N-Butyllithium

N-Butyllithium

Overview

n-Butyllithium is an organolithium reagent
Organolithium reagent
An organolithium reagent is an organometallic compound with a direct bond between a carbon and a lithium atom. As the electropositive nature of lithium puts most of the charge density of the bond on the carbon atom, effectively creating a carbanion, organolithium compounds are extremely powerful...

. It is widely used as a polymerization
Polymerization
In polymer chemistry, polymerization is a process of reacting monomer molecules together in a chemical reaction to form three-dimensional networks or polymer chains...

 initiator in the production of elastomer
Elastomer
An elastomer is a polymer with the property of viscoelasticity , generally having notably low Young's modulus and high yield strain compared with other materials. The term, which is derived from elastic polymer, is often used interchangeably with the term rubber, although the latter is preferred...

s such as polybutadiene
Polybutadiene
Polybutadiene is a synthetic rubber that is a polymer formed from the polymerization process of the monomer 1,3-butadiene.It has a high resistance to wear and is used especially in the manufacture of tires, which consumes about 70% of the production...

 or styrene-butadiene-styrene (SBS)
Styrene-butadiene
Styrene-Butadiene or Styrene-Butadiene-Rubber is a synthetic rubber copolymer consisting of styrene and butadiene. It has good abrasion resistance and good aging stability when protected by additives, and is widely used in car tires, where it may be blended with natural rubber...

. Also, it is broadly employed as a strong base
Base (chemistry)
For the term in genetics, see base A base in chemistry is a substance that can accept hydrogen ions or more generally, donate electron pairs. A soluble base is referred to as an alkali if it contains and releases hydroxide ions quantitatively...

 (superbase
Superbase
In chemistry, a superbase is an extremely strong base, that is a compound that has a high affinity for protons. Hydroxide ion is the strongest base possible in aqueous solutions, but bases exist with pKb's well outside of the aqueous range. Such bases are valuable in organic synthesis and are...

) 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 alkane
Alkane
Alkanes are chemical compounds that consist only of hydrogen and carbon atoms and are bonded exclusively by single bonds without any cycles...

s such as pentane
Pentane
Pentane is an organic compound with the formula C5H12 — that is, an alkane with five carbon atoms. The term may refer to any of three structural isomers, or to a mixture of them: in the IUPAC nomenclature, however, pentane means exclusively the n-pentane isomer; the other two being called...

, hexane
Hexane
Hexane is a hydrocarbon with the chemical formula C6H14; that is, an alkane with six carbon atoms.The term may refer to any of four other structural isomers with that formula, or to a mixture of them. In the IUPAC nomenclature, however, hexane is the unbranched isomer ; the other four structures...

s, and heptane
Heptane
n-Heptane is the straight-chain alkane with the chemical formula H3C5CH3 or C7H16. When used as a test fuel component in anti-knock test engines, a 100% heptane fuel is the zero point of the octane rating scale...

s. Solutions in diethyl ether
Diethyl ether
Diethyl ether, also known as ethyl ether, simply ether, or ethoxyethane, is an organic compound in the ether class with the formula . It is a colorless, highly volatile flammable liquid with a characteristic odor...

 and THF
ThF
Follicular B helper T cells , are antigen-experienced CD4+ T cells found in the B cell follicles of secondary lymphoid organs such as lymph nodes, spleens and Peyer's patches, and are identified by their constitutive expression of the B cell follicle homing receptor CXCR5...

 can be prepared, but are not stable enough for storage.
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Encyclopedia

n-Butyllithium is an organolithium reagent
Organolithium reagent
An organolithium reagent is an organometallic compound with a direct bond between a carbon and a lithium atom. As the electropositive nature of lithium puts most of the charge density of the bond on the carbon atom, effectively creating a carbanion, organolithium compounds are extremely powerful...

