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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

References

Bellamy, L. J., 1958 The Infrared Spectra of Complex Molécules London Methuen 64–160.Google Scholar
Carter, J. C. and Devia, E., 1973 Vibrational analysis of methylcarbamate and N,N-dichloromethylcarbamate Spectrochim. Acta 29A 623–632.CrossRefGoogle Scholar
Cloos, P., Moreale, A., Broer, C. and Badot, C., 1979 Adsorption and oxidation of aniline and p-chloroaniline by montmorillonite Clay Miner. 14 307–321.CrossRefGoogle Scholar
Exner, O., Kovac, S. and Solcaniova, E., 1972 Substituent effects in infrared spectroscopy. II. Characteristic frequences of the nitrogroup in meta and para-substituted nitro-benzenes Coll. Czech. Chem. Comm. 37 2156–2168.CrossRefGoogle Scholar
Fripiat, J. J., Cruz, M. I., Bohor, B. F., Thomas, J. Jr., 1974 Interlamellar adsorption of carbon dioxide by smectites Clays & Clay Minerals 22 23–30.CrossRefGoogle Scholar
Fusi, P., Ristori, G. G. and Franci, M., 1981 Oxidative pro-cesses related to degradation of Asulam adsorbed on smectites Ann. Chim. 71 443–451.Google Scholar
Fusi, P., Ristori, G. G. and Malquori, A., 1980 Montmoril-lonite-Asulam interactions. I. Catalytic decomposition of Asulam adsorbed on H- and Al-clay Clay Miner. 15 147–155.CrossRefGoogle Scholar
Gould, S. E., 1962 Mechanism and Structure in Organic Chemistry New York Holt, Rinehart & Winston 200–218.Google Scholar
Heller, L. and Yariv, S., 1969 Sorption of some anilines by Mn-, Co-, Ni-, Cu-, Zn-, and Cd-montmorillonite Proc. Int. Clay Conf., Tokyo, 1969 1 741–755.Google Scholar
Mortland, M. M. and Raman, K. V., 1967 Catalytic hydrol-ysis of some organic phosphate pesticides by copper(II) J. Agr. Food Chem. 15 163–167.CrossRefGoogle Scholar
Nakamoto, K., 1978 Infrared and Raman Spectra of Inor-ganic and Coordination Compounds 3rd ed. New York Wiley 225.Google Scholar
Pinchas, S., Samuel, D. and Silver, B. L., 1964 The infrared adsorption spectrum of 18O-labeled nitrobenzene Spectrochim. Acta 20 179–185.CrossRefGoogle Scholar
Rao, C. N. R., 1963 Chemical Application of Infrared Spectroscopy New York Academic Press 156–195.Google Scholar
Ristori, G. G., Fusi, P. and Franci, M., 1981 Montmorillon-ite-Asulam interactions. II. Catalytic decomposition of Asulam adsorbed on Mg-, Ba-, Ca-, Li-, Na-, K- and Cs-clay Clay Miner. 16 125–137.CrossRefGoogle Scholar
Saltzman, S. and Yariv, S., 1976 Infrared and X-ray study of Parathion-montmorillonite sorption complexes Soil Sci. Soc. Amer. Proc. 40 34–38.CrossRefGoogle Scholar
Tahoun, S. A. and Mortland, M. M., 1966 Complexes of montmorillonite with primary, secondary and tertiary amides: II. Coordination of amides on the surface of mont-morillonite Soil Sci. 102 314–321.CrossRefGoogle Scholar
Tanaka, Y. and Tanaka, Y., 1968 Infrared absorption spectra of organic sulfur Compounds. IV. Studies on characteristic absorption bands of o-, m- and p-substituted benzenesul-phonamide derivatives Yakugaku Zasshi 88 695–698.CrossRefGoogle Scholar
Vogel, A. I., 1961 A Text-Book of Pratical Organic Chemistry Including Qualitative Organic Analysis London Longmans 543–544.Google Scholar
Walsh, J. T. and Merrit, C., 1960 Qualitative functional group analysis of gas Chromatographie effluents Anal. Chem. 32 1378–1381.CrossRefGoogle Scholar
White, J. L. and Bailey, S. W., 1975 Protonation and hydrolysis of s-triazines by Ca-montmorillonite as influenced by substitution at the 2-, 4- and 6-positions Proc. Int. Clay Conf, Mexico City, 1975 Illinois Applied Publishing, Wilmette 391–398.Google Scholar
Yariv, S., Russell, J. D. and Farmer, V. C., 1966 Infrared study of the adsorption of benzoic acid and nitrobenzene in montmorillonite Israel J. Chem. 4 201–213.CrossRefGoogle Scholar