Play interactions between mothers identified as having obsessional or hysteroid character-styles and their preschool children

The chemistry and spectroscopy of three 1,8-naphthoquinodimethanes were investigated. The precursor to the parent system, 1,4dihydronaphtho[1,8-de][l,2]diazepine, is prepared in several steps from 1,8-bis(hydroxymethyl)naphthalene. Photolytic n,π^* excitation of the cis azo compound causes isomerization to the highly strained trans compound, which rapidly undergoes acid-catalyzed tautomerization to 1,2-dihydronaphtho[1,8- de][1,2]diazepine. . Photolytic π,π ^* excitation of the azo compound causes nitrogen elimination, giving acenaphthene. The triplet state of the parent 1,8-naphthoquinodimethane was observed via its esr spectrum when the azo compound was photolyzed in a hexafluorobenzene matrix at 77 K. A Curie law study conducted below 20 K showed this triplet state to be a thermally accessible excited state, but later work showed this finding to be in error; the triplet state is the ground state of the molecule. Attempts to trap the quinodimethane with oxygen during the photodecomposition of the azo compound were unsuccessful, but some species present during the photolysis reaction was apparently trapped by nitric oxide. In an alternate route into the unbridged 1,8-naphthoquinodimethane system, cis- and trans-l,2-dihydro-l,2-diphenylacenaphthylene were pyrolyzed and found to undergo cis-trans isomerization, but the exact nature of the intermediate in this process is unknown. Photolysis of these hydrocarbons did not cause isomerization.

The precursor to the one-carbon-bridged 1,8-naphthoquinodimethane, 6b,7a-dihydro-7H-cycloprop[a]acenaphthylene, is prepared by

the reaction of copper, iodine, and methylene iodide with acenaphthylene. Previous deuterium labelling studies indicate that this compound thermally undergoes epimerization faster than a [2,3] hydrogen shift, producing lH-phenalene. Kinetics measurements which assume the 1,8-naphthoquinodimethane to be a common intermediate in the two

19 times fasters than the hydrogen shift. Failure to trap this presumed intermediate with either oxygen or nitric oxide may indicate that it is not in fact present during the thermal reactions of the cyclopropane.

The precursor to the two-carbon-bridged 1,8-naphthoquinodimethane, 1,4-dihydro-1,4-ethanonaphtho[1,8-de][1,2]diazepine, is prepared in three steps from cyclohepta[de]naphthalene. Both photolysis and thermolysis of the azo compound give 6b,7,8,8a-tetrahydrocyclobut[a]acenaphthalene and 1,8-diethenylnaphthalene in an approximate ratio of 7:l regardless of solvent. Previous deuterium labelling studies show that the quinodimethane 'is an intermediate in both processes. A new Curie law study of the esr spectrum of this species indicates that it has a triplet ground state, which is further supported by its electronic spectra and molecular orbital calculations. Photolysis of the azo compound in the presence of oxygen gives a combined 73% yield of the two hydrocarbon products in their normal ratio and a 27% yield of an oxygen adduct. Similar thermal decomposition does not give this adduct. Nitric oxide traps the intermediate of both the thermal and photochemical decompositions to some extent. All of these results are explained by spin statistics.