n-Butyllithium space-filling model
Close-up of the delocalized bonds between butyl and lithium
|Jmol-3D images||Image 1|
|Molar mass||64.06 g mol−1|
|Density||0.68 g/cm³, solvent defined|
-76 °C (<273 K)
|Solubility in water||Reaction|
|Solubility||Diethyl ether, cyclohexane|
|Acidity (pKa)||50|
|Molecular shape||tetrameric in solution|
|Dipole moment||0 D|
|Main hazards||pyrophoric (inflames in air),
decomposes to corrosive LiOH
|Related compounds||lithium hydroxide|
| (what is: / ?)
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
n-Butyllithium (abbreviated n-BuLi) is an organolithium reagent. It is widely used as a polymerization initiator in the production of elastomers such as polybutadiene or styrene-butadiene-styrene (SBS). Also, it is broadly employed as a strong base (superbase) in organic synthesis, both industrially and in the laboratory.
Butyllithium is commercially available as solutions (15%, 25%, 2 M, 2.5 M, 10 M, etc.) in alkanes such as pentane, hexanes, and heptanes. Solutions in diethyl ether and THF can be prepared, but are not stable enough for storage. Annual worldwide production and consumption of butyllithium and other organolithium compounds is estimated at 1800 tonnes.
Although it is a colourless liquid, n-butyllithium is usually encountered as a pale yellow solution in alkanes. Such solutions are stable indefinitely if properly stored, but in practice, they degrade upon aging. Fine white precipitate (lithium hydroxide) is deposited and the color changes to orange.
Structure and bonding 
n-BuLi exists as a cluster both in the solid state and in a solution. The tendency to aggregate is common for organolithium compounds. The aggregates are held together by delocalized covalent bonds between lithium and the terminal carbon of the butyl chain. In the case of n-BuLi, the clusters are tetrameric (in ether) or hexameric (in cyclohexane). The cluster is a distorted cubane structure with Li and CH2R groups at alternating vertices. An equivalent description describes the tetramer as a Li4 tetrahedron interpenetrated with a tetrahedron [CH2R]4. Bonding within the cluster is related to that used to describe diborane, but more complex since eight atoms are involved. Reflecting its "electron-deficient character," n-butyllithium is highly reactive toward Lewis bases.
Due to the large difference between the electronegativities of carbon (2.55) and lithium (0.98), the C-Li bond is highly polarized. The charge separation has been estimated to be 55-95%. For practical purposes, n-BuLi can often be considered to react as the butyl anion, n-Bu−, and a lithium cation, Li+.
- 2 Li + C4H9X → C4H9Li + LiX
- where X = Cl, Br
If the lithium used for this reaction contains 1–3% sodium, the reaction proceeds more quickly than if pure lithium is used. Solvents used for this preparation include benzene, cyclohexane, and diethyl ether. When BuBr is the precursor, the product is a homogeneous solution, consisting of a mixed cluster containing both LiBr and BuLi, together with a small amount of octane. BuLi forms a weaker complex with LiCl, so that the reaction of BuCl with Li produces a precipitate of LiCl.
The concentration of butyllithium in commercially available solutions tends to decrease over time as the BuLi reacts with air. Subsequently, butyllithium is often titrated prior to use to ascertain its true concentration. The BuLi is added to a known amount of a weakly acidic compound, such as an alcohol. Because butyllithium is a strong base, it quickly and quantitatively reacts with weak acids to give the corresponding lithium salts and butane. An indicator, such as 1,10-phenanthroline or 2,2'-bipyridine, is commonly used to signal the endpoint of the titration. Both compounds form colored complexes with butyllithium once the titrand is consumed.
- C4H9Li + CH2=CH-CH=CH2 → C4H9-CH2-CH=CH-CH2Li
Isoprene can be polymerized stereospecifically in this way. Also of commercially importance is the use of butyllithium for the production of styrene-butadiene polymers. Even ethylene will insert into BuLi.
Butyllithium is a strong base (pKa ≈ 50), but it is also a powerful nucleophile and reductant, depending on the other reactants. Furthermore, in addition to being a strong nucleophile, n-BuLi binds to aprotic Lewis bases, such as ethers and tertiary amines, which partially disaggregate the clusters by binding to the lithium centers. Its use as a strong base is referred to as metalation. Reactions are typically conducted in tetrahydrofuran and diethyl ether, which are good solvents for the resulting organolithium derivatives (see below).
One of the most useful chemical properties of n-BuLi is its ability to deprotonate a wide range of weak Brønsted acids. t-Butyllithium and s-butyllithium are more basic. n-BuLi can deprotonate (that is, metalate) many types of C-H bonds, especially where the conjugate base is stabilized by electron delocalization or one or more heteroatoms (non carbon atoms). Examples include acetylenes (H-CC-R), methyl sulfides (H-CH2SR), thioacetals (H-CH(SR)2, e.g. dithiane), methylphosphines (H-CH2PR2), furans, thiophenes and ferrocene (Fe(H-C5H4)(C5H5)). In addition to these, it will also deprotonate all more acidic compounds such as alcohols, amines, enolizable carbonyl compounds, and any overtly acidic compounds, to produce alkoxides, amides, enolates and other -ates of lithium, respectively. The stability and volatility of the butane resulting from such deprotonation reactions is convenient, but can also be a problem for large-scale reactions because of the volume of a flammable gas produced.
