Inclusion of the insecticide fenitrothion in dimethylated-β-cyclodextrin: unusual guest disorder in the solid state and efficient retardation of the hydrolysis rate of the complexed guest in alkaline solution

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dc.contributor.authorCruickshank, Dyanne L
dc.contributor.authorRougier, Natalia M
dc.contributor.authorVico, Raquel V
dc.contributor.authorBourne, Susan A
dc.contributor.authorBuján, Elba I
dc.contributor.authorCaira, Mino R
dc.contributor.authorde Rossi, Rita H
dc.date.accessioned2021-10-08T06:20:12Z
dc.date.available2021-10-08T06:20:12Z
dc.date.issued2013
dc.description.abstractAn anhydrous 1:1 crystalline inclusion complex between the organophosphorus insecticide fenitrothion [O,O-dimethyl O-(3-methyl-4-nitrophenyl)phosphorothioate] and the host compound heptakis(2,6-di-O-methyl)-β-cyclodextrin (DIMEB) was prepared and its structure elucidated by single-crystal X-ray diffraction. This revealed two independent host molecules in the asymmetric unit. In one of these, the cavity is occupied by two disordered guest components (distinguishable as rotamers with respect to the P–OAr bond) while in the other, three distinct guest components with site-occupancies 0.44, 0.29 and 0.27 appear, the last having a reversed orientation relative to all the other components. Kinetic studies of the alkaline hydrolysis of fenitrothion in the presence of DIMEB showed a remarkable reduction of 84% in the rate of this reaction relative to that for the free substrate, a value exceeding those previously attained with the native hosts, β- and γ-cyclodextrin, and fully methylated β-cyclodextrin.
dc.identifier.apacitationCruickshank, D. L., Rougier, N. M., Vico, R. V., Bourne, S. A., Buján, E. I., Caira, M. R., & de Rossi, R. H. (2013). Inclusion of the insecticide fenitrothion in dimethylated-β-cyclodextrin: unusual guest disorder in the solid state and efficient retardation of the hydrolysis rate of the complexed guest in alkaline solution. <i>Beilstein Journal of Organic Chemistry</i>, 9(4), 106 - 117. http://hdl.handle.net/11427/34222en_ZA
dc.identifier.chicagocitationCruickshank, Dyanne L, Natalia M Rougier, Raquel V Vico, Susan A Bourne, Elba I Buján, Mino R Caira, and Rita H de Rossi "Inclusion of the insecticide fenitrothion in dimethylated-β-cyclodextrin: unusual guest disorder in the solid state and efficient retardation of the hydrolysis rate of the complexed guest in alkaline solution." <i>Beilstein Journal of Organic Chemistry</i> 9, 4. (2013): 106 - 117. http://hdl.handle.net/11427/34222en_ZA
dc.identifier.citationCruickshank, D.L., Rougier, N.M., Vico, R.V., Bourne, S.A., Buján, E.I., Caira, M.R. & de Rossi, R.H. 2013. Inclusion of the insecticide fenitrothion in dimethylated-β-cyclodextrin: unusual guest disorder in the solid state and efficient retardation of the hydrolysis rate of the complexed guest in alkaline solution. <i>Beilstein Journal of Organic Chemistry.</i> 9(4):106 - 117. http://hdl.handle.net/11427/34222en_ZA
dc.identifier.issn1860-5397
dc.identifier.issn2195-951X
dc.identifier.ris TY - Journal Article AU - Cruickshank, Dyanne L AU - Rougier, Natalia M AU - Vico, Raquel V AU - Bourne, Susan A AU - Buján, Elba I AU - Caira, Mino R AU - de Rossi, Rita H AB - An anhydrous 1:1 crystalline inclusion complex between the organophosphorus insecticide fenitrothion [O,O-dimethyl O-(3-methyl-4-nitrophenyl)phosphorothioate] and the host compound heptakis(2,6-di-O-methyl)-β-cyclodextrin (DIMEB) was prepared and its structure elucidated by single-crystal X-ray diffraction. This revealed two independent host molecules in the asymmetric unit. In one of these, the cavity is occupied by two disordered guest components (distinguishable as rotamers with respect to the P–OAr bond) while in the other, three distinct guest components with site-occupancies 0.44, 0.29 and 0.27 appear, the last having a reversed orientation relative to all the other components. Kinetic studies of the alkaline hydrolysis of fenitrothion in the presence of DIMEB showed a remarkable reduction of 84% in the rate of this reaction relative to that for the free substrate, a value exceeding those previously attained with the native hosts, β- and γ-cyclodextrin, and fully methylated β-cyclodextrin. DA - 2013 DB - OpenUCT DP - University of Cape Town IS - 4 J1 - Beilstein Journal of Organic Chemistry LK - https://open.uct.ac.za PY - 2013 SM - 1860-5397 SM - 2195-951X T1 - Inclusion of the insecticide fenitrothion in dimethylated-β-cyclodextrin: unusual guest disorder in the solid state and efficient retardation of the hydrolysis rate of the complexed guest in alkaline solution TI - Inclusion of the insecticide fenitrothion in dimethylated-β-cyclodextrin: unusual guest disorder in the solid state and efficient retardation of the hydrolysis rate of the complexed guest in alkaline solution UR - http://hdl.handle.net/11427/34222 ER - en_ZA
dc.identifier.urihttp://hdl.handle.net/11427/34222
dc.identifier.vancouvercitationCruickshank DL, Rougier NM, Vico RV, Bourne SA, Buján EI, Caira MR, et al. Inclusion of the insecticide fenitrothion in dimethylated-β-cyclodextrin: unusual guest disorder in the solid state and efficient retardation of the hydrolysis rate of the complexed guest in alkaline solution. Beilstein Journal of Organic Chemistry. 2013;9(4):106 - 117. http://hdl.handle.net/11427/34222.en_ZA
dc.language.isoeng
dc.publisher.departmentDepartment of Chemistry
dc.publisher.facultyFaculty of Science
dc.sourceBeilstein Journal of Organic Chemistry
dc.source.journalissue4
dc.source.journalvolume9
dc.source.pagination106 - 117
dc.source.urihttps://dx.doi.org/10.3762/bjoc.9.14
dc.subject.othercrystal structure
dc.subject.othercyclodextrin
dc.subject.otherfenitrothion
dc.subject.otherhydrolysis
dc.subject.otherinclusion complex
dc.subject.otherOrganic chemistry
dc.subject.otherQD241-441
dc.subject.otherChemistry
dc.subject.otherQD1-999
dc.subject.otherScience
dc.subject.otherQ
dc.subject.otherDOAJ:Organic Chemistry
dc.subject.otherDOAJ:Chemistry
dc.titleInclusion of the insecticide fenitrothion in dimethylated-β-cyclodextrin: unusual guest disorder in the solid state and efficient retardation of the hydrolysis rate of the complexed guest in alkaline solution
dc.typeJournal Article
uct.type.publicationResearch
uct.type.resourceJournal Article
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