Relationship between Structure and Solubility of Organic Lithium Compounds

Kamienski, Conrad W.; Lewis, Dennis H.

doi:10.1021/jo01021a051

Cited by 51 publications

(22 citation statements)

References 2 publications

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“…Kamienski and Lewis have conducted the most detailed study of the solubility of lithium alkoxides, concluding that alkoxides with branching have increased solubility in hydrocarbon solvents and ethers but lower solubility in alcohols. [ 33 ] While this work also demonstrated that the solubility of straight chain alkoxides in ethers and hydrocarbons is low, they did observe a slight increase in solubility as the chain length of the alkoxide increases.…”

Section: Resultsmentioning

confidence: 68%

Chain‐growth polycondensation via the substituent effect: Investigation of the monomer structure on synthesis of poly(N‐octyl‐benzamide)

Prehn

Etz

Reese

et al. 2020

Journal of Polymer Science

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A systematic study of the behavior of different leaving groups on a variety of ester‐based monomers was performed for the chain‐growth polycondensation synthesis of poly(N‐octyl benzamide). Linear and branched alkane esters were compared with their phenyl analogs using both computational and experimental methods. Kinetic experiments along with qualitative solubility observations were used, with the aid of nuclear magnetic resonance spectroscopy and gel‐permeation chromatography, to determine progress of the reaction, molecular weights, and molecular weight distributions. It was found that the reactivity of the monomer's ester group depends more on the stability of the leaving alkoxide than the electrophilicity of the carbonyl carbon, which contradicts previous literature. The order of reactivity increases for the alkyl esters with decreasing steric hindrance and decreasing pKa of the substituent. For the phenyl ester derivatives, the more electron withdrawing character of a para substituent increases the reactivity of the ester group, due to the higher resonance stabilization of the leaving phenoxide anion, not due to an increase in the electrophilicity of the carbonyl carbon.

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Section: Resultsmentioning

confidence: 68%

Chain‐growth polycondensation via the substituent effect: Investigation of the monomer structure on synthesis of poly(N‐octyl‐benzamide)

Prehn

Etz

Reese

et al. 2020

Journal of Polymer Science

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“…The biological use of Li in plants is negligible (Hogan and Blum, 2003;Marschner, 2012), however it is a trace element in marine plankton (Misra and Froelich, 2012), which are a major constituent of Type II kerogen (Tissot et al, 1974). The stability of Li-C straight and branched chain alkanes and amines has been studied in hydrocarbon solutions (Kamienski and Lewis, 1965) showing that Li-alkoxides are stable at temperatures of hydrocarbon generation (to 80˚C).…”

Section: Evidence For Organic LI and B In Kerogenmentioning

confidence: 99%

Tracing hydrocarbons in gas shale using lithium and boron isotopes: Denver Basin USA, Wattenberg Gas Field

2015

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Bentonites are altered volcanic ash layers commonly used as marker beds in sedimentary basins. The ash (glass) alters to diagenetic mixed-layered illite-smectite (I-S), and the illite incorporates trace elements from the interacting porefluid, recording paleofluid changes over time. Among these trace elements, lithium and boron are common heteroatoms of organic macerals released during thermal maturation into the porefluids, and are incorporated by the diagenetic illite, potentially becoming useful tracers of hydrocarbon-related fluids. This study examines Li and B in bentonite samples in the Wattenberg Gas Field, Denver Basin, Colorado (USA). Using secondary ion mass spectrometry, different crystal size fractions of IS extracted from the bentonite were measured. Illite incorporates Li in octahedral sites and B in tetrahedral sites of the framework during diagenetic crystallization, recording distinctly light isotopic signatures of the organic source. The  7 Li of IS in outcrops outside of the gas field range from-7 to +4‰, compared to samples within the gas field, which generally range from-18 to-4‰. One exception is in the highly mature region, where vitrinite reflectance values (%Ro) reach 1.3. The  7 Li is +12‰ in the finer clay fraction (<0.1 µm) containing first nucleated illite while the coarser size fraction (0.1-2.0 µm) of the same sample shows the lowest  7 Li value of-18‰. This 30‰ decrease in  7 Li within the same sample suggests influx of 6 Li dominated fluid coinciding with gas generation during illitization. K-Ar dating of the illite in this sample indicates that influx of the 6 Li-rich fluid occurred at 60 ± 3Ma, before local igneous activity (~40Ma) related to the Laramide Orogeny (Colorado Mineral Belt) increased vitrinite %Ro. B-isotopes ranged from-15 to-7‰, showing no significant change between different size fractions, but the B-content in the gas field reaches 180 ppm, and decreases radially away from the thermally mature region. We conclude that isotopically light B influx coincides with generation of oil and isotopically light Li is associated with influx of gas related fluids, and therefore the age of the illites record the timing of oil and gas generation.

