The chemistry of 1,2-quinone monooximes hi« been reviewed. The synthesis of 5-amlno, 5-alkylamino and 5-acylamino substituted 1,2-benzoquinone monooximes was systematically studied. Thus, It has been found that 5-amino-1,2-benzoquinone-2-oxime (5-AqoH), 5-ethylamino-4-methyl 1-1,2- benzoquinone-2-ox I me (5-Et-4-MeqoH), 5-hexylamino-1,2-benzoquinone-2-oxime (5-HxqoH) and 5-heptylamino-1,2-benzoquinone-2-oxime (5-HptqoH) were best prepared by the reaction of the corresponding phenol with sodium nitrite In the presence of concentrated hydrochloric acid. Under these conditions, N-nitrosation was inhibited and the 1,2-benzoquinone- 2-oxlme hydrochlorides were formed. The 5-acylaminc1,2-benzoqulnone-2- oximes, 5-propionylamino-1,2-benzoquinone-2-oxime (5-PrqoH), 5-butyrylamino-l,2-benzoquinone-2-oxime (5-BuqoH), 5-pentanoylamino-1,2-benzoquinone-2-oxime (5-PeqoH), and 5—heptanoylamino-1,2-benzoquinone-2-oxime (5-HpqoH) were obtained from their metal complexes, since the direct reaction of the phenol with sodium nitrite failed to give the compounds giving the corresponding l,4-benzoquinone-4-oximes,3- proplonylamino-1,4-benzoquinone-4-oxime (3-PrqoH), 3-butyrylamino-1,4- benzoquinone-4-oxlme (3-BuqoH), 3-pentanoylamino-1,4-benzoquinone-4- oxime (3-PeqoH) and 3-heptanoylamino-1,4-benzoquinone-4-oxime (3-HpqoH) instead. Spectroscopic analysis has shown the compounds to exist in the quinone oximic rather than In the nitrosophenollc form. X-ray crystallographic studies of 5-HxqoH, 5-Et-4-MeqoH and 5- Et-4-MeqoH.HCI have shown ail three compounds to have some 1,4-oxime- imino character. The synthesis of nlckel(ll), copper(ll), palladium(ll) and platinum(ll) complexes of the acylamino and alkylamino substituted 1.2- benzoqulnone-2- oximes both by the direct and nitrosation methods was examined. The nitrosation method gave rise to complexes NI(qo)2.nH20, Cu(qo)2.nH20 and Pd(qo)2 but failed to give the corresponding platinum complexes. The latter were only obtained by the direct method. The nickel(ll) and oopper(ll) complexes reacted with pyridine and 2,2-dlpyrldyl to give adducts of the type NI(qo)2(py)2 Cu(qo) (py) and M(qo) (dipy) respectively. The palladium and platinum complexes however failed to react with either of the Lewis bases. Magnetic moment studies showed the hydrated complexes and Lewis base adducts to be magnetically dilute and thus monomeric. Such studies, as well as IR and LSIMS mass spectral analysis of the anhydrous complexes Ni(qo) and Cu(qo) , showed them to be associated both in the solid State and in solution. The reaction of selected 1,2-quinone monooximes (qoH) and metal 1.2- quinone monooximates (M(qo)2; qoH = 1,2-nap ht hoqu I none-1-oxime (1-nqoH), 1,2-naphthoquinone-2-oxime (2-nqoH), 3-butyrylamino-1,2-benzo-quinone-2-oxime, 4-chlora-1,2-benzoquinone-2-oxlme (4-ClqoH), 4-bromo-1,2-benzoquinone-2-oxime (4-BrqoH), 5-acetylamino-1,2-benzoquinone-2-oxime (5-AcqoH), 5-hydroxy-1,2-benzoquinone-2-oxlme (5-HqoH); M = Nl and Cu) with dimethyl acetylenedicarboxylate (DMAD) was systematically examined. The reaction of 1-nqoH and 5-HqoH gave rise to nucleophile addition products cis- and trans-(0-1,2-dicarbomethoxyethenyl)-1,2-naphthoquinone-1 -oxime, trans-(0-dicarbomethoxyethenyI)-5-hydroxy-1,2-benzoquinone-2-oxime. The yields were enhanced by the presence of small amounts of alkali and alkaline earth metal chlorides. With M(1-nqo)2 and M(Buqo)2 (M = Ni, Cu) 1,4-oxazines were the only products formed. However, M(4-Clqo)2 and M(4-Brqo)2 1,4-benzoxazinones and 1,4-benzoxazines were isolated. The reaction of the structurally related 1,2-dloxlmes emd metal 1,2-dioxlmates M(dmgH)2 and M(dagH)2» (dmgH2 = dimethylglyoxime; dagH_ = 1,2-dlaminoethanedlone dIoxIme; M = NI, Cu) with DMAD was also examined. The dimethylglyoxime and its metal complexes failed to afford any adducts while the 1,2-diaminoethanedione dioxIme and its metal complexes gave nucleophilic addition products cis- and trans-bls(0-1,2-dicarboxyethenyl)-1,2-diaminoethanedione dioxime. Mechanisms for the reaction of DMAD with both the quinone monooximes and the 1,2-dioximes have been proposed.

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.

Considerable interest has recently been shown in the field of marine traffic engineering. Real life data sources made available for maritime studies are often expensive and inconvenient to collect. The marine radar simulator presents the researcher with a relatively inexpensive and readily available source of navlgatlonal data. With the improvement of remote vessel traffic monitoring systems the potential for inexpensive real life data analysis Is enhanced. The work of this study has been to allow the analysis of data archived from the Channel Navigation Information Service Automatic Data Processing system (CNIS AOP) installed at St. Margarets Bay Dover using contemporary digital computer graphical facilities, and to compare mariners' behaviour In a real life and simulator collision avoidance situation. For this comparison certain navigational situations known as encounters have been automatically detected using an extension of the Range to Domain Over Range Rate (RDRR) method (Colley et al 1983), referred to as the RDRR+ technique. A statistical comparison has been completed using non parametric techniques.

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).