Origin of the [C4H9O]+ ions in the mass spectrum of n-butyl ethyl ether

The mechanisms of formation of m/z 73 ions in the mass spectrum of the ionized title compound were investigated by deuterium substitution and by examining the decompositions of metastable ions. Two routes to the [C₄H₉O]⁺ ions were found in the normal spectrum. The ethyl lost by the major pathway contains the α- and β-hydrogens and a γ-hydrogen from the butyl group. The minor route involves the loss of ethylene from the [M? H]⁺ ion. There were metastable peaks for losses of ethyl, ethanol and methyl from the molecular ion. The ethyl contains the α- and β-methylenes and a γ-hydrogen, while the methyl is the δ-methyl of the butyl group. The labeling data rule out a previous mechanistic proposal for the loss of ethyl and support a mechanism involving stepwise isomerization to the sec-butyl ethyl ether molecular ion. However, the metastable ion chemistries of the molecular ions from the n- and sec-butyl ethyl ethers are highly dissimilar, perhaps due to decompositions from different electronic states. The n-pentyl methyl ether ions loses both ethyl and propyl, apparently following rearrangements to the 3-pentyl and 2-pentyl ether ions. Di n-butyl and n-butyl methyl ethers also give metastable peaks for loss of methyl, ethyl and the shorter chain alcohol.     

Use of metastable peak shapes in determining ring size in cyclic rearrangements in the mass spectrometer

A general method is described in which the mechanism of a reaction occurring in the ion source is inferred from the kinetic energy release accompanying further fragmentation of metastable product ions. In several cases the probe reaction occurred competitively by two mechanisms, and if high energy resolution is available this allows the detailed metastable peak shapes and not merely the average kinetic energy released, to be used to characterize the product ion formed in the fast (ion source) reaction. It is found that most substituted benzaldoxime O-methyl ethers undergo HCN elimination via a five-centered methoxyl transfer in the ion source, but that the p-methoxy substituted compound reacts through both a four- and a five-membered cyclic intermediate. The slow reactions of the corresponding metastable ions occur predominantly through a four-centered transition state in the p-methoxy compound and probably through both four- and five-membered intermediates for the less strongly electron donating substituents. The fraction of the excess energy of the products is higher than expected from a consideration of energy partitioning data for other systems involving activated complexes of comparable tightness.     

Unimolecular decomposition of ethoxytrimethylsilane

A study of the metastable spectra from ethoxytrimethylsilane and the mass shifts of the deuterium-labeled species permitted the rationalization of the fragmentation mechanism for forming all major ions in the mass spectrum. A new mechanistic pathway for the formation of [Si(CH₃)₃]⁺ (m/z 73) is demonstrated. A strong metastable ion for elimination of neutral acetaldehyde from the parent ion was observed despite the absence of a detectable daughter ion.     

The dependence of collision induced fragmentation pattern on the internal energy of the precursor ion

A Method is presented whereby product organic ions formed as the result of fragmentation of metastable ions can be selected on the basis of their internal energies. The method requires requires angular collimation of the beam of reactant ions issuing from the ion source and that the fragmentation of the metastable ions is studied in the first field free region of a reversed geometry double focusing mass spectrometer. The product ions that make up the metastable peak are allowed to fall on the intermediate resolving slit and, by adjusting the magnet current over a small range, ions contained in different regions of the peak can be allowed into the second field free region. It is shown that the position of an ion within the metastable peak correlates with its internal energy, ions near the edges of the peak being the least excited. The ions entering the second field free region can be investigated by collisional activation. This has been done for molecular ions of p-chlorophenol, methylbenzoate, benzaldehyde, m-chlorotoluene and n-butane. The in which the collision induced fragmentation pattern varies with internal energy of the ions is illustrated.     

Hydrogen shifts in the decomposition of branched chain alkane radical cations

Heat of formation data are consistent with formation of the t-butyl ion when C₃H₇ is eliminated from the molecular ion of 2-methylhexane. The 1–2 hydrogen shift that must accompany this reaction is confirmed via a deuterium isotope effect upon the low energy metastable decomposition.     

The scope of metastable peak observations

This short review focuses attention upon the present status of metastable ion studies with emphasis upon the relationship between metastable peak shapes, ion structur and fragmentation mechanisms. Some recommendations are made concerning nomenclature and the reporting of observations on Gaussian-type metastable peaks. Experimental methods for recording relative abundances of metastable peaks are critically appraised. The relationship between metastable ion phenomena and isomerization of gaseous ions is reviewed with particular attention drawn to the effect of rate-determining isomerizations. The shapes of Gaussian-type metastable peaks are discussed in some detail and selected examples from recent studies are used to show that such peaks may, by appropriate experiments, be separated into two Gaussian-type components thus revealing new features of the fragmentation reaction. The magnitude and significance of released kinetic energies, T, are considered and it is stated that few conclusions can be drawn from the evaluation of T alone; the importance of accurate thermochemical data as an aid to understanding and interpreting kinetic energy release data is emphasized. Other topics discussed include composite metastable peaks, metastable peaks produced in chemical ionization and field ionization and the partitioning of internal energy of the fragmenting ion into translational degrees of freedom of the products, for reactions with and without a reverse energy barrier.     

