| Revision as of 13:49, 6 December 2011 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 457668129 of page Sec-Butyllithium for the Chem/Drugbox validation project (updated: ''). |
Latest revision as of 16:37, 19 December 2023 edit JWBE (talk | contribs)Extended confirmed users10,126 edits added Category:Sec-Butyl compounds using HotCat |
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{{DISPLAYTITLE:''sec''-Butyllithium}} |
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{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}} |
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{{Chembox |
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{{Chembox |
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| verifiedrevid = 429661642 |
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|verifiedrevid = 464388187 |
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| Name = ''sec''-Butyllithium |
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|Name = ''sec''-Butyllithium |
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| ImageFile = Sec-butyllithium-monomer-2D-skeletal.png |
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|ImageFile = Sec Butyllithium structure.svg |
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| ImageFile_Ref = {{chemboximage|correct|??}} |
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|ImageFile_Ref = {{chemboximage|correct|??}} |
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| ImageSize = 121 |
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|ImageSize = 121 |
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| ImageName = Skeletal formula of sec-butyllithium |
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| ImageFile1 = Sec-butyllithium-2D-skeletal.png |
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|ImageName = Skeletal formula of sec-butyllithium |
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|ImageFile1 = Sec-butyllithium-2D-skeletal.png |
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| ImageFile1_Ref = {{chemboximage|correct|??}} |
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|ImageFile1_Ref = {{chemboximage|correct|??}} |
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| ImageSize1 = 121 |
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|ImageSize1 = 121 |
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| ImageName1 = Skeletal formula of tetrameric sec-butyllithium |
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|ImageName1 = Skeletal formula of tetrameric sec-butyllithium |
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| IUPACName = ''sec''-Butyllithium |
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|IUPACName = ''sec''-Butyllithium |
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| SystematicName = Butan-2-yllithium{{Reference necessary|date = March 2010}} |
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|SystematicName = Butan-2-yllithium |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| CASNo = 598-30-1 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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|CASNo = 598-30-1 |
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|CASNo_Ref = {{cascite|correct|CAS}} |
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|UNII_Ref = {{fdacite|correct|FDA}} |
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| PubChem = 102446 |
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|UNII = 5YV3GII1TB |
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| PubChem_Ref = {{Pubchemcite|correct|PubChem}} |
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| ChemSpiderID = 10254345 |
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|PubChem = 102446 |
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|ChemSpiderID = 10254345 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| EINECS = 209-927-7 |
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|EINECS = 209-927-7 |
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| Beilstein = 3587206 |
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|Beilstein = 3587206 |
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| SMILES = C(C)CC |
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|SMILES = C(C)CC |
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| SMILES1 = CC()CC |
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|SMILES1 = CC()CC |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI = 1S/C4H9.Li/c1-3-4-2;/h3H,4H2,1-2H3; |
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|StdInChI = 1S/C4H9.Li/c1-3-4-2;/h3H,4H2,1-2H3; |
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| InChI = 1/C4H9.Li/c1-3-4-2;/h3H,4H2,1-2H3;/rC4H9Li/c1-3-4(2)5/h4H,3H2,1-2H3 |
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|InChI = 1/C4H9.Li/c1-3-4-2;/h3H,4H2,1-2H3;/rC4H9Li/c1-3-4(2)5/h4H,3H2,1-2H3 |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = VATDYQWILMGLEW-UHFFFAOYSA-N |
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|StdInChIKey = VATDYQWILMGLEW-UHFFFAOYSA-N |
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| InChIKey = VATDYQWILMGLEW-MHILWDCKAX |
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|InChIKey = VATDYQWILMGLEW-MHILWDCKAX |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| C = 4 |
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|C=4 | H=9 | Li=1 |
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| H = 9 |
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|pKa = 51 |
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| Li = 1 |
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| ExactMass = 64.086429337 g mol<sup>-1</sup> |
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| Section3 = {{Chembox Hazards |
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|Section3={{Chembox Hazards |
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'''''sec''-Butyllithium''' is an ] with the ] CH<sub>3</sub>CHLiCH<sub>2</sub>CH<sub>3</sub>, abbreviated ''sec''-BuLi or ''s''-BuLi. This ] ] is used as a source of ''sec''-butyl ] in ].<ref name=Ovaska>{{cite encyclopedia|author=Ovaska, T. V.|title=s-Butyllithium| encyclopedia =Encyclopedia of Reagents for Organic Synthesis|year=2001|publisher=John Wiley & Sons|location=New York|doi=10.1002/047084289X.rb397| isbn=0471936235 }}.</ref> |
