{"id":{"repo_id":"vt","oai_identifier":"oai:vtechworks.lib.vt.edu:10919/88660"},"canonical_url":"https://search.dev.ndltd.org/etd/vt/oai:vtechworks.lib.vt.edu:10919/88660","repository":{"repo_id":"vt","name":"Virginia Tech","base_url":"https://vtechworks.lib.vt.edu/oai/request"},"display":{"title":"The preparation of polynuclear compounds containing the thiophene ring system","abstract":"The process of C. K. Bradsher for preparing mesosubstituted anthracene and 1,2-benzanthracene derivatives has been widely extended. The purpose of this research was to extend this process to the thiophene series, in addition to continuing some work on the 9-(dimethyl)- phenylanthracene series and some newly developed l,2-dimethyl-10-phenyl)-anthracene series. 2'-Thienyl-2-benzylbenzophenone was prepared and cyclized to 9-(2-thienyl)-anthracene by the conventional methods in good yields. 3'-Thienyl-2-benzylbenzophenone was prepared in a different way, indirect and tedious. Thiophene was iodinated to tetraiodothiophene and tetraiodothiophene was reduced with aluminum-amalgam to 3-iodothiophene. 3-Thienylmagnesiumiodide was prepared by the entrainment technique and condensed with 2-cyanodiphenylmethane to 3'-thienyl-2-benzylbenzophenone. This ketone was cyclized to 9-(3'-thienyl)-anthracene by the standard acid mixture. 2-(1-Naphthylmethyl)-phenyl-2-thienylketimine formed from the condensation between 2-(1'-naphthylmethyl)- benzonitrile and 2-thienylmagnesiumbromide resisted hydrolysis to the corresponding ketone but cyclized quantitatively to 10-(2-thienyl)-l,2-benzanthracene. Following the classical Bradsher process, the reaction between 2-thienylmagnesiumbromide and o-chlorobenzaldehyde was unsuccessful because the hydrol formed was so reactive that it polymerized rapidly and ended up with tars. A cross-condensation reaction between 2-ethynylmagnesium bromide and o-chlorobenzylchloride was utilized to give the expected 2-(2'-chlorobenzyl)- thiophene in one step. This new procedure has been widely extended to the other series. It is preferred to. the conventional Bradsher process and the Friedel-Crafts method in terms of time, chemicals, and unequivocal products formed. 2-(2'-Chlorobenzyl)-thiophene so formed by the new procedure was converted by von Braun reaction to the corresponding nitrile and the nitrile was allowed to react with phenylmagnesiumbromide to give 2-(2-thienylmethyl)-benzophenone. The above ketone was cyclized almost quantitatively to 4-phenyl-thiophanthrene. The thiophene-containing ketones prepared in this research are very viscous oils. In order to have crystalline derivatives for identification purposes these ketones were oxidized to the corresponding diketones. 2-Thienyl-2-benzylbenzophenone and 2-(2'-thienylmethyl)- benzophenone gave the identical diketone, 2-benzoyl-2'- thienyl-benzophenone. 3 1 -Thienyl-2-benzylbenzophenone was oxidized to anthraquinone by using 25% sulfuric .acid, acetic acid and sodium dichromate. The formation of anthraquinone indicates that the monoketone cyclized first and then split off the thiophene ring. Apparently, the 3-thienyl group is more susceptible to oxidation than the 2’-thienyl group. A study of the oxidation of anthracene derivatives for structure proof was made using 9-phenylanthracene as a model compound. It was oxidized to 10-phenyl-10-hydroxyanthrone which resisted further oxidation to anthraquinone. It is obvious that the tertiary alcohol system stabilized the phenyl ring. In continuing the work on the 9-(dimethyl)-phenylanthracene series, the yields of three ketimine salts and one ketone were improved. Satisfactory analytical data was obtained for 2’,6’-dimethyl-2-benzylbenzophenone. In an attempt to overcome the steric effects offered by 2,6-ortho groups, 2-(2',3'-dimethylbenzyl)-benzonitrile was prepared. The starting material for this series, l-bromo-2,3-dimethylbenzene has been prepared in 47% yield by diazotization in comparison with the previous yield of 30%.","abstract_html":"The process of C. K. Bradsher for preparing mesosubstituted anthracene and 1,2-benzanthracene derivatives has been widely extended. The purpose of this research was to extend this process to the thiophene series, in addition to continuing some work on the 9-(dimethyl)- phenylanthracene series and some newly developed l,2-dimethyl-10-phenyl)-anthracene series. 