{"id":{"repo_id":"vt","oai_identifier":"oai:vtechworks.lib.vt.edu:10919/41951"},"canonical_url":"https://search.dev.ndltd.org/etd/vt/oai:vtechworks.lib.vt.edu:10919/41951","repository":{"repo_id":"vt","name":"Virginia Tech","base_url":"https://vtechworks.lib.vt.edu/oai/request"},"display":{"title":"The preparation of some unsymmetrical ortho substituted ̲o-dibenzoylbenzenes and 1,3-diphenylisobenzofurans","abstract":"A review of the more important methods of synthesis of 1,3-diarylisobenzofurans (III) and o-diaroylbenzenes (II) was made. These were compared with the possibilities involved in the type of synthesis in which substituted o-benzylbenzophenones (I) are oxidized to o-diaroylbenzenes (II) and subsequently reduced to 1,3-diarylisobenzofurans (III). It is seen that this latter method affords a greater variety of substituents for these types of compounds than the other methods. The possible orientations of substituents are also greater. Two o-benzylbenzophenones (I), 2’-methyl-2-benzylbenzophenone (LIII) and 2'-methoxy-2-benzylbenzophenone (LVI), were prepared by the action of the appropriate Grignard reagent on o-benzylbenzonitrile (LII) and subsequent hydrolysis of the intermediate ketimine. These were oxidized to the corresponding o-dibenzoylbenzenes (II), 2’-methyl-2-benzoy1 benzophenone (LIV), and 2'-methoxy-2- benzoylbenzophenone (LVII), by the use of sodium dichromate and sulfuric acid, Reduction of these with zinc dust in acetic acid gave the corresponding 1,3-diarylisobenzofurans (III), 1-(2‘-methylpheny1)-3-phenylisobenzofuran (LV) and 1-2\" -methoxyphenyl)-3-phenyl isobenzofuran (LVIII). Attempts were made to prepare 2'-chloro-2-benzylbenzophenone (I; Reo-Cl and R'=R) by the same method as that in the above-mentioned paragraph. None of the ketone could be obtained. A small amount of a hydrocarbon was obtained in one case which was analyzed as C₂₀H₁₄. The action of the Grignard reagent of 4-iodo-1, 3-dimethylbenzene on o-chlorobenzaldehyde gave 2-chloro-2', 4'-dimethylbenzohydrol (LI). New compounds synthesized are 2‘-methy1-2~benzoylbenzophenone (LIV), 2'-methoxy-2-benzoyl benzophenone (LVII), 1-(2'-methylphenyl)-3-phenylisobenzofuran (LV), 1-(2'-methoxyphenyl1)-3-phenylisobenzofuran (LVIII), and 2-chloro-2! ,4'-dimethylbenzohydrol (LI).","abstract_html":"A review of the more important methods of synthesis of 1,3-diarylisobenzofurans (III) and o-diaroylbenzenes (II) was made. These were compared with the possibilities involved in the type of synthesis in which substituted o-benzylbenzophenones (I) are oxidized to o-diaroylbenzenes (II) and subsequently reduced to 1,3-diarylisobenzofurans (III). It is seen that this latter method affords a greater variety of substituents for these types of compounds than the other methods. The possible orientations of substituents are also greater. Two o-benzylbenzophenones (I), 2’-methyl-2-benzylbenzophenone (LIII) and 2'-methoxy-2-benzylbenzophenone (LVI), were prepared by the action of the appropriate Grignard reagent on o-benzylbenzonitrile (LII) and subsequent hydrolysis of the intermediate ketimine. These were oxidized to the corresponding o-dibenzoylbenzenes (II), 2’-methyl-2-benzoy1 benzophenone (LIV), and 2'-methoxy-2- benzoylbenzophenone (LVII), by the use of sodium dichromate and sulfuric acid, Reduction of these with zinc dust in acetic acid gave the corresponding 1,3-diarylisobenzofurans (III), 1-(2‘-methylpheny1)-3-phenylisobenzofuran (LV) and 1-2" -methoxyphenyl)-3-phenyl isobenzofuran (LVIII). Attempts were made to prepare 2'-chloro-2-benzylbenzophenone (I; Reo-Cl and R'=R) by the same method as that in the above-mentioned paragraph. None of the ketone could be