The metabolism of two polycyclic aromatic hydrocarbons i.e. anthracene and 9,10-dimethylanthracene by Micrococcus sp., Pseudomonas sp. and Bacillus macerans was examined. The above compounds were used as a sole carbon source for their growth. Using the reversed-phase thin layer chromatography techniques a number of anthracene and 9,10-dimethylanthracene metabolites were isolated and their structures identified spectroscopically. These included anthracene and 9,10-dimethylanthracene cis-dihydrodiols, hydroxy-methyl-derivatives and various phenolic compounds. Bacteria metabolize hydrocarbons using the dioxygenase enzyme system, which differs from the mammalian cytochrome P-450 monoxygenase. ...
In-vitro stereoselective metabolism of methylated anthracenes by rat liver microsomes, and the configurations and optical purity of the trans-dihydrodiol metabolites were investigated. Liver microsomes from untreated immature male Sprague-Dawley-rats and from rats pretreated with either 3-methylcholanthrene (3-MC) or phenobarbital (PB) were incubated with 9-methylanthracene (779022) (9-MA), 9-hydroxymethylanthracene (9-OHMA), or 9,10-dimethylanthracene (781431) (9,10-DMA) for 60 minutes. Metabolites were separated by reverse phase high performance liquid chromatography (HPLC). Results indicated that 9-MA, 9-OHMA and 9,10-DMA were metabolized by 3-MC, PB and control microsomes in a stereoselective manner. With the exception of the formation of 9-OHMA-trans-3,4 dihydrodiol by PB microsomes, all of the trans-dihydrodiol metabolites formed from the three microsomal enzyme systems were predominantly the R,R enantiomers. The 3-MC microsomes exhibited much higher stereoselectivity than the Pb or control microsomes in the formation of trans-dihydrodiols from anthracene, 9-MA, 9-OHMA and 9,10-DMA. Optical purities of the trans-dihydrodiol metabolites, determined by analysis of the chiral stationary phase HPLC profiles of the dihydrodiols or their corresponding tetrahydrodiol derivatives, ranged from 76 to 98 percent, 4 to 76 percent and 4 to 60 percent for 3-MC, PB and control microsomes, respectively. Methyl and hydroxymethyl substituents slightly decreased the stereoselectivity of the trans-dihydrodiol formation. The authors conclude that the lower optical purities of the trans-dihydrodiols formed by either PB or control microsomes are clearly due to the lower stereoselectivity of the cytochrome-P-450 enzymes or epoxidation of the polycyclic aromatic hydrocarbon substrates, but not due to the change of the stereoselectivity of the epoxide hydrolase enzymes.
The metabolism of the weakly-carcinogenic hydrocarbon, 9,10-dimethylanthracene (DMA) by rat-liver microsomal preparations has been examined. 9-Hydroxymethyl-10-methylanthracene (9-OHMeMA) and 9,10-dihydroxymethyl-anthracene (9,10-DiOHMeA) were identified as metabolites by comparing their chromatographic and spectral properties with those of the authentic compounds. The trans-1,2-dihydro-1,2-dihydroxy derivative of DMA (DMA 1,2-diol) was the major metabolite formed which was identified by its chromatographic, u.v., n.m.r. and mass spectral properties. The dihydrodiol was also formed in the oxidation of DMA in an ascorbic acid-ferrous sulphate-EDTA system. Two other dihydrodiols that were formed from DMA by metabolism appeared to be the trans-1,2- and 3,4-dihydrodiols of 9-OHMeMA (9-OHMeMA 1,2-diol and 9-OHMeMA 3,4-diol) and the further metabolism of DMA 1,2-diol yielded both of these dihydrodiols. When 9-OHMeMA was further metabolized, two main metabolites were formed; one was identified as 9,10-DiOHMeA and the other appeared to be 9-OHMeMA 3,4-diol. No metabolites were detected when 9,10-DiOHMeA was incubated with rat-liver microsomal fractions.
IDENTIFICATION AND USE: 9-10-Dimethylanthracene (9,10-DMA) is a solid polycyclic hydrocarbon. HUMAN EXPOSURE AND TOXICITY: There are no data available. ANIMAL STUDIES: 9,10-DMA was not mutagenic in the recessive lethal assay. 9,10-Dimethylanthracene showed a rather weak genotoxicity in Drosophila melanogaster studies. The fraction of all genotoxic events which are due to mitotic recombination was 83%. ECOTOXICITY STUDIES: 9,10-DMA suppressed cell proliferation of the freshwater species of fish, Lepomis macrochirus (bluegill).
