- Regioselective Activation of a Sterically More Hindered C?C Bond of Biphenylenes Using an Alkene as Both a Directing Group and a Reaction Moiety
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The Rh-catalyzed intramolecular reaction of 1-(2-vinylaryl)-substituted biphenylenes was used to construct a dihydrobenzo[b]fluoranthene skeleton. This transformation was achieved by regioselective C?C bond cleavage of a sterically more hindered biphenylene site by using alkene as both a directing group and a reaction moiety. Furthermore, we measured and analyzed the photophysical properties of the new multicyclic fused compounds.
- Takano, Hideaki,Ito, Takeharu,Kanyiva, Kyalo Stephen,Shibata, Takanori
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Read Online
- benzo(b)fluoranthene compounds and organic light emitting diode comprising the same
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The present invention relates to a benzo(b)fluoranthene-based compound, capable of improving the driving voltage and efficiency, and to an organic light emitting device including the same. The benzo(b)fluoranthene-based compound is represented by chemical formula 1.COPYRIGHT KIPO 2019
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Paragraph 0091; 0098-0101
(2019/07/24)
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- Extended Study of Visible-Light-Induced Photocatalytic [4 + 2] Benzannulation: Synthesis of Polycyclic (Hetero)Aromatics
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Herein we report an extended study of [4 + 2] benzannulation reactions of 2-(hetero)aryl-substituted anilines with alkynes by visible light photocatalysis. The method requires the use of tBuONO as a diazotizing agent and 0.3 mol % of fac-Ir(ppy)3 as a photocatalyst at room temperature. The reaction proceeded in a chemo- and regioselective manner with high functional group tolerance under mild conditions allowing the preparation of a wide variety of polycyclic (hetero)aromatic compounds, including phenanthrenes, in moderate to high yields. This procedure is amenable to gram-scale synthesis of 9-phenylphenanthrene.
- Chatterjee, Tanmay,Lee, Da Seul,Cho, Eun Jin
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p. 4369 - 4378
(2017/04/28)
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- Synthesis of cyclopenta-fused polycyclic aromatic hydrocarbons utilizing aryl-substituted anilines
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Cyclopenta-fused polycyclic aromatic hydrocarbons (CP-PAHs), potentially electronically and biologically highly active materials, were synthesized from readily available 2-aryl-substituted anilines. Reactions occur under extremely mild, room temperature conditions using tBuONO as the sole reagent. The use of a nitrite source generates a reactive diazonium intermediate in situ that then reacts with a tethered polycyclic aromatic moiety by intramolecular aromatic substitution. This protocol could be presented as one of the simplest methods to access CP-PAHs.
- Choi, Yeojin,Chatterjee, Tanmay,Kim, Jun,Kim, Jun Soo,Cho, Eun Jin
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p. 6804 - 6810
(2016/07/23)
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- Tandem [4 + 2]/[2 + 2] cycloaddition reactions involving indene or benzofurans and arynes
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The reaction of arynes with indene/benzofurans has been developed. The arynes were generated from 2-(trimethylsilyl)aryl triflates by the fluoride-induced 1,2-elimination react with indene or various benzofurans proceeding via a cascade reaction involving
- Bhojgude, Sachin Suresh,Thangaraj, Manikandan,Suresh, Eringathodi,Biju, Akkattu T.
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supporting information
p. 3576 - 3579
(2014/07/21)
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- Gold-catalyzed cyclizations of cis-enediynes: Insights into the nature of gold-aryne interactions
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Golden aryne? Gold aryne complexes are inferred as transition states in dual gold-catalyzed cyclizations of cis-enediynes (see scheme; DCE=1,2-dichloroethane). They are better described as ortho-aurophenyl cations, which react with weak nucleophiles and undergo facile intramolecular insertions into C(sp3)-H bonds. Indanes, fused heteroarenes, and phenol derivatives are readily prepared using this method. Copyright
- Wang, Youliang,Yepremyan, Akop,Ghorai, Subir,Todd, Robert,Aue, Donald H.,Zhang, Liming
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p. 7795 - 7799
(2013/08/23)
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- Bidentate phosphines as ligands in the palladium-catalyzed intramolecular arylation: the intermolecular base-assisted proton abstraction mechanism
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The palladium-catalyzed arylation of aryl bromides can be carried out in the presence of bidentate phosphines, such as dppm, dppe, dppf, and Xantphos under mild conditions. The experimental results and the DFT calculations fully support for this reaction
- Pascual, Sergio,de Mendoza, Paula,Braga, Ataualpa A.C.,Maseras, Feliu,Echavarren, Antonio M.
