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In
organic chemistry Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J ...
, a methyl group is an
alkyl In organic chemistry, an alkyl group is an alkane missing one hydrogen. The term ''alkyl'' is intentionally unspecific to include many possible substitutions. An acyclic alkyl has the general formula of . A cycloalkyl is derived from a cycloa ...
derived from
methane Methane ( , ) is a chemical compound with the chemical formula (one carbon atom bonded to four hydrogen atoms). It is a group-14 hydride, the simplest alkane, and the main constituent of natural gas. The relative abundance of methane ...
, containing one
carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—its atom making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table. Carbon ma ...
atom bonded to three
hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-to ...
atoms, having chemical formula . In formulas, the group is often abbreviated as Me. This
hydrocarbon In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ...
group occurs in many organic compounds. It is a very stable group in most molecules. While the methyl group is usually part of a larger
molecule A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and b ...
, bounded to the rest of the molecule by a single covalent bond (), it can be found on its own in any of three forms: methanide
anion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conve ...
(), methylium
cation An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conven ...
() or methyl
radical Radical may refer to: Politics and ideology Politics * Radical politics, the political intent of fundamental societal change *Radicalism (historical), the Radical Movement that began in late 18th century Britain and spread to continental Europe an ...
(). The anion has eight valence electrons, the radical seven and the cation six. All three forms are highly reactive and rarely observed.


Methyl cation, anion, and radical


Methyl cation

The methylium cation () exists in the gas phase, but is otherwise not encountered. Some compounds are considered to be sources of the cation, and this simplification is used pervasively in organic chemistry. For example,
protonation In chemistry, protonation (or hydronation) is the adding of a proton (or hydron, or hydrogen cation), (H+) to an atom, molecule, or ion, forming a conjugate acid. (The complementary process, when a proton is removed from a Brønsted–Lowry acid ...
of methanol gives an electrophilic methylating reagent that reacts by the SN2 pathway: : Similarly,
methyl iodide Iodomethane, also called methyl iodide, and commonly abbreviated "MeI", is the chemical compound with the formula CH3I. It is a dense, colorless, volatile liquid. In terms of chemical structure, it is related to methane by replacement of one ...
and methyl triflate are viewed as the equivalent of the methyl cation because they readily undergo SN2 reactions by weak
nucleophile In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they ar ...
s.


Methyl anion

The methanide anion () exists only in rarefied gas phase or under exotic conditions. It can be produced by electrical discharge in ketene at low pressure (less than one
torr The torr (symbol: Torr) is a unit of pressure based on an absolute scale, defined as exactly of a standard atmosphere (). Thus one torr is exactly (≈ ). Historically, one torr was intended to be the same as one " millimeter of merc ...
) and its enthalpy of reaction is determined to be about .G. Barney Ellison , P. C. Engelking , W. C. Lineberger (1978), "An experimental determination of the geometry and electron affinity of methyl radical CH3" Journal of the American Chemical Society, volume 100, issue 8, pages 2556–2558. It is a powerful superbase; only the lithium monoxide anion () and the diethynylbenzene dianions are known to be stronger. In discussing mechanisms of organic reactions, methyl lithium and related Grignard reagents are often considered to be salts of ; and though the model may be useful for description and analysis, it is only a useful fiction. Such reagents are generally prepared from the methyl halides: : where M is an
alkali metal The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names ...
.


Methyl radical

The methyl
radical Radical may refer to: Politics and ideology Politics * Radical politics, the political intent of fundamental societal change *Radicalism (historical), the Radical Movement that began in late 18th century Britain and spread to continental Europe an ...
has the formula . It exists in dilute gases, but in more concentrated form it readily
dimer Dimer may refer to: * Dimer (chemistry), a chemical structure formed from two similar sub-units ** Protein dimer, a protein quaternary structure ** d-dimer * Dimer model, an item in statistical mechanics, based on ''domino tiling'' * Julius Dimer ( ...
izes to ethane. It can be produced by thermal decomposition of only certain compounds, especially those with an –N=N– linkage.


Reactivity

The reactivity of a methyl group depends on the adjacent
substituent A substituent is one or a group of atoms that replaces (one or more) atoms, thereby becoming a moiety in the resultant (new) molecule. (In organic chemistry and biochemistry, the terms ''substituent'' and ''functional group'', as well as '' side ...
s. Methyl groups can be quite unreactive. For example, in organic compounds, the methyl group resists attack by even the strongest
acid In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a se ...
s.


