Methyl group

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. 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 either 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]

Methyl cation, anion, and radical

Methyl cation

The methylium cation (CH3+) exists in the gas phase, but is otherwise not encountered. Some compounds are considered to be sources of "CH3+", and this simplification is used pervasively in organic chemistry. For example, protonation of methanol gives a strongly electrophilic methylating reagent:

CH3OH + H+ → CH3+ + H2O

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

The methanide anion (CH3−) similarly 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 was determined as about 252.2±3.3 kJ/mol.[2]

In discussing mechanisms of organic reactions, it is often a useful simplification to consider methyl lithium and related Grignard reagents as salts of "CH3−", although this view is fiction. Such reagents are generally prepared from the methyl halides:

M + CH3X → MCH3

where M is an alkali metal.

Methyl radical

Main article: Methyl radical

The methyl radical has the formula CH3. 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

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

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

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.[3]

Deprotonation

Certain methyl groups can be deprotonated. For example, the acidity of the methyl groups in acetone ((CH3)2CO) is about 1020 more acidic than methane. The resulting carbanions are key intermediates in many reactions in organic synthesis and biosynthesis. Fatty acids arise in this way.

Free radical reactions

When placed in benzylic or allylic positions, the C-H bond strength 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.[4]

"Chiral methyl"

In the special case where one hydrogen is replaced by deuterium (D) and another hydrogen by tritium (T), the methyl substituent becomes chiral.[5] 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 elucidated.[6]

Etymology

French chemists Jean-Baptiste Dumas and Eugene Peligot, after determining methanol's chemical structure, introduced "methylene" from the Greek methy = "wine" + hȳlē = "wood" (patch of trees) with the intention of highlighting its origins, "alcohol made from wood (substance)".[7][8] The term "methyl" was derived in about 1840 by back-formation from "methylene", and was then applied to describe "methyl alcohol".

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

References

  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 CH
    3    " Journal of the American Chemical Society, volume 100, issue 8, pages 2556–2558. doi:10.1021/ja00476a054
  3. ↑ Thauer, R. K., "Biochemistry of Methanogenesis: a Tribute to Marjory Stephenson", Microbiology, 1998, volume 144, pages 2377–2406.
  4. ↑ M. Rossberg et al. “Chlorinated Hydrocarbons” in Ullmann’s Encyclopedia of Industrial Chemistry 2006, Wiley-VCH, Weinheim. doi:10.1002/14356007.a06_233.pub2
  5. ↑ http://www2.lsdiv.harvard.edu/labs/evans/pdf/smnr_2000-2001_Burch_Jason.pdf
  6. ↑ Heinz G. Floss, Sungsook Lee "Chiral methyl groups: small is beautiful" Acc. Chem. Res., 1993, volume 26, pp 116–122. doi:10.1021/ar00027a007
  7. ↑ 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.)
  8. ↑ Note that the correct Greek word for the substance "wood" is xylo-.