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p. 6021 - 6029
(2008/12/20)
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- Role of temperature and hydrochloric acid on the formation of chlorinated hydrocarbons and polycyclic aromatic hydrocarbons during combustion of paraffin powder, polymers, and newspaper
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Formation of chlorinated hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) were determined using a laboratory-scale incinerator when combusting materials at different temperatures, different concentrations of hydrochloric acid (HCl), and when combusting various types of polymers/newspaper. Polychlorobenzenes (PCBz), polychlorophenols (PCPhs), polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and their toxic equivalency (TEQ) and PAHs were highlighted and reported. Our results imply maximum formation of chlorinated hydrocarbons at 400°C in the following order; PCBz≥PCPhs?PCDFs>PCDDs>TEQ on a parts-per-billion level. Similarly, a maximum concentration of chlorinated hydrocarbons was noticed with an HCl concentration at 1000 ppm with the presence of paraffin powder in the following order; PAHs>PCBz≥PCPhs?PCDFs>PCDDs>TEQ an a parts-per-billion level. PAHs were not measured at different temperatures. Elevated PAHs were noticed with different HCl concentrations and paraffin powder combustion (range: 27-32 μg/g). While, different polymers and newspaper combusted, nylon and acrylonitrile butadiene styrene (ABS) produced the maximum hydrogen cyanide (HCN) concentration, concentrations of PCDD/FS, dioxin-like polychlorinated biphenyls (DL-PCBs), and TEQ were in a decreasing order: polyvinylchloride (PVC)newspaperpolyethyleneterephthalate (PET) polyethylene (PE) polypropylene (PP) ABS = blank. Precursors of PCBs were in a decreasing order: PPnylonPEnewspaperABSPVCblankPET. Precursors of PCDD/Fs were in a decreasing order: newspaper PP= nylonPEABSPVC= blankPET. BTX formation was in a decreasing order; PEnylonnewspaperABSPP. PAHs formation were elevated with parts-per-million levels in the decreasing order of PPnylonPE newspaperblankABS PETPVC.
- Takasuga, Takumi,Umetsu, Norihito,Makino, Tetsuya,Tsubota, Katsuya,Sajwan, Kenneth S.,Kumar, Kurunthachalam Senthil
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- Emission factors and importance of PCDD/Fs, PCBs, PCNs, PAHs and PM 10 from the domestic burning of coal and wood in the U.K.
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This paper presents emission factors (EFs) derived for a range of persistent organic pollutants (POPs) when coal and wood were subject to controlled burning experiments, designed to simulate domestic burning for space heating. A wide range of POPs were emitted, with emissions from coal being higher than those from wood. Highest EFs were obtained for particulate matter, PM10, (～ 10 g/kg fuel) and polycyclic aromatic hydrocarbons (～ 100 mg/ kg fuel for ΣPAHs). For chlorinated compounds, EFs were highest for polychlorinated biphenyls (PCBs), with polychlorinated naphthalenes (PCNs), dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) being less abundant. EFs were on the order of 1000 ng/kg fuel for ΣPCBs, 100s ng/ kg fuel for ΣPCNs and 100 ng/kg fuel for ΣPCDD/Fs. The study confirmed that mono- to trichlorinated dibenzofurans, Cl1,2,3DFs, were strong indicators of low temperature combustion processes, such as the domestic burning of coal and wood. It is concluded that numerous PCB and PCN congeners are routinely formed during the combustion of solid fuels. However, their combined emissions from the domestic burning of coal and wood would contribute only a few percent to annual U.K. emission estimates. Emissions of PAHs and PM 10 were major contributors to U.K. national emission inventories. Major emissions were found from the domestic burning for Cl1,2,3DFs, while the contribution of PCDD/F-ΣTEQ to total U.K. emissions was minor.
- Lee, Robert G. M.,Coleman, Peter,Jones, Joanne L.,Jones, Kevin C.,Lohmann, Rainer
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p. 1436 - 1447
(2007/10/03)
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- Experimental study on the removal of PAHs using in-duct activated carbon injection
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This paper presents the incineration tests of municipal solid waste (MSW) in a fluidized bed and the adsorption of activated carbon (AC) on polycyclic aromatic hydrocarbons (PAHs). An extraction and high performance liquid chromatography (HPLC) technique was used to analyze the concentrations of the 16 US EPA specified PAHs contained in raw MSW, flue gas, fly ash, and bottom ash. The aim of this work was to decide the influence of AC on the distribution of PAHs during the incineration of MSW. Experimental researches show that there were a few PAHs in MSW and bottom ash. With the increase of AC feeding rate, the concentrations of three- to six-ring PAHs in fly ash increased, and the concentration of two-ring PAH decreased. The total-PAHs in flue gas were dominated by three-, and four-ring PAHs, but a few two-, five-ring PAHs and no six-ring PAHs were found. PAHs could be removed effectively from flue gas by using in-duct AC injection and the removal efficiencies of PAHs were about 76-91%. In addition, the total toxic equivalent (TEQ) concentrations of PAH in raw MSW, bottom ash, fly ash, and flue gas were 1.24 mg TEQ kg-1, 0.25 mg TEQ kg-1, 6.89-9.67 mg TEQ kg-1, and 0.36-1.50 μg TEQ N m-3, respectively.
