The consecutive loss of two H2O molecules from protonated 1,2- and 1,3- cyclohexanediols in the gas phase: An example for the incidence of skeletal rearrangement in chemical ionization mass spectrometry

The consecutive dehydration of protonated molecules [MH]⁺ of 1,2- and 1,3-cyclohexanediols (cis and trans isomers) by loss of two H₂O molecules has been investigated. Analysis of ²H labelled compounds showed that loss of the first H₂O molecule represents a simple heterolysis, i.e. a dissociation without exchange of hydrogens between O—H and C—H bonds. Subsequent elimination of the second H₂O molecule in the process [MH–H₂O]⁺→[MH–2H₂O]⁺ followed several competing paths. The two major ones corresponded formally (with reference to an intact 6-ring skeleton) to 1,3- and 1,4-eliminations; in comparison, the alternative 1,2-elimination is only a minor route at most. At least for the 1,3-elimination, water loss from the [MH–H₂O]⁺ ions is not direct, but is associated with skeletal rearrangement, most probably of the Wagner-Meerwein-type, effecting contraction of the 6- to a 5-membered ring.     

Elimination of water from the molecular ion of cycloheptanol

Under electron impact cycloheptanol decomposes by four fragmentation paths: (1) α-cleavage with subsequent losses of C¹-C⁵ fragments, (2) elimination of water, (3) loss of the hydrogen atom from C-1 and (4) loss of the hydroxyl group. The mechanism of water elimination was investigated by means of deuterium labelling. 1,4-Elimination of water predominates in cycloheptanol, with the stereospecific cis-1,3-elimination also being operative. The loss of water is preceded by extensive exchange of the hydroxyl hydrogen with those of the ring. This is attributed to a very facile transannular interaction of the hydroxyl group with the C-3 to C-6 positions that are made accessible due to conformational properties of the 7-membered ring. A kinetic model is proposed, describing migrations of the ring hydrogen atoms.     

A combined time-resolved and stereospecific deuterium labelling study of the elimination of methanol from the molecular ion of methoxycyclohexane

It is shown by field ionization kinetics in combination with both site-specific and stereospecific D-labelling that the loss of a molecule of methanol from the molecular ion of methoxycyclohexane can occur via 1,4- and 1,3-eliminations. The 1,4-elimination predominates at molecular ion lifetimes of ≥10^?10.1 s. It is found that ～19% of this reaction channel corresponds to a stereospecific cis-elimination, whereas the remaining 81% is only site-specific. At molecular ion lifetimes of between 10^?10 and 10^?9 s, a very sudden increase of the 1,3-elimination is observed at the expense of the 1,4-elimination. A stereospecific loss of methanol, however, is not observed at all for the 1,3-elimination within the limits of error. Possible intermediates and reaction pathways, which can account for the observations made, are discussed.     

Mechanistic Details of the Fe+-Mediated C?C and C?H Bond Activations in Propane: A Theoretical Investigation

Quantum-chemical calculations employing a density-functional theory/Hartree-Fock hybrid method (B3LYP) have been used to explore the mechanistic details of the C? C and C? H bond-activation processes in propane mediated by a bare Fe⁺ ion. While the theoretically predicted results are in complete accord with all available experimental data, they give rise to a different mechanistic picture than envisaged previously. In contrast to earlier speculation, the activation barriers for the initial insertion steps of Fe⁺ into a C? H or C? C bond are found to be significantly below the Fe⁺ + C₃H₈ channel. The rate-determining steps for both, the C? C and the C? H bond activation branches of the [FeC₃H₈]⁺ potential-energy surface rather occur late on the respective reaction coordinates and are connected with saddle points of concerted rearrangement processes. The C? C bond activation, which leads to the exothermic reductive elimination of methane, occurs via the C? C inserted species and not as a side channel originating from a C? H inserted ion, as assumed hitherto. For the C? H bond-activation processes, which finally results in the exothermic expulsion of molecular hydrogen, two energetically similar reaction channels for an [1,2]-elimination exist. The results clearly show, that an [1,3]-H₂-elimination mechanism cannot compete with the [1,2]-elimination paths, in line with the experimental findings. Overall, a lower energy demand for the reductive elimination of methane compared to the loss of H₂ is obtained, straightforwardly explaining the preference of the former process observed experimentally.     

