Mass spectral fragmentation pattern

Thiazole disulfides absorb at 235 and 258 nm (320-322) and characteristic infrared bands are reported in Ref. 320. The activities of 2-cyclo-hexyldithiomethylthiazoles as vulcanization accelerators have been correlated with their mass-spectral fragmentation patterns (322). 

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). 

The structures of the isoxazoles (393) were all consistent with their mass spectral fragmentation patterns. The reaction of hydroxylamine with 3-phenylchromone (394) gave exclusively 5-(o-hydroxyphenyl)isoxazole (395) (78ACH(97)69). 

Mass spectral fragmentation patterns are usually complex, and the molecular ion is often not the base peak. The mass spectrum of propane in Figure 12.2, for instance, shows a molecular ion at m/z = 44 that is only about 30% as high as the base peak at m/z = 29. In addition, many other fragment ions are present. 

Because mass-spectral fragmentation patterns are usually complex, it s often difficult to assign structures to fragment ions. Most hydrocarbons fragment in many ways, as the mass spectrum of hexane shown in Figure 12.4 demonstrates. The hexane spectrum shows a moderately abundant molecular ion at m/z = 86... 

Mass spectral fragmentation pattern of dime thy l-nitramine, CH3N(N02)CH3, mw 90 Instrument, CEC 21-104 Ionization Voltage 70 eV... 

The purity of the product is greater than 99% as determined by gas chromatographic analysis using a 6-m. column of 30% Carbowax 20M on 60-80 Chromosorb W. The major impurity (<1%) was shown to be 3-heptanol by comparison of gas chromatographic retention times and mass spectral fragmentation patterns with those of an authentic sample. 

Mass spectrometric studies yield principally three types of information useful to the radiation chemist the major primary ions one should be concerned with, their reactions with neutral molecules, and thermodynamic information which allows one to eliminate certain reactions on the basis of endothermicity. In addition, attempts at theoretical interpretations of mass spectral fragmentation patterns permit estimates of unimolecular dissociation constants for excited parent ions. 

The total yield of hydrogen under the conditions of these measurements was about 1.6 molecules/100 e.v. If one-half resulted from the primary dissociation also leading to acetylene ion, a yield of 0.8 acetylene ions/100 e.v. may be estimated. This value is a minimum since acetylene ion production can also be accompanied by hydrogen atom formation and is highly uncertain but consistent with the mass spectral fragmentation pattern of acetylene and W which lead to an estimate of ca. 0.94 acetylene ions/100 e.v. 

The reaction products from 2,4-dichlorophenol were tetrachloro-phenoxyphenols and tetrachlorodihydroxybiphenyls (Figure 5), as determined from their mass spectra and those of their methyl ethers. 4,6-Dichloro-2-(2, 4 -dichlorophenoxy)phenol (V) was the major phenoxy-phenol the mass spectral fragmentation pattern of o-hydroxyphenol ethers is quite characteristic since a hydrogen transfer occurs during the fragmentation (Figure 6). A trace of a trichlorophenoxyphenol also was detected and was formed presumably by the unsensitized reductive loss of chlorine, discussed previously. 

Figure k. Low and high resolution mass spectral fragmentation patterns of Component II. 

Molecular structures from mass-spectral fragmentation patterns... 

Mass spectra of the cis- and /ram-isomers of the pyrimido[2,TA [l,3]thiazin-6-ones 294 and 295 were studied. Retro-Diels-Alder fragmentation of the hydrocarbon ring was of medium to low stereospecificity. A number of highly selective processes were discovered allowing differentiation between stereoisomers <1996RCM721>. The mass spectral fragmentation pattern of 296 was studied in detail <1996PS(113)67>. 

Table 5. Mass spectral fragmentation pattern of miconazole...

One of the major problems has been to determine the site of attachment of the PAH to the base. Some information may be obtained directly from the nmr spectra eliminating certain points of attachment. As mentioned above, if the C-8 proton of guanine or adenine can be identified, then this cannot be the point of attachment of the carcinogen. Estimation of the pKa s of the adducts either by titration (108) or partition (110) has, however, provided additional valuable information. Mass spectral fragmentation patterns can be of help in determining the site of substitution as well as in determining which bases are involved in binding (108.111-113). Substantial advances have been made in recent years on the mass spectral analysis of involatile compounds and derivatization is not always essential (114-118). X-ray analysis of DNA adducts has, to date, only been applied to model systems (119-121). 

Pyrazolo[3,2-c]pyrido[4,3- ][l,2,4]triazine oxides704 were prepared by cyclization of the hydrazone derivatives 703 with ethanolic sodium hydroxide. Subsequent reduction of 704 gave 705 (76JPR835). Hydrazone 703 was prepared by condensation of 4-hydrazino-3-nitropyridine with 702. The mass spectral fragmentation patterns for 704 and 705 and their benzo analogues were studied (77ZC142). 

A proposed mass spectral fragmentation pattern of 2-amino-5-(4-trifluoroethoxyphenyl)-l,3,4-oxadiazole 28 is shown in Scheme 1 <1999JFC39>. 

A different mass spectral fragmentation pattern has been reported for diastereomehc steroidal sulfoxides (239). For instance, the sulfoxide 207 undergoes fragmentation to give a more abundant [M—CH3—SOH] ion than the other three diastereomeric sulfoxides. This indicates that in some cases the correlation of mass spectra with configuration is possible. 

Karminski-Zamola G, Dogan J, Boykin DW, Bajic M. 1995. Mass spectral fragmentation patterns of some new benzo [bjthiophene- and thieno[2,3-b] thiopene-2,5-dicarbonyl-dichlroide and -dicarbonyldianBides and anBidoquino-lones. Rapid Commun Mass Spectrom 9 282. 

Mass spectrometry Characteristic mass spectral fragmentation patterns 664... 

Electronic databases of the mass spectral fragmentation patterns of known molecules can be rapidly searched by computer. The pattern and intensity of fragments in the mass spectrum is characteristic of an individual compound so comparison of the experimental mass spectrum of a compound with those in a library can be used to positively identify it, if its spectrum has been recorded previously. 

Section VIII),and several accounts of the mass spectral fragmentation patterns of meso-ionic compounds have been published. " Measurement of electric dipole moments encouraged the assignment of the original meso-ionic structures to the sydnones. More recently, electric dipole moment studies have given powerful support to the formulation of several new classes of heterocycle as meso-ionic compounds. ... 

The role of size exclusion chromatography is the separation of rather complex coal liquids into simpler fractions. The retention volume can be used to help Identify the chemical structure where GC-MS is unable to identify its possible structure. For example biphenyl and dihydroacenaphthene have the same molecular formula as well as similar mass spectral fragmentation patterns. Coal liquids contain both species. The one which appears first (lower SEC retention volume) is biphenyl (GC ret. time = 17 min. in Figure 5-6). Dihydroacenaphthene appears later at longer SEC retention volume and is identified in Figure 5-12 at GC retention time of 13 minutes. The former has a longer structure compared to the latter. 

Extensive nuclear magnetic resonance and ultraviolet spectroscopy methods were reviewed in <1996CHEC-II(7)363>, as well as mass spectral fragmentation patterns of [l,2,3]triazolo[4,5-/ ]pyridines (Section 7.10.8.1). More recently, furoxan rearrangement of some pyridofuroxan derivatives has been studied by H, and... 

Scheme 11 Mass-spectral fragmentation pattern for 1,2,4-triazine...

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