n-Butyllithium

n-Butyllithium C4H9Li (abbreviat ed n-BuLi) is an organolit hium reagent . It is widely used as a

polymerizat ion init iat or in t he product ion of elast omers such as polybut adiene or st yrene-
but adiene-st yrene (SBS). Also, it is broadly employed as a st rong base (superbase) in t he
synt hesis of organic compounds as in t he pharmaceut ical indust ry.

Glass bottles containing butyllithium

But yllit hium is commercially available as solut ions (15%, 25%, 1.5 M, 2 M, 2.5 M, 10 M, et c.) in
alkanes such as pent ane, hexanes, and hept anes. Solut ions in diet hyl et her and THF can be
prepared, but are not st able enough for st orage. Annual worldwide product ion and consumpt ion
of but yllit hium and ot her organolit hium compounds is est imat ed at 2000 t o 3000 t onnes.[2]

Alt hough but yllit hium is colorless, n-but yllit hium is usually encount ered as a pale yellow solut ion
in alkanes. Such solut ions are st able indefinit ely if properly st ored,[3] but in pract ice, t hey degrade
upon aging. Fine whit e precipit at e (lit hium hydride) is deposit ed and t he color changes t o
orange.[3][4]
Structure and n
-Butyllithium
bonding
n -BuLi exist s as a clust er bot h in t he solid
st at e and in a solut ion. The t endency t o
aggregat e is common for organolit hium
compounds. The aggregat es are held t oget her
by delocalized covalent bonds bet ween
lit hium and t he t erminal carbon of t he but yl n- n-
chain.[5] In t he case of n-BuLi, t he clust ers are
t et rameric (in et her) or hexameric (in Butyllithium Butyllith
cyclohexane). The clust er is a dist ort ed
cubane-t ype clust er wit h Li and C H2R groups
tetramer hexam
at alt ernat ing vert ices. An equivalent
descript ion describes t he t et ramer as a Li4
t et rahedron int erpenet rat ed wit h a
t et rahedron [C H2R]4. Bonding wit hin t he
clust er is relat ed t o t hat used t o describe
diborane, but more complex since eight at oms
are involved. Reflect ing it s elect ron-rich
charact er, n-but yllit hium is highly react ive
t oward Lewis acids. Close-up of the
Due t o t he large difference bet ween t he
elect ronegat ivit ies of carbon (2.55) and lit hium delocalized bonds
(0.98), t he C−Li bond is highly polarized. The
charge separat ion has been est imat ed t o be between butyl and
55–95%. For pract ical purposes, n-BuLi can
oft en be considered t o react as t he but yl lithium
anion, n-Bu−, and a lit hium cat ion, Li+ .

Names
 IUPAC name
Preparation
butyllithium,
The st andard preparat ion for n-BuLi is react ion tetra- μ3-butyl-
of 1-bromobut ane or 1-chlorobut ane wit h Li
met al:[3] tetralithium
2 Li + C4H9X → Other names
C4H9Li + LiX NBL, BuLi,
(X = Cl, Br) 1-lithiobutane
If t he lit hium used for t his react ion cont ains
1–3% sodium, t he react ion proceeds more
Identifiers
quickly t han if pure lit hium is used. Solvent s
used for t his preparat ion include benzene, CAS 109-72-8
cyclohexane, and diet hyl et her. When BuBr is
Number
t he precursor, t he product is a homogeneous
solut ion, consist ing of a mixed clust er
(https://c
cont aining bot h LiBr and BuLi, t oget her wit h a
small amount of oct ane. BuLi forms a weaker ommonc
complex wit h LiCl, so t hat t he react ion of BuCl
wit h Li produces a precipit at e of LiCl. hemistry.
Solut ions of but yllit hium, which are
suscept ible t o degradat ion by air, are
cas.org/
st andardized by t it rat ion. A popular weak acid
is biphenyl-4-met hanol, which gives a deeply detail?ca
colored dilit hio derivat ive at t he end point .[6]
s_rn=109
-72-8)
 3D Interactive
Applications model
image (htt
(JSmol)
But yllit hium is principally valued as an init iat or ps://chem
for t he anionic polymerizat ion of dienes, such
as but adiene.[7] The react ion is called apps.stol
"carbolit hiat ion":
af.edu/jm
C4H9Li +
ol/jmol.ph
CH2=CH−CH=CH2 p?model=
→ CCCC%5B
C4H9−CH2−CH=C Li%5D)
H−CH2Li ChEBI CHEBI:5146
Isoprene can be polymerized
st ereospecifically in t his way. Also of
9 (https://ww
commercial import ance is t he use of
but yllit hium for t he product ion of st yrene- w.ebi.ac.uk/c
but adiene polymers. Even et hylene will insert
int o BuLi.[8] hebi/searchI
d.do?chebiId
Reactions =51469)