- Zhou, Hong-Cang,Zhong, Zhao-Ping,Jin, Bao-Sheng,Huang, Ya-Ji,Xiao, Rui
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p. 861 - 869
(2007/10/03)
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- Relationship between pressure fluctuations and generation of organic pollutants with different particle size distributions in a fluidized bed incinerator
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The hydrodynamic behaviors of fluidization perhaps significantly influence the uniformity of fluidization in fluidized bed incinerator. Good uniformity of fluidization expressed the air across uniformly through the bed and the particles being distributed well in the fluid stream. The aggregates, flocs and channels of particles do not happen during fluidization. The Good uniformity will maintain high heat and mass distribution to improve reaction efficiency. These parameters include the height of static bed, gas velocity, mixing and distribution of bed particle, which have rarely been studied in previous investigations. Consequently, this study examines how the hydrodynamic parameters affect the generation of organic pollutants (BTEXs and PAHs) during incineration. The statistical and power spectral analysis of the measured pressure fluctuation during incineration are used to elucidate the relationship between behaviors of fluidization and generation of pollutants during incineration. Experimental results show the organic concentration does not increase with uniformity of fluidization decreasing. The reason may be the explosion of the gas and the consequent thermal shock destroy the coalescent bubbles to form small bubbles again and enhance the efficiency of transfer of oxygen to increase combustion efficiency. Additionally, the mean amplitude and fluidized index of pressure fluctuation similarly vary with the concentration of organic pollutants. These two indices can be used to assess the efficiency of combustion. The four particle size distributions could be divided into two groups by statistical analysis. The Gaussian and narrow distributions belong to one group and the binary and flat the other. The organic concentration of the Gaussian and narrow distributions are lower than that of the other distributions. Consequently, the bed materials should maintain narrow or Gaussian distributions to maintain a good combustion efficiency during incineration.
- Lin, Chiou-Liang,Wey, Ming-Yen,Cheng, Han-Tsung
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p. 911 - 922
(2007/10/03)
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- Semivolatile and volatile compounds in combustion of polyethylene
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The evolution of semivolatile and volatile compounds in the combustion of polyethylene (PE) was studied at different operating conditions in a horizontal quartz reactor. Four combustion runs at 500 and 850°C with two different sample mass/air flow ratios and two pyrolytic runs at the same temperatures were carried out. Thermal behavior of different compounds was analyzed and the data obtained were compared with those of literature. It was observed that α,ω-olefins, α-olefins and n-paraffins were formed from the pyrolytic decomposition at low temperatures. On the other hand, oxygenated compounds such as aldehydes were also formed in the presence of oxygen. High yields were obtained of carbon oxides and light hydrocarbons, too. At high temperatures, the formation of polycyclic aromatic hydrocarbons (PAHs) took place. These compounds are harmful and their presence in the combustion processes is related with the evolution of pyrolytic puffs inside the combustion chamber with a poor mixture of semivolatile compounds evolved with oxygen. Altogether, the yields of more than 200 compounds were determined. The collection of the semivolatile compounds was carried out with XAD-2 adsorbent and were analyzed by GC-MS, whereas volatile compounds and gases were collected in a Tedlar bag and analyzed by GC with thermal conductivity and flame ionization detectors.
- Font, Rafael,Aracil, Ignacio,Fullana, Andrés,Conesa, Juan A.
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p. 615 - 627
(2007/10/03)
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- Synthesis of fused polycycles by 1,4-palladium migration chemistry
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Novel palladium migration/arylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement with the idea that these palladium-catalyzed C-H activation reactions parallel electrophilic aromatic substitution.
- Huang, Qinhua,Campo, Marino A.,Yao, Tuanli,Tian, Qingping,Larock, Richard C.