2'-Thienyl-2-benzylbenzophenone was prepared and cyclized to 9-(2-thienyl)-anthracene by the conventional methods in good yields. 3'-Thienyl-2-benzylbenzophenone was prepared in a different way, indirect and tedious. Thiophene was iodinated to tetraiodothiophene and tetraiodothiophene was reduced with aluminum-amalgam to 3-iodothiophene. 3-Thienylmagnesiumiodide was prepared by the entrainment technique and condensed with 2-cyanodiphenylmethane to 3'-thienyl-2-benzylbenzophenone. This ketone was cyclized to 9-(3'-thienyl)-anthracene by the standard acid mixture. 2-(1-Naphthylmethyl)-phenyl-2-thienylketimine formed from the condensation between 2-(1'-naphthylmethyl)- benzonitrile and 2-thienylmagnesiumbromide resisted hydrolysis to the corresponding ketone but cyclized quantitatively to 10-(2-thienyl)-l,2-benzanthracene. Following the classical Bradsher process, the reaction between 2-thienylmagnesiumbromide and o-chlorobenzaldehyde was unsuccessful because the hydrol formed was so reactive that it polymerized rapidly and ended up with tars. A cross-condensation reaction between 2-ethynylmagnesium bromide and o-chlorobenzylchloride was utilized to give the expected 2-(2'-chlorobenzyl)- thiophene in one step. This new procedure has been widely extended to the other series. It is preferred to. the conventional Bradsher process and the Friedel-Crafts method in terms of time, chemicals, and unequivocal products formed. 2-(2'-Chlorobenzyl)-thiophene so formed by the new procedure was converted by von Braun reaction to the corresponding nitrile and the nitrile was allowed to react with phenylmagnesiumbromide to give 2-(2-thienylmethyl)-benzophenone. The above ketone was cyclized almost quantitatively to 4-phenyl-thiophanthrene. The thiophene-containing ketones prepared in this research are very viscous oils. In order to have crystalline derivatives for identification purposes these ketones were oxidized to the corresponding diketones. 2-Thienyl-2-benzylbenzophenone and 2-(2'-thienylmethyl)- benzophenone gave the identical diketone, 2-benzoyl-2'- thienyl-benzophenone. 3 1 -Thienyl-2-benzylbenzophenone was oxidized to anthraquinone by using 25% sulfuric .acid, acetic acid and sodium dichromate. The formation of anthraquinone indicates that the monoketone cyclized first and then split off the thiophene ring. Apparently, the 3-thienyl group is more susceptible to oxidation than the 2’-thienyl group. A study of the oxidation of anthracene derivatives for structure proof was made using 9-phenylanthracene as a model compound. It was oxidized to 10-phenyl-10-hydroxyanthrone which resisted further oxidation to anthraquinone. It is obvious that the tertiary alcohol system stabilized the phenyl ring. In continuing the work on the 9-(dimethyl)-phenylanthracene series, the yields of three ketimine salts and one ketone were improved. Satisfactory analytical data was obtained for 2’,6’-dimethyl-2-benzylbenzophenone. In an attempt to overcome the steric effects offered by 2,6-ortho groups, 2-(2',3'-dimethylbenzyl)-benzonitrile was prepared. The starting material for this series, l-bromo-2,3-dimethylbenzene has been prepared in 47% yield by diazotization in comparison with the previous yield of 30%.","abstract_has_math":false,"creators":["Quo, Sih-gwan"],"institution":"Virginia Polytechnic Institute","degree_name":"Doctor of Philosophy","degree_level":"doctoral","degree_discipline":null,"degree_department":"Chemistry","school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1959,"date_issued":"1959","date_published":"1959","updated_at":"2026-07-22T22:19:57Z","subjects":[],"languages":["en_US"],"rights":["In Copyright"],"rights_urls":["http://rightsstatements.org/vocab/InC/1.0/"],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/10919/88660","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":["Quo, Sih-gwan"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2019-03-26T19:53:12Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2019-03-26T19:53:12Z"]},{"key":"dc:date.issued","label":"Date","values":["1959"]},{"key":"dc:publisher","label":"Institution","values":["Virginia Polytechnic Institute"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation"]},{"key":"dc:type.dcmitype","label":"Dc Type