Cross correlation analysis of the reactions of 4-nitrophenyloxirane with arylsulfonic acids in dioxane

Shpan'ko, I. V.; Sadovaya, I. V.; Kitaigorodskii, Anatolii M.

doi:10.1070/mc2001v011n02abeh001368

Mendeleev Communications

2001

DOI: 10.1070/mc2001v011n02abeh001368

|View full text |Cite

Cross correlation analysis of the reactions of 4-nitrophenyloxirane with arylsulfonic acids in dioxane

I. V. Shpan'ko

I. V. Sadovaya

Anatolii M. Kitaigorodskii

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2005

2011

Publication Types

Select...

Article3

Relationship

Self Cite0

Independent3

Authors

Journals

Cited by 3 publications

(7 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…While studying the joint effect of the structure of arenesulfonic acids (YC 6 H 4 SO 3 H) and temperature on the kinetics of oxirane ring opening in 4-nitrophenyloxirane in dioxane, we showed that quantitative estimation of the reactivity in terms of a polylinear regression model (which includes statistically significant cross correlation coefficient ρ YT = -5.8 ± 0.4 [6]) requires that nonadditive effects of factors being varied be taken into consideration. Nonadditive effect of structural factors was found in reactions of X-substituted phenyloxiranes with Y-substituted benzoic acids in acetonitrile at 343 K (ρ XY = -1.1 ± 0.2 [7]).…”

mentioning

confidence: 99%

“…We previously [6,7] made an attempt to simulate the reactivity of the system epoxy substrate-acid reagent by mathematical modeling with the aid of cross correlation analysis of the results of multifactor kinetic experiments. While studying the joint effect of the structure of arenesulfonic acids (YC 6 H 4 SO 3 H) and temperature on the kinetics of oxirane ring opening in 4-nitrophenyloxirane in dioxane, we showed that quantitative estimation of the reactivity in terms of a polylinear regression model (which includes statistically significant cross correlation coefficient ρ YT = -5.8 ± 0.4 [6]) requires that nonadditive effects of factors being varied be taken into consideration.…”

mentioning

confidence: 99%

“…

We previously [6,7] made an attempt to simulate the reactivity of the system epoxy substrate-acid reagent by mathematical modeling with the aid of cross correlation analysis of the results of multifactor kinetic experiments.

…”

mentioning

confidence: 99%

“…Reactions accompanied by opening of oxirane ring have long attracted researchers' attention due to their diversity, specificity of their mechanisms under catalytic and noncatalytic conditions, and wide application in organic synthesis (in particular, in the preparation of polymeric epoxy compounds [1][2][3][4][5][6]. An important problem in the chemistry of oxiranes is to reveal quantitative relations holding in opening of the oxirane ring upon variation of internal (structure of the reactants and catalysts) and external factors (reaction medium, temperature).…”

mentioning

confidence: 99%

See 3 more Smart Citations

Structure and Temperature Effects on the Reaction Rate of Aryloxiranes with 3,5-Dinitrobenzoic Acid in Acetonitrile

Shpan'ko

Sadovaya

2005

Russ J Org Chem

View full text Add to dashboard Cite

The effects of temperature and structure of aryloxiranes on the rate of their reaction with 3,5-dinitrobenzoic acid in acetonitrile are additive, and the process is entropy-controlled.Reactions accompanied by opening of oxirane ring have long attracted researchers' attention due to their diversity, specificity of their mechanisms under catalytic and noncatalytic conditions, and wide application in organic synthesis (in particular, in the preparation of polymeric epoxy compounds [1][2][3][4][5][6]. An important problem in the chemistry of oxiranes is to reveal quantitative relations holding in opening of the oxirane ring upon variation of internal (structure of the reactants and catalysts) and external factors (reaction medium, temperature).We previously [6,7] made an attempt to simulate the reactivity of the system epoxy substrate-acid reagent by mathematical modeling with the aid of cross correlation analysis of the results of multifactor kinetic experiments. While studying the joint effect of the structure of arenesulfonic acids (YC 6 H 4 SO 3 H) and temperature on the kinetics of oxirane ring opening in 4-nitrophenyloxirane in dioxane, we showed that quantitative estimation of the reactivity in terms of a polylinear regression model (which includes statistically significant cross correlation coefficient ρ YT = -5.8 ± 0.4 [6]) requires that nonadditive effects of factors being varied be taken into consideration. Nonadditive effect of structural factors was found in reactions of X-substituted phenyloxiranes with Y-substituted benzoic acids in acetonitrile at 343 K (ρ XY = -1.1 ± 0.2 [7]).The goal of the present work was to examine joint effect of temperature and structure of aryloxiranes on the rate of their reactions with 3,5-dinitrobenzoic acid (HA) in acetonitrile. The products of these reactions are primary alcohols, 1-aryl-2-hydroxyethyl 3,5-dinitrocarboxylates (Scheme 1) [7]. The kinetic relations holding in the process were studied using more than tenfold excess of the oxirane substrate (S) with respect to 3,5-dinitrobenzoic acid [S] 0 >> [HA] 0 , 0.08-0.17 M, according to the procedure described in [7]. The procedure is based on acid-base titration of the unreacted acid reagent with an aqueous solution of sodium hydroxide. Under the given conditions, the reaction was of first order with respect to the substrate and of second order with respect to HA, in keeping with the following kinetic equation:In all cases, the apparent pseudosecond rate constants k 2 (l mol -1 s -1 ) remained unchanged during the process until an acid reagent conversion of 70-80% (the error in the determination of k 2 did not exceed 7%). The third-order rate constants (k 3 = k 2 /[S] 0 ; Table 1) increased as the temperature rose, as well as the electron-acceptor power of the X substituent decreased. The latter relation is consistent with the negative sign of ρ + . The ρ + (r) values calculated for particular reaction series at 323, 333, and 343 K are, respectively, -3.0 ± 0.2 (0.999), -2.9 ± 0.1 (0.998), and -3.1 ± 0.2 (0.993). The ...