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p. 8251 - 8257
(2007/10/03)
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- 1,4-Palladium migration via C-H activation, followed by arylation: Synthesis of fused polycycles
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A novel palladium migration/arylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement with the idea that these palladium-catalyzed C-H activation reactions parallel electrophilic aromatic substitution. Copyright
- Campo, Marino A.,Huang, Qinhua,Yao, Tuanli,Tian, Qingping,Larock, Richard C.
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p. 11506 - 11507
(2007/10/03)
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- A new Suzuki-Heck-type coupling cascade: Indeno[1,2,3]-annelation of polycyclic aromatic hydrocarbons
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Under palladium catalysis, o-bromobenzeneboronic acid can be coupled with 1-bromonaphthalene (6) and with oligocyclic bromoarenes to furnish indeno-annelated polycyclic aromatic hydrocarbons 1-4 and 25 in a single operation in moderate to good yields (27-87%). Alternatively, o-dibromoarenes and 1,2-dibromocycloalkenes can be cross-coupled with 1-naphthaleneboronic acid under the same conditions to yield analogous products (6-87%), and indenocorannulene (19) can be prepared likewise in a single step from pinacol corannuleneboronate (18) (40%).
- Wegner, Hermann A.,Scott, Lawrence T.,De Meijere, Armin
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p. 883 - 887
(2007/10/03)
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- Transient puffs of trace organic emissions from a batch-fed waste propellant incinerator
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Emissions data have been obtained from a waste propellant incinerator. The incinerator is a dual fixed hearth, controlled air incinerator equipped with acid gas and particulate scrubbing. Puffing has been evident in this waste propellant incinerator by spikes in the CO concentration. Transient puffs of organics may travel down the combustion chambers and lead to stack emissions. The major conclusions from this study are that (1) transient puffs are formed due to the semi-batch feed nature of the combustion process (causing a local oxygen deficiency) and high water content of the desensitized propellant; (2) in batch-fed combustors, puffs can contribute to most of the organic emissions (which are relatively low) measured with US EPA sampling and analytical methods; (3) it is estimated that batch-fed combustion contributes up to 7-18 times more emissions than steady-state combustion will generate; (4) by applying dispersion analyses to determine the amount of oxygen deficiency in the flame zone, the combustion zone concentration of CO during batch-fed operation could be as high as 160,000 ppm, compared to a measured peak stack concentration of 1200 ppm CO; and (5) an organic sample is collected and averaged over at least a 2-h period that smooths out the transient peaks of organics emissions during batch-fed operation. For emissions that are associated with long-term potential health impacts, this is an appropriate sampling method. However, if a compound has a short-term potential health impact, it may be important to measure the time-resolved emissions of the compound.
- Hart, John R.
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p. 559 - 569
(2007/10/03)
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- Removal of dioxins and related aromatic hydrocarbons from flue gas streams by adsorption and catalytic destruction
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The dioxin removing capacity of the shell dedioxin system (SDDS a - Ti/V oxidative type catalyst) has been tested using the Umefa lab-scale incinerator over the temperature range 100 -230°C and at space velocities of 8000 and 40,000 h-1. Other analogous organic compounds, such as PCBs, PAHs, chlorobenzenes and chlorophenols have also been investigated. Results show a high degree of dioxin removal already at 100°C (82%), which occurs mainly by adsorption. When the temperature is raised a transition towards destruction is seen and at 150°C, gas hour space velocity (GHSV) 8000 and at 230°C, GHSV 40,000 virtually all removal is by destruction. High PCDD/F destruction efficiencies are reported (> 99.9%, based on I-TEQ); the other dioxin-related species and PAHs are also removed and destroyed to a significant extent. The SDDS has proved to be an effective means of destroying organic compounds in the gas phase, particularly dioxins, at temperatures as low as 150°C.
- Liljelind, Per,Unsworth, John,Maaskant, Onno,Marklund, Stellan
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p. 615 - 623
(2007/10/03)
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- Characterization of emissions during the heating of tyre contaminated scrap
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In order to characterize the compounds (type and quantities) emitted during melting of organic contaminated scrap and to investigate the mechanism of their formation, an experimental set-up has been designed and built to study precisely the influence of temperature and gas atmosphere in the conditions of an electric arc furnace. These experiments lead to the determination of mass balances (C, H, O, S) and to the quantification of unburnt compounds (tars, carbon monoxide, volatile organic compounds (VOCs), benzene, toluene, ethylbenzene and xylenes (BTEX), polyaromatic compounds (PAHs)). Degradation conditions (gas atmosphere and temperature) corresponding to different areas in the electric furnace have also been investigated. Such experiments lead to a better understanding of degradation mechanisms; this interpretation is not possible from investigations performed in an industrial furnace since there are many uncontrolled parameters (large dispersion of the results).
