Carbocation-like isomerisations at radical sites precede methyl losses from ionised butanoic acid

McAdoo, David J.; Zwinselman, J. J.; Nibbering, Nico M. M.

doi:10.1039/p29850001703

Cited by 21 publications

(2 citation statements)

References 4 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For example, the 1,2-migration of the [C(OHh] +. radical cation occurs in the dissociation of carboxylic acids [8][9][10][11][12], and the 1,2-migration of the [C(OH)(OCH 3 ) ] +. radical cation in the case of esters [13].…”

Section: Resultsmentioning

confidence: 99%

Electron ionization induced fragmentation of macrocyclic amines C_nH_2n−1NH₂: Evidence for the rearrangement of aminocarbene radical cations and a comparison with long-chain esters

Mollova

Longevialle

1990

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

Section: Resultsmentioning

confidence: 99%

Electron ionization induced fragmentation of macrocyclic amines C_nH_2n−1NH₂: Evidence for the rearrangement of aminocarbene radical cations and a comparison with long-chain esters

Mollova

Longevialle

1990

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

“…McAdoo of the University of Texas Medical Center in Galveston, Texas, that showed extensive hydrogen and carbon skeletal rearrangements at increasing molecular ion lifetimes, concerned n ‐butanoic acid. Its molecular ion eliminates the original terminal methyl group and ethylene, containing the carbon and hydrogen atoms of positions 3 and 4, at lifetimes <10 −9 sec, but at longer times all the alkyl carbon atoms and all hydrogens participate in these reactions as shown by the extensive 13 C‐ and deuterium labeling applied (Zwinselman et al, 1983a; McAdoo et al, 1985). The methyl elimination is initiated by a 1,4‐H shift from the 3‐position to the carbonyl oxygen, followed by a 1,2‐shift of the protonated carboxyl group from the 2‐position to the 3‐position after which the methyl group can be eliminated to give protonated acrylic acid.…”

Section: Field Ionization Kinetics and Field Desorption Mass Specmentioning

confidence: 99%

Four decades of joy in mass spectrometry

Nibbering

2006

Mass Spectrometry Reviews

View full text Add to dashboard Cite

Tremendous developments in mass spectrometry have taken place in the last 40 years. This holds for both the science and the instrumental revolutions in this field. In chemistry the research was heavily focused on organic molecules that upon electron ionization fragmented via complex mechanistic pathways as shown by isotopic labeling experiments. These studies, including ion structure determinations, were performed with use of double focusing mass spectrometers of both conventional and reversed geometry, and equipped with various types of metastable ion scanning and collision-induced dissociation techniques developed by physical and analytical chemists. Time-resolved mass spectrometry by use of the field ionization kinetics method, developed by physical chemists, was another powerful way to unravel details of unimolecular gas phase ion dissociations. Then the development of new ionization methods, such as desorption chemical ionization, field desorption, and fast atom bombardment permitted not only to analyze unvolatile, thermally labile and higher molecular weight compounds, but also to study their chemical behavior in the gas phase, initially with use of double focusing instruments and later on with multisector and hybrid mass spectrometers. These ionization methods also enabled to study organometallic compounds and increasingly the field of medium-sized to large biomolecules, the latter being exploded in the last decade by the development of electrospray- and matrix-assisted laser desorption ionization/time-of-flight mass spectrometry. Another area of research concerned the bimolecular chemistry of organic ions with organic molecules in the gas phase. Initially this was performed with use of among others drift-cell ion cyclotron resonance spectroscopy, that later on was replaced by the developed method of ion trapping and Fourier transform ion cyclotron resonance. Combination of the latter with the afore-mentioned ionization methods has shifted also in this case the research on organic molecules to organometallic/inorganic systems, and predominantly to biomolecules in the last decade. This invited review will describe the research efforts made by the author's group over the last 40 years together with some personal experiences during his career.

show abstract

The chemistry of ionized enols in the gas phase

Tureček

1990

PATAI'S Chemistry of Functional Groups

View full text Add to dashboard Cite

Carbocation-like isomerisations at radical sites precede methyl losses from ionised butanoic acid

Cited by 21 publications

References 4 publications

Electron ionization induced fragmentation of macrocyclic amines C_nH_2n−1NH₂: Evidence for the rearrangement of aminocarbene radical cations and a comparison with long-chain esters

Electron ionization induced fragmentation of macrocyclic amines C_nH_2n−1NH₂: Evidence for the rearrangement of aminocarbene radical cations and a comparison with long-chain esters

Four decades of joy in mass spectrometry

The chemistry of ionized enols in the gas phase

Contact Info

Product

Resources

About

Carbocation-like isomerisations at radical sites precede methyl losses from ionised butanoic acid

Cited by 21 publications

References 4 publications

Electron ionization induced fragmentation of macrocyclic amines CnH2n−1NH2: Evidence for the rearrangement of aminocarbene radical cations and a comparison with long-chain esters

Electron ionization induced fragmentation of macrocyclic amines CnH2n−1NH2: Evidence for the rearrangement of aminocarbene radical cations and a comparison with long-chain esters

Four decades of joy in mass spectrometry

The chemistry of ionized enols in the gas phase

Contact Info

Product

Resources

About

Electron ionization induced fragmentation of macrocyclic amines C_nH_2n−1NH₂: Evidence for the rearrangement of aminocarbene radical cations and a comparison with long-chain esters

Electron ionization induced fragmentation of macrocyclic amines C_nH_2n−1NH₂: Evidence for the rearrangement of aminocarbene radical cations and a comparison with long-chain esters