Oxidation

The
oxidation Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or ...
of a methyl group occurs widely in nature and industry. The oxidation products derived from methyl are –, –CHO, and –COOH. For example,
permanganate A permanganate () is a chemical compound containing the manganate(VII) ion, , the conjugate base of permanganic acid. Because the manganese atom is in the +7 oxidation state, the permanganate(VII) ion is a strong oxidizing agent. The ion is a ...
often converts a methyl group to a carboxyl (–COOH) group, e.g. the conversion of
toluene Toluene (), also known as toluol (), is a substituted aromatic hydrocarbon. It is a colorless, water-insoluble liquid with the smell associated with paint thinners. It is a mono-substituted benzene derivative, consisting of a methyl group (CH3) ...
to
benzoic acid Benzoic acid is a white (or colorless) solid organic compound with the formula , whose structure consists of a benzene ring () with a carboxyl () substituent. It is the simplest aromatic carboxylic acid. The name is derived from gum benzoin ...
. Ultimately oxidation of methyl groups gives
proton A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron mass ...
s and
carbon dioxide Carbon dioxide ( chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is t ...
, as seen in combustion.


Methylation

Demethylation (the transfer of the methyl group to another compound) is a common process, and
reagent In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...
s that undergo this reaction are called methylating agents. Common methylating agents are
dimethyl sulfate Dimethyl sulfate (DMS) is a chemical compound with formula (CH3O)2SO2. As the diester of methanol and sulfuric acid, its formula is often written as ( CH3)2 SO4 or Me2SO4, where CH3 or Me is methyl. Me2SO4 is mainly used as a methylating agent ...
,
methyl iodide Iodomethane, also called methyl iodide, and commonly abbreviated "MeI", is the chemical compound with the formula CH3I. It is a dense, colorless, volatile liquid. In terms of chemical structure, it is related to methane by replacement of one ...
, and methyl triflate.
Methanogenesis Methanogenesis or biomethanation is the formation of methane coupled to energy conservation by microbes known as methanogens. Organisms capable of producing methane for energy conservation have been identified only from the domain Archaea, a group ...
, the source of natural gas, arises via a demethylation reaction. Together with ubiquitin and phosphorylation, methylation is a major biochemical process for modifying protein function.


Deprotonation

Certain methyl groups can be deprotonated. For example, the acidity of the methyl groups in
acetone Acetone (2-propanone or dimethyl ketone), is an organic compound with the formula . It is the simplest and smallest ketone (). It is a colorless, highly volatile and flammable liquid with a characteristic pungent odour. Acetone is miscibl ...
() is about 1020 times more acidic than methane. The resulting
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 ...
s are key intermediates in many reactions in
organic synthesis Organic synthesis is a special branch of chemical synthesis and is concerned with the intentional construction of organic compounds. Organic molecules are often more complex than inorganic compounds, and their synthesis has developed into one o ...
and
biosynthesis Biosynthesis is a multi-step, enzyme-catalyzed process where substrates are converted into more complex products in living organisms. In biosynthesis, simple compounds are modified, converted into other compounds, or joined to form macromolecul ...
.
Fatty acid In chemistry, particularly in biochemistry, a fatty acid is a carboxylic acid with an aliphatic chain, which is either saturated or unsaturated. Most naturally occurring fatty acids have an unbranched chain of an even number of carbon atoms, f ...
s are produced in this way.


Free radical reactions

When placed in
benzylic In organic chemistry, benzyl is the substituent or molecular fragment possessing the structure . Benzyl features a benzene ring () attached to a methylene group () group. Nomenclature In IUPAC nomenclature, the prefix benzyl refers to a substi ...
or
allylic In organic chemistry, an allyl group is a substituent with the structural formula , where R is the rest of the molecule. It consists of a methylene bridge () attached to a vinyl group (). The name is derived from the scientific name for garlic, . ...
positions, the strength of the C–H bond is decreased, and the reactivity of the methyl group increases. One manifestation of this enhanced reactivity is the photochemical chlorination of the methyl group in
toluene Toluene (), also known as toluol (), is a substituted aromatic hydrocarbon. It is a colorless, water-insoluble liquid with the smell associated with paint thinners. It is a mono-substituted benzene derivative, consisting of a methyl group (CH3) ...
to give
benzyl chloride Benzyl chloride, or α-chlorotoluene, is an organic compound with the formula C6H5CH2Cl. This colorless liquid is a reactive organochlorine compound that is a widely used chemical building block. Preparation Benzyl chloride is prepared in ...
.M. Rossberg et al. “Chlorinated Hydrocarbons” in Ullmann’s Encyclopedia of Industrial Chemistry 2006, Wiley-VCH, Weinheim.


