Interaction of 3,4‐diphenyl‐1,2,5‐thiadiazole 1,1‐dioxide with proton donor solvents

Mirífico, María Virginia; Caram, José Alberto; Vasini, Enrique Julio; Sicre, J. E.

doi:10.1002/poc.610060605

Cited by 25 publications

(27 citation statements)

References 7 publications

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“…Anion I-has a similar structure although it must be much less stable. Follow-up reactions involving anion I-such as an aldolic-type condensation (reaction [2]), are also possible and have been observed in related compounds (8). The consumption of the substrate by the follow-up reactions can account for the reduced number of electrons per mole observed in the electrolysis experiments.…”

Section: Resultsmentioning

confidence: 98%

3,4-Disubstituted derivatives of 1,2,5-thiadiazole 1,1-dioxide. Ethanol addition reactions and electroreduction of 3-methyl-4-phenyl and 3,4-dimethyl derivatives in acetonitrile and ethanol solvents

Caram¹,

Mirífico²,

Aimone³

et al. 1996

Can. J. Chem.

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3-Methyl-4-phenyl-l,2,5-thiadiazole 1,l-dioxide (TMP), as well as 3,4-dimethyl-1,2,5-thiadiazole 1,l-dioxide (TMM), react with ethanol (EtOH), which adds to one of their C=N double bonds. The equilibrium constants for the addition reaction are measured in mixed acetonitrile (ACN) -EtOH solvents by means of UV spectroscopy in the case of TMP, and by I3c NMR spectroscopy in the case of TMM, since TMM presents only terminal UV absorption. Both equilibrium constants are also estimated through cyclic voltammetry (CV) experiments. In the case of TMP, the ethanol molecule adds to the C=N bond located on the methyl-substituted side of the substrate, according to 13c NMR spectroscopy and CV results. The electroreduction characteristics of the substrates and their ethanol addition products are studied using CV techniques in ACN, EtOH, and ACN-EtOH solvent mixtures. The radical anion formed by the first electron transfer to TMM is unstable and decomposes rapidly while that corresponding to T M P undergoes a relatively slow homogeneous second-order reaction with the substrate (k = 3 x lo2 M-' S-I). The equilibrium constant for EtOH addition and the voltammetric properties of the substrates are compared with those of the previously studied 3,4-diphenyl derivative (TPP).Key words: electrochemistry, thiadiazoles, structure-reactivity relations, kinetics.

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Section: Resultsmentioning

confidence: 98%

3,4-Disubstituted derivatives of 1,2,5-thiadiazole 1,1-dioxide. Ethanol addition reactions and electroreduction of 3-methyl-4-phenyl and 3,4-dimethyl derivatives in acetonitrile and ethanol solvents

Caram¹,

Mirífico²,

Aimone³

et al. 1996

Can. J. Chem.

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“…HF/6±31G** electrostatic potential of 3-methyl-4-phenyl-1,2,5-thiadiazole 1,1-dioxide (II) on the molecular plane our studies on the nucleophilic addition of alcohols to the C=N double bond of 1,2,5-thiadiazole 1,1-dioxide derivatives, we have found that the addition reaction takes place at a measurable rate for I, II 36 and III. 5 The addition occurs preferentially on C(2) for II. We have also observed that II and III hydrolyze at a measurable rate depending on the experimental conditions.…”

Section: Discussionmentioning

confidence: 99%

“…1 Furthermore, 1,2,5-thiadiazole derivatives exhibit interesting pharmacological properties. 2 Following our previous studies on kinetics, 3,4 UV-VIS and NMR spectra 5 and electrochemistry 6,7 of several 3,4-disubstituted 1,1-dioxide derivatives of 1,2,5-thiadiazole, we report here single-crystal x-ray diffraction studies on the molecular structure of 3,4-dimethyl (I), 3-methyl-4-phenyl (II) and 3,4-diphenyl (III) derivatives. Ab initio HF/6-31G** Hartree-Fock LCAO molecular orbital (MO) calculations were also performed for all these compounds.…”

Section: Introductionmentioning

confidence: 99%

Crystallographic study and molecular orbital calculations of 1,2,5-thiadiazole 1,1-dioxide derivatives

Castellano

Piro

Caram

et al. 1998

J. Phys. Org. Chem.

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Single-crystal x-ray diffraction studies are reported for 3,4-dimethyl (I), 3-methyl-4-phenyl (II) and 3,4-diphenyl (III) derivatives of 1,2,5-thiadiazole 1,1-dioxide. Ab initio MO calculations on the electronic structure, conformation and reactivity of I, II and III are also reported and compared with the x-ray results. The structural data are related to previous kinetic and electrochemical experimental results on these compounds.

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“…Thus 3-and 4-alkyl or aryl substituted 1,2,5-thiadiazole-1,1-dioxides have the ability to bind covalently water and alcohols. Spectroscopic 130,131 and electrochemical [131][132][133][134] studies proved additions of numerous alcohols to the thiaziazole ring either in a acetonitrile solution or using the same alcohol both as a reagent and as a solvent. The equilibria in acetonitrile solutions are rather slowly established.…”

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confidence: 99%

Additions of water, hydroxide ions, alcohols and alkoxide ions to carbonyl and azomethine bonds

Zuman¹

2002

Arkivoc

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In this review are discussed equilibria involved in nucleophilic additions of H 2 O, HO -, ROH, and RO -(where R is an alkyl) to compounds containing carbonyl and azomethine bonds. These reactions result in a formation of covalent bonds between the heteroatom of the nucleophile and the carbon of the carbonyl double bond. After a brief summary of reactions resulting in additions to aliphatic carbonyl compounds, attention is paid to additions to benzaldehydes and formyl aromatic heterocycles. Equilibria involving additions to pyridoxal and some related compounds are dealt with in some detail. Discussion of additions of stated nucleophiles to azomethine bonds is practically restricted to additions to C=N bonds in heterocyclic rings. The reactivity of nucleophiles in such additions depends on the number of heteroatoms (in particular nitrogen) in the attacked ring, as well as on the number and position of substituents in such rings. In polynuclear compounds the reactivity depends on the number and kind of annelled rings, on the number and mutual position of heteroatoms and on the kind, number and position of substituents. In particular additions to pyrimidines, quinazolines, 1,2,4-and 1,3,5-triazines, pteridines and other heterocycles with four nitrogens, as well as 8-azapurines are mentioned.

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Interaction of 3,4‐diphenyl‐1,2,5‐thiadiazole 1,1‐dioxide with proton donor solvents

Cited by 25 publications

References 7 publications

3,4-Disubstituted derivatives of 1,2,5-thiadiazole 1,1-dioxide. Ethanol addition reactions and electroreduction of 3-methyl-4-phenyl and 3,4-dimethyl derivatives in acetonitrile and ethanol solvents

3,4-Disubstituted derivatives of 1,2,5-thiadiazole 1,1-dioxide. Ethanol addition reactions and electroreduction of 3-methyl-4-phenyl and 3,4-dimethyl derivatives in acetonitrile and ethanol solvents

Crystallographic study and molecular orbital calculations of 1,2,5-thiadiazole 1,1-dioxide derivatives

Additions of water, hydroxide ions, alcohols and alkoxide ions to carbonyl and azomethine bonds

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