Zum Mechanismus massenspektrometrischer Fragmentierungsreaktionen—IXSterische Effekte in den Massenspekten der Stereoisomeren von Decalin-2,3-diolen,Decalin-2,4-Diolen und Ihen Dimethyläthern

The mass spectra of all stereoisomers of decalin-2,3-diol, the corresponding dimethyl ethers and of some deuterated derivatives are discussed. The mass spectra of isomeric decalin-2,3-diols differ only slightly in ion intensities. The mass spectra of the stereoisomeric 2,3-dimethoxy-decalins are nearly identical within the series of transand cisderivatives. A mass spectrometric identification of the stereoisomers of these compounds is therefore diffucult. Stereoselective eliminations from the molecular ion are not observed. The mass spectra -of stereoisomeric decalin-1,4-diols show characteristic differences in the intensities of the[M ? H₂O]⁺˙-ions, which can be related to the geometry of the molecules in a similiar mode as was the case with cyclohexane-1,4-diols, The sterechemical control of the elimination of H₂O from the molecular ions has been confirmed by deuterium labelling. The mass spectra of stereoismeric 1,4-dimethoxy-decalins also differ characteristically in the intensities of the [M ? CH₃OH]⁺˙ ions. Furthermore peak due to the [M ? CH₂O]⁺˙ ions are only observed in the mass spectra of those stereoisomers, which have at least one conformation with a short distance between the two methoxy. The stereospecifity of the CH₃OH- and CH₂O-eliminationjs has also been determined by deuterium labelling.     

Stereochemical effects in the electron impact mass spectra of cis-trans isomeric 1,2,3,4-tetramethylcyclohexanes

The mass spectra of six cis-trans isomeric 1,2,3,4-tetramethylcyclohexanes are discussed. The intensity ratio of [M? CH₃]⁺/[M? C₂H₅]⁺ correlates with the strain energies of the stereoisomers. Therefore, the identification of cis-trans isomers is possible by means of their mass spectra. The mass spectra of deuterium labelled compounds demonstrate favoured fragmentation of the axial methyl groups and ring opening between the cis substituted carbon atoms of the cyclohexane.     

Fingerprinting stereoisomers by survivor-ion mass spectrometry

Survivor-ion mass spectrometry is used to distinguish stereoisomeric cis- and trans-4-methylcyclohexanol. The method involves producing ions by electron impact ionization and submitting them without mass selection to collisional neutralization and reionization, followed by selective monitoring of non-dissociating ions. The differences in the electron impact mass spectra of the stereoisomers, due to the different fragment ion elemental compositions and structures, are highlighted by collisional neutralization with Xe, NO and CH₃SSCH₃, followed by reionization with oxygen. The differences in the survivor-ion spectra are due to different neutralization efficiencies of the isobaric and isomeric ions produced by electron impact ionization, different stabilities of the intermediate neutral species, different reionization efficiencies and reionized ion stabilities. Neutralization-reionization spectra of the C₇H₁₂^+., C₆H₉⁺, C₃H₆O^+. and C₃H₅O⁺ ions from stereoisomeric 4-methylcyclohexanols are also reported.     

Mass spectrometric investigation of stereosomeric 1,2-dimethyl-4-substituted decahydroquinol-4-ol N-oxides. Concerning the configuration of the asymmetric nitrogen atom

The main fragmentation pathways of the N-1, C-2 and C-4 stereoisomers of the 1,2-dimethyl-4-R-transdecahydroquinoline-4-ol N-oxides (R=C?CH, CH?CH₂ and C₂H₅) under electron impact are discussed. The correlation between the mass spectrometric chromatographic behaviour and the configuration of polar groups in the N-oxides examined is discussed. The mass spectra of the N-1 stereoisomers may be subdivided into two groups, depending only on the orientation of N→O group and not of the 4-OH group. The spectra of N-oxides with the axial N-oxide group reveal less intense ions and much more intense [M? CH₃]⁺, [M? O]⁺, [M? OH]⁺ and ions, whereas in the spectra of their equatorial epimers the abundance of the ions exceeds the intensities of the latter ions.     

Stereochemical effects in the electron impact mass spectra of cis–trans isomeric 1,2,3,5-tetramethylcyclohexanes and some trimethylcyclohexanes

The mass spectra of 10 isomeric trimethylcyclohexanes and six cis–trans isomeric 1,2,3,5-tetramethylcyclohexanes are discussed. The thermochemically stable isomers show a higher abundance of the [M? CH₃]⁺ ions and a lower abundance of the [M? C₂H₅]⁺ ions than the strained isomers. The log of the intensity ratio for loss of methyl and ethyl from the molecular ions correlates well with the strain energies and with the mean number of gauche arrangements of the stereoisomers.     

