Acenaphthylene is a colorless crystalline solid. Insoluble in water. Used in dye synthesis, insecticides, fungicides, and in the manufacture of plastics.
Metabolic scission of the 5-membered ring of acenaphthylene to yield 1,8-naphthalic acid proceeds via the cis- and trans-acenaphthene-1,2-diols and scission of the diols has been shown to be affected by microsomal prepn of rat liver.
A Beijerinckia species and a mutant strain, Beijerinckia species strain B8/36, were shown to oxidize the polycyclic aromatic hydrocarbons acenaphthene and acenaphthylene. Both organisms oxidized acenaphthene to the same spectrum of metabolites, which included 1-acenaphthenol, 1-acenaphtheneone, 1,2-acenaphthenediol, acenaphthenequinone, and a compound that was tentatively identified as 1,2-dihydroxyacenaphthylene. In contrast, acenaphthylene was oxidized to acenaphthenequinone and the compound tentatively identified as 1,2-dihydroxyacenaphthylene was also formed when the organism was incubated with synthetic cis-1,2-acenaphthenediol. A metabolite identified as cis-1,2-acenaphthenediol was formed from acenaphthylene by the mutant Beijerinckia species strain B8/36. Cell extracts prepared from the wild-type Beijerinckia strain contain a constitutive pyridine nucleotide-dependent dehydrogenase which can oxidize 1-acenaphthenol and 9-fluorenol. The results indicate that although acenaphthene and acenaphthylene are both oxidized to acenaphthenequinone, the pathways leading to the formation of this end product are different.
Stenotrophomonas sp. RMSK capable of degrading acenaphthylene as a sole source of carbon and energy was isolated from coal sample. Metabolites produced were analyzed and characterized by TLC, HPLC, and mass spectrometry. Identification of naphthalene-1,8-dicarboxylic acid, 1-naphthoic acid, 1,2-dihydroxynaphthalene, salicylate and detection of key enzymes namely 1,2-dihydroxynaphthalene dioxygenase, salicylaldehyde dehydrogenase, and catechol-1,2-dioxygenase in the cell free extract suggest that acenaphthylene metabolized via 1,2-dihydroxynaphthalene, salicylate and catechol. The terminal metabolite, catechol was then metabolized by catechol-1,2-dioxygenase to cis,cis-muconic acid, ultimately forming TCA cycle intermediates. Based on these studies, the proposed metabolic pathway in strain RMSK is,acenaphthylene --> naphthalene-1,8-dicarboxylic acid --> 1-naphthoic acid --> 1,2-dihydroxynaphthalene --> salicylic acid --> catechol --> cis,cis-muconic acid.
The acenaphthylene-degrading bacterium Rhizobium sp. strain CU-A1 was isolated from petroleum-contaminated soil in Thailand. This strain was able to degrade 600 mg/liter acenaphthylene completely within three days. To elucidate the pathway for degradation of acenaphthylene, strain CU-A1 was mutagenized by transposon Tn5 in order to obtain mutant strains deficient in acenaphthylene degradation. Metabolites produced from Tn5-induced mutant strains B1, B5, and A53 were purified by thin-layer chromatography and silica gel column chromatography and characterized by mass spectrometry. The results suggested that this strain cleaved the fused five-membered ring of acenaphthylene to form naphthalene-1,8-dicarboxylic acid via acenaphthenequinone. One carboxyl group of naphthalene-1,8-dicarboxylic acid was removed to form 1-naphthoic acid which was transformed into salicylic acid before metabolization to gentisic acid.
PAH metabolism occurs in all tissues, usually by cytochrome P-450 and its associated enzymes. PAHs are metabolized into reactive intermediates, which include epoxide intermediates, dihydrodiols, phenols, quinones, and their various combinations. The phenols, quinones, and dihydrodiols can all be conjugated to glucuronides and sulfate esters; the quinones also form glutathione conjugates. (L10)
IDENTIFICATION AND USE: Acenaphthylene is a solid. It is used for research purposes. Polycyclic aromatic hydrocarbons are a group of chemicals that are formed during the incomplete burning of coal, oil, gas, wood, garbage, or other organic substances, such as tobacco and charbroiled meat. HUMAN EXPOSURE AND TOXICITY: Blood polycyclic aromatic hydrocarbon (PAH) levels in children, including acenaphthylene, significantly correlated with oxidative stress and altered antioxidant status. It induced cytokine production and reduced nitric oxide formation in human coronary artery endothelial cell cultures. Metabolic activation of PAHs and aryl- and heterocyclic amines to genotoxic products was examined in Salmonella typhimurium, and it was found that P450 2A13 and 2A6 (as well as P450 1B1) were able to activate several of these procarcinogens. Acenaphthylene is oxidized by human P450s 2A6 and 2A13 and other P450s to form several mono- and dioxygenated products. It is not classifiable as to human carcinogenicity. ANIMAL STUDIES: No tumors were observed in a lifetime study when 0.25% acenaphthylene was applied to the skin of mice. Survival was 65% at 6 months, and 35% at 1 year. Acenaphthylene is an aromatic hydrocarbon-responsive receptor (AHR)-independent inducer of murine CYP1A2 and CYP1B1 mRNA. Acenaphthylene (1 mM) yielded positive results in a Salmonella typhimurium forward mutation assay, but was not positive in a Salmonella typhimurium TA98 and TA100 with metabolic activation. ECOTOXICITY STUDIES: Acenaphthylene modified the hemolytic alternative complement activity after 4 hr of incubation in peripheral blood of the European sea bass. It was also directly cytotoxic to a cell line from the rainbow trout gill.