The mechanism for elimination of acetic acid from 1-acetoxy- and 2-acetoxytetralin

By employing deuterium substitution and metastable ion defocusing methods, it has been determined that 1-acetoxytetralin undergoes a highly regiospecific (>98%) 1,4-elimenation of acetic acid. The mechanism closely parallels that for loss of water from 1-tetralol in terms of specificity. However, unlike the water loss, which shows a significant kinetic isotope effect (K_H/K_D = 2.0) and a large release of translational energy (270 meV), the expulsion of acetic acid occurs without an isotope effect and with release of only 10 meV of kinetic energy. Competitive with acetic acid loss is the elimination of ketene which has been shown to occur by a 4-centered transition state. The 2-acetoxytetralin exhibits the more traditional 1,2-elimination of acetic acid which contrasts with a 1,3-elemination of water for the corresponding alcohol.     

Studies on the Conversions of Diols and Cyclic Ethers. Part 48. Dehydration of alcohols and diols on the action of dimethylsulfoxide

The transformations of 13 alcohols and 13 diols in the presence of a small amount dimethylsulfoxide (1/16 mol) were studied. Relationships were found between the type of the hydroxy compound and the selectivity of the transformation, and conclusions were drawn regarding the transformation mechanism. The ether formation observed with certain alcohols proceeds via a carbenium cation. The reaction conditions applied were found suitable for inducing water elimination from the ditertiary 1,2- and 1,3-diols (pinacol rearrangement, 1,2-elimination). From the 1,4- and 1,5-diols the corresponding oxacycloalkanes can be obtained in good yield. Cyclodehydration occurs by intramolecular nucleophilic substitution, via a concerted mechanism. The effect of DMSO is exerted directly, and protoncatalysis occurs simultaneously.     

The methoxycarbonylcarbene insertion into 1,3-dithiolane and 1,3-oxathiolane rings

Treatment of substituted 1,3-dithiolanes and 1,3-oxathiolanes with methyl diazoacetate in the presence of Rh₂(OAc)₄ effects ring expansion to the corresponding substituted 1,4-dithiane-2-carboxylates and 1,4-oxathiane-3-carboxylates. The sulfur ylides initially generated in these reactions undergo Stevens rearrangement in competition with both [2,3]-C-C-sigmatropic rearrangement and intramolecular fragmentation. In the case of 2-styryl-substituted 1,3-oxathiolane and 1,3-dithiolane, ring expansion on one-, three- and four-carbons subsequently takes place.     

The mechanisms of decomposition of the 1- and 2-phenyltetralin radical cations

Mechanisms for decomposition of 1- and 2-phenyltetralins were investigated using low resolution mass spectrometry and metastable ion techniques. Four primary decompositions were observed for 1-phenyltetralin radical cations: (1) the loss of C₆H₆ via a 1,4-elimination; (2) the elimination of ethene via competing losses from carbons 3 + 4 and carbons 2 + 3; (3) the loss of C₈H₈, probably through a stepwise Diels-Alder cycloreversion to expel styrene; and (4) the loss of methyl radical involving carbon 2 and possibly carbon 4. Three major decompositions were observed for 2-phenyltetralin radical cations: (1) the loss of C₈H₈, possibly through a Diels-Alder cycloreversion to expel styrene; (2) the loss of C₆H₆ via a 1,3 elimination; and (3) the loss of methyl radical from carbon 1. Various exchange reactions occur prior to these losses, but they proved to be incomplete even for metastable ions.     

