0000000000532319
AUTHOR
Vitalba Pace
Can the absence of solvation of neutral reagents by ionic liquids be responsible for the high reactivity in base-assisted intramolecular nucleophilic substitutions in these solvents?
[reaction: see text] The kinetics of the rearrangement of the Z-phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole (1a) into the relevant 4-benzoylamino-2,5-diphenyl-1,2,3-triazole (2a) induced by amines have been studied in two room-temperature ionic liquids (IL-1, [BMIM][BF4] and IL-2, [BMIM][PF6]). The data collected show that the reaction occurs faster in ionic liquids than in other conventional solvents previously studied (both polar or apolar, protic or aprotic). Presumably, this could depend on their peculiar ability to minimize the strong substrate-solvent, amine-solvent and amine-amine interactions occurring in conventional solvents.
Effetto dei sostituenti sulla reattività di alcuni Z-fenilidrazoni del 5-ammino-3-benzoil-1,2,4-ossadiazolo in diossano/acqua
On the Rearrangement in Dioxane/Water of (Z)-Arylhydrazones of 5-Amino-3-benzoyl-1,2,4-oxadiazole into (2-Aryl-5-phenyl-2H-1,2,3-triazol-4-yl)ureas: Substituent Effects on the Different Reaction Pathways
We have recently evidenced an interesting differential behavior in the reactivity in dioxane/water between the (Z)-2,4-dinitrophenylhydrazone (1a) and the (Z)-phenylhydrazone (1b) of 5-amino-3-benzoyl-1,2,4- oxadiazole. The former rearranges into the relevant triazole 2a only at pS+ > 4.5 while undergoing hydrolysis at high proton concentration (pS+ < 3.5); on the contrary, the latter rearranges into 2b in the whole pS+ range examined (0.1 e pS+ e 14.9). Thus, for a deeper understanding of these differences we have now collected kinetic data on the rearrangement in dioxane/water of a series of 3- or 4-substituted (Z)-phenylhydrazones (1c-l) of 5-amino-3-benzoyl-1,2,4-oxadiazole in a wide ra…
Abilità organizzante di liquidi ionici: effetto sulla velocità di reazioni di trasposizione mononucleare di eterocicli.
Reattività dello Z-fenilidrazone del 5-ammino-3-benzoil-1,2,4-ossadiazolo in toluene in presenza di acidi aloacetici.
On the application of the extended Fujita-Nishioka equation to polysubstitued system. A kinetic study of the rearrangement of several poly-substitued Z-arylhydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadiazole into 2-aryl-4-benzoylamino-5-phenyl-1,2,3-triazoles in dioxane/water
Abstract The rearrangement rates of several di-, tri-, tetra- or penta-substituted Z -arylhydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadiazole ( 1a – 18a ) into the relevant 2-aryl-4-benzoylamino-5-phenyl-1,2,3-triazoles ( 1b – 18b ) have been determined in 1:1 (v:v) dioxane/water in a wide range of p S + (3.80–12.50) at different temperatures. The kinetic data obtained have been correlated with those previously collected for the rearrangement of ortho -, meta - and para -substituted Z -arylhydrazones ( 19a – 38a ) by means of an extension of the linear free-energy relationship (LFER) proposed by Fujita and Nishioka, thus considering steric ( E s ) and field ( F o ) proximity effects in additi…
Effect of ionic liquid organizing ability and amine structure on the rate and mechanism of base induced elimination of 1,1,1-tribromo-2,2-bis(phenyl-substituted)ethanes
Abstract The kinetics of the elimination reaction of 1,1,1-tribromo-2,2-bis(phenyl-substituted)ethanes into the corresponding 1,1-dibromo-2,2-bis(phenyl-substituted)ethenes induced by amines were studied in three room temperature ionic liquids ([BMIM][BF 4 ], [BMIM][PF 6 ], [BdMIM][BF 4 ]). In order to have information about reagent–ionic liquid interactions, the reaction was carried out over the temperature range (293.1–313.1 K). To study the effect of the amine on the rate and occurrence of the elimination reaction, several primary, secondary and tertiary amines with different structure (cyclic and acyclic), basicity and steric requirements were used. The data collected show that the reac…
Room temperature ionic liquids structure and its effect on the mononuclear rearrangement of heterocycles: an approach using thermodynamic parameters.
The kinetics of the rearrangement of the Z-phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole (1) into the relevant 4-benzoylamino-2,5-diphenyl-1,2,3-triazole (2) induced by amines have been studied in five room-temperature ionic liquids (RTILs) at different temperatures. The kinetic data collected show that both cationic and anionic parts of RTILs significantly influence the reactivity of the title reaction. The calculated activation parameters allow us to advance hypotheses about the weak interactions operating in RTIL solutions.
Studio cinetico della reazione di eliminazione di 1,1,1-tribromo-2,2-bis(dimetossifenil)etano in liquidi ionici.
Ring-to-ring interconversion: a reactivity study of some substituted Z-phenylhydrazones of the 5-amino-3-benzoyl-1,2,4-oxadiazole.
The “perturbative” effect of cosolvents on the structure of neat bmimBF4 and bmimNTf2 evaluated by means of kinetic measurements.
Catalisi da Cu(II) nelle reazioni di interconversione di anello: uno studio meccanicistico.
Studio cinetico della reazione di sostituzione nucleofila aromatica di alcuni 2-X-3-nitro e 2-X-5-nitrotiofeni in BMIMBF4.
Reattività degli Z-idrazoni, semicarbazoni e fenilsemicarbazoni del 3-benzoil-5-fenil-1,2,4-ossadiazolo: effetto della struttura della catena laterale
Catalisi da sali di Cu(II) nelle reazioni di trasposizione eterociclica mononucleare.
