Substituent Effects in Pericyclic Reactions of Radical Cations:  The Ring Opening of 3-Substituted Cyclobutene Radical Cations

2000 ◽  
Vol 65 (20) ◽  
pp. 6708-6714 ◽  
Author(s):  
David J. Swinarski ◽  
Olaf Wiest
Keyword(s):  
Ring Opening ◽  
Substituent Effects ◽  
Radical Cations ◽  
Pericyclic Reactions

Electrostatic effects on ionization equilibria: An MNDO study of proton and hydrogen transfer reactions of 4-fluorobutylamine

1990 ◽  
Vol 55 (1) ◽  
pp. 1-9 ◽  
Author(s):  
Zdeněk Friedl ◽  
Stanislav Böhm
Keyword(s):  
Hydrogen Transfer ◽  
Substituent Effects ◽  
Radical Cations ◽  
Transfer Reactions ◽  
Protonated Forms ◽  
Minor Part ◽  
Bond Strengths ◽  
Ionization Equilibria ◽  
A Minor ◽  
Gas Phase Basicities

The relative enthalpies of proton transfer δ ΔH0and homolytic bond strengths δDH0(B-H+) were calculated by the MNDO method for the sp and ap conformers of 4-flurobutylamine. The data obtained, along with the experimental gas phase basicities, are compared with the values predicted by the electrostatic theory. It is shown that the substituent polar effects FD on the basicities of amines are predominantly due to interactions in their protonated forms (X-B-H+) and/or radical-cations (X-B+.), those in the neutral species (X-B) playing a minor part. A contribution, which is considerably more significant in the sp conformer than in the ap conformer, arises probably also from substituent effects on the homolytic bond strength DH0(B-H+.

scholarly journals Substituent Effects on EI-MS Fragmentation Patterns of 5-Allyloxy-1-aryl-tetrazoles and 4-Allyl-1-aryl-tetrazole-5-ones; Correlation with UV-Induced Fragmentation Channels

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3282
Author(s):  
Alina Secrieru ◽  
Rabah Oumeddour ◽  
Maria L. S. Cristiano
Keyword(s):  
Theoretical Calculations ◽  
Substituent Effects ◽  
Radical Cations ◽  
Electronic Effects ◽  
Diverse Range ◽  
The Matrix ◽  
Electron Impact Mass ◽  
Fragmentation Patterns ◽  
Tetrazole Derivatives ◽  
Impact Mass

1,4- and 1,5-disubstituted tetrazoles possess enriched structures and versatile chemistry, representing a challenge for chemists. In the present work, we unravel the fragmentation patterns of a chemically diverse range of 5-allyloxy-1-aryl-tetrazoles and 4-allyl-1-aryl-tetrazolole-5-ones when subjected to electron impact mass spectrometry (EI-MS) and investigate the correlation with the UV-induced fragmentation channels of the matrix-isolated tetrazole derivatives. Our results indicate that the fragmentation pathways of the selected tetrazoles in EI-MS are highly influenced by the electronic effects induced by substitution. Multiple pathways can be envisaged to explain the mechanisms of fragmentation, frequently awarding common final species, namely arylisocyanate, arylazide, arylnitrene, isocyanic acid and hydrogen azide radical cations, as well as allyl/aryl cations. The identified fragments are consistent with those found in previous investigations concerning the photochemical stability of the same class of molecules. This parallelism showcases a similarity in the behaviour of tetrazoles under EI-MS and UV-irradiation in the inert environment of cryogenic matrices of noble gases, providing efficient tools for reactivity predictions, whether for analytical ends or more in-depth studies. Theoretical calculations provide complementary information to articulate predictions of resulting products.

Substituent Effects in Mechanochemical Allowed and Forbidden Cyclobutene Ring-Opening Reactions

2021 ◽  
Author(s):  
Cameron L. Brown ◽  
Brandon H. Bowser ◽  
Jan Meisner ◽  
Tatiana B. Kouznetsova ◽  
Stefan Seritan ◽  
...  
Keyword(s):  
Ring Opening ◽  
Substituent Effects ◽  
Ring Opening Reactions

Substituent Effects in Regio- and Stereoselective Ring-Opening Reaction of Aziridines with Et3N·3HF for β-Fluoroamine Synthesis

Heterocycles ◽  
2018 ◽  
Vol 97 (2) ◽  
pp. 823
Author(s):  
Shigeru Sasaki ◽  
Satono Watanabe ◽  
Kaori Shiino ◽  
Yuko Yanaka ◽  
Shiho Kaneko ◽  
...  
Keyword(s):  
Ring Opening ◽  
Substituent Effects ◽  
Ring Opening Reaction

scholarly journals Radical Cations of Phenyl-Substituted Aziridines: What Are the Conditions for Ring Opening?

2005 ◽  
Vol 11 (4) ◽  
pp. 1294-1304 ◽  
Author(s):  
Carsten Gaebert ◽  
Jochen Mattay ◽  
Marion Toubartz ◽  
Steen Steenken ◽  
Beat Müller ◽  
...  
Keyword(s):  
Ring Opening ◽  
Radical Cations
Sign in / Sign up

Export Citation Format

Share Document