The products and mechanisms of some photo-reactions of indenes and naphthalene with acrylonitrile have been studied. Indene reacts with acrylonitrile with the hydrocarbon absorbs light, or when a triplet sensitizer is absorbing. Photolysis under the former condition yields 2-(1-indenyl)- and 2-(3-indenyl)propionitrile, and 6-cyano-2,3-benzobicyclo[3,2,0]hep-2-ene. Base-catalyzed isomerizations of the substituted indenes are reported. On sensitization, cis- and trans-isomers of 7-cyano-2,3-benzobicyclo[3,2,0]hep-2-ene are formed; the known indene dimer is a minor product. Adducts 1,1-dimethyl- and 1,1-diphenylidene with acrylonitrile are also described. Naphthalene adds to acrylonitrile on photolysis to afford trans-8-cyano-2,3-benzobicyclo[4.2.0] octa-2,4-diene and 1- and 2-naphthyl-2-propionitriles. Sensitization gives no detectable products. Studies on fluorescence quenching, solvent effect and deuterium-labelling indicates that exciplexes are formed between acrylonitrile and the excited hydrocarbons. Inter- or intra-molecular protonation of the exciplexes with subsequent reaction of the carbonium ion formed, is suggested to produce indenes or naphthalenes. Possible mechanisms for the formation of other products are proposed. / Thesis / Doctor of Philosophy (PhD)
| Identifer | oai:union.ndltd.org:mcmaster.ca/oai:macsphere.mcmaster.ca:11375/17977 |
| Date | 05 1900 |
| Creators | Huang, Chaog-wei |
| Contributors | McCullough, J. J., Chemistry |
| Source Sets | McMaster University |
| Language | English |
| Detected Language | English |
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