The reaction of 2-methoxy-3-nitrothiophene with N-benzylmethylamine in methanol

The kinetics of the title reaction has been studied in methanol as a function of amine and methoxide ion concentrations. The kinetic coefficients obtained point out that the reaction is catalysed by methoxide through a SB catalysis mechanism.

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.

Mononuclear rearrangement of heterocycles in ionic liquids catalyzed by copper(II) salts

Abstract The reactivity of E- and Z-phenylhydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadiazole in the presence of CuCl2 and Cu(ClO4)2·6H2O has been studied in four imidazolium ionic liquids [bmim][X] (X=BF4−, PF6−, SbF6− and CF3SO3−). The reaction may follow different mechanistic patterns, depending on the nature of the ionic liquid anion, accounting for both qualitative and kinetic data. In the presence of CuCl2, two processes take place at the same time, i.e., the E⇆Z isomerization and the rearrangement of Z-isomer into the relevant 4-benzoylamino-2,5-diphenyl-1,2,3-triazole. In contrast, in the presence of Cu(ClO4)2·6H2O, the rearrangement occurs only in solution of [bmim][BF4] and [bmim][C…

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…

Mononuclear Rearrangement of the Z-Phenylhydrazones of Some 3-Acyl-1,2,4-oxadiazoles: Effect of Substituents on the Nucleophilic Character of the &gt;C═N–NH–C6 H5 Chain and on the Charge Density of N-2 of the 1,2,4-Oxadiazole Ring (Electrophilic Counterpart)

The reaction rates for the mononuclear rearrangement of the Z-phenylhydrazones of 3-acyl-1,2,4-oxadiazoles 3a-c into the relevant 2-phenyl-2 H-1,2,3-triazoles (4a-c) have been measured in dioxane/water at different temperatures in a large range of proton concentrations. The occurrence of two different reaction pathways (one uncatalyzed, water assisted, and the other general base catalyzed) has- been observed. The obtained results have been able to furnish information about the effects of the nature of the 3-acyl structure and of the 5-substituents in the 1,2,4-oxadiazole ring on the reactivity of the examined rearrangements: they are well in line with the previsions carried out considering …

Abilità organizzante di liquidi ionici: effetto sulla velocità di reazioni di trasposizione mononucleare di eterocicli.

Ciclodestrine borate. Sintesi, acidità e attività catalitica

Electron Ionization Induced Fragmentation of some 3-Aroylamino-5-Methyl-1,2,4- Oxadiazoles and 3-Acetylamino-5-Aryl-1,2,4-Oxadiazoles

: Background and objectives. 1,2,4-Oxadiazoles show a high reactivity and represent starting compounds for the synthesis of several other heterocycles. Some their derivatives can give the so called Boulton-Katritzky Reactions (BKR) which opens the way to the synthesis of several azoles. For this reason we have registered the mass spectra of several 3-aroylamino-5-methyl-1,2,4-oxadiazoles and 3-acetylamino-5-aryl-1,2,4-oxadiazoles. Methods and results. Thus, studying the mass spectra of the isomeric couple 3-benzoylamino-5-methyl-1,2,4-oxadiazole (1A) and 3-acetylamino-5-phenyl-1,2,4-oxadiazoles (1B) we have observed that MIKE and CID MIKE spectra of their molecular ions and of the [M – CH2C…

Reattività dello Z-fenilidrazone del 5-ammino-3-benzoil-1,2,4-ossadiazolo in toluene in presenza di acidi aloacetici.

Acid- and Base-Catalysis in the Mononuclear Rearrangement of Some (Z)-arylhydrazones of 5-Amino-3-benzoyl-1,2,4-oxadiazole in Toluene: Effect of Substituents on the Course of Reaction

The reaction rates for the rearrangement of eleven (Z)-arylhydrazones of 5-amino-3-benzoyl-1,2,4-oxadiazole 3a-k into the relevant (2-aryl-5-phenyl-2H-1, 2,3-triazol-4-yl)ureas 4a-k in the presence of trichloroacetic acid or of piperidine have been determined in toluene at 313.1 K. The results have been related to the effect of the aryl substituent by using Hammett and/or Ingold-Yukawa-Tsuno correlations and have been compared with those previously collected in a protic polar solvent (dioxane/water) as well as with those on the analogous rearrangement of the corresponding (Z)-arylhydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadiazole 1a-k in benzene. Some light can thus be shed on the general di…

