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Adsorption and Catalytic Decomposition of 4-Nitrobenzenesulphonylmethylcarbamate by Smectite

Published online by Cambridge University Press:  02 April 2024

Paolo Fusi ,
Giuseppe Gabriele Ristori  and
Marco Franci
Paolo Fusi
Affiliation:
Istituto di Chimica Agraria e Forestale, Università di Firenze, Piazzale delle Cascine 28, Florence, Italy
Giuseppe Gabriele Ristori
Affiliation:
Centro di Studio per i Colloidi del Suolo, C.N.R., Firenze, Piazzale delle Cascine 28, Florence, Italy
Marco Franci
Affiliation:
Centro di Studio per i Colloidi del Suolo, C.N.R., Firenze, Piazzale delle Cascine 28, Florence, Italy
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Abstract

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Adsorption and catalytic decomposition of 4-nitrobenzenesulphonylmethylcarbamate (herbicide Nisulam) on Upton, Wyoming, bentonite saturated with different cations was studied using thin-layer chromatography and infrared spectroscopy. Nisulam is adsorbed at room temperature by coordination through the NO2 group to the exchange cation regardless of the cation's nature. On moderate heating (75°–90°C) this molecule decomposes to 4-nitrobenzenesulphonamide whereas a similar compound (herbicide Asulam) containing the NH2 functional group instead of NO2 is adsorbed by protonation at room temperature and decomposes into different products. For cations having a high polarizing power, a coordination bond between the Asulam molecule's C=O group and the exchange cation is established, and the molecule decomposes to sulphanilic and carbamic acid. In contrast, for cations having a low polarizing power there is no coordination, and the molecule decomposes mainly into sulphanilamide. Nisulam's coordination to the exchange cation through the NO2 group instead of C=O is ascribed to inductive and conjugation effects, typical of the nitro group.

Резюме

Резюме

Адсорбция и каталитическая декомпозиция 4-нитробензеносульфонилметилкарбоната (Гербицид Нисулам) бентонитом из Уптон, Лаеминг, насыщенным различными катионами, исследовалась путем хроматографии тонких слоев и инфракрасной спектроскопии. Нисулам адсорбируется в комнатной температуре путем координирования группы NO2 с обменным катионом независимо от типа этого катиона. При небольшом нагреве (75-90°С) молекула Нисулама раскладывается на 4-нитробензеносульфонамид, тогда как похожее соединение (гербицид Асулам), содержащее функциональную группу NН2 вместо NО2 адсорбируется путем протонирования в комнатной температуре и раскладывается на различные продукты. Для катионов с большой силой поляризации устанавливается координационная связь между группой С = 0 молекулы Асулана и обменным катионом, и молекула раскладывается на сульфаниловую и карбаминовую кислоту. В противоположность, для катионов с низкой силой поляризации координация не выступает и молекула разлагается в основном на сульфаниламид. Координация Нисулама с обменным катионом посредством группы NO2 вместо двойной связи С = 0 приписана индуктивным и соединяющим эффектам, характерным для нитрогруппы. [Е.С.]

Resümee

Resümee

Es wurde die Adsorption und die katalytische Zersetzung von 4-Nitrobenzensulfonylmethylcarbamat (Herbizid Nisulam) durch ben Bentonit von Upton, Wyoming, der mit verschiedenen Kationen gesättigt war, mittels Dünnschichtchromatographie und Infrarotspektroskopie untersucht. Nisulam wird bei Raumtemperatur—unabhängig von der Art des Kations—durch die Koordination der NO2-Gruppe mit dem austauschbaren Kation adsorbiert. Bei mßigem Erhitzen (75–90°C) zerfällt dieses Molekül in 4-Nitrobenzensulfonamid während eine ähnliche Verbindung(Herbizid Asulam), die eine NH2-funktionelle Gruppe anstelle der NO2-Gruppe enthält, bei Raumtemperatur durch Protonierung adsorbiert wird und in verschiedene Produkte zerfällt. Bei Kationen, die ein großes Polarisierungsvermögen haben, bildet sich eine koordinative Bindung zwischen der C=O-Gruppe des Asulam-Moleküls und dem austauschbaren Kation, und das Molekül zerfällt in eine Sulfanilsäure und eine Carbamidsäure. Bei Kationen, die dagegen ein niedriges Polarisierungsvermögen haben, tritt keine Koordination auf und das Molekül zerfällt hauptsächlich in Sulfanilamid. Die Koordination von Nisulam an das austauschbare Kation durch die NO2-Gruppe anstelle der C=O-Gruppe wird Induktions- und Konjugations-Effekten zugeschrieben, die für die NO2-Gruppe typisch sind. [U.W.]

Résumé

Résumé

On a etudié par chromatographie de fines couches et par spectroscopie infrarouge l'adsorption et la décomposition catalytique de nitrobenzènesulphonylméthylcarbamate-4 (l'herbicide Nisulam) sur une bentonite d'Upton, Wyoming, saturée de cations différents. Le Nisulam est adsorbé à température ambiante par coordination par le groupe NO2 au cation d’échange sans égards pour la nature du cation. Echauffée modérément (75°–90°C), cette molécule se décompose en nitrobenzènesulphonamide-4, alors qu'un composé similaire (l'herbicide Asulam) contenant le groupe fonctionnel NH2 au lieu de NO2 est adsorbé par protonation à température ambiante et se décompose en produits différents. Pour des cations ayant une puissance polarisante élevée, un lien de coordination entre le groupe C=O de la molécule Asulam et le cation d’échange est établi, et la molécule se décompose en acides sulphanilique et carbamique. Par contraste, pour les cations ayant une puissance polarisante basse, il n'y a pas de coordination, et la molécule se décompose principalement en sulphanilamide. La coordination du Nisulam au cation d’échange par le groupe NO2 au lieu de C=O est assignée à des effets d'induction et de conjugaison typiques du groupe nitro. [D.J.]

Keywords

AdsorptionAsulamBentoniteDecompositionHerbicideNisulam
Type
Research Article
Information
Clays and Clay Minerals , Volume 30 , Issue 4 , August 1982 , pp. 306 - 310
Copyright
Copyright © 1982, The Clay Minerals Society

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