show abstract

mentioning

confidence: 99%

mentioning

confidence: 99%

“…

…”

mentioning

confidence: 99%

mentioning

confidence: 99%

See 2 more Smart Citations

Structure and Temperature Effects on the Reaction Rate of Aryloxiranes with 3,5-Dinitrobenzoic Acid in Acetonitrile

Shpan'ko

Sadovaya

2005

Russ J Org Chem

View full text Add to dashboard Cite

show abstract

“…The nature of the substituent has the most significant effect on the activation entropy (S ¹ ). In order to quantitatively take into account the cross effect of the substituent R¢ and the temperature on the rate of reaction (1), we used the following relation, based on the additivity principle [9]: The calculated values of the coefficients from Eq. (7) show that the reaction has significant sensitivity to a change in temperature and rather moderate sensitivity to the steric factor.…”

mentioning

confidence: 99%

Effect of the structure of carboxylic acids on activation parameters for catalytic acidolysis of epichlorohydrin

2010

View full text Add to dashboard Cite

We have studied the effect of temperature and the structure of the reagent on the rate of the reaction between 1-chloro-2,3-epoxypropane (epichlorohydrin) and aliphatic monocarboxylic acids in the presence of an ammonium salt: (3-chloro-2-hydroxypropyl)trimethylammonium chloride, obtained from trimethylammonium chloride and epichlorohydrin. We have done a correlation analysis of the effect of the substituent within the structure of the carboxylic acid and the temperature on the reaction rate. Using ab initio quantum chemical methods, we have estimated the structures and energy parameters of the transition states for the limiting step of the process, and have formulated hypotheses for the reaction mechanism.a-Oxides are one of the most promising and best studied classes of compounds in organic chemistry. Epoxide compounds are widely used in drug, pesticide, and polymer chemistry. The interest in oxirane chemistry is due to the unique structure of the ring, which makes it possible to carry out conversions with a very broad range of options when treated with different types of reagents, and epoxide ring opening reactions are considered as model reactions in studying biologically active systems and the complex processes involved in curing epoxy resins [1][2][3][4][5][6][7].A significant number of papers are known to date relating to opening of the oxirane ring when treated with nucleophilic reagents, in particular aliphatic carboxylic acids [2, 3, 7]:It has been established that the reactivity of carboxylic acids in reaction (1) is affected by a number of factors, such as their acidity, their ability to dimerize, the steric accessibility of the nucleophilic center, and temperature [2][3][4][5][6][7]. Note that the reactivity of aliphatic carboxylic acids generally increases compared with acetic acid when either electron-donor or electron-acceptor substituents are introduced [2, 3, 5]. In order to explain such behavior and to establish its nature, we first of all need to estimate how the substituent on the carboxylic acid and the temperature affect the state of the reacting species, the structure of the transition state.The aim of this work was to study the effect of temperature and structural factors on the reaction rate and mechanism for catalytic acidolysis of the a-oxide 1-chloro-2,3-epoxypropane (epichlorohydrin) by aliphatic monocarboxylic acids. In 190 0040-5760/10/4603-0190

show abstract

Nonadditive effects of structural factors in reactions of aryloxiranes with arenesulfonic acids. Observation of isoparametricity phenomenon

2011

View full text Add to dashboard Cite

In reactions of aryloxiranes XC 6 H 4(3) CH(O)CH 2 with arenesulfonic acids YC 6 H 4 SO 3 H in a mixture of dioxane with diglyme (1 : 1) at 265 K the nonadditive effects of substituents X and Y were strongly revealed, therefore it was possible to observe experimentally the isoparametricity phenomenon: In the isoparametric point σ X IP = 1.42 with respect to the X substituent constant the rate of the oxirane ring opening did not depend on the structure of Y (ρ Y X = 0).The versatility and features of the mechanisms of oxirane reactions, their unique synthetic possibilities and practical value have attracted the attention of researchers for several decades. The interest in oxirane chemistry is still strong nowadays as show the numerous recent publications (see, e.g., [1]). However although the research on oxiranes is very versatile, the quantitative aspects of their reactions are still poorly understood. The establishment of quantitative laws taking into account the effect of the structure, solvent, temperature, pH of the medium and the other internal and external factors on the rate and regioselectivity of reactions of oxirane substrates with reagents of diverse character is a topical problem. In this respect a special attention should be paid to cross reaction series where occurs the interaction (nonadditivity) of effects of mutually varied factors. These series should be described with the use of polylinear equations with cross terms whose coeffi cients take into account such interactions and therefore their prognostic value signifi cantly grows [2].The goal of this work is the study of the combined effect of substituents X and Y on the reaction rate of substituted aryloxiranes with substituted arenesulfonic acids in a mixture dioxane-bis(2-methoxyethyl) ether (diglyme), 1:1 (Scheme 1). Scheme 1.

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

Cross correlation analysis of the reactions of 4-nitrophenyloxirane with arylsulfonic acids in dioxane

Cited by 3 publications

References 2 publications

Structure and Temperature Effects on the Reaction Rate of Aryloxiranes with 3,5-Dinitrobenzoic Acid in Acetonitrile

Structure and Temperature Effects on the Reaction Rate of Aryloxiranes with 3,5-Dinitrobenzoic Acid in Acetonitrile

Effect of the structure of carboxylic acids on activation parameters for catalytic acidolysis of epichlorohydrin

Nonadditive effects of structural factors in reactions of aryloxiranes with arenesulfonic acids. Observation of isoparametricity phenomenon

Contact Info

Product

Resources

About