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Revision as of 12:28, 10 January 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 468212255 of page Tert-Butyllithium for the Chem/Drugbox validation project (updated: '').		Latest revision as of 18:59, 3 December 2024 edit Smokefoot (talk | contribs)Autopatrolled, Extended confirmed users, Pending changes reviewers, Rollbackers74,550 edits rm capricious {{cn}}
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			{{DISPLAYTITLE:''tert''-Butyllithium}}
	{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}}
	{{Chembox		{{Chembox
	| Watchedfields = changed		|Watchedfields = changed
	| verifiedrevid = 451593004		|verifiedrevid = 470602967
	| Name = ''tert''-Butyllithium		|Name = ''tert''-Butyllithium
			|ImageFile1 = TBuLitetramer.svg
	| ImageFile = Tert-Butyllithium.png
			|ImageName1 =
	| ImageFile_Ref = {{chemboximage|correct|??}}
			|ImageFile2 = Tert-Butyllithium.png
	| ImageName = Skeletal formula of ''tert''-butyllithium with all implicit hydrogens shown, and partial charges added
			|ImageFile_Ref = {{chemboximage|correct|??}}
	| PIN = ''tert''-Butyllithium{{Citation needed|date = October 2011}}
			|ImageName2 = Skeletal formula of ''tert''-butyllithium with all implicit hydrogens shown, and partial charges added
	| Section1 = {{Chembox Identifiers
			|ImageFile3 = Tert-butyllithium-tetramer-from-xtal-3D-bs-A.png
	| CASNo = 594-19-4
			|PIN = ''tert''-Butyllithium{{Citation needed|date=October 2011}}
	| CASNo_Ref = {{cascite|correct|CAS}}
			|Section1={{Chembox Identifiers
	| PubChem = 638178
			|CASNo = 594-19-4
	| PubChem_Ref = {{Pubchemcite|correct|Pubchem}}
			|CASNo_Ref = {{cascite|correct|CAS}}
	| ChemSpiderID = 10254347
			|PubChem = 638178
	| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
			|ChemSpiderID = 10254347
	| EINECS = 209-831-5
			|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
	| UNNumber = 3394
			|EINECS = 209-831-5
	| MeSHName = n-butyllithium
			|UNNumber = 3394
	| Beilstein = 3587204
			|Beilstein = 3587204
	| SMILES = C(C)(C)C
	| StdInChI = 1S/C4H9.Li/c1-4(2)3;/h1-3H3;		|SMILES = C(C)(C)C
			|StdInChI = 1S/C4H9.Li/c1-4(2)3;/h1-3H3;
	| StdInChI_Ref = {{stdinchicite|correct|chemspider}}		|StdInChI_Ref = {{stdinchicite|correct|chemspider}}
	| StdInChIKey = BKDLGMUIXWPYGD-UHFFFAOYSA-N		|StdInChIKey = BKDLGMUIXWPYGD-UHFFFAOYSA-N
	| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}		|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
	}}		}}
	| Section2 = {{Chembox Properties		|Section2={{Chembox Properties
	| Formula = {{Chem|LiC|4|H|9}}		|Formula = {{Chem|LiC|4|H|9}}
	| MolarMass = 64.055 g mol<sup>-1</sup>		|MolarMass = 64.055 g mol<sup>−1</sup>
			|Appearance = Colorless solid
	| ExactMass = 64.086429337 g mol<sup>-1</sup>
			|Density = 660 mg cm<sup>−3</sup>
	| Appearance = Colorless solid
			|BoilingPtC = 36 to 40
	| Density = 660 mg cm<sup>-3</sup>
			|Solubility = Reacts
	| BoilingPtCL = 36
			|pKa = 45–53
	| BoilingPtCH = 40
	| Solubility = Reacts
	}}		}}
	| Section3 = {{Chembox Hazards		|Section3={{Chembox Hazards
	| GHSPictograms = {{GHS flame}} {{GHS corrosion}} {{GHS exclamation mark}} {{GHS health hazard}} {{GHS environment}}		|GHSPictograms = {{GHS flame}} {{GHS corrosion}} {{GHS exclamation mark}} {{GHS health hazard}} {{GHS environment}}
	| GHSSignalWord = '''DANGER'''		|GHSSignalWord = '''DANGER'''
	| HPhrases = {{H-phrases|225|250|260|304|314|336|411}}		|HPhrases = {{H-phrases|225|250|260|300|304|310|314|330|336|411}}
	| PPhrases = {{P-phrases|210|222|223|231+232|370+378|422}}		|PPhrases = {{P-phrases|210|222|223|231+232|370+378|422}}
			|NFPA-H = 4
	| EUClass = {{Hazchem F}} {{Hazchem C}} {{Hazchem N}}
			|NFPA-F = 4
	| RPhrases = {{R11}}, {{R15}}, {{R17}}, {{R34}}, {{R51/53}}, {{R65}}, {{R66}}, {{R67}}, {{R50/53}}, {{R38}}
			|NFPA-R = 4
	| SPhrases = {{S26}}, {{S36/37/39}}, {{S43}}, {{S45}}, {{S62}}, {{S61}}, {{S16}}, {{S33}}
	| NFPA-H = 3		|NFPA-S = W <!-- COR, POI ?-->
			|FlashPtC = -6.6
	| NFPA-F = 3
	| NFPA-R = 4
	| NFPA-O = W
	| FlashPt = -6.6 °C
	}}		}}
	| Section4 = {{Chembox Related		|Section4={{Chembox Related
	| OtherCpds = ]<br />		|OtherCompounds = ]<br>
	]		]
	}}		}}
	}}		}}
			'''''tert''-Butyllithium''' is a ] with the ] (CH<sub>3</sub>)<sub>3</sub>CLi. As an ], it has applications in ] since it is a strong ], capable of deprotonating many carbon molecules, including ]. ''tert''-Butyllithium is available commercially as solutions in hydrocarbons (such as pentane); it is not usually prepared in the laboratory.
