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.     

Zur Photochemie von 3,5-Diaryl-2-isoxazolinen. 30. Mitteilung über Photoreaktionen

Irradiation of 3,5-diphenyl- or 3-(p-tolyl)-5-phenyl-2-isoxazoline ( 12 and 13 , respectively) in benzene with a high-pressure mercury lamp yields 4,5-diphenyl- or 4-(p-tolyl)-5-phenyl-3-oxazoline ( 17 and 19 , respectively) and the β-amino-chalcones 18 or 20 in addition to benzaldehyde, benzonitrile and p-tolunitrile, respectively (scheme 6 and ‘Anmerkg.’ p. 2600). The 3-oxazolines 17 and 19 are formed by route a (scheme 8) via 3-phenyl- or 3-(p-tolyl)-2H-azirine ( 23 , R = H and CH₃, respectively) and their photochemically rearranged successors, the nitrile methylides 24 , as intermediates. The discovery of this reaction has served as a basis for the quickly developing photochemistry of 3-aryl-2H-azirines [2] [24]. Photolysis of the 2-isoxazoline 13 in methanol leads to the formation of a mixture of syn/anti-p-tolyl trans-styryl ketoximes (syn/anti, trans- 30 ) and anti, cis- 30 , 2-(p-tolyl)-quinoline ( 29 ), the 4-hydroxymethylated derivative 32 of the latter (in small amounts), besides the β-aminochalcone 20 , benzaldehyde, p-tolualdehyde and p-tolunitrile (scheme 9). It could be shown that the stereoisomeric ketoximes 30 are photochemically interconvertible (scheme 12) and that at least one mechanism of formation of 2-(p-tolyl)-quinoline ( 29 ) is the photo-induced cyclisation of p-tolyl-cis-styryl ketoximes (cis- 30 ) (scheme 13). A tentative mechanism for the formation of p-tolual-dehyde is given in scheme 10; the crucial step is the protonation of p-tolunitrile methylide ( 24 , R = CH₃) by methanol at the nitrile carbon atom, after which hydrolysis yields the aldehyde.     

Mass Spectral Fragmentation Patterns of 11-(o- and p-R-Anilino)-5H-dibenzo[b,e][1,4]diazepines. IV

The mass spectral fragmentation patterns of eleven 11-(o- and p-R-anilino)-5H-dibenzo[b,e][1,4]diazepines obtained by electron impact have been studied. All the spectra analyzed contain molecular ions, which are base peak for para isomers and the principal fragmentation routes takes place either from the molecular ion, or from (M⁺ - 1) ion. There are, however, some deviations from the general fragmentation pattern in the case of 1,4-dibenzodiazepines with o-amino and p-methoxy substituents caused by direct interaction of these groups with the dibenzodiazepine ring.     

The substituent effect in the fragmentation of phenylcyclohexanols

All the main fragmentation pathways undergone by trans-4- and trans-2-p-substituted phenylcyclohexanols have been studied, and the ionic abundances have been correlated with the σ constants. This analysis shows that electron withdrawing substituents, increasing the fraction of molecular ions having sufficient energy to decompose, favour all fragmentations. However, along with this ‘non-specific’ substituent effect, there is a ‘specific’ effect, in the opposite sense, increasing the formation of the [M—59]⁺ and [M—85]⁺ ions with increasing electron releasing power of the substituents. The loss of water, although it is almost exclusively a 1,4 elimination in the case of trans phenyl cyclohexanols, is not specifically influenced by the substituents.     

Der zweistufige Carbanion-Mechanismus der Fragmentierung von 3-Aminopropylbenzoaten. Fragmentierungs-Reaktionen. 25. Mitteilung