Mass spectra of phenoxyacetyl derivatives

The electron-impact-induced mass spectra of substituted N-phenylphenoxyacetamides are discussed. The structure of the rearrangement ion at m/z 108 is investigated and compared with the molecular ion of anisole by metastable ion and corrected collisionally activated dissociation spectra.     

On the nature of the transition state leading to elimination of ketene from acetanilide

Examination of metastable peak abundance ratios for the elimination of HNC vs. DNC from the [M-ketene]⁺· ion of various deuterium-labeled acetanilides shows that the structure of this ion resembles aniline rather than cyclohexadieneimine. This is suggested to hold also for substituted acetanilides.     

Mass spectrometry of heterocyclic compounds. VII—Evidence for common structure(s) of 1,2-benzisothiazole and benzothiazole molecular ions produced by electron-impact

1,2-Benzisothiazole and benzothiazole ion kinetic energy spectra, and metastable ion relative abundances of the same primary and secondary decomposition processes are compared. The results are interpretable as postulating slow (metastable) process(es) involving common structures and fast process(es)which are structurally dependent. Analogous indications are given by the interring H/D scrambling data, preceding the loss of DCN (or HCN) from 1,2-benzisothiazole-3-d₁ and benzothiazole-2-d₁ molecular ions, measured in either metastable or normal daughter ions at various electron beam energies.     

The [M?OH]+ ions of m- and p-ethylnitrobenzene: A common structure?

The structures of the [M? OH]⁺ ions of m- and pethylnitrobenzene have been compared by measurements of metastable ion spectra, collisional activation spectra, kinetic energy releases and critical energies for the formation of these ions and their subsequent decomposition. Normalized rates of fragmentation of metastable molecular ions and metastable [M? OH]⁺ ions have been compared for ion lifetimes up to 30 μs. The energy measurements fail to distinguish between the structures of the [M? OH]⁺ ions, but the normalized fragmentation rates and the collisional activation spectra show their structures to be different.     

The ion kinetic energy and mass spectra of isomeric methyl indoles

The mass spectra of the seven isomeric methylindoles were recorded and the [metastable ion]/[daughter ion] ratios for the reactions m/e 130 → m/e 103 and m/e 103 → m/e 77 have been obtained. The ratios indicate that the decomposing [M — 1] ions (m/e 130) from the 4, 5, 6 and 7 isomers are energetically similar as are the [M — 1] ions from the 2 and 3 isomers. The results observed for the m/e → 103 m/e 77 reaction showed that the decomposing m/e 103 ions from the 2, 3, 4, 5, 6 and 7 isomers all have the same energy distribution. N-Methylindole gave ratios which were similar to the 4 to 7 isomers at 70eV but different at 20 eV. The ion kinetic energy (IKE) spectra of all the isomeric methylindoles were also obtained and the results compared with the data obtained from the [metastable ion]/[daughter ion] approach. The results from the IKE spectra indicated that the energy distributions of the [M — 1] and [(M — 1) — HCN] ions from 1-methylindole and the [(M — 1) — HCN] ions from 2-methylindole could readily be distinguished from other isomers whose [metastable ion]/[daughter ion] ratios were similar. Thus by using both techniques certain ambiguities can be resolved.     

A test of the concept of ‘charge localisation’ in methionine

A previous re-investigation of methionine has shown that the [C₂H₅S]⁺ ion is generated via rather complicated routes from the molecular ion. This has been interpreted as evidence against charge localisation in the fragmentation of the title compound. Deuterium labelling, high resolution mass measurements and metastable transitions have revealed, however, that the formation of the [C₂H₅S]⁺ ion is not in contradiction with the predicting capabilities of the concept of charge localisation.     

Vergleichende Untersuchung von Reaktivitäten und Ionenstrukturen beim monomolekularen Abbau isomerer Hydroxyzimtsäuremethylester unter Elektronenbeschuss

Comparative investigation of reactivities and ion structures upon electron impact induced degradations of the isomeric hydroxy cinnamic acid methyl esters By analysis of energy release data in metastable peaks it is shown that m- and p-hydroxy cinnamic acid methylesters retain specific structural features upon degradation under electron impact, although their spectra are very similar and the shapes of the metastable peaks due to the initial methoxy cleavage are identical. A pronounced charge radical localization in the molecular ion is indicated. The o-isomer is found to yield a coumarin type structure by elimination of methanol, whose further degradation by decarbonylation involves at least three different mechanisms. The resulting ion structures are different from benzofuran.     

