Effect of base on alkyltriphenylphosphonium salts in polar aprotic solvents
When arylmethyl phosphonium salts are treated with a base (e.g., t-BuOK or NaH) they homocouple to form symmetric 1,2-diarylethenes. In some cases, dilution and (or) use of excess base lead to very high yields of the product. This reaction is solvent sensitive: the reaction occurs only when polar ap...
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Veröffentlicht in: | Canadian journal of chemistry 2008-07, Vol.86 (7), p.668-675 |
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creator | Ngwendson, Julius N Schultze, Cassandra M Bollinger, Jordan W Banerjee, Anamitro |
description | When arylmethyl phosphonium salts are treated with a base (e.g., t-BuOK or NaH) they homocouple to form symmetric 1,2-diarylethenes. In some cases, dilution and (or) use of excess base lead to very high yields of the product. This reaction is solvent sensitive: the reaction occurs only when polar aprotic solvents such as acetonitrile or DMSO are used. Other alkyl phosphonium salts (e.g., ethoxycarbonylmethyltriphenylphosphonium bromide and n-butyltriphenylphosphonium bromide) form a ylid (when an α-carbonyl group is present) or lose a phenyl group to form alkyldiphenylphosphine oxides when treated with the base. Mechanistic investigation of the homocoupling reaction indicates that the reaction proceeds through a ylid that acts as a nucleophile on an unreacted phosphonium salt. The resulting adduct undergoes elimination to form the observed product. The E/Z ratio seems to depend on the amount of the base used and the phosphonium salt involved.Key words: phosphonium salts, homocoupling, 1,2-diarylalkene, Ylids. |
doi_str_mv | 10.1139/v08-056 |
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In some cases, dilution and (or) use of excess base lead to very high yields of the product. This reaction is solvent sensitive: the reaction occurs only when polar aprotic solvents such as acetonitrile or DMSO are used. Other alkyl phosphonium salts (e.g., ethoxycarbonylmethyltriphenylphosphonium bromide and n-butyltriphenylphosphonium bromide) form a ylid (when an α-carbonyl group is present) or lose a phenyl group to form alkyldiphenylphosphine oxides when treated with the base. Mechanistic investigation of the homocoupling reaction indicates that the reaction proceeds through a ylid that acts as a nucleophile on an unreacted phosphonium salt. The resulting adduct undergoes elimination to form the observed product. The E/Z ratio seems to depend on the amount of the base used and the phosphonium salt involved.Key words: phosphonium salts, homocoupling, 1,2-diarylalkene, Ylids.</description><identifier>ISSN: 0008-4042</identifier><identifier>EISSN: 1480-3291</identifier><identifier>DOI: 10.1139/v08-056</identifier><language>eng</language><publisher>Ottawa, Canada: NRC Research Press</publisher><subject>Chemical reactions ; Phosphonates ; Properties</subject><ispartof>Canadian journal of chemistry, 2008-07, Vol.86 (7), p.668-675</ispartof><rights>COPYRIGHT 2008 NRC Research Press</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c529t-8ade9520affd192809943ebbdf59ccf39bd9e3f566af5549d453d0055312758f3</citedby><cites>FETCH-LOGICAL-c529t-8ade9520affd192809943ebbdf59ccf39bd9e3f566af5549d453d0055312758f3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids></links><search><creatorcontrib>Ngwendson, Julius N</creatorcontrib><creatorcontrib>Schultze, Cassandra M</creatorcontrib><creatorcontrib>Bollinger, Jordan W</creatorcontrib><creatorcontrib>Banerjee, Anamitro</creatorcontrib><title>Effect of base on alkyltriphenylphosphonium salts in polar aprotic solvents</title><title>Canadian journal of chemistry</title><addtitle>Revue canadienne de chimie</addtitle><description>When arylmethyl phosphonium salts are treated with a base (e.g., t-BuOK or NaH) they homocouple to form symmetric 1,2-diarylethenes. In some cases, dilution and (or) use of excess base lead to very high yields of the product. This reaction is solvent sensitive: the reaction occurs only when polar aprotic solvents such as acetonitrile or DMSO are used. Other alkyl phosphonium salts (e.g., ethoxycarbonylmethyltriphenylphosphonium bromide and n-butyltriphenylphosphonium bromide) form a ylid (when an α-carbonyl group is present) or lose a phenyl group to form alkyldiphenylphosphine oxides when treated with the base. Mechanistic investigation of the homocoupling reaction indicates that the reaction proceeds through a ylid that acts as a nucleophile on an unreacted phosphonium salt. The resulting adduct undergoes elimination to form the observed product. 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In some cases, dilution and (or) use of excess base lead to very high yields of the product. This reaction is solvent sensitive: the reaction occurs only when polar aprotic solvents such as acetonitrile or DMSO are used. Other alkyl phosphonium salts (e.g., ethoxycarbonylmethyltriphenylphosphonium bromide and n-butyltriphenylphosphonium bromide) form a ylid (when an α-carbonyl group is present) or lose a phenyl group to form alkyldiphenylphosphine oxides when treated with the base. Mechanistic investigation of the homocoupling reaction indicates that the reaction proceeds through a ylid that acts as a nucleophile on an unreacted phosphonium salt. The resulting adduct undergoes elimination to form the observed product. 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subjects | Chemical reactions Phosphonates Properties |
title | Effect of base on alkyltriphenylphosphonium salts in polar aprotic solvents |
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