Protonazione del p-nitrofenato di sodio in liquidi ionici: una "sonda" per la determinazione della forza acida

Ru(bpy)2Cl2: A catalyst able to shift the course of the photorearrangement in the Boulton-Katritzky reaction

The Boulton-Katritzky reaction represents one of the most popular and efficient strategies used to realize azole-into-azole conversions. For example, under different experimental conditions, it allows the rearrangement of Z-arylhydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadiazoles (1) into 2-aryl-4-benzoylamino-5-phenyl-2H-1,2,3-triazoles (2) in very high yields. Moreover, we have recently realized this conversion also by UV-photostimulation. Now we have enlarged the scope of the reaction irradiating with visible or UV light an acetonitrile solution of some Z-arylhydrazones (1a-e) in the presence of catalytic amounts of Ru(bpY)(2)Cl-2. We have observed the unexpected formation of the 1-aryl-5-…

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…

On the Nucleophilic Reactivity of 4,6-Dichloro-5-nitrobenzofuroxan with Some Aliphatic and Aromatic Amines: Selective nucleophilic substitution

The reaction rates for the nucleophilic aromatic substitution of 4,6-dichloro-5-nitrobenzofuroxan 1 with eight aliphatic amines (characterized by very different basicities/ nucleophilicities) and three anilines have been measured in both methanol and toluene. The obtained rates have been related to the basicity (pKaH in water and Kb in benzene) or nucleophilicity (N Mayr constants) of the tested amines. The whole of the obtained kinetic data has furnished useful information on the high nucleophilic reactivity of benzofuroxan derivatives, which has been related essentially to two factors: the high electron-drawing ability/power of the condensed furoxan ring and the low aromatic character of …

A Generalized Synthesis of 3-Amino-5-aryl-, 3-Amino-5-polyfluorophenyl-, and 3-Amino-5-alkyl-1,2,4-oxadiazoles through Ring-degenerate Rearrangements

A generalized synthesis of 3-amino-5-aryl-, 3-amino-5-poly- fluorophenyl- and 3-amino-5-alkyl-1,2,4-oxadiazoles has been developed starting from the 3-amino-5-methyl-1,2,4-oxadiazole as a common synthon. Aroylation or alkanoylation of this aminooxadiazole, followed by thermally- induced ring-degenerate equilibration of resulting 3-acylamino compounds, and final acid hydrolysis of the 3-acetylamino-5-aryl- (or 5-polyfluorophenyl-), or 3- acetylamino-5-alkyl-1,2,4-oxadiazoles counterpart which is formed, gave the expected 3-amino-5-substituted 1,2,4-oxadiazoles. In the case of some 3- aroylamino compounds, yields of final 3-amino-5-aryloxadiazoles are higher than that expected on the basis of…

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…

Reazioni di isomerizzazione e trasposizione di fenilidrazoni in liquidi ionici: catalisi da sali di rame (II)

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.

Convergent results from experimental and theoretical DFT studies of the intramolecular rearrangement of Z-hydrazones of 3-acetyl-1,2,4-oxadiazoles

A combined kinetic and theoretical study of the monocyclic rearrangements of heterocycles (MRH) has been carried out. The interconversion of the Z-hydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole into the corresponding triazole has been experimentally investigated in dioxane/water in the pS(+) range 5.5(5)-13.9. The uncatalyzed region has been examined at the DFT level using a model system formed by the Z-hydrazone of 3-formyl-1,2,4-oxadiazole and one or two water molecules. The environmental effect of the solvent has been emulated using a continuum model (COSMO) approach. The kinetic data suggest a concerted process where the magnitude of the activation barrier is determined by the interpl…

Reazione di eliminazione di Kemp: una sonda per lo studio delle proprietà microscopiche di liquidi ionici

Studio cinetico della reazione di eliminazione di 1,1,1-tribromo-2,2-bis(dimetossifenil)etano in liquidi ionici.

