Synthetic plant-growth regulators derived from fluorene-9-carboxylic acid ('morphactins') are introduced and the literature on them is reviewed. Similar herbicidal activity has been found with 9,9-bishydroxymethylfluorene, a compound which can be obtained directly from the hydrocarbon fluorene. There follows a detailed review of the chemistry of fluorene and 9,9- bishydroxymethylfluorene. 9-Substituted and ring-substituted derivatives of this diol have been synthesised and their chemistry and biological activity are discussed. The hydroxymethylation of substituted fluorenes is possible on a small scale in suitable solvents which do not stabilise the corresponding radical anions. This radical anion formation, when it occurs, seriously reduces the yield of hydroxymethylated product. Acetonitrile as solvent and aqueous benzyltrimethyl ammonium hydroxide as base were found to be a particularly useful system for these reactions. Methyl 2-chloro-9-hydroxymethylfluorene-9-carboxylate was found to be the most active compound synthesised. It was concluded that a 9-carboxylic acid group is required for high activity. None of the compounds examined were found to be more active than 'chlorflurecol’, the commercial product.

No description available.

As part of a program to synthesise and investigate macrocyclic polynuclear arrays, a new range of phenol based pseudocalixarene macrocycles have been synthesized, combining some of the properties of the Schiff-base and calixarene macrocycle systems. A series of dinuclear complexes of the pseudocalixarene macrocycle H6LI containing two 2,2'-methylenediphenol groups have been synthesised and structurally characterised.

The work described in this thesis forms part of an attempt to understand some of the factors controlling the acid-catalysed rearrangements of 1-methoxybenzobarrelenes. A review is presented in chapter one of the important features of the rearrangement-chemistry of dibenzo- and benzo-barrelenes. The commonly observed interconversion of the bicyclo[2,2,2]octadien-2-yl and bicyclo[3,2,1]octadien-2-yl cations is discussed in detail and finally some of the extensive rearrangements of highly substituted benzobarrelenes are presented to illustrate the more subtle aspects of the rearrangements.

The conversion of [4-3H]- and [4-3H; 3,5-2H2]-phenyl-alanine into tyrosine by cultures of Pseudomonas sp. (NCIB 9289) has been studied. Fromm a consideration of the degree of retention of tritium observed during the hydroxylation of the two precursors a kinetic isotope effect, kD/kT = 2.8 ± 0.1 (kH/kD = 10 ± 1), has been calculated for the final aromatisation process following the NIH shift. The relevance of this result to the overall reaction pathway is discussed in the light of similar data derived from possible chemical models for the biological process.

The oxidation of aniline and substituted anilines by sodium hypochlorite was studied in buffer solutions at 5°C when sodium hypochlorite was added to an excess of aniline suspended in alkaline buffer, azobenzene, 4-anilinoazobenzene, azophenine (2,5-dianilinobenzoquinonedianil), p-hydroxyazobenzene, indoaniline, a black material, possibly aniline black and a rose-red compound, possibly phenosafranone, were formed, When aniline was added to an excess of sodium hypochlorite, azobenzene, azophenine, 4-anilinoazobenzene, 2,5-dianilinobenzoquinone imide anil, and 4-aminodiphenylamine were obtained. The structure of these compounds were determined by spectroscopy and mass-spectroscopy and confirmed by comparison with authentic specimens. The nature of the products obtained is consonant with hydrazobenzene, 4-aminophenol and 4-aminodiphenyl amine being the initially formed compounds. p-Chloroaniline under similar conditions yielded tetra-p-chloroazophenine, 4,4'-dichloroazobenzene, asymmetrical azo-compounds, and blue-violet products. 2,4-Dichioroaniline and 2,4,6-trichloroaniline gave the corresponding azo-compounds, o-p- and m Nitroaniline similarly produced azo-compounds except for o-nitroaniline which was oxidised to benzofurazanoxide at pH 10 but to the azo-compound at pH 8. 2,4-Dinitroaniline yielded an azo-compound but 2,4,6-trinitroaniline failed to react. Mesidine (2,4,6-trimethylaniline) and p-aminobenzoic acid were oxidised to azo-compounds in high yields; the latter also gave appreciable amount of 2,4,6,2',4',6-hexachloroazobenzene. The hypochlorite oxidation of hydrazobenzene and nitroso-benzene gave high yields of azobenzene and nitrobenzene respectively; the oxidation of phenylhydroxylamine gave azobenzene, 4-anilino-azobenzene and other products. Acetanilide was oxidised but failed to yield any of the products obtained from aniline, the alkaline decomposition of N-chloroacetanilide follows a similar path. These reactions are compared with those of other oxidising agents and their possible mechanism are discussed. It is shown that routes involving the formation and reaction of phenylnitrenium ions (PhNH) or phenylnitrenes (PhN) are possible; the intervention of phenylamine radical (PhNH-) appears less likely.