Mass spectra of chlorinated esters: 2—Methyl mono- and dichlorobutanoates

The mass spectral fragmentations of methyl mono- and dichlorobutanates have been studied. Deutrium labelling and metastable ion analysis were used to elucidate the fragmentation mechanisms. The molecular ion peaks of the esters are weak and show only in the spectra of the monochloro isomers. A McLafferty rearrangement gives the base peaks in the spectra of methyl 2-chloro-, 4-chloro- and 4,4-dichlorobutanoate; α-cleavage, [COOCH₃]⁺, in methyl 2,2- and 2,4-dichlorobutanoate; [M? Cl]⁺, in methyl 3-chlorobutanoate; [M? Cl? HCl]⁺, in methyl 3,4-dichlorobutanoate; [M? Cl? CH₂CO]⁺, in methyl 3,3-dichlorobutanoate and [M? Cl? COOCH₃]^+˙, in methyl erythro- and threo-2,3-dichlorobutanoate. The mass spectra of the stereoisomers are nearly identical, the loss of a chlorine atom and the McLafferty rearrangement giving the higher peaks in the spectrum of the threo form.     

Mass-spectrometric differentiation of diexo- and diendo-fused isomers of norbornane/ene-condensed 2-thiouracil and 1,3-thiazino[3,2-a]-pyrimidine derivatives: Stereoselectivity of retro-Diels-Alder fragmentations under EI and CI conditions

The stereoisomers of the title compounds produce nearly identical electron ionization (EI) mass spectra, which are dominated in the case of the norbornene-condensed derivatives by retro-Diels-Alder (RDA) fragmentation of the hydrocarbon ring. The RDA fragmentation mainly occurs with H transfer and gives rise to [M-C₅H₅]⁺. For the norbornane-condensed derivatives, the main fragmentation routes include the formation of [M-C₅H₇]⁺ (protonated thiouracil) and [M-C₇H₉]⁺ (only from thiazinopyrimidines). The latter species are formed via RDA decomposition of the pyrimidone subunit of the heterocyclic system, a process previously observed for cyclohexane-condensed analogs of these compounds. Only minor differences could be detected between the EI spectra of the diexo and diendo isomers. Under chemical ionization (CI) conditions, the norbornane-condensed compounds produced no significant fragment peaks with either isobutane or methane as reagent gas. In contrast, the isobutane and methane CI spectra of the norbornene-condensed compounds exhibited prominent peaks of [MH-C₅H₆]⁺ and [(M+C_xH_y)-C₅H₆]⁺ originating from moderately stereoselective RDA fragmentations. The relative abundances of the RDA ions obtained from the respective stereoisomers with the same reagent gas were consistently different over a range of experimental conditions. The non-occurrence of RDA fragmentation of the thiazinopyrimidine ring under CI conditions suggested that its energy of activation is higher than that for either of the norbornene-ring RDA fragmentations (with or without H transfer) observed under EI and CI conditions.     

Mass spectrometry of bis-quinolizidine alkaloids: 13-keto and hydroxy substituted derivatives of sparteine and lupanine

The mass spectral fragmeutations of 13-ketosparteine, 13-hydroxysparteine, 13-epihydroxysparteine, 13-ketolupanine, 13-keto-α-isolupanine, 13-hydroxylupanine, 13-hydroxy-α-isolupanine, 13-epihydroxylupanine and 13-epihydroxy-α-isolupanine are reinvestigated and discussed. Fragmentation pathways, elucidation of which was assisted by accurate mass measuiements and metastable transitions, are proposed. The fragmentation assignments are not consistent with those previously reported in the literature. Many fragment species of the same m/z (low-resolution spectra) are composed of two fragment ions of different elemental compositions (high-resolution spectra). The obtained data create a safe basis for distinguishing structural and stereoisomers.     

Etude par spectrométrie de masse des O-isopropylidène-1,2-thréo- et -érythro-furannoses et des quatre désoxy-5-O-isopropylidène-1,2-pentofurannoses

The mass spectra of the O-isopropylidene derivatives of threo- and erythro-furanose and those of the four C(4) methylated stereoisomers have been studied. Fragmentation modes based upon deuterium labelling, metastable peaks and high-resolution measurements are proposed. Each stereoisomer can be characterized by its low-resolution mass spectrum.     

