Kinetic Studies on the Nucleophilic Aromatic Substitution of Fluoronitrobenzene Derivatives with Polyvinylamine in Water Mediated by 2,6-<i>O</i>-Dimethyl-β-cyclodextrin

Roth, Isabelle; Spange, Stefan

doi:10.1021/ma0518609

Cited by 13 publications

(25 citation statements)

References 35 publications

(87 reference statements)

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“…The mixture was refluxed for 8 h at 100 o C. The product was precipitated in ice-cold acetone, centrifuged, washed with acetone and dried under vacuum at room temperature for several days. Further details of synthesis and characterization of PVAms have been described elsewhere in detail (32,33), for pertinent details of the polymers used in this study see Table I.…”

Section: Methodsmentioning

confidence: 99%

A Comparative Spectroelectrochemical Study of the Redox Electrochemistry of N-(Polyvinylamine)-Substituted-o-Nitroaniline

et al. 2010

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The electrochemistry and spectroelectrochemistry of polyvinylamine (PVAm) and N-(polyvinylamine)-substituted-o-nitroaniline at a polycrystalline gold electrode in contact with different electrolyte solutions (0.1 M HClO 4 and 0.1 M KClO 4 ) have been investigated with cyclic voltammetry and surface enhanced Raman spectroscopy (SERS). Cyclic voltammograms recorded with in acidic electrolyte solution showed formation of N-(polyvinylamine)-o-phenylenediamine in the negative going potential scan; in neutral solution reduction proceeds only to N-(polyvinylamine)-o-phenylhydroxylamine. Vibrational modes are discussed and assigned to monomer-surface interactions of adsorbates at the gold surface in both electrolyte solutions. A variety of adsorption behaviors of these polymers at a gold surface is concluded; they apparently depend on the applied electrode potential, pH of electrolyte (acidic or neutral), type and mole percentage of the o-nitroaniline moiety. The adsorption at the gold surface is strongly enhanced with 12.7 mole% of o-nitroaniline moiety, respectively, at its PVAm-backbone. The direct coordination of these polymers with the gold surface occurred via the nitro-group of the o-nitroaniline moiety and primary amino-groups located at the polymer backbone.

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Section: Methodsmentioning

confidence: 99%

A Comparative Spectroelectrochemical Study of the Redox Electrochemistry of N-(Polyvinylamine)-Substituted-o-Nitroaniline

et al. 2010

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“…Increasing the temperature in a reaction, not only provides the necessary energy for the reaction to take place, but also favors kinetics [1]. Elimination reactions [2], nucleophilic substitutions [3], thermal cycloadditions [4], intramolecular rearrangements [5] and palladium catalyzed reactions [6] are some of the reactions that demand moderate temperatures. Other reactions involving thermal decompositions require higher temperatures, since in these processes it is necessary to break chemical bonds of reagents [7].…”

Section: Introductionmentioning

confidence: 99%

Design, fabrication and characterization of microreactors for high temperature syntheses

Martínez-Cisneros

Pedro

Puyol

et al. 2012

Chemical Engineering Journal

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Microfluidic reactors offer many potential advantages in several research and industrial fields such as processes intensification, which includes a better reaction control (kinetics and thermodynamics), a high throughput and a safer operational environment (reduced manipulation of dangerous reagents and low sub-products generation). Nevertheless, scaling-down limitations appear concerning the materials used in the fabrication of microreactors for most of the liquid-phase reactions, since they usually require high temperatures (up to 300ºC), solvents and organic reagents. In this work, the development of a set of modular and monolithic microreactors based on the integration of microfluidics and a thermal platform (sensor/high-temperature heater) is proposed to perform high temperature reactions. The reliability and performance of both configurations were evaluated through an exhaustive characterization process regarding their thermal and microfluidic performance. Obtained results make the devices viable for their application in controlled and reproducible synthetic processes occurring at high temperatures such as the synthesis of quantum dots. The proposed microfluidic approach emerge as an engaging tool for processes intensification, since it provides better mass and temperature transfer than conventional methods with a reduction not only of the size and energy consumption, but also of by-products and reagents consumption.

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“…The functionalization reaction of choice is the nucleophilic aromatic substitution of PVAm with the fluoro compound in water mediated by cyclodextrins as reported previously (Scheme 1). [7,8] PVAms (Lupamine 1 ), when functionalized using 4-fluoro-3-nitroaniline and N,N-dimethyl-4-fluoro-3-nitroaniline, respectively, are here named polymer 1 and polymer 2. Polymer 3 is a completely N-methylsubstituted PVAm when functionalized with N,N-dimethyl-4-fluoro-3-nitroaniline.…”

Section: Introductionmentioning

confidence: 99%

2‐Nitro‐1,4‐diaminobenzene‐Functionalized Poly(vinyl amine)s as Water‐Soluble UV‐Vis‐Sensitive pH Sensors

Roth

Jbarah

Holze

et al. 2006

Macromol. Rapid Commun.

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Summary: Nucleophilic aromatic substitution of 2,6‐O‐dimethyl‐β‐cyclodextrin (β‐DMCD)‐complexed 4‐fluoro‐3‐nitroaniline derivatives with poly(vinyl amine) (PVAm) in water results in 2‐nitro‐1,4‐benzenediamine‐functionalized water‐soluble PVAms in one step. The 2‐nitro‐1,4‐benzenediamine moiety linked to the polymer is solvatochromic and undergoes protonation and deprotonation as function of pH as shown by UV‐Vis spectroscopy. The occurrence of an isosbestic point in the UV‐Vis spectrum is suitable to directly determine the pKa value using the Henderson‐Hasselbalch equation. The influence of the methyl group substitution of the polymer and the 2‐nitro‐1,4‐benzenediamine moiety on the pKa is discussed.Structure of the 4‐N,N‐dimethyl‐2‐nitro‐1,4‐benzenediamine‐functionalized PVAm and its solution in water at varying pH.imageStructure of the 4‐N,N‐dimethyl‐2‐nitro‐1,4‐benzenediamine‐functionalized PVAm and its solution in water at varying pH.

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Kinetic Studies on the Nucleophilic Aromatic Substitution of Fluoronitrobenzene Derivatives with Polyvinylamine in Water Mediated by 2,6-O-Dimethyl-β-cyclodextrin

Cited by 13 publications

References 35 publications

A Comparative Spectroelectrochemical Study of the Redox Electrochemistry of N-(Polyvinylamine)-Substituted-o-Nitroaniline

A Comparative Spectroelectrochemical Study of the Redox Electrochemistry of N-(Polyvinylamine)-Substituted-o-Nitroaniline

Design, fabrication and characterization of microreactors for high temperature syntheses

2‐Nitro‐1,4‐diaminobenzene‐Functionalized Poly(vinyl amine)s as Water‐Soluble UV‐Vis‐Sensitive pH Sensors

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