The Bingel reaction in

fullerene chemistry Fullerene chemistry is a field of organic chemistry devoted to the chemical properties of fullerenes. Research in this field is driven by the need to functionalize fullerenes and tune their properties. For example, fullerene is notoriously insolub ...

is a

fullerene A fullerene is an allotrope of carbon whose molecule consists of carbon atoms connected by single and double bonds so as to form a closed or partially closed mesh, with fused rings of five to seven atoms. The molecule may be a hollow sphere, ...

cyclopropanation reaction to a methanofullerene first discovered by C. Bingel in 1993 with the bromo derivative of

diethyl malonate Diethyl malonate, also known as DEM, is the diethyl ester of malonic acid. It occurs naturally in grapes and strawberries as a colourless liquid with an apple-like odour, and is used in perfumes. It is also used to synthesize other compounds su ...

in the presence of a base such as

sodium hydride Sodium hydride is the chemical compound with the empirical formula Na H. This alkali metal hydride is primarily used as a strong yet combustible base in organic synthesis. NaH is a saline (salt-like) hydride, composed of Na+ and H− ions, in ...

DBU The decibel (symbol: dB) is a relative unit of measurement equal to one tenth of a bel (B). It expresses the ratio of two values of a power or root-power quantity on a logarithmic scale. Two signals whose levels differ by one decibel have a po ...

. The 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

steric strain 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. Van der Waals strain is also called Van der Waals repul ...

. 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. The Bingel reaction

Reaction mechanism

The

reaction mechanism In chemistry, a reaction mechanism is the step by step sequence of elementary reactions by which overall chemical change occurs. A chemical mechanism is a theoretical conjecture that tries to describe in detail what takes place at each stage o ...

for this reaction is as follows: a base abstracts the acidic malonate proton generating a

carbanion In organic chemistry, a carbanion is an anion in which carbon is trivalent (forms three bonds) and bears a formal negative charge (in at least one significant resonance form). Formally, a carbanion is the conjugate base of a carbon acid: :R3 ...

enolate In organic chemistry, enolates are organic anions derived from the deprotonation of carbonyl () compounds. Rarely isolated, they are widely used as reagents in the synthesis of organic compounds. Bonding and structure Enolate anions are electr ...

which reacts with the electron deficient fullerene

double bond In chemistry, a double bond is a covalent bond between two atoms involving four bonding electrons as opposed to two in a single bond. Double bonds occur most commonly between two carbon atoms, for example in alkenes. Many double bonds exist betwee ...

in a

nucleophilic addition In organic chemistry, a nucleophilic addition reaction is an addition reaction where a chemical compound with an electrophilic double or triple bond reacts with a nucleophile, such that the double or triple bond is broken. Nucleophilic additions d ...

. This in turn generates a carbanion which displaces bromine in a

nucleophilic aliphatic substitution In chemistry, a nucleophilic substitution is a class of chemical reactions in which an electron-rich chemical species (known as a nucleophile) replaces a functional group within another electron-deficient molecule (known as the electrophile). Th ...

in an intramolecular ring

cyclopropane Cyclopropane is the cycloalkane with the molecular formula (CH2)3, consisting of three methylene groups (CH2) linked to each other to form a ring. The small size of the ring creates substantial ring strain in the structure. Cyclopropane itself i ...

ring closure.

Scope

The Bingel reaction is a popular method in fullerene chemistry. The

malonate The conjugate acids are in :Carboxylic acids. {{Commons category, Carboxylate ions, Carboxylate anions Carbon compounds Oxyanions ...

(functionalized with the

halide In chemistry, a halide (rarely halogenide) is a binary chemical compound, of which one part is a halogen atom and the other part is an element or radical that is less electronegative (or more electropositive) than the halogen, to make a flu ...

atom) is often obtained

in situ ''In situ'' (; often not italicized in English) is a Latin phrase that translates literally to "on site" or "in position." It can mean "locally", "on site", "on the premises", or "in place" to describe where an event takes place and is used in ...

in a mixture of base and

tetrabromomethane Tetrabromomethane, CBr4, also known as carbon tetrabromide, is a carbon bromide. Both names are acceptable under IUPAC nomenclature. Physical properties Tetrabromomethane has two polymorphs: crystalline II or β below 46.9 °C (320.0 ...

iodine Iodine is a chemical element with the Symbol (chemistry), symbol I and atomic number 53. The heaviest of the stable halogens, it exists as a semi-lustrous, non-metallic solid at standard conditions that melts to form a deep violet liquid at , ...

. The reaction is also known to take place with the

ester In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides ...

groups replaced by

alkyne \ce \ce Acetylene \ce \ce \ce Propyne \ce \ce \ce \ce 1-Butyne In organic chemistry, an alkyne is an unsaturated hydrocarbon containing at least one carbon—carbon triple bond. The simplest acyclic alkynes with only one triple bond and n ...

groups in dialkynylmethanofullerenes. An alternative to the Bingel reaction is a fullerene

diazomethane Diazomethane is the chemical compound CH2N2, discovered by German chemist Hans von Pechmann in 1894. It is the simplest diazo compound. In the pure form at room temperature, it is an extremely sensitive explosive yellow gas; thus, it is almost ...

reaction. N-(Diphenylmethylene)glycinate Esters in a Bingel reaction take a different conjugate course and react to a fullerene dihydropyrrole.

Retro-Bingel reaction

Protocols exist for the removal of the methano group based on

electrolytic reduction An electrolytic cell is an electrochemical cell that utilizes an external source of electrical energy to force a chemical reaction that would not otherwise occur. The external energy source is a voltage applied between the cell′s two electrode ...

or amalgamated

magnesium Magnesium is a chemical element with the symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 of the periodic ...

References

{{DEFAULTSORT:Bingel Reaction Addition reactions Carbon-carbon bond forming reactions Fullerenes Name reactions