Kinetic study of solvent effects on the aminolysis of O‐ethyl S‐aryl dithiocarbonates

Millán, Daniela; Santos, José G.; Castro, Enrique A.

doi:10.1002/poc.2988

Cited by 8 publications

(3 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…13 Consistently, only parameters obtained from fitting with eq 1 were analyzed herein, which best describes the solvent effect in Figure 4, also adopted in similar reports. 13,15 For the nucleophilic reactions, the negative coefficients obtained for all three parameters in eq 1 indicate that they contribute decreasing the rate constant (Table 2). The most significant contribution for lowering the reaction rate is SPP (P coefficient) pointing that the medium polarity stabilizes the reagents and probably also the transition states, although this is expected since water, DMSO, and the binary mixtures present high and similar values of polarity/polarizabilty parameter (SPP water = 1.00 and SPP DMSO = 0.962, given in Supporting Information).…”

Section: ■ Results and Discussionmentioning

confidence: 97%

“…This scale takes into account acidity (SA), basicity (SB), and polarity/polarizability (SPP) parameters for different solvents mixtures, obtained from the studies by Catalán and co-workers . Similar methodology was adopted in a recent solvent effect study related to the aminolysis of dithiocarbonates …”

Section: Introductionmentioning

confidence: 99%

“…14 Similar methodology was adopted in a recent solvent effect study related to the aminolysis of dithiocarbonates. 15 To the best of our knowledge, there are no studies reporting quantitative solvent effects in dephosphorylation reactions with IMZ derivatives, which is indubitably important when mimicking biological reactions in their complex environment. Further, many potentially catalytic IMZ derivatives of pharmaceutical interest are solubilized significantly only in organic media, and in order to comprehend these reactions, the solvent effect should foremost be understood.…”

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Reactivity of Imidazole Derivatives toward Phosphate Triester in DMSO/Water Mixtures: A Comprehensive Study on the Solvent Effect

et al. 2015

View full text Add to dashboard Cite

Many imidazole (IMZ) derivatives of pharmaceutical interest, which are potentially catalytic in dephosphorylation reactions, are soluble solely in mixtures of water and organic solvent. In order to understand these poorly explored reactions and properly compare them, a thorough study related to solvent effects for the analogous spontaneous reaction and with common IMZ derivatives is necessary, which is lacking in the literature. Herein, we report a quantitative solvent effect analysis in DMSO/water mixtures for (i) the hydrolysis reaction of diethyl 2,4-dinitrophenylphosphate (DEDNPP) and (ii) the nucleophilic reaction of IMZ and 1-methylimidazole (MEI) with DEDNPP. The solvent effect was fitted satisfactorily with multiple regression analysis, correlating the obtained second-order rate constants with solvent parameters such as acidity, basicity, and polarity/polarizability from Catalán's scale. The contribution of these parameters can be taken into account to elucidate the reactivity in these media. Interestingly, IMZ is more reactive than MEI in DMSO, compared to water alone, which is attributed to the availability of hydrogen-bond formation. Nuclear magnetic resonance spectroscopy ((1)H, (13)C, and (31)P), mass spectrometry, thermodynamic analysis, and density functional theory calculations were carried out to corroborate the proposed nucleophilic mechanism.

show abstract

Section: ■ Results and Discussionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Reactivity of Imidazole Derivatives toward Phosphate Triester in DMSO/Water Mixtures: A Comprehensive Study on the Solvent Effect

et al. 2015

View full text Add to dashboard Cite

show abstract

Reaction Mechanism in Ionic Liquids: Kinetics and Mechanism of the Aminolysis of 4-Nitrophenyl Acetate

Pavez

Millán

Rojas

et al. 2016

Int. J. Chem. Kinet.

Self Cite

View full text Add to dashboard Cite

In this work, we report a kinetic study of the reactions of the title compound with secondary alicyclic amines at different temperatures in acetonitrile and several ionic liquids (ILs). From this study, we have described that the reactions in MeCN and in the studied ILs occur by a concerted mechanism and that the activation parameters are sensitive to the structural properties of the ILs. The pKa values of all amines used in both MeCN and ILs were determined.

show abstract

Influence of the ionic liquid on the rate and the mechanism of reaction of p-nitrophenyl acetate with secondary alicyclic amines

et al. 2013

Self Cite

View full text Add to dashboard Cite

The reaction of p-nitrophenyl acetate (1) with piperidine was studied in nine organic solvents and in nine ionic liquids. The aminolysis of 1 by four different secondary amines was also studied in [Bmim]BF 4 and their basicities were determined in this solvent using two different methods. Medium effects were analysed and interpreted by comparing the rate constants of aminolysis for the two sets of solvents.

show abstract

Kinetic study of solvent effects on the aminolysis of O‐ethyl S‐aryl dithiocarbonates

Cited by 8 publications

References 23 publications

Reactivity of Imidazole Derivatives toward Phosphate Triester in DMSO/Water Mixtures: A Comprehensive Study on the Solvent Effect

Reactivity of Imidazole Derivatives toward Phosphate Triester in DMSO/Water Mixtures: A Comprehensive Study on the Solvent Effect

Reaction Mechanism in Ionic Liquids: Kinetics and Mechanism of the Aminolysis of 4-Nitrophenyl Acetate

Influence of the ionic liquid on the rate and the mechanism of reaction of p-nitrophenyl acetate with secondary alicyclic amines

Contact Info

Product

Resources

About