The unsubstituted and p-substituted benzoates 2b – 2e of 3-dimethylamino-2,2bis(p-nitrophenyl)-propanol ( 2a ) undergo quantitative fragmentation in 80% ethanol yielding 1,1-bis(p-nitrophenyl)-ethylene ( 5 ) besides formaldehyde and dimethylamine, the hydrolysis products of the imonium ion 3 . The corresponding alcohol 2a , however, yields 2,2-bis(p-nitrophenyl)-ethanol ( 9 ) in addition to fragmentation products. Conversely, no fragmentation is observed with the benzoates 6b – 6e of 3-dimethylamino-2,2-diphenylpropanol ( 6a ) which lack electronwithdrawing substituents in the β-phenyl groups. These results are in agreement with a two-step carbanion mechanism (Scheme 2) involving the ionization of the aminoalkohol 2a and its esters 2b – 2e to the imonium ion 3 and the carbanions 4a – 4e . The latter undergo competitive cleavage, recombination and protonation to 5 , 2 and 9 , respectively, depending on the nucleofugal activity of –X. These conclusions are supported by the first-order rate constants for the benzoates 2b – 2e which differ merely by a factor of three. Since the p-substituents in the benzoate groups have only a minor effect on the reaction rate the bonds to the nucleofugal groups are not appreciably broken in the rate determining step.     

Polar Effects in the Solvolysis of 4-Substituted Bicyclo [2.2.2]octyl p-Nitrobenzenesulfonates. Polar effects. VII

Hydrolysis of bicyclo[2.2.2]octylp-nitrobenzenesulfonate ( 14a , X = p-NO₂C₆H₄SO₃), and nineteen 4-R-substituted derivatives 14b–14t in 70% aqueous dioxane yield the corresponding bicyclo[2.2.2]octanols 14 (X = OH), exclusively. The 7-center fragmentation to 1,4-dimethylidene-cyclohexane ( 15 ) is not observed. The logarithms of most of the rate constants, measured in 80% ethanol, correlate well with the corresponding inductive substituent constants σ of R. Hence, in these cases ionization rate is controlled by the inductive effect of R only. Poor correlations result when the substituents are potentially electrofugal groups, such as COO^?, CH₂OH, CH₂NH₂, CONH₂ and H, the deviations from the inductive regression line corresponding to rate enhancements of 1.6 to 8. These exalted substituent effects are tentatively ascribed to extended hyperconjugation involving two σ-bonds. This study corroborates previous evidence that the inductive effect alone does not fully account for the polar effect of some substituents in reactions involving carbocations.     

Bio-based vinylphenol family: Synthesis via decarboxylation of naturally occurring cinnamic acids and living radical polymerization for functionalized polystyrenes

A series of bio-based vinylphenols or hydroxystyrenes is prepared by simple decarboxylation of various naturally occurring cinnamic acids such as o-, m-, and p-coumaric; caffeic; ferulic; and sinapinic acids, which possess hydroxy groups and other substituents at different positions on the aromatic ring. After protection of the phenolic moieties with trialkylsilyl groups, reversible addition–fragmentation chain-transfer polymerization is accomplished with cumyl dithiobenzoate to afford various bio-based hydroxyl-protected polystyrenes with controlled molecular weights and narrow molecular weight distributions. Subsequent deprotection of the silyl groups under mild conditions results in a series of well-defined functionalized polystyrenes possessing different numbers (mono-, di-, tri-) of hydroxy groups at different positions (o, m, p). The obtained functionalized polystyrenes show unique thermal properties depending on the substituents, and those with phenol and catechol groups serve as reducing agents for silver ions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 91–100     

Hydrogen migration in the electron impact induced retro diels-alder fragmentation of N-aryl-4H-5,7a-epoxyisoindolines

The electron impact induced fragmentations of the C-5 unsubstituted and 5-methyl N-aryl-4H-5,7a-epoxyisoindolines (where aryl is pheny, p-tolyl, p-methoxyphenyl, o-methoxyphenyl and p-chlorophenyl) were investigated. The fragmentation patterns deduced were supported by exact mass measurements of prominent ions and by deuterium labelling. The retro Diels-Alder fragmentation turned out to be a predominant process in all the compounds investigated. In the mass spectra of the 5-methyl N-aryl-4H-5,7a-epoxyisoindolines hydrogen migration preceding fragmentation occurred. From the mass spectrum of the specifically deuterated compound it was concluded that the transferred hydrogen originates exclusively from the 5-methyl group.     

