Solvent effects on Diels-Alder reactions. The use of aqueous mixtures of fluorinated alcohols and the study of reactions of acrylonitrile

Cativiela, Carlos; Garcı́a, José I.; Gil, José María Mengual; Martı́nez, Rosa; Mayoral, José A.; Salvatella, Luis; Urieta, José S.; Mainar, Ana M.; Abraham, Michael H.

doi:10.1039/a601717g

Cited by 87 publications

(61 citation statements)

References 19 publications

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“…This dual-parameter model represents a significant improvement with regard to the single-parameter models only with Sp (r ϭ 0.591 and only with E T N ). Similar works in Dielsr ϭ 0.132 Alder reactions show lower regression coefficients for the reaction of cyclopentadiene with (r ϭ 0.961 acrylonitrile [18] and for cyclopentadiene r ϭ 0.942 with methyl acrylate [19]). …”

Section: Resultssupporting

confidence: 58%

Kinetics of 1,3-dipolar cycloaddition reaction between C,N-diphenylnitrone and dimethyl fumarate in various solvents and aqueous solutions

Gholami

Yangjeh

2000

Int. J. Chem. Kinet.

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Second-order rate constants and activation parameters of 1,3-dipolar cycloaddition reaction between C,N-diphenylnitrone and dimethyl fumarate were obtained in various solvents and aqueous solutions at 65ЊC. Second-order rate constants of the reaction in water and ethylene glycol are approximately 33 and 8 times faster than those expected from solvent polarity, respectively. Increase of the reaction rate in aqueous solutions of ethanol is higher than that of propan-1-ol. A multiparameter correlation of log k 2 vs Sp and E T N in various solvents and aqueous solutions of ethanol shows that solvophobicity and solvent polarity parameter are important factors in occurrence of the reaction.

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Section: Resultssupporting

confidence: 58%

Kinetics of 1,3-dipolar cycloaddition reaction between C,N-diphenylnitrone and dimethyl fumarate in various solvents and aqueous solutions

Gholami

Yangjeh

2000

Int. J. Chem. Kinet.

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“…The cycloaddition of cyclopentadiene to methyl acrylate (Scheme 1) is perhaps the most intensively studied Diels-Alder reaction, and has been conducted in organic solvents, [2,6,19,20] water [7,8] and in a series of room temperature ionic liquids. [11,13,14,16,18,21] As such, the reaction was chosen for the study described herein.…”

Section: Resultsmentioning

confidence: 99%

Rationalisation of Solvent Effects in the DielsAlder Reaction Between Cyclopentadiene and Methyl Acrylate in Room Temperature Ionic Liquids

et al. 2005

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The Diels-Alder reaction between cyclopentadiene and methyl acrylate in ionic liquids has been studied in detail. The effect of contamination of the ionic liquids by common impurities, viz. sodium and chloride ions, and water, on the selectivity has been investigated. The presence of high concentrations of chloride was found to decrease the selectivity. Anion and, in particular, cation effects have been investigated using an extensive series of air-stable room temperature ionic liquids, and kinetic parameters have been determined. It has been found that strongly interacting groups, particularly electrophilic moieties on the cation, accelerate the formation of the endo products. Substrate solubility intimately connected to the selectivity was found to be mainly anion dependent. An NMR-based solvent parameter scale and semi-empirical models are used to analyse the results and provide a tool for the prediction of selectivities in ionic liquids.

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“…[1][2][3] To obtain a significant correlation, it is crucial that appropriate descriptors be employed, whether they are empirical or theoretical. [2][3][4][5][6][7][8][9] The linear solvation energy relationship (LSER) descriptors based on linear free energy relationship (LFER) are demonstrated to be successful in correlating a wide range of chemical and physical properties involving solutesolvent interactions as well as biological activities of compounds. 3 A major step forward in applying LSER to solute-solvent interactions was the work of Kamlet and Taft.…”

Section: Introductionmentioning

confidence: 99%

Prediction of Solvent Effects on Rate Constant of [2+2] Cycloaddition Reaction of Diethyl Azodicarboxylate with Ethyl Vinyl Ether Using Artificial Neural Networks

Habibi‐Yangjeh

Nooshyar²

2005

Bulletin of the Korean Chemical Society

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Artificial neural networks (ANNs), for a first time, were successfully developed for the modeling and prediction of solvent effects on rate constant of [2+2] cycloaddition reaction of diethyl azodicarboxylate with ethyl vinyl ether in various solvents with diverse chemical structures using quantitative structure-activity relationship. The most positive charge of hydrogen atom (q + ), dipole moment (µ), the Hildebrand solubility parameter (δ H 2 ) and total charges in molecule (q t ) are inputs and output of ANN is log k 2 . For evaluation of the predictive power of the generated ANN, the optimized network with 68 various solvents as training set was used to predict log k 2 of the reaction in 16 solvents in the prediction set. The results obtained using ANN was compared with the experimental values as well as with those obtained using multi-parameter linear regression (MLR) model and showed superiority of the ANN model over the regression model. Mean square error (MSE) of 0.0806 for the prediction set by MLR model should be compared with the value of 0.0275 for ANN model. These improvements are due to the fact that the reaction rate constant shows non-linear correlations with the descriptors.

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Solvent effects on Diels-Alder reactions. The use of aqueous mixtures of fluorinated alcohols and the study of reactions of acrylonitrile

Cited by 87 publications

References 19 publications

Kinetics of 1,3-dipolar cycloaddition reaction between C,N-diphenylnitrone and dimethyl fumarate in various solvents and aqueous solutions

Kinetics of 1,3-dipolar cycloaddition reaction between C,N-diphenylnitrone and dimethyl fumarate in various solvents and aqueous solutions

Rationalisation of Solvent Effects in the DielsAlder Reaction Between Cyclopentadiene and Methyl Acrylate in Room Temperature Ionic Liquids

Prediction of Solvent Effects on Rate Constant of [2+2] Cycloaddition Reaction of Diethyl Azodicarboxylate with Ethyl Vinyl Ether Using Artificial Neural Networks

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