Synthesis and cycloaddition chemistry 1,3-Bis(phenylsulfonyl)propadiene

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dc.contributor.advisorBull, James Ren_ZA
dc.contributor.advisorHunter, Rogeren_ZA
dc.contributor.authorDesmond-Smith, Nicholas Stuarten_ZA
dc.date.accessioned2016-03-30T14:51:14Z
dc.date.available2016-03-30T14:51:14Z
dc.date.issued1998en_ZA
dc.description.abstractAn 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.en_ZA
dc.identifier.apacitationDesmond-Smith, N. S. (1998). <i>Synthesis and cycloaddition chemistry 1,3-Bis(phenylsulfonyl)propadiene</i>. (Thesis). University of Cape Town ,Faculty of Science ,Department of Chemistry. Retrieved from http://hdl.handle.net/11427/18429en_ZA
dc.identifier.chicagocitationDesmond-Smith, Nicholas Stuart. <i>"Synthesis and cycloaddition chemistry 1,3-Bis(phenylsulfonyl)propadiene."</i> Thesis., University of Cape Town ,Faculty of Science ,Department of Chemistry, 1998. http://hdl.handle.net/11427/18429en_ZA
dc.identifier.citationDesmond-Smith, N. 1998. Synthesis and cycloaddition chemistry 1,3-Bis(phenylsulfonyl)propadiene. University of Cape Town.en_ZA
dc.identifier.ris TY - Thesis / Dissertation AU - Desmond-Smith, Nicholas Stuart AB - 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. DA - 1998 DB - OpenUCT DP - University of Cape Town LK - https://open.uct.ac.za PB - University of Cape Town PY - 1998 T1 - Synthesis and cycloaddition chemistry 1,3-Bis(phenylsulfonyl)propadiene TI - Synthesis and cycloaddition chemistry 1,3-Bis(phenylsulfonyl)propadiene UR - http://hdl.handle.net/11427/18429 ER - en_ZA
dc.identifier.urihttp://hdl.handle.net/11427/18429
dc.identifier.vancouvercitationDesmond-Smith NS. Synthesis and cycloaddition chemistry 1,3-Bis(phenylsulfonyl)propadiene. [Thesis]. University of Cape Town ,Faculty of Science ,Department of Chemistry, 1998 [cited yyyy month dd]. Available from: http://hdl.handle.net/11427/18429en_ZA
dc.language.isoengen_ZA
dc.publisher.departmentDepartment of Chemistryen_ZA
dc.publisher.facultyFaculty of Scienceen_ZA
dc.publisher.institutionUniversity of Cape Town
dc.subject.otherChemistryen_ZA
dc.titleSynthesis and cycloaddition chemistry 1,3-Bis(phenylsulfonyl)propadieneen_ZA
dc.typeMaster Thesis
dc.type.qualificationlevelMasters
dc.type.qualificationnameMScen_ZA
uct.type.filetypeText
uct.type.filetypeImage
uct.type.publicationResearchen_ZA
uct.type.resourceThesisen_ZA
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