obtained. A small amount of a hydrocarbon was obtained in one case which was analyzed as C₂₀H₁₄. The action of the Grignard reagent of 4-iodo-1, 3-dimethylbenzene on o-chlorobenzaldehyde gave 2-chloro-2', 4'-dimethylbenzohydrol (LI). New compounds synthesized are 2‘-methy1-2~benzoylbenzophenone (LIV), 2'-methoxy-2-benzoyl benzophenone (LVII), 1-(2'-methylphenyl)-3-phenylisobenzofuran (LV), 1-(2'-methoxyphenyl1)-3-phenylisobenzofuran (LVIII), and 2-chloro-2! ,4'-dimethylbenzohydrol (LI).","abstract_has_math":false,"creators":["Spangler, Martin Ord Lee"],"institution":"Virginia Tech","degree_name":"Master of Science","degree_level":"masters","degree_discipline":"Chemistry","degree_department":"Chemistry","school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1953,"date_issued":"1953","date_published":"1953","updated_at":"2026-07-22T22:19:16Z","subjects":[],"languages":["en"],"rights":["In Copyright"],"rights_urls":["http://rightsstatements.org/vocab/InC/1.0/"],"identifier_entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["etd-04072010-020010"],"render_values":[{"text":"etd-04072010-020010","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/10919/41951","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.department","label":"Department","values":["Chemistry"]},{"key":"dc:creator","label":"Author","values":["Spangler, Martin Ord Lee"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2014-03-14T21:33:08Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2014-03-14T21:33:08Z","2010-04-07"]},{"key":"dc:date.issued","label":"Date","values":["1953"]},{"key":"dc:publisher","label":"Institution","values":["Virginia Tech"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.dcmitype","label":"Dc Type Dcmitype","values":["Text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["masters"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Master of Science"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Virginia Polytechnic Institute"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["In Copyright"]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://rightsstatements.org/vocab/InC/1.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["etd-04072010-020010"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/10919/41951"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["A review of the more important methods of synthesis of 1,3-diarylisobenzofurans (III) and o-diaroylbenzenes (II) was made. These were compared with the possibilities involved in the type of synthesis in which substituted o-benzylbenzophenones (I) are oxidized to o-diaroylbenzenes (II) and subsequently reduced to 1,3-diarylisobenzofurans (III). It is seen that this latter method affords a greater variety of substituents for these types of compounds than the other methods. The possible orientations of substituents are also greater. Two o-benzylbenzophenones (I), 2’-methyl-2-benzylbenzophenone (LIII) and 2'-methoxy-2-benzylbenzophenone (LVI), were prepared by the action of the appropriate Grignard reagent on o-benzylbenzonitrile (LII) and subsequent hydrolysis of the intermediate ketimine. These were oxidized to the corresponding o-dibenzoylbenzenes (II), 2’-methyl-2-benzoy1 benzophenone (LIV), and 2'-methoxy-2- benzoylbenzophenone (LVII), by the use of sodium dichromate and sulfuric acid, Reduction of these with zinc dust in acetic acid gave the corresponding 1,3-diarylisobenzofurans (III), 1-(2‘-methylpheny1)-3-phenylisobenzofuran (LV) and 1-2\" -methoxyphenyl)-3-phenyl isobenzofuran (LVIII). Attempts were made to prepare 2'-chloro-2-benzylbenzophenone (I; Reo-Cl and R'=R) by the same method as that in the above-mentioned paragraph. None of the ketone could be obtained. A small amount of a hydrocarbon was obtained in one case which was analyzed as C₂₀H₁₄. The action of the Grignard reagent of 4-iodo-1, 3-dimethylbenzene on o-chlorobenzaldehyde gave 2-chloro-2', 4'-dimethylbenzohydrol (LI). New compounds synthesized are 2‘-methy1-2~benzoylbenzophenone (LIV), 2'-methoxy-2-benzoyl benzophenone (LVII), 1-(2'-methylphenyl)-3-phenylisobenzofuran (LV), 1-(2'-methoxyphenyl1)-3-phenylisobenzofuran (LVIII), and 2-chloro-2! ,4'-dimethylbenzohydrol (LI)."