A study of the fragmentation of cyclopentane-1,3-diols and of cyclopentane-1,2,4-triols

The mass spectra of the two cyclopentane-1,3-diol and of the three cyclopentane-1,2,4-triol stereoisomers have been studied. Extensive deuterium labelling allows the detection of complex processes, especially for the elimination of water from the [M – H_2OO]⁺· and [M]⁺· ions.     

Differentiation of stereoisomers with electron impact mass spectrometry: (E)- and (Z)-α-hydroxyoximes

The electron impact mass spectra of 5,8-diethyl-7-hydroxydodecan-6-one (Z)-oxime and (E)-oxime provide a basis for distinguishing these stereoisomers.     

Electron and chemical ionization mass spectrometry in stereochemical differentiation of some 1,3-amino alcohols

Mass spectral fragmentations of two cyclopentane, eight cyclohexane and four norbornane/one 1,3-amino alcohols were studied under electron ionization (EI) by low-resolution, high-resolution, metastable ion analysis and collision-induced dissociation (CID) techniques. All stereoisomeric compounds gave rise to identical 70 eV EI mass spectra. However, the spectra of positional isomers clearly differed. The main fragmentation pathway for the saturated compounds began as an α-cleavage reaction with respect to the nitrogen atom. For the norbornene compounds a retro-Diels—Alder reaction was favoured. Relative to the aminomethyl-substituted compounds the fragmentation patterns for the compounds having the amino group connected directly to the ring were more complicated. The chemical ionization (CI) mass spectra were recorded using ammonia, isobutane, methane, dichloromethane and acetone as reagent gas. From the norbornane/One compounds the di-exo isomers decomposed more easily than the di-endo isomers with most of the reagent gases used. Differences between stereoisomers were observed directly only under methane CI. The decomposition products of the [M + H]⁺ ions generated under ammonia and isobutane CI were studies by recording their CID mass spectra. These spectra allowed the differentiation of the stereoisomers, at least to some extent.     

Study of two diastereomeric pairs of regiosomeric 2-isoxazolines by tandem mass spectrometry with electron impact ionization

On electron impact (EI) ionization, two cis/trans pairs of 4-methyl-5-phenyl and 4-phenyl-5-methyl regioisomeric 3-carbethoxy-2-isoxazolines showed normal mass spectra and mass-analysed ion kinetic energy (MIKE) spectra of metastable (MI) and collision-activated (CA) molecule ions, allowing unequivocal differentiation of the regioisomers. The cis/trans stereoisomers of each regioisomer showed very similar normal mass spectra. Very interestingly, the cis- and trans-4-phenyl-5-methyl stereoisomers appeared reasonably differentiated by the molecule ion MIKE spectra, whereas the 4-methyl-5-phenyl regioisomeric pair of stereoisomers did not. The influence of the phenyl substituent to the fragmentation processes was notable. Some fragments of interest were studied by comparison of their MIKE spectra with those of model ions, generated by EI from suitable substrates, including (i) the isomeric α,β-unsaturated oxime, namely ethyl (Z)-2-(hydroxymino)-3-methyl-4-phenylbut-3-enoate, a by-product of importance for the mechanism(s) of the addition/cycloaddition reactions of nitrile oxides to alkenes and (ii) trans-β-methylstyrene, a dipolarophilic reactant in the same reactions. The favoured heterocyclic C(5)–O(1) bond cleavage occurred only for the ionized 4-methyl-5-phenyl 2-isoxazoline pair, leading to a distonic ion of relevance, as it can represent either a reasonable precursor for both the isomerization to the ionized α,β-unsaturated oxime and the EI-induced cycloreversion yielding ionized β-methylstyrene, or the ionized form of a zwitterionic intermediate, which had been proposed previously for the addition/cycloaddition mechanism(s) in the solution phase, currently under study.     

Etude par spectrométrie de masse des cyclopenténols,cyclopentène-diols-3,4 et cyclopentène-triols-3,4,5

The mass spectra of cyclopentene-1-ol-3, -1-o1-4, those of cis- and trans-cyclopentene-3,4-diol and of the three stereoisomers of cyclopentene-3,4,5-triol have been studied. Decomposition modes based upon results obtained using deuterium labelled analogues are discussed.     

