scholarly journals Reactivity of cyclohex-1-enylcarboxylic and 2-methylcyclohex-1-enylcarboxylic acids with diazodiphenylmethane in aprotic solvents

2000 ◽  
Vol 65 (12) ◽  
pp. 839-846
Author(s):  
Jasmina Nikolic ◽  
Gordana Uscumlic ◽  
Vera Krstic
Keyword(s):  
Hydrogen Bond ◽  
Rate Constants ◽  
Kinetic Data ◽  
Linear Regression Analysis ◽  
Spectroscopic Method ◽  
Reaction Rates ◽  
Aprotic Solvents ◽  
Experimental Conditions ◽  
Hydrogen Bond Acceptor ◽  
Protic Solvents

Rate constants for the reaction of diazodiphenylmethane with cyclohex-1-enylcarboxylic acid and 2-methylcyclohex-1-enylcarboxylic acid were determined in nine aprotic solvents, as well as in seven protic solvents, at 30?C using the appropriate UV-spectroscopic method. In protic solvents the unsubsituted acid displayed higher reaction rates than the methyl-substituted one. The results in aprotic solvents showed quite the opposite, and the reaction rates were considerably lower. In order to explain the obtained results through solvent effects, reaction rate constants (k) of the examined acids were correlated using the total solvatochromic equation of the form: log k=logk0+s?*+a?+b?, where ?* is the measure of the solvent polarity, a represents the scale of the solvent hydrogen bond donor acidities (HBD) and b represents the scale of the solvent hydrogen bond acceptor basicities (HBA). The correlation of the kinetic data were carried out by means of multiple linear regression analysis and the opposite effects of aprotic solvents, as well as the difference in the influence of protic and aprotic solvents on the reaction of the two examined acids with DDM were discussed. The results presented in this paper for cyclohex-1-enylcarboxylic and 2-methylcyclohex-1-enylcarboxylic acids were compared with the kinetic data for benzoic acid obtained in the same chemical reaction, under the same experimental conditions.

scholarly journals The reactivity of α,β-unsaturated carboxylic acids. Part XVI. The kinetics of the reaction of cycloalkenecarboxylic and cycloalkenylacetic acids with diazodiphenylmethane in various alcohols

2002 ◽  
Vol 67 (2) ◽  
pp. 77-85 ◽  
Author(s):  
Gordana Uscumlic ◽  
Jasmina Nikolic ◽  
Vera Krstic
Keyword(s):  
Hydrogen Bond ◽  
Rate Constants ◽  
Kinetic Data ◽  
Linear Regression Analysis ◽  
Spectroscopic Method ◽  
Solvent Polarity ◽  
Multiple Linear Regression Analysis ◽  
Hydrogen Bond Donor ◽  
Experimental Conditions ◽  
Hydrogen Bond Acceptor

The rate constants for the reaction of diazodiphenylmethane with 1-cyclopentenecarboxylic, 1-cycloheptenecarboxylic, cyclopent-1-enylacetic and cyclohept-1-enylacetic acids were determined in eight alcohols at 30 ?C using the appropriate UV-spectroscopic method. In order to explain the kinetic results through solvent effects, the second order rate constants of the examined acids were correlated using a total solvatochromic equation, of the form: log k = A0+ s?*+a??+ b?, where ?* is a measure of the solvent polarity, ??represents the scale of solvent hydrogen bond acceptor basicities and ? represents the scale of solvent hydrogen bond donor acidities. The correlations of the kinetic data were carried out by means of multiple linear regression analysis. The opposite sings of the electrophilic and the nucleophilic parameters are in agreement with the well-known reaction mechanism. The results presented in this paper were compared with the kinetic data for 1-cyclohexenecarboxylic and cyclohex-1-enylacetic acids obtained under the same experimental conditions.

scholarly journals Investigations of the reactivity of pyridine carboxylic acids with diazodiphenylmethane in protic and aprotic solvents, Part I: Pyridine mono-carboxylic acids

2005 ◽  
Vol 70 (4) ◽  
pp. 557-567 ◽  
Author(s):  
Aleksandar Marinkovic ◽  
Sasa Drmanic ◽  
Bratislav Jovanovic ◽  
Milica Misic-Vukovic
Keyword(s):  
Carboxylic Acids ◽  
Rate Constants ◽  
Kinetic Data ◽  
Reaction Rate ◽  
Linear Regression Analysis ◽  
Multiple Linear Regression Analysis ◽  
Aprotic Solvents ◽  
Solvent Parameters ◽  
Protic Solvents ◽  
Pyridine Carboxylic