- Arion,Baronnet,Lartiges,Birat
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p. 853 - 859
(2007/10/03)
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- Evaluation of acute toxicity and genotoxicity of liquid products from pyrolysis of Eucalyptus grandis wood
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Slow pyrolysis of Eucalyptus grandis wood was performed in an oven laboratory, and smoke was trapped and condensed to yield liquid products. Polycyclic aromatic hydrocarbons (PAHs) and phenolic fractions were isolated from the former liquid products using adsorption column chromatography (ACC) and identified by GC/MS. Concentrations of PAH and phenolic fractions in total pyrolysis liquids were respectively 48.9 μg/g and 8.59% (w/w). Acute toxicity of total samples of pyrolysis liquids and the phenolic fraction was evaluated by means of two bioassays, namely, 24-h immobilization bioassay with Daphnia magna and Microtox(TM) bioassays, the latter employing the luminescent bacteria Photobacterium phosphoreum. Total pyrolysis liquids and the PAH fraction were evaluated for genotoxicity by the Microtox(TM) bioassay conducted using rehydrated freeze-dried dark mutant of the luminescent bacteria Vibrio fisheri strain M169. Total pyrolysis liquids and the phenolic fraction, respectively, in concentrations of 170 and 68 mg/L were able to immobilize 50% (EC50) of the D. magna population following 24-h exposure. Concentrations of 19 and 6 mg/L, respectively, for total pyrolysis liquids and phenolic fraction were the effective concentrations that resulted in a 50% (EC50) reduction in light produced by bacteria in the Microtox(TM) bioassay. Accordingly, the Microtox(TM) bioassay was more sensitive to toxic effects of both kind of samples than the D. magna bioassay, particularly for the phenolic fraction. Regarding to the genotoxicity evaluation, the results achieved by Microtox(TM) bioassay showed that total pyrolysis liquids had no genotoxic effects with and without exogenous metabolic activation using rat liver homogenate (S9). However, the PAH fraction showed toxic effects with rat liver activation and had a dose-response number (DRN) equal to 1.6, being in this way suspected genotoxic. The lowest detected concentration (LDC) of the PAH fraction able to cause genotoxic effects was 375 μg/L.
- Pimenta,Bayona,Garcia,Solanas
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p. 169 - 175
(2007/10/03)
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- The effect of oils on PAH, PCDD, PCDF, and PCB emissions from a spark engine fueled with leaded gasoline
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The effect of synthetic and mineral oils on the formation of polyaromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) in emissions from a spark ignition engine was studied on a Skoda Favorit engine fueled with leaded gasoline. The test cycle simulated urban traffic conditions on a chassis dynamometer, in accordance with the ECC 83.00 test. The data for selected PAHs as well as PCDDs, PCDFs, and PCBs congener profiles are presented. PCDD/Fs emissions for an unused oil and the oil after 10 000-km operation varied from 300 to 2000 fmol/m3, PCBs emissions from 75 to 178 pmol/m3, and PAHs emissions from 150 to 420 μg/m3. The content of PCBs in oils varied from 2 to 920 mg/kg.
- Broz, Jan,Grabic, Roman,Kilian, Juraj,Lojkasek, Milan,Marklund, Stellan,Ocelka, Tomas,Pekarek, Vladimir,Pribyl, Josef,Tydlitat, Vratislav,Vyska, Jan
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p. 1905 - 1911
(2007/10/03)
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- Influence of combustion conditions on the PCDD/F-, PCB-, PCBz- and PAH- concentrations in the post-combustion chamber of a waste incineration pilot plant
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Experiments at a pilot scale waste incinerator (0.5 MW thermal power) showed that the conditions in the postcombustion chamber (650-900°C) are strongly influencing the formation of chlorinated and non-chlorinated aromatics. Non-optimal combustion conditions resulted in increased concentrations of mono- to trichlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and polycyclic aromatic hydrocarbons (PAH), while chlorinated benzenes (PCBz), polychlorinated biphenyls (PCB) and the higher chlorinated PCDD/F are only weakly affected or even decrease. The changes in concentration of the compounds investigated over a time span of hours gave hints on 'memory effects' in this combustion zone. For mono- and dichlorinated benzenes, a high correlation (r2 = 0.80) with the international toxicity equivalent (I-TEQ) value of PCDD/F was observed. As recently has been demonstrated, this correlation can be utilized for an indirect on-line measurement of the I-TEQ by a novel laser mass spectrometric technique (REMPI-TOFMS). (C) 2000 Elsevier Science Ltd.
