A pilot study of per- and polyfluoroalkyl substances in automotive lubricant oils from the United States
ENVIRONMENTAL TECHNOLOGY & INNOVATION
Authors: Zhu, Hongkai; Kannan, Kurunthachalam
Abstract
Per- and polyfluoroalkyl substances (PFASs) were reported to be used as additives in automotive lubricant oils and hydraulic fluids, to reduce surface tension, prevent fires and evaporation. Little is known, however, with regard to the occurrence of PFASs in automotive lubricants. In this study, concentrations and profiles of 13 perfluoroalkyl acids (PFAAs), encompassing nine perfluoroalkyl carboxylic acids (PFCAs; C4-C12) and four perfluoroalkyl sulfonic acids (PFSAs; C4-C10), were determined in 18 automotive lubricants purchased in the United States. The lubricant extracts were analyzed before and after oxidization, to measure PFAAs and their precursors, using the total oxidizable precursor (TOP) assay. Following oxidation, lubricant extracts yielded Sigma PFAA concentrations up to two orders of magnitude higher (range: 196-8300 ng/g; mean: 1840 ng/g) than those measured prior to oxidation (5.96-344 ng/g; 71.6 ng/g), which suggested the presence of notable amounts of PFAA precursors. Long-chain PFCAs (C8-C12; similar to 70% of total) were the major PFASs detected (prior to oxidation). The mean molar increase in the concentration (pM/g) upon oxidation of lubricant extracts varied among the nine PFCAs in the following decreasing order: C4 (1350) > C12 (670) > C11 (570) = C5 (570) > C10 (460) > C9 (300) > C7 (140) = C6 (140) > C8 (110). Principal component analysis of PFCA profiles revealed that PFAAs originate from their respective precursors. (c) 2020 Elsevier B.V. All rights reserved.
Palladium-catalyzed C8-H alkoxycarbonylation of 1-naphthylamines with alkyl chloroformates
ORGANIC & BIOMOLECULAR CHEMISTRY
Authors: Shi, Yaqi; Yang, Fan; Wu, Yangjie
Abstract
A simple and efficient protocol for palladium-catalyzed C8-H alkoxycarbonylation of 1-naphthylamine derivatives with alkyl chloroformates has been developed, exhibiting broad functional group tolerance, high regioselectivity, and oxidant-free conditions. Furthermore, the reaction features its ease of further functionalization and transformation. For example, the concise synthesis of one BET bromodomain inhibitor was accomplishedviabenz[cd]indol-2(1H)-one after multistep transformations from the obtained alkoxycarbonylation product. In addition, the control experiments suggest that the reaction might involve a radical process and the C-H bond cleavage might not be involved in the rate-determining step.