Outstanding Chiroptical Properties: A Signature of Enantiomerically Pure Alleno–Acetylenic Macrocycles and Monodisperse Acyclic Oligomers

A second series of shape‐persistent alleno–acetylenic macrocycles and monodisperse acyclic oligomers with conformationally less flexible backbones were synthesized in enantiomerically pure form by short, high‐yielding routes starting from optically active 1,3‐diethynylallenes. All seven stereoisomers—two pairs of enantiomers and three achiral stereoisomers—in the macrocyclic series were separated and configurationally assigned. The electronic circular dichroism (ECD) spectra of the D₂‐symmetric, (P,P,P,P)‐ and (M,M,M,M)‐configured macrocycles display remarkably intense chiroptical responses. A strong amplification of chirality is observed in the acyclic oligomeric series. Their preference for helical secondary structures of one handedness was supported by X‐ray analysis and computational studies. This new set of data provides proof that outstanding ECD responses are a hallmark of alleno–acetylenic macrocyclic and acyclic oligomeric chromophores.     

Stereospecific fragmentation of starfish polyhydroxysteroids in electrospray ionization mass spectrometry

Electrospray ionization mass spectra and collision-induced dissociation mass spectra in positive and negative ion modes of five polyhydroxysteroid compounds from starfish were studied. Tandem mass spectra exhibit extensive fragmentation, including sequential neutral losses of H₂O molecules and cleavages in the tetracyclic nucleus and side chains. The relative intensity of some peaks in tandem mass spectra enables stereoisomers with the different orientations of the hydroxyl group at C15 in the tetracyclic nucleus to be distinguished. Some data on the fragmentation mechanisms were obtained by H–D exchange and mass spectrometry analysis.     

Etude par spectrométrie de masse de la fragmentation des cyclopentane-triols-1,2,3, des cyclopentane-tétrols et des cyclopentane-pentols

The mass spectra of the three cyclopentane-1,2,3-triols, six cyclopentane-tetrols and four cyclopentane-pentols stereoisomers have been studied. Complex processes, especially regarding the H₂O eliminations, were detected by extensive deuterium labelling.     

Stereochemical applications of mass spectrometry. II—Chemical ionization mass spectra of isomeric dicarboxylic acids and derivatives

The H₂ and CH₄, chemical ionization mass spectra of the cis dicarboxylic acids, maleic and citraconic acid, show much more extensive loss of H₂O from [MH]⁺ than the trans isomers, fumaric acid and mesaconic acid. Similarly, esters of maleic acid show a much more facile loss of ROH (R=alkyl or phenyl) from [MH]⁺ than do esters of fumaric acid. Similar differences are observed in the chemical ionization mass spectra of the isomeric phthalic and isophthalic acids and derivatives, where the ortho isomers show more extensive fragmentation of [MH]⁺ than the meta isomers. The facile fragmentation of [MH]⁺ for the cis and ortho isomers is attributed to ROH elimination involving interaction between the two carboxylate functions and forming the stable cyclic anhydride structure for the fragment ion. By contrast ROH elimination from [MH]⁺ for the trans and metu isomers requires a symmetry-forbidden [1,3]-H migration in the carboxyl protonated species and cannot lead to the cyclic anhydride structure. The chemical ionization mass spectra of cis and trans cyclohexane-1,2-dicarboxylic acids are essentially identical and show extensive fragmentation of the [IMH]⁺ ion. Experiments using deuterium labelling show extensive carboxyl group interactions for both isomers. The chemical ionization mass spectra of maleanilic and phthalanilic acids and of the related anhydrides and imides also are reported, as are the electron impact mass spectra of diphenyl maleate, diphenyl fumarate, diphenyl phthalate, maleanilic acid and phthalanilic acid.     

Mass spectrometric studies of structural isomers—II: Mono-and bicyclic C6H10 molecules

The electron-impact-induced ionization and fragmentation of six C₆H₁₀ structural isomers have been studied in order to determine the effect of isomerism upon their mass spectrometric behavior. The 70 eV mass spectra, metastable transitions and appearance potentials of the principal ions are reported. Significant differences between the mass spectra of the six isomers were observed; however, metastable transition and appearance potential data indicate that the fragmentation path-ways are the same for all the C₆H₁₀ molecules. Experimentally determined ionization potentials for the structural isomers are presented and compared to ionization potentials calculated by the bond orbital method. Utilizing fragmentation pathways deduced from general features in the mass spectra and from observed metastable transitions, we calculated heats of formation (ΔH_f) for the observed principal ions and compared these values to ΔH_f values for isomeric ions from other molecules.