Mass spectral cycloreversion reactions of 2-chloro-3,6-diaryl-3,4-dihydro-1,3,2-oxazaphosphorin-2-oxides

The mass spectral fragmentation modes of various 2-chloro-3,6-diaryl-3,4-dihydro-1,3,2-oxazaphosphorin-2-oxides—a novel ring system—reveal cycloreversion by two pathways. Retro Diels-Alder reaction by a stepwise mechanism is prominent in this system. The relative abundances of the enone and dienophile ions depend on the nature of the substituent attached to the double bond in this ring. Another retro Diels-Alder fragmentation process, involving the loss of PO₂Cl from the molecular ion, is preceded by a 1,3-allylic rearrangement and is the major fragmentation mode in the metastable time scale. Further fragmentation of the [M? PO₂Cl]⁺ imine ion seems to occur from cyclic dihydroquinoline intermediates by substitution elimination steps.     

Mass spectrometric fragmentation of isomeric 2-alkyl-substituted 1,3-indandiones and 3-alkylidenephthalides: a seven-step consecutive isomerization of regular and distonic molecular radical cations

The electron impact-induced fragmentation of 2,2-dimethyl- and 2-ethyl-1,3-indandione, 1 and 2, and their isomers, 3-isopropylidene- and 3-propylidenephthalide, 3 and 4, respectively, was studied in detail by mass-analysed ion kinetic energy (MIKE) and collision-induced dissociation (CID-MIKE) spectrometry, including ²H and ¹³C. labelled analogues of 1 and 2. In all regimes of internal energy, the molecular ions 1^+. ? 4^+. interconvert by up to seven consecutive, reversible isomerization steps prior to the main fragmentation processes, viz. loss of CH₃^. and C₂H₄. 1,3-Indandione and 3-methylenephthalide ions with identical alkylidene moieties (i.e. 1^+.?3^+. and 2^+.?4^+.) equilibrate rapidly and completely prior to fragmentation, whereas these pairs of isomers interconvert only slowly via a five-step rearrangement of the indandione ions 1^+.?2^+.. Distinct from the behaviour of simpler ionized carbonyl species, a 1,2-C shift of a (formally) neutral carbonyl group is found to occur along with that of a protonated one. Also distinct from simpler cases, methyl loss does not take place from the ionized enol intermediates formed within the interconversion 1^+.?2^+. of the diketone ions but rather from the n-propylidenephthalide ions 4^+.. This follows from CID-MIKE spectrometry of the [M ? CH₃]⁺ ions of 1–4 and two reference C₁₀H₇O₂⁺ (m/z 159) ions of authentic structures (protonated 2-methylene-1,3-indandione and protonated 1,4-naphthoquinone). The characteristic CID fragmentation of the C₁₀H₇O₂⁺ ions is rationalized. Finally, the multistep isomerization of ionized 1,3-indandiones apparently also extends to higher homologues [e.g. 5^+. from 2-ethyl-2-methyl-1,3-indandione (5) and 6^+. from 2,2-diethyl-1,3-indandione (6)]: the ionized phthaloyl group of 1,3-indandione radical cations 1^+., 2^+., 5^+. and 6^+., originally attached with its two acyl functionalities to the same carbon of the aliphatic chain, performs, in fact, a ‘multi-step migration’.     

Assigning structures to isomeric [C5H10]+ ions: The generation of ionized ethylcyclopropane from pentan-1-ol and 1-chloropentane

The charge-stripping mass spectra of the ten C₅H₁₀ isomers and of cyclopropane and propene have been re-evaluated. Oxygen is the preferred collision gas for the former group and helium for the latter pair. A con bined study of the low-energy mass spectra, charge-stripping mass spectra and appearance energy measurements had to the conclusion that loss of H₂O from ionized pentan-1-ol and loss of HCl from ionized 1-chloropentane both predominantly produce ionized ethylcyclopropane as the fragment ion. For the alcohol, a 1,4-elimination followed by an energetically favoured 1,2-H shift is involved, whereas for the halide a direct 1,3-elimination obtains.     