Unidirectional triple and double hydrogen rearrangement reactions in the radical cations of γ-arylalkanols

A novel fragmentation reaction accompanied by the unidirectional migration of three hydrogen atoms has been found in the radical cations of γ-arylpropanols with electron-donating substituents in the para position. This triple hydrogen (3H) rearrangement reaction is the dominant fragmentation channel of the long-lived molecular ions of trans-2-(4′-dimethylaminobenzyl)-l-indanol, 2, but it occurs also in simpler γ-arylpropanol ions. Deuterium labelling of 2 reveals that the three hydrogen atoms originate with extraordinarily high specificity from the C(l), C(2) and O positions of the alcohol moiety. Cis- and 3′-substituted isomers do not undergo this reaction. Along with the 3H rearrangement reaction a unidirectional double hydrogen (2H) rearrangement reaction takes place independently and with less specificity in the trans-2-(4′-X-benzyl)-l-indanol ions 1⁺˙ and 2⁺˙. No hydrogen exchange occurs during the 3H and 2H rearrangement reactions. Mechanistic alternatives of these unusual fragmentation reactions are discussed; the experimental evidence strongly favours pathways via several intermediate ion–neutral complexes.     

Mass spectra of 5,10-dihydrophenarsazines, 5,10-dihydrophenarsazine and phenophosphazine oxides,and related heterocycles

The electron-impact-induced fragmentation of eight 5,10-dihydrophenarsazines and three 5,10-dihydrophenarsazine oxides proceeds by loss of the exocyclic arsenic substituents to give the stable ion (II) as the base peak followed by loss of arsenic to give a carbazole species (III). The fragmentation pattern is independent of substituents at either hetero-atom in the cases examined. Dihydrophenophosphazine oxides behave similarly but give as the base peak an ion in which the phosphoryl grouping is retained. 10,11-Dihydro-5-phenyl-5H-dibenzo[b, f][1,4]azarsepine and 2,3-dihydro-1,2-diphenyl-1H-benz [c]azarsole fragment by different pathways. It is suggested that the ability of arsenic and phosphorus to sustain a positive charge by dπ-pπ bonding is the dominating factor in these fragmentations.     

Ortho effects of a nitro group in 2′,3′ and 4′monosubstituted-trans-2,4-dinitrostilbenes on electron impact. IV

The mass spectral fragmentation patterns of thirteen 2′,3′ and 4′-R-trans-2,4-dinitrostilbenes obtained by electron impact have been studied. The main routes of fragmentation involves loss from the molecular ion due to the ortho effects of the 2-nitro substituents. Substitution on positions 2′,3′ and 4′ of stilbene moiety does not influence the fragmentation patterns.     

Irreversible enzyme inhibitors. XCI. candidate active-site directed irreversible inhibitors of thymidylate synthetase. II. 2-amino-6-methyl-5-(p-tolylsulfonamidopropyl)-4-pyrimidinols with N-substituents on the sulfonamide moiety

Three derivatives of 2-amino-6-methyl-5-(p-tolylsulfonamidopropyl)-4-pyrimidinol (I) with N - substituents on the sulfonamide group, namely bromoacetamidopropyl (XVI), m-bromoacetamidobenzyl (XXIVa), and p-bromoacetamidobenzyl (XXIVb), were synthesized as candidate active-site-directed irreversible inhibitors of thymidylate synthetase. The bromoacetamidopropyl derivative, (XVI), the p-bromoacetamidobenzyl derivative (XXIVb), and iodoacetamide showed irreversible inhibition of thymidylate synthetase, but XXIVa did not. Since iodoacetamide did inactivate the enzyme, but XXIVa did not, it cannot be ascertained whether XXIVb and XVI inactivate the enzyme by a random bimolecular mechanism or by the active-site-directed mechanism without evaluation of additional candidate inhibitors. Two synthetic routes were employed. The key intermediates for the bromoacetamidobenzyl sulfonamides (XXIV) were the corresponding nitrobenzyl sulfonamides (XXI); the latter were best prepared by reductive alkylation of 2-amino-5-aminopropyl-6-methyl-4-pyrimidinol (XXV) with a nitrobenzaldehyde followed by tosylation. The key intermediate for XVI was a toluenesulfonamide with a carbobenzoxyaminopropyl substituent on the nitrogen (XIV); the latter was synthesized via N-carbobenzoxy-N'-tosyl-1,3-diaminopropane (XI).     

