Acenaphthylene, structure

Similar acenaphth-(9,10)-acenaphthylene structures were described in the literature [199]. The formation of polymers may lead to novel highly condensed... 

Atkinson, R., Aschmann, S.M. (1988) Kinetics of the reactions of acenaphthene and acenaphthylene and structurally-related aromatic compounds with OH and NOs radicals, N2Os and 03 at 296 2 K. Int. J. Chem. Kinet. 20, 513-539. 

Photolytic. Based on data for structurally similar compounds, acenaphthylene may undergo photolysis to yield quinones (U.S. EPA, 1985). In a toluene solution, irradiation of acenaphthylene at various temperatures and concentrations all resulted in the formation of dimers. In water, ozonation products included 1,8-naphthalene dialdehyde, 1,8-naphthalene anhydride, 1,2-epoxyacenaphthylene, and 1-naphthoic acid. In methanol, ozonation products included 1,8-naphthalene dialdehyde, 1,8-naphthalene anhydride, methyl 8-formyl-1-naphthoate, and dimethoxyacetal 1,8-naphthalene dialdehyde (Chen et al., 1979). Acenaphthylene reacts with photochemically produced OH radicals and ozone in the atmosphere. The rate constants and corresponding half-life for the vapor-phase reaction of acenaphthylene with OH radicals (500,000/cm ) at 25 °C are 8.44 x lO " cmVmolecule-sec and 5 h, respectively. The rate constants and corresponding half-life for the vapor-phase reaction of acenaphthylene with ozone at 25 °C are... 

A particularly interesting group of compounds in combustion effluents are those with a vinylic bridge such as acenaphthylene (peak 4) and cyclopenteno[cd]pyrene (peak 32). Peak 23, although not labeled, has been positively identified as acephenanthrylene, a compound which also has a vinylic bridge. We emphasize this structural feature because of its chemical reactivity (compared to the fully aromatic portions of the PAH). We shall see later that this reactivity is important when considering the fate of PAH in the atmosphere. 

The products of polyethylene modification are mixed Mock and graft copolymers of three dimensional structures (with acrylic acid, methacrylamide and acrylonitrile) or linear structures (acenaphthylene and maleic anhydride). This is again consistent with the nature of the monomers and the activity of their radicals. 

In the case of indene and acenaphthylene slightly syn prevalent fluoro methoxy adduct formation was observed, while in the case of 1-phenyl-substituted benzocyclene triads the profound effect of the structure of the alkene and the reaction conditions on the stereochemical result of the reaction was established.76 ... 

The yellow, nonfluorescent, hydrocarbon acenaphthylene in solution dimerizes on irradiation to form a product with a cyclobutane structure ... 

Sulfuration of acenaphtho[l,2- ]acenaphthylene 80 with elemental sulfur (1 molar amount as Sg) in DMF at 130°C gave the pentathiepane 7, with a [5.3.3]propellane structure, as the sole product, in 88% yield (Scheme 15) <1998TL2605, 1999EJ0597>. In the case of 3-phenylacenaphtho[l,2- ]acenaphthylenes 83, pentathiepanes were separated as a mixture of two conformers 8 and 9 in the equilibrium ratio of 55 45. Both isomers 8 and 9 slowly isomerized into each other in solution at room temperature. 

The mass spectra of binuclear iron carbonyl complexes of acenaphthylene and azulene have been briefly reported 26). The acenaphthylene complex previously 43> reported as Ci2H8Fe2(CO)6 exhibits Ci2H8Fe2 (CO)5 as the highest m/e ion the implied pentacarbonyl formulation was later 44> confirmed by X-ray crystallography which indicated structure 16. The reaction between azulene and Fe(CO)s has been reported 45> to give dark red CioHgFegfCOJs this formulation was confirmed by... 

The reaction schemes of carbonization have also been investigated (11-15). The molecular structure of the carbonization intermediates can influence strongly the optical anisotropy of the resultant coke. The carbonization intermediates have been reported for the pyrolysis of acenaphthylene, which provides a rare example of atmospheric carbonization of a pure organic chemical (11). The carbonization scheme is illustrated in Figure 2. The intermediates II, III, and VI are proposed based on... 