But yllit hium is a st rong base (pKb ≈ 50), but it ChemSpi 10254339
is also a powerful nucleophile and reduct ant ,
depending on t he ot her react ant s. der (https://w
Furt hermore, in addit ion t o being a st rong
nucleophile, n-BuLi binds t o aprot ic Lewis ww.chem
bases, such as et hers and t ert iary amines,
which part ially disaggregat e t he clust ers by spider.co
binding t o t he lit hium cent ers. It s use as a
st rong base is referred t o as met alat ion. m/Chemi
React ions are t ypically conduct ed in
t et rahydrofuran and diet hyl et her, which are
good solvent s for t he result ing organolit hium
cal-Struct
derivat ives (see below).
ure.1025
4339.htm
Metalation l)

One of t he most useful chemical propert ies ECHA 100.003.36

of n-BuLi is it s abilit y t o deprot onat e a wide
range of weak Brønst ed acids. t-But yllit hium
and s -but yllit hium are more basic. n-BuLi can
InfoCard (https://ech
deprot onat e (t hat is, met alat e) many t ypes of
C−H bonds, especially where t he conjugat e
a.europa.e
base is st abilized by elect ron delocalizat ion or
one or more het eroat oms (non-carbon at oms). u/substanc
Examples include acet ylenes (H−CC−R),
met hyl sulfides (H−CH2SR), t hioacet als -informatio
(H−CH(SR)2, e.g. dit hiane), met hylphosphines
(H−CH2PR2), furans, t hiophenes and ferrocene n/-/substan
(Fe(H−C5H4)(C5H5)).[9] In addit ion t o t hese, it
will also deprot onat e all more acidic
compounds such as alcohols, amines,
ceinfo/100.
enolizable carbonyl compounds, and any
overt ly acidic compounds, t o produce 003.363)
alkoxides, amides, enolat es and ot her salt s of
lit hium, respect ively. The st abilit y and
volat ilit y of t he but ane result ing from such
PubChem 61028 (ht
deprot onat ion react ions is convenient , but can CID
also be a problem for large-scale react ions tps://pub
because of t he volume of a flammable gas
produced. chem.ncb

LiC4H9 + RH → i.nlm.nih.
gov/com
C4H10 + RLi
pound/6
The kinet ic basicit y of n-BuLi is affect ed by
t he solvent or cosolvent . Ligands t hat
complex Li+ such as t et rahydrofuran (THF),
1028)
t et ramet hylet hylenediamine (TMEDA),
hexamet hylphosphoramide (HMPA), and 1,4- UNII 09W9A6B8Z
diazabicyclo[2.2.2]oct ane (DABCO) furt her
polarize t he Li−C bond and accelerat e t he
met alat ion. Such addit ives can also aid in t he
C (https://pre
isolat ion of t he lit hiat ed product , a famous
example of which is dilit hioferrocene. cision.fda.go
v/uniisearch/
Fe(C5H5)2 + 2
srs/unii/09W
LiC4H9 + 2 TMEDA
9A6B8ZC)
→ 2 C4H10 +
CompTox DTXSID102
Fe(C5H4Li)2(TMED Dashboard
821 (https:/
A)2 (EPA)
comptox.ep
Schlosser's base is a superbase produced by
t reat ing but yllit hium wit h pot assium t- a.gov/dash
but oxide. It is kinet ically more react ive t han
but yllit hium and is oft en used t o accomplish
difficult met alat ions. While some n-
oard/chemi
but ylpot assium is present and is a st ronger
base t han n-BuLi, t he react ivit y of t he mixt ure al/details/D
is not exact ly t he same as isolat ed n-
but ylpot assium.[10] XSID10268
An example of t he use of n-but yllit hium as a
base is t he addit ion of an amine t o met hyl
1)
carbonat e t o form a met hyl carbamat e, where
n -but yllit hium serves t o deprot onat e t he InChI
amine:

InChI=1S/C4H9.L
n-BuLi + R2NH + i/c1-3-4-2;/h1,3
(MeO)2CO → -4H2,2H3;
Key: MZRVEZGGR
R2NCO2Me + BJDDB-UHFFF
AOYSA-N
LiOMe + BuH
InChI=1/C4H9.Li/
c1-3-4-2;/h1,3-
Halogen–lithium 4H2,2H3;/rC4
exchange H9Li/c1-2-3-4-
5/h2-4H2,1H3
But yllit hium react s wit h some organic Key: MZRVEZGGR
bromides and iodides in an exchange react ion
t o form t he corresponding organolit hium BJDDB-NESCH
derivat ive. The react ion usually fails wit h
organic chlorides and fluorides:
KHYAE