Fragmentation of substituted 4-hydroxy-2-quinolones under the influence of electron impact

The general principles of the mass-spectral disintegration of 4-hydroxy-2-quinoline derivatives containing various substituents attached to the nitrogen in the 3 position were established. It was found that the disintegration of 4-hydroxy-2-quinolone and its N-substituted derivatives proceeds primarily through cleavage of the heterocyclic ring, while the principal pathways of the disintegration of 3-acyl derivatives are associated with fragmentation of the acyl group.     

Norbornanes. Part 10. Solvolysis of the Stereoisomeric 6-Cyano-2-norbornyl p-Toluenesulfonates. A Correction

The solvolysis products of the stereoisomeric 6-cyano-2-norbornyl p-toluene sulfonates 1 - 4 (R ? CN) in dioxane/water 7 : 3 have been determined. In contrast to an earlier report the 6exo-cyano-2exo-norbornyl p-toluenesulfonate ( 1 ; R?CN) yields 30% of the 2endo-alcohol 9 (R?CN) beside the 2exo-alcohol 10 and the norbornenes 12 and 13. The results confirm that - I substituents at C(6) reduce 1,3-bridging in the intermediate norbornyl cation and hence its rate of rearrangement. The relatively high rate constants for some 6-fluoro- and 6-cyano-2exo norbornyl p-toluenesulfonates are ascribed to C, C-hyperconjugation assisted by the conjugative effects of the 6-fluoro and cyano substituents.     

Tautomerism of 2-(o-hydroxyphenyl)-azines

The tautomeric properties ofo-hydroxyphenylazines have been investigated by¹⁷O NMR and UV spectroscopy. 2-(o-Hydroxyphenyl)-pyridine and itsp-nitrophenole analog II exist in chloroform or ethanol as a phenol A. In the case of 2-(2-hydroxy-5-nitrophenyl)-quinoline the NH-tautomer is realized, the content of which increases when going to the dinitro-analog IV.

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Die Tautomerie von 2-(o-Hydroxyphenyl)-azinen (Kurze Mitteilung)

Zusammenfassung Es wurden die tautomeren Eigenschaften vono-Hydroxyphenylazinen mittels¹⁷O-NMR und UV-Spektroskopie untersucht. 2-(o-Hydroxyphenyl)-pyridin und seinp-Nitrophenol-Analog II existieren in Chloroform und Ethanol als Phenol A. Das 2-(2-Hydroxy-5-nitrophenyl)-chinolin liegt als NH-Tautomer vor, dessen Anteil im Dinitro-Analog IV noch steigt.

     

Acetylenchemie, 33. Mitt.: Synthese von 2-substituierten Dihydrofuro[2,3-b]chinolinen

Summary The reaction of 3-iodo-4-methoxy-2(1H)-quinolinone (1) and 3-iodo-4,6,8-trimethoxy-2(1H)-quinolinone (2) with 2-methyl-3-butyn-2-ol under modified Heck-conditions gave the 2-substituted derivatives 2-(1-hydroxy-1-methylethyl)-4-methoxyfuro[2,3-b]-quinoline (3) and 2-(1-hydroxy-1-methylethyl-4,6,8-trimethoxyfuro[2,3-b]-quinoline (4). By a subsequent hydrogenation-reaction with a homogeneous catalyst (PtO₂/Rh₂O₃), the furoquinoline-derivatives yielded the dihydrofuro-[2,3-b]quinolines, identified as 2-(1-hydroxy-1-methylethyl-4-methoxy-2,3-dihydrofuro[2,3-b]quinoline (5) (racemic platydesmine) and 2-(1-hydroxy-1-methylethyl)-4,6,8-trimethoxy-2,3-dihydrofuro-[2,3-b]quinoline (6) (racemic precursor of O⁴-methylptelefolonium salt).

     

Synthesis and mass spectral fragmentation of 2-methylthio-7-(p-R-phenyl)-8-phenoxy-4,5-benzo-3-aza-2-nonem. III

A series of new 2-methylthio-7-(p-R-phenyl)-8-phenoxy-4,5-benzo-3-aza-2-nonem, IIIa, have been synthesized by regiospecific cycloaddition of phenoxyacetyl on to 2-methylthio-4-(p- R -phenyl)-3H-1,5-benzodiazepines IV. The structure was established by ir, ¹H-nmr and ms spectral data together with ¹³C-nmr spectral data of desulfurization products, VIa. Likewise, a study has been made of the fragmentation upon electron impact of IIIa and IV. All the spectra analyzed contain molecular ions and the principal fragmentation routes takes place either from the molecular ion or from m/e (M⁺ — 134) ion. This ion is the base peak for all the compounds analyzed.     