- Blumenstock,Zimmermann,Schramm,Kettrup
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p. 987 - 993
(2007/10/03)
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- Characterization of the combustion products of polyethylene
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Polyethylene (PE) was burned in a tube-type furnace with an air flow at a temperature of 600~900°C. Combustion products were collected with glass wool, glass fiber filter, and XAD-2 adsorbent. The analysis of the products was performed with GC-FID and GC-MSD. At low temperature, hydrocarbons were the major components, while at higher temperature the products were composed of polycyclic aromatic hydrocarbons. With the high performance of the Hewlett-Packard 6890GC-5973MSD, more compounds were identified in comparison with previous studies.
- Piao, Mingjun,Chu, Shaogang,Zheng, Minghui,Xu, Xiaobai
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p. 1497 - 1512
(2007/10/03)
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- Effects of an oxidation catalytic converter and a biodiesel fuel on the chemical, mutagenic, and particle size characteristics of emissions from a diesel engine
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This study was conducted to obtain additional information on exhaust emissions with potential health importance from an indirect injection diesel engine, typical of those in use in underground mines, when operated using a soy-derived, fatty-acid mono-ester (or biodiesel) fuel and an oxidation catalytic converter (OCC). Compared to emissions with the diesel fuel without the OCC, use of the diesel (D2) and biodiesel fuel with the OCC had similar reductions (50-80%) in total particulate matter (TPM). The solid portion of the TPM was lowered with the biodiesel fuel. Particle-associated polynuclear aromatic hydrocarbon and 1-nitropyrene emissions were lower with use of the biodiesel fuel as compared to the D2 fuel, with or without the OCC. Vapor- phase PAH emissions were reduced (up to 90%) when the OCC was used with either fuel. Use of the OCC resulted in over 50% reductions in both particle and vapor-phase-associated mutagenic activity with both fuels. No vapor- phase-associated mutagenic activity was detected with the biodiesel fuel; only very low levels were detected with the D2 fuel and the OCC. Use of the OCC caused a moderate shift in the particle size/volume distribution of the accumulation mode particles to smaller particles for the diesel fuel and a reduction of particle volume concentrations at some of the tested conditions for both fuels. The nuclei mode did not contribute significantly to total particle volume concentrations within the measured particle size range (~0.01-1.0 μm). The biodiesel fuel reduced total particle volume concentrations. Overall, use of this OCC for the engine conditions tested with the biodiesel fuel, in particular, resulted in generally similar or greater reductions in emissions than for use of the D2 fuel. Use of the biodiesel fuel should not increase any of the potentially toxic, health- related emissions that were monitored as part of this study. Detailed information necessary to evaluate impact of using a biodiesel fuel on potentially health-related emissions from a diesel engine typical of those used in many underground mining operations are provided. Compared to emissions with the diesel fuel without the oxidation catalytic converter (OCC), use of the diesel (D2) and biodiesel fuel with the OCC had a similar reductions in total particulate matter (TPM). The solid portion of the TPM was lowered with the biodiesel fuel. Particle-associated polynuclear aromatic hydrocarbon and 1-nitropyrene emissions were lower with use of the biodiesel fuel as compared to the D2 fuel, with or without the OCC.
- Bagley, Susan T.,Gratz, Linda D.,Johnson, John H.,McDonald, Joseph F.
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p. 1183 - 1191
(2007/10/03)
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- The impact of turbulent mixing on the oxidation of a chlorinated hydrocarbon
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Combustion of chlorinated wastes can lead to the formation of hazardous byproducts. Rates of mixing of fuel and air in combustion systems can have an impact on the composition of the byproducts. Methyl chloride and methane were burned in a turbulent diffusion flame in a combustion wind tunnel with a coflow of air. Reynolds numbers were varied from 3500 to 7200. A water- cooled sampling probe was used to obtain gas samples from within the flame at a number of locations and at various Reynolds numbers. The postflame gases and particulate matter were trapped above the flames with sorbent tubes and filters. The samples were desorbed and analyzed for aromatic species and other trace products of incomplete combustion. Destruction of the methyl chloride was essentially complete for all the Reynolds numbers that were studied. Small amounts of low molecular weight chlorinated compounds were fOUnd within the flame and in the postflame gases. The major chlorinated species in the postflame gases was chloronaphthalene. Low Reynolds number flames were found to Yield larger amounts of aromatic and chlorinated aromatic species than the high Reynolds number flames. Fluoranthene was present in greater amounts on the soot particles at lower Reynolds numbers, suggesting that the rate of mixing of reactants could have an impact on the toxicity of the combustion byproducts. Combustion of chlorinated wastes can lead to the formation of hazardous byproducts. Rates of mixing of fuel and air in combustion systems can have an impact on the composition of the byproducts. Methyl chloride and methane were burned in a turbulent diffusion flame in a combustion wind tunnel with a coflow of air. Reynolds numbers were varied from 3500 to 7200. A water-cooled sampling probe was used to obtain gas samples from within the flame at a number of locations and at various Reynolds numbers. The postflame gases and particulate matter were trapped above the flames with sorbent tubes and filters. The samples were desorbed and analyzed for aromatic species and other trace products of incomplete combustion. Destruction of the methyl chloride was essentially complete for all the Reynolds numbers that were studied. Small amounts of low molecular weight chlorinated compounds were found within the flame and in the postflame gases. The major chlorinated species in the postflame gases was chloronaphthalene. Low Reynolds number flames were found to yield larger amounts of aromatic and chlorinated aromatic species than the high Reynolds number flames. Fluoranthene was present in greater amounts on the soot particles at lower Reynolds numbers, suggesting that the rate of mixing of reactants could have an impact on the toxicity of the combustion byproducts.
