PMID: 11929252Apr 4, 2002Paper

Antihydrophobic cosolvent effects for alkylation reactions in water solution, particularly oxygen versus carbon alkylations of phenoxide ions

Journal of the American Chemical Society
Ronald BreslowM U Mayer

Abstract

Antihydrophobic cosolvents such as ethanol increase the solubility of hydrophobic molecules in water, and they also affect the rates of reactions involving hydrophobic surfaces. In simple reactions of hydrocarbons, such as the Diels-Alder dimerization of 1,3-cyclopentadiene, the rate and solubility data directly reflect the geometry of the transition state, in which some hydrophobic surface becomes hidden. In reactions involving polar groups, such as alkylations of phenoxide ions or S(N)1 ionizations of alkyl halides, cosolvents in water can have other effects as well. However, solvation of hydrophobic surfaces is still important. By the use of structure-reactivity relationships, and comparing the effects of ethanol and DMSO as solvents, it has been possible to sort out these effects. The conclusions are reinforced by an ab initio computer model for hydrophobic solvation. The result is a sensible transition state for phenoxide ion as a nucleophile, using its oxygen n electrons to avoid loss of conjugation. The geometry of alkylation of aniline is very different, involving packing (stacking) of the aniline ring onto the phenyl ring of a benzyl group in the benzylation reaction. The alkylation of phenoxide ions by benzylic chlori...Continue Reading

References

Jan 1, 1990·Proceedings of the National Academy of Sciences of the United States of America·R Breslow, T Guo
May 24, 2000·Organic Letters·R BreslowM U Mayer

❮ Previous
Next ❯

Citations

Jul 17, 2009·The Journal of Biological Chemistry·L Sangeetha VedulaPatrick J Loll
Nov 5, 2004·Organic Letters·Mark R BiscoeRonald Breslow
Nov 17, 2007·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Takeshi Sunakawa, Chiaki Kuroda
Oct 4, 2014·Chemistry : a European Journal·Emil LindbäckKenneth Wärnmark
Dec 13, 2005·Angewandte Chemie·Ulf M Lindström, Fredrik Andersson
Sep 12, 2008·The Journal of Biological Chemistry·Ronald Breslow
Jul 30, 2014·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Arpan Manna, Anil Kumar
Mar 27, 2013·Chemical Society Reviews·Manoj B GawandeRajender S Varma
Dec 25, 2013·Chemical Society Reviews·Matthieu RaynalPiet W N M van Leeuwen
Nov 17, 2012·Angewandte Chemie·Alexander Gutmann, Bernd Nidetzky
Oct 29, 2009·The Journal of Physical Chemistry. a·Shraeddha Tiwari, Anil Kumar
Aug 10, 2006·Chemical Reviews·Vernon E AndersonMichael E Harris
Jan 11, 2014·Journal of the American Chemical Society·Marta Diez-CastellnouPaolo Scrimin
Jun 27, 2019·The Journal of Organic Chemistry·Robert J MayerHerbert Mayr
Nov 19, 2005·The Journal of Organic Chemistry·Yumi NakaikeMasahiro Ariga
Oct 16, 2003·Journal of the American Chemical Society·Mark R Biscoe, Ronald Breslow
Nov 6, 2003·Journal of the American Chemical Society·Maciej TurowskiEdward R Thornton

❮ Previous
Next ❯

Related Concepts

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.