n-Butyllithium

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n-Butyllithium
3D ball-and-stick model of n-butyllithium
n-Butyllithium space-filling model
N-butyllithium-tetramer-3D-balls.png
n-Butyllithium tetramer
Butyllithium-hexamer-from-xtal-3D-balls-A.png
n-Butyllithium hexamer
Butyllithium-hexamer-from-xtal-3D-balls-C.png
Close-up of the delocalized bonds between butyl and lithium
Identifiers
CAS number 109-72-8 YesY
PubChem 61028
ChemSpider 10254339 YesY
ChEBI CHEBI:51469 YesY
Jmol-3D images Image 1
Properties
Molecular formula C4H9Li
Molar mass 64.06 g mol−1
Appearance colorless liquid
unstable
usually obtained
as solution
Density 0.68 g/cm³, solvent defined
Melting point -76 °C (<273 K)
Boiling point decomposes
Solubility in water Reaction
Solubility Diethyl ether, cyclohexane
Acidity (pKa) 50[citation needed]
Structure
Molecular shape tetrameric in solution
Dipole moment 0 D
Hazards
Main hazards pyrophoric (inflames in air),
decomposes to corrosive LiOH
NFPA 704
Flammability code 4: Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Flash point below 23 °C (73 °F). E.g., propane Health code 3: Short exposure could cause serious temporary or residual injury. E.g., chlorine gas Reactivity code 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g., fluorine Special hazard W: Reacts with water in an unusual or dangerous manner. E.g., cesium, sodiumNFPA 704 four-colored diamond
Related compounds
Related organolithium
reagents
sec-butyllithium
tert-butyllithium
hexyllithium
methyllithium
Related compounds lithium hydroxide
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 YesY (verify) (what is: YesY/N?)
Infobox references
Glass bottles containing butyllithium

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.[citation needed]

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,[1] but in practice, they degrade upon aging. Fine white precipitate (lithium hydroxide) is deposited and the color changes to orange.

Structure and bonding[edit]

Main article: Organolithium reagent

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.[2] 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+.

Preparation[edit]

The standard preparation for n-BuLi is reaction of 1-bromobutane or 1-chlorobutane with Li metal:[1]

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.

Applications[edit]

Butyllithium is principally valued as an initiator for the anionic polymerization of dienes, such as butadiene.[3] The reaction is called "carbolithiation":

C4H9Li + CH2=CH-CH=CH2 → C4H9-CH2-CH=CH-CH2Li

Isoprene can be polymerized stereospecifically in this way. Also of commercial importance is the use of butyllithium for the production of styrene-butadiene polymers. Even ethylene will insert into BuLi.[citation needed]

Reactions[edit]

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).

Metalation[edit]

Main article: Organolithium reagent

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)).[4] 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[edit]

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).[1]

Transmetalations[edit]

A related family of reactions are the transmetalations, wherein two organometallic compounds exchange their metals. Many examples of such reactions involve Li exchange with Sn:

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[edit]

Organolithium reagents, including n-BuLi are used in synthesis of specific aldehydes and ketones. One such synthetic pathway is the reaction of an organolithium reagent with disubstituted amides:

R1Li + R2CONMe2 → LiNMe2 + R2C(O)R1

Degradation of THF[edit]

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[edit]

When heated, n-BuLi, analogously to other alkyllithium reagents with "β-hydrogens", undergoes β-hydride elimination to produce 1-butene and LiH:

C4H9Li → LiH + CH3CH2CH=CH2

Safety[edit]

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

References[edit]

  1. ^ a b c Brandsma, L.; Verkruijsse, H. D. (1987). Preparative Polar Organometallic Chemistry I. Berlin: Springer-Verlag. ISBN 3-540-16916-4. .
  2. ^ Elschenbroich, C. ”Organometallics” (2006) Wiley-VCH: Weinheim. ISBN 3-527-29390-6.
  3. ^ 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.
  4. ^ 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[edit]