NDLI: Electronic and solvent effects on kinetics of SNAr substitution reactions of substituted anilines with 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole in MeOH–Me2SO mixtures of varying composition: one reaction with two mechanistic pathways

Please wait, while we are loading the content...

Potentiometric determination of stability constants and thermodynamic data for dimethyltin(IV) dichloride complexes with iminobis(methylphosphonic acid) in water and dioxane–water mixtures

Investigation of the electrochemical behavior of some dihydroxybenzoic acids in aqueous solution

Kinetics, mechanism, and equilibrium studies of the reactions between a ruthenium(II) complex and some nitrogen- and sulfur-donor nucleophiles

Physicochemical studies on the interaction of gold(III) trichlorophenanthridine complex with calf thymus DNA

Syntheses, structures, and photoluminescence properties of Zn(II)/Cd(II) supramolecular architectures based on 1,5-naphthalenedisulfonate and 1,10-phenanthroline ligands

A comparative study on the antioxidant properties of bractein and cernuoside by the DFT method

Solvatochromic and quantum chemical investigations of newly synthesized succinimides: substituent effect on intramolecular charge transfer

Electronic and solvent effects on kinetics of SNAr substitution reactions of substituted anilines with 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole in MeOH–Me2SO mixtures of varying composition: one reaction with two mechanistic pathways

Investigation on the reduction of sulfonyl chlorides with sulfur dioxide in water as solvent

Magnetic nanoparticle supported hyperbranched polyglycerol catalysts for synthesis of 4H-benzo[b]pyran

Synthesis, anticancer, and antimicrobial activities of some new antipyrine-based heterocycles

Green chemistry: ZrOCl2·8H2O catalyzed regioselective synthesis of 5-amino-1-aryl-1H-tetrazoles from secondary arylcyanamides in water

Synthesis and antitumor activity of 1-deoxybaccatin III analogs from 1-deoxybaccatin VI

A short and facile stereoselective total synthesis of cryptocarya diacetate

Monatshefte für Chemie - Chemical Monthly : Volume 144, Issue 9, September 2013

Monatshefte für Chemie - Chemical Monthly : Volume 144, Issue 8, August 2013

Monatshefte für Chemie - Chemical Monthly : Volume 144, Issue 7, July 2013

Monatshefte für Chemie - Chemical Monthly : Volume 144, Issue 6, June 2013

Monatshefte für Chemie - Chemical Monthly : Volume 144, Issue 5, May 2013

Monatshefte für Chemie - Chemical Monthly : Volume 144, Issue 4, April 2013

Monatshefte für Chemie - Chemical Monthly : Volume 144, Issue 3, March 2013

Monatshefte für Chemie - Chemical Monthly : Volume 144, Issue 2, February 2013

Monatshefte für Chemie - Chemical Monthly : Volume 144, Issue 1, January 2013

Monatshefte für Chemie - Chemical Monthly : Volume 143

Monatshefte für Chemie - Chemical Monthly : Volume 142

Monatshefte für Chemie - Chemical Monthly : Volume 141

Monatshefte für Chemie - Chemical Monthly : Volume 140

Monatshefte für Chemie - Chemical Monthly : Volume 139

Monatshefte für Chemie - Chemical Monthly : Volume 138

Monatshefte für Chemie - Chemical Monthly : Volume 137

Monatshefte für Chemie - Chemical Monthly : Volume 136

Monatshefte für Chemie - Chemical Monthly : Volume 135

Monatshefte für Chemie - Chemical Monthly : Volume 134

Monatshefte für Chemie - Chemical Monthly : Volume 133

Monatshefte für Chemie - Chemical Monthly : Volume 132

Monatshefte für Chemie - Chemical Monthly : Volume 131

Monatshefte für Chemie - Chemical Monthly : Volume 130

Monatshefte für Chemie - Chemical Monthly : Volume 129

Monatshefte für Chemie - Chemical Monthly : Volume 128

Electronic and solvent effects on kinetics of SNAr substitution reactions of substituted anilines with 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole in MeOH–Me2SO mixtures of varying composition: one reaction with two mechanistic pathways

Content Provider	Springer Nature Link
Author	El Guesmi, Nizar Berionni, Guillaume Asghar, Basim H.
Copyright Year	2013
Abstract	The kinetics and mechanism of the aromatic nucleophilic substitution reactions of 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole with para-X-substituted anilines (X = OH, OMe, Me, H, F, I, Cl) were studied in MeOH–Me2SO mixtures and pure Me2SO at 25.0 °C. The second-order rate coefficients depend on the substitutent in aniline and give good Hammett and Brønsted correlations; a polar SNAr reaction is proposed for the reaction in different MeOH–Me2SO mixtures. The measured rate coefficients of the reaction demonstrated dramatic variations for aniline donor with the increasing dimethyl sulfoxide composition in MeOH–Me2SO mixtures. In this case, the Hammett and Brønsted plots are biphasic and concave upwards with a break point at 4-methylaniline. These results indicate a change in mechanism from the polar (SNAr) for less basic nucleophiles (X = 4-Cl, 4-I, 4-F, and H) to the single electron transfer (SET) for more basic nucleophiles (X = 4-OH, 4-OMe and 4-Me). The changes of the structure of the transitions states with substituents and solvent are in accordance with the results of kinetics studies. The solvation model described is well supported by the solvatochromism exhibited by aniline in the solvent mixture under investigation. These results provide an ideal framework for understanding the paramount importance of the specific molecular structure of solvent molecules in determining chemical reactivity versus solvent effects.
Starting Page	1537
Ending Page	1545
Page Count	9
File Format	PDF
ISSN	00269247
Journal	Monatshefte für Chemie - Chemical Monthly
Volume Number	144
Issue Number	10
e-ISSN	14344475
Language	English
Publisher	Springer Vienna
Publisher Date	2013-07-12
Publisher Place	Vienna
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Kinetics Solvent effect Solvatochromic parameters Single electron transfer (SET) pathway Biphasic concave upward free energy relationship Chemistry/Food Science Organic Chemistry Inorganic Chemistry Analytical Chemistry Physical Chemistry Theoretical and Computational Chemistry
Content Type	Text
Resource Type	Article
Subject	Chemistry

