Graduate Thesis Or Dissertation
 

The synthesis and electrocyclization of some linear and cross-conjugated hexatrienes

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  • As part of the continuing investigation of the thermal cis- 1, 3, 5-hexatriene to 1,3-cyclohexadiene rearrangement, four new trienes and a cross-conjugated pentaene have been prepared and their thermal reactions studied. A new route to the synthesis of highly substituted trienes has been developed. The synthesis of three of these polyenes was described using the hydrogenation of enynenes to generate the polyene system. A recently reported coupling reaction was extended to the coupling of enynes and vinyl halides and gives enynenes in high yield. The electrocyclization of all of the polyenes was described. Electrocyclization of trans, cis, trans-l-phenyl -1,3,5-heptatriene 74 (k= 2.1 X 10⁻⁴ sec⁻¹ at 134.4°C, AH* = -29.0 kcal/mole, ΔS* = -6.8 cal deg⁻¹ mole⁻¹ gave cis -5- phenyl -6- methyl -1,3- cyclohexadiene and the trans isomer in a ratio = 550:1. Trans, cis, cis-I-phenyl-1,3,5- heptatriene 77 was shown to cyclize about 200 times slower than 74. Electrocyclization of ethyl 3-(trans-2-styrylcyclohexen- l-yl)-transpropenoate 108 and ethyl 3-{trans-2-(4'-methoxystyrl) cyclohexen-l-yl] -trans-propenoate 116 (for both k= 4.00 X 10⁻⁴ sec⁻¹ at 410.9°K, ΔH* = 28.9 kcal/mole, ΔS* = -9.0 cal deg⁻¹ mole⁻¹ gave cis substituted 1,2,3,4,6,7-hexahydronapthalenes. Finally the thermolysis of 3-ethylidene- 1,5-(dicyclohexen-l-y1)-1,4-pentadiene gave a tetracyclic molecule.
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