Substituent effects on the mass spectra of substituted phenyl acetates

The mass spectra of a series of meta- and para-substituted phenyl acetates have been examined. Substituent effects have been correlated with Δ (AP-IP) values and by using the Harrison and Chin approach. The bond-cleavage and rearrangement reactions of phenyl accetates are compared with the corresponding reactions of acetanilides and the differences attributed to the degree of transmission of polar effects in the two systems.     

Substituent effects in the mass spectra of acetanilides

The kinetic shifts for an ion decomposition involving loss of CH₂CO from a series of substituted acetanilide ions have been calculated using the Rice-Ramsperger-Kassel-Marcus theory. The results indicate that in the main the observed changes in appearance potential-ionisation potential for this reaction are due to a change in the number of degrees of freedom on introducing the substituent and not due to a substituent effect on the critical energy of reaction.     

Substituent effects in the mass spectra of benzoyl hetarenes

The mass spectra of several benzoyl hetarenes, of 2-benzoyl pyridines substituted at the phenyl and pyridyl group, respectively, and of phenyl substituted 2-benzoyl pyrroles, have been studied with respect to the formation of benzoyl and hetaroyl ions. A correlation between the intensity of benzoyl ions, relative to molecular ion intensity, and the π-electron density at the substituted carbon atom of the hetarene has been observed for benzoyl hetarenes. The relative intensities of (substituted) benzoyl ions of substituted 2-benzoyl pyridines and 2-benzoyl pyrroles are not easily related to substituent constants of Hammett equations. The relative ionization energies of phenyl substituted 2-benzoyl pyridines, however, and the relative appearance energies of substituted benzoyl ions derived therefrom follow the σ_IP⁺-constant of Bentley and Johnstone and the σ⁺-constants of Brown, respectively.     

Substituent effects in mass spectra of monosubstituted benzils

The mass spectra of a series of thirteen m- and p-substituted benzils have been determined at several ionising voltages below 20 eV and at 70 eV. At ionising voltages up to 5 eV above the ionisation potentials the benzil molecular ions decompose entirely by two pathways to give substituted and unsubstituted benzoyl ions. Fractional intensities of the molecular ion (F_M), substituted (F_X) and unsubstituted (F_H) benzoyl ions were obtained for each benzil as a function of energy from measured ionisation efficiency curves, and ionisation and appearance potentials for all major ions determined from the ionisation efficiency curves by a semilogarithmic method. Various correlations of ion intensity and energy parameters with δ⁺ and δ constants are examined; these are generally poor. Fair correlations are obtained between log (F_X/F_H) or (AP – AP) and δ or δ⁺, and these are interpreted in terms of the expected effect of substituents on the stabilities of the product ions in the decompositions. A good correlation is observed between log (F_X/F_H) and AP · AP; this suggests that substituents affect F_X/F_H mainly by changing the activation energies for the competing decompositions of the molecular ions. The competitive shift has a marked effect on these appearance potentials so that in this system AP – IP is not a good measure of the activation energy for the primary decompositions.     

Substituent effects in the field ionization mass spectra of acetophenones

Substituent effects in the electron-impact and field ionization mass spectra of acteophenones are compared. No Hammett correlation could be found for the fragments formed on the surface of the field anode. A straight line log z/z0 versus σ⁺ was observed, however, for the metastable decomposition of para-substituted acetophenones (and also some benzophenones). Meta-substituted compounds did not yield such straight lines.     

Low-temperature SIMS mass spectra of diethyl ether

For the first time a secondary ion mass spectrum of diethyl ether was obtained at low temperature. The spectrum recording became possible by carefully selecting the range of experimental conditions for the production of a cluster-type spectrum. This range is specified by the threshold for spectrum appearance above the melting temperature of the frozen sample and a fairly short time span of existence of the liquid estimated as only a few minutes. The latter necessitates rather rapid spectrum detection. In practice, about 1 min was available for recording of the cluster-type spectra. The secondary emission mass spectrum of diethyl ether appeared to be rich in peaks: along with abundant protonated clusters M(n).H(+) (n = 1-12), unusually intense [M(n) - H](+) and weaker M(n) (+.) peaks were present accompanied by several sets of fragmented clusters, [M(n) - 15](+), [M(n) - 29](+), [M(n) - 27](+), [M(n) - 45](+), and monohydrates, M(n).H(2)O.H(+). The analysis of all the peaks showed that the pattern of fragment clusters is qualitatively similar to the pattern of fragmentation of the diethyl ether molecular ion under high-energy electron impact. The general features of the behaviour of diethyl ether under low-temperature mass spectrometric conditions were similar to those observed earlier for some other organic solvents.     