Apolar versus polar solvents: a comparison of the strength of some organic acids against different bases in toluene and in water

The constants of ion-pair formation with 3-nitroaniline (3NO(2)A) for eight halogenoacetic acids (HAAs, 3a-h: TFA, TCA, TBA, DFA, DCA, DBA, MCA, and MBA), and five 2,2-dichloroalkanoic acids containing 3-8 carbon atoms (HAs, 5a-e: DCPA, DCBA, DCMBA, DCVA, and DCOA) have been determined in TOL at 298.1 K. The results obtained brought to evidence for HAAs the formation of ion-pairs with two different stoichiometries (base-acid, 1:1 or 1:2), while in contrast the HAs furnish only the 1:1 pairs. The different steric and electronic requirements of HAAs and HAs seem to be responsible for such an unlikely behavior. At the same time, the acid-catalyzed MRH of the (Z)-phenylhydrazone of 5-amino-3-be…

Organizzazione strutturale di liquidi ionici mono- e dicationici: un approccio combinato

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.

Reactivity of phenylhydrazones in ionic liquids solution: the effect of copper(II) salts

CuCl catalyzed radical cyclisation of N-alpha-perchloroacyl-ketene-N,S-acetals: a new way to prepare disubstituted maleic anhydrides

The discovery that cycloalkanes can form thermomorphic systems with typical polar organic solvents has led to the development of less-polar electrolyte solutions. Their mixing and separation can be regulated reversibly at a moderate temperature range. The phase switching temperature can be controlled by changing the solvent compositions. While biphasic conditions are maintained below the phase switching temperature, conductive monophasic conditions as less-polar electrolyte solutions are obtained above the phase switching temperature. After the electrochemical transformations, biphasic conditions are reconstructed below the phase switching temperature, facilitating the separation of cycloal…

Studio cinetico della reazione di sostituzione nucleofila aromatica di alcuni 2-X-3-nitro e 2-X-5-nitrotiofeni in BMIMBF4.

New examples of specific base catalysis in mononuclear rearrangements of heterocycles found via a designed modification of the side chain structure

To select suitable candidates for the occurrence of specific-base-catalysis in MRH of (Z)-hydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadiazole we have designed a modification of the side-chain structure by linking a strong electron-withdrawing system to the hydrazono group. Thus we have synthesized the (Z)-semicarbazone (3d), the (Z)-phenylsemicarbazone (3e), and the (Z)-acetylhydrazone (3f) of the above oxadiazole and examined their kinetic behavior in dioxane/water in a large range of proton concentrations (pS + 4.0 14.5). In all the pS+ range examined only a base-catalyzed process has been evidenced (no uncatalysed path occurs). The behavior at the largest pS+ values (the reactivity tends t…

Mononuclear heterocyclic rearrangements 5. Kinetic Investigation of the behaviour of (e)- and (z)-phenylhydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadiazole in benzene. Isomerization and rearrangement

The kinetic behaviour of the geometrical isomers I-E and I-Z of the title compound in the presence of piperidine in benzene has been investigated. The kinetic results suggest that I-Z rearranges directly into 2,5-diphenyl-4-benzoylamino-1,2,3-triazole (II), whereas I-E probably rearranges only through the intermediate I-Z formed by isomerization. All the reactions studied are piperidine-catalyzed.

Substituent effects on the mechanism changeover in a multipathway reaction: A model for the behavior of biological systems?

By studying the rearrangement in dioxane/water of a series of (Z)-arylhydrazones of 5-amino-3- benzoyl-1,2,4-oxadiazole (1a-k) into the relevant (2-aryl-5-phenyl-2H-1,2,3-triazol-4-yl)ureas (2a-k) in a wide range of pS + (an operational scale of proton concentration in the mixed solvent used; dioxane/water, 1:1, v:v), the occurrence of three different reaction pathways (specific-acid- catalyzed, uncatalyzed, and general-base-catalyzed) for the relevant SNi process has been recently enlightened. The significantly different substituent effects on the three pathways cause some crossovers in the log kA,R versus pS + plots. Both the pS + value at which the crossover occurs and the width of the u…

Reattività degli Z-idrazoni, semicarbazoni e fenilsemicarbazoni del 3-benzoil-5-fenil-1,2,4-ossadiazolo: effetto della struttura della catena laterale

Heterocyclic rearrangements. Phenylhydrazones andN-methyl-N-phenylhydrazones of 3-acylisoxazoles

The reaction of 3-benzoyl-5-phenylisoxazole (4) and 3-acetyl-5-methylisoxazole (5) with phenylhydrazine and N-methyl-N-phenylhydrazine has been investigated and the reactivity of (E)- and (Z)-phenylhydrazones and N-methyl-N-phenylhydrazones has been studied.