The ability of PAH's to bind to blood proteins such as albumin allows them to be transported throughout the body. Many PAH's induce the expression of cytochrome P450 enzymes, especially CYP1A1, CYP1A2, and CYP1B1, by binding to the aryl hydrocarbon receptor or glycine N-methyltransferase protein. These enzymes metabolize PAH's into their toxic intermediates. The reactive metabolites of PAHs (epoxide intermediates, dihydrodiols, phenols, quinones, and their various combinations) covalently bind to DNA and other cellular macromolecules, initiating mutagenesis and carcinogenesis. (L10, L23, A27, A32)
CLASSIFICATION: D; not classifiable as to human carcinogenicity. BASIS FOR CLASSIFICATION: Based on no human data and inadequate data from animal bioassays. HUMAN CARCINOGENICITY DATA: None. ANIMAL CARCINOGENICITY DATA: Inadequate.
来源:Hazardous Substances Data Bank (HSDB)
毒理性
致癌物分类
蒽醌存在于杂酚油中，杂酚油可能对人体有致癌性（2A组）。
Acenaphthylene is found in creosotes, which are probably carcinogenic to humans (Group 2A). (L135)
PAHs are carcinogens and have been associated with the increased risk of skin, respiratory tract, bladder, stomach, and kidney cancers. They may also cause reproductive effects and depress the immune system. (L10)
来源:Toxin and Toxin Target Database (T3DB)
吸收、分配和排泄
一些植物叶片和果实表面的蜡质可以通过表面吸附集中多环芳烃。/多核芳烃/
The waxy surface of some plant leaves and fruits can concentrate polyaromatic hydrocarbons through surface adsorption. /Polynuclear aromatic hydrocarbons/
Dietary absorption efficiencies and elimination rates of acenaphthylene, 1-phenyl naphthalene, 2-methyl anthracene, 9-methyl anthracene, triphenylene, perylene, benzo[b]fluorene, dibenzo[a,h]anthracene, benzo [ghi]perylene and coronene were examined in rainbow trout. Subadult fish were exposed to 10 mg of each chemical over 5 days and polycyclic aromatic hydrocarbon (PAH) levels were monitored during the following 25 days. The results indicated that PAHs were not accumulated by trout through dietary exposure because of the combined effects of poor absorption efficiencies and rapid elimination rates. Phenyl naphthalene was more persistent than the other PAHs examined, with a half-life of 25 days.
Carbopalladation of Nitriles: Synthesis of 2,3-Diarylindenones and Polycyclic Aromatic Ketones by the Pd-Catalyzed Annulation of Alkynes and Bicyclic Alkenes by 2-Iodoarenenitriles
作者：Alexandre A. Pletnev、Qingping Tian、Richard C. Larock
DOI：10.1021/jo026178g
日期：2002.12.1
represents one of the first examples of the addition of an organopalladium moiety to the carbon-nitrogentriplebond of a nitrile. The reaction is compatible with a number of functional groups. A reaction mechanism, as well as a model accounting for the electronic effects of substituents on the aromatic ring of the nitrile, is proposed.
extensive studies on FSO2+‐type reagents, a radicalfluorosulfonylation reaction with a fluorosulfonyl radical (FSO2.) remains elusive so far, probably owing to its instability and difficulty in generation. Herein, the development of the first radicalfluorosulfonylation of alkenes based on FSO2 radicals generated under photoredox conditions is reported. This radical approach provides a new and general access
A silver‐mediated oxidative difluoromethylation of styrenes and vinyl trifluoroborates with TMSCF2H is reported for the first time. This method enables direct and facile access to CF2H‐alkenes from abundant alkenes with excellent functional‐group compatibility. Moreover, this Ag/TMSCF2H protocol could further enable a series of radical difluoromethylation reactions of a wide array of substrates, offering
Radical-Mediated Strategies for the Functionalization of Alkenes with Diazo Compounds
作者：Yong-Liang Su、Geng-Xin Liu、Jun-Wen Liu、Linh Tram、Huang Qiu、Michael P. Doyle
DOI：10.1021/jacs.0c05183
日期：2020.8.12
reported. Here we report a novel reaction of diazo compounds utilizing a radical-mediated addition strategy to achieve difunctionalization of diverse alkenes. Diazo compounds are transformed to carbon radicals with a photocatalyst or an iron catalyst through PCET processes. The carbon radical selectively adds to diverse alkenes delivering new carbon radical species, then forms products through hydroalkylation
Nickel‐Catalyzed, Regio‐ and Enantioselective Benzylic Alkenylation of Olefins with Alkenyl Bromide
作者：Jiandong Liu、Hegui Gong、Shaolin Zhu
DOI：10.1002/anie.202012614
日期：2021.2.19
A NiH‐catalyzed migratory hydroalkenylation reaction of olefins with alkenyl bromides has been developed, affording benzylic alkenylation products with high yields and excellent chemoselectivity. The mild conditions of the reaction preclude olefinic products from undergoing further isomerization or subsequent alkenylation. Catalytic enantioselective hydroalkenylation of styrenes was achieved by using