. It is widely used as a polymerization
Polymerization
In polymer chemistry, polymerization is a process of reacting monomer molecules together in a chemical reaction to form three-dimensional networks or polymer chains...

 initiator in the production of elastomer
Elastomer
An elastomer is a polymer with the property of viscoelasticity , generally having notably low Young's modulus and high yield strain compared with other materials. The term, which is derived from elastic polymer, is often used interchangeably with the term rubber, although the latter is preferred...

s such as polybutadiene
Polybutadiene
Polybutadiene is a synthetic rubber that is a polymer formed from the polymerization process of the monomer 1,3-butadiene.It has a high resistance to wear and is used especially in the manufacture of tires, which consumes about 70% of the production...

 or styrene-butadiene-styrene (SBS)
Styrene-butadiene
Styrene-Butadiene or Styrene-Butadiene-Rubber is a synthetic rubber copolymer consisting of styrene and butadiene. It has good abrasion resistance and good aging stability when protected by additives, and is widely used in car tires, where it may be blended with natural rubber...

. Also, it is broadly employed as a strong base
Base (chemistry)
For the term in genetics, see base A base in chemistry is a substance that can accept hydrogen ions or more generally, donate electron pairs. A soluble base is referred to as an alkali if it contains and releases hydroxide ions quantitatively...

 (superbase
Superbase
In chemistry, a superbase is an extremely strong base, that is a compound that has a high affinity for protons. Hydroxide ion is the strongest base possible in aqueous solutions, but bases exist with pKb's well outside of the aqueous range. Such bases are valuable in organic synthesis and are...

) 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 alkane
Alkane
Alkanes are chemical compounds that consist only of hydrogen and carbon atoms and are bonded exclusively by single bonds without any cycles...

s such as pentane
Pentane
Pentane is an organic compound with the formula C5H12 — that is, an alkane with five carbon atoms. The term may refer to any of three structural isomers, or to a mixture of them: in the IUPAC nomenclature, however, pentane means exclusively the n-pentane isomer; the other two being called...

, hexane
Hexane
Hexane is a hydrocarbon with the chemical formula C6H14; that is, an alkane with six carbon atoms.The term may refer to any of four other structural isomers with that formula, or to a mixture of them. In the IUPAC nomenclature, however, hexane is the unbranched isomer ; the other four structures...

s, and heptane
Heptane
n-Heptane is the straight-chain alkane with the chemical formula H3C5CH3 or C7H16. When used as a test fuel component in anti-knock test engines, a 100% heptane fuel is the zero point of the octane rating scale...

s. Solutions in diethyl ether
Diethyl ether
Diethyl ether, also known as ethyl ether, simply ether, or ethoxyethane, is an organic compound in the ether class with the formula . It is a colorless, highly volatile flammable liquid with a characteristic odor...

 and THF
ThF
Follicular B helper T cells , are antigen-experienced CD4+ T cells found in the B cell follicles of secondary lymphoid organs such as lymph nodes, spleens and Peyer's patches, and are identified by their constitutive expression of the B cell follicle homing receptor CXCR5...

 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 hydride
Lithium hydride
Lithium hydride is the inorganic compound with the formula LiH. It is a colorless solid, although commercial samples are gray. Characteristic of a salt-like, or ionic, hydride, it has a high melting point and is not soluble in any solvent with which it does not react...

) 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
Cyclohexane
Cyclohexane is a cycloalkane with the molecular formula C6H12. Cyclohexane is used as a nonpolar solvent for the chemical industry, and also as a raw material for the industrial production of adipic acid and caprolactam, both of which being intermediates used in the production of nylon...

). The cluster is a distorted cubane
Cubane
Cubane is a synthetic hydrocarbon molecule that consists of eight carbon atoms arranged at the corners of a cube, with one hydrogen atom attached to each carbon atom. A solid crystalline substance, cubane is one of the Platonic hydrocarbons. It was first synthesized in 1964 by Philip Eaton, a...

 structure with Li and CH2R groups at alternating vertices. An equivalent description describes the tetramer as a Li4 tetrahedron
Tetrahedron
In geometry, a tetrahedron is a polyhedron composed of four triangular faces, three of which meet at each vertex. A regular tetrahedron is one in which the four triangles are regular, or "equilateral", and is one of the Platonic solids...

