Positive and negative ion mass spectrometric studies of dioximes of α-diketones and their nickel complexes

The positive and negative ion mass spectra of glyoxime, methylglyoxime, dimethylglyoxime, diphenyl glyoxime and of their nickel(II) complexes are reported. Both the positive and negative ion mass spectra of the dioximes show loss of OH^˙ and H₂O from the molecular ion to give fragment ions which probably have cyclic furazan type structures. The positive ion spectra of the complexes fragment mainly by loss of ligand radicals whereas the negative ion spectra show mainly loss of OH^˙ and H₂O.     

Pyrones. II—the mass spectra and fragmentation mechanisms of methyl maltol (3-methoxy-2-methyl-4H-pyran-4-one) and methyl allomaltol (5-methoxy-2-methyl-4H-pyran-4-one)

The mass spectra of methyl maltol (3-methoxy-2-methyl-4H-pyran-4-one) and methylallomaltol (5-methoxy-2-methyl-4H-pyran-4-one) and a number of deuterium labelled analogues have been studied in detail. The two pyrones have common fragmentation pathways, all of which can be traced back to a primary rearrangement of the molecular ion. The loss of water from the molecular ion occurs by two processes, both involving the methoxymethyl protons. The loss of methyl from the molecular ion also occurs by two routes, only one of which involves the methoxy methyl protons directly.     

Synthesis,Spectroscopic and Magnetic Studies on Metal Complexes of 5-Methyl-3-(2-Hydroxyphenyl)Pyrazole

A tridentate ONN donor ligand, 5-methyl-3-(2-hydroxyphenyl)pyrazole; H₂L, was synthesized by reaction of 2-(3-ketobutanoyl)phenol with hydrazine hydrate. The ligand was characterized by IR, ¹H NMR and mass spectra. ¹H NMR spectra indicated the presence of the phenolic OH group and the imine NH group of the heterocyclic moiety. Different types of mononuclear metal complexes of the following formulae [(HL)₂M][sdot]xH₂O (M=VO, Co, Ni, Cu, Zn and Cd), [(HL)₂M(H₂O)₂] (M=Mn and UO₂) and [(HL)LFe(H₂O)₂] were obtained. The Fe(III) complex, [(HL)LFe(H₂O)₂] undergoes solvatochromism. Elemental analyses, IR, electronic and ESR spectra as well as thermal, conductivity and magnetic susceptibility measurements were used to elucidate the structures of the newly prepared metal complexes. A square-pyramidal geometry is suggested for the VO(IV) complex, square-planar for the Cu(II), Co(II) and Ni(II) complexes, octahedral for the Fe(III) and Mn(II) complexes and tetrahedral for the Zn(II) and Cd(II) complexes, while the UO₂(VI) complex is eight-coordinate. Transmetallation of the UO₂(VI) ion in its mononuclear complex by Fe(III), Ni(II) or Cu(II) ions occurred and mononuclear Fe(III), Ni(II) and Cu(II) complexes were obtained. IR spectra of the products did not have the characteristic UO₂ absorption band and the electronic spectra showed absorption bands similar to those obtained for the corresponding mononuclear complexes. Also, transmetallation of the Ni(II) ion in its mononuclear complex by Fe(III) has occurred. The antifungal activity of the ligand and the mononuclear complexes were investigated.     

Synthesis and mass spectral fragmentation of 2-methylthio-7-(p-R-phenyl)-8-phenoxy-4,5-benzo-3-aza-2-nonem. III

A series of new 2-methylthio-7-(p-R-phenyl)-8-phenoxy-4,5-benzo-3-aza-2-nonem, IIIa, have been synthesized by regiospecific cycloaddition of phenoxyacetyl on to 2-methylthio-4-(p- R -phenyl)-3H-1,5-benzodiazepines IV. The structure was established by ir, ¹H-nmr and ms spectral data together with ¹³C-nmr spectral data of desulfurization products, VIa. Likewise, a study has been made of the fragmentation upon electron impact of IIIa and IV. All the spectra analyzed contain molecular ions and the principal fragmentation routes takes place either from the molecular ion or from m/e (M⁺ — 134) ion. This ion is the base peak for all the compounds analyzed.     