Dcmitype","values":["Text"]},{"key":"thesis:degree_level","label":"Degree Level","values":["doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy"]},{"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_US"]},{"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.uri","label":"Identifier URI","values":["http://hdl.handle.net/10919/88660"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The process of C. K. Bradsher for preparing mesosubstituted anthracene and 1,2-benzanthracene derivatives has been widely extended. The purpose of this research was to extend this process to the thiophene series, in addition to continuing some work on the 9-(dimethyl)- phenylanthracene series and some newly developed l,2-dimethyl-10-phenyl)-anthracene series. 2'-Thienyl-2-benzylbenzophenone was prepared and cyclized to 9-(2-thienyl)-anthracene by the conventional methods in good yields. 3'-Thienyl-2-benzylbenzophenone was prepared in a different way, indirect and tedious. Thiophene was iodinated to tetraiodothiophene and tetraiodothiophene was reduced with aluminum-amalgam to 3-iodothiophene. 3-Thienylmagnesiumiodide was prepared by the entrainment technique and condensed with 2-cyanodiphenylmethane to 3'-thienyl-2-benzylbenzophenone. This ketone was cyclized to 9-(3'-thienyl)-anthracene by the standard acid mixture. 2-(1-Naphthylmethyl)-phenyl-2-thienylketimine formed from the condensation between 2-(1'-naphthylmethyl)- benzonitrile and 2-thienylmagnesiumbromide resisted hydrolysis to the corresponding ketone but cyclized quantitatively to 10-(2-thienyl)-l,2-benzanthracene. Following the classical Bradsher process, the reaction between 2-thienylmagnesiumbromide and o-chlorobenzaldehyde was unsuccessful because the hydrol formed was so reactive that it polymerized rapidly and ended up with tars. A cross-condensation reaction between 2-ethynylmagnesium bromide and o-chlorobenzylchloride was utilized to give the expected 2-(2'-chlorobenzyl)- thiophene in one step. This new procedure has been widely extended to the other series. It is preferred to. the conventional Bradsher process and the Friedel-Crafts method in terms of time, chemicals, and unequivocal products formed. 2-(2'-Chlorobenzyl)-thiophene so formed by the new procedure was converted by von Braun reaction to the corresponding nitrile and the nitrile was allowed to react with phenylmagnesiumbromide to give 2-(2-thienylmethyl)-benzophenone. The above ketone was cyclized almost quantitatively to 4-phenyl-thiophanthrene. The thiophene-containing ketones prepared in this research are very viscous oils. In order to have crystalline derivatives for identification purposes these ketones were oxidized to the corresponding diketones. 2-Thienyl-2-benzylbenzophenone and 2-(2'-thienylmethyl)- benzophenone gave the identical diketone, 2-benzoyl-2'- thienyl-benzophenone. 3 1 -Thienyl-2-benzylbenzophenone was oxidized to anthraquinone by using 25% sulfuric .acid, acetic acid and sodium dichromate. The formation of anthraquinone indicates that the monoketone cyclized first and then split off the thiophene ring. Apparently, the 3-thienyl group is more susceptible to oxidation than the 2’-thienyl group. A study of the oxidation of anthracene derivatives for structure proof was made using 9-phenylanthracene as a model compound. It was oxidized to 10-phenyl-10-hydroxyanthrone which resisted further oxidation to anthraquinone. It is obvious that the tertiary alcohol system stabilized the phenyl ring. In continuing the work on the 9-(dimethyl)-phenylanthracene series, the yields of three ketimine salts and one ketone were improved. Satisfactory analytical data was obtained for 2’,6’-dimethyl-2-benzylbenzophenone. In an attempt to overcome the steric effects offered by 2,6-ortho groups, 2-(2',3'-dimethylbenzyl)-benzonitrile was prepared. The starting material for this series, l-bromo-2,3-dimethylbenzene has been prepared in 47% yield by diazotization in comparison with the previous yield of 30%."