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the univalent radical CH3- derived from methane (同)methyl_group, methyl radical

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2013/07/05 18:08:54」(JST)

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Methyl cation, anion, and radical[edit]

Methyl cation[edit]

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 S_N2 reactions by weak nucleophiles.

Methyl anion[edit]

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[edit]

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[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 dimethylsulfate, methyl iodide, and methyl triflate. Methanogenesis, the source of natural gas, arises via a demethylation reaction.^[3]

Deprotonation[edit]

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[edit]

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]

Etymology[edit]

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)",^[5] but with Greek language errors: the Greek for "wood (substance)" is xylo-. 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.

References[edit]

^ March, Jerry (1992). Advanced organic chemistry: reactions, mechanisms, and structure. John Wiley & Sons. ISBN 0-471-60180-2.
^ 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
^ Thauer, R. K., "Biochemistry of Methanogenesis: a Tribute to Marjory Stephenson", Microbiology, 1998, volume 144, pages 2377–2406.
^ M. Rossberg et al. “Chlorinated Hydrocarbons” in Ullmann’s Encyclopedia of Industrial Chemistry 2006, Wiley-VCH, Weinheim. doi:10.1002/14356007.a06_233.pub2
^ Annales de chimie et de physique. 1835. p. 9.

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