World Library  
Flag as Inappropriate
Email this Article


Article Id: WHEBN0003452614
Reproduction Date:

Title: Tert-Butyllithium  
Author: World Heritage Encyclopedia
Language: English
Subject: Butyllithium, Hexyllithium, Bases, Ferrocene, Lithium
Collection: Bases, Organolithium Compounds, Reagents for Organic Chemistry
Publisher: World Heritage Encyclopedia


Skeletal formula of tert-butyllithium with all implicit hydrogens shown, and partial charges added
Preferred IUPAC name
ChemSpider  Y
EC number 209-831-5
Jmol-3D images Image
UN number 3394
Molar mass 64.055 g mol−1
Appearance Colorless solid
Density 660 mg cm−3
Boiling point 36 to 40 °C (97 to 104 °F; 309 to 313 K)
Acidity (pKa) 53
GHS pictograms The flame pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS) The corrosion pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS) The exclamation-mark pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS) The health hazard pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS) The environment pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS)
GHS signal word DANGER
H225, H250, H260, H304, H314, H336, H411
P210, P222, P223, P231+232, P370+378, P422
Extremely Flammable F+ Corrosive C Dangerous for the Environment (Nature) N Very Toxic T+
R-phrases R50/53, R38
S-phrases S26, S36/37/39, S43, S45, S62, S61, S16, S33
NFPA 704
Flash point −6.6 °C (20.1 °F; 266.5 K)
Related compounds
Related compounds


Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
 Y  (: Y/N?)

tert-Butyllithium is a base, capable of deprotonating many carbon acids, including benzene. tert-Butyllithium is available commercially as hydrocarbon solutions; it is not usually prepared in the laboratory. Its synthesis was first reported by R. B. Woodward in 1941.[1]


  • Structure and bonding 1
  • Chemical properties 2
  • Safety 3
  • References 4

Structure and bonding

Like other organolithium compounds, tert-butyllithium is a cluster. Whereas n-butyllithium exists both as a hexamer and a tetramer, tert-Butyllithium exists as tetramer with a cubane structure. Bonding is organolithium clusters, involves sigma delocalization and significant Li---Li bonding.[2]

The lithium–carbon bond in tert-butyllithium is highly polarized, having about 40 percent ionic character. The molecule reacts like a carbanion, as is represented by these two resonance structures.[3] (Given the polarity calculations on the C–Li bond, the "real" structure of a single molecule of t-butyllithium is likely a near-average of the two resonance contributors shown, in which the central carbon atom has a ~50% partial negative charge while the lithium atom has a ~50% partial positive charge.)

Chemical properties

Similar to n-butyllithium, tert-butyllithium can be used for the exchange of lithium with halogens and for the deprotonation of amines and activated C—H compounds.

This compound and other alkyllithium compounds are known to react with ether solvents; the half-life of tert-butyllithium is 60 minutes at 0 °C in diethyl ether, 40 minutes at -20 °C in tetrahydrofuran (THF),[4] and about 11 minutes at -70 °C in dimethoxyethane.[5] In this example, the reaction of tert-butyllithium with (THF) is shown:

To minimize degradation by these solvents, reactions involving tert-butyllithium are often conducted very low temperatures in special solvents, such as the Trapp solvent mixture.


tert-Butyllithium is a pyrophoric substance, meaning that it easily catches fire on exposure to air. (A precise definition of a pyrophoric material is one "that ignite[s] spontaneously in air at or below 54.55 °C (130.19 °F)".[6]) The solvents used in common commercial preparations are themselves flammable. While it is possible to work with this compound using cannula transfer, traces of tert-butyllithium at the tip of the needle or cannula may catch fire and clog the cannula with lithium salts. While some researchers take this "pilot light" effect as a sign that the product is "fresh" and has not degraded due to time or improper storage/handling, some workers prefer to enclose the needle tip or cannula in a short glass tube, which is flushed with an inert gas and sealed at each end with septa.[7] Serious laboratory accidents involving tert-butyllithium have occurred. For example, in 2008 a staff research assistant, Sheharbano Sangji, in the lab of Patrick Harran[8] at the University of California, Los Angeles, died after being severely burned by a fire ignited by tert-butyllithium.[9][10][11]

Large-scale reactions may lead to runaway reactions, fires, and explosions when tert-butyllithium is mixed with ethers such as diethyl ether, tetrahydrofuran, and glymes. The use of hydrocarbon solvents may be preferred.

Air-free techniques are important so as to prevent this compound from reacting violently with oxygen and moisture in the air:

t-BuLi + O2t-BuOOLi
t-BuLi + H2O → t-BuH + LiOH


  1. ^ Bartlett, Paul D.; C. Gardner Swain; Robert B. Woodward (1941). "t-Butyllithium". J. Am. Chem. Soc. 63 (11): 3229–3230.  
  2. ^ Elschenbroich, C. ”Organometallics” (2006) Wiley-VCH: Weinheim. ISBN 978-3-527-29390-2
  3. ^ Organometallic reagents: sources of nucleophilic carbon for alcohol synthesis. K. P. C. Vollhardt, N. E. Schore: Organic Chemistry : Structure And Function. 3rd edition, 1999, §8.7.
  4. ^ Stanetty, P; Koller, H.; Mihovilovic, M. (1992). "Directed ortho lithiation of phenylcarbamic acid 1,1-dimethylethyl ester (N-BOC-aniline). Revision and improvements".  
  5. ^ Fitt, J. J.; Gschwend, H. E. (1984). "Reaction of n-, sec-, and tert-butyllithium with dimethoxyethane (DME): a correction".  
  6. ^ SEMI, standard F6-92, Guide for Secondary Containment of Hazardous Gas Piping Systems, as cited by
  7. ^ Errington, R. M. (1997). Advanced practical inorganic and metalorganic chemistry ( 
  8. ^ "Harran Lab: UCLA". 
  9. ^ Jyllian Kemsley (2009-01-22). "Researcher Dies After Lab Fire".  
  10. ^ Jyllian Kemsley (2009-04-03). "Learning From UCLA: Details of the experiment that led to a researcher’s death prompt evaluations of academic safety practices".  
  11. ^ , 2009-03-01Los Angeles Times
This article was sourced from Creative Commons Attribution-ShareAlike License; additional terms may apply. World Heritage Encyclopedia content is assembled from numerous content providers, Open Access Publishing, and in compliance with The Fair Access to Science and Technology Research Act (FASTR), Wikimedia Foundation, Inc., Public Library of Science, The Encyclopedia of Life, Open Book Publishers (OBP), PubMed, U.S. National Library of Medicine, National Center for Biotechnology Information, U.S. National Library of Medicine, National Institutes of Health (NIH), U.S. Department of Health & Human Services, and, which sources content from all federal, state, local, tribal, and territorial government publication portals (.gov, .mil, .edu). Funding for and content contributors is made possible from the U.S. Congress, E-Government Act of 2002.
Crowd sourced content that is contributed to World Heritage Encyclopedia is peer reviewed and edited by our editorial staff to ensure quality scholarly research articles.
By using this site, you agree to the Terms of Use and Privacy Policy. World Heritage Encyclopedia™ is a registered trademark of the World Public Library Association, a non-profit organization.

Copyright © World Library Foundation. All rights reserved. eBooks from Project Gutenberg are sponsored by the World Library Foundation,
a 501c(4) Member's Support Non-Profit Organization, and is NOT affiliated with any governmental agency or department.