That is, the ordered structure of the cholesteric mesophase affects the formation of the traTO-adduct advantageously. Furthermore, the trans/cis product ratio depends significantly on the initial acenaphthylene concentration. In isotropic solutions, the dimerization of singlet-excited acenaphthylene molecules is known to yield exclusively the czv-adduct, whereas a mixture of cis- and traTO-adducts results from triplet-excited solute molecules. The lowering of cu-adduct production in the mesophase has been attributed to the enhanced efficiency of the triplet reaction in comparison with the singlet reaction, as shown by quantum yield measurements [732]. The increase in triplet reaction efficiencies has been ascribed to the increase in the fraction of acenaphthylene-acenaphthylene collisions which have coplanar or parallel-plane orientations with respect to the surrounding solvent molecules, and not to the increase in the total number of collisions per unit time [732]. See references [713, 732, 733] for a more detailed discussion of this photodimerization reaction. 

The 1,4-dicyanonaphthalene-sensitized photocyclodimerization of the vinyl ethers (192), yielding (193) has been described. 9,10-Dicyanoanthracene-sensitized dimerization of cyclohexa-1,3-diene affords the two [4+2] adducts (194) and (195) in a total yield of 60% and in a ratio of 4 1. This is to be contrasted with the previous report of cyclohexadiene dimerization where [2 + 2] dimers were also obtained." A detailed study of the photodimerization of some acenaphthylenes (196) has been reported. " The structures and configurations of the products have been elucidated by spectroscopic methods." ... 

Synonyms 1,2-Dihydroacenaphthylene 1,8-Dihy-droacenaphthalene 1,8-Ethylenenaphthalene Acenaphthylene Naphthyleneethylene Periethyl-enenaphthalene Ethylenenaphthylene Chemical/Pharmaceutical/Other Class Arene belonging to the class of polycyclic aromatic hydrocarbons Chemical Structure ... 

The spectroscopic studies 83,84) afforded chemical applications. The reductive alkylation of dianion 82 gave alkylated products only in the periphery121K This observation confirms the structure So2 suggested by Rabinovitz and Hafner 84b). Contrary to the reductive alkylation of 232 the quench of dianion 82 did not afford any alkylated product at the central atom C-l 1. The alkylated acenaphthylene served as a starting material for the preparation of acephenanthrylene 34z (vide supra)121). 

The XH NMR spectrum shows bands in the region 4.0-6.0 ppm (See Table 6). Following the discussion of priority of paths of delocalization of aceheptylene dianion 232 and acenaphthylene dianion 82 also 332 and 342 show that specific paths of delocalization are favoured. While in the neutral structure 33 and 34 the competition is between aromatic and nonaromatic structures, in the respective dianions the competition is between nonaromatic and antiaromatic structures (Fig. 9). From the spectroscopic parameters, i.e., chemical shifts and coupling constants of the bridge protons it can be concluded that the neutral systems are best represented by structures with an aromatic skeleton connected to a virtually isolated double bond. In the charged systems, viz. 332 and 342 it seems that a nonaromatic path of conjugation is preferred to an antiaromatic path (Fig. 9). These considerations are also reflected in the carbon chemical shifts and in their HOMO-LUMO gap (AE) (vide infra) 122). It can be concluded from all these observations that there is a tendency of aromatic systems to remain so and to avoid as much as possible paratropic antiaromatic contributions. 

Appendix II presents the structures of organic compounds. Structure 1 provides the number, names, and adiabatic electron affinities of the Bergman Dewar set. Structure 2 gives the adiabatic electron affinities, gas phase acidities, and names of the DNA and RNA bases. Structure 3 shows the charge transfer complex acceptors. Structure 4 gives the numbering system of naphthalene and biphenyl and compares the structures of acenaphthylene and biphenylene. 

---