C4H9Li + RX → SMILES
CCCC[Li]
C4H9X + RLi
(X = Br, I) Properties
This lit hium–halogen exchange react ion is
useful for preparat ion of several t ypes of RLi Chemical C4H9Li
compounds, part icularly aryllit hium and some
vinyllit hium reagent s. The ut ilit y of t his
formula
met hod is significant ly limit ed, however, by t he
presence in t he react ion mixt ure of n-BuBr or
n -BuI, which can react wit h t he RLi reagent
Molar 64.06 g·mol−
formed, and by compet ing
mass 1
dehydrohalogenat ion react ions, in which n-BuLi
serves as a base:

Appeara colorless
2 C4H9Br + RLi →
nce liquid
2 C4H9R + LiBr
unstable
2 C4H9Li + usually
R′CH=CHBr → 2 obtained

C4H10 + R′C≡CLi + as
solution
LiBr
These side react ion are significant ly less Density 0.68
import ant for RI t han for RBr, since t he iodine–
lit hium exchange is several orders of g/cm3,
magnit ude fast er t han t he bromine–lit hium
exchange. For t hese reasons, aryl, vinyl and
primary alkyl iodides are t he preferred
solvent
subst rat es, and t-BuLi rat her t han n-BuLi is
usually used, since t he formed t-BuI is
defined
immediat ely dest royed by t he t-BuLi in a
dehydrohalogenat ion react ion (t hus requiring
t wo equivalent s of t-BuLi). Alt ernat ively, vinyl
lit hium reagent s can be generat ed by direct
react ion of t he vinyl halide (e.g. cyclohexenyl
chloride) wit h lit hium or by t in–lit hium Melting −76 °C
exchange (see next sect ion).[3]

point (−105 °F;

197 K)
Transmetalations (<273 K)
A relat ed family of react ions are t he
t ransmet alat ions, wherein t wo organomet allic Boiling 80 C
compounds exchange t heir met als. Many
examples of such react ions involve lit hium point
exchange wit h t in:

Solubility Exothermic
C4H9Li + Me3SnAr in water
decomposit
→ C4H9SnMe3 +
on
LiAr (where
Solubility Ethers such
Ar is aryl and Me
as THF,
is methyl)
hydrocarbo
The t in–lit hium exchange react ions have one
major advant age over t he halogen–lit hium s
exchanges for t he preparat ion of
organolit hium reagent s, in t hat t he product t in
compounds (C4H9SnMe 3 in t he example Acidity 50 (of the
above) are much less react ive t owards lit hium
reagent s t han are t he halide product s of t he (pKa) conjugate
corresponding halogen–lit hium exchanges
(C4H9Br or C4H9Cl). Ot her met als and
met alloids which undergo such exchange
acid)[1]
react ions are organic compounds of mercury,
selenium, and t ellurium. Structure

Molecular tetrameric
shape
Carbonyl in solution
additions Dipole 0D
Organolit hium reagent s, including n-BuLi are
moment
used in synt hesis of specific aldehydes and
ket ones. One such synt het ic pat hway is t he Hazards
react ion of an organolit hium reagent wit h
disubst it ut ed amides:
Occupational safety
R1Li + R2CONMe2 and health
→ LiNMe2 + (OHS/OSH):
R2C(O)R1 Main Pyrophoric
hazards
(spontaneo
Degradation of
sly combus
THF
in air),
THF is deprot onat ed by but yllit hium,
especially in t he presence of TMEDA, by loss decompos
of one of four prot ons adjacent t o oxygen.
This process, which consumes but yllit hium t o to corrosiv
generat e but ane, induces a ring opening t o
give enolat e of acet aldehyde and et hylene.[11] LiOH
Therefore, react ions of BuLi in THF are
t ypically conduct ed at low t emperat ures,
such as –78 °C, as is convenient ly produced by NFPA 3
4
3
a freezing bat h of dry ice and acet one. Higher
W
t emperat ures (−25 °C or even −15 °C) are also
704
used.

(fire diam
ond)
Thermal
Related compounds
decomposition
Related sec-
When heat ed, n-BuLi, analogously t o ot her
organolithium
alkyllit hium reagent s wit h "β-hydrogens",
butyllithium
undergoes β-hydride eliminat ion t o produce 1-
but ene and lit hium hydride (LiH):
reagents
tert-
C4H9Li → LiH + butyllithium
CH3CH2CH=CH2 hexyllithium
methyllithiu
Safety
Related lithium
compounds
Alkyl-lit hium compounds are st ored under inert hydroxide
gas t o prevent loss of act ivit y and for reasons
of safet y. n-BuLi react s violent ly wit h wat er:

C4H9Li + H2O →
C4H10 + LiOH
This is an exergonic and highly exot hermic
react ion. If oxygen is present t he but ane Except where
produced may ignit e.
otherwise noted,
BuLi also react s wit h CO2 t o give lit hium
pent anoat e:
data are given for
materials in their
C4H9Li + CO2 → standard state (at
C4H9CO2Li 25 °C [77 °F],
100 kPa).

