Fragmentation of cyclobutane derivatives upon electron impact: Transformation pathways elucidated by mass spectrometric methods and semiempirical quantum chemical calculations

I. Pálinkó, P. Szabó, Béla Török, Z. Kele, Irén Kapocsi

Research output: Contribution to journalArticle

Abstract

The fragmentation behaviour of cyclobutane derivatives (carboxylic acids, esters, cyclobutanediols, silyl ethers of the hydroxy compounds) was first studied by the GC/MS method under electron impact (EI) ionization. Then, in order to establish the sequence of transformations, MS/MS, and in situ deuteration as well as accurate mass measurements, were performed. Analysis of these measurements revealed characteristic transformation pathways: (i) the substituents were easily cleaved, (ii) in most cases the cyclobutane ring was opened with the rupture of the C-C bonds opposite to each other, (iii) upon ring opening, the most substituted ring C-C bond was cleaved first and preferentially (iv) primary fragmentation was followed by secondary reactions including further cleavage of the ions as well as rearrangement reactions. For cyclobutanediols and their silyl ethers symmetric ring scission was observed providing only one primary fragment with m/z half that of the molecular weight. This type of fragmentation was consistent with semiempirical quantum chemical calculation.

Original languageEnglish
Pages (from-to)1771-1776
Number of pages6
JournalRapid Communications in Mass Spectrometry
Volume12
Issue number22
Publication statusPublished - 1998

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Cyclobutanes
Ethers
Derivatives
Impact ionization
Electrons
Carboxylic Acids
Esters
Molecular weight
Ions

ASJC Scopus subject areas

  • Analytical Chemistry
  • Spectroscopy

Cite this

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title = "Fragmentation of cyclobutane derivatives upon electron impact: Transformation pathways elucidated by mass spectrometric methods and semiempirical quantum chemical calculations",
abstract = "The fragmentation behaviour of cyclobutane derivatives (carboxylic acids, esters, cyclobutanediols, silyl ethers of the hydroxy compounds) was first studied by the GC/MS method under electron impact (EI) ionization. Then, in order to establish the sequence of transformations, MS/MS, and in situ deuteration as well as accurate mass measurements, were performed. Analysis of these measurements revealed characteristic transformation pathways: (i) the substituents were easily cleaved, (ii) in most cases the cyclobutane ring was opened with the rupture of the C-C bonds opposite to each other, (iii) upon ring opening, the most substituted ring C-C bond was cleaved first and preferentially (iv) primary fragmentation was followed by secondary reactions including further cleavage of the ions as well as rearrangement reactions. For cyclobutanediols and their silyl ethers symmetric ring scission was observed providing only one primary fragment with m/z half that of the molecular weight. This type of fragmentation was consistent with semiempirical quantum chemical calculation.",
author = "I. P{\'a}link{\'o} and P. Szab{\'o} and B{\'e}la T{\"o}r{\"o}k and Z. Kele and Ir{\'e}n Kapocsi",
year = "1998",
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journal = "Rapid Communications in Mass Spectrometry",
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TY - JOUR

T1 - Fragmentation of cyclobutane derivatives upon electron impact

T2 - Transformation pathways elucidated by mass spectrometric methods and semiempirical quantum chemical calculations

AU - Pálinkó, I.

AU - Szabó, P.

AU - Török, Béla

AU - Kele, Z.

AU - Kapocsi, Irén

PY - 1998

Y1 - 1998

N2 - The fragmentation behaviour of cyclobutane derivatives (carboxylic acids, esters, cyclobutanediols, silyl ethers of the hydroxy compounds) was first studied by the GC/MS method under electron impact (EI) ionization. Then, in order to establish the sequence of transformations, MS/MS, and in situ deuteration as well as accurate mass measurements, were performed. Analysis of these measurements revealed characteristic transformation pathways: (i) the substituents were easily cleaved, (ii) in most cases the cyclobutane ring was opened with the rupture of the C-C bonds opposite to each other, (iii) upon ring opening, the most substituted ring C-C bond was cleaved first and preferentially (iv) primary fragmentation was followed by secondary reactions including further cleavage of the ions as well as rearrangement reactions. For cyclobutanediols and their silyl ethers symmetric ring scission was observed providing only one primary fragment with m/z half that of the molecular weight. This type of fragmentation was consistent with semiempirical quantum chemical calculation.

AB - The fragmentation behaviour of cyclobutane derivatives (carboxylic acids, esters, cyclobutanediols, silyl ethers of the hydroxy compounds) was first studied by the GC/MS method under electron impact (EI) ionization. Then, in order to establish the sequence of transformations, MS/MS, and in situ deuteration as well as accurate mass measurements, were performed. Analysis of these measurements revealed characteristic transformation pathways: (i) the substituents were easily cleaved, (ii) in most cases the cyclobutane ring was opened with the rupture of the C-C bonds opposite to each other, (iii) upon ring opening, the most substituted ring C-C bond was cleaved first and preferentially (iv) primary fragmentation was followed by secondary reactions including further cleavage of the ions as well as rearrangement reactions. For cyclobutanediols and their silyl ethers symmetric ring scission was observed providing only one primary fragment with m/z half that of the molecular weight. This type of fragmentation was consistent with semiempirical quantum chemical calculation.

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