Browsing by Author "Woolhouse, Anthony David"

Now showing 1 - 2 of 2

Restricted
The attempted synthesis of benzo [4,5] cyclohepta [de] naphthalene and 8-azabenzo [4,5] cyclohepta [de] naphthalene
(Te Herenga Waka—Victoria University of Wellington, 1969) Woolhouse, Anthony David
In 1952 Pullmann et al. Pullmann, B., Pullmann, A., Berthier, G., and Pontis, J., J. chim. Phys., (1952), 49, 20 made a theoretical study of pleiadiene (1), acepleiadylene (2), pleiadene (3), and benzo [4,5] cyclohepta [de] naphthalene (4). Boekelheide and Vick Boekelheide, V., and Vick, G.K., J. Am. chem. Soc. (1956), 78, 653 have synthesised pleiadiene (1) and acepleiadylene (2), and they have shown that their properties, both chemical and physical, agreed with those predicted by calculation. Attempted syntheses of pleiadene (3) and its acenaphthylene analogue (5) were described by Cava and Schlessinger Cava, M.P., and Schlessinger, R.H., J.Am. chem. Soc. (1963), 85, 835 in 1963. They showed that these compounds were much less stable than pleiadiene or acepleiadylane; neither compound could be isolated, both being obtained as the dimer resulting from a Diels-Alder self-condensation reaction. As Craig, J.T., Aust. J. Chem., (1966), 19, 1927 has indicated, this instability might have been predicted by analogy with the increasing reactivity in the acene series which results from linear fusion of six membered rings. On the other hand, the hydrocarbon, benzo [4,5] cyclohepta [de] naphthalene (4), resulting from angular fusion of a six membered ring to one of the formally fixed double bonds of pleiadiene (l) might be expected to be more stable than, or at least as stable as, pleiadiene itself.
Restricted
Studies of Some Strained Ring Systems
(Te Herenga Waka—Victoria University of Wellington, 1973) Woolhouse, Anthony David
The present study has been directed towards investigating two facets of small, strained-ring chemistry. The first part of the work describes the attempts made at introducing aziridine functions into a series of appropriately substituted bicyclo[2.2.1]hept-2-enes and bicyclo[2.2.1]hepta-2,5-dienes, primarily through decomposition of the corresponding Δ2-triazoline cycloadducts. The thermal and photochemical modes of nitrogen elimination from these Δ2-triazolines have been examined. From both modes of decomposition, the adducts derived from bicycloheptenes have been shown to lead stereospecifically to the corresponding 3-azatricyclo[3.2.1.02,4]octanes. The photochemically-induced deazetation of unsaturated adducts derived from bicycloheptadiene also proceeds stereospecifically and provides a convenient and simple synthesis of 3-azatricyclo[3.2.1.02,4]oct-6-ene derivatives. However, the thermal decomposition of these same adducts proceeds by retrodiene fragmentation rather than via the elimination of molecular nitrogen. The stereochemistries of the fused aziridines and the Δ2-triazoline precursors have been determined by nmr spectroscopy. The second part of this work has involved a study of substituted arocyclopropenes. The addition of secondary diazoalkanes to 1,4-quinone-N,N'-dibenzenesulphonylimines, previously reported to yield gem-diarylarocyclopropenes, has been reinvestigated and the addition extended to other 1,4-quinonoid systems. The products obtained are reassigned as simple fused cyclopropane derivatives and not arocyclopropenes. Attempts to obtain gem-dihalogenobenzocyclopropenes by base-induced dehydrohalogenation of appropriate bicyclo[4.1.0]hept-3-enes have been examined, and the systematic chemistry of 7,7-dichloro-2,5-diphenylbenzocyclopropene studied. In particular, a series of replacement reactions leading to gem-dialkyl and diaryl benzocyclopropenes and, in several instances, to products resulting from subsequent intramolecular rearrangement have been developed. Substantial evidence is presented for the existence of the benzocyclopropenyl cation.