- LiC4H9 + R-H → C4H10 + R-Li
The kinetic basicity of n-BuLi is affected by the solvent or cosolvent. Ligands that complex Li+ such as tetrahydrofuran (THF), tetramethylethylenediamine (TMEDA), hexamethylphosphoramide (HMPA), and 1,4-diazabicyclo[2.2.2]octane (DABCO) further polarize the Li-C bond and accelerate the metalation. Such additives can also aid in the isolation of the lithiated product, a famous example of which is dilithioferrocene.
- Fe(C5H5)2 + 2 LiC4H9 + 2 TMEDA → 2 C4H10 + Fe(C5H4Li)2(TMEDA)2
Schlosser's base is a superbase produced by treating butyllithium with potassium tert-butoxide. It is kinetically more reactive than butyllithium and is often used to accomplish difficult metalations. The butoxide anion complexes the lithium and effectively produces butylpotassium, which is more reactive than the corresponding lithium reagent.
An example of the use of n-butyllithium as a base is the addition of an amine to methyl carbonate to form a methyl carbamate, where n-butyllithium serves to deprotonate the amine:
- n-BuLi + R2NH + (MeO)2CO → R2N-CO2Me + LiOMe + BuH
Halogen-lithium exchange 
Butyllithium reacts with some organic bromides and iodides in an exchange reaction to form the corresponding organolithium derivative. The reaction usually fails with organic chlorides and fluorides:
- C4H9Li + RX → C4H9X + RLi (X = Br, I)
This reaction is useful for preparation of several types of RLi compounds, particularly aryllithium and some vinyllithium reagents. The utility of this method is significantly limited, however, by the presence in the reaction mixture of n-BuBr or n-BuI, which can react with the RLi reagent formed, and by competing dehydrohalogenation reactions, in which n-BuLi serves as a base:
- 2 C4H9Br + RLi → 2 C4H9R + LiBr
- 2 C4H9Li + R'CH=CHBr → 2 C4H10 + R'C≡CLi + LiBr
These side reaction are significantly less important for RI than for RBr, since the iodine-lithium exchange is several orders of magnitude faster than the bromine-lithium exchange. For these reasons, aryl, vinyl and primary alkyl iodides are the preferred substrates, and t-BuLi rather than n-BuLi is usually used, since the formed t-BuI is immediately destroyed by the t-BuLi in a dehydrohalogenation reaction (thus requiring 2 equiv of t-BuLi). Alternatively, vinyl lithium reagents can be generated by direct reaction of the vinyl halide (e.g. cyclohexenyl chloride) with lithium or by tin-lithium exchange (see next section).
- C4H9Li + Me3SnAr → C4H9SnMe3 + LiAr
- where Ar is aryl and Me is methyl
The tin-lithium exchange reactions have one major advantage over the halogen-lithium exchanges for the preparation of organolithium reagents, in that the product tin compounds (C4H9SnMe3 in the example above) are much less reactive towards lithium reagents than are the halide products of the corresponding halogen-lithium exchanges (C4H9Br or C4H9Cl). Other metals and metaloids which undergo such exchange reactions are organic compounds of mercury, selenium, and tellurium.
Carbonyl additions 
- R1Li + R2CONMe2 → LiNMe2 + R2C(O)R1
Degradation of THF 
THF is deprotonated by butyllithium, especially in the presence of TMEDA, by loss of one of four protons adjacent to oxygen. This process, which consumes butyllithium to generate butane, induces a reverse cycloaddition to give enolate of acetaldehyde and ethylene. Therefore, reactions of BuLi in THF are typically conducted at low temperatures, such as –78 °C, as is conveniently produced by a freezing bath of dry ice/acetone. Higher temperatures (−25 °C or even −15 °C) are also used.
Thermal decomposition 
- C4H9Li → LiH + CH3CH2CH=CH2
Alkyl-lithium compounds are stored under inert gas to prevent loss of activity and for reasons of safety. n-BuLi reacts violently with water:
- C4H9Li + H2O → C4H10 + LiOH
BuLi also reacts with CO2 to give lithium pentanoate:
- C4H9Li + CO2 → C4H9CO2Li
- Brandsma, L.; Verkraijsse, H. D. (1987). Preparative Polar Organometallic Chemistry I. Berlin: Springer-Verlag. ISBN 3-540-16916-4..
- Elschenbroich, C. ”Organometallics” (2006) Wiley-VCH: Weinheim. ISBN 3-527-29390-6.
- Ulrich Wietelmann and Richard J. Bauer “Lithium and Lithium Compounds” in Ullmann's Encyclopedia of Industrial Chemistry, 2002, Wiley-VCH, Weinheim. doi:10.1002/14356007.a15_393.
- Sanders, R.; Mueller-Westerhoff, U. T. (1996). "The Lithiation of Ferrocene and Ruthenocene — A Retraction and an Improvement". Journal of Organometallic Chemistry 512 (1-2): 219–224. doi:10.1016/0022-328X(95)05914-B.
Further reading 
- FMC Lithium manufacturer's product sheets
- Environmental Chemistry directory
- Weissenbacher, Anderson, Ishikawa, Organometallics, July 1998, p681.7002, Chemicals Economics Handbook SRI International
- HPV test plan, submitted by FMC Lithium to EPA
- Ovaska, T. V. e-EROS Encyclopedia of Reagents for Organic Synthesis "n-butyllithium." Wiley and sons. 2006. doi:10.1002/047084289X.rb395
- Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements, 2nd ed. 1997: Butterworth-Heinemann, Boston.