Aqueous Chlorination of D-Limonene

Lebedev, Albert T. (author), Detenchuk, Elena Andreevna (author), Latkin, Tomas B. (author), Bavcon Kralj, Mojca (author), Trebše, Polonca (author)

Limonene (1-methyl-4-(1-methylethenyl)-cyclohexene) is one of the most widespread monocyclic terpenes, being both a natural and industrial compound. It is widely present in the environment, including in water supplies. Therefore, it may be subjected to aqueous chlorination at water treatment stations during drinking water preparation. Besides, being a component of numerous body care and cosmetic products, it may present at high levels in swimming pool waters and could also be subjected to aqueous chlorination. Laboratory experiments with aqueous chlorination of D-limonene demonstrated the prevalence of the conjugated electrophilic addition of HOCl molecule to the double bonds of the parent molecule as the primary reaction. The reaction obeys the Markovnikov rule, as the levels of the corresponding products were higher than those of the alternative ones. Fragmentation pattern in conditions of electron ionization enabled the assigning of the structures for four primary products. The major products of the chlorination are formed by the addition of two HOCl molecules to limonene. The reactions of electrophilic addition are usually accompanied by the reactions of elimination. Thus, the loss of water molecules from the products of various generations results in the reproduction of the double bond, which immediately reacts further. Thus, a cascade of addition-elimination reactions brings the most various isomeric polychlorinated species. At a ratio of limonene/active chlorine higher than 1:10, the final products of aqueous chlorination (haloforms) start forming, while brominated haloforms represent a notable portion of these products due to the presence of bromine impurities in the used NaOCl. It is worth mentioning that the bulk products of aqueous chlorination are less toxic in the bioluminescence test on V. fischeri than the parent limonene.

• Language: English
• Keywords: limonene, aqueous chlorination, GC-HRMS, haloforms, electrophilic addition, disinfection by-products
• Work type: Article
• Typology: 1.01 - Original Scientific Article
• Organization: ZF - Faculty of Health Sciences
• Publication status: Published
• Publication version: Version of Record
• Publication date: 06.05.2022
• Year: 2022
• Number of pages: 14 str.
• Numbering: Vol. 27, iss. 9, art. 2988
• PID: 20.500.12556/RUL-136502
• UDC: 543.422.3
• ISSN on article: 1420-3049
• DOI: 10.3390/molecules27092988
• COBISS.SI-ID: 107060739
• Publication date in RUL: 09.05.2022

Record is a part of a journal

• Title: Molecules
• Shortened title: Molecules
• Publisher: MDPI
• ISSN: 1420-3049
• COBISS.SI-ID: 18462981

Licences

• License: CC BY 4.0, Creative Commons Attribution 4.0 International
• Link: http://creativecommons.org/licenses/by/4.0/
• Description: This is the standard Creative Commons license that gives others maximum freedom to do what they want with the work as long as they credit the author.
• Licensing start date: 06.05.2022

Secondary language

• Language: Undetermined
• Keywords: limonen, vodno kloriranje, GC-HRMS, haloforme, elektrofilni dodatek, stranski proizvodi dezinfekcije

Projects

• Funder: ARRS - Slovenian Research Agency
• Project number: P3-0388
• Name: Mehanizmi varovanja zdravja

• Funder: Other - Other funder or multiple funders
• Funding programme: RFBR
• Project number: 19-33-90042