Mass spectral fragmentation studies in usnic acid and related compounds

A study of the fragmentation patterns of the naturally occurring lichen substance, usnic acid (I) and various other chemically and biochemically derived compounds is reported and discussed. From these results it is demonstrated that the characteristic fragmentation patterns observed are of considerable utility in determining not only the substitution patterns on these highly oxygenated molecules, but also the structural elucidation of new compounds within the series.     

Mass spectral fragmentation reactions of a therapeutic 4-azasteroid and related compounds

Mass spectra were acquired for a therapeutic 4-azasteroid (dutasteride), and some related compounds, using various ionization conditions (EI, CI, APCI and ESI) in both positive and negative ion modes. The ionization and fragmentation behavior of the compound dutasteride, its precursors and several analogs is reported. Positive atmospheric pressure chemical ionization (APCI+) and positive electrospray ionization (ESI+) produced distinctive collision-induced dissociation (CID) spectra for the respective [MH]+ ions of dutasteride. The spectral differences are attributed to ion populations having either different structures or different internal energy distributions (as a consequence of the method of ionization). Irrespective of their origin, the protonated molecules undergo interesting fragmentation reactions when collisionally activated. The identity of the major fragmentation products was confirmed by accurate mass measurement. The negative APCI mass spectrum of dutasteride displays extensive dehydrohalogenation, apparently due to the thermal component of the APCI process. Some of the resulting radical anions display remarkable stability toward collisional decomposition. Details of the fragmentation behavior for the negative ion species and their relationship to the positive ion results are discussed.     

Mass spectral fragmentation of functionalized lanostanes-I

Mass spectra of various functionalized lanostanes and their deuterated analogs are compared. It is proposed that the transfer of a hydrogen from the 18-methyl group to the 11-oxo group via a McLafferty rearrangement is made geometrically possible by prior ionization of the 13,14 bond which allows an optimum interatomic distance between the oxygen and hydrogen to be acquired; the 8,9 double bond is a requisite for electronic induction of this specific process. Transfer of the hydrogen from the 7β-hydroxy group to position 14 is implicated in the mass spectrum of 3β-acetoxy-7β-hydroxy-5α-lanostan-11-one.     

Mass spectral fragmentation and rearrangement of isatin derivatives

Mass spectral fragmentation pathways were formulated for 1-alkylisatins, 1-alkyl-3-arylimino-2-indolinones and 3-arylimino-2-indolinons bearing no substituent at the 1-position. Deuterium-labelled and ¹³C-labelled compounds were utilized in this study. An interesting rearrangement of the 1-alkyl compounds, in which the 1-alkyl substituent is incorporated into a fulvene ion, was established.     

Mass spectral fragmentation of benzofurazan-1-oxide

Fragmentations in the mass spectrum of benzofurazan-1-oxide have been studied using linked scan, accelerating voltage scan and mass-analysed ion kinetic energy spectrometric techniques. Major pathways involve NO·+ NO· and NO·+CO loss, these double losses occurring in such rapid succession as to appear ‘concerted’ in some experiments. Minor pathways are loss of CO₂, C₂N₂O₂, or C₂HN₂O₂ from the molecular ion. The major fragment ion, m/z 76, in the conventional mass spectrum is not detected in a mass-analysed ion kinetic energy spectrometric experiment with the molecular ion until collision activation is provided. The conventional electron impact spectrum invariably includes ions from benzofurazan which is produced by thermal deoxygenation in the source.     

Mass spectral fragmentation of some phosphaaromatic compounds

The behaviour of 2-phosphanaphthalene, 3-methyl-phosphanaphthalene and 10-methyl-9-phosphaanthracene upon electron-impact has been compared with that of the carbon and nitrogen analogues. A close resemblance to the fragmentation pattern of the [M ? H]+ ions of 2-methyl-and 2-ethylbenzo[b]thiophene has been observed. It is concluded from the σ₄₀ intensities of the molecular ions, the relatively high intensities of the doubly charged molecular ions and the fragmentation patterns, that these phosphorin derivatives behave as aromatic compounds under electron-impact. From the molecular ion of 2-phosphanaphthalene a remarkable expulsion of a phosphours atom is observed.     

