Iodomethane
Encyclopedia : I : IO : IOD : Iodomethane
| Iodomethane | |
|---|---|
| |
| General | |
| Systematic name | Iodomethane |
| Other names | Methyl iodide |
| Molecular formula | CH3I |
| SMILES | CI |
| Molar mass | 141.94 g/mol |
| Appearance | colourless liquid |
| CAS number | [74-88-4] |
| Properties | |
| Density and phase | 2.28 g/mL, liquid |
| Solubility in water | Slightly soluble |
| Solubility in organic solvents | Fully miscible |
| Melting point | -66.5 °C (206.7 K) |
| Boiling point | 42.4 °C (315.6 K) |
| Viscosity | ? cP at ? °C |
| Structure | |
| Molecular shape | Tetrahedral |
| Dipole moment | 1.59 D (gas) |
| Hazards | |
| MSDS | External MSDS |
| EU classification | Toxic (T') Carc. Cat. 3 |
| NFPA 704 | |
| R-phrases | R21, R23/25 R37/38, R40 |
| S-phrases | S1/2, S36/37 S38, S45 |
| RTECS number | PA9450000 |
| Supplementary data page | |
| Structure & properties | n, εr, etc. |
| Thermodynamic data | Phase behaviour Solid, liquid, gas |
| Spectral data | UV, IR, NMR, MS |
| Related compounds | |
| Other methyl halides | Fluoromethane Chloromethane Bromomethane |
| Other iodomethanes | Diiodomethane Iodoform Tetraiodomethane |
| Except where noted otherwise, data are given for materials in their standard state (at 25°C, 100 kPa) [Chemical infoboxInfobox disclaimer and references] | |
Iodomethane, commonly called methyl iodide and commonly abbreviated "MeI", is a dense volatile liquid. It is colourless, although it is light sensitive and may develop a purplish tinge caused by iodine, thus it is usually stabilised by storage over copper metal. Methyl iodide is widely used in organic synthesis to deliver a methyl group into a structure, a process called methylation, usually via SN2 substitution. It is naturally emitted by rice plantations in small amounts.
Chemical properties
Methyl iodide is an excellent reagent for SN2 substitution reactions – it is sterically open for attack by nucleophiles, and it has an excellent leaving group (iodide), making it a reactive substrate for such reactions. For example, it can be used for the methylation of phenols or carboxylic acids:
In both of these example the base (K2CO3 or Li2CO3) removes the acidic proton to form an anion, which serves as the nucleophile in the SN2 substitution.
The iodide is a soft leaving group, so that methylation tends to occur at the "softer" end of an ambident nucleophile- for example, reaction with thiocyanate ion favours attack at "soft" rather than "hard" , leading mainly to CH3SCN rather than CH3NCS. This is valuable in the methylation of stabilized enolates (such as those from 1,3-dicarbonyl compounds), where alkylation of an enolate may occur on the harder oxygen atom rather than the (usually desired) carbon atom. With methyl iodide, C-alkylation nearly always predominates.
Iodomethane is also an important precursor to methylmagnesium iodide or "MeMgI", which is a common reagent. Because MeMgI forms readily, its preparation is widely used in teaching laboratories as an illustration of Grignard reagents. The use of MeMgI has been somewhat superceded by the commercially available methyl lithium, "MeLi", which is prepared from methyl bromide and lithium metal.
Preparation
Iodomethane is rarely prepared in the laboratory since it is inexpensive, but it is formed via the exothermic reaction that occurs when iodine is added to a mixture of methanol with red phosphorus:
The iodinating reagent is phosphorus triiodide that is formed in situ.
The CH3I can easily be distilled from the mixture and purified by washing with Na2S2O3 (to remove iodine) and then water, aq. Na2CO3 and water. It is then dried over CaCl2 and distilled. Another purification method involves percolation of the product through silica gel or activated alumina.
An alternative preparation involves the addition of dimethyl sulfate to a stirred suspension of calcium carbonate in aqueous potassium iodide:
(CH3O)2SO2 + KI → CH3I + CH3OSO2OK
Both methods of preparation give high chemical yields of methyl iodide.
Methyl iodide can be formed during nuclear accidents by the reaction of organic matter with the "fission iodine."
Disadvantages to MeI as a methylating agent
Although MeI an excellent methylation reagent, its use is often disfavored for a variety of reasons. MeI has a high equivalent weight: one mole of MeI weighs almost 3x as much as one mole of methyl chloride, which is a poorer but often still competent methylating reagent. Iodides are expensive relative to the more common chlorides and bromides. Also, the iodide leaving group is potentially problematic as it is an reasonable nucleophile, leading often to secondary reactions. Finally, being highly reactive, MeI is more dangerous for laboratory workers than related chlorides and bromides. Alternatives to MeI offer different advantages and disadvantages in cost, risk, chemical selectivity, and ease of reaction work-up.References
- March, J. (1992). Advanced Organic Chemistry (4th Edn.), New York:Wiley. ISBN 0-471-60180-2
- Sulikowski, G. A.; Sulikowski, M. M. (1999). in Coates, R.M.; Denmark, S. E. (Eds.) Handbook of Reagents for Organic Synthesis, Volume 1: Reagents, Auxiliaries and Catalysts for C-C Bond Formation New York: Wiley, pp. 423–26.
External links
- [International Chemical Safety Card 0509]
- [NIOSH Pocket Guide to Chemical Hazards]
- [IARC Monograph: "Methyl Iodide"]
- [European Chemicals Bureau]
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