Rate constants for the reaction of diazodiphenylmethane with isomeric pyridine carboxylic acids were determined in chosen protic and aprotic solvents at 30 ?C, using the well known UV spectrophotometric method. The values of the rate constants of the investigated acids in protic solvents were higher than those in aprotic solvents. The second order rate constants were correlated with solvent parameters using the Kamlet-Taft solvatochromic equation in the form: logk = logk0 + s?*+ a? + b?. The correlation of the obtained kinetic data were performed by means of multiple linear regression analysis taking appropriate solvent parameters. The signs of the equation coefficients were in agreement with the postulated reaction mechanism. The mode of the influence of the solvent on the reaction rate in all the investigated acids are discussed on the basis of the correlation results.

scholarly journals The kinetics of the reactions of 2-substituted nicotinic acids with diazodiphenylmethane in various alcohols

2003 ◽  
Vol 68 (7) ◽  
pp. 515-524 ◽  
Author(s):  
Sasa Drmanic ◽  
Bratislav Jovanovic ◽  
Aleksandar Marinkovic ◽  
Milica Misic-Vukovic
Keyword(s):  
Hydrogen Bond ◽  
Rate Constants ◽  
Linear Regression Analysis ◽  
Solvent Polarity ◽  
Multiple Linear Regression Analysis ◽  
Hydrogen Bond Donor ◽  
Initial State ◽  
Experimental Conditions ◽  
Hydrogen Bond Acceptor ◽  
Reaction Rate Constants

The rate constants of 2-substituted nicotinic acids in reaction with diazodiphenylmethane (DDM) in eight alcohols at 30 ?C have been determined. In order to explain the obtained results through solvent effects, the second order reaction rate constants (k) of the examined acids were correlated using the appropriate solvent parameters by the equation: logk=logk0 af(?) + b?* + cn?H where f(?) is the measure of solvent ability as a dielectric to stabilize the separation of opposite charges in the activated complex, ?* is the measure of solvent ability to stabilize proton in the initial state and n?H represents the ability of protic solvents to form hydrogen bond with the negative end of the ion-pair intermediate. These constants were correlated also by using solvatochromic equation of the form logk=logk0 + s?* + a? + b? where ?* is the measure of the solvent polarity, ? represents the scale of the solvent hydrogen bond donor acidities (HBD) and ? represents the scale of the solvent hydrogen bond acceptor basicities (HBA). The correlations of the kinetic data were carried out by means of multiple linear regression analysis. The results obtained for 2-substituted nicotinic acids were compared with the results for ortho-substituted benzoic acid under the same experimental conditions.

scholarly journals The comparative study of linear solvatation energy relationship for the reactivity of pyridine carboxylic acids with diazodiphenylmethane in protic and aprotic solvents

2012 ◽  
Vol 77 (10) ◽  
pp. 1311-1338 ◽  
Author(s):  
Sasa Drmanic ◽  
Jasmina Nikolic ◽  
Aleksandar Marinkovic ◽  
Bratislav Jovanovic
Keyword(s):  
Solvent Effects ◽  
Kinetic Data ◽  
Aprotic Solvent ◽  
Isonicotinic Acid ◽  
Linear Regression Analysis ◽  
Multiple Linear Regression Analysis ◽  
Reaction Rates ◽  
Aprotic Solvents ◽  
Pyridine Carboxylic ◽  
The Comparative Study

Protic and aprotic solvent effects on the reactivity of picolinic, nicotinic and isonicotinic acid, as well as of some substituted nicotinic acids with diazodiphenylmethane (DDM) were investigated. In order to explain the kinetic results through solvent effects, the second-order rate constants for the reaction of the examined acids with DDM were correlated using the Kamlet-Taft solvatochromic equation. The correlations of the kinetic data were carried out by means of the multiple linear regression analysis and the solvent effects on the reaction rates were analyzed in terms of the contributions of the initial and the transition state. The signs of the equation coefficients support the already known reaction mechanism. The solvatation models for all the investigated acids are suggested and related to their specific structure.

scholarly journals Effects of solvent and structure on the reactivity of 2-substituted nicotinic acids with diazodiphenylmethane in aprotic solvents