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==Synthesis== |
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''sec''-BuLi can be prepared by the reaction of ''sec''-butyl ] with lithium metal:<ref>{{cite journal |author1=Hay, D. R. |author2=Song, Z. |author3=Smith, S. G. |author4=Beak, P. | title = Complex-induced proximity effects and dipole-stabilized carbanions: kinetic evidence for the role of complexes in the α-lithiations of carboxamides | journal = ] | year = 1988 | volume = 110 | pages = 8145–8153 | doi = 10.1021/ja00232a029 | issue = 24}}</ref> |
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] |
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== Properties == |
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=== Physical properties === |
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''sec''-Butyllithium is a colorless viscous liquid.<ref name=Ovaska/><ref name=":0">{{Citation |last1=Wietelmann |first1=Ulrich |title=Lithium and Lithium Compounds |date=2000-06-15 |url=https://onlinelibrary.wiley.com/doi/10.1002/14356007.a15_393 |encyclopedia=Ullmann's Encyclopedia of Industrial Chemistry |pages=a15_393 |editor-last=Wiley-VCH Verlag GmbH & Co. KGaA |place=Weinheim, Germany |publisher=Wiley-VCH Verlag GmbH & Co. KGaA |language=en |doi=10.1002/14356007.a15_393 |isbn=978-3-527-30673-2 |access-date=2022-05-07 |last2=Bauer |first2=Richard J.}}</ref> Using ], it was determined that the pure compound has a tetrameric structure.<ref>{{Cite journal |last1=Plavsic |first1=D. |last2=Srzic |first2=D. |last3=Klasinc |first3=Leo |date=1986 |title=Mass spectrometric investigations of alkyllithium compounds in the gas phase |url=https://pubs.acs.org/doi/abs/10.1021/j100401a020 |journal=The Journal of Physical Chemistry |language=en |volume=90 |issue=10 |pages=2075–2080 |doi=10.1021/j100401a020 |issn=0022-3654}}</ref> It also exists as tetramers when dissolved in organic solvents such as ], ] or ].<ref name=":0" /> The cyclopentane solution has been detected with <sup>6</sup>Li-] to have a hexameric structure at temperatures below −41 °C.<ref>{{Cite journal |last1=Fraenkel |first1=Gideon |last2=Henrichs |first2=Mark |last3=Hewitt |first3=Michael |last4=Su |first4=Biing Ming |date=1984 |title=Structure and dynamic behavior of a chiral alkyllithium compound: carbon-13 and lithium-6 NMR of sec-butyllithium |url=https://pubs.acs.org/doi/abs/10.1021/ja00313a052 |journal=Journal of the American Chemical Society |language=en |volume=106 |issue=1 |pages=255–256 |doi=10.1021/ja00313a052 |issn=0002-7863}}</ref> In electron-donating solvents such as ], there exists an equilibrium between monomeric and dimeric forms.<ref>{{Cite journal |last1=Bauer |first1=Walter. |last2=Winchester |first2=William R. |last3=Schleyer |first3=Paul von R. |date=1987-11-01 |title=Monomeric organolithium compounds in tetrahydrofuran: tert-butyllithium, sec-butyllithium, supermesityllithium, mesityllithium, and phenyllithium. Carbon-lithium coupling constants and the nature of carbon-lithium bonding |url=https://pubs.acs.org/doi/abs/10.1021/om00154a017 |journal=Organometallics |language=en |volume=6 |issue=11 |pages=2371–2379 |doi=10.1021/om00154a017 |issn=0276-7333}}</ref> |
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=== Chemical properties === |
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The carbon-lithium bond is highly polar, rendering the carbon ], as in other ] reagents. ''Sec''-butyllithium is more basic than the primary ] reagent, ]. It is also more sterically hindered. ''sec''-BuLi is employed for deprotonations of particularly weak carbon acids where the more conventional reagent ''n''-BuLi is unsatisfactory. It is, however, so basic that its use requires greater care than for ''n''-BuLi. For example ] is attacked by ''sec''-BuLi at room temperature in minutes, whereas ether solutions of ''n''-BuLi are stable.<ref name="Ovaska"/> |
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The compound decomposes slowly at room temperature and more rapidly at higher temperatures, giving ] and a mixture of ].<ref>{{Cite journal |last1=Glaze |first1=William H. |last2=Lin |first2=Jacob |last3=Felton |first3=E. G. |date=1965 |title=The Thermal Decomposition of sec-Butyllithium |url=https://pubs.acs.org/doi/abs/10.1021/jo01015a514 |journal=The Journal of Organic Chemistry |language=en |volume=30 |issue=4 |pages=1258–1259 |doi=10.1021/jo01015a514 |issn=0022-3263}}</ref><ref>{{Cite journal |last1=Glaze |first1=William H. |last2=Lin |first2=Jacob |last3=Felton |first3=E. G. |date=1966 |title=The Pyrolysis of Unsolvated Alkyllithium Compounds |url=https://pubs.acs.org/doi/abs/10.1021/jo01346a044 |journal=The Journal of Organic Chemistry |language=en |volume=31 |issue=8 |pages=2643–2645 |doi=10.1021/jo01346a044 |issn=0022-3263}}</ref> |
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==Applications== |
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Many transformations involving ''sec''-butyllithium are similar to those involving other organolithium reagents. |
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In combination with ] as a ], sec-butyllithium is useful in enantioselective deprototonations.<ref>{{cite journal |doi=10.15227/orgsyn.082.0022| title=Preparation of (S,S)-1,2-bis(''tert''-Butylmethylphosphino)ethane ((''S,S'')-t-bu-bisp*) as a Rhodium Complex | journal=Organic Syntheses | year=2005 | volume=82 | page=22|first1=Karen V. L.|last1=Crépy|first2= Tsuneo|last2=Imamoto |doi-access=free}}</ref> It is also effective for lithiation of arenes.<ref>{{cite journal |doi=10.15227/orgsyn.072.0163|first1=X.|last1=Wang|first2=S. O.|last2=de Silva|first3=J. N.|last3=Reed|first4=R.|last4=Billadeau|first5=E. J.|last5=Griffen|first6=A.|last6=Chan|first7=V.|last7=Snieckus|title=7-Methoxyphthalide|journal=Org. Synth.|year=1995|volume=72|page=163}}</ref> |
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==References== |
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{{reflist}} |
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{{Lithium compounds}} |
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{{DEFAULTSORT:Butyllithium, sec-}} |
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] |