2-Mercaptobenzenemethaol 14 was prepared by LAH reduction of 2-mercaptobenzoic acid (thiosalicylic acid) in 95% yield. Oxidation of it with PCC afforded 2,2'-dithiobenzaldehyde 15 in 52% yield. A selective reduction of disulfide 15 to 2-mercaptobvenzaldehyde 16 was achieved using triphenylphosphene in MeOH-H2O-DMF solvent mixture. The reaction of 16 with KOH in the presence of 18-crown-6 followed by addition of 1,4-dibromobutane resulted in 4-(o-formylphenthio)butyl bromide 17 which was converted to triphenylphosphonium bromide salt 18 in 75% yield. Wittig cyclization of 18 with K-t-BuO afforded 3,4-dihydro-2H-1-benzthiocin 19 in 71% yield. In an attempt to prepare 2H-1-benzthiocin 13 via dehydrobromination of bromo compound 20, compound 19 was treated with NBS in the presence of catalytic amount of benzoyl peroxide. However, from the complex reaction mixture, only the dibromo compound 21 was isolated and identified.
","abstract_html":"<p>2-Mercaptobenzenemethaol <strong>14</strong> was prepared by LAH reduction of 2-mercaptobenzoic acid (thiosalicylic acid) in 95% yield. Oxidation of it with PCC afforded 2,2'-dithiobenzaldehyde <strong>15</strong> in 52% yield. A selective reduction of disulfide <strong>15</strong> to 2-mercaptobvenzaldehyde <strong>16</strong> was achieved using triphenylphosphene in MeOH-H<sub>2</sub>O-DMF solvent mixture. The reaction of <strong>16</strong> with KOH in the presence of 18-crown-6 followed by addition of 1,4-dibromobutane resulted in 4-(o-formylphenthio)butyl bromide <strong>17</strong> which was converted to triphenylphosphonium bromide salt <strong>18</strong> in 75% yield. Wittig cyclization of <strong>18</strong> with K-t-BuO afforded 3,4-dihydro-2H-1-benzthiocin <strong>19</strong> in 71% yield. In an attempt to prepare 2H-1-benzthiocin <strong>13</strong> via dehydrobromination of bromo compound <strong>20</strong>, compound <strong>19</strong> was treated with NBS in the presence of catalytic amount of benzoyl peroxide. However, from the complex reaction mixture, only the dibromo compound <strong>21</strong> was isolated and identified.</p>","abstract_has_math":false,"creators":["Tang, Mingnam"],"institution":null,"degree_name":"MS (Master of Science)","degree_level":"Thesis - restricted","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2001,"date_issued":"2001-12-01T08:00:00Z","date_published":"2001-12-01T08:00:00Z","updated_at":"2026-07-24T02:18:50Z","subjects":["Oganic synthesis of 1-Benzthiocin","Chemistry","Physical Sciences and Mathematics"],"languages":[],"rights":["Copyright by the authors."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://dc.etsu.edu/etd/50","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Tang, Mingnam"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["1990-01-01T08:00:00Z"]},{"key":"dc:date.issued","label":"Date","values":["2001-12-01T08:00:00Z"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Thesis - restricted"]},{"key":"thesis:degree_name","label":"Degree Name","values":["MS (Master of Science)"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Oganic synthesis of 1-Benzthiocin","Chemistry","Physical Sciences and Mathematics"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["Copyright by the authors."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://dc.etsu.edu/context/etd/article/1100/viewcontent/tangm112701b.pdf","https://dc.etsu.edu/etd/50"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["2-Mercaptobenzenemethaol 14 was prepared by LAH reduction of 2-mercaptobenzoic acid (thiosalicylic acid) in 95% yield. Oxidation of it with PCC afforded 2,2'-dithiobenzaldehyde 15 in 52% yield. A selective reduction of disulfide 15 to 2-mercaptobvenzaldehyde 16 was achieved using triphenylphosphene in MeOH-H2O-DMF solvent mixture. The reaction of 16 with KOH in the presence of 18-crown-6 followed by addition of 1,4-dibromobutane resulted in 4-(o-formylphenthio)butyl bromide 17 which was converted to triphenylphosphonium bromide salt 18 in 75% yield. Wittig cyclization of 18 with K-t-BuO afforded 3,4-dihydro-2H-1-benzthiocin 19 in 71% yield. In an attempt to prepare 2H-1-benzthiocin 13 via dehydrobromination of bromo compound 20, compound 19 was treated with NBS in the presence of catalytic amount of benzoyl peroxide. However, from the complex reaction mixture, only the dibromo compound 21 was isolated and identified.
"]},{"key":"dc:title","label":"Title","values":["Synthesis of 2H-1-Benzthiocin: a Precursor for the Generation of the \"4n+2\" Pi-electron 1-Benzthiocinide Anion."]}]}],"canonical_facts":{"dc:creator":["Tang, Mingnam"],"dc:date.available":["1990-01-01T08:00:00Z"],"dc:date.issued":["2001-12-01T08:00:00Z"],"dc:description.abstract":["2-Mercaptobenzenemethaol 14 was prepared by LAH reduction of 2-mercaptobenzoic acid (thiosalicylic acid) in 95% yield. Oxidation of it with PCC afforded 2,2'-dithiobenzaldehyde 15 in 52% yield. A selective reduction of disulfide 15 to 2-mercaptobvenzaldehyde 16 was achieved using triphenylphosphene in MeOH-H2O-DMF solvent mixture. The reaction of 16 with KOH in the presence of 18-crown-6 followed by addition of 1,4-dibromobutane resulted in 4-(o-formylphenthio)butyl bromide 17 which was converted to triphenylphosphonium bromide salt 18 in 75% yield. Wittig cyclization of 18 with K-t-BuO afforded 3,4-dihydro-2H-1-benzthiocin 19 in 71% yield. In an attempt to prepare 2H-1-benzthiocin 13 via dehydrobromination of bromo compound 20, compound 19 was treated with NBS in the presence of catalytic amount of benzoyl peroxide. However, from the complex reaction mixture, only the dibromo compound 21 was isolated and identified.
"],"dc:identifier":["https://dc.etsu.edu/context/etd/article/1100/viewcontent/tangm112701b.pdf","https://dc.etsu.edu/etd/50"],"dc:rights":["Copyright by the authors."],"dc:subject":["Oganic synthesis of 1-Benzthiocin","Chemistry","Physical Sciences and Mathematics"],"dc:title":["Synthesis of 2H-1-Benzthiocin: a Precursor for the Generation of the \"4n+2\" Pi-electron 1-Benzthiocinide Anion."],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Thesis - restricted"],"thesis:degree_name":["MS (Master of Science)"]},"updated_at":"2026-07-24T02:18:50Z"}