 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
Electronegativity
Electronegativity, symbol χ , is a chemical property that describes the tendency of an atom or a functional group to attract electrons towards itself. An atom's electronegativity is affected by both its atomic number and the distance that its valence electrons reside from the charged nucleus...

 of carbon
Carbon
Carbon is the chemical element with symbol C and atomic number 6. As a member of group 14 on the periodic table, it is nonmetallic and tetravalent—making four electrons available to form covalent chemical bonds...

 (2.55
Electronegativity
Electronegativity, symbol χ , is a chemical property that describes the tendency of an atom or a functional group to attract electrons towards itself. An atom's electronegativity is affected by both its atomic number and the distance that its valence electrons reside from the charged nucleus...

) and lithium
Lithium
Lithium is a soft, silver-white metal that belongs to the alkali metal group of chemical elements. It is represented by the symbol Li, and it has the atomic number 3. Under standard conditions it is the lightest metal and the least dense solid element. Like all alkali metals, lithium is highly...

 (0.98
Electronegativity
Electronegativity, symbol χ , is a chemical property that describes the tendency of an atom or a functional group to attract electrons towards itself. An atom's electronegativity is affected by both its atomic number and the distance that its valence electrons reside from the charged nucleus...

), 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


The standard preparation for n-BuLi is reaction of 1-bromobutane
1-Bromobutane
1-Bromobutane is a colorless liquid that is insoluble in water, but soluble in ethanol and diethyl ether. As a primary alkyl halide, it is especially prone to SN2 type reactions...

 or 1-chlorobutane
1-Chlorobutane
1-Chlorobutane is an alkyl halide with the chemical formula C4H9Cl. It reacts with lithium metal to give n-butyllithium:...

 with Li metal:
2 Li + C4H9X → C4H9Li + LiX
where X = Cl, Br

The lithium for this reaction contains 1-3% sodium
Sodium
Sodium is a chemical element with the symbol Na and atomic number 11. It is a soft, silvery-white, highly reactive metal and is a member of the alkali metals; its only stable isotope is 23Na. It is an abundant element that exists in numerous minerals, most commonly as sodium chloride...

. Solvents used for this preparation include benzene
Benzene
Benzene is an organic chemical compound. It is composed of 6 carbon atoms in a ring, with 1 hydrogen atom attached to each carbon atom, with the molecular formula C6H6....

, 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
Octane
Octane is a hydrocarbon and an alkane with the chemical formula C8H18, and the condensed structural formula CH36CH3. Octane has many structural isomers that differ by the amount and location of branching in the carbon chain...

. BuLi forms a weaker complex with LiCl, so that the reaction of BuCl with Li produces a precipitate of LiCl
Lithium chloride
Lithium chloride is a chemical compound with the formula LiCl. The salt is a typical ionic compound, although the small size of the Li+ ion gives rise to properties not seen for other alkali metal chlorides, such as extraordinary solubility in polar solvents and its hygroscopic...

.

Applications


Butyllithium is principally valued as an initiator for the anionic polymerization
Polymerization
In polymer chemistry, polymerization is a process of reacting monomer molecules together in a chemical reaction to form three-dimensional networks or polymer chains...

 of diene
Diene
In organic chemistry a diene or diolefin is a hydrocarbon that contains two carbon double bonds.Conjugated dienes are functional groups, with a general formula of CnH2n-2. Dienes and alkynes are functional isomers...

s, such as butadiene. The reaction is called "carbolithiation":
C4H9Li + CH2=CH-CH=CH2 → C4H9-CH2-CH=CH-CH2Li

Isoprene
Isoprene
Isoprene , or 2-methyl-1,3-butadiene, is a common organic compound with the formula CH2=CCH=CH2. Under standard conditions it is a colorless liquid...

 can be polymerized stereospecifically in this way. Also of commercially importance is the use of butyllithium for the production of styrene-butadiene
Styrene-butadiene
Styrene-Butadiene or Styrene-Butadiene-Rubber is a synthetic rubber copolymer consisting of styrene and butadiene. It has good abrasion resistance and good aging stability when protected by additives, and is widely used in car tires, where it may be blended with natural rubber...

 polymers. Even ethylene
Ethylene
Ethylene is a gaseous organic compound with the formula . It is the simplest alkene . Because it contains a carbon-carbon double bond, ethylene is classified as an unsaturated hydrocarbon. Ethylene is widely used in industry and is also a plant hormone...

 will insert into BuLi.

