Association of tert-C4H9O Li in vapors

Simonov, A. P.; Shigorin, D. N.; Talalaeva, T. V.; Kocheshkov, K. A.

doi:10.1007/bf00905240

Cited by 6 publications

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“…Indeed, pairing t -BuOLi ( 34 ) with hindered alkoxides 35 or 36 afforded remarkable spectral complexity (Figure ) exceeding even that anticipated for an ensemble of tetramers ( A 4 - A 3 B - A 2 B 2 - AB 3 - B 4 ) . It seems probable, therefore, that the hindered alkoxides are hexameric (possibly only partially solvated), − as indicated by X-ray crystallography , and colligative measurements for t -BuOLi in benzene . The large number of hexamer stoichiometries (seven) and the existence of positional isomers within hexagonal drums would result in 38 magnetically inequivalent 6 Li resonances .…”

Section: Resultsmentioning

confidence: 96%

Solution Structures of Lithium Enolates, Phenolates, Carboxylates, and Alkoxides in the Presence of N,N,N′,N′-Tetramethylethylenediamine: A Prevalence of Cyclic Dimers

et al. 2008

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The method of continuous variation was used to characterize lithium enolates, phenolates, carboxylates, and alkoxides solvated by N,N,N',N'-tetramethylethylenediamine (TMEDA). The method relies on characterizing an ensemble of homo-and heteroaggregates using 6 Li NMR spectroscopy. A combination of aggregate counts and symmetries, nearly statistical distributions, and quantitative parametric fits revealed that cyclic dimers are the dominant form. Non-statistical distributions favoring heteroaggregated dimers were observed when hindered enolates and lithium carboxylates were mixed with unhindered enolates. Nonstatistical distributions favoring homoaggregates observed when hindered (tertiary) alkoxides were paired with other O-lithiated forms were traced to the formation of higher aggregates (hexamers) of the tertiary alkoxides. Highly hindered lithium phenolates appear to form TMEDA-solvated monomers.

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Section: Resultsmentioning

confidence: 96%

Solution Structures of Lithium Enolates, Phenolates, Carboxylates, and Alkoxides in the Presence of N,N,N′,N′-Tetramethylethylenediamine: A Prevalence of Cyclic Dimers

et al. 2008

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“…Liquefaction of these masses to yield clear solutions occurs at 75-80°. 6 Lithium f-butoxide also forms solid crystalline masses with ¿-butyl alcohol, but these complexes do not form clear solutions on heating to reflux. apparent solubility of lithium n-butoxide in n-heptane was found to increase with an increase in n-butyllithium concentration in a directly proportionate manner.…”

Section: Resultsmentioning

confidence: 99%

Relationship between Structure and Solubility of Organic Lithium Compounds

Kamienski¹,

Lewis²

1965

J. Org. Chem.

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Azaaldol Condensation of a Lithium Enolate Solvated by N,N,N′,N′-Tetramethylethylenediamine: Dimer-Based 1,2-Addition to Imines

et al. 2013

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The lithium enolate of tert-amylacetate solvated by N,N,N’,N’-tetramethylethylenediamine (TMEDA) is shown to be a doubly-chelated dimer. Adding the dimeric enolate to 4-fluorobenzaldehyde-N-phenylimine affords an N-lithiated β-amino ester shown to be monomeric using 6Li and 15N NMR spectroscopies. Rate studies using 19F NMR spectroscopy reveal reaction orders consistent with a transition structure of stoichiometry [(ROLi)2(TMEDA)2(imine)]‡. Density functional theory computations explore several possible dimer-based transition structures with monodentate and bidentate coordination of TMEDA. Supporting rate studies using N,N,N’,N’-tetramethylcyclohexanediamine showing analogous rates and rate law suggest that TMEDA is fully chelated.

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Association of tert-C4H9O Li in vapors

Cited by 6 publications

References 0 publications

Solution Structures of Lithium Enolates, Phenolates, Carboxylates, and Alkoxides in the Presence of N,N,N′,N′-Tetramethylethylenediamine: A Prevalence of Cyclic Dimers

Solution Structures of Lithium Enolates, Phenolates, Carboxylates, and Alkoxides in the Presence of N,N,N′,N′-Tetramethylethylenediamine: A Prevalence of Cyclic Dimers

Relationship between Structure and Solubility of Organic Lithium Compounds

Azaaldol Condensation of a Lithium Enolate Solvated by N,N,N′,N′-Tetramethylethylenediamine: Dimer-Based 1,2-Addition to Imines

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