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http://hdl.handle.net/11375/17977
Title: | Photo-additions of lndenes and Naphthalene with Acrylonitrile |
Authors: | Huang, Chaog-wei |
Advisor: | McCullough, J. J. |
Department: | Chemistry |
Keywords: | chemistry;photo-addition; photolysis;indene;naphthalene;acrylonitrile |
Publication Date: | May-1969 |
Abstract: | 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. |
URI: | http://hdl.handle.net/11375/17977 |
Appears in Collections: | Open Access Dissertations and Theses |
Files in This Item:
File | Description | Size | Format | |
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Huang_Chaog-wei_1969May_PhD.pdf | 25.25 MB | Adobe PDF | View/Open |
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