Steric effects in the mass spectra of the stereoisomers of decalin-1,3-diol and of 1,3-dimethoxy-decalin

The stereoisomers 1a–8a of decalin-1,3-diol have been synthesized by LAH-reduction of cis- and trans-decalin-1, 3-dione, respectively. With the exception of trans-decalin-1a,3e- and -1e,3a-diols, 7a and 8a, the stereoisomers have been isolated by column chromatography, and their configurations have been determined by ¹H-NMR, IR and chemical methods. It is shown by the aid of deuterated derivatives, that the elimination of H₂O, MeOH and CH₂O from the molecular ions of the stereoisomeric diols and di-O-methyl ethers, respectively, occurs predominantly by stereospecific reactions, if the ground state conformation of the molecule corresponds to the geometry of the transition state of the elimination reaction. The steric control of the fragmentations is greatly reduced, if conformational changes of the molecular ions have to occur prior to fragmentation. No clear steric effects are observed, if none of the conformations of the intact molecular ions corresponds to the transition state. These steric effects can be used to identify the various stereoisomers of decalin-1,3-diol and 1,3-dimethoxy-decalin by mass spectrometry.     

Reactions of 1-halocyclohexenes and methyl substituted 1-halocyclohexenes with potassium t-butoxide

Reactions of 1-halocyclohexenes and 1-halo-4-methylcyclohexenes with potassium t-butoxide (t-BuOK) in dimethyl sulfoxide and tetrahydrofuran have been shown to take place by three competing dehydrohalogenation mechanisms. These are: dehydrohalogenation across the C₁C₆ bond to give a cyclohexyne; dehydrohalogenation across the C₁C₆ bond to give a 1,2-cyclohexadiene: and prototropic rearrangement to the corresponding 3-halocyclohexene, followed by β-elimination to a 1,3-cyclohexadiene. The highly strained cyclohexyne and 1,2-cyclohexadiene intermediates react with t-BuOK to give 1-t-butoxycyclohexene, which is obtained in yields ranging from 5–20% in DMSO to about 60% in THF. Competitive with the substitution reaction is dimerization of 1,2-cyclohexadiene to tricyclo[6.4.0.0^2,7]-dodeca-2,12-diene, and 1,2- and 1,4-cycloaddition of 1,2- and 1,3-cyclohexadiene.     

Beitrag zur massenspektrometrischen retro-Diels-Alder-Reaktion: 1,2,3,4-Tetrahydrophenanthren. 35. Mitteilung über massenspektrometrische Untersuchungen

Contribution to the Mass Spectral retro-Diels-Alder Reaction: 1,2,3,4-Tetrahydrophenanthrene [1,4-¹³C]-1,2,3,4-Tetrahydrophenanthrene (1) was synthesized starting from [1,4-¹³C]-succinic acid. The mass spectral behavior (EI./MS., 70eV) of 1 is very similar to that of tetraline [2] concerning its loss of ethylene from the molecular ion. Similarly the fragmentation reaction of the synthetic precursors, ketones 7 and 8 , seems to partly undergo a carbon rearrangement reaction prior to the elimination of ethylene which is unlike to the behavior of α-tetralone.     

Mass spectra of some high molecular weight tetra(alkyl)silanes

The mass spectra of tetra(alkyl)silanes having one short and three long alkyl groups were recorded (C₂₀? C₃₂). These silanes did not give molecular ions, and the dominant course of fragmentation involved the loss of alkyl groups, followed by elimination of alkenes. The loss of alkyl groups, followed by elimination of alkenes. The loss of alkyl groups followed the sequence iso-Pr>Et, Pr,… C₁₄H₂₉» Me. With alkyl groups longer than hexyl, a rearrangement was observed in which n-alkanes were eliminated from the base ion. When the alkyl group was hexyl, the alkane eliminated was methane; when the alkyl group was heptyl, ethane was expelled; with octyl, it was propane; and with decyl, n-pentane was expelled. Deuterium labeling showed that at least two modes of rearrangement were occurring.     