Dissociation of positively charged aliphatic epoxides. II. [C5H10O]+˙ epoxides and α,β unsaturated ethers

The unimolecular dissociations of C₅ epoxides ions mono- or disubstituted at C₁ give exclusive loss of CH₃ and exclusive formation of methoxy vinyl carbenium ion, both in the source and in the 2nd field-free region. In the case of the 1,2-disubstituted ion in the 2nd field-free region the loss of ethene is the only pathway, while a competition occurs for the trisubstituted ion leading to [C₃H₆O]⁺˙ and [C₄H₇O]⁺˙ ions, the structure of which are demonstrated. The first step of the different mechanisms is the cleavage of the heterocyclic C? C bond.     

Mass spectral fragmentation mechanisms of some dibenzo[c,f][1,2] diazepines

The fragmentation mechanisms of 11H-dibenzo[c,f][1,2]diazepine (I), its 3,8-dichloro derivative (II), 3,8-dichlorodibenzo[c,f] [1,2]diazepin-11-one (III) and 3,8-dichloro-11H-dibenzo-[c,f][1,2]diazepin-N-oxide (IV) are discussed. The initial loss of molecular nitrogen is characteristic of I, II and III. Compound IV has a strong molecular ion, that competitively eliminates cither NO or Cl- and N₂O. The common radical ion, m/166 e present in the mass spectra of I, fluorene, 2-methyl-9,10-anthraquinone and 2-methylbenzo[c]cinnoline, appears to be formed in different states.     

An unusual rearrangement observed in the mass spectra of several 1-alkyl-2-substituted-5-nitroimidazoles

The mass spectra of several l-alkyl-2-substituted-5-nitro imidazoles exhibit prominent rearrangement ions corresponding to the loss of C_nH_2nO from the molecular ion. The effect on this rearrangement upon variation of the group at position 2 is discussed.     

Electron-impact induced fragmentation of some natural products containing bis-2,2-dimethylchromene and bis-2,2-dimethylchroman ring systems

Derivatives of eriostoic and eriostemoic acids (II and III) and their tetrahydro analogs (VI and IX) which contain the bis-2,2-dimethylchromene and the bis-2,2-dimethylchroman ring systems respectively, fragment subsequent to electron-impact in characteristic fashion. The former yield mass spectra dominated by the loss of a methyl radical from their molecular ions while the latter exhibit preferential fragmentation of the heterocyclic ring system. In particular the hydrogen transfer process accompanying elemination of C₄H₇ from the parent ion of bis-2,2-dimethylchromans was investigated by deuterium labeling studies. Fragment ions containing the bis-2,2-dimethylchroman ring undergo further fragmentation by the loss of C₄H₈ rather than C₄H₇. An unusual elimination of CH₅ (accompanied by the appropriate metastable ion) from the molecular ions of the 3,5-dinitrobenzoate esters (XIV and XV) was observed in their mass spectra.     

Determination of the fragmentation mechanisms of organophosphorus ions by H2O and D2O atmospheric-pressure ionization tandem mass spectrometry

Dimethylmethyl phosphonate (DMMP), dimethyl phosphite (DMPI), trimethyl phosphite (TMPI) and trimethyl phosphate (TMP) were investigated using H₂O and D₂O atmospheric-pressure ionization (API) tandem mass Spectrometry. All daughter ions could be explained by losses of one or a successive number of stable molecules as opposed to losses of radicals such as the hydride, methyl and methoxy species. Losses of neutral methanol and dimethyl ether and of protonated methanol and formaldehyde ions from all four organophosphorus pseudo-molecular ions were observed. The DMMP and DMPI MH⁺ pseudomolecular ions produced the losses of neutral C₂H₆ and water, respectively. Formaldehyde loss was not observed for the MH⁺ ions, but it was well represented in the decomposition pathways of daughter ions. The D₂O reagent gas highlighted the role of the ionizing proton/ deuteron in the various daughter ions, including m/z 95, 79, 65, 49, 33, 31 and 47. The last ion was found to be isobaric in that m/z 47 and 48 both appeared with similar abundances in the D₂O-API daughter ion mass spectra of TMPI and TMP.     