See also verify (https://en.wi

kipedia.org/w/index.
Propynyllithium, php?title=Special:Co

an organometallic mparePages&rev1=
445283361&page2=
compound.
N-Butyllithiu
References m) (what is ?)
Infobox references
1. Bernier, David.
"Some useful pKa
values" (https://w
eb.archive.org/we
 b/20170509123404/http://www.d-bernier.f
r/pKa.php) . Org@Work. Archived from the
original (http://www.d-bernier.fr/pKa.php)
on 9 May 2017. Retrieved 26 May 2017.

2. Schwindeman, James A. (1 August 2014).

"Preparation, Properties, and Safe Handling
of Commercial Organolithiums:
Alkyllithiums, Lithium sec-Organoamides,
and Lithium Alkoxides". Organic Process
Research & Development. 18 (10): 1192–
1210. doi:10.1021/op500161b (https://doi.
org/10.1021%2Fop500161b) .

3. Brandsma, L.; Verkruijsse, H. D. (1987).

Preparative Polar Organometallic
Chemistry I. Berlin: Springer-Verlag. ISBN 3-
540-16916-4..
4. "n-Butyllithium solution" (https://www.sigm
aaldrich.com/GB/en/product/sial/20160) .
sigmaaldrich.com. Retrieved 17 August
2023.

5. Elschenbroich, C. ”Organometallics” (2006)

Wiley-VCH: Weinheim. ISBN 3-527-29390-6.

6. Juaristi, E.; Martínez-Richa, A.; García-

Rivera, A.; Cruz-Sánchez, J. S. (1983). "Use
of 4-Biphenylmethanol, 4-Biphenylacetic
Acid and 4-Biphenylcarboxylic
Acid/Triphenylmethane as Indicators in the
Titration of Lithium Alkyls. Study of the
Dianion of 4-Biphenylmethanol". The
Journal of Organic Chemistry. 48 (15):
2603–2606. doi:10.1021/jo00163a038 (htt
ps://doi.org/10.1021%2Fjo00163a038) .
7. 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 (https://do
i.org/10.1002%2F14356007.a15_393) .

8. Delaney, M. S. (20 January 1991). "The rate

of ethylene polymerization initiated by
various chelating tertiary diamine : n‐
butyllithium complexes". Journal of Applied
Polymer Science. 42 (2): 533–541.
doi:10.1002/app.1991.070420226 (https://
doi.org/10.1002%2Fapp.1991.07042022
6) .
 9. 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 (http
s://doi.org/10.1016%2F0022-328X%2895%
2905914-B) .

10. Schlosser, Manfred; Strunk, Sven (January

1984). "The "super-basic"
butyllithium/potassium tert-butoxide
mixture and other lickor-reagents" (https://li
nkinghub.elsevier.com/retrieve/pii/S00404
03901800149) . Tetrahedron Letters. 25
(7): 741–744. doi:10.1016/S0040-
4039(01)80014-9 (https://doi.org/10.101
6%2FS0040-4039%2801%2980014-9) .
11. Clayden, Jonathan; Yasin, Samreen A. (11
February 2002). "Pathways for
decomposition of THF by organolithiums:
the role of HMPA" (https://pubs.rsc.org/en/
content/articlelanding/2002/nj/b109604
d) . New Journal of Chemistry. 26 (2): 191–
192. doi:10.1039/B109604D (https://doi.or
g/10.1039%2FB109604D) . ISSN 1369-
9261 (https://www.worldcat.org/issn/1369-
9261) .

Further reading

FMC Lithium manufacturer's product

sheets (https://web.archive.org/web/20
050923163434/http://fmclithium.com/p
roducts/products_p.asp)
Environmental Chemistry directory (htt
p://environmentalchemistry.com/yogi/ch
emicals/cn/Butyllithium.html)
Weissenbacher, Anderson, Ishikawa,
Organometallics, July 1998, p681.7002,
Chemicals Economics Handbook SRI
International
HPV test plan, submitted by FMC
Lithium to EPA (https://web.archive.org/
web/20041116061121/http://www.epa.
gov/chemrtk/butylith/c13633.pdf)
Ovaska, T. V. e-EROS Encyclopedia of
Reagents for Organic Synthesis "n-
Butyllithium." Wiley and sons. 2006.
doi:10.1002/047084289X.rb395 (https://
 doi.org/10.1002%2F047084289X.rb39
5)
Greenwood, N. N.; Earnshaw, A.
Chemistry of the Elements, 2nd ed. 1997:
Butterworth-Heinemann, Boston.

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