Superbase - Wikipedia, the free encyclopedia

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Superbase
From Wikipedia, the free encyclopedia

In chemistry, a superbase is an extremely basic compound or substance that has a high affinity for protons. The
hydroxide ion is the strongest base possible in aqueous solutions, but bases exist with much greater strengths
than can exist in water. Such bases are valuable in organic synthesis and are fundamental to physical organic
chemistry. Superbases have been described and used since the 1850s.[1] Reactions involving superbases often
require special techniques since they are destroyed by water and atmospheric carbon dioxide as well as oxygen.
Inert atmosphere techniques and low temperatures minimize these side reactions. Superbases also have a
corrosive effect.

Contents
1 Definitions
2 Classes of superbases
2.1 Organic
2.2 Organometallic
2.3 Inorganic
3 See also
4 References

Definitions
IUPAC defines superbases simply as a "compound having a very high basicity, such as lithium
diisopropylamide."[2] Caubre defines superbases qualitatively but more precisely: "The term superbases should
only be applied to bases resulting from a mixing of two (or more) bases leading to new basic species possessing
inherent new properties. The term superbase does not mean a base is thermodynamically and/or kinetically
stronger than another, instead it means that a basic reagent is created by combining the characteristics of several
different bases."[3]
Superbases have also been defined semi-quantitatively as any species with a higher absolute proton affinity
(APA = 245.3 kcal/mol) and intrinsic gas phase basicity (GB = 239 kcal/mol) than Alder's canonical proton
sponge (1,8-bis-(dimethylamino)-naphthalene).[4]

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Classes of superbases
There are three main classes of superbases: organic, organometallic and inorganic.

Organic
Organic superbases are almost always neutral, nitrogen-containing species. Despite enormous proton affinity,
organosuperbases are prized for their heightened reactivity tempered by low nucleophilicity and relatively mild
conditions of use. Increasingly important in organic synthesis, these include the phosphazenes, amidines and
guanidines. Other organic compounds also meet the physicochemical or structural definitions of 'superbase'.
Proton chelators like the aromatic proton sponges and the bispidines are also superbases. Multicyclic
polyamines, like DABCO might also be loosely included in this category.[5]

Organometallic
Organometallic compounds of reactive metals are often superbases, including organolithium and
organomagnesium (Grignard reagent) compounds. Another type of organic superbase has a reactive metal
exchanged for a hydrogen on a heteroatom, such as oxygen (unstabilized alkoxides) or nitrogen (metal amides
such as lithium diisopropylamide). A desirable property in many cases is low nucleophilicity, i.e. a nonnucleophilic base. Unhindered alkyllithiums, for example, cannot be used with electrophiles such as carbonyl
groups, because they attack the electrophiles as nucleophiles.
The Schlosser base (or Lochmann-Schlosser base), the combination of n-butyllithium and potassium tertbutoxide, is a commonly used superbase. n-Butyllithium and potassium tert-butoxide form a mixed aggregate of
greater reactivity than either reagent alone and with distinctly different properties in comparison to tertbutylpotassium.[6]

Inorganic
Inorganic superbases are typically salt-like compounds with small, highly charged anions, e.g. lithium nitride.
Alkali and earth alkali metal hydrides potassium hydride and sodium hydride are superbases. Such species are
insoluble in all solvents owing to the strong cation-anion interactions, but the surfaces of these materials are
highly reactive and slurries are useful in synthesis.

See also
Superacid
Phosphazene

References
1. "BBC - h2g2 - History of Chemistry - Acids and Bases". Retrieved 2009-08-30.
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2. IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006)
"superacid (http://goldbook.iupac.org/S06135.html)".
3. Caubre, P (1993). "Unimetal super bases". Chemical Reviews 93: 23172334. doi:10.1021/cr00022a012.
4. Raczynska, E. D.; Decouzon, M.; Gal, J.-F.; et al. (1998). "Superbases and superacids in the gas phase". Trends in
Organic Chemistry 7: 95103.
5. Superbases for Organic Synthesis Ed. Ishikawa, T., John Wiley and Sons, Ltd.: West Sussex, UK. 2009.
6. Schlosser, M. (1988). "Superbases for organic synthesis". Pure Appl. Chem. 60 (11): 16271634.
doi:10.1351/pac198860111627.

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Categories: Bases
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