Charge localization and aromatic stabilization in large ring ions: Mass spectra of ms-porphyrins

The major mass spectrometric fragments of ms-tetraphenylporphin and ms-tetra(p-chloro)phenylporphin are [M ? H]⁺˙ and [M ? Cl]⁺˙, respectively. Metal derivatives of these compounds give a modified characteristic fragmentation pattern with peak groups ending in the ions [M ? 4H]⁺˙, [M ? ? ? 5H]⁺˙ and [M ? 2? ? 2H]⁺˙ for the metallo ms-tetraphenylporphins, and [M ? ?Cl ? 2Cl ? 3H]⁺˙ and [M ? 2?Cl ? Cl ? H]⁺˙ for Mgms-tetra(p-chloro)phenylporphin. Deuterated metal derivatives indicate random hydrogen loss from both phenyl and pyrrole carbons. However, metal substituents do not significantly modify the fragmentation pattern in the case of ms-tetra(p-methoxy)phenylporphin. These patterns can be explained in terms of aromatic stabilization of the fragmentation products, coupled with charge localization on the π system in the free base, on the metal atom in the metallo derivatives and on the methoxy function in the p-methoxyphenyl derivative.     

Highly Emissive Diborylphenylene‐Containing Bis(phenylethynyl)benzenes: Structure–Photophysical Property Correlations and Fluoride Ion Sensing

A series of 2,5‐bis(dimesitylboryl)‐1,4‐bis(arylethynyl)benzenes 1 – 6 that contain various p‐substituents on the terminal benzene rings, including NPh₂ ( 1 ), OMe ( 2 ), Me ( 3 ), H ( 4 ), CF₃ ( 5 ), and CN ( 6 ) groups, were synthesized, and the effects of the p‐substituents on the absorption and fluorescence properties were investigated both in solution and in the solid state. Linear relationships were obtained not only between the Hammett σ_p⁺ constants of the p‐substituents and the absorption and fluorescence maxima, quantum yields, and excited‐state dynamics parameters in solution, but also between the σ_p⁺ constants and the fluorescence quantum yields in the solid state. An important finding extracted from these results is that the suppressed fluorescence quenching in the solid state is a common feature for the present laterally boryl‐substituted π‐conjugated skeletons. Hence, the diborylphenylene can serve as a useful core unit to develop highly emissive organic solids. In fact, most of the derivatives showed more intense emission in the solid state than in solution. In addition to these studies, the titration experiment of 1 by the addition of nBu₄NF was conducted, which showed the stepwise bindings of two fluoride ions with high association constants as well as a drastic change in the fluorescence spectra, while constantly maintaining high quantum yields (0.61–0.76), irrespective of the binding modes. This result also demonstrated the potential utility of the present molecules as an efficient fluorescent fluoride ion sensor.     

BECKMANN-Umlagerung und Fragmentierung; V. Teil Mechanismus der 7-Zentren-Fragmentierung von 1-Oxo-5-oximino-9-methyl-trans-decalin. Fragmentierungsreaktionen, 22. Mitteilung

The reaction rates of heterolytic fragmentation of 5-(p, -toluenesulfonyloxyimino)-1-oxo-9-methyl-trans-decalin ( 1 ), induced by sodium hydroxide in 80% ethanol and by sodium ethoxide in 100% ethanol, has been determined. The reaction of the oxime tosylate 1 with sodium ethoxide is first order with respect to both reactants. A similar base-dependence is observed in the reaction of the oxime tosylate 1 with sodium hydroxide. These results are explained in terms of an addition-fragmentation mechanism. This involves reversible addition of NaOH or NaOC₂H₅ to the carbonyl group of the oxime tosylate 1 and concerted fragmentation of the addition compounds 5a and 5b , yielding 9-cyano-6-methyl-trans-non-5-enoic acid ( 4a ) and the corresponding ethyl ester 4b , respectively. These reaction appear to be the first cases of concerted and stereospecific 7-centre fragmentation.