ChemInform Abstract: LEAD TETRAACETATE OXIDATION OF PHENYLHYDRAZONES OF 3-BENZOYLAZOLES. SYNTHESIS OF AZOACETATES AND THEIR CONVERSION INTO INDAZOLES

Lead tetraacetate (LTA) oxidation of (E)- and (Z)-phenylhydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadiazole, 3-benzoyl-5-phenylisoxazole, and 3-benzoyl-4-methyl-1,2,5-oxadiazole has been studied. Conversion of azoacetate products into 3-(azol-3-yl)-substituted indazoles has been achieved by reacting them with aluminium chloride in benzene at room temperature.

Influenza dei liquidi ionici sulla reazione di trasposizione eterociclica mononucleare catalizzata da Cu(II)

Heterocyclic rearrangements. Synthesis of 1,2,4-oxadiazolo[2,3-a]pyrimidinium systems and their ring opening into pyrimidineN-oxides

Reaction des methyl- et phenyl-5 amino-3 oxadiazoles-1,2,4 avec l'acetylacetone ou la benzoylacetone en presence d'acide perchlorique: obtention de methyl- et phenyl-2 methyl- et phenyl-5 methyl-7 oxadiazolo [2,3-a] pyrimidiniums-4 qui se decyclisent ensuite en oxydes-1 d'acylamino-2- et amino-2 methyl-4 methyl- et phenyl-6 pyrimidines

Catalisi da sali di Cu(II) nelle reazioni di trasposizione eterociclica mononucleare.

Mononuclear heterocyclic rearrangements. Part 12. Rearrangement of 1,2,4-oxadiazoles into indazoles

The first example of a mononuclear heterocyclic rearrangement involving an XYZ = CCN side-chain sequence is reported. The 3-(o-aminophenyl)-, and 3-(o-methylaminophenyl)-5-methyl-1,2,4-oxadiazoles (3a,b) gave a thermally induced rearrangement into 3-acylaminoindazoles (4a,b). On the other hand, the 3-(o-acetylaminophenyl)-5-methyl-1,2,4-oxadiazole (3c) produced a base induced rearrangement into 3-acetylaminoindazole (4a).

15N NMR: Substituent effect analysis inpara-andmeta-substituted phenylhydrazines

15N NMR spectra of phenylhydrazine and of 14 para- and meta-substituted phenylhydrazines were measured at natural isotope abundance in DMSO-d6 solution. The substituent present exerts a larger influence on the chemical shift of the nitrogen atom directly bound to the aromatic ring (N-1) than on the second one (N-2), which shows an attenuated and inverted trend. The chemical shifts of N-1 and N-2 give a good cross correlation in both series of compounds if p-NO2 and m-F derivatives are excluded from the correlations of para- and meta-substituted phenylhydrazines, respectively. Moreover, N-1 SCS values show good linear correlations with Hammett substituent constants, with SCSs of directly bou…

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…

On the use of multi-parameter free energy relationships: the rearrangement of (Z)-arylhydrazones of 5-amino-3-benzoyl-1,2,4-oxadiazole into (2-aryl-5-phenyl-2H-1,2,3-tryazol-4-yl)ureas

Abstract By using a multi-parameter approach (a combination of Hammett/Ingold-Yukawa-Tsuno/Fujita-Nishioka free energy relationships) the mononuclear rearrangements of heterocycles (MRH) rates for five new ortho-substituted and ten new di-, tri-, or tetra-substituted (Z)-arylhydrazones of 5-amino-3-benzoyl-1,2,4-oxadiazole into the relevant (2-aryl-5-phenyl-2H-1,2,3-triazol-4-yl)ureas (in dioxane/water and in a large range of pS+ values) have been related to the electronic and proximity effects exerted by the present substituents, also considering previous results on some mono meta- and para-substituted (Z)-arylhydrazones. In every case, excellent correlation coefficients have been calculat…