Substituent effects in the fragmentation reactions of acetanilides and phenyl acetates

The mass spectra of a group of m- and p-substituted acetanilides were measured to determine the effect of the substituents, if any, on the rate of C₂H₂O expulsion (rearrangement) vs. the rate of [CH₃CO]⁺ formation (simple cleavage). Our results agree with observations of others in that substituents which raise the ionization potential of the aromatic ring appear to localize, on the average, less charge density on this locus, and conversely. The atomic composition of the substituent, however, irrespective of its position, seems to determine the relative rates of the competing reaction. Although in several cases Z_m/Z_p values were close to unity, rearrangement of isomeric molecular ions to a common species is shown not to occur.     

The mass spectra of alkyl phenyl tellurides

The mass spectra of several alkyl phenyl tellurides, C₆H₅TeR (R = CH₃, CD₃, C₂H₅, n-C₃H₇, i-C₃H₇ and n-C₄H₉) have been studied with special emphasis on the fragmentation patterns involving cleavage of the alkyl and aryl tellurium–carbon bonds. Each compound exhibited intense parent ions. The rearrangement ions [C₆H₆Te]⁺? and [C₆H₆]⁺? were found in the spectra of phenyl ethyl and higher tellurides. Two other rearrangement ions [HTe]⁺ and [C₇H₇]⁺ were observed in the spectrum of each compound. Examination of the mass spectrum of phenyl methyl-d₃ telluride demonstrated that the [HTe]⁺ ions derive hydrogen from the phenyl group.     

Electron-impact-induced hydrogen migration in organic molecules I–Substituent effects in the mass spectra of pivlanilides

Substited pivalanilides give rise to fragments corresponding to anilies on electron-impact, which is due to the migration of a hydrogen atom from the t-butyl group to the nitrogen. The Hammett correlation indicates that the formation of this fragment is favoured by electron-donating groups. The other interesting feature of these spectra is the migration of the aryl group to the t-butyl carbon with the elimination of the neutral ketemine.     

Substituent and coupling effects in the IR spectra of arylidenecyclanones

By studying the IR spectra of arylidenecyclanones possessing exocyclic CC double bonds, a correlation has been found between the wave number and intensity values of the ν CO and ν CC vibrations and the substituent constants. Transmissive factors of the CC double bond have been calculated and these indicated that the most pronounced conjugation occurs in the case of the indanones and the smallest for 1-thiochromanones. It has also been established that the substituent effect transmitted by the CC double bond is mainly of a resonant character. Coupling of the ν CO and ν CC vibrations has been studied by the method of Taylor and Smith. It has been concluded that in the case of arylidene-indanones possessing strong coupling, of the two intense bands between 1600 and 1800 cm⁻¹ the one found at higher wave number is a result of an out-of-phase (ν_as) coupling of the ν CO and ν CC vibrations while the other originates from an in-phase (ν_s) coupling. Coupling was less in the case of the other compounds investigated. Our studies prove that for the evaluation of the substituent effects the coupling phenomena should be taken into consideration.     

Substituent effects on the photoelectron spectra of benzene derivatives

Systematics in the ionization energies corresponding to the different π orbitals of para, meta and ortho-disubstituted benzenes obtained from PES have been investigated. The data have been discussed in terms of correlations with substituents constants and such correlations are shown to provide the basis to differentiate steric from electronic effects in the case of ortho derivatives. Ionization energies from PES corresponding to the lone pair orbitals of substituents in related series of p-disubstituted benzenes are shown to vary systematically with the substituent constants.     