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Doctor of Philosophy"]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["The preparation of polynuclear compounds containing the thiophene ring system"]}]}],"canonical_facts":{"dc:contributor.department":["Chemistry"],"dc:creator":["Quo, Sih-gwan"],"dc:date.accessioned":["2019-03-26T19:53:12Z"],"dc:date.available":["2019-03-26T19:53:12Z"],"dc:date.issued":["1959"],"dc:description.abstract":["The process of C. K. Bradsher for preparing mesosubstituted anthracene and 1,2-benzanthracene derivatives has been widely extended. The purpose of this research was to extend this process to the thiophene series, in addition to continuing some work on the 9-(dimethyl)- phenylanthracene series and some newly developed l,2-dimethyl-10-phenyl)-anthracene series. 2'-Thienyl-2-benzylbenzophenone was prepared and cyclized to 9-(2-thienyl)-anthracene by the conventional methods in good yields. 3'-Thienyl-2-benzylbenzophenone was prepared in a different way, indirect and tedious. Thiophene was iodinated to tetraiodothiophene and tetraiodothiophene was reduced with aluminum-amalgam to 3-iodothiophene. 3-Thienylmagnesiumiodide was prepared by the entrainment technique and condensed with 2-cyanodiphenylmethane to 3'-thienyl-2-benzylbenzophenone. This ketone was cyclized to 9-(3'-thienyl)-anthracene by the standard acid mixture. 2-(1-Naphthylmethyl)-phenyl-2-thienylketimine formed from the condensation between 2-(1'-naphthylmethyl)- benzonitrile and 2-thienylmagnesiumbromide resisted hydrolysis to the corresponding ketone but cyclized quantitatively to 10-(2-thienyl)-l,2-benzanthracene. Following the classical Bradsher process, the reaction between 2-thienylmagnesiumbromide and o-chlorobenzaldehyde was unsuccessful because the hydrol formed was so reactive that it polymerized rapidly and ended up with tars. A cross-condensation reaction between 2-ethynylmagnesium bromide and o-chlorobenzylchloride was utilized to give the expected 2-(2'-chlorobenzyl)- thiophene in one step. This new procedure has been widely extended to the other series. It is preferred to. the conventional Bradsher process and the Friedel-Crafts method in terms of time, chemicals, and unequivocal products formed. 2-(2'-Chlorobenzyl)-thiophene so formed by the new procedure was converted by von Braun reaction to the corresponding nitrile and the nitrile was allowed to react with phenylmagnesiumbromide to give 2-(2-thienylmethyl)-benzophenone. The above ketone was cyclized almost quantitatively to 4-phenyl-thiophanthrene. The thiophene-containing ketones prepared in this research are very viscous oils. In order to have crystalline derivatives for identification purposes these ketones were oxidized to the corresponding diketones. 2-Thienyl-2-benzylbenzophenone and 2-(2'-thienylmethyl)- benzophenone gave the identical diketone, 2-benzoyl-2'- thienyl-benzophenone. 3 1 -Thienyl-2-benzylbenzophenone was oxidized to anthraquinone by using 25% sulfuric .acid, acetic acid and sodium dichromate. The formation of anthraquinone indicates that the monoketone cyclized first and then split off the thiophene ring. Apparently, the 3-thienyl group is more susceptible to oxidation than the 2’-thienyl group. A study of the oxidation of anthracene derivatives for structure proof was made using 9-phenylanthracene as a model compound. It was oxidized to 10-phenyl-10-hydroxyanthrone which resisted further oxidation to anthraquinone. It is obvious that the tertiary alcohol system stabilized the phenyl ring. In continuing the work on the 9-(dimethyl)-phenylanthracene series, the yields of three ketimine salts and one ketone were improved. Satisfactory analytical data was obtained for 2’,6’-dimethyl-2-benzylbenzophenone. In an attempt to overcome the steric effects offered by 2,6-ortho groups, 2-(2',3'-dimethylbenzyl)-benzonitrile was prepared. The starting material for this series, l-bromo-2,3-dimethylbenzene has been prepared in 47% yield by diazotization in comparison with the previous yield of 30%."],"dc:description.degree":["Doctor of Philosophy"],"dc:format.mimetype":["application/pdf"],"dc:identifier.uri":["http://hdl.handle.net/10919/88660"],"dc:language.iso":["en_US"],"dc:publisher":["Virginia Polytechnic Institute"],"dc:rights":["In Copyright"],"dc:rights.uri":["http://rightsstatements.org/vocab/InC/1.0/"],"dc:title":["The preparation of polynuclear compounds containing the thiophene ring system"],"dc:type":["Dissertation"],"dc:type.dcmitype":["Text"],"thesis:degree_level":["doctoral"],"thesis:degree_name":["Doctor of Philosophy"],"thesis:institution_name":["Virginia Polytechnic Institute"]},"updated_at":"2026-07-22T22:19:57Z"}