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“…The reduction chemistries yield lithium ethoxide from DEE and lithium n-butoxide from THF as by-products. Lithium ethoxide is soluble only up to 0.035M in DEE while various lithium butoxides have solubilities in excess of 2M in THF (15). The kinetic stability of DEE and DEE blends may be due simply to an insoluble, protective lithium ethoxide film, electronically insulating but Li+-ion conducting.…”

Section: Mechanistic Considerations--earliermentioning

confidence: 99%

Specular Lithium Deposits from Lithium Hexafluoroarsenate/Diethyl Ether Electrolytes

Koch

Goldman

Mattos

et al. 1982

J. Electrochem. Soc.

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JANUARY 1982 ABSTRACTA new class of aprotic organic electrolytes in which to cycle the lithium electrode has been developed. Blends of diethyl ether (DEE) and tetrahydrofuran (THF) incorporating LiAsF6 have been found to afford Li electrode cycling efficiencies in excess of 98%. In addition, specular deposits of up to 10 C/cm 2 may be plated from these systems. The kinetic stability of these blended electrolytes toward Li is thought to be due to the formation of a protective lithium ethoxide film.Our ongoing search for electrolytes suitable for use in ambient temperature secondary Li batteries has led us to investigate solutions of LiAsF6 in propylene carbonate (PC) (1), tetrahydrofuran (THF) (2), and 2-methyltetrahydrofuran (2-Me-THF) (3). Average cycling efficiencies for the Li electrode in these media are 84, 88, and 96%, respectively (1C Li/cm 2 at 5 mA/ cm2). In this paper, we elaborate on the discovery of a class of diethyl ether (DEE)-based electrolytes which afford cycling efficiencies in excess of 98% (4,5). Moreover, Li plate morphologies are so regular and dendrite free that they may be deemed specular in appearance.Electrolytes comprising DEE have found use in ambient temperature Li primary batteries (6). More recently, Higgens reported on the stability of purified DEE toward Li and found that 1M LiAsF6/DEE was stable for over one month at 71~ (7). To our knowledge, however, no reports of DEE-based electrolytes employed in secondary Li batteries have surfaced in the open literature.While a variety of cosolvents have been found to improve the conductivity of LiAsF6/DEE electrolyte without degrading Li cycling performance (5), the best electrolyte to date comprises a 90:10 v/v mixture of DEE and THF, 2.5M in LiAsF6. We refer to this mixture as . This paper also explores the variation of Li half-cell cycling efficiencies with LiAsF6 concentration and with the addition of asymmetric ether cosolvents. ExperimentalGeneral.--All purification procedures subsequent to distillation and the electrochemical experiments were conducted at ambient temperature under Ar atmosphere in a Vacuum-Atmospheres Corporation dry box equipped with a Model He-493 Dri-Train.

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Relationship between Structure and Solubility of Organic Lithium Compounds

Cited by 51 publications

References 2 publications

Chain‐growth polycondensation via the substituent effect: Investigation of the monomer structure on synthesis of poly(N‐octyl‐benzamide)

Chain‐growth polycondensation via the substituent effect: Investigation of the monomer structure on synthesis of poly(N‐octyl‐benzamide)

Tracing hydrocarbons in gas shale using lithium and boron isotopes: Denver Basin USA, Wattenberg Gas Field

Specular Lithium Deposits from Lithium Hexafluoroarsenate/Diethyl Ether Electrolytes

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