A new polymeric [Cu(SO3(CH2)3S–S(CH2)3SO3)(H2O)4]n complex molecule produced from constituents of a super-conformational copper plating bath: Crystal structure,infrared and Raman spectra and thermal behaviour

The formation and characterisation of a polymeric copper complex produced by chemical reaction between copper (II) ions and 3-mercapto-1-propanesulphonate sodium salt (MPSA) were studied. The formation of this complex, followed by sequential UV–visible spectroscopic measurements, involves the reduction of Cu(II) ions to Cu(I) by MPSA, the latter being oxidised to bis-(3-sulphopropyl)-disulphide (SPS), a dimer of MPSA. In the presence of oxygen, the re-oxidation of Cu(I) to Cu(II) results in the formation of polymeric complex species consisting of [Cu(SO₃(CH₂)₃S–S(CH₂)₃SO₃)(H₂O)₄] units. Single crystal X-ray diffraction shows that this polymeric copper complex crystallizes in the monoclinic C2/c space group. The Cu(II) ion in the complex structure lies on an inversion centre in an elongated octahedral environment, equatorially coordinated to four water molecules and axially to two MPSA ligands through one of their sulphonic oxygen atoms. The complex units are arranged in the lattice as polymeric [Cu(SPS)(H₂O)₄]_n molecules extending along the crystal [101] direction. The IR and Raman spectra as well as TGA and DTA data are reported. The stepwise thermal decomposition from room temperature up to 1000 °C begins with the loss of water molecules and ends with the formation of copper sulphide species.     

Translational energy release and stereochemistry of steroids. XI—Determination of the configuration of α,β-unsaturated 3-keto steroid alcohols with the hydroxyl group in rings C and D

The elimination of water from metastable molecular ions of epimeric hydroxy steroids of the Δ⁴-3-keto series containing a hydroxyl group in the conformationally rigid rings C and D has been studied. The measurement of translational energy released during the loss of water and collision-induced decomposition (CID) mass-analysed ion kinetic energy (MIKE) spectrometry were the techniques used. It was found that it is possible to determine the configuration of the hydroxy steroids of this series on the basis of the CID MIKE spectra of [M ? H₂O]^+˙ ions formed by dehydration of metastable molecular ions in the first field-free region of a reversed geometry double-focusing mass spectrometer.     

On the mechanism of isomerization reactions in the esters of some simple α,β-unsaturated carboxylic acids

It is shown from a detailed examination of first field free region metastable peak shapes that the molecular ion of the methyl ester of acrylic acid rearranges into 2- and 3-butenoic acid ions prior to metastable fragmentations involving the losses of H₂O, CH₃˙ and CO. The key intermediate ion in this ester-acid isomerization is shown to be the enol form of ionized γ-butyrolactone. The C-5 homologues methylmethacrylate and ethylacrylate display a similar mechanism for H₂O loss, but the loss of CH₃˙ shows additional mechanistic complexities. It was shown from the metastable peak shapes of ¹³C and deuterium labelled compounds that the larger part of the methyl loss does not occur from acid type ions, but directly from methyl substituted enol ions of γ-butyrolactone. The mechanistic proposals also account for the presence of a pronounced loss of CH₃˙ from the isomeric ester methylcrotonate and the absence of H₂O loss in both methylcrotonate and the methyl ester of 3-butenoic acid.     