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

Mononuclear heterocyclic rearrangement. Part 6 . Studies on base catalysis of the rearrangement of the (Z)-p-nitrophenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole in benzene: Effect of piperidine, triethylamine and of some secondary amines

ChemInform Abstract: Heterocyclic Rearrangements. Synthesis of 1,2,4-Oxadiazolo(2,3-a)pyrimidinium Systems and Their Ring Opening into Pyrimidine N-Oxides.

Reaction des methyl- et phenyl-5 amino-3 oxadiazoles-1,2,4 avec l'acetylacetone ou la benzoylacetone en presence d'acide perchlorique: obtention de methyl- et phenyl-2 methyl- et phenyl-5 methyl-7 oxadiazolo [2,3-a] pyrimidiniums-4 qui se decyclisent ensuite en oxydes-1 d'acylamino-2- et amino-2 methyl-4 methyl- et phenyl-6 pyrimidines

On the rearrangement of some Z-arylhydrazones of 3-benzoyl-5-phenylisoxazoles into 2-aryl-4-phenacyl-2H-1,2,3-triazoles: a kinetic study of the substituent effects in Boulton-Katritzky reactions

Abstract The rearrangement of eight new Z -arylhydrazones of 3-benzoyl-5-phenylisoxazoles ( 3d – k ) into the relevant 2-aryl-4-phenacyl-2 H -1,2,3-triazoles ( 4d – k ) in dioxane/water solution at different proton concentrations has been quantitatively studied in a wide temperature range (293–333 K). The data collected together with some our previous ones on compounds 3a – c have allowed a deep study of the substituent effects on the course of the rearrangement, thus increasing our knowledge on the Boulton–Katritzky reactions in isoxazole derivatives and on the temperature effects on free energy relationships.

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

Effect of ionic liquids in acid-promoted heterocyclic rearrangement reaction

Photochemical isomerization of aryl hydrazones of 1,2,4-oxadiazole derivatives into the corresponding triazoles

The photochemical version of the Boulton-Katritzky reaction has been studied, examining the behaviour of the arylhydrazones of 3-benzoyl-5-X-1,2,4-oxadiazoles. The effect of several modifications of the substrates structure (the E and/or Z structures of arylhydrazones, the possible presence of substituents in the arylhydrazono moiety, and the nature of substituents at C-5 of the 1,2,4-oxadiazole ring) on the course of the photochemical rearrangement has been examined.

A green way to gamma-lactams through a copper catalyzed ARGET-ATRC in ethanol and in the presence of ascorbic acid

Abstract A ‘green’ ARGET-ATRC, for the CuCl[PMDETA] catalysed cyclo -isomerization of N -allyl-α-polychloroamides to γ-lactams is described. The process works efficiently (yields 78–96%), uses a bio-solvent, as ethanol, and exploits the reducing feature of ascorbic acid to limit, at a low level (2–4%), the amount of catalyst. To preserve the efficacy of the catalytic cycle, addition of Na 2 CO 3 is essential, which quenches the HCl released during the CuCl[PMDETA] regeneration step. Profitable features of the process are: mild reaction temperatures (25–37 °C), relatively short reaction times (usually 5 h) and low solvent volumes (2 mmol of substrate/mL of ethanol). The method, upon stoichio…

A study of the mechanism of the oxidative cyclization of benzaldehyde semicarbazones induced by cupric perchlorate in acetonitrile

Treatment of benzaldehyde semicarbazones 1a-i with cupric perchlorate in acetonitrile at 40 provided selectively the corresponding 1,2,4-triazolin-5-ones 2a-i. The relative rate constants for 2a-i formation were determined by the competitive method. The results obtained showed that electron-donating substituents (methyl and methoxy) increase the reaction rate, while the reverse was found for electron-withdrawing substituents (chloro and nitro group). The reactivity data are discussed on the grounds of two possible mechanisms.