Reactions


Butyllithium is a strong base (pKa ≈ 50), but it is also a powerful nucleophile
Nucleophile
A nucleophile is a species that donates an electron-pair to an electrophile to form a chemical bond in a reaction. All molecules or ions with a free pair of electrons can act as nucleophiles. Because nucleophiles donate electrons, they are by definition Lewis bases.Nucleophilic describes the...

 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 amine
Amine
Amines are organic compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are derivatives of ammonia, wherein one or more hydrogen atoms have been replaced by a substituent such as an alkyl or aryl group. Important amines include amino acids, biogenic amines,...

s, which partially disaggregate the clusters by binding to the lithium centers. Its use as a strong base
Base (chemistry)
For the term in genetics, see base A base in chemistry is a substance that can accept hydrogen ions or more generally, donate electron pairs. A soluble base is referred to as an alkali if it contains and releases hydroxide ions quantitatively...

 is referred to as metalation
Metalation
Metalation is a chemical reaction which results in a metal atom beingattached to a molecule.Lithium metal in contact with an organohalide lithiates the organic molecule and gives the organolithium reagent and lithium halide...

. Reactions are typically conducted in tetrahydrofuran
Tetrahydrofuran
Tetrahydrofuran is a colorless, water-miscible organic liquid with low viscosity at standard temperature and pressure. This heterocyclic compound has the chemical formula 4O. As one of the most polar ethers with a wide liquid range, it is a useful solvent. Its main use, however, is as a precursor...

 and diethyl ether
Diethyl ether
Diethyl ether, also known as ethyl ether, simply ether, or ethoxyethane, is an organic compound in the ether class with the formula . It is a colorless, highly volatile flammable liquid with a characteristic odor...

, which are good solvents for the resulting organolithium derivatives (see below).

Metalation



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
Dithiane
A dithiane is a heterocyclic compound composed of a cyclohexane core structure wherein two methylene units are replaced by sulfur centres. The three isomeric parent heterocycles are 1,2-dithiane, 1,3-dithiane and 1,4-dithiane....

), methylphosphines (H-CH2PR2), furan
Furan
Furan is a heterocyclic organic compound, consisting of a five-membered aromatic ring with four carbon atoms and one oxygen. The class of compounds containing such rings are also referred to as furans....

s, thiophene
Thiophene
Thiophene is a heterocyclic compound with the formula C4H4S. Consisting of a flat five-membered ring, it is aromatic as indicated by its extensive substitution reactions. Related to thiophene are benzothiophene and dibenzothiophene, containing the thiophene ring fused with one and two benzene...

s and ferrocene
Ferrocene
Ferrocene is an organometallic compound with the formula Fe2. It is the prototypical metallocene, a type of organometallic chemical compound consisting of two cyclopentadienyl rings bound on opposite sides of a central metal atom. Such organometallic compounds are also known as sandwich compounds...

 (Fe(H-C5H4)(C5H5)). In addition to these, it will also deprotonate all more acidic compounds such as alcohols, amines, enol
Enol
Enols are alkenes with a hydroxyl group affixed to one of the carbon atoms composing the double bond. Alkenes with a hydroxyl group on both sides of the double bond are called enediols. Deprotonated anions of enols are called enolates...

izable carbonyl compounds, and any overtly acidic compounds, to produce alkoxides, amides, enolates and other -ates of lithium, respectively. The stability and volatility
Volatility (chemistry)
In chemistry and physics, volatility is the tendency of a substance to vaporize. Volatility is directly related to a substance's vapor pressure. At a given temperature, a substance with higher vapor pressure vaporizes more readily than a substance with a lower vapor pressure.The term is primarily...

 of the butane
Butane
Butane is a gas with the formula C4H10 that is an alkane with four carbon atoms. The term may refer to any of two structural isomers, or to a mixture of them: in the IUPAC nomenclature, however, butane refers only to the unbranched n-butane isomer; the other one being called "methylpropane" or...

 resulting from such deprotonation
Deprotonation
Deprotonation is the removal of a proton from a molecule, forming the conjugate base.The relative ability of a molecule to give up a proton is measured by its pKa value. A low pKa value indicates that the compound is acidic and will easily give up its proton to a base...

