Sharts, Clay M. (1959) Some fluorinated cyclobutenes and their derivatives. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-02232006-152633
Cyclobutene structures were established for the cycloaddition products of 1-ethynylcyclohex-l-ene with trifluorochloroethylene or difluorodichloroethylene. The orientations of the addends were in accord with theories developed previously.
Hydrolysis of the fluorinated cyclobutenes with sulfuric acid gave halogen-substituted cyclohex1encyclobutenones as well as cyclohex-1-enylcyclobutadienoquinone. Some halide displace merit reactions of the adducts were found to give, in general, products corresponding to reaction by SN2 mechanisms. Trifluro-2-chlaro-3-(cyclox-1-enyl)-cyclobutene gave Dials-Alder adducts with maleic anhydride and dicarbethoxyacetylene. 1,1-Difluoro-2,4-dicloro-3-(cyclohex-1-enyl)-cyclobutene with triethylamine underwent dehydrohalogenation and afforded, by means of an unusual rearrangements, 2-fluoro-1,3-dichloro-5,6,7,8-tetrahydronaphthalene.
The nuclear magnetic resonance (NMR) spectra of the fluorinated cyclobutenes and cyclobutenones showed spectra which were anomalous in terms of simple NMR theory but which could be explained by assumption of cross-ring spin-spin coupling between hydrogen and fluorine.
|Item Type:||Thesis (Dissertation (Ph.D.))|
|Degree Grantor:||California Institute of Technology|
|Division:||Chemistry and Chemical Engineering|
|Thesis Availability:||Public (worldwide access)|
|Defense Date:||1 January 1959|
|Default Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Imported from ETD-db|
|Deposited On:||02 Mar 2006|
|Last Modified:||26 Dec 2012 02:31|
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