Isomerization and rearrangement of (E)- and (Z)-phenylhydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadiazole: evidence for a “new” type of acid-catalysis by copper(II) salts in mononuclear rearrangement of heterocycles

A kinetic investigation in methanol of the title reaction has evidenced the occurrence of two processes: the 1-E1-Z isomerization and the rearrangement of the (Z)-isomer into the relevant 4-benzoylamino-2,5-diphenyl-1,2,3-triazole (1-Z  T). The latter reaction is in line with the ability of the (Z)-phenylhydrazones of 3-benzoyl-1,2,4-oxadiazoles to undergo the so called mononuclear rearrangement of heterocycles (MRH). The occurrence of both the examined reactions is dependent on a Lewis-acid-catalysis. The obtained results have shown the possibility of a ‘new’ type of acid-catalysis (bifunctional catalysis by Lewis salts) in the MRH. This catalysis operates through a completely different me…

ChemInform Abstract: On the Reactivity of Nitrosoimidazoles with Acids (the Cusmano-Ruccia Reaction): A Continuous Source of New Ring-into-Ring Interconversion.

Abstract An extension of the ‘Cusmano–Ruccia’ reaction is reported. 6-(4-chlorophenyl)-3-methyl-5-nitrosoimidazo[2,1- b ]oxazole by the action of hydrochloric acid gives 3-(4-chlorobenzoyl)-5-methyl-1,2,4-oxadiazole ( 13 ); presumably via ammonium ion, CO 2 and methanol elimination. The relevance of the nature of the atom of the B -ring linked to C-2 of the imidazole for the occurrence of the ring-into-ring interconversion has been once more confirmed.

The effect of ionic liquids on the rate of an intramolecular nucleophilic substitution: the study of a monocyclic rearrangement of heterocycles

Mononuclear heterocyclic rearrangements. Part III. Rearrangement of theP-methoxyphenylhydrazone and them-nitrophenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole in dioxane/water in thepS+range 3.8-11.5

The rates of the mononuclear heterocyclic rearrangement of the p-methoxyphenylhydrazone (Ib) and the m-nitrophenylhydrazone (1c) of 3-benzoyl-5-phenyl-1,2,4-oxadiazole have been measured in the range of pS+ 3.8–11.5 (solvent: dioxane/water 1:1, v:v) and compared with those of the unsubstituted phenylhydrazone (Ia). The obtained results show that in the base-catalyzed range, electron-repelling as well as electron-withdrawing substituents accelerate the rearrangement rates.

The influence of steric effects on the strength of some organic acids in toluene and water

Breakthrough in the α-Perchlorination of Acyl Chlorides

The preparation of -perchloroacyl chlorides, from reaction of the corresponding unfunctionalized acyl halides with chlorine, was efficiently achieved under base-catalysis, using a tetraalkylammonium chloride as catalyst. The process is solvent-free and the procedure is easy, inexpensive, and suitable for scale-up.

Unexpected Substituent Effects in the Iso-Heterocyclic Boulton-Katritzky Rearrangement of 3-Aroylamino-5-methyl-1,2,4-oxadiazoles: A Mechanistic Study.

The kinetics of the iso-heterocyclic mononuclear rearrangement of some 3-aroylamino-5-methyl-1,2,4-ozadiazoles was carefully examined under largely variable acidic or alkaline conditions. This reaction may proceed via two different mechanistic pathways (an uncatalyzed and a base-catalyzed one), as accounted for also by the evaluation of the relevant activation parameters. Substituent effects, as quantified by means of the Hammett’s equation, appear relatively modest; however, they reveal some interesting anomalies, which enabled us to draw a very precise picture of the intimate reaction course.

