Fragmentation processes

Using a guided ion beam instrument the translational energy dependent reaction cross sections of endothemiic fragmentation processes can be detemiined [32]. Modelling these cross sections ultimately yields their energy tln-esholds and a great deal of valuable themiochemical infomiation has been derived with this teclmique. Precision of 0.2 eV can be obtained for reaction tln-esholds. Bimolecular reactions can also be studied and reaction enthalpies derived from the analysis of the cross section data. 

The main features are the molecular ions as the base peak and the M-t-1 ions arising from another species. For 2-aminothiazole the m/e 73 ion (M-HCN) is shifted to m/e 75 in the spectrum of the dideuteroamino derivative and, therefore, largely arises via rupture of 2-3 and 4-5 bonds (Scheme 18). This fragmentation process could involve the kind of intermediates postulated in photochemical rearrangements (see Chapter III, Section IX.3.B). The other fragments fit well the general pattern of fragmentation proposed by Clarke (136). 

An analogous fragmentation process occurs m the mass spectra of sulfides As with other sulfur containing compounds the presence of sulfur can be inferred by a peak at m/z of M-l-2... 

Mass Spectrometry Aside from a peak for the molecular ion which is normally easy to pick out aliphatic carboxylic acids undergo a variety of fragmentation processes The dominant fragmentation m aromatic acids corresponds to loss of OH then loss of CO... 

Now consider the same fragmentation process, but this time the ion (mi+) dissociates outside the ion source. Initially, as for m2, mjVi = 2zV, and V, =. When fragmentation occurs, the total... 

Again, as for metastable ions, linked scanning of the first and third quadrupoles reveals important information on fragmentation processes, viz., which normal ions fragment to give which product ions. 

Rearrangement ion. An electrically charged dissociation product, of a molecular or parent ion, in which atoms or groups of atoms have transferred from one portion of the molecule or molecular moiety to another during the fragmentation process. 

In the present section, attention will focus on the size of fragments created in a violent fragmentation event. The objective will be to explore some theoretical ideas which appear important to the dynamic fragmentation process. The two underlying phenomena that have dominated theoretical efforts in this area of dynamic fracture mechanics are the presence of an inherent flaw structure, and energy balance in the fracture process. 

The energy which drives the fragmentation process (elastic plus kinetic) is determined by the dynamic loading conditions and does not directly depend on the properties of the material at issue. The fragmentation energy, on the other hand, is an intimate property of the material and can depend in a complex way on the thermal and dynamic conditions at spall, as well as on the deformation history of the material leading to spall. 

The one-dimensional geometry of a radially expanding ring is perhaps the simplest for considering fundamental aspects of the fracture and fragmentation process. In a ductile metal ring, fracture proceeds through the multiple... 

The total synthesis of caryophyllene and its Z-isomer involved a photochemical [2 + 2] cycloaddition reaction to generate the 4-membered ring and a fragmentation process Helv. Chim. Acta, 1951, 34, 2338) to establish the 9-membered ring. Caryophyllene and various oxygenated derivatives protect plants against insects. 

Strategy Calculate the mass of the molecular ion, and identify the functional groups in the molecule. Then write the fragmentation processes you might expect, and compare the masses of the resultant fragments with those peaks present in the spectrum. 

Scheme 17. Danishefsky s radical addition/fragmentation process in a synthesis of (+)-3-demethoxyery-thratidinone [( )-93].

It should be noted that the cyano group is lost by a retro-Claisen-type fragmentation 6->7 which gives automatically the pyrrocorphin 7 on the hexahydro oxidation level rather than by a /i-elimination-type process which would give a tetrahydroporphyrin. A similar fragmentation process has been observed in the total syntheses of chlorophyll a (sec Section 1.2.1.) and of a tolyporphin model (see Section 1.3). 

Stansbury and Bailey. A review by Colombam on addition-fragmentation processes is also relevant. Monomers used in ring-opening are typically vinyl (e.g. vinylcyclopropane - Scheme 4.20 Section 4.4.2.1) or methylene substituted cyclic compounds (e.g. ketene acetals - Section 4.4.2.2) where addition to the double bond is followed by p-scission. 

The high temperature polymerization of acrylates with the backbiting-fragmentation process has been used to synthesize macromonomers based on acrylate esters. 277,312 Interestingly, fragmentation shows a strong preference for giving the polymeric macromonomer 64 and a small radical 65. 276.277 An explanation for this specificity has yet to be proposed. 

It is interesting to note here that two a-mesyl sulfonyl chlorides (109 and 110) have been found to exhibit a fragmentation process shown in equation (34)48a. 

Dimethyl a-disulfone forms the fragments shown in equation (35) under electron impact at 70 eV. The fragmentation processes are closely related to the thermal484 and photochemical48 results reported for diaryl a-disulfones. In contrast to MeS02SMe, MeS02S02Me shows no indication of the formation of MeS(OH)2 + 48b. 

Abstract Molecular spectroscopy is one of the most important means to characterize the various species in solid, hquid and gaseous elemental sulfur. In this chapter the vibrational, UV-Vis and mass spectra of sulfur molecules with between 2 and 20 atoms are critically reviewed together with the spectra of liquid sulfur and of solid allotropes including polymeric and high-pressure phases. In particular, low temperature Raman spectroscopy is a suitable technique to identify single species in mixtures. In mass spectra cluster cations with up to 56 atoms have been observed but fragmentation processes cause serious difficulties. The UV-Vis spectra of S4 are reassigned. The modern XANES spectroscopy has just started to be applied to sulfur allotropes and other sulfur compounds. 

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