A new class of organosuperbases, N-alkyl- and N-aryl-1,3-dialkyl-4,5-dimethylimidazol-2-ylidene amines: synthesis, structure, pK(BH+) measurements, and properties

Chemistry : a European Journal
Roman KunetskiyIlya M Lyapkalo

Abstract

A series of stable organosuperbases, N-alkyl- and N-aryl-1,3-dialkyl-4,5-dimethylimidazol-2-ylidene amines, were efficiently synthesized from N,N'-dialkylthioureas and 3-hydroxy-2-butanone and their basicities were measured in acetonitrile. The derivatives with tert-alkyl groups on the imino nitrogen were found to be more basic than the tBuP(1) (pyrr) phosphazene base in acetonitrile. The origin of the high basicity of these compounds is discussed. In acetonitrile and in the gas phase, the basicity of the alkylimino derivatives depends on the size of the substituent at the imino group, which influences the degree of aromatization of the imidazole ring, as measured by (13)C NMR chemical shifts or by the calculated ΔNICS(1) aromaticity parameters, as well as on solvation effects. If a wider range of imino-substituents, including electron-acceptor substituents, is treated in the analysis then the influence of aromatization is less predominant and the gas-phase basicity becomes more dependent on the field-inductive effect, polarizability, and resonance effects of the substituent.

References

Sep 19, 2000·The Journal of Organic Chemistry·P B KisangaR Schwesinger
Jun 5, 2001·Organic Letters·B Kovacevic, Z B Maksic
Apr 5, 2002·Chemistry : a European Journal·Volker RaabJörg Sundermeyer
Dec 15, 2005·Journal of the American Chemical Society·Alexander A KolomeitsevIvo Leito
Jan 26, 2007·Organic & Biomolecular Chemistry·Matthias TammJörg Grunenberg
Feb 3, 2007·The Journal of Physical Chemistry. a·Ivari KaljurandIvo Leito
Jun 28, 2007·Chemistry : a European Journal·Eva-Ingrid RõõmYuji Miyahara
Dec 25, 2007·Acta Crystallographica. Section A, Foundations of Crystallography·George M Sheldrick
Apr 10, 2008·Angewandte Chemie·F Ekkehardt Hahn, Mareike C Jahnke
Apr 15, 2010·Angewandte Chemie·Hans BrunsManuel Alcarazo
Nov 26, 2010·Chemical Communications : Chem Comm·Nena Peran, Zvonimir B Maksić
Dec 9, 2010·Chemical & Pharmaceutical Bulletin·Tsutomu Ishikawa
Jul 3, 1996·Journal of the American Chemical Society·Paul von Ragué SchleyerNicolaas J R van Eikema Hommes

❮ Previous
Next ❯

Citations

Jul 9, 2016·The Journal of Organic Chemistry·Jaan SaameIvo Leito
Oct 16, 2016·Chemical Reviews·Ewa D RaczyńskaPierre-Charles Maria
Oct 26, 2016·Chemistry : a European Journal·Paul MehlmannFabian Dielmann
Sep 22, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Jovana BogojeskiŽivadin D Bugarčić
Feb 26, 2013·Chemistry : a European Journal·Ágnes KozmaManuel Alcarazo
Sep 24, 2020·Journal of Computational Chemistry·Neha PatelPrasad V Bharatam
Aug 7, 2014·Chemical Communications : Chem Comm·Ines Despotović, Robert Vianello
Jun 6, 2017·Physical Chemistry Chemical Physics : PCCP·Khaleel I AssafAla'a F Eftaiha
Jun 20, 2015·Angewandte Chemie·Ivo LeitoJaan Saame
Jun 9, 2016·Mass Spectrometry Reviews·Guy Bouchoux, Mirjana Eckert-Maksic
Aug 7, 2019·Chemistry : a European Journal·Idir BenaissaVincent César
Feb 15, 2020·Chemical Science·Sebastian UllrichJörg Sundermeyer
Mar 16, 2021·European Journal of Pharmaceutical Sciences : Official Journal of the European Federation for Pharmaceutical Sciences·Giuseppe ErmondiGiulia Caron
Jul 27, 2021·Accounts of Chemical Research·Katarina VazdarUllrich Jahn
Aug 29, 2013·Inorganic Chemistry·Alexander G TskhovrebovKay Severin
Nov 16, 2012·The Journal of Organic Chemistry·Natsuko UchidaTakaki Kanbara
Nov 13, 2018·Inorganic Chemistry·Alex McSkimming, Daniel L M Suess
Apr 18, 2014·The Journal of Organic Chemistry·Chen YangJin-Pei Cheng
Oct 26, 2021·Angewandte Chemie·Lukas F B WilmFabian Dielmann
Dec 17, 2021·Organic Letters·Daiya Kase, Ryosuke Haraguchi

❮ 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.