On the characterization of some [bmim][X]/co-solvent binary mixtures: a multidisciplinary approach by using kinetic, spectrophotometric and conductometric investigations
Abstract In order to study the intrinsic characteristics and to evaluate the structural variations determined by the addition of a co-solvent to 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF 4 ]) we examined the behaviour of some probes in [bmim][BF 4 ]/co-solvent binary mixtures. The rate constants of the piperidino-catalyzed rearrangement of the Z -phenylhydrazone of the 3-benzoyl-5-phenyl-1,2,4-oxadiazole into the relevant 4-benzoylamino-2,5-diphenyl-1,2,3-triazole as well as the spectrometric properties of pyrene and Nile Red were evaluated. With the same purpose also 1 H NMR and conductivity measurements were carried out. By comparison the behaviour of 1-butyl-3-methylimidaz…
Evidences of the organising ability of ionic liquids on the rate of the elimination reaction.
Studio cinetico della trasposizione di Z-fenilidrazoni polisostituiti del 3-benzoil-5-fenil-1,2,4-ossadiazolo nei corrispondenti 2-aril-5-fenil-1,2,3-triazoli in H2O/Diossano
Study of aromatic nucleophilic substitution with amines on nitrothiophenes in room-temperature ionic liquids: are the different effects on the behavior of para-like and ortho-like isomers on going from conventional solvents to room-temperature ionic liquids related to solvation effects?
The kinetics of the nucleophilic aromatic substitution of some 2-L-5-nitrothiophenes (para-like isomers) with three different amines (pyrrolidine, piperidine, and morpholine) were studied in three room-temperature ionic liquids ([bmim][BF4], [bmim][PF6], and [bm(2)im][BF4], where bmim = 1-butyl-3-methylimidazolium and bm(2)im = 1-butyl-2,3-dimethylimidazolium). To calculate thermodynamic parameters, a useful instrument to gain information concerning reagent-solvent interactions, the reaction was carried out over the temperature range 293-313 K. The reaction occurs faster in ionic liquids than in conventional solvents (methanol, benzene), a dependence of rate constants on amine concentration…
Trasposizioni eterocicliche mononucleari. Reattività di Z-arilidrazoni del 5-ammino-3-benzoil-1,2,4-ossadiazolo in D/W: effetto dei sostituenti
Multidisciplinary learning at the University scientific museums: the Bunsen burner
We report on a laboratory activity carried out together with secondary school (high-school) students, with the aim of increasing their interest toward historical scientific instruments and stimulate their approach to scientific knowledge. To this purpose, we propose a hands-on activity that can be fruitfully performed at the University scientific museums. We organized a one-week summer stage at the Historical Collection of Physics Instruments and at the Museum of Chemistry of the University of Palermo. A group of selected students attended it, under the tutoring of university researchers. They were showed some Bunsen burners belonging to the collections, how they are restored, how they work…
The effect of ionic liquids on the rate of an intramolecular nucleophilic substitution: the study of a monocyclic rearrangement of heterocycles
On the Dichotomic Behavior of the Z-2,4-Dinitrophenylhydrazone of 5-Amino-3-benzoyl-1,2,4-oxadiazole with Acids in Toluene and in Dioxane/Water: Rearrangement versus Hydrolysis
The mononuclear rearrangement (MRH) of the Z-2,4-dinitrophenylhydrazone (4a) and of the Z-phenylhydrazone (4b) of 5-amino-3-benzoyl-1,2,4-oxadiazole into the relevant triazoles 5a and 5b in toluene has been quantitatively investigated in the presence of trichloroacetic acid (TCA) and of piperidine at 313.1 K. While the behavior in the presence of piperidine recalls the one previously evidenced for some Z-hydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadiazole, the study of the reactivity in the presence of TCA has most interestingly evidenced a general-acid-catalyzed rearrangement for “both” 4a and 4b. Thus, 4a offers the first example of a solvent-dependent dichotomic behavior in MRH processes o…
Effetto della struttura dei liquidi ionici sulla reazione di trasposizione eterociclica mononucleare: un approccio usando i parametri termodinamici
L'assenza di solvatazione può giustificare l'aumento della velocità dei processi di interconversione di anello in liquidi ionici?
Trasposizioni eterocicliche mononucleari. Applicazione dell'equazione di Fujita-Nishioka alla reattività di Z-fenilidrazoni di- e poli-sostituiti del 3-benzoil-5-fenil-1,2,4-ossadiazolo.
Reattività dei fenilidrazoni E e Z del 3-benzoil-5-fenil-1,2,4-ossadiazolo in presenza di sali di Cu(II)
Study of aromatic nucleophilic substitution with amines on nitrothiophenes in RTILs: are the different effects on the behavior of para-like and orto-like isomers on going from conventional solvents to RTILs related to solvation effects?.
The kinetics of the nucleophilic aromatic substitution of some 2-L-5-nitrothiophenes (para-like isomers) with three different amines (pyrrolidine, piperidine, and morpholine) were studied in three roomtemperature ionic liquids ([bmim][BF4], [bmim][PF6], and [bm2im][BF4], where bmim ) 1-butyl-3- methylimidazolium and bm2im ) 1-butyl-2,3-dimethylimidazolium). To calculate thermodynamic parameters, a useful instrument to gain information concerning reagent-solvent interactions, the reaction was carried out over the temperature range 293-313 K. The reaction occurs faster in ionic liquids than in conventional solvents (methanol, benzene), a dependence of rate constants on amine concentration sim…