Methyl group

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See also: Methylation

Different ways of representing a methyl group (highlighted in blue)

A methyl group is an alkyl derived from methane, containing

one carbon atom bonded to three hydrogen atoms — CH3. In formulas, the group is
often abbreviated Me. Such hydrocarbon groups occur in many organic compounds. It
is a very stable group in most molecules. While the methyl group is usually part of a
larger molecule, it can be found on its own in any of three
forms: anion, cation or radical. The anion has eight valence electrons, the radical seven
and the cation six. All three forms are highly reactive and rarely observed. [1]

Contents

 1Methyl cation, anion, and radical

o 1.1Methyl cation
o 1.2Methyl anion
o 1.3Methyl radical
  2Reactivity
o 2.1Oxidation
o 2.2Methylation
o 2.3Deprotonation
o 2.4Free radical reactions
 3Chiral methyl
 4Rotation
 5Etymology
 6See also
 7References

Methyl cation, anion, and radical[edit]

Methyl cation[edit]
Main article: Methenium
The methylium cation (CH+
3) exists in the gas phase, but is otherwise not encountered. Some compounds are

considered to be sources of the CH+

3 cation, and this simplification is used pervasively in organic chemistry. For

example, protonation of methanol gives an electrophilic methylating reagent that reacts

by the SN2 pathway:
CH3OH + H+ → CH
3OH
+

Similarly, methyl iodide and methyl triflate are viewed as

the equivalent of the methyl cation because they readily
undergo SN2 reactions by weak nucleophiles.
Methyl anion[edit]
The methanide anion (CH−
3) 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) and
its enthalpy of reaction is determined to be
about 252.2±3.3 kJ/mol.[2] It is a powerful superbase; only
the lithium monoxide anion (LiO−
) and the diethynylbenzene dianions are known to be
stronger.[3]
In discussing mechanisms of organic reactions, methyl
lithium and related Grignard reagents are often considered
to be salts of "CH−
3"; 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:
2 M + CH3X → MCH3 + MX
where M is an alkali metal.
Methyl radical[edit]
Main article: Methyl radical
The methyl radical has the formula CH•
3. It exists in dilute gases, but in more concentrated form

it readily dimerizes to ethane. It can be produced

by thermal decomposition of only certain compounds,
especially those with an –N=N– linkage.

Reactivity[edit]
The reactivity of a methyl group depends on the
adjacent substituents. Methyl groups can be quite
unreactive. For example, in organic compounds, the
methyl group resists attack by even the strongest acids.
Oxidation[edit]
The oxidation of a methyl group occurs widely in nature
and industry. The oxidation products derived from
methyl are CH2OH, CHO, and CO2H. For
example, permanganate often converts a methyl group
to a carboxyl (–COOH) group, e.g. the conversion
of toluene to benzoic acid. Ultimately oxidation of
methyl groups gives protons and carbon dioxide, as
seen in combustion.
Methylation[edit]
Main article: Methylation
Demethylation (the transfer of the methyl group to
another compound) is a common process,
and reagents that undergo this reaction are called
methylating agents. Common methylating agents
are dimethyl sulfate, methyl iodide, and methyl
triflate. Methanogenesis, the source of natural gas,
arises via a demethylation reaction. [4] Together with
ubiquitin and phosphorylation, methylation is a major
biochemical process for modifying protein function. [5]
Deprotonation[edit]
Certain methyl groups can be deprotonated. For
example, the acidity of the methyl groups
in acetone ((CH3)2CO) is about 1020 times more acidic
than methane. The resulting carbanions are key
intermediates in many reactions in organic
synthesis and biosynthesis. Fatty acids are produced in
this way.
Free radical reactions[edit]
When placed in benzylic or allylic 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 to give benzyl chloride.[6]

Chiral methyl[edit]
In the special case where one hydrogen is replaced
by deuterium (D) and another hydrogen by tritium (T),
the methyl substituent becomes chiral.[7] Methods exist
to produce optically pure methyl compounds, e.g.,
chiral acetic acid (CHDTCO2H). Through the use of
chiral methyl groups, the stereochemical course of
several biochemical transformations have been
analyzed.[8]

Rotation[edit]
A methyl group may rotate around the R—C axis. This
is a free rotation only in the simplest cases like gaseous
CClH3. 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 C2H6 this is discussed
under the name ethane barrier. In condensed phases,
neighbour molecules also contribute to the potential.
Methyl group rotation can be experimentally studied
using quasielastic neutron scattering.[9]

Etymology[edit]
French chemists Jean-Baptiste Dumas 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)".[10][11] The term "methyl"
was derived in about 1840 by back-formation from
"methylene", and was then applied to describe "methyl
alcohol" (which since 1892 is called "methanol").
Methyl is the IUPAC nomenclature of organic
chemistry term for an alkane (or alkyl) molecule, using
the prefix "meth-" to indicate the presence of a single
carbon.

See also[edit]
 AdoMet

References[edit]
1. ^ March, Jerry (1992). Advanced organic chemistry:
reactions, mechanisms, and structure. John Wiley &
Sons.  ISBN  0-471-60180-2.
2. ^ 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. doi:10.1021/ja00476a054
3. ^ Poad, Berwyck L. J.; Reed, Nicholas D.; Hansen,
Christopher S.; Trevitt, Adam J.; Blanksby, Stephen
J.; Mackay, Emily G.; Sherburn, Michael S.; Chan,
Bun; Radom, Leo (2016).  "Preparation of an ion with
the highest calculated proton affinity: ortho-
diethynylbenzene dianion". Chemical Science. 7  (9):
6245–6250.  doi:10.1039/C6SC01726F.  PMC 60242
02.  PMID  30034765.
4. ^ Thauer, R. K., "Biochemistry of Methanogenesis: a
Tribute to Marjory Stephenson", Microbiology, 1998,
volume 144, pages 2377–2406.
5. ^ Clarke, Steven G. (2018). "The ribosome: A hot
spot for the identification of new types of protein
methyltransferases".  Journal of Biological
Chemistry.  293  (27): 10438–
10446. doi:10.1074/jbc.AW118.003235. PMC  6036
201.  PMID  29743234.
6. ^ M. Rossberg et al. “Chlorinated Hydrocarbons” in
Ullmann’s Encyclopedia of Industrial Chemistry
2006, Wiley-VCH,
Weinheim. doi:10.1002/14356007.a06_233.pub2
7. ^ "Archived copy"  (PDF). Archived from the
original  (PDF)  on 2010-07-14. Retrieved  2013-11-
26.
8. ^ Heinz G. Floss, Sungsook Lee "Chiral methyl
groups: small is beautiful" Acc. Chem. Res., 1993,
volume 26, pp 116–122. doi:10.1021/ar00027a007
9. ^ Press,W: Single-particle rotation in molecular
crystals (Springer tracts in modern physics 92),
Springer: Berlin (1981).
10. ^ J. Dumas and E. Péligot (1835) "Mémoire sur
l'espirit de bois et sur les divers composés ethérés
 qui en proviennent" (Memoir on spirit of wood and on
the various ethereal compounds that derive
therefrom), Annales de chimie et de physique, 58 :
5-74; from page 9: Nous donnerons le nom de
méthylène (1) à un radical … (1) μεθυ, vin, et υλη,
bois; c'est-à-dire vin ou liqueur spiritueuse du
bois. (We will give the name "methylene" (1) to a
radical … (1) methy, wine, and hulē, wood; that is,
wine or spirit of wood.)
11. ^ Note that the correct Greek word for the substance
"wood" is xylo-.

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Functional groups
Categories: 
 Alkyl groups
 Functional groups
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