Fragments, breakdown

Time-of-flight mass spectrometers have been used as detectors in a wider variety of experiments tlian any other mass spectrometer. This is especially true of spectroscopic applications, many of which are discussed in this encyclopedia. Unlike the other instruments described in this chapter, the TOP mass spectrometer is usually used for one purpose, to acquire the mass spectrum of a compound. They caimot generally be used for the kinds of ion-molecule chemistry discussed in this chapter, or structural characterization experiments such as collision-induced dissociation. Plowever, they are easily used as detectors for spectroscopic applications such as multi-photoionization (for the spectroscopy of molecular excited states) [38], zero kinetic energy electron spectroscopy [39] (ZEKE, for the precise measurement of ionization energies) and comcidence measurements (such as photoelectron-photoion coincidence spectroscopy [40] for the measurement of ion fragmentation breakdown diagrams). 

If it is assumed that effects on the ground state are amplified in the transition state, this purely empirical thermodynamic anomeric effect is transformed into a predictive kinetic anomeric effect (Kirby, 1983). In the transition state for breakdown of a tetrahedral species containing the X—C—X—C fragment, breakdown of the isomer with the scissile bond antiperiplanar to a heteroatom lone pair will proceed more rapidly, under stereoelectronic acceleration (Scheme 17). The theory has obvious utility in predicting product distribution when a single species may break down by a number of possible pathways (Deslongchamps, 1983). However, the hypothesis has not been without its detractors. Some of the experimental work used... 

Mass spectral fragmentation patterns of alkyl and phenyl hydantoins have been investigated by means of labeling techniques (28—30), and similar studies have also been carried out for thiohydantoins (31,32). In all cases, breakdown of the hydantoin ring occurs by a-ftssion at C-4 with concomitant loss of carbon monoxide and an isocyanate molecule. In the case of aryl derivatives, the ease of formation of Ar—NCO is related to the electronic properties of the aryl ring substituents (33). Mass spectrometry has been used for identification of the phenylthiohydantoin derivatives formed from amino acids during peptide sequence determination by the Edman method (34). 

Chlorination of Hydrocarbons or Chlorinated Hydrocarbons. Chlorination at pyrolytic temperatures is often referred to as chlorinolysis because it involves a simultaneous breakdown of the organics and chlorination of the molecular fragments. A number of processes have been described for the production of carbon tetrachloride by the chlorinolysis of various hydrocarbon or chlorinated hydrocarbon waste streams (22—24), but most hterature reports the use of methane as the primary feed. The quantity of carbon tetrachloride produced depends somewhat on the nature of the hydrocarbon starting material but more on the conditions of chlorination. The principal by-product is perchloroethylene with small amounts of hexachloroethane, hexachlorobutadiene, and hexachloroben2ene. In the Hbls process, a 5 1 mixture by volume of chlorine and methane reacts at 650°C the temperature is maintained by control of the gas flow rate. A heat exchanger cools the exit gas to 450°C, and more methane is added to the gas stream in a second reactor. The use of a fluidi2ed-bed-type reactor is known (25,26). Carbon can be chlorinated to carbon tetrachloride in a fluidi2ed bed (27). 

The mass spectra of pyridopyrimidines in general show many features in common with those of other related N-heterocycles, in particular quinazolines and pteridines. The pyridopyrimidines show strong molecular ions, and when breakdown of the hetero ring occurs, fragments arising from loss of CO, CN, HCN and HCNO are observed. 

Low ionizing potentials or soft ionization methods are necessary to observe the parent ions in the mass spectra of many S-N compounds because of their facile thermal decomposition. Mass spectrometry has been used to investigate the thermal breakdown of S4N4 in connection with the formation of the polymer (SN). On the basis of the appearance potentials of various S Ny fragments, two important steps were identified ... 

W as an important factor which influenced the fragmentation pattern. 2-Furylpyrido[4,3-d]pyrimidin-4(3i7)-one (154, Rj=furyl, R2 = H,) showed six different primary breakdown peaks originating from the molecular ion. These corresponded to the loss (in decreasing order of probability) of H-, C1H3O, -CN, CO, HCN, C4H3O-, and HCNO. 

Bnich-kupfer, n. scrap copper, -last, /. breaking load, -metall, n. broken metal, scrap metal, -modul, m. modulus of rupture, -probe, /. breaking test, breakdown test, -punkt, m. breaking point, -riss, m. (Meial.) failure crack, -silber, n. broken silver, scrap silver, -spaonung,/. breaking stress tensile strength, -stein, m. quarry stone broken stone, -stelle,/. broken place, place of fracture. -strich, m. (Math.) fraction stroke (between numerator and denominator), -stiick, n. fragment shred, -stiicke, pi. debris scrap, -teil, m. fraction, -zahl, /. fractional number. 

An interesting feature of 5-tocopherylacetic acid (51) and its derivatives was their appreciable thermal stability up to 200 °C. In contrast to 5a-substituted tocopherols carrying an electronegative substituent at C-5a, the homopolar C—C bond in the C2-unit at the 5-position of the tocopherol skeleton was shown to be very stable. Thermal decomposition of 51 at temperatures above 250 ° C caused a complete breakdown of the chroman structure, the C3-unit consisting of C-2, C-2a, and C-3 being eliminated as propyne, the side chain as 4,8,12-trimethyltridec-l-ene (Fig. 6.38). Fragmentation... 

Soft ionisation modes, such as API, which leave the (pseudo)molecular ion intact without much fragmentation, offer more sensitivity, and are ideal for quantitative work at low levels (e.g. breakdown products). With the use of soft ionisation techniques in LC-MS, tandem MS... 

Second, linear chain polymers are thermodynamically unstable at elevated temperatures. Entropic influences favor a breakdown to small molecules either by random fragmentation or by depolymerization. The latter process involves a reversion of the polymer to monomer or small molecule rings. Depolymerization to small rings is a feature common to many inorganic polymers at temperatures above 200-250°C. 

---