 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
Tetrahydrofuran
Tetrahydrofuran is a colorless, water-miscible organic liquid with low viscosity at standard temperature and pressure. This heterocyclic compound has the chemical formula 4O. As one of the most polar ethers with a wide liquid range, it is a useful solvent. Its main use, however, is as a precursor...

 (THF), tetramethylethylenediamine
Tetramethylethylenediamine
Tetramethylethylenediamine is a chemical compound with the formula 2NCH2CH2N2. This species is derived from ethylenediamine by replacement of the four N-H groups with four N-methyl groups. Its odor is remarkably similar to that of fish.-As a reagent in organic and inorganic synthesis:TMEDA is...

 (TMEDA), hexamethylphosphoramide
Hexamethylphosphoramide
Hexamethylphosphoramide, often abbreviated HMPA, is a phosphoramide having the formula [2N]3PO. This colorless liquid is a useful polar aprotic solvent and additive in organic synthesis.-Structure and reactivity:...

 (HMPA), and 1,4-diazabicyclo[2.2.2]octane (DABCO
DABCO
DABCO or 1,4-diazabicyclo[2.2.2]octane is a chemical compound. It is a polyurethane and Baylis-Hillman reaction catalyst, complexing ligand and Lewis base. It is used to regulate the reaction rate in Flexplay time-limited DVDs by adjusting pH. Antioxidants, like DABCO, are used to improve the...

) 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
Schlosser's base
Schlosser's base describes various superbasic mixtures of an alkyllithium compound and a potassium alkoxide. Commonly, the mixture is composed of n-butyllithium and potassium tert-butoxide. The reagent is named after Manfred Schlosser, though he uses the term LICKOR superbase ....

 is a superbase
Superbase
In chemistry, a superbase is an extremely strong base, that is a compound that has a high affinity for protons. Hydroxide ion is the strongest base possible in aqueous solutions, but bases exist with pKb's well outside of the aqueous range. Such bases are valuable in organic synthesis and are...

 produced by treating butyllithium with potassium tert-butoxide
Potassium tert-butoxide
Potassium tert-butoxide is the chemical compound with the formula 3COK. This colourless solid is a strong base useful in organic synthesis. It exists as a tetrameric cubane-like cluster...

. It is kinetically more reactive than butyllithium and is often used to accomplish difficult metalation
Metalation
Metalation is a chemical reaction which results in a metal atom beingattached to a molecule.Lithium metal in contact with an organohalide lithiates the organic molecule and gives the organolithium reagent and lithium halide...

s. 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
Carbamate
Carbamates are organic compounds derived from carbamic acid . A carbamate group, carbamate ester, and carbamic acids are functional groups that are inter-related structurally and often are interconverted chemically. Carbamate esters are also called urethanes.-Synthesis:Carbamic acids are derived...

, 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 aryl
Aryl
In the context of organic molecules, aryl refers to any functional group or substituent derived from an aromatic ring, be it phenyl, naphthyl, thienyl, indolyl, etc....

lithium and some vinyl
Vinyl
A vinyl compound is any organic compound that contains a vinyl group ,which are derivatives of ethene, CH2=CH2, with one hydrogen atom replaced with some other group...

lithium 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
Dehydrohalogenation
Dehydrohalogenation is an organic reaction from which an alkene is obtained from an alkyl halide . It is also called a β-Elimination reaction and is a type of elimination reaction....

 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
Tert-Butyllithium
tert-Butyllithium is a chemical compound with the formula 3CLi. As an organometallic compound, it has applications in organic synthesis since it is a sufficiently strong base to deprotonate many carbon acids, including benzene...