			==Preparation==
			''tert''-Butyllithium is produced commercially by treating ] with ]. Its synthesis was first reported by ] in 1941.<ref>{{cite journal |last=Bartlett |first=Paul D. |author2=C. Gardner Swain |author3=Robert B. Woodward |journal=J. Am. Chem. Soc. |title=t-Butyllithium |year=1941 |volume=63 |issue=11 |pages=3229–3230 |doi=10.1021/ja01856a501}}</ref>
			==Structure and bonding==
			Like other organolithium compounds, ''tert''-butyllithium is a ]. Whereas ] exists both as a hexamer and a tetramer, ''tert''-butyllithium exists exclusively as a tetramer with a ]. Bonding in organolithium clusters involves ] and significant Li−Li bonding.<ref name=Elschenbroich>{{cite book |author=Elschenbroich, C. |title=Organometallics |year=2006 |publisher=Wiley-VCH |location=Weinheim |isbn=978-3-527-29390-2}}</ref> Despite its complicated structure, ''tert''-butyllithium is usually depicted in equations as a monomer.
			The lithium–carbon bond in ''tert''-butyllithium is highly polarized, having about 40 percent ]. The molecule reacts like a ], as is represented by these two ]:<ref>{{cite book |chapter=Organometallic reagents: sources of nucleophilic carbon for alcohol synthesis |author=K. P. C. Vollhardt, N. E. Schore |title=Organic Chemistry : Structure And Function, 3rd edition |year=1999}}</ref>
			:]
			==Reactions==
			''tert''-Butyllithium is renowned for deprotonation of carbon acids (C-H bonds). One example is the double deprotonation of ].<ref>{{cite journal |doi=10.15227/orgsyn.066.0014 |title=(1-Oxo-2-Propenyl)Trimethylsilane |journal=Organic Syntheses |year=1988 |volume=66 |page=14 |author=Rick L. Danheiser, David M. Fink, Kazuo Okano, Yeun-Min Tsai, Steven W. Szczepanski}}</ref> Other examples are the deprotonation of ].<ref>{{cite journal |author=John A. Soderquist |doi=10.15227/orgsyn.068.0025 |title=Acetyltrimethylsilane |journal=Organic Syntheses |year=1990 |volume=68 |page=25}}</ref><ref>{{cite journal |doi=10.15227/orgsyn.073.0215 |title=4-Ketoundecanoic Acid |journal=Organic Syntheses |year=1996 |volume=73 |page=215 |author=M. A. Tschantz, L. E. Burgess, A. I. Meyers}}</ref><ref>{{cite journal |doi=10.15227/orgsyn.079.0011 |title=1,2-Metallate Rearrangement: (Z)-4-(2-Propenyl)-3-Octen-1-Ol |journal=Organic Syntheses |year=2002 |volume=79 |page=11 |author=Krzysztof Jarowicki, Philip J. Kocienski, Liu Qun}}</ref>
			In combination with ''n''-butyllithiium, ''tert''-butylllithium monolithiates ].<ref>{{cite journal |doi=10.15227/orgsyn.090.0316 |title=Practical Synthesis of Di-''tert''-Butylphosphinoferrocene |journal=Organic Syntheses |year=2013 |volume=90 |page=316 |author=Carl A. Busacca, Magnus C. Eriksson, Nizar Haddad, Z. Steve Han, Jon C. Lorenz, Bo Qu, Xingzhong Zeng, Chris H. Senanayake |doi-access=free}}</ref> ''tert''-Butyllithium deprotonates ]:<ref>{{cite journal |doi=10.1021/om50005a008 |title=Homologation of Boronic Esters to α-Chloro Boronic Esters |year=1983 |last1=Matteson |first1=Donald S. |last2=Majumdar |first2=Debesh |journal=Organometallics |volume=2 |issue=11 |pages=1529–1535}}</ref>
			:{{Chem2|H2CCl2 + RLi -> HCCl2Li + RH}}
			Similar to ''n''-butyllithium, ''tert''-butyllithium can be used for ] reactions.<ref>{{cite journal |doi=10.15227/orgsyn.078.0051 |title=Synthesis of 4-, 5-, and 6-Methyl-2,2'-bipyridine by a Negishi Cross-Coupling Strategy: 5-Methyl-2,2'-bipyridine |journal=Organic Syntheses |year=2002 |volume=78 |page=51 |author=Adam P. Smith, Scott A. Savage, J. Christopher Love, Cassandra L. Fraser}}</ref><ref>{{cite journal |doi=10.15227/orgsyn.074.0248 |title=Regioselective Synthesis of 3-Substituted Indoles: 3-Ethylindole |journal=Organic Syntheses |year=1997 |volume=74 |page=248 |author=Mercedes Amat, Sabine Hadida, Swargam Sathyanarayana, Joan Bosch}}</ref>
			===Solvent compatibility===
			To minimize degradation by solvents, reactions involving ''tert''-butyllithium are often conducted at very low temperatures in special solvents, such as the ] mixture.