Mass spectral and pyrolytic fragmentation paths for o-nitroanisole

The mass spectral and pyrolytic dissociations of o-nitroanisole are reported. The parent ion dissociates by two pathways, principally through loss of CH₂O, but a significant fraction through loss of NO. The parent-less-30 peak is therefore a doublet, as shown by high resolution measurements. The thermal decomposition at 600°C and above proceeds also by two pathways, but these are the loss of HNO and HNO₂, to form 1,2-methylenedioxybenzene and benzaldehyde respectively.     

Mass spectral fragmentation of metal dithiocarbamate complex salts

A summary of the mass spectra of metal dithiocarbamate complex salts (ML₂ and ML₃) is presented. Only divalent metal dithiocarbamate ions without an electronic configuration containing an inert s-orbital electron pair exhibited both expulsion of a ligand radical (L) and the neutral even electron species (L–H) generated from the ligand via hydrogen transfer to the metal-containing fragment ion. Divalent metal dithiocarbamate ions can be generated either by direct electron impact ionization of gas phase ML₂ molecules or ionization of ML₃ molecules followed by loss of a ligand radical. A highly stable sp² hybridized, gas phase ion of a monobidentate lead dithiocarbamate complex is proposed.     

Mass spectral fragmentation studies in monomeric and dimeric coumarins

A study on the behavior of a large number of monomeric and dimeric coumarins in the mass spectrometer is reported and discussed. The results illustrate that the observed characteristic fragmentation patterns are of considerable utility in the application of mass spectrometry to structure elucidation in this series.     

Chemistry of thienopyridines. XXXIV. Mass spectral fragmentation patterns of some secondary amines and related imines

The mass spectra of some secondary amines and aldimines in the thieno[2,3-b]pyridine ( 3 ) system are presented. α, α-Bis(4-thieno[2,3-b]pyridylamino)toluene ( 1 ) undergoes (a) electron impact-induced dissociation at 80° to give the spectrum of 4-amino- 3 (3b) and (b) thermal dissociation at 200° to give a composite spectrum of 3b and its benzylidene derivative. Spectra of benzylamino and dimethylaminobenzylamino derivatives of 3 are dominated by benzyl-type fragments, while benzylideneimino derivatives show more varied fragmentation.     

Mass spectral fragmentation pathways in cyclic difluoramino and nitro compounds

The recently synthesized compounds 4, 4-bis(difluoramino)-1-nitropiperidine (I), 1,4,4-trinitropiperidine (II), 1,1,4,4-tetranitrocyclohexane (III), 1,1,4, 4-tetrakis(difluoramino)cyclohexane (IV) and 3,3,7, 7-tetrakis(difluora-mino)octahydro-1,5-dinitro-1,5-diazocine (HNFX, V) are being considered as potential energetic materials. The mass spectra of these compounds were studied using electron ionization (EI) mass spectrometry. A collision-induced dissociation (CID) study of the major EI peaks was carried out using a Finnigan TSQ 700 tandem mass spectrometer. The mass fragmentation pathways are constructed and discussed. The decomposition of HNFX (V), under EI, appeared to parallel the thermal decomposition of nitramines where N-NO(2) cleavage is often the first step. However, the two nitramines with a six-membered ring structure (I and II) underwent initial loss of a geminal substituent; loss of a nitramine nitro group was the secondary step. The two cyclohexane structures (III and IV) showed similar initial fragmentation pathways, featuring successive losses of nitro or difluoramino groups. Copyright 2000 John Wiley & Sons, Ltd.     

Electron ionization mass spectral fragmentation of deoxynivalenol and related tricothecenes

Careful analysis of the electron impact (EI) mass spectral data obtained for the trimethylsilyl (TMS) ethers of known trichothecene mycotoxins of the deoxynivalenol group permitted the construction of a database useful for the identification of these mycotoxins directly from a gas chromatography/mass spectrometry (GC/MS) run. Structures of the ions at m/z 103, 117, 147 and 191 were elucidated by high-resolution mass spectrometry (HRMS) and a fragmentation scheme was suggested. The relative abundances of these ions in the mass spectra of the trichothecenes allowed a fast structural diagnosis during analysis of biological matrices. A new mycotoxin of this group, 3-acetylnivalenol, was tentatively identified by using MS data interpretation only.     