A deep insight into the mechanism of the acid-catalyzed rearrangement of the Z-phenylhydrazone of 5-amino-3-benzoyl-1,2,4-oxadiazole in a non-polar solvent

The conversion of the Z-phenylhydrazone of 5-amino-3-benzoyl-1,2,4-oxadiazole (1a) into the relevant 1,2,3-triazole (2a) has been quantitatively studied in toluene in the presence of several halogenoacetic acids (HAAs, 3a–h). Again, the occurrence of two reaction pathways has been pointed out: they require one or two moles of acid, respectively, thus repeating the situation previously observed in the presence of trichloroacetic acid. The observed rate constant ratios (kIII/kII) are only slightly affected by the nature of the acid used. To gain a deeper insight into the action of the acids used we have measured the association constants of the HAAs (3a–h) with 4-nitroaniline (4) in toluene. …

Effetto della struttura dei liquidi ionici sulla reazione di trasposizione eterociclica mononucleare: un approccio usando i parametri termodinamici

Heterocyclic rearrangements.N,N-diphenylhydrazones, oximes andO-methyloximes of 3-benzoyl-5-phenyl-1,2,4-oxadiazole

The behaviour of (E)- and (Z)-N,N-diphenylhydrazones and O-Methyloximes of 3-benzoyl-5-phenyl-1,2,4-oxadiazole has been studied. When refluxed in benzene, or in dioxane-water (1:1), the (Z)-N,N-diphenylhydrazone 8Z gave the indazole 11 or the substituted semicarbazide 12, respectively. The O-methyloxime 14Z did not give any rearrangement. A criticism of the oximation reaction of 3-benzoyl-5-phenyl-1,2,4-oxadiazole is also reported.

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.

Reazione di eliminazione di Kemp in liquidi ionici: uno studio cinetico

NMR Study of the (Z)-Phenylhydrazones of 5-Alkyl- and 5-Aryl-3-benzoyl-1,2,4-oxadiazoles: Support for the Interpretation of Kinetic Results on the Rearrangement of 1,2,4-Oxadiazoles to 1,2,3-Triazoles

An analysis of the 1H, 13C, and 15N NMR substituent chemical shifts (SCSs) of the title compounds in CDCl3 solution has been carried out by using the SCSs of other classes of compounds (arenes, methyl esters or amides), Hammett substituent constants or kinetic data. The results obtained provide information concerning the ground-state electronic distribution of the compounds examined. The results relevant to the carbon and nitrogen atoms of the 1,2,4-oxadiazole ring can be considered of special interest, as the effects of the substit- Introduction For several years our research group has been involved in the use of NMR spectroscopic data (1H, 13C, 15N, and 17O) to obtain information about th…

Synthesis of 3-alkyl-4-(cholomethyl)-1-RSO2-1-H-pyrrol-2-(5H)ones, using a sequential ATCR/[1,2] elimination, from 2,2-dichloro-N-(2-chloroallyl)-N-RSO2 amides

Nitrogen-15 NMR Studies on Hydrazines. 2— Substituent Effect Analysis inortho-Substituted Phenylhydrazines and Anilines

15N and 13C NMR spectra of some ortho-substituted phenylhydrazines were measured at natural isotope abundance in DMSO-d6 solutions. The substituent present exerts a larger effect on the chemical shift of the nitrogen atom directly bound to the aromatic ring (N-1), the second one (N-2) showing an attenuated trend of similar sign. Contrary to what observed for para and meta isomers, the cross-correlation between N-1 and N-2 SCS values of ortho-substituted phenylhydrazines is not satisfactory; on the other hand, N-1 SCSs show a reasonably good linear regression with the σR− constants. As expected, no correlation was found between N-1 and C-1 or H-1 SCS values. Correlations between 13C and 15N …

Miscela binaria liquido ionico/[bmim][N3]: un mezzo efficace per la sintesi di arilazidi mediante SNAr

Il laboratorio di chimica

Kinetic study of methoxide-promoted elimination reactions of some 1,1,1-trichloro-2,2-bis(phenyl-substituted)ethanes

The methoxide-promoted elimination reaction of some 1,1,1-trichloro-2,2-bis(phenyl-substituted)ethanes (1) was investigated. The ortho-substituted derivatives were found to be less reactive than the corresponding ortho-unsubstituted derivatives, irrespective of the nature of their substituent. The reactivity data were correlated with the 13C NMR chemical shift values of C-β of either 1,1,1-trichloro-2,2-bis(phenyl-substituted)ethanes or 1,1-dichloro-2,2-bis(phenyl-substituted)ethenes and the better result was obtained for the former correlation. Activation parameters for the methoxide-promoted elimination of 1 show very similar values for ortho-substituted derivatives. The total data set se…

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…

ChemInform Abstract: Ru(bpy)2Cl2: A Catalyst Able to Shift the Course of the Photorearrangement in the Boulton-Katritzky Reaction.