Chiral methyl

In the special case where one hydrogen is replaced by
deuterium Deuterium (or hydrogen-2, symbol or deuterium, also known as heavy hydrogen) is one of two stable isotopes of hydrogen (the other being protium, or hydrogen-1). The nucleus of a deuterium atom, called a deuteron, contains one proton and one ...
(D) and another hydrogen by tritium (T), the methyl substituent becomes chiral. Methods exist to produce optically pure methyl compounds, e.g., chiral
acetic acid Acetic acid , systematically named ethanoic acid , is an acidic, colourless liquid and organic compound with the chemical formula (also written as , , or ). Vinegar is at least 4% acetic acid by volume, making acetic acid the main componen ...
(). Through the use of chiral methyl groups, the stereochemical course of several
biochemical Biochemistry or biological chemistry is the study of chemical processes within and relating to living organisms. A sub-discipline of both chemistry and biology, biochemistry may be divided into three fields: structural biology, enzymology an ...
transformations have been analyzed.


Rotation

A methyl group may rotate around the R–C axis. This is a free rotation only in the simplest cases like gaseous
methyl chloride Chloromethane, also called methyl chloride, Refrigerant-40, R-40 or HCC 40, is an organic compound with the chemical formula . One of the haloalkanes, it is a colorless, odorless, flammable gas. Methyl chloride is a crucial reagent in industria ...
. In most molecules, the remainder R breaks the ''C'' symmetry of the R–C axis and creates a potential ''V''(''φ'') that restricts the free motion of the three protons. For the model case of ethane , this is discussed under the name
ethane barrier Ethane ( , ) is an organic chemical compound with chemical formula . At standard temperature and pressure, ethane is a colorless, odorless gas. Like many hydrocarbons, ethane is isolated on an industrial scale from natural gas and as a petro ...
. In condensed phases, neighbour molecules also contribute to the potential. Methyl group rotation can be experimentally studied using
quasielastic neutron scattering Quasielastic neutron scattering (QENS) designates a limiting case of inelastic neutron scattering, characterized by energy transfers being small compared to the incident energy of the scattered particles. In a more strict meaning, it denotes scatte ...
.


Etymology

French chemists
Jean-Baptiste Dumas Jean Baptiste André Dumas (14 July 180010 April 1884) was a French chemist, best known for his works on organic analysis and synthesis, as well as the determination of atomic weights (relative atomic masses) and molecular weights by measuring ...
and Eugene Peligot, after determining methanol's chemical structure, introduced "methylene" from the Greek ''methy'' "wine" and ''hȳlē'' "wood, patch of trees" with the intention of highlighting its origins, "alcohol made from wood (substance)".Note that the correct Greek word for the substance "wood" is ''xylo-''. The term "methyl" was derived in about 1840 by
back-formation In etymology, back-formation is the process or result of creating a new word via inflection, typically by removing or substituting actual or supposed affixes from a lexical item, in a way that expands the number of lexemes associated with the ...
from "methylene", and was then applied to describe "methyl alcohol" (which since 1892 is called "
methanol Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical and the simplest aliphatic alcohol, with the formula C H3 O H (a methyl group linked to a hydroxyl group, often abbreviated as MeOH). It is ...
"). ''Methyl'' is the
IUPAC nomenclature of organic chemistry In chemical nomenclature, the IUPAC nomenclature of organic chemistry is a method of naming organic chemical compounds as recommended by the International Union of Pure and Applied Chemistry (IUPAC). It is published in the '' Nomenclature of O ...
term for an
alkane In organic chemistry, an alkane, or paraffin (a historical trivial name that also has other meanings), is an acyclic saturated hydrocarbon. In other words, an alkane consists of hydrogen and carbon atoms arranged in a tree structure in wh ...
(or alkyl) molecule, using the prefix "meth-" to indicate the presence of a single carbon.


See also

*
AdoMet ''S''-Adenosyl methionine (SAM), also known under the commercial names of SAMe, SAM-e, or AdoMet, is a common cosubstrate involved in methyl group transfers, transsulfuration, and aminopropylation. Although these anabolic reactions occur through ...


References

{{DEFAULTSORT:Methyl Group Alkyl groups Functional groups