A complete reinvestigation of the nitration of coronene has been carried out, it having been found that the literature methods and descriptions were unreliable; the preparations of nitrocoronene, dinitrocoronene, trinitro-coronene, and hexanitrocoronene have been carefully studied and precise conditions of their preparations are reported. Nitrocoronene and dinitrocoronene were converted to tri-nitrocoronene and hexanitrocoronene by use of 85% nitric acid and fuming nitric acid respectively. Similarly, tri-nitrocoronene was transformed into hexanitrocoronene by treatment with fuming nitric acid. The infrared spectra of the various nitro derivatives and of the coronene-hexanitro-coronene complex have been discussed. Treatment of nitrocoronene, dinitrocoronene, and trinitrocoronene with phenylhydrazine provided the corresponding amines, which on acetylation with acetic anhydride in pyridine, at room temperature, gave the corresponding N-acetyl derivatives. On prolonged heating under reflux with an excess of acetic anhydride, NN-diacetyl derivatives of the amines were obtained. Oxidation of coronene with sodium dichromate in acetic acid at 118° gave corono-1,2-quinone. Nitrocoronene, on oxidation under similar reaction conditions, furnished nitrocorono-1,2-quinone, which being an ortho-quinone formed the corresponding quinoxaline derivative with o-phenylene-diamine. Corono-1,2-quinone on nitration with 75% nitric acid yielded a dinitrocorono-1,2-quinone, whilst with 85% nitric acid a trinitrocorono-1,2-quinone was formed. In an attempt to determine the orientation of the substituents of bis-(diacetylamino)coronene and hence diaminocoronene and dinitrocoronene, a study of dipole moments was made. The dipole moments of NN-diacetyl derivatives of aminocoronene and diaminocoronene were determined. For the evaluation of the orientation of the substituents within these compounds, the angle of the group moment of the NN-diacetylamino group with its axis of rotation has been calculated from the observed dipole moments of NN-diacetyl-aniline and NNN'N'-tetra-acetyl-p-phenylenediamine, and also from the observed dipole moments of NN-diacetyl-2-naphthylamine, and 2,7-bis-(diacetylamino)naphthalene. From a consideration of the dipole moment data, infrared and n. m. r. spectra, it has been suggested that the most likely structure for the dinitrocoronene mentioned above, is that of 1,5-dinitrocoronene. For trinitrocoronene although 1,4,5-, 1,4,8-, 1,5,9- and 2,3,7-trisubstitutions are probable, the most likely formula is felt to be the 2,3,7 -trinitrocoronene. For hexanitrocoronene a structure having one nitro group on each outer ring is indicated, likely structures are 1,3,6,7,9,12- and 1,3,5,7,9,12-hexanitrocoronene.

The preparation and purification of acetylcoronene, coronaldehyde, and methylcoronene has been reinvestigated. The oxidation of these compounds, under a variety of conditions, has been attempted; the expected oxidation of acetylcoronene and coronaldehyde to coronene-carboxylic acid has not been observed. The preparation of diethyl coronylidenemalonate and cyanocoronene is reported; the latter, on hydrolysis, gives coronenecarboxylic acid. The nitration of the monosubstituted coronene derivatives has been attempted. Under mild nitration conditions in no experiment was one nitro group introduced, in three cases - from acetylcoronene, methylcoronene, and diethyl coronylidenemalonate - were two nitro groups introduced. The low solubility of these compounds in appropriate solvents did not allow proton magnetic resonance studies to be carried out. Under strong nitration conditions acetylcoronene, cyanocoronene, coronaldehyde, and coronenecarboxylic acid gave pentanitroderivatives; the attempted interconversions of these products are reported. Their relationship with the known compound, hexanitrocoronene, has been investigated. Formylation of methylcoronene and dimethylcoronene, to give methylcoronaldehyde and dimethylcoronaldehyde respectively, was carried out by treatment with n-butyl dichloromethyl ether, in the presence of titanium tetrachloride; the aldehydes, on reduction with hydrazine hydrate (100%) and potassium hydroxide in trigol, gave dimethylcoronene and trimethylcoronene, respectively. Methylcorononitrile has been prepared from methylcoronaldehyde. The base-catalysed interaction between diethyl malonate and methylcoronaldehyde, and between diethyl maIonate and difmethylcoranaldehyde gave the appropriate condensates. All of the products resulting from the formylation processes appear to be mixtures.

A number of reactions of tetrahalogenobenzynes have been investigated. The reactions of tetrafluorobenzyne with 2-methyl- and 2,5-dimethylfuran gave the expected Diels–Alder adducts (dihydro-tetrafluoroepoxinaphthalene derivatives) which on treatment with butadiene afforded 9-methyl- and 9,10-dimethyltetrahydrotetrafluoroanthracenes. Further reactions with tetrafluorobenzyne followed by dehydrogenation gave 9-methyl- and 9,10-dimethyloctafluorotriptycenes which were used to study new examples of long-range 19F–1H spin–spin coupling 1H NMR spectroscopy.

A review of recent advances of the chemistry of polyhalogenaromatic compounds, with an emphasis placed on the uses of the corresponding lithium and Grignard derivatives in the formation of polyhalogenaromatic complexes of metals and metalloids is presented. 1,2,3-Tribromotrifluorobenzene was prepared by the decomposition of 1-lithio-2-bromotetrafluorobenzene in the presence of dry lithium bromide, and its structure elucidated from 19F and 13C nuclear magnetic resonance studies. Mass spectral analysis of the reaction products showed the presence of 1,2,3,4-tetrabromodifluorobenzene, formed by further attack of n-butyllithium on the tri-bromo-derivative with subsequent decomposition in the presence of lithium bromide. Polybromobiphenyls, having molecular formulae C12F7Br3 and C12F6Br4 were detected in the reaction products by mass spectrometry and mechanisms are given to account for their formation.