- Yang, Gosu,Jones, A. Daniel,Kennedy, Ian M.
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p. 1265 - 1268
(2007/10/03)
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- Synthesis of Spiro Polycyclic Aromatic Hydrocarbons by Intramolecular Palladium-Catalyzed Arylation
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The palladium-catalyzed intramolecular arylation reaction has been applied to the synthesis of the spiro polycyclic aromatic hydrocarbons and planar polycyclic aromatic hydrocarbons by formation of a six-membered ring. The reaction proceeds more readily with aryl bromides substituted with electron-withdrawing groups by using palladium acetate in N,N-dimethylformamide as the solvent. For the less reactive p-methoxyaryl derivatives the use of LiI as an additive was shown to give the best results. The results obtained in the cyclization of nitro derivatives 21 and 23 suggest that the second step of the cyclization reaction is not an electrophilic substitution reaction.
- Gonzalez, Juan J.,Garcia, Nuria,Gomez-Lor, Berta,Echavarren, Antonio M.
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p. 1286 - 1291
(2007/10/03)
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- A novel and practical synthesis of polycyclic fluoranthenes
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A novel and general preparation of polycyclic fluoranthenes is described. The synthesis involves a Michael addition of silyl enol ethers to dibenzofulvene followed by cyclization and aromatization.
- Cho, Bongsup P.
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p. 2403 - 2406
(2007/10/02)
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- An Intramolecular Arene-Triflate Coupling Reaction for the Regiospecific Synthesis of Substituted Benzofluoranthenes
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An intramolecular triflate-arene coupling reaction mediated by bis(triphenylphosphine)palladium(II) chloride has been developed for the synthesis of each of the isomeric benzofluoranthenes.This reaction, which results in formation of a new five-membered ring, proceeds in highest yields when performed using 0.1 equiv of the palladium catalyst, 3 eqiv of lithium chloride, and 1.2 eqiv of 1,8-diazabicycloundec-7-ene in N,N-dimethylformamide at 140 deg C.The biaryl precursors needed for the coupling reaction can be prepared by nickel(II) chloride catalyzed coupling of an aryl bromide with an magnesium bromide (prepared by ortho-lithiation of an aryl methoxymethyl ether followed by transmetalation with magnesium bromide).Using this procedure benzofluoranthene, benzofluoranthene, benzofluoranthene, and benzofluoranthene were prepared in yields of 84percent, 85percent, 93percent and 64percent, respectively.The reaction to prepare benzofluoranthene was regiospecific and afforded none of the six-membered ring product, perylene.This method was extended to the preparation of benzofluoranthene (BbF) derivatives with fluoro or methoxy groups on the benzo ring.The cyclization of compounds posessing a methoxy group on the same ring as the triflate required the addition of 0.4 equiv of triphenylphosphine to the reaction mixture.Strategies are reported for the regiospecific preparation of 4-, 5-, 6-, and 7-substituted benzofluoranthenes.Evidence is presented wich suggests the intermediacy of radicals in the oxidative-addition of aryl triflates to the palladium catalyst.