Consecutive reactions in the vitamin D series. A New insight into the mechanism of vitamin D and provitamin D isomerizations in the mass spectrometer

The individual steps of the consecutive reactions arising from metastable molecular ions, derived from vitamin D₃, vitamin D₂ and their respective provitamins (7-dehydrocholesterol, ergosterol), were examined in different field-free regions of a triple-sector mass spectrometer of B/E/E geometry. The comparison of the translational energy release (T) and the metastable peak shapes corresponding to these reactions, as well as unimolecular and collision-induced dissociation mass-analysed ion kinetic energy spectra, showed that there are probably two structures of the [M – H₂O]⁺˙ and [M – CH₃˙]⁺ ions depending upon whether the respective ions are formed in the ion source through high-energy reactions, or from the fragmentation of metastable molecular ions through slow, low-energy processes which occur in the first field-free region.     

A feature of the fragmentation mechanism of exo-2-norbornyl chloride. Stereoselective hydrogen atom abstraction revealed by metastable ion studies

The position of deuterium in the products of the addition of HCL and DCI to exo 5, 6-d₂ norbornene has been determined mass spectrometrically by measuring metastable ion abundances. The results show a stereo-selective hydrogen atom abstraction when the molecular ion of exo-2-norbornyl chloride fragements by loss of a chloroethyl radical.     

Kinetic energy release in metastable ions from β-keto esters

The kinetic energy release, T, in metastable ion transitions accompanying the main fragmentation reaction by electron impact has been determined for methyl-, ethyl- and propyl-pivaloyl acetates. The measurements have been made using a MAT 311 mass spectrometer with inverse Nier–Johnson geometry, by high voltage and mass-analysed ion kinetic energy methods. The peak width at 50% height has been used in the calculations. The T values and the shape of the metastable peaks are correlated to reaction types and to the alcohol radical.     

Studies of consecutive reactions of organic ions in a reversed geometry mass spectrometer

Over thirty consecutive reactions of a type m₁⁺ → m₂⁺ → m₃⁺ have been studied in a variety of organic compounds using a reversed geometry mass spectrometer. Two field free regions allow the separation of the two steps that make up the consecutive reaction sequence. Translational energy release measurements are used in the comparison of m₂⁺ ions formed as a result of a high energy process in the ion source with m₂⁺ ions formed as a product of a metastable decomposition. In some cases the structures of such ions have been found to be different. Examples have also been found where consecutive fragmentations of metastable ions do not occur although, when higher energy ions within the source are studied, the two-step reaction does take place. Furthermore, it has been found that a control over ion internal energy may be achieved by selecting portions of a peak due to the fragmentation of a metastable ion. Unimolecular reactions may then be used to study the reactivity of such ‘energy-selected’ ions; collision induced reactions can be used to study the structure of both the reactive and unreactive energy selected ions.     

Metastable ions in chemical ionization

The ion [C₃H₅]⁺ generated in a chemical ionization source by a variety of methods, including protonation and charge exchange, exhibits a metastable peak for H₂ loss which is two orders of magnitude weaker than that formed in an electron impact source. The stable [C₃H₅]⁺ ions generated by electron impact and chemical ionization undergo collision-induced dissociation to a comparable extent, both losing H₂ by only one of the two competitive mechanisms observed for metastable ions. In contrast to the behavior of [C₃H₅]⁺, the molecular ions of p-substituted nitrobenzene, generated by charge exchange at high source pressure, yield composite metastable peaks for NO loss which are very similar in shape and intensity to those generated by electron impact. The contrasting behavior of the metastable ions extracted from high pressure ion sources in the two systems may be due to differences in the efficiencies of quenching of the ionic states responsible for fragmentation as metastable ions. It is noteworthy that the NO loss reactions require considerably lower activation energies than does the H₂ loss reaction.     

The structures of [C5H5O]+ ions formed from isomers of nitrophenol in the gaseous phase

Translational energy release measurments on metastable ions are used in the comparison of the structures of isomeric ions. Metastable ions, m₂⁺, formed from m₁⁺ ions as the result of a high energy process in the ion source are compared with isomeric metastable ions formed as daughters from fragmentation of metastable m₁⁺ ions in a field. In the case of o-, m- and p-nitrophenol the structure of the [C₅H₅O]⁺ ions formed from [C₆H₅O]⁺ ions by these two independent methods is different as verified by comparison of the behaviour of [C₅H₅O]⁺ ions formed from several other compounds.     

Specific and random processes in the fragmentation of cyclohexanol

The mass spectra of cyclohexanol and eleven deuterated analogues have been studied. Detailed mechanisms, consistent with peak intensity and defocused metastable abundance data, have been proposed for the loss of water from the molecular ion and for the subsequent loss of a methyl radical. The importance of specific eliminations and the absence of any processes involving complete hydrogen atom scrambling in these fragmentations has been demonstrated. Scrambling has also been shown to be absent in the formation of the base peak m/e 57, the [C₃H₅O]⁺ ion.