000110640 001__ 110640
000110640 005__ 20240124152521.0
000110640 0247_ $$2doi$$a10.1038/s41598-021-88060-7
000110640 0248_ $$2sideral$$a125756
000110640 037__ $$aART-2021-125756
000110640 041__ $$aeng
000110640 100__ $$aBescós, A.
000110640 245__ $$aTheoretical insight on the treatment of ß-hexachlorocyclohexane waste through alkaline dehydrochlorination
000110640 260__ $$c2021
000110640 5060_ $$aAccess copy available to the general public$$fUnrestricted
000110640 5203_ $$aThe occurrence of 4.8–7.2 million tons of hexachlorocyclohexane (HCH) isomers stocked in dumpsites around the world constitutes a huge environmental and economical challenge because of their toxicity and persistence. Alkaline treatment of an HCH mixture in a dehydrochlorination reaction is hampered by the low reactivity of the ß-HCH isomer (HCl elimination unavoidably occurring through syn H–C–C–Cl arrangements). More intriguingly, the preferential formation of 1, 2, 4-trichlorobenzene in the ß-HCH dehydrochlorination reaction (despite the larger thermodynamical stability of the 1, 3, 5-isomer) has remained unexplained up to now, though several kinetic studies had been reported. In this paper, we firstly show a detailed Density Functional study on all paths for the hydroxide anion-induced elimination of ß-HCH through a three-stage reaction mechanism (involving two types of reaction intermediates). We have now demonstrated that the first reaction intermediate can follow several alternative paths, the preferred route involving abstraction of the most acidic allylic hydrogen which leads to a second reaction intermediate yielding only 1, 2, 4-trichlorobenzene as the final reaction product. Our theoretical results allow explaining the available experimental data on the ß-HCH dehydrochlorination reaction (rate-determining step, regioselectivity, instability of some reaction intermediates). © 2021, The Author(s).
000110640 536__ $$9info:eu-repo/grantAgreement/ES/DGA-ERDF/E37-20R$$9info:eu-repo/grantAgreement/ES/MCIU/RTI2018-093431-B-100
000110640 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000110640 590__ $$a4.997$$b2021
000110640 592__ $$a1.005$$b2021
000110640 591__ $$aMULTIDISCIPLINARY SCIENCES$$b19 / 74 = 0.257$$c2021$$dQ2$$eT1
000110640 593__ $$aMultidisciplinary$$c2021$$dQ1
000110640 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000110640 700__ $$0(orcid)0000-0002-7272-8506$$aHerrerías, C.I.$$uUniversidad de Zaragoza
000110640 700__ $$0(orcid)0000-0002-8805-4374$$aHormigón, Z.
000110640 700__ $$0(orcid)0000-0003-1570-4257$$aMayoral, J.A.$$uUniversidad de Zaragoza
000110640 700__ $$0(orcid)0000-0003-2010-9540$$aSalvatella, L.$$uUniversidad de Zaragoza
000110640 7102_ $$12013$$2765$$aUniversidad de Zaragoza$$bDpto. Química Orgánica$$cÁrea Química Orgánica
000110640 773__ $$g11, 1 (2021), 8777 [8 pp]$$pSci. rep. (Nat. Publ. Group)$$tScientific reports (Nature Publishing Group)$$x2045-2322
000110640 8564_ $$s1119310$$uhttps://zaguan.unizar.es/record/110640/files/texto_completo.pdf$$yVersión publicada
000110640 8564_ $$s2364469$$uhttps://zaguan.unizar.es/record/110640/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000110640 909CO $$ooai:zaguan.unizar.es:110640$$particulos$$pdriver
000110640 951__ $$a2024-01-24-15:17:38
000110640 980__ $$aARTICLE