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4-Dimethylaminopyridine

Dimethyl(pyridin-4-yl)amine N,N-Dimethyl-4-aminopyridine DMAP 4-Dimethylaminopyridine 4-(Dimethylamino)azine N,N-dimethyl-4-aminoazine 4-(Dimethylamino)azabenzene N,N-Dimethyl-4-aminoazabenzene mice: oral, 350 mg/kg/day rat: oral, 250 mg/mL fly: oral, 0.15 mg/mL

4-Dimethylaminopyridine (DMAP) is a derivative of pyridine with the chemical formula (CH3)2NC5H4N. This white solid is of interest because it is more basic than pyridine, owing to the resonance stabilisation from the NMe2 substituent.

Because of its basicity, DMAP is a useful nucleophilic catalyst for a variety of reactions such as esterifications with anhydrides, the Baylis-Hillman reaction, hydrosilylations, tritylation, the Steglich rearrangement, Staudinger synthesis of β-lactams and many more. DMAP analogues are used in kinetic resolution experiments of mainly secondary alcohols and Evans auxiliary type amides.

Preparation

DMAP can be prepared in a two-step procedure from pyridine, which is first oxidized to 4-pyridylpyridinium cation. This cation then reacts with dimethylamine:

:[[File:Preparation of DMAP.png|450px]]

Esterification catalyst

Main article: Steglich esterification

In the case of esterification with acetic anhydrides the currently accepted mechanism involves three steps. First, DMAP and acetic anhydride react in a pre-equilibrium reaction to form an ion pair of acetate and the acetylpyridinium ion. In the second step the alcohol adds to the acetylpyridinium, and elimination of pyridine forms an ester. Here the acetate acts as a base to remove the proton from the alcohol as it nucleophilically adds to the activated acylpyridinium. The bond from the acetyl group to the catalyst gets cleaved to generate the catalyst and the ester. The described bond formation and breaking process runs synchronous concerted without the appearance of a tetrahedral intermediate. The acetic acid formed will then protonate the DMAP. In the last step of the catalytic cycle the auxiliary base (usually triethylamine or pyridine) deprotonates the protonated DMAP, reforming the catalyst. The reaction runs through the described nucleophilic reaction pathway irrespective of the anhydride used, but the mechanism changes with the pKa value of the alcohol used. For example, the reaction runs through a base-catalyzed reaction pathway in the case of a phenol. In this case, DMAP acts as a base and deprotonates the phenol, and the resulting phenolate ion adds to the anhydride.

Safety

DMAP has a relatively high toxicity and is particularly dangerous because of its ability to be absorbed through the skin. It is also corrosive.

References

References

  1. Kaljurand, I.. (2005). "Extension of the Self-Consistent Spectrophotometric Basicity Scale in Acetonitrile to a Full Span of 28 pKa Units: Unification of Different Basicity Scales". J. Org. Chem..
  2. (9 February 2015). "Organocatalysis Paradigm Revisited: Are Metal-Free Catalysts Really Harmless?". Biomacromolecules.
  3. (2001). "Catalysis by 4-dialkylaminopyridines". [[Arkivoc]].
  4. Höfle, G.. "4-Dialkylaminopyridines as Highly Active Acylation Catalysts". [[Angew. Chem. Int. Ed. Engl.]].
  5. Ryan P. Wurz. (2007). "Chiral Dialkylamine Catalysts in Asymmetric Synthesis". [[Chem. Rev.]].
  6. (2007). "Pyridine and Pyridine Derivatives".
  7. S. Xu. (2005). "The DMAP-Catalyzed Acetylation of Alcohols - A Mechanistic Study (DMAP = 4-(dimethylamino)-pyridine)". [[Chem. Eur. J.]].
  8. [http://fscimage.fishersci.com/msds/60863.htm DMAP MSDS - Fischer Science]
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reagents-for-organic-chemistry 4-pyridyl-compounds catalysts dimethylamino-compounds 4-aminopyridines
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