Sn, Pb, n = 0-3) were prepared and studied using multinuclear N.M.R. spectroscopy.

A series of dibenzo macrocyclic tetraamine ligands with 14-, 15-, 16-, 17- and 19-membered inner great lings (L14 to L15) has been synthesized to investigate the effect of ring size variation on their complexation behaviour with the metal-ions, Ni(Il), Zn(ll) and Cd(II).

3-Hydroxytetrahydrofuran, 3,4-epoxybutan-1-o1 and 3,4-epoxy-3- methylbutan-1-o1 were synthesized. The corresponding methacrylate esters were also prepared and their spectroscopic data are presented. The commercially available 3-methyloxetan-3- ylmethanol was converted to its methacryloyl ester and the analytical data was presented.

The use of oxo-transition metal complexes (particularly molybdenum and vanadium) as catalysts for a number of synthetically important reactions is described. The ability of alkyl hydroperoxides to epoxidise alkenes in the presence of transition metal catalysts is well known and is reviewed here along with the more conventional methods of preparing epoxides in the laboratory, with particular emphasis on their application in asymmetric epoxidations. In this work a number of novel oxo-vanadium and oxo-molybdenum complexes containing bulky and/or chiral ligand systems have been prepared and their application as potential catalysts for regio and/or asymmetric epoxidation has been studied. A synthesis of the oxo-vanadium complex of the known ligand NN''-ethylenebis(iminomethylCcunphof ) was developed and the complex characterised. The synthesis and structure of oxo-molybdenum complexes containing novel tridentate ligands derived from substituted salicylaldéhydes and chiral 2-aminoalcohols are also described along with a D(-)-2,3- butandiol complex of dioxomolybdeniam(VI ). As in a number of examples recently reported in the literature, epoxidation of geraniol and related compounds in the presence of these catalysts showed regioselectivity with exclusive reaction of the allylic double bond. The latter complex was also found to give low asymmetric induction in epoxidations of geraniol. In addition to using pre-formed chiral complexes as asymmetric epoxidation catalysts the possibility of using chiral catalysts prepared in situ from simple molybdenum complexes and an excess of the chiral ligand has also been studied. Some of these systems appeared to give the highest asymmetric inductions in epoxidations of geraniol. During the studies of the epoxidation reaction it was found that some of the oxo-vanadium and oxo-molybdenum complexes were very efficient catalysts for the isomerization of allylic alcohols. The scope of rearrangement reactions of this type was examined for ten structurally different allylic alcohols. It was shown that in most cases isomerization leads to an equilibrium mixture and in some cases the position of equilibria differ from that which would be predicted from classical considerations. Several attempts were also made to prepare more reactive isomerization catalysts by synthesising oxo-vanadium complexes with fluorine containing ligands.