Four oxoindole‐linked α‐alkoxy‐β‐amino acid derivatives

Four structures of oxoindolyl α‐hydroxy‐β‐amino acid derivatives, namely, methyl 2‐{3‐[(tert‐butoxycarbonyl)amino]‐1‐methyl‐2‐oxoindolin‐3‐yl}‐2‐methoxy‐2‐phenylacetate, C₂₄H₂₈N₂O₆, (I), methyl 2‐{3‐[(tert‐butoxycarbonyl)amino]‐1‐methyl‐2‐oxoindolin‐3‐yl}‐2‐ethoxy‐2‐phenylacetate, C₂₅H₃₀N₂O₆, (II), methyl 2‐{3‐[(tert‐butoxycarbonyl)amino]‐1‐methyl‐2‐oxoindolin‐3‐yl}‐2‐[(4‐methoxybenzyl)oxy]‐2‐phenylacetate, C₃₁H₃₄N₂O₇, (III), and methyl 2‐[(anthracen‐9‐yl)methoxy]‐2‐{3‐[(tert‐butoxycarbonyl)amino]‐1‐methyl‐2‐oxoindolin‐3‐yl}‐2‐phenylacetate, C₃₈H₃₆N₂O₆, (IV), have been determined. The diastereoselectivity of the chemical reaction involving α‐diazoesters and isatin imines in the presence of benzyl alcohol is confirmed through the relative configuration of the two stereogenic centres. In esters (I) and (III), the amide group adopts an anti conformation, whereas the conformation is syn in esters (II) and (IV). Nevertheless, the amide group forms intramolecular N—H...O hydrogen bonds with the ester and ether O atoms in all four structures. The ether‐linked substituents are in the extended conformation in all four structures. Ester (II) is dominated by intermolecular N—H...O hydrogen‐bond interactions. In contrast, the remaining three structures are sustained by C—H...O hydrogen‐bond interactions.     

Mass spectral studies on steroidal compounds—V: Rings B and A seco 5-keto compounds in the cholestane series

The mass spectra of several structurally related ring B seco 5-keto compounds (I to VII) have been examined. The mass spectra of I, II, III and IV are conspicuous by an intense peak at m/e112(C₇H₁₂O) and those of V (highest mass peak at [M ? CH₃COOH]), VI and VII by a prominent peak at m/e 100 (C₇H₁₀O), which apparently results from McLafferty rearrangement involving 5-keto function and an appropriate γ-hydrogen at C-8 and C-11. This rearrangement, leading to the aforementioned ions, is of diagnostic value in the characterisation of such compounds. The mass spectrum of VIII exhibits a prominent ion peak at m/e 332 (C₂₃H₄₀O) resulting from McLafferty rearrangement involving the 5-keto function and C2? H. This offers an excellent means of differentiating between the isomeric acids (III and VIII). The fragmentation pathways suggested are supported by accurate mass measurement of the salient fragment ions and in some cases by appropriate metastable peaks.     

Mechanisms of mass spectrometric fragmentations: X–Interaction between remote or-groups in decalin-1,5-diols and their dimethyl ethers

The mass spectra of the five stereoisomers of decalin-1,5-diol and its dimethyl ether have been investigated. The differences in the mass spectra of stereoisomers I to III with a trans- decalin ting system are small. The differences are much larger in the mass spectra of the two isomers IV and V of the cis-decalin series and the elimination of CH₂O, formed by interaction between the two methoxy groups, from the molecular ion is only observed in the mass spectrum of Vb.     

Mass spectra of methoxy-substituted 4-aminopyrimidines

In a study of the mass spectra of methoxy-substituted 4-aminopyrimidines it has been shown that in the molecular ion the positive charge is predominantly concentrated on the oxygen atom of the methoxy group, which explains the appearance of the fragmentary ions (M-H)⁺ and (M-CH₂O)⁺. In contrast to the halopyrimidines, the molecular ion does not exist in the imine form, which is characteristic only for the fragmentary ions (M-CH₂O)⁺.     