/SRP:/ Immediate first aid: Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand-valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR as necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Aromatic hydrocarbons and related compounds/
/SRP:/ Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Monitor for shock and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 mL/kg up to 200 mL of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool. Administer activated charcoal ... . /Aromatic hydrocarbons and related compounds/
/SRP:/ Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious, has severe pulmonary edema, or is in severe respiratory distress. Consider drug therapy for pulmonary edema ... . Positive-pressure ventilation techniques with a bag valve mask device may be beneficial. Consider drug therapy for pulmonary edema ... . Consider administering a beta agonist such as albuterol for severe bronchospasm ... . Monitor cardiac rhythm and treat arrhythmias if necessary ... Start IV administration of D5W /SRP: "To keep open", minimal flow rate/. Use 0.9% saline (NS) or lactated Ringer's (LR) if signs of hypovolemia are present. For hypotension with signs of hypovolemia, administer fluid cautiously. Watch for signs of fluid overload ... .Treat seizures with diazepam or lorazepam ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Aromatic hydrocarbons and related compounds/
来源:Hazardous Substances Data Bank (HSDB)
毒理性
非人类毒性摘录
遗传毒性... 9,10-二甲基蒽在测试条件下进行的隐性致死分析中并未显示出致突变性。
/GENOTOXICITY/ ... DA (9,10-dimethylanthracene) was not mutagenic in the recessive lethal assay under the conditions of the test.
Dynamics of Proton Transfer from Radical Cations. Addition−Elimination or Direct Proton Transfer?
作者：Vernon D. Parker、You Tein Chao、Gang Zheng
DOI：10.1021/ja973031b
日期：1997.11.1
addition−elimination mechanism for the proton transfer reaction between 9-methylanthracene radicalcation and 2,6-lutidine in acetonitrile−Bu4NPF6 (0.1 M) and in dichloromethane−Bu4NPF6 (0.2 M). Isotopic substitution of D for H at the 10-position results in inverse deuterium kinetic isotope effects (kH/kD) equal to 0.83 due to nucleophilic attack on the radicalcation by 2,6-lutidine. Primary kH/kD of 3.5−5.9 were
Host–Guest-Induced Electron Transfer Triggers Radical-Cation Catalysis
作者：Rebecca L. Spicer、Athanasios D. Stergiou、Tom A. Young、Fernanda Duarte、Mark D. Symes、Paul J. Lusby
DOI：10.1021/jacs.9b11273
日期：2020.2.5
principle of capsule catalysis. Here we show an alternative strategy, wherein catalytic activation of otherwise inactive quinone "co-factors" by a simple Pd2L4 capsule pro-motes a range of bulk-phase, radical-cation cycloadditions. Solution electron transfer experiments and cyclic voltammetry show the cage anodically shifts the redox potential of the encapsulated quinone by a significant 1 V. Moreover, the
1,2-Dibutoxyethane-Promoted Oxidative Cleavage of Olefins into Carboxylic Acids Using O<sub>2</sub> Under Clean Conditions
作者：Jinhua Ou、Hong Tan、Saiyu He、Wei Wang、Bonian Hu、Gang Yu、Kaijian Liu
DOI：10.1021/acs.joc.1c01701
日期：2021.11.5
the oxidative cleavage of olefins to carboxylic acids using a 1,2-dibutoxyethane/O2 system under clean conditions. This novel oxidation system also has excellent functional-group tolerance and is applicable for large-scale synthesis. The target products were prepared in good to excellent yields by a one-pot sequential transformation without an external initiator, catalyst, and additive.
catalyst-free decarboxylative amidation of α-ketoacids with aminesundermildconditions has been developed. Advantages of the new protocol include avoidance of metal catalysts and high levels of functional group tolerance. In addition, the reaction can be scaled up and shows high chemoselectivity. Preliminary mechanistic studies suggest that singlet oxygen, generated from oxygen under irradiation, is the key
Application of Non-Steady-State Kinetics to Resolve the Kinetics of Proton-Transfer Reactions between Methylarene Radical Cations and Pyridine Bases
作者：Vernon D. Parker、Yixing Zhao、Yun Lu、Gang Zheng
DOI：10.1021/ja982682k
日期：1998.12.1
base reactions in dichloromethane (0.2 M tetrabutylammonium hexafluorophosphate) were observed to increase toward a constant value with increasing extent of reaction. The reactions were studied by derivative cyclic voltammetry (DCV), and rate constants were assigned by comparing the experimental with the theoretical DCV data. The kinetic results rule out a simple second-order proton-transfer reaction
观察到在二氯甲烷（0.2 M 四丁基六氟磷酸铵）中的四种不同甲基芳烃自由基阳离子-吡啶碱反应的表观氘动力学同位素效应（KIEapp）随着反应程度的增加而向恒定值增加。通过导数循环伏安法 (DCV) 研究反应，并通过将实验与理论 DCV 数据进行比较来指定速率常数。动力学结果排除了简单的二级质子转移反应，并暗示了一种机制，其中首先形成复合物，然后进行质子转移，然后分离产物。在达到稳态之前观察到 KIEapp 是反应依赖程度。