2012 ◽  
Vol 77 (5) ◽  
pp. 569-579
Author(s):  
Sasa Drmanic ◽  
Jasmina Nikolic ◽  
Bratislav Jovanovic
Keyword(s):  
Rate Constants ◽  
Substituent Effect ◽  
Kinetic Data ◽  
Reaction Rate ◽  
Linear Regression Analysis ◽  
Multiple Linear Regression Analysis ◽  
Aprotic Solvents ◽  
Solvent Interaction ◽  
Complete Form ◽  
Solute Solvent Interaction

The rate constants for the reactions of diazodiphenylmethane (DDM) with 2-substituted nicotinic acids in nine aprotic solvents at 30?C were determined. The obtained second order rate constants in aprotic solvents were correlated using the Kamlet?Taft solvatochromic equation in the complete form: log k = log k0 + s?* + a??+ b?. The correlations of the kinetic data were realized by means of multiple linear regression analysis. The obtained results were analyzed in terms of the initial and the transition state of the reaction and compared with previously determined kinetic data for nicotinic acid. The signs of the equation coefficients (s, a and b) are in agreement with the reaction mechanism and the influence of the solvent on the reaction rate is discussed based on the correlation results. The mode of the transmission of the substituent effect is discussed in light of the contribution of solute?solvent interaction to the reactivity of the acid. The substituent effect was additionally analyzed by the Hammett equation, log k = p??+ log k0.

scholarly journals The influence of the solvent on organic reactivity. Part II. Hydroxylic solvent effects on the reaction rates of diazodiphenylmethane with 2-(2-substituted cyclohex-1-enyl)acetic and 2-(2-substituted

2004 ◽  
Vol 69 (8-9) ◽  
pp. 601-610 ◽  
Author(s):  
Jasmina Nikolic ◽  
Gordana Uscumlic ◽  
Vera Krstic
Keyword(s):  
Hydrogen Bond ◽  
Solvent Effects ◽  
Linear Regression Analysis ◽  
Solvent Polarity ◽  
Multiple Linear Regression Analysis ◽  
Reaction Rates ◽  
Hydrogen Bond Donor ◽  
Initial State ◽  
Hydrogen Bond Acceptor ◽  
Acetic Acids

The rate constants for the reaction of diazodiphenylmethane with 2-(2-substituted cyclohex-1-enyl)acetic acids and 2-(2-substituted phenyl)acetic acids, previously determined in seven hydroxylic solvents, were correlated using the total solvatochromic equation, of the form logk = logk0 + s?*+ a? + b?, the two-parameter model, logk=logk0 + s?*+ a? and a single parameter model logk = logk0 + b?, where ?*is a measure of the solvent polarity, ? represents the scale of solvent hydrogen bond acceptor basicities and ? represents the scale of solvent hydrogen bond donor acidities. The correlations of the kinetic data were carried out by means of multiple linear regression analysis and the solvent effects on the reaction rates were analyzed in terms of initial state and transition state contributions.

scholarly journals Effects of solvent and structure on the reactivity of 6-substituted nicotinic acids with diazodiphenylmethane in aprotic solvents

2009 ◽  
Vol 74 (12) ◽  
pp. 1359-1370 ◽  
Author(s):  
Sasa Drmanic ◽  
Aleksandar Marinkovic ◽  
Bratislav Jovanovic
Keyword(s):  
Rate Constants ◽  
Substituent Effect ◽  
Reaction Rate ◽  
Linear Regression Analysis ◽  
Multiple Linear Regression Analysis ◽  
Aprotic Solvents ◽  
Solvent Interaction ◽  
Protic Solvents ◽  
Linear Solvation Energy ◽  
Nucleophilic Solvation

The rate constants for the reactions of diazodiphenylmethane (DDM) with 6-substituted nicotinic acids in aprotic solvents at 30?C were determined. The obtained second order rate constants in aprotic solvents, together with literature data for benzoic and nicotinic acids in protic solvents, were used for the calculation of solvent effects, employing the Kamlet-Taft solvatochromic equation (linear solvation energy relationship - LSER) in the form: log k = log k0 + + s?*+ a? + b?. The correlations of the kinetic data were performed by means of multiple linear regression analysis taking appropriate solvent parameters. The sign of the equation coefficients (s, a and b) were in agreement with the postulated reaction mechanism, and the mode of the solvent influences on the reaction rate is discussed based on the correlation results. A similar contribution of the non-specific solvent effect and electrophilic solvation was observed for all acids, while the highest contribution of nucleophilic solvation was influenced by their high acidity. Correlation analysis of the rate data with substituent ?p parameters in an appropriate solvent using the Hammett equation was also performed. The substituent effect on the acid reactivity was higher in aprotic solvents of higher dipolarity/polarizability. The mode of the transmission of the substituent effect is discussed in light of the contribution of solute-solvent interaction on the acid reactivity.

scholarly journals Solvent effect on electronic absorption spectra of cyclohex-1-enylcarboxylic and 2-methylcyclohex-1-enylcarboxylic acids

2000 ◽  
Vol 65 (5-6) ◽  
pp. 353-359 ◽  
Author(s):  
Jasmina Nikolic ◽  
Gordana Uscumlic ◽  
Vera Krstic
Keyword(s):  
Hydrogen Bond ◽  
Absorption Spectra ◽  
Electronic Absorption Spectra ◽  
Linear Regression Analysis ◽  
Solvent Polarity ◽  
Multiple Linear Regression Analysis ◽  
Ultraviolet Absorption ◽  
Aprotic Solvents ◽  
Hydrogen Bond Donor ◽  
Hydrogen Bond Acceptor

The ultraviolet absorption spectra of cyclohex-1-enylcarboxylic acid and 2- methylcyclohex-1-enylcarboxylic acid were determined in six protic and nine aprotic solvents in the wavelength range from 200 to 400 nm. The position of the ?max of the two examined acids showed that the ultraviolet absorption maximums of cyclohex-1-enylcarboxylic acid were at consistently longer wavelengths in protic solvents than those of methylcyclohex-1-enylcarboxylic acid. The opposite was true in aprotic solvents. In order to explain the obtained results, the ultraviolet absorption frequencies of the electronic transitions in the carboxy carbonyl group of the examined acids were correlated using a total solvatochromic equation of the form: v = v0 + s?* + a? + b?, where ?* is a measure of the solvent polarity, ? represents the scale of solvent hydrogen bond acceptor basicities and a represents the scale of solvent hydrogen bond donor acidities. The correlation of the spectroscopic data was carried out by means of multiple linear regression analysis. The opposing solvent effects on the ultraviolet absorption maximums of the two examined acids were discussed.

scholarly journals Solvent effect on electronic absorption spectra of some 2-aminobenzimidazoles

2002 ◽  
pp. 93-99
Author(s):  
Nada Perusic-Janjic ◽  
Jevrem Janjic ◽  
Sanja Podunavac-Kuzmanovic
Keyword(s):  
Hydrogen Bond ◽  
Electronic Absorption Spectra ◽  
Linear Regression Analysis ◽  
Solvent Polarity ◽  
Multiple Linear Regression Analysis ◽  
Proton Donor ◽  
Proton Acceptor ◽  
Aprotic Solvents ◽  
Hydrogen Bond Donor ◽  
Hydrogen Bond Acceptor

The effect of protic and aprotic solvents on electronic apsorption spectra of 1-(3-X-benzil)-2-aminobenzimidazoles (X=CH3;OCH3; Cl) was examined. UV-apsorption spectra (200-400 nm) were recorded in five protic and four aprotic solvents. Batochromic shift of absorption maxima, ?max, occurs from the solvent with the highest proton-donor ability to the proton acceptor solvent (from water to DMSO). Positions of absortion maxima in various solvents are in correlation with the dielectric constant of the solvent. In order to explain the obtained results, the ultraviolet absorption frequences of the electronic transitions of the compounds were correlated using a total solvatochromic equation of the form: ?max = ?0 + s?* + a? + b?, where??* is the measure of solvent polarity. Prepresents the scale of solvent hydrogen bond acceptor basicities and ? represents the scale of solvent hydrogen bond donor acidities. Correlation of spectroscopic data was carried out by means of multiple linear regression analysis.

Hydrogen-bond promoted nucleophilic fluorination: concept, mechanism and applications in positron emission tomography

2016 ◽  
Vol 45 (17) ◽  
pp. 4638-4650 ◽  
Author(s):  
Ji-Woong Lee ◽  
Maria Teresa Oliveira ◽  
Hyeong Bin Jang ◽  
Sungyul Lee ◽  
Dae Yoon Chi ◽  
...  
Keyword(s):  
Positron Emission Tomography ◽  
Hydrogen Bond ◽  
Alkali Metal ◽  
Reaction Rates ◽  
Emission Tomography ◽  
Protic Solvents ◽  
Metal Fluorides ◽  
Positron Emission ◽  
Nucleophilic Fluorination ◽  
Excellent Selectivity

This Tutorial Review summarizes the recent breakthroughs in SN2-type nucleophilic fluorination reactions using alkali metal fluorides promoted by protic solvents, inducing excellent selectivity and high reaction rates.

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