Josef Ruzicka

Collision-induced dissociation mass spectra of glucosinolate anions

Collision-induced dissociation (CID) mass spectra of differently substituted glucosinolates were investigated under negative-ion mode. Data obtained from several glucosinolates and their isotopologues ((34)S and (2)H) revealed that many peaks observed are independent of the nature of the substituent group. For example, all investigated glucosinolate anions fragment to produce a product ion observed at m/z 195 for the thioglucose anion, which further dissociates via an ion/neutral complex to give two peaks at m/z 75 and 119. The other product ions observed at m/z 80, 96 and 97 are characteristic for the sulfate moiety. The peaks at m/z 259 and 275 have been attributed previously to glucose 1-sulfate anion and 1-thioglucose 2-sulfate anion, respectively. However, based on our tandem mass spectrometric experiments, we propose that the peak at m/z 275 represents the glucose 1-thiosulfate anion. In addition to the common peaks, the spectrum of phenyl glucosinolate (beta-D-Glucopyranose, 1-thio-, 1-[N-(sulfooxy)benzenecarboximidate] shows a substituent-group-specific peak at m/z 152 for C(6)H(5)-C(=NOH)S(-), the CID spectrum of which was indistinguishable from that of the anion of synthetic benzothiohydroxamic acid. Similarly, the m/z 201 peak in the spectrum of phenyl glucosinolate was attributed to C(6)H(5)-C(=S)OSO(2)(-).

Loss of benzene to generate an enolate anion by a site-specific double-hydrogen transfer during CID fragmentation of o-alkyl ethers of ortho-hydroxybenzoic acids

Collision-induced dissociation of anions derived from ortho-alkyloxybenzoic acids provides a facile way of producing gaseous enolate anions. The alkyloxyphenyl anion produced after an initial loss of CO(2) undergoes elimination of a benzene molecule by a double-hydrogen transfer mechanism, unique to the ortho isomer, to form an enolate anion. Deuterium labeling studies confirmed that the two hydrogen atoms transferred in the benzene loss originate from positions 1 and 2 of the alkyl chain. An initial transfer of a hydrogen atom from the C-1 position forms a phenyl anion and a carbonyl compound, both of which remain closely associated as an ion/neutral complex. The complex breaks either directly to give the phenyl anion by eliminating the neutral carbonyl compound, or to form an enolate anion by transferring a hydrogen atom from the C-2 position and eliminating a benzene molecule in the process. The pronounced primary kinetic isotope effect observed when a deuterium atom is transferred from the C-1 position, compared to the weak effect seen for the transfer from the C-2 position, indicates that the first transfer is the rate determining step. Quantum mechanical calculations showed that the neutral loss of benzene is a thermodynamically favorable process. Under the conditions used, only the spectra from ortho isomers showed peaks at m/z 77 for the phenyl anion and m/z 93 for the phenoxyl anion, in addition to that for the ortho-specific enolate anion. Under high collision energy, the ortho isomers also produce a peak at m/z 137 for an alkene loss. The spectra of meta and para compounds show a peak at m/z 92 for the distonic anion produced by the homolysis of the O-C bond. Moreover, a small peak at m/z 136 for a distonic anion originating from an alkyl radical loss allows the differentiation of para compounds from meta isomers.

Defensive Chemicals of Two Species of Trachypachus Motschulski

Analyses of pygidial gland contents of two species of a previously uninvestigated family of beetles (Trachypachidae) by Gas Chromatography-Mass Spectrometry (GC-MS) revealed that their chemistry is similar to that reported from many members of the family Carabidae. Nevertheless, the composition ofDefensive gland fluids of the two species Trachypachus slevini and T. gibbsii differs sufficiently to distinguish between the two species solely on the basis of theirDefensive chemistry. The major components of T. slevini glandular fluid are methacrylic, tiglic, and octanoic (= caprylic) acids, together with the hydrocarbon (Z)-9-pentacosene. In contrast, the glandular contents of T. gibbsii contain a rather unique mixture of polar and nonpolar compounds, the principal constituents of which are methacrylic and ethacrylic acids (= 2-ethylacrylic acid), together with 2-phenylethanol, 2-phenylethyl methacrylate, 2-phenylethyl ethacrylate, and (Z)-9-pentacosene.

Collision-induced dissociation mass spectra of positive ions derived from tetrahydropyranyl (THP) ethers of primary alcohols

Peaks for [M + H](+) are not observed when electrospray ionization mass spectra of tetrahydropyranyl (THP) ethers are recorded under acidic conditions. However, gaseous [M + H](+) ions can be generated from ammonium adducts of THP ethers of primary alcohols by in-source fragmentation. The product ion spectra of these proton adducts show two significant peaks at m/z 85 and 103. Tandem mass spectrometric data obtained from appropriately deuteriated derivatives and ab initio calculations indicate that the m/z 85 ion originates from more than one mechanism and represents two structurally different species. A charge-directed E1-elimination mechanism or an inductive cleavage mechanism can produce the 3,4,5,6-tetrahydropyrylium ion as one of the structures for the m/z 85 ion, whereas a charge-remote process with ring contraction can generate the 5-methyl-3,4-dihydro-2H-furylium ion as the other structure. A comparison of the relative abundances of product ions from different isotopologues showed that the charge-remote process is the preferred mechanism. This is congruent with the ab initio calculations, which showed that the dihydrofurylium ion bears the lowest energy structure. The less abundant m/z 103 ion, which represents a protonated tetrahydropyran-2-ol, is formed by a charge-remote process via a proton transfer from the alkyl substituent. This process involves the formation and rearrangement of a carbenium ion in close association with a hydroxypentanal molecule. A proton transfer from the carbenium ion to the aldehyde is followed by elimination of an alkene.