1-Methylimidazole Explained

1-Methylimidazole or N-methylimidazole is an aromatic heterocyclic organic compound with the formula CH3C3H3N2. It is a colourless liquid that is used as a specialty solvent, a base, and as a precursor to some ionic liquids. It is a fundamental nitrogen heterocycle and as such mimics for various nucleoside bases as well as histidine and histamine.

Basicity

With the N-methyl group, this particular derivative of imidazole cannot tautomerize. It is slightly more basic than imidazole, as indicated by the pKa's of the conjugate acids of 7.0 and 7.4.[1] Methylation also provides a significantly lower melting point, which makes 1-methylimidazole a useful solvent.

Synthesis

1-Methylimidazole is prepared mainly by two routes industrially. The main one is acid-catalysed methylation of imidazole by methanol. The second method involves the Radziszewski reaction from glyoxal, formaldehyde, and a mixture of ammonia and methylamine.[2]

(CHO)2 + CH2O + CH3NH2 + NH3 → H2C2N(NCH3)CH + 3 H2O

The compound can be synthesized on a laboratory scale by methylation of imidazole at the pyridine-like nitrogen and subsequent deprotonation.[3] Similarly, 1-methylimidazole may be synthesized by first deprotonating imidazole to form a sodium salt followed by methylation.[4] [5]

H2C2N(NH)CH + CH3I → [H<sub>2</sub>C<sub>2</sub>(NH)(NCH<sub>3</sub>)CH]I

[H<sub>2</sub>C<sub>2</sub>(NH)(NCH<sub>3</sub>)CH]I + NaOH → H2C2N(NCH3)CH + H2O + NaI

Applications

In the research laboratory, 1-methylimidazole and related derivatives have been used as mimic aspects of diverse imidazole-based biomolecules.

1-Methylimidazole is also the precursor for the synthesis of the methylimidazole monomer of pyrrole-imidazole polyamides. These polymers can selectively bind specific sequences of double-stranded DNA by intercalating in a sequence dependent manner.[6]

Ionic liquid precursor

1-Methylimidazole alkylates to form dialkyl imidazolium salts. Depending on the alkylating agent and the counteranion, various ionic liquids result, e.g. 1-butyl-3-methylimidazolium hexafluorophosphate ("BMIMPF6"):[7]

BASF has used 1-methylimidazole as a means to remove acid during their industrial-scale production of diethoxyphenylphosphine. In this biphasic acid scavenging using ionic liquids (BASIL) process, 1-methylimidazole reacts with HCl to produce 1-methylimidazolium hydrochloride, which spontaneously separates as a separate liquid phase under the reaction conditions.[7] [8]

2 MeC3N2H3 + C6H5PCl2 + 2 C2H5OH → 2 [MeC<sub>3</sub>N<sub>2</sub>H<sub>4</sub>]Cl + C6H5P(OC2H5)2

Donor properties

1-methylimidazole (NMIz) as a ligand forms octahedral ions M(NMIz)62+with M = Fe, Co, Ni, and a square-planar ion Cu(NMIz)42+. [9] 1-methylimidazole forms adducts with Lewis acids such as molybdenum perfluorobutyrate and [Rh(CO)<sub>2</sub>Cl]2. The donor properties of 1-methylimidazole have been analyzed by the ECW model yielding EB= 1.16 and CB= 4.92.

See also

Notes and References

  1. Albert, A., Heterocyclic Chemistry, 2nd ed.; 1968 Athlone Press,
  2. Ueber die Constitution des Lophins und verwandter Verbindungen. By the Constitution of the Lophins and related compounds. German. Bronislaw Radziszewski . . 15 . 2. 1493–1496 . 1882 . 10.1002/cber.18820150207 .
  3. Gilchrist, T. L., Heterocyclic Chemistry, 2nd ed.; 1992 Longman Scientific & Technical,
  4. Grimmett, M. R., Imidazole and Benzimidazole Synthesis; 1997 Academic Press,
  5. Gupta, R. R., Kumar, M., Gupta, V., Heterocyclic Chemistry II: Five Membered Heterocycles; 1999 Springer,
  6. Eldon E. . Baird . Peter B. . Dervan . 1996 . Solid Phase Synthesis of Polyamides Containing Imidazole and Pyrrole Amino Acids . Journal of the American Chemical Society . 118 . 26 . 6141–6 . 10.1021/ja960720z.
  7. Book: G. Wytze . Meindersma . Matthias . Maase . André B. . De Haan . 2007 . Ionic Liquids . Ullmann's Encyclopedia of Industrial Chemistry . Weinheim . Wiley-VCH . 10.1002/14356007.l14_l01 . 978-3-527-30673-2.
  8. Welton. Tom. Solvents and sustainable chemistry. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences. 11 November 2015. 471. 2183. 20150502. 10.1098/rspa.2015.0502. 4685879. 26730217. 2015RSPSA.47150502W .
  9. Reedijk,R. . 1969. Pyrazoles and imidazoles as ligands. II. Coordination compounds of N-methyl imidazole with metal perchlorates and tetrafluoroborates. Inorganica Chimica Acta. 3. 517–522. 10.1016/S0020-1693(00)92544-1.