			More so than other alkyllithium compounds, ''tert''-butyllithium reacts with ]s.<ref name=Elschenbroich/> In ], the ] of ''tert''-butyllithium is about 60 minutes at 0&nbsp;°C. It is even more reactive toward ] (THF); the half-life in THF solutions is about 40 minutes at −20&nbsp;°C.<ref>{{cite journal |author1=Stanetty, P |author2=Koller, H. |author3=Mihovilovic, M. |title=Directed ortho Lithiation of Phenylcarbamic acid 1,1-Dimethylethyl Ester (''N''-BOC-aniline). Revision and Improvements |journal=Journal of Organic Chemistry |year=1992 |volume=57 |pages=6833–6837 |doi=10.1021/jo00051a030 |issue=25}}</ref> In ], the half-life is about 11 minutes at −70&nbsp;°C<ref>{{cite journal |author1=Fitt, J. J. |author2=Gschwend, H. E. |title=Reaction of n-, sec-, and tert-butyllithium with dimethoxyethane (DME): a correction |journal=] |year=1984 |volume=49 |pages=209–210 |doi=10.1021/jo00175a056}}</ref>
			In this example, the reaction of ''tert''-butyllithium with (THF) is shown:
			:]
			:]
			==Safety==
			''tert''-butyllithium is a ] substance, meaning that it spontaneously ignites on exposure to air. ]s are important so as to prevent this compound from reacting violently with oxygen and moisture:
			:''t''-BuLi + O<sub>2</sub> → ''t''-BuOOLi
			:''t''-BuLi + H<sub>2</sub>O → ''t''-BuH + LiOH
			The solvents used in common commercial preparations are themselves flammable. While it is possible to work with this compound using ], traces of ''tert''-butyllithium at the tip of the needle or cannula may ignite 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, others 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.<ref>{{cite book |author=Errington, R. M. |title=Advanced practical inorganic and metalorganic chemistry |publisher=Blackie Academic & Professional |location=London |year=1997 |pages=47–48 |isbn=978-0-7514-0225-4 |url=https://books.google.com/books?id=yI_mq_mCf2AC&pg=PA47 |format=] excerpt}}</ref> Serious laboratory accidents involving ''tert''-butyllithium have occurred. For example, in 2008 a staff research assistant, ], in the lab of ]<ref>{{cite web |title=Harran Lab: UCLA |url=http://faculty.chemistry.ucla.edu/institution/personnel?personnel_id=552980 |access-date=2011-09-21 |archive-date=2012-10-13 |archive-url=https://web.archive.org/web/20121013013907/http://faculty.chemistry.ucla.edu/institution/personnel?personnel%5Fid=552980 |url-status=dead}}</ref> at the ], died after being severely burned by a fire ignited by ''tert''-butyllithium.<ref>{{cite news |publisher=] |author=Jyllian Kemsley |title=Researcher Dies After Lab Fire |date=2009-01-22 |url=http://pubs.acs.org/cen/news/87/i04/8704news1.html}}</ref><ref>{{cite news |publisher=] |author=Jyllian Kemsley |title=Learning From UCLA: Details of the experiment that led to a researcher's death prompt evaluations of academic safety practices |date=2009-04-03 |url=http://pubs.acs.org/cen/science/87/8731sci1.html}}</ref><ref></ref>
			Large-scale reactions may lead to runaway reactions, fires, and explosions when ''tert''-butyllithium is mixed with ethers such as diethyl ether, and tetrahydrofuran. The use of hydrocarbon solvents may be preferred.
			==See also==
			* ]
			==References==
			{{Reflist}}
			{{Lithium compounds}}
			{{DEFAULTSORT:Butyllithium, t-}}
			]
			]
			]
			]