29446-15-9

We herein report a simple and clean photo-induced metal-free reduction of C-X bond under an atmosphere of air at room temperature. Isopropanol is used as both the reducing reagent and solvent. Various functional groups (acids, esters, alcohols, anilines, phenols, indoles, pyridines, cyano and trifluoromethyl groups) and other heterocyclic compounds are tolerated. Different organic halides (including C-I, C-Br and C-Cl bonds) can be dehalogenated with moderate to excellent yields. Polyhalides are also reduced chemoselectively and efficiently. DFT calculation suggests a six-membered ring transition state via C-X H-O hydrogen bonding to decrease the activation energy.

Correlations between products of incomplete combustion (PIC), e.g., chloroaromatic compounds, can be used to characterise the emissions from combustion processes, like municipal or hazardous waste incineration. A possible application of such relationships may be the on-line real-time monitoring of a characteristic surrogate, e.g., with Resonance-Enhanced Multiphoton Ionization-Time-of-Flight Mass Spectrometry (REMPI-TOFMS). In this paper, we report the relationships of homologues and individual congeners of chlorinated benzenes (PCBz), dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and phenols (PCPh) to the International Toxicity Equivalent (I-TEQ) of the PCDD/F (I-TEQ value) in the flue gas and stack gas of a 22 MW hazardous waste incinerator (HWI). As the REMPI detection sensitivity is decreasing with the increase of the degree of chlorination, this study focuses on the lower chlorinated species of the compounds mentioned above. Lower chlorinated species, e.g., chlorobenzene (MCBz), 1,4-dichlorobenzene, 2,4,6-trichlorodibenzofuran or 2,4-dichlorophenol, were identified as I-TEQ surrogates in the flue gas. In contrast to the higher chlorinated phenols, the lower chlorinated phenols (degree of chlorination 4) were not reliable as surrogates in the stack gas. The identified surrogates are evaluated in terms of their detectability by REMPI-TOFMS laser mass spectrometry. The outcome is that MCBz is the best suited surrogate for (indirect) on-line measuring of the I-TEQ value in the flue gas by REMPI-TOFMS. The correlation coefficient r of the MCBz concentration to the I-TEQ in the flue gas was 0.85.

Total homologue concentrations and select congener concentrations from amongst the mono- to tri-chlorinated dibenzodioxins (CDDs) and dibenzofurans (CDFs) are used to model both Total (mono- to octa-) CDD + CDF emissions and the toxicity equivalent (TEQ) of the 2,3,7,8-chlorine-substituted emissions. Analysis of emission data from two facilities indicates that use of total homologue concentrations shows limited, facility-specific correlations with Total CDDs/CDFs and TEQ. Concentrations of select mono- to tri-CDD/CDF congeners show promising correlation with CDD/CDF TEQ across facilities, suggesting that these compounds can act as TEQ indicators. (C) 2000 Elsevier Science Ltd.

The aim of this study was to investigate the influence of variation in combustion conditions on the primary formation of organic micropollutants (OMPs). The flue gas samples were taken at a relatively high flue gas temperature (650°C), to enable mechanistic studies on the high temperature formation (primary formation). Eleven experiments were performed in a laboratory scale fluidized bed reactor fed with an artificial municipal solid waste (MSW). The samples were analyzed for mono- to octachlorinated dibenzo- p-dioxins and dibenzofurans (CDDs/Fs), tri- to decachlorinated biphenyls (CBs), di- to hexachlorinated benzenes (CBzs), and di- to pentachlorinated phenols (CPhs). In addition to chlorinated OMPs, nonchlorinated dibenzo-p- dioxin (DD), dibenzofuran (DF), and biphenyl (BP) were analyzed. The experiments show that variations in the CE influence the degree of chlorination of the organic micropollutants. A correlation between low CE and formation of non- and low-chlorinated DMPs was seen and a distinct relationship of higher chlorinated homologues and efficient combustion condition. Thus, the DiCDFs and DiCBzs are formed during low combustion efficiency (CE), while the PeCDF and PeCBzs formation take place at higher CE. The distribution between primary and secondary air is important for the formation of higher CDD/Fs and CBzs. The primary formation of CDDs and CDFs is through different mechanisms. The CDDs are mainly formed by condensation of CPhs, while the CDFs are formed through a non- or a low-chlorinated precursor followed by further chlorination reactions.

The conversion of dibenzodioxin with CuCl2