Acenaphthylene with maleic anhydride

The photocycloaddition of maleic anhydride to acenaphthylene has been studied by Hartmann and Heine.(107a> Irradiation of acenaphthylene in the presence of maleic anhydride in light-atom solvents (dioxane, acetone, or acetonitrile) yields only dimers or copolymers of acenaphthylene. In heavy-atom solvents (dichloromethane, dibromomethane, or iodomethane), however, dimerization is suppressed and cycloaddition with maleic anhydride predominates ... 

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. 

The susceptibility order of monomers to mechanosynthesis (acrylic acid > acrylonitrile > methacrylamide > acenaphthylene > maleic anhydride) is consistent with related chemistry. Maleic anhydride, which has the lowest susceptibility and is not homopolymerizable, probably combines as a single monomer unit... 

Thermolysis of indenone oxides (151) is an equally useful route to the betaines (150). Dimethyl acetylenedicarboxylate and compound 151 (R = R = Ph) at 175°C give adduct 153, and cyclohexanone at 150 C gives adduct 154. - Similarly, 1,3-dipolar adducts (e.g., 155) have been obtained using a wide variety of olefins—including cis- and [rans-, 2-dichloroethylene, dimethyl maleate, dimethyl fumarate, maleic anhydride, cis- and tran -stilbene, fran -dibenzoylethylene, tra .y-l,2-dicyanoethylene, A -phenylmaleimide, vinylene carbonate, acenaphthylene, and norbor-nadiene. With cis olefins the endo adduct (155) is usually the predominant isomer. Diphenylcyclopropenone gives compound 156 by spontaneous elimination of carbon monoxide from the initial adduct (157). Adduct 156... 

The reaction of nitrone 101 with cyclic olefins, such as maleic anhydride.61 W-phenylmaleimide,77 cyclopentene,77 norbornene,77 in-dene.77 and acenaphthylene,77 is normal and gives isoxazolidine of type V. Some reactions of a-(6-uracilyl) jV-phenylnitrone are also reported those with allyl alcohol, methyl acrylate, acrylamide, and styrenes, all give 5 substituted 3-uracilylisoxazolidines (type I).79,80 With methyl methacrylate a type III cycloadduct was formed.79,80... 

On the other hand, cis or trans and cyclic 1,2-disubstituted ethylenes have been well-known till 1980 to be not homopolymerized with a radical initiator owing to the much more increased steric effect of the substituents except for a few exceptions, e.g., fluoro-substituted ethylenes and cyclic derivatives, vinylene carbonate (VCa), maleic anhydride (MAn), yV-substituted maleimides (RMI), and acenaphthylene. However, if 1,2-disubstituted and tri- or tetra-substituted ethylenes can homopolymerize, the polymers with a substituted polymethylene structure, which is different from the above polyethylenes, would be obtained (eqs. 1 and 2), i.e., the polymers would be less flexible (more rigid), and have higher glass transition temperatures than those for the polyethylenes, although their processabilities would decrease. 

A detailed study on the possibility of modifying polyethylene by mechanical methods was performed by Protasov and Baramboim [32, 49]. In their investigation they used a low-density polyethylene of 35,400 and several solid monomers (methacrylamide, maleic anhydride, acenaphthylene, acrylic acid, and acrylonitrile). The mechanical dispersion was performed in a four-position eccentric vibromill with cavities and balls, diameter 6-8 mm, made of the same stainless steel. The vibration frequency was 50 Hz with an amplitude of 2-4 mm. The reaction was carried out in air at temperatures from -30 to -65" C. The formation of copolymeric products, after separation by extraction, was confirmed by many techniques (qualitative reaction... 

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