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Synthesis and cycloaddition chemistry 1,3-Bis(phenylsulfonyl)propadiene
An efficient synthesis of the highly activated I J-bis(phenylsulfonyl)propadiene is described. Starting from benzenesulfonyl chloride and propargyl bromide the key step of the synthesis is the addition of benzene sulfonyl iodide to phenylsulfonylpropyne. This is demonstrated to occur under thermal c...
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| Format: | Thesis |
| Language: | English |
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Department of Chemistry
2016
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| _version_ | 1867613312542310400 |
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| access_status_str | Open Access |
| author | Desmond-Smith, Nicholas Stuart |
| author2 | Bull, James R |
| author_browse | Bull, James R Desmond-Smith, Nicholas Stuart |
| author_facet | Bull, James R Desmond-Smith, Nicholas Stuart |
| author_sort | Desmond-Smith, Nicholas Stuart |
| collection | Thesis |
| description | An efficient synthesis of the highly activated I J-bis(phenylsulfonyl)propadiene is described. Starting from benzenesulfonyl chloride and propargyl bromide the key step of the synthesis is the addition of benzene sulfonyl iodide to phenylsulfonylpropyne. This is demonstrated to occur under thermal conditions in the presence of a radical initiator to obtain (E)-2-iodo-1 ,3-bis(phenylsulfonyl)prop-I-ene. Triethylamine induced dehydroiodination of the above addition product afforded high quality 1,3bis( phenylsulfonyl)propadiene after an aqueous reverse quench procedure without further purification. I ,3-Bis(phenylsulfonyl)propadiene was sho'TI to be stable under refluxing conditions towards diethyl ether, chloroform, ethyl acetate and benzene. Reaction with methanol occurred to yield (E)-2-methoxy-1 ,3-bis(phenylsulfonyl)prop-I-ene and with tetrahydrofuran to yield 2-(2-tetrahydrofuranyl)-(E)-1 ,3-bis(phenylsulfonyl)propene, in a novel insertion reaction. The homocyclisation of 1,3-bis(phenylsulfonyl)propadiene under thermal conditions was demonstrated to yield the highly substituted 2,7bis( phenylsulfonylmethylene)-3,4,5,6-tetraphenylsulfonyI-spiro[3.3.0]heptane. Reaction with cyclopentadiene, furan, butadiene and Danishefsky's diene has been conducted in a regio- and peri-selectivity study to yield the [4+2] cycloadducts. Treatment of the furan cycloadducts with potassium t-butoxide opened up the oxygen bridge of three of the furan cycloadducts and resulted in aromatisation to the 3-phenylsulfonyl-2phenylsulfonylmethylphenol. The remaining cycloadduct was converted to the phenol derivative by treatment with sodium hydride. Potassium methoxide treatment of the furan cycloadducts resulted in the isolation of a methoxide addition product together with the aromatised adduct. Procedures for the synthesis ofphenylsulfinylpropadiene and phenylsulfonylpropadiene are described. |
| format | Thesis |
| id | oai:open.uct.ac.za:11427/18429 |
| institution | University of Cape Town (South Africa) |
| language | eng |
| last_indexed | 2026-06-10T12:34:08.683Z |
| license_str | Not specified — see source repository |
| provenance_str_mv | Harvested via OAI-PMH from UCTD — University of Cape Town Open Access Repository |
| publishDate | 2016 |
| publishDateRange | 2016 |
| publishDateSort | 2016 |
| publisher | Department of Chemistry |
| publisherStr | Department of Chemistry |
| record_format | dspace |
| source_str | UCTD — University of Cape Town Open Access Repository |
| spelling | oai:open.uct.ac.za:11427/18429 Synthesis and cycloaddition chemistry 1,3-Bis(phenylsulfonyl)propadiene Desmond-Smith, Nicholas Stuart Bull, James R Hunter, Roger Chemistry An efficient synthesis of the highly activated I J-bis(phenylsulfonyl)propadiene is described. Starting from benzenesulfonyl chloride and propargyl bromide the key step of the synthesis is the addition of benzene sulfonyl iodide to phenylsulfonylpropyne. This is demonstrated to occur under thermal conditions in the presence of a radical initiator to obtain (E)-2-iodo-1 ,3-bis(phenylsulfonyl)prop-I-ene. Triethylamine induced dehydroiodination of the above addition product afforded high quality 1,3bis( phenylsulfonyl)propadiene after an aqueous reverse quench procedure without further purification. I ,3-Bis(phenylsulfonyl)propadiene was sho'TI to be stable under refluxing conditions towards diethyl ether, chloroform, ethyl acetate and benzene. Reaction with methanol occurred to yield (E)-2-methoxy-1 ,3-bis(phenylsulfonyl)prop-I-ene and with tetrahydrofuran to yield 2-(2-tetrahydrofuranyl)-(E)-1 ,3-bis(phenylsulfonyl)propene, in a novel insertion reaction. The homocyclisation of 1,3-bis(phenylsulfonyl)propadiene under thermal conditions was demonstrated to yield the highly substituted 2,7bis( phenylsulfonylmethylene)-3,4,5,6-tetraphenylsulfonyI-spiro[3.3.0]heptane. Reaction with cyclopentadiene, furan, butadiene and Danishefsky's diene has been conducted in a regio- and peri-selectivity study to yield the [4+2] cycloadducts. Treatment of the furan cycloadducts with potassium t-butoxide opened up the oxygen bridge of three of the furan cycloadducts and resulted in aromatisation to the 3-phenylsulfonyl-2phenylsulfonylmethylphenol. The remaining cycloadduct was converted to the phenol derivative by treatment with sodium hydride. Potassium methoxide treatment of the furan cycloadducts resulted in the isolation of a methoxide addition product together with the aromatised adduct. Procedures for the synthesis ofphenylsulfinylpropadiene and phenylsulfonylpropadiene are described. 2016-03-30T14:51:14Z 2016-03-30T14:51:14Z 1998 Master Thesis Masters MSc http://hdl.handle.net/11427/18429 eng application/pdf Department of Chemistry Faculty of Science University of Cape Town |
| spellingShingle | Chemistry Desmond-Smith, Nicholas Stuart Synthesis and cycloaddition chemistry 1,3-Bis(phenylsulfonyl)propadiene |
| thesis_degree_str | Master's |
| title | Synthesis and cycloaddition chemistry 1,3-Bis(phenylsulfonyl)propadiene |
| title_full | Synthesis and cycloaddition chemistry 1,3-Bis(phenylsulfonyl)propadiene |
| title_fullStr | Synthesis and cycloaddition chemistry 1,3-Bis(phenylsulfonyl)propadiene |
| title_full_unstemmed | Synthesis and cycloaddition chemistry 1,3-Bis(phenylsulfonyl)propadiene |
| title_short | Synthesis and cycloaddition chemistry 1,3-Bis(phenylsulfonyl)propadiene |
| title_sort | synthesis and cycloaddition chemistry 1 3 bis phenylsulfonyl propadiene |
| topic | Chemistry |
| url | http://hdl.handle.net/11427/18429 |
| work_keys_str_mv | AT desmondsmithnicholasstuart synthesisandcycloadditionchemistry13bisphenylsulfonylpropadiene |