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Master of Science"]},{"key":"dc:format.medium","label":"Dc Format Medium","values":["BTD"]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["The preparation of some unsymmetrical ortho substituted ̲o-dibenzoylbenzenes and 1,3-diphenylisobenzofurans"]}]}],"canonical_facts":{"dc:contributor.department":["Chemistry"],"dc:creator":["Spangler, Martin Ord Lee"],"dc:date.accessioned":["2014-03-14T21:33:08Z"],"dc:date.available":["2014-03-14T21:33:08Z","2010-04-07"],"dc:date.issued":["1953"],"dc:description.abstract":["A review of the more important methods of synthesis of 1,3-diarylisobenzofurans (III) and o-diaroylbenzenes (II) was made. These were compared with the possibilities involved in the type of synthesis in which substituted o-benzylbenzophenones (I) are oxidized to o-diaroylbenzenes (II) and subsequently reduced to 1,3-diarylisobenzofurans (III). It is seen that this latter method affords a greater variety of substituents for these types of compounds than the other methods. The possible orientations of substituents are also greater. Two o-benzylbenzophenones (I), 2’-methyl-2-benzylbenzophenone (LIII) and 2'-methoxy-2-benzylbenzophenone (LVI), were prepared by the action of the appropriate Grignard reagent on o-benzylbenzonitrile (LII) and subsequent hydrolysis of the intermediate ketimine. These were oxidized to the corresponding o-dibenzoylbenzenes (II), 2’-methyl-2-benzoy1 benzophenone (LIV), and 2'-methoxy-2- benzoylbenzophenone (LVII), by the use of sodium dichromate and sulfuric acid, Reduction of these with zinc dust in acetic acid gave the corresponding 1,3-diarylisobenzofurans (III), 1-(2‘-methylpheny1)-3-phenylisobenzofuran (LV) and 1-2\" -methoxyphenyl)-3-phenyl isobenzofuran (LVIII). Attempts were made to prepare 2'-chloro-2-benzylbenzophenone (I; Reo-Cl and R'=R) by the same method as that in the above-mentioned paragraph. None of the ketone could be obtained. A small amount of a hydrocarbon was obtained in one case which was analyzed as C₂₀H₁₄. The action of the Grignard reagent of 4-iodo-1, 3-dimethylbenzene on o-chlorobenzaldehyde gave 2-chloro-2', 4'-dimethylbenzohydrol (LI). New compounds synthesized are 2‘-methy1-2~benzoylbenzophenone (LIV), 2'-methoxy-2-benzoyl benzophenone (LVII), 1-(2'-methylphenyl)-3-phenylisobenzofuran (LV), 1-(2'-methoxyphenyl1)-3-phenylisobenzofuran (LVIII), and 2-chloro-2! ,4'-dimethylbenzohydrol (LI)."],"dc:description.degree":["Master of Science"],"dc:format.medium":["BTD"],"dc:format.mimetype":["application/pdf"],"dc:identifier.other":["etd-04072010-020010"],"dc:identifier.uri":["http://hdl.handle.net/10919/41951"],"dc:language.iso":["en"],"dc:publisher":["Virginia Tech"],"dc:rights":["In Copyright"],"dc:rights.uri":["http://rightsstatements.org/vocab/InC/1.0/"],"dc:title":["The preparation of some unsymmetrical ortho substituted ̲o-dibenzoylbenzenes and 1,3-diphenylisobenzofurans"],"dc:type":["Thesis"],"dc:type.dcmitype":["Text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["masters"],"thesis:degree_name":["Master of Science"],"thesis:institution_name":["Virginia Polytechnic Institute"]},"updated_at":"2026-07-22T22:19:16Z"}