"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.
Stoffer, James O.
Hanna, Samir B.
McDonald, H. O. (Hector O.)
Beistel, Donald W.
Johnson, James W., 1930-2002
Russell, Robert R.
Ph. D. in Chemistry
United States. Department of Health, Education, and Welfare
University of Missouri--Rolla. Department of Chemistry
University of Missouri--Rolla
ix, 96 pages
© 1970 Joseph Terril Bohanon, All rights reserved.
Dissertation - Open Access
Library of Congress Subject Headings
Ring formation (Chemistry)
Print OCLC #
Electronic OCLC #
Link to Catalog Recordhttp://laurel.lso.missouri.edu/record=b1066953~S5
Bohanon, Joseph Terril, "Substitution and photolytic rearrangements in three-member ring compounds" (1970). Doctoral Dissertations. 2282.