Sl.	Authority	Responsibilities	Communication Details
1	Ministry of Education (GoI), Department of Higher Education	Sanctioning Authority	https://www.education.gov.in/ict-initiatives
2	Indian Institute of Technology Kharagpur	Host Institute of the Project: The host institute of the project is responsible for providing infrastructure support and hosting the project	https://www.iitkgp.ac.in
3	National Digital Library of India Office, Indian Institute of Technology Kharagpur	The administrative and infrastructural headquarters of the project	Dr. B. Sutradhar bsutra@ndl.gov.in
4	Project PI / Joint PI	Principal Investigator and Joint Principal Investigators of the project	Dr. B. Sutradhar bsutra@ndl.gov.in Prof. Saswat Chakrabarti will be added soon
5	Website/Portal (Helpdesk)	Queries regarding NDLI and its services	support@ndl.gov.in
6	Contents and Copyright Issues	Queries related to content curation and copyright issues	content@ndl.gov.in
7	National Digital Library of India Club (NDLI Club)	Queries related to NDLI Club formation, support, user awareness program, seminar/symposium, collaboration, social media, promotion, and outreach	clubsupport@ndl.gov.in
8	Digital Preservation Centre (DPC)	Assistance with digitizing and archiving copyright-free printed books	dpc@ndl.gov.in
9	IDR Setup or Support	Queries related to establishment and support of Institutional Digital Repository (IDR) and IDR workshops	idr@ndl.gov.in

Electronic and solvent effects on kinetics of SNAr substitution reactions of substituted anilines with 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole in MeOH–Me2SO mixtures of varying composition: one reaction with two mechanistic pathways

Electronic and solvent effects on kinetics of SNAr substitution reactions of substituted anilines with 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole in MeOH–Me2SO mixtures of varying composition: one reaction with two mechanistic pathways

Single Electron Transfer (SET) Pathway: Nucleophilic Substitution Reaction of 4-Chloro-7-nitrobenzofurazan with Anilines in MeOH-MeCN Mixtures

Kinetic Studies on the Nucleophilic Substitution Reaction of 4-X-Substituted-2,6-dinitrochlorobenzene with Pyridines in MeOH-MeCN Mixtures

Synthesis, kinetic study, and reaction mechanism: nucleophilic substitution reactions of butyl methyl chlorophosphate with substituted anilines and deuterated substituted anilines in acetonitrile

Electrophilic Bromination of meta-Substituted Anilines with N-Bromosuccinimide: Regioselectivity and Solvent Effect

Photochemical Nucleophilic Substitution Reactions of Methyl Substituted Derivatives of p- and o-Nitroanisole

Solvent Hydrogen Bonding and Structural Effects on Nucleophilic Substitution Reactions: Part 5 – Reaction of 2-Bromo-5-nitropyridine with para-Substituted Anilines in Acetonitrile/Dimethylformamide Mixtures

Easy Access to Isomeric 7-Deazapurine–1,2,3-Triazole Conjugates via SNAr and CuAAC Reactions of 2,6-Diazido-7-deazapurines

Electronic and solvent effects on kinetics of SNAr substitution reactions of substituted anilines with 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole in MeOH–Me2SO mixtures of varying composition: one reaction with two mechanistic pathways

Similar Documents

Electronic and solvent effects on kinetics of SNAr substitution reactions of substituted anilines with 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole in MeOH–Me2SO mixtures of varying composition: one reaction with two mechanistic pathways

Electronic and solvent effects on kinetics of SNAr substitution reactions of substituted anilines with 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole in MeOH–Me2SO mixtures of varying composition: one reaction with two mechanistic pathways

Single Electron Transfer (SET) Pathway: Nucleophilic Substitution Reaction of 4-Chloro-7-nitrobenzofurazan with Anilines in MeOH-MeCN Mixtures

Kinetic Studies on the Nucleophilic Substitution Reaction of 4-X-Substituted-2,6-dinitrochlorobenzene with Pyridines in MeOH-MeCN Mixtures

Synthesis, kinetic study, and reaction mechanism: nucleophilic substitution reactions of butyl methyl chlorophosphate with substituted anilines and deuterated substituted anilines in acetonitrile

Electrophilic Bromination of meta-Substituted Anilines with N-Bromosuccin­imide: Regioselectivity and Solvent Effect

Photochemical Nucleophilic Substitution Reactions of Methyl Substituted Derivatives of p- and o-Nitroanisole

Solvent Hydrogen Bonding and Structural Effects on Nucleophilic Substitution Reactions: Part 5 – Reaction of 2-Bromo-5-nitropyridine with para-Substituted Anilines in Acetonitrile/Dimethylformamide Mixtures

Easy Access to Isomeric 7-Deazapurine–1,2,3-Triazole Conjugates via SNAr and CuAAC Reactions of 2,6-Diazido-7-deazapurines

Electronic and solvent effects on kinetics of SNAr substitution reactions of substituted anilines with 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole in MeOH–Me2SO mixtures of varying composition: one reaction with two mechanistic pathways

Electrophilic Bromination of meta-Substituted Anilines with N-Bromosuccinimide: Regioselectivity and Solvent Effect