Electron-impact studies. LXXXIV—Substituent effects in the negative ion mass spectra of aryl esters

Linear plots may be obtained for the fragmentations of aryl p-cyanobenzoates using the McLafferty approach, but the correlations are not as satisfactory as those observed¹ for aryl nitrobenzoates. Some satisfactory correlations of substituent effects are noted in the negative ion spectra of substituted benzyl-p-nitrobenzoates and substituted phenyl-(p-nitrophenyl)acetates. Pronounced rearrangement peaks are observed in the spectra of substituted phenyl-(p-nitrophenyl)acetates. Appearance potential studies suggest that the similarities in ρ values obtained¹ for the fragmentations of aryl m- and p-nitrobenzoate molecular anions are probably due to the correspondence between Hammett σ values and appearance potentials in the two series.     

The mass spectra of some phenyl pyridyl ketones

The mass spectra of phenyl 2-pyridyl, phenyl 3-methoxy-2-pyridyl, phenyl 4-methoxy-2-pyridyl, phenyl 5-methoxy-2-pyridyl, phenyl 6-methoxy-2-pyridyl ketones, phenyl 3-pyridyl and phenyl 6-methoxy-3-pyridyl ketones, and phenyl 4-pyridyl ketone were studied. The major fragmentation pathway of all the ketones results in the formation of[C₆H₅CO]⁺ and [C₅H₄NCO]⁺ type ions. Another fragmentation path is the loss of carbon monoxide with formation of an [M ? CO]⁺ ion after skeletal rearrangement.     

Substituent effects in the mass spectral fragmentation of aryl esters

The mass spectra of m- and p-substituted phenyl acetates, phenyl propionates, phenyl chloroacetates and phenyl fluoroacetates have been determined. The fragmentation of aryl esters is affected by acyl substituents as well as by aryl substituents. Esters having acyl groups of low ionization potential show greater changes in fragmentation because of aryl substituents than those having acyl groups of high ionization potential. Each series has a fairly definite crossover point where fragmentation changes from predominant rearrangement to predominant cleavage.     

Substituent and H/D randomization in the mass spectra of substituted diphenylacetylenic compounds

The mass spectra of several substituted diphenylacetylenes are reported and the [metastable ion]/[daughter ion] ratios for the isomeric chloro- and bromodiphenylacetylenes suggested substituent scrambling in their respective molecular ions. The metastable ion data also indicated equilibration of the chloro substituents in a series of isomeric dichlorodiphenylacetylenes. In addition, the fragmentation patterns for the amino- and nitrodiphenylacetylenes differed somewhat from most other aromatic amino and nitro compounds. The aminodiphenylacetylenes fragment with expulsion of H₂CN from the molecular ion and the expulsion of HCN from the [M – 1]⁺ ion was only a relatively minor reaction. 4-Nitrodiphenylacetylene loses NO from the molecular ion and OH from the [M – NO]⁺˙, whereas the more familiar loss of OH from the molecular ion was not observed. The mass spectra of several deuterated substituted diphenylacetylenes clearly showed extensive (but not complete) H/D equilibration in the molecular ion or some subsequent decomposition ion. Comparative studies between 4-chloro and 4-bromo substituted biphenyl, diphenylacetylene and diphenyldiacetylene indicated similar degrees of H/D randomization, and the results showed that the ? C?C? group did not inhibit the proton equilibration between the two phenyl groups.     

C NMR spectra of cyclomercurated ferrocenylimines: Substituent effects and conformations in the ferrocenes

Three series of cyclomercurated ferrocenylimines (2-chloromercurio-ferrocenylimines) have been studied using ¹³C NMR spectroscopy. Good to excellent linear relationships have been found to exist between the chemical shifts of the carbon atoms in the ferrocenyl moiety and normal Hammett substituent constants σ_m and σ_p. The δ values of the iminyl carbon atoms show excellent linear correlations with the σ values. In three series of the ferrocenes, the sensitivity of the carbon atoms to the substituent effect is different, which is discussed in terms of the twist angle between the N-phenyl ring and the C---C=N---C plane. The relative sensitivity of the chemical shifts on different positions in ferrocenyl moiety to the substituent effect has also been presented.