Electron impact induced fragmentation of β-allenic and γ-acetylenic alcohols

The main fragmentation pathway of ionized hydroxyallenes (1) consists of a methyl loss. Extensive deuterium-labelling experiments indicate that the terminal allenic carbon is implied in this fragmentation. Collisional activation spectra indicate a propenyl-acylium structure (a) for these [M – CH₃]⁺ ions which can originate from a 1,4-hydroxyl migration followed by hydrogen rearrangements. Isomeric hydroxyacetylenes (2) behave similarly, also giving rise, by methyl loss, to acylium ions a. It is proposed that 2^{+ ˙} is irreversibly isomerized into 1^{+ ˙} by a 1,3-hydrogen transfer ‘catalysed’ by the hydroxy group. The proposed internal proton-bound complex justifies also the easier loss of water from 2⁺˙. Ethyl loss is also a prominent fragmentation for the hydroxyallene and hydroxy-acetylene homologues.     

Negative-ion fast atom bombardment mass spectrometry of N-phosphoamino acids

The fragmentation patterns of N-phosphoamino acids in negative-ion fast atom bombardment mass spectrometry (FABMS) showed different characteristics to those in positive-ion FABMS. Six typical N-diisopropyloxyphorphorylamino acids all had intense [M ? 1]^? peaks, and they underwent similar fragmentation pathways. In general, the elimination of one alkene molecule followed by the loss of one molecule of alcohol occurred. They also favoured an N → O rearrangement reaction, followed by fragmentation to (RO)₂ PO₂^? and (RO) (HO)PO₂^?.     

Etude par Spectrométrie de Masse de la Fragmentation d'une Série de Diols Aliphatiques

The mass spectrometric fragmentation of a series of diols having the general formula HO? (CH₂)_n? OH with n = 2-11 has been studied. Extensive labelling of n-butane-1,4 diol and n-hexane-1,6 diol with deuterium allows fragmentation modes to be proposed. The labelling reveals that intramolecular exchange of H atoms often precedes the fragmentation and becomes more important when the length of the chain increases.     

Stereochemical studies. Part 67. Saturated heterocycles. Part 52. The mass spectra of some condensed skeleton 1,3-oxazin-4-one derivatives

The mass spectrometric behaviour of twenty saturated heterocyclic compounds with a 1,3-oxazin-4-one moiety fused with cis or trans anellation to a cycloalkane ring (C₅-C₈) was studied. The roles of the C-2 and N-3 substituent(s) were found to be characteristic, while the size of the cycloalkane ring seemed to be unimportant. Some fragmentation processes involving breakdown of the oxazinone ring of the cis or trans isomers displayed significant stereoselectivity. A striking new decomposition process involving significant chlorine elimination from the molecular ion of some 2-p-chlorophenyl derivatives was observed and was studied in some detail.     

Mass spectra and structures of isomeric phenylaminopyrazoles

The processes involved in the dissociative ionization of isomeric phenylaminopyrazoles under the influence of electron impact were studied. The pathways of fragmentation of the molecular ion (M⁺) were proved rigorously by means of the spectra of the metastable ions. The empirical compositions of the fragment ions were confirmed by the high-resolution mass spectra. It was established on the basis of the mass spectra of the amino-group-deuterated analogs that M⁺ exists exclusively in the amide from. A rearrangement leading to the formation of benzodiazepine cation radicals precedes fragmentation of M⁺. The elimination of an HCN particle in the first step of the fragmentation of M⁺ does not involve the amino group. The pK_a values are presented for all of the investigated phenylaminopyrazoles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1381–1388, October, 1978.