The\u00a0Bingel reaction<\/strong>\u00a0in\u00a0fullerene chemistry\u00a0is a\u00a0fullerene\u00a0cyclopropanation reaction\u00a0to a\u00a0methanofullerene\u00a0<\/strong>first discovered by C. Bingel in 1993 with the\u00a0bromo\u00a0derivative of\u00a0diethyl malonate\u00a0in the presence of a\u00a0base\u00a0such as\u00a0sodium hydride\u00a0or\u00a0DBU.^{[1]<\/sup>\u00a0The preferred double bonds for this reaction on the fullerene surface are the shorter bonds at the junctions of two hexagons (6-6 bonds) and the driving force is relief of\u00a0steric strain.<\/p>\n}

$\"Figure$ <\/p>\n

The reaction is of importance in the field of chemistry because it allows the introduction of useful extensions to the fullerene sphere. These extensions alter their properties for instance solubility and electrochemical behavior and therefore widen the range of potential technical applications.<\/p>\n

Bingel reaction mechanism:\u00a0E<\/strong>\u00a0strong\u00a0electron withdrawing group,\u00a0L<\/strong>\u00a0leaving group<\/div>\n
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The\u00a0reaction mechanism\u00a0for this reaction is as follows: a\u00a0base\u00a0abstracts the acidic malonate proton generating a\u00a0carbanion\u00a0or\u00a0enolatewhich reacts with the electron deficient fullerene\u00a0double bond\u00a0in a\u00a0nucleophilic addition. This in turn generates a carbanion which displaces bromine in a\u00a0nucleophilic aliphatic substitution\u00a0in an\u00a0intramolecular\u00a0ring\u00a0cyclopropane\u00a0ring closure.<\/div>\n
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The Bingel reaction is a popular method in fullerene chemistry. The\u00a0malonate\u00a0(functionalized with the\u00a0halide\u00a0atom) is often obtained\u00a0in situ\u00a0in a mixture of\u00a0base\u00a0and\u00a0tetrachloromethane\u00a0or\u00a0iodine.^{[2]<\/sup>\u00a0The reaction is also known to take place with the\u00a0ester\u00a0groups replaced byalkyne\u00a0groups in\u00a0dialkynylmethanofullerenes<\/strong>.^{[2]<\/sup><\/p>\n}}
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Bingel reaction of\u00a0fullerene\u00a0with a\u00a0malonate\u00a0ester\u00a0and a)\u00a0sodium hydride\u00a0or\u00a0DBUin\u00a0toluene\u00a0at room temperature 45% yield.<\/div>\n<\/div>\n<\/div>\n<\/div>\n
An alternative to the Bingel reaction is a fullerene\u00a0diazomethane\u00a0reaction. N-(Diphenylmethylene) glycinate Esters\u00a0^{[3]<\/sup>\u00a0in a Bingel reaction take a different conjugate course and react to a fullerene\u00a0dihydropyrrole.<\/p>\n}
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Bingel reaction with N-(Diphenylmethylene)glycinate Ester<\/div>\n<\/div>\n<\/div>\n<\/div>\n<\/div>\n
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\u00a0Bingel, Carsten (1993). “Cyclopropanierung von Fullerenen”.\u00a0Chemische Berichte<\/em>126<\/strong>\u00a0(8): 1957.\u00a0doi<\/a>:10.1002\/cber.19931260829<\/a>.<\/li>\n
Yosuke Nakamura, Masato Suzuki, Yumi Imai, and Jun Nishimura (2004). “16”.\u00a0Org. Lett.<\/a><\/em>6<\/strong>\u00a0(16): 2797\u20132799.doi<\/a>:10.1021\/ol048952n<\/a>.\u00a0 PMID<\/a>15281772<\/a>.<\/li>\n
Graham E. Ball, Glenn A. Burley, Leila Chaker, Bill C. Hawkins, James R. Williams, Paul A. Keller, and Stephen G. Pyne (2005). “Structural Reassignment of the Mono- and Bis-Addition Products from the Addition Reactions of N-(Diphenylmethylene)glycinate Esters to [60]Fullerene under Bingel Conditions”.\u00a0J. Org. Chem.<\/a><\/em>70<\/strong>\u00a0(21): 8572\u20138574.\u00a0doi<\/a>:10.1021\/jo051282u<\/a>.\u00a0 PMID<\/a>16209611<\/a>.<\/li>\n
Kessinger, Roland; Crassous, Jeanne; Herrmann, Andreas; R\u00fcttimann, Markus; Echegoyen, Luis; Diederich, Fran\u00e7ois (1998). “Preparation of Enantiomerically Pure C76 with a General Electrochemical Method for the Removal of Di(alkoxycarbonyl)methano Bridges from Methanofullerenes: The Retro-Bingel Reaction”.\u00a0Angewandte Chemie International Edition<\/em>37<\/strong>\u00a0(13-14): 1919.doi<\/a>:10.1002\/(SICI)1521-3773(19980803)37:13\/14<1919::AID-ANIE1919>3.0.CO;2-X<\/a>.<\/li>\n
Herranz, M. \u00c1Ngeles; Cox, Charles T.; Echegoyen, Luis (2003). “Retrocyclopropanation Reactions of Fullerenes:\u00a0 Complete Product Analyses”.\u00a0The Journal of Organic Chemistry<\/em>68<\/strong>\u00a0(12): 5009.\u00a0doi<\/a>:10.1021\/jo034102u<\/a>.\u00a0 PMID<\/a>12790625<\/a>.<\/li>\n
Moonen, Nicolle N. P.; Thilgen, Carlo; Diederich, Fran\u00e7ois; Echegoyen, Luis (2000). “The chemical retro-Bingel reaction: selective removal of bis(alkoxycarbonyl)methano addends from C60 and C70 with amalgamated magnesium”.\u00a0Chemical Communications<\/em>\u00a0(5): 335.\u00a0doi<\/a>:10.1039\/a909704j<\/a>.<\/li>\n<\/ol>\n
Protocols exist for the removal of the methano group based, on\u00a0electrolytic reduction\u00a0^{[4]<\/sup>^{[5]<\/sup>\u00a0or amalgamated\u00a0magnesium\u00a0^{[6]<\/sup><\/p>\n}}}
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Bingel fullerene The Bingel reaction in fullerene chemistry The\u00a0Bingel reaction\u00a0in\u00a0fullerene chemistry\u00a0is a\u00a0fullerene\u00a0cyclopropanation reaction\u00a0to a\u00a0methanofullerene\u00a0first discovered by C. Bingel in 1993 with the\u00a0bromo\u00a0derivative of\u00a0diethyl malonate\u00a0in the presence of a\u00a0base\u00a0such as\u00a0sodium hydride\u00a0or\u00a0DBU.[1]\u00a0The preferred double bonds for this reaction on the fullerene surface are the shorter bonds at the junctions of two hexagons (6-6 bonds) and the driving… Continue reading The Bingel reaction in fullerene chemistry<\/span><\/a><\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"footnotes":""},"categories":[3,4],"tags":[18,143,144],"_links":{"self":[{"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/posts\/576"}],"collection":[{"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/comments?post=576"}],"version-history":[{"count":10,"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/posts\/576\/revisions"}],"predecessor-version":[{"id":608,"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/posts\/576\/revisions\/608"}],"wp:attachment":[{"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/media?parent=576"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/categories?post=576"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/tags?post=576"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}