Abstract The Boulton–Katritzky reaction represents one of the most popular and efficient strategies used to realize azole-into-azole conversions. For example, under different experimental conditions, it allows the rearrangement of Z-arylhydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadiazoles (1) into 2-aryl-4-benzoylamino-5-phenyl-2H-1,2,3-triazoles (2) in very high yields. Moreover, we have recently realized this conversion also by UV-photostimulation. Now we have enlarged the scope of the reaction irradiating with visible or UV light an acetonitrile solution of some Z-arylhydrazones (1a–e) in the presence of catalytic amounts of Ru(bpy)2Cl2. We have observed the unexpected formation of the 1-a…

Reattività di Z-arilidrazoni del 5-ammino-3-benzoil-1,2,4-ossadiazolo in presenza di acido tricloroacetico e di piperidina in toluene: confronto con i dati in diossano-acqua

Effetto del cosolvente sulla velocità della reazione di trasposizione eterociclica mononucleare della Z-fenilidrazone del 3-benzoil-5-fenil-1,2,4-ossadiazolo in liquido ionico

On the reactivity of nitrosoimidazoles with acids (the Cusmano–Ruccia reaction): a continuous source of new ring-into-ring interconversion

Abstract An extension of the ‘Cusmano–Ruccia’ reaction is reported. 6-(4-chlorophenyl)-3-methyl-5-nitrosoimidazo[2,1- b ]oxazole by the action of hydrochloric acid gives 3-(4-chlorobenzoyl)-5-methyl-1,2,4-oxadiazole ( 13 ); presumably via ammonium ion, CO 2 and methanol elimination. The relevance of the nature of the atom of the B -ring linked to C-2 of the imidazole for the occurrence of the ring-into-ring interconversion has been once more confirmed.

The Boulton-Katritzky Reaction: A Kinetic Study of the Effect of 5-Nitrogen Substituents on the Rearrangement of Some (Z)-Phenylhydrazones of 3-Benzoyl-1,2,4-oxadiazoles

The kinetics of the ring-into-ring conversion of some new (Z)-phenylhydrazones of 3-benzoyl-1,2,4-oxadiazole containing different nitrogen-substituents at C-5 (3b–d; X = NHMe, NMe2, and NHCOMe) into the relevant triazoles 4b–d have been examined in a wide range of pS+ (0.1–11.9) in 1:1 (v/v) dioxane/water solution. The obtained results have been compared with previous data concerning the (Z)-phenylhydrazone of 5-amino-3-benzoyl-1,2,4-oxadiazole (3a; X = NH2). All of the studied (Z)-phenylhydrazones rearrange through three different pathways (specific acid-catalysed, uncatalysed and general base-catalysed). The different effects of the substituents on the course of the rearrangement in the t…

The azide/tetrazole equilibrium: an investigation in the series of furo- and thieno[2,3-e]tetrazolo[3,2-d]pyrimidine derivatives

Abstract Starting from 7(8)-chlorofuro(thieno)[3,2- d ]pyrimidines 1 , the corresponding 7(8)-hydrazinofuro(thieno)[3,2- d ]pyrimidines 2 were obtained by reaction with hydrazine. By treatment with nitrous acid, compounds 2 gave fused furo- and thieno[2,3- e ]tetrazolo[1,5- c ]pyrimidines 3 T and 4 T in excellent yields, which in solution exist in equilibrium with 7(8)-azidofuro(thieno)[3,2- d ]pyrimidines 3 A and 4 A . Compounds 3 T / 3 A and 4 T / 4 A represent useful substrates for investigating the azide/tetrazole equilibrium: it has been examined as a function of solvent, temperature, and their structure. We have observed that, in solution, in both 3 and 4 the equilibrium was strongly …

CCDC 1029103: Experimental Crystal Structure Determination

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CCDC 1411816: Experimental Crystal Structure Determination

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