- Rice, Joseph E.,Cai, Zhen-Wei
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p. 1415 - 1424
(2007/10/02)
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- A Palladium-Catalyzed Intramolecular Arene-Triflate Coupling for the Synthesis of Fluoranthrenes and Benzofluoranthrenes
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A method for the preparation of fluoranthrenes and benzofluoranthrenes from aryl bromides and aryl methoxymethyl ethers is described.The key step in this synthesis is an intramolecular triflate-arene coupling mediated by bis(triphenylphosphine)palladium(II)chloride.Fluoranthrene, benzofluoranthrene, benzofluoranthrene, and indenopyrene were prepared in yields of 84-91percent.The regiospecific synthesis of substituted benzofluoranthrenes was demonstrated by the preparation of 6-fluorobenzofluoranthrene (72percent yield) and 5- and 6-methoxybenzofluoranthrene in yields of 73percent and 62percent respectively when the reaction was conducted in the presence of excess triphenylphosphine.Key Words: synthesis; palladium; triflate; fluoranthrene; benzofluoranthrene
- Rice, Joseph E.,Cai, Zhen-Wei
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p. 1663 - 1678
(2007/10/02)
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- Policyclic Fluoranthene Hydrocarbons. 2. A New General Synthesis
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A novel and efficient synthetic approach to policyclic fluoranthene hydrocarbons is described.The method entails fusion of an indeno ring to an appropriate alternant hydrocarbon via reaction of its aryllithium derivative with cyclohexene oxide, followed by oxidation, cyclodehydration, and aromatization.Cyclization of the cyclohexanone and cyclohexanol derivatives of the policyclic aromatic ring systems studied proceeds with high regioselectivity, and the direction of ring closure is predictable by molecular orbital methods.This synthetic approach provides a convenient general route to polyaromatic fluoranthene compounds, including potentially carcinogenic members of this class.Hydrocarbons synthesized by this method include benzacephenanthrylene (1), indenopyrene (2), indenochrysene (3), benzindenochrysene (4), fluorenochrysene (5), dibenzaceanthrylene (6), dibenzaceanthrylene (7), benzaceanthrylene (8), benzindenochrysene (9), fluorenochrysene (10), and dibenzacephenanthrylene (11).
- Cho, Bongsup P.,Harvey, Ronald G.
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p. 5668 - 5678
(2007/10/02)
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- Syntheses of Cyclopentene-Fused Polynuclear Aromatic Hydrocarbons
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Regioselective α or β ring opening of bicyclic α-arylcyclobutanones permits the synthesis of linear and angular cyclopentene-fused polynuclear aromatic hydrocarbons (PAH), respectively.The syntheses of the cyclopentene-fused PAHs, aceanthrylene, acephenanthrylene, benzaceanthrylene, and benzacephenanthrylene are detailed utilizing this novel methodology.
- Chung, Ying-Sheng,Kruk, Henry,Barizo, Ophelia M.,Katz, Morris,Lee-Ruff, Edward
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p. 1284 - 1288
(2007/10/02)
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- SYNTHESIS OF POLYCYCLIC AROMATIC FLUORANTHENES
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A general synthetic approach to polycyclic aromatic hydrocarbons containing a fluoranthene ring system is described.The method entails fusion of an indeno ring to an alternant hydrocarbon via reaction of an aryllithium derivative with cyclohexene oxide.
- Cho, Bongsup P.,Harvey, Ronald G.
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p. 861 - 864
(2007/10/02)
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- Synthesis and Mutagenicity of Dihydrodiol Metabolites of Benzofluoranthene
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The syntheses of the two major hepatic microsomal dihydrodiol metabolites of the environmental carcinogen, benzofluoranthene, are described. 1,2-Dihydro-1,2-dihydroxybenzofluoranthene was prepared from 11H-benzofluorene-11-carboxylic acid.The key
- Amin, Shantu,Hussain, Nalband,Brielmann, Harry,Hecht, Stephen S.
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p. 1091 - 1095
(2007/10/02)
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- The Addition of Benzyne to Benzofuran. A Ready Route to Benzacephenanthrylene
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The title reaction affords the 2+2 cycloadduct cis-4b,9b-dihydrobenzocyclobutabenzofuran (13) together with the bis-adduct (4aα,8bα,9β,13bβ)-8b,9-dihydro-9,13b-epoxy-13bH-benzocyclobutaphenanthrene (14) in a ratio of c. 1 : 8.The m
- Anthony, Ian J.,Wege, Dieter
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p. 1283 - 1292
(2007/10/02)
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- Synthesis of Dihydro Diols as Potential Proximate Carcinogens of Benzofluoranthenes
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Dihydro diols which are potential proximate carcinogens of the environmental agents benzofluoranthene (1), benzofluoranthene (2), and benzofluoranthene (3) were synthesized.The dihydro diols synthesized were trans-9,10-dihydro-9,10-dihydrobenzob
- Amin, Shantilal,Bedenko, Victoria,LaVoie, Edmond,Hecht, Stephen S.,Hoffmann, Dietrich
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p. 2573 - 2578
(2007/10/02)
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