Similarities and differences in the electron ionization-induced fragmentation of structurally related N-alkoxymethyl lactams and sultams

Unimolecular fragmentation patterns of the molecular ions of selected lactams and sultams bearing alkoxymethyl group at the nitrogen atom were studied. The main common fragmentation reaction observed for all compounds studied in this work is the elimination of an aldehyde molecule. This reaction is considered to proceed via two different mechanisms. For lactams, hydrogen rearrangement within an alkoxymethyl group is observed, which leads to the appropriate N-methyl derivatives. For sultams, transfer of the methyl group to the nitrogen and oxygen atoms, proceeding through an ion-neutral complex, dominates. Another important fragmentation channel characteristic exclusively for lactams is the loss of an alkyl radical. This process takes place within the N-alkoxymethyl moiety, yielding the appropriate protonated ion of N-formyllactams. This process is accompanied by relatively high kinetic energy release.     

Mass spectral fragmentation of 1,5-disubstituted tetrazoles and rearrangement of the resulting nitrenes

In agreement with the thermolysis characteristics of 1,5-disubstituted tetrazoles, the fragmentation pattern of 1-(o-, m-, and p-tolyl)-5-phenyltetrazoles has been shown to consist of a sequence of reactions, namely, initial tautomeric conversion to an azide structure, followed by elimination of a molecule of nitrogen, and rearrangement of the resulting nitrene intermediate to a cation-radical derivative of a methyl-substituted 2-phenylbenzimidazole compound. In the case of 1-(o-tolyl)-5-phenyltetrazole an alternative pathway is observed, involving cyclization of the nitrene intermediate at the methyl group (an insertion reaction into a C-H bond) to form dihydroquinazoline derivatives. An analogous cyclization process has been noted for the thermolysis process as well.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 925–930, July, 1988.     

Exploring microsolvation of the anesthetic propofol

Propofol (2,6-diisopropylphenol) is a broadly used general anesthetic. By combining spectroscopic techniques such as 1- and 2-color REMPI, UV/UV hole burning, infrared ion-dip spectroscopy (IRIDS) obtained under cooled and isolated conditions with high-level ab initio calculations, detailed information on the molecular structure of propofol and on its interactions with water can be obtained. Four isomers are found for the bare propofol, while only three are detected for the monohydrated species and two for propofol·(H(2)O)(2). The isopropyl groups do not completely block the OH solvation site, but reduce considerably the strength of the hydrogen bonds between propofol and water. Such results may explain the high mobility of propofol in the GABA(A) active site, where it cannot form a strong hydrogen bond with the tyrosine residue.     

Mass spectral fragmentation patterns of heterocycles Part 1. 1,4-Benzodioxans

The mass spectral fragmentation pattern of a series of substituted 1,4-benzodioxans is reported. The 2,3-disubstituted compounds show a characteristic fragment peak at mass 121. The 2-monosubstituted compounds do not show this as fragment peak. The mass peak at 121 has been assigned the empirical formula of C₇ H₅ O₂.     

Mass spectral fragmentation reactions of angiotensin-converting enzyme (ACE) inhibitors

A variety of mass spectrometric techniques have been employed in the study of a series of structurally similar compounds used in the treatment of hypertension. The compounds, known collectively as angiotensin-converting enzyme (ACE) inhibitors, all share the amino acid residue proline or some variant thereof, as a common structural element. The gas phase fragmentation behavior of these compounds has been explored systematically using various instruments and techniques. An interesting dissociation process (rearrangement) unique to one of the compounds, lisinopril, has been investigated using isotopic labeling experiments and exact mass measurements. The general nature of the process has been probed through both the positive and negative ion analyses of fourteen related compounds exhibiting structural homology.