Bingel reaction of fullerene with a malonate ester and a) sodium hydride or DBU in toluene at room temperature 45% yield

The Bingel reaction in organic chemistry is a fullerene cyclopropanation reaction to a methanofullerene first discovered by C. Bingel in 1993 with the bromo derivative of diethyl malonate in the presence of a base such as sodium hydride or DBU ^[1]. The prefered 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 steric strain. Jump to: navigation, search Image File history File links Bingel_reaction. ... Jump to: navigation, search Fullerene C540 Fullerenes are one of only four types of naturally occurring forms of carbon (the other three being diamond, graphite and ceraphite). ... The malonate (also propanedioate) ion is CH2(COO)22- (malonic acid minus two hydrogen ions). ... Jump to: navigation, search In organic chemistry and biochemistry, esters are rubbish compounds where an organic group (symbolised by R in this article) replaces a hydrogen atom (or more than one) in an oxygen acid. ... Sodium hydride is a highly flammable, and corrosive chemical compound with formula NaH and CAS number 7646-69-7. ... DBU or 1,8-diazabicyclo(5. ... Toluene, also known as methylbenzene or phenylmethane is a clear water-insoluble liquid with the typical smell of paint thinners, reminiscent of the sweet smell of the related compound benzene. ... Room temperature, in laboratory reports, is taken to be roughly 21–23 degrees Celsius (70 degrees Fahrenheit), or 294–296 kelvins. ... Yield in chemistry, also known as chemical yield and reaction yield, is the amount of product obtained in a chemical reaction. ... Jump to: navigation, search Organic chemistry is the scientific study of the structure, properties, composition, reactions, and synthesis of organic compounds that by definition contain carbon. ... Jump to: navigation, search Fullerene C540 Fullerenes are one of only four types of naturally occurring forms of carbon (the other three being diamond, graphite and ceraphite). ... Molecule structure formula of cyclopropane Cyclopropane is a cycloalkane molecule with the molecular formula C3H6 consisting of three carbon atoms linked to each other to form a ring, with each carbon atom bearing two hydrogen atoms. ... General Name, Symbol, Number bromine, Br, 35 Series halogens Group, Period, Block 17 (VIIA), 4, p Density, Hardness 3119 kg/m3 (300 K), NA Appearance Gas: red-brown solid: metallic luster Atomic properties Atomic weight 79. ... Diethyl malonate (DEM) has the structure (EtOOC)(CH2)(COOEt) Reactions Malonic ester synthesis DEM → monosubstituded acetic acid See also barbituric acid Categories: Malonates ... The common (Arrhenius) definition of a base is a chemical compound that either donates hydroxide ions or absorbs hydrogen ions when dissolved in water. ... Sodium hydride is a highly flammable, and corrosive chemical compound with formula NaH and CAS number 7646-69-7. ... DBU or 1,8-diazabicyclo(5. ... Jump to: navigation, search In chemistry van der Waals strain is strain resulting from van der Waals repulsion when two substituents in a molecule approach each other with a distance less than the sum of their van der Waals radii. ...

Reaction mechanism

Bingel reaction mechanism: E strong electron withdrawing group, L leaving group

The reaction mechanism for this reaction is as follows: a base abstracts the acidic malonate proton generating a carbanion or enolate which reacts with the electron deficient fullerene double bond in a nucleophilic addition. This in turn generates a carbanion which displaces bromine in a nucleophilic aliphatic substitution in an intramolecular ring cyclopropane ring closure. Jump to: navigation, search Image File history File links Bingel_reaction_mechanism. ... A leaving group is an atom or molecule that detaches from an organic molecule, which, after detachment, is called the residual or main part. ... An overall description of how a reaction occurs. ... A carbanion is an anion in which carbon has an unshared pair of electrons and bears a negative charge usually with three substituents for a total of eight valence electrons. ... Enol (or, more officially, but less commonly: alkenol) is an alkene with hydroxyl group on one of the carbon atoms of the double bond. ... Covalent bonding is a form of chemical bonding characterized by the sharing of one or more pairs of electrons between atoms, in order to produce a mutual attraction, which holds the resultant molecule together. ... In organic chemistry, a nucleophilic addition reaction is an addition reaction where in a chemical compound a pi bond is removed by the creation of two new covalent bonds by the addition of a nucleophile. ... Jump to: navigation, search In chemistry, nucleophilic substitution is a class of substitution reaction in which an electron-rich nucleophile attacks a molecule and replaces a group or atom, called the leaving group. ... Intramolecular describes a process or characteristic limited within the structure of a single, or each molecule; a property or phenomenon limited to the extent of a single, or each molecule. ... Molecule structure formula of cyclopropane Cyclopropane is a cycloalkane molecule with the molecular formula C3H6 consisting of three carbon atoms linked to each other to form a ring, with each carbon atom bearing two hydrogen atoms. ...

Scope

Bingel reaction with N-(Diphenylmethylene)glycinate Ester

The Bingel reaction is a popular method in fullerene functionalization. A malonate halide is often obtained in situ in a mixture of base and tetrachloromethane or iodine ^[2]. The reaction is also known to take place with the ester groups replaced by alkyne groups in dialkynylmethanofullerenes ^[3]. An alternative to the Bingel reaction is a fullerene diazomethane reaction. N-(Diphenylmethylene)glycinate Esters ^[4] in a Bingel reaction take a different conjugate course and react to a fullerene dihydropyrrole. Jump to: navigation, search Image File history File links Bingel_example. ... In situ (in place in Latin), a term used in: biology, where it means to examine the phenomenon exactly in place where it occurs (without removing it in some special medium etc. ... Carbon tetrachloride CCl4 is a synthetic chemical compound formerly widely used in fire extinguishers and refrigeration, but now largely abandoned due to its toxicity. ... Jump to: navigation, search General Name, Symbol, Number iodine, I, 53 Chemical series halogens Group, Period, Block 17, 5, p Appearance violet-dark gray, lustrous Atomic mass 126. ... Jump to: navigation, search In organic chemistry and biochemistry, esters are rubbish compounds where an organic group (symbolised by R in this article) replaces a hydrogen atom (or more than one) in an oxygen acid. ... Alkynes are hydrocarbons that have at least one triple bond between two carbon atoms. ... A diazo compund is any class of organic substances that have the characteristic atomic grouping: as a part of their molecular structure. ... Pyrrole is a heterocyclic aromatic organic compound. ...

External links

• Fullerene chemistry @ Erlangen University

References

1. ^  C. Bingel, Chem. Ber. 1993, 126, 1957.
2. ^  Structural Reassignment of the Mono- and Bis-Addition Products from the Addition Reactions of N-(Diphenylmethylene)glycinate Esters to [60]Fullerene under Bingel Conditions Graham E. Ball, Glenn A. Burley, Leila Chaker, Bill C. Hawkins, James R. Williams, Paul A. Keller, and Stephen G. Pyne J. Org. Chem.; 2005; 70(21) pp 8572 - 8574 DOI Graphical Abstract
3. ^  Synthesis of [60]Fullerene Adducts Bearing Carbazole Moieties by Bingel Reaction and Their Properties Yosuke Nakamura, Masato Suzuki, Yumi Imai, and Jun NishimuraOrg. Lett.; 2004; 6(16) pp 2797 - 2799; DOI Graphical Abstract
4. ^  Covalent fullerene chemistry FranGois Diederich Pure &Appl. Chem., Vol. 69, No. 3, pp. 395-400, 1997 Online Article