 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).

Transmetalations


A related family of reactions are the transmetalation
Transmetalation
Transmetalation is a general chemical reaction type in organometallic chemistry describing the exchange of ligands between two metal centers....

s, wherein two organometallic compounds exchange their metals. Many examples of such reactions involve Li exchange with Sn
Tin
Tin is a chemical element with the symbol Sn and atomic number 50. It is a main group metal in group 14 of the periodic table. Tin shows chemical similarity to both neighboring group 14 elements, germanium and lead and has two possible oxidation states, +2 and the slightly more stable +4...

:
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 metal
Metal
A metal , is an element, compound, or alloy that is a good conductor of both electricity and heat. Metals are usually malleable and shiny, that is they reflect most of incident light...

s and metaloids which undergo such exchange reactions are organic compounds of mercury
Organomercury
Organomercury refers to the group of organometallic compounds that contain mercury. Typically the Hg-C bond is stable toward air and moisture but sensitive to light. Important organomercury compounds are the methylmercury cation, CH3Hg+; ethylmercury cation, C2H5Hg+; dimethylmercury, 2Hg,...

, selenium
Organoselenium chemistry
Organoselenium compounds are chemical compounds containing carbon-to-selenium chemical bonds. Organoselenium chemistry is the corresponding science exploring their properties and reactivity. Selenium belongs with oxygen and sulfur to the group 16 elements and similarities in chemistry are to be...

, and tellurium.

Carbonyl additions


Organolithium reagents, including n-BuLi are used in synthesis of specific aldehyde
Aldehyde
An aldehyde is an organic compound containing a formyl group. This functional group, with the structure R-CHO, consists of a carbonyl center bonded to hydrogen and an R group....

s and ketone
Ketone
In organic chemistry, a ketone is an organic compound with the structure RCR', where R and R' can be a variety of atoms and groups of atoms. It features a carbonyl group bonded to two other carbon atoms. Many ketones are known and many are of great importance in industry and in biology...

s. One such synthetic pathway is the reaction of an organolithium reagent with disubstituted amide
Amide
In chemistry, an amide is an organic compound that contains the functional group consisting of a carbonyl group linked to a nitrogen atom . The term refers both to a class of compounds and a functional group within those compounds. The term amide also refers to deprotonated form of ammonia or an...

s:
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
Cycloaddition
A cycloaddition is a pericyclic chemical reaction, in which "two or more unsaturated molecules combine with the formation of a cyclic adduct in which there is a net reduction of the bond multiplicity." The resulting reaction is a cyclization reaction.Cycloadditions are usually described by the...

 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
Dry ice
Dry ice, sometimes referred to as "Cardice" or as "card ice" , is the solid form of carbon dioxide. It is used primarily as a cooling agent. Its advantages include lower temperature than that of water ice and not leaving any residue...

/acetone. Higher temperatures (-25 °C or even -15 °C) are also used.

Thermal decomposition


When heated, n-BuLi, analogously to other alkyllithium reagents with "β-hydrogens", undergoes β-hydride elimination
Beta-hydride elimination
Beta-hydride elimination is a reaction in which an alkyl group bonded to a metal centre is converted into the corresponding metal-bonded hydride and an alkene. The alkyl must have hydrogens on the beta carbon. For instance butyl groups can undergo this reaction but methyl groups cannot...

 to produce 1-butene
1-Butene
1-Butene is an organic chemical compound, linear alpha-olefin , and one of the isomers of butene. The formula is .-Stability:1-Butene is stable in itself but polymerizes exothermically. It is highly flammable and readily forms explosive mixtures with air...

 and LiH:
C4H9Li → LiH + CH3CH2CH=CH2

Safety


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
Lithium hydroxide
Lithium hydroxide is an inorganic compound with the formula LiOH. It is a white hygroscopic crystalline material. It is soluble in water and slightly soluble in ethanol...


BuLi also reacts with CO2 to give lithium pentanoate:
C4H9Li + CO2 → C4H9CO2Li

Further reading