Mass spectral fragmentation common fragment ions

The nonclassical thiophenes (6), (12) and (13) show intense molecular ions (over 70%) as well as pronounced doubly charged M2+ ions. Other characteristic fragment ions result from the loss of phenyl or methyl substituents as the case may be. The thiobenzoyl fragment at m/e 121 (10-20%) is another common fragment in these molecules. The mass spectral fragmentation of tetraphenylthieno[3,4-c]thiophene (6) is presented in Scheme 6. 

In Table IV some physical data and spectral characteristics of 6,7-secoberbines are listed. Only methyl corydalate (55) is optically active. Formula 55 presents the spatial structure of this compound, deduced by Nonaka et al. (65) and confirmed by Cushman et al. by both correlation with (+)-mesotetrahydrocorysamine (72) (<5S) and total synthesis (69). It is difficult to find common characteristic features in both the mass and H-NMR spectra of these alkaloids because they differ significantly from each other in their structures. On one hand, corydalic acid methyl ester (55) incorporates a saturated nitrogen heterocycle, while the three aromatic bases (56-58) differ in the character of the side chain nitrogen. For example, in mass fragmentation, ions of the following structures may be ascribed to the most intensive bands in the spectrum of 55 ... 

A common method for identification of organic compounds is mass spectrometry (MS) in combination with GC. After separation of the component by GC the mass spectrometer transform the analyte into gaseous ions in vacuum in the ion source. For electron impact ionization this results in different mass fragmentation patterns with different mass-to-charge ratios (m/z). From this fragmentation pattern it will be possible to identify the compound by comparison with commercial mass spectral libraries. Identification of unknown compounds can be facilitated by... 

The quadrupole MS detector was the first, and is still the most common, detector used for LC/MS, but a number of other mass spectrometers have been adapted to this application. Both three-dimensional spherical (ITD) and linear (LIT) ion trap detectors offer tremendous potential for general, inexpensive LC/MS systems. They both offer the ability to be used as either a mass spectral detector or as a MS/MS detector. The 3D ITD (Fig. 15.5) allows ions to be trapped in the ion trap where they can be fragmented by heavy gas collision and the fragments released by scanning the dc/RF frequency of the trap. 

Mass spectral peaks are often seen corresponding to loss of small, stable molecules. Loss of a small molecule is usually indicated by a fragment peak with an even mass number, corresponding to loss of an even mass number. A radical cation may lose water (mass 18), CO (28), C02 (44), and even ethene (28) or other alkenes. The most common example is the loss of water from alcohols, which occurs so readily that the molecular ion is often weak or absent. The peak corresponding to loss of water (the M-18 peak) is usually strong, however. 

C N.m.r. chemical shifts and spin-relaxation times have been reported for /3-cyclocitral.246 Mass spectral data have been recorded for a -pyronene (147), which fragments similarly to allo-ocimene through common ions.247 Brief acid-catalysed treatment of a-pyronene (147) gives predominantly the diene... 

The premise is to utilise a liquid film to provide a reaction environment which can be dynamically controlled in terms of heat and mass flux (influx/effiux) and to complement this with the on-line monitoring technique of Atmospheric Pressure chemical Ionisation (APcI)-Ion Trap Mass Spectrometry (ITMS). This technique allows the flux of protonated molecular ions (Mlf to be directly monitored (mass spectral dimension 1) and to fragment these species under tailored conditions within the ion trap (Collision Induced Dissociation (CID),mass spectral dimension 2), to produce fragment ions representative of the parent ion. This capability is central to allowing species with a common molecular weight to be quantified, for example butan-2,3-dione (MW=86 MH =87, glucose degradation product) and 3-methylbutanal (MW=86 MH =87, Strecker aldehyde from leucine). 

---