Nucleophilicity in ionic liquids. 3. Anion effects on halide nucleophilicity in a series of 1-butyl-3-methylimidazolium ionic liquids

The Journal of Organic Chemistry
N Llewellyn Lancaster, Tom Welton

Abstract

We have continued the study of halide nucleophilicity in ionic liquids, concentrating on the effect of changing the anion ([BF(4)](-), [PF(6)](-), [SbF(6)](-), [OTf](-), and [N(Tf)(2)](-)) when the cation is [bmim](+) (where bmim = 1-butyl-3-methylimidazolium). It was found that the nucleophilicities of all the halides were lower in all of the ionic liquids than in dichloromethane. Changing the anion affected the order of halide nucleophilicity, e.g., in [bmim][BF(4)] the order of nucleophilicity was Cl(-)>Br(-)>I(-) while in [bmim][N(Tf)(2)] the order was Cl(-)<Br(-)<I(-). It was also found that the nucleophilicity of each halide was different in each ionic liquid, with chloride being almost four times as nucleophilic in [bmim][BF(4)] as in [bmim][SbF(6)]. Similarly bromide was more than four times as nucleophilic in [bmim][BF(4)] as in [bmim][PF(6)]. The activation parameters DeltaG++, DeltaH++, and DeltaS++ have been measured for the reaction of chloride in each of the ionic liquids, plus the reaction of bromide in [bmim][BF(4)] and [bmim][PF(6)]. These data were also compared to each other as well as to a similar reaction in dichloromethane (where these parameters have been estimated for both the free ion and the ion-pair)....Continue Reading

References

Nov 25, 2000·Angewandte Chemie·P Wasserscheid, W Keim
Mar 30, 2001·Organic Letters·C ChiappeD Pieraccini
Sep 21, 2002·Chemical Communications : Chem Comm·R Sheldon
Sep 26, 2002·Chemical Communications : Chem Comm·Andrew J McLeanIan R Dunkin
Nov 21, 2002·Journal of the American Chemical Society·Jared L AndersonDaniel W Armstrong
May 24, 2003·The Journal of Organic Chemistry·Dong Wook KimDae Yoon Chi

❮ Previous
Next ❯

Citations

Apr 8, 2011·Chemical Reviews·Jason P Hallett, Tom Welton
Nov 6, 2013·Inorganic Chemistry·Klaus PokornyRudi van Eldik
Jun 28, 2007·Chemical Communications : Chem Comm·Carlos A M AfonsoJoão N Rosa
Jul 26, 2008·Chemical Communications : Chem Comm·Hon Man YauJason B Harper
Jan 12, 2016·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Elizabeth D KochlyAnne Marie Deh-Lee
Mar 26, 2008·The Journal of Chemical Physics·Guilherme M Arantes, Mauro C C Ribeiro
Apr 12, 2016·Physical Chemistry Chemical Physics : PCCP·Umme SalmaLorenzo Gontrani
Oct 8, 2014·Magnetic Resonance in Chemistry : MRC·Bradley J ButlerJason B Harper
Feb 11, 2010·Physical Chemistry Chemical Physics : PCCP·Seigo HayakiShigeyoshi Sakaki
May 6, 2019·International Journal of Molecular Sciences·Peng ZhuHongzhong Zhang
May 20, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Isabel Correia, Tom Welton
Jul 19, 2012·Chemistry : a European Journal·Matthias SchmeisserRudi van Eldik
Jun 8, 2017·Topics in Current Chemistry·Susann Wegner, Christoph Janiak
Oct 4, 2013·Organic & Biomolecular Chemistry·Eden E L TannerJason B Harper
Jul 22, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Matthias Schmeisser, Rudi van Eldik
Oct 11, 2019·Organic & Biomolecular Chemistry·Karin S Schaffarczyk McHaleJason B Harper
Oct 13, 2020·Physical Chemistry Chemical Physics : PCCP·Alexandra SchindlChristof M Jäger
May 5, 2010·The Journal of Organic Chemistry·Guido AngeliniGabriella Siani
Nov 17, 2009·The Journal of Organic Chemistry·Riccardo BiniBenedetta Parisi
Oct 10, 2008·Journal of the American Chemical Society·Takuya NakashimaTsuyoshi Kawai
Jun 22, 2010·The Journal of Organic Chemistry·Francesca D'AnnaRenato Noto
Jan 12, 2010·Journal of Chemical Theory and Computation·Cinzia ChiappeChristian Silvio Pomelli
Dec 22, 2005·Journal of the American Chemical Society·Xavier CrearyMadeleine Gagnon
Sep 16, 2004·Journal of the American Chemical Society·Lorna CrowhurstTom Welton
Jul 16, 2008·The Journal of Organic Chemistry·Francesca D'AnnaRenato Noto
Jul 30, 2009·The Journal of Organic Chemistry·Guido AngeliniGabriella Siani
Nov 11, 2014·The Journal of Physical Chemistry. a·Steven D ChambreauStephen R Leone
Nov 4, 2006·The Journal of Organic Chemistry·Lorna CrowhurstTom Welton
Sep 9, 2006·The Journal of Organic Chemistry·Shifang LiuJianliang Xiao

❮ Previous
Next ❯

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.