Substitution and photolytic rearrangements in three-member ring compounds

"An investigation into the substitution and photolytic rearrangements of 1,2,3-triphenylcyclopropenes was conducted. Triphenylcyclopropenyl t̲-butyl ether was found to undergo alkyl group exchange with refluxing methanol, ethanol, or 2-propanol to yield the corresponding 1,2,3-triphenylcyclopropenyl alkyl ether when a trace impurity of a 1,2,3-triphenylcyclopropenium halide is present to catalyse the reaction. This forms hydrogen halide with solvent. Upon standing for long periods of time, the 1,2,3-triphenylcyclopropenyl ethers were observed to partially rearrange to new products. A sample of 1,2,3-triphenylcyclopropenyl methyl ether was subjected to photolysis in hexane and yielded 3-methoxy-1,2-diphenylindene, 2,3- diphenylindenone, tolane, benzoic acid, 1,2,3-triphenylpropen-1-one and a polymer. Samples of 1,2,3-triphenylcyclopropene, 3-methyl-, 3-phenyl-, and 3-benzyl-1,2,3-triphenylcyclopropene were prepared and subjected to photolytic rearrangement. Each product yielded the corresponding 3- alkyl- or 3-aryl-1,2-diphenylindene, analogous to the 3-methoxy-1,2- diphenylindene obtained by photolysis of the methyl ether, except the triphenylcyclopropene which yielded isomers of 1,2,3,4,5,6-hexaphenyltricyclo-[ 3,1,0,0²'⁴] hexane. The 3-methyl-1,2,3-triphenylcyclopropene, upon photolysis, yielded the indene exclusively and was only partially isomerized after 68 hours. The 1,2,3,3-tetraphenylcyclopropene yielded 50-75% 1,2,3-triphenylindene and 5-20% of a second product identified as 13-phenyl-13-H̲-indeno [1,2-1̲] phenanthrene. The parent cyclopropene was completely rearranged in 24 hours. The 3-benzyl-1,2,3-triphenylcyclopropene was completely rearranged in 24 hours and gave 47% of 3-benzyl-1,2-indene, a mixture of 1,2,3,4-tetraphenylbutadienes, and a trace of 1,2,3-triphenylnaphthalene"--Abstract, pages ii-iii.

Name thesis:degree_name

Ph. D. in Chemistry

Grantor

University of Missouri--Rolla

Year dc:date.available

2016

Author dc:creator

• Bohanon, Joseph Terril

• Chemistry

Repository record dc:identifier

https://scholarsmine.mst.edu/doctoral_dissertations/2282

OAI identifier oai:identifier

oai:scholarsmine.mst.edu:doctoral_dissertations-3284