Addition of organolithium reagents to 1,1-diphenylethylene in tetrahydrofuran. Kinetics and structure-reactivity relationship

Waack, Richard; Doran, Mary A.

doi:10.1021/ja01038a010

Cited by 51 publications

(18 citation statements)

References 3 publications

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“…Broken reaction orders concerning the reaction of 2 with different substrates were also identified by other works , (shown in detail in Supporting Information S3.2). It was found that, with regard to 2 , the reaction order either varied between 0.25 and 0.33 , or amounted to the reciprocal of the degree of association of the organolithium compound , thereby supporting the results outlined above.…”

Section: Resultsmentioning

confidence: 99%

In Situ Reaction Monitoring of Unstable Lithiated Intermediates through Inline FTIR Spectroscopy

2019

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Because a multitude of reactions with n‐butyllithium are of high industrial significance, an in‐depth process understanding is required to render potential scale‐up from the laboratory to production more efficient. The objective of this work is to illuminate the mechanism underlying the deprotonation reaction of a CH‐acidic hydrocarbon compound with n‐butyllithium. Combining microreactor technology with inline FTIR spectroscopy, it was possible to quickly determine reliable kinetic data. It is shown that a complex reaction mechanism is involved in the synthesis of a highly reactive, nonisolable, lithiated component. Several kinetic approaches are studied in detail, and a possible mechanism based on the formation of butyllithium aggregates in tetrahydrofuran is postulated.

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Section: Resultsmentioning

confidence: 99%

In Situ Reaction Monitoring of Unstable Lithiated Intermediates through Inline FTIR Spectroscopy

2019

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“…In recent years, many investigations have focused on the reactivity of organolithium compounds in various solvents. For instance, while McGarrity et al found dimers as the most reactive species when n -BuLi is utilized, Waack and Doran asserted that monomers are the most reactive. Bearing this information in mind, the nature of organolithium compounds in solvents has a modulating impact on their reactivity with substrates, such as p -bromoanisole.…”

Section: Resultsmentioning

confidence: 99%

Halogen–Lithium Exchange Reaction Using an Integrated Glass Microfluidic Device: An Optimized Synthetic Approach

Shirejini

Mohammadi

2017

Org. Process Res. Dev.

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A telescoped approach was developed for the efficient synthesis of methoxybenzene through the generation of an unstable intermediate reagent, based on the Br−Li exchange reaction of p-bromoanisole and n-BuLi, followed by its reaction with water. In the first stage, p-methoxyphenyllithium was synthesized and consumed immediately in the second stage. For this purpose, an integrated glass microfluidic device was fabricated using laser ablation followed by the thermal fusion bonding method. The impact of various parameters, including solvent, reaction time, molar ratio, concentration of reagents, and flow rates were investigated to achieve the highest yield of the desired product, leading to an optimized condition for the synthetic approach. It was found that the yield varies significantly with change in solvent composition. While p-bromoanisole does not react with n-BuLi in pure n-hexane, the existence of a small amount of THF (or 2-MeTHF) in n-hexane facilitates pbromoanisole reaction with n-BuLi. Moreover, the reaction is complete within 1 s by the yield of 95% using the microfluidic device, whereas in a batch system, the best result is obtained in 1 min by the yield of 49%. In addition, the optimal molar ratio of n-BuLi to p-bromoanisole was found to be 1.2. Furthermore, the higher flow rates of the reagents result in a higher yield of the desired product. Finally, under the optimized condition, the generated p-methoxyphenyllithium, by the Br−Li exchange reaction of p-bromoanisole and n-BuLi, was reacted with various electrophiles using the microfluidic device.

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“…Ph2N-NH2 -PhzN-N:20, 2 Lio + PhN-@PhZ0, 2 Li@ (38) whereas the corresponding monoanion (as lithium salt) does not undergo [1,2] phenyl migration even at 100°C in bis(2-methoxyethyl) ether.…”

Section: Chplimentioning

confidence: 99%

Skeletal Rearrangements of Organoalkali Metal Compounds

Grovenstein

1978

Angew. Chem. Int. Ed. Engl.

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Dedicated to Professor Avery A. Morton on the occasion of his 85th birthdayOrganometallic compounds of the alkali metals undergo concerted [ 1 ,n] sigmatropic migration of aryl, vinyl, carbonyl, alkoxycarbonyl, silyl, germyl, and related groups. Sigmatropic migration of alkyl, benzyl, and hydrogen occur only under special circumstances and then may occur by an alternate fragmentation-recombination pathway. Ally1 groups may migrate by the latter process or by a concerted [2,3] sigmatropic reaction. These molecular rearrangements are discussed from the viewpoint of simple molecular orbital theory. By suitable choice of the alkali metal, temperature, ligands of the alkali cation and/or the solvent, considerable control may be exercised over the rate of rearrangement, the relative migratory aptitude of groups, and the mechanistic pathway.

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Addition of organolithium reagents to 1,1-diphenylethylene in tetrahydrofuran. Kinetics and structure-reactivity relationship

Cited by 51 publications

References 3 publications

In Situ Reaction Monitoring of Unstable Lithiated Intermediates through Inline FTIR Spectroscopy

In Situ Reaction Monitoring of Unstable Lithiated Intermediates through Inline FTIR Spectroscopy

Halogen–Lithium Exchange Reaction Using an Integrated Glass Microfluidic Device: An Optimized Synthetic Approach

Skeletal Rearrangements of Organoalkali Metal Compounds

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