{"id":{"repo_id":"must-thes","oai_identifier":"oai:scholarsmine.mst.edu:doctoral_dissertations-3284"},"canonical_url":"https://search.dev.ndltd.org/etd/must-thes/oai:scholarsmine.mst.edu:doctoral_dissertations-3284","repository":{"repo_id":"must-thes","name":"Missouri University of Science and Technology","base_url":"https://scholarsmine.mst.edu/do/oai/"},"display":{"title":"Substitution and photolytic rearrangements in three-member ring compounds","abstract":"\"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.","abstract_html":""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.","abstract_has_math":false,"creators":["Bohanon, Joseph Terril"],"institution":"University of Missouri--Rolla","degree_name":"Ph. D. in Chemistry","degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2016,"date_issued":"2016-02-10T08:00:00Z","date_published":"2016-02-10T08:00:00Z","updated_at":"2026-07-24T03:19:04Z","subjects":["Chemistry"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://scholarsmine.mst.edu/doctoral_dissertations/2282","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Bohanon, Joseph Terril"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["2016-02-10T08:00:00Z"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation - Open Access"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph. D. in Chemistry"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Missouri--Rolla"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://scholarsmine.mst.edu/doctoral_dissertations/2282"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["\"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."]},{"key":"dc:title","label":"Title","values":["Substitution and photolytic rearrangements in three-member ring compounds"]}]}],"canonical_facts":{"dc:creator":["Bohanon, Joseph Terril"],"dc:date.available":["2016-02-10T08:00:00Z"],"dc:description.abstract":["\"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."],"dc:identifier":["https://scholarsmine.mst.edu/doctoral_dissertations/2282"],"dc:subject":["Chemistry"],"dc:title":["Substitution and photolytic rearrangements in three-member ring compounds"],"dc:type":["Dissertation - Open Access"],"thesis:degree_name":["Ph. D. in Chemistry"],"thesis:institution_name":["University of Missouri--Rolla"]},"updated_at":"2026-07-24T03:19:04Z"}