Double complexes [Co(NH3)5(H2O)]2[Zr3F18]·6H2O and [Co(NH3)6]2[Zr3F18]·6H2O

The structures of orthorhombic bis[pentaammineaquacobalt(III)] tetra‐μ₂‐fluorido‐tetradecafluoridotrizirconium(IV) hexahydrate (space group Ibam), [Co(NH₃)₅(H₂O)]₂[Zr₃F₁₈]·6H₂O, (I), and bis[hexaamminecobalt(III)] tetra‐μ₂‐fluorido‐tetradecafluoridotrizirconium(IV) hexahydrate (space group Pnna), [Co(NH₃)₆]₂[Zr₃F₁₈]·6H₂O, (II), consist of complex [Co(NH₃)_x(H₂O)_y]³⁺ cations with either m [in (I)] or and 2 [in (II)] symmetry, [Zr₃F₁₈]⁶⁻ anionic chains located on sites with 222 [in (I)] or 2 [in (II)] symmetry, and water molecules.     

Fragmentation of selected C6H10O isomers: Evidence for a common [C5H7O]+ ion generated by methyl loss from cyclohexene oxide and 5,6-dihydro-4-methyl-2H-pyran

The loss of CH₃˙ from the molecular ions of cyclohexene oxide and 5,6-dihydro-4-methyl-2H-pyran has been investigated. On the basis of metastable peak shape analysis, collision-induced dissociation/mass-analysed ion kinetic energy spectra and thermochemical data it is concluded that the same [C₅H₇O]⁺ ion is formed in both cases.     

Mass spectrometric studies on o-terphenyl-2-13C: Identification of compounds related to its synthesis and fragmentation processes

After identification of the impurities, separated from synthesized orthoterphenyl (I) labelled in position 2 with ¹³C, i.e. o-xenylcyclohexanol (II), o-xenylcyclohexene (III), hexahydrotriphenylene (IV) and o-xenylcyclohexane (V), the fragmentation processes under electron-impact of molecules I, II and IV have been studied, advantage being taken of their ¹³C labelling. Mass spectrometric studies were carried out on an AEI MS-9 for determination of the atomic composition of the main ions and on a MAT CH-4 instrument for quantitative determination of ¹²C and ¹³C species, at low energy, assuming an equal sensitivity. The ¹³C labelling of position 2 in I, has not yet given clear evidence of a formerly assumed rearrangement into phenanthrenic structure after ring opening. The fragmentation of molecule II occurs in two ways, i.e. into a series of hydrocarbon fragments, produced from the molecular ion by loss of H₂O or into fragments still containing the oxygen atom. The difference between the fragmentation processes of the two series depends on the fact that the loss of H₂O from the molecule stabilizes the two carbon atoms adjacent to the C carrying the hydroxyl group. This is shown by the relatively higher ¹³C content of the hydrocarbon fragment in C¹⁵ compared with that of the equivalent oxygenated fragment. The labelling in IV shows how the rupture of the saturated ring occurs under electron-impact, the first C removed being the one nearest to the central ring.     

Stereochemical applications of mass spectrometry 4. Energy-resolved study of the fragmentation of esters of maleic and fumaric acids

The fragmentation of the dimethyl and diethyl esters of maleic and fumaric acids have been studied as a function of the internal energy of the molecular ions using charge exchange techniques and metastable ion studies in combination with isotopic labelling. The dimethyl ester molecular ions show distinctive behaviours at both low and high internal energies, indicating that interconversion of the molecular ions does not occur. The fumarate molecular ion fragments by elimination of CH₂O and (CO₂ + CH₃) in the metastable ion time-frame, while the maleate ester fragments primarily by loss of CH₃O. At higher internal energies both molecular ions fragment primarily by loss of CH₃O but the fragment ion from the maleate ester shows a greater stability, presumably because it assumes the cyclic cationated maleic anhydride structure. The diethyl maleate and diethyl fumarate molecular ions show identical metastable ion characteristics; in addition the [COS]⁺· charge exchange mass spectra are very similar. These results indicate that low-energy molecular ions interconvert. At higher internal energies interconversion does not occur, and, although both moiecular ions fragment by loss of C₂H₅O, the resultsint fragment ions show different stabilities and fragmentation reactions.