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
Reaktivnost α,β-nezasićenih kiselina. Deo XVI. Kinetika reakcije cikloalkenilkarbonskih i cikloalkenilsirćetnih kiselina sa diazodifenilmetanom u različitim alkoholima
Article (Published version)
Metadata
Show full item recordAbstract
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 ºC 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¶*+aα+ bβ, where ¶* is a measure of the solvent polarity, βrepresents the scale of solvent hydrogen bond acceptor basicities and β 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 cyclo...hex-1-enylacetic acids obtained under the same experimental conditions.
Konstante brzina za reakciju između diazodifenilmetana (DDM) i 1-ciklopentenkarbonske, 1-cikloheptenkarbonske, ciklopent-1-enilsirćetne i ciklohept-1-enilsirćetne kiseline su određene u osam alkoholnih rastvarača na 30 ºC odgovarajućim UV-spektrofotometrijskim metodom. Da bi se dobijeni kinetički rezultati objasnili kroz efekte rastvarača konstante brizna reakcije (k) su korelisane totalnom solvatohromnom jednačinom oblika: log k = A0+ s¶*+aα+ bβ, gde je ¶* mera polarnosti rastvarača, βpredstavlja skalu baznosti rastvarača kao akceptora protona u vodoničnoj vezi, a αskalu kiselosti rastvarača kao donora protona u vodoničnoj vezi. Korelacija kinetičkih parametara je izvršena metodom višestruke linearne regresione analize. Suprotni znaci uz elektrofilni i nukleofilni parametear u saglasnosti su sa izvedenim mehanizmom reakcije. Rezultati prikazani u ovom radu su upoređeni sa kinetičkim podacima za 1-cikloheksenkarbonsku i cikloheks-1-enilsirćetnu kiselinu, dobijenim pod istim eksperim...entalnim uslovima.
Keywords:
cycloalkenecarboxylic acids / cycloalkenylacetic acids / diazodiphenyl-methane / kinetic measurements / protic solventsSource:
Journal of the Serbian Chemical Society, 2002, 67, 2, 77-85Publisher:
- Serbian Chemical Society, Belgrade
Institution/Community
Tehnološko-metalurški fakultetTY - JOUR AU - Ušćumlić, Gordana AU - Nikolić, Jasmina AU - Krstić, Vera V. PY - 2002 UR - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/489 AB - 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 ºC 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¶*+aα+ bβ, where ¶* is a measure of the solvent polarity, βrepresents the scale of solvent hydrogen bond acceptor basicities and β 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. AB - Konstante brzina za reakciju između diazodifenilmetana (DDM) i 1-ciklopentenkarbonske, 1-cikloheptenkarbonske, ciklopent-1-enilsirćetne i ciklohept-1-enilsirćetne kiseline su određene u osam alkoholnih rastvarača na 30 ºC odgovarajućim UV-spektrofotometrijskim metodom. Da bi se dobijeni kinetički rezultati objasnili kroz efekte rastvarača konstante brizna reakcije (k) su korelisane totalnom solvatohromnom jednačinom oblika: log k = A0+ s¶*+aα+ bβ, gde je ¶* mera polarnosti rastvarača, βpredstavlja skalu baznosti rastvarača kao akceptora protona u vodoničnoj vezi, a αskalu kiselosti rastvarača kao donora protona u vodoničnoj vezi. Korelacija kinetičkih parametara je izvršena metodom višestruke linearne regresione analize. Suprotni znaci uz elektrofilni i nukleofilni parametear u saglasnosti su sa izvedenim mehanizmom reakcije. Rezultati prikazani u ovom radu su upoređeni sa kinetičkim podacima za 1-cikloheksenkarbonsku i cikloheks-1-enilsirćetnu kiselinu, dobijenim pod istim eksperimentalnim uslovima. PB - Serbian Chemical Society, Belgrade T2 - Journal of the Serbian Chemical Society T1 - 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 T1 - Reaktivnost α,β-nezasićenih kiselina. Deo XVI. Kinetika reakcije cikloalkenilkarbonskih i cikloalkenilsirćetnih kiselina sa diazodifenilmetanom u različitim alkoholima EP - 85 IS - 2 SP - 77 VL - 67 UR - https://hdl.handle.net/21.15107/rcub_technorep_489 ER -
@article{ author = "Ušćumlić, Gordana and Nikolić, Jasmina and Krstić, Vera V.", year = "2002", abstract = "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 ºC 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¶*+aα+ bβ, where ¶* is a measure of the solvent polarity, βrepresents the scale of solvent hydrogen bond acceptor basicities and β 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., Konstante brzina za reakciju između diazodifenilmetana (DDM) i 1-ciklopentenkarbonske, 1-cikloheptenkarbonske, ciklopent-1-enilsirćetne i ciklohept-1-enilsirćetne kiseline su određene u osam alkoholnih rastvarača na 30 ºC odgovarajućim UV-spektrofotometrijskim metodom. Da bi se dobijeni kinetički rezultati objasnili kroz efekte rastvarača konstante brizna reakcije (k) su korelisane totalnom solvatohromnom jednačinom oblika: log k = A0+ s¶*+aα+ bβ, gde je ¶* mera polarnosti rastvarača, βpredstavlja skalu baznosti rastvarača kao akceptora protona u vodoničnoj vezi, a αskalu kiselosti rastvarača kao donora protona u vodoničnoj vezi. Korelacija kinetičkih parametara je izvršena metodom višestruke linearne regresione analize. Suprotni znaci uz elektrofilni i nukleofilni parametear u saglasnosti su sa izvedenim mehanizmom reakcije. Rezultati prikazani u ovom radu su upoređeni sa kinetičkim podacima za 1-cikloheksenkarbonsku i cikloheks-1-enilsirćetnu kiselinu, dobijenim pod istim eksperimentalnim uslovima.", publisher = "Serbian Chemical Society, Belgrade", journal = "Journal of the Serbian Chemical Society", title = "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, Reaktivnost α,β-nezasićenih kiselina. Deo XVI. Kinetika reakcije cikloalkenilkarbonskih i cikloalkenilsirćetnih kiselina sa diazodifenilmetanom u različitim alkoholima", pages = "85-77", number = "2", volume = "67", url = "https://hdl.handle.net/21.15107/rcub_technorep_489" }
Ušćumlić, G., Nikolić, J.,& Krstić, V. V.. (2002). 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. in Journal of the Serbian Chemical Society Serbian Chemical Society, Belgrade., 67(2), 77-85. https://hdl.handle.net/21.15107/rcub_technorep_489
Ušćumlić G, Nikolić J, Krstić VV. 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. in Journal of the Serbian Chemical Society. 2002;67(2):77-85. https://hdl.handle.net/21.15107/rcub_technorep_489 .
Ušćumlić, Gordana, Nikolić, Jasmina, Krstić, Vera V., "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" in Journal of the Serbian Chemical Society, 67, no. 2 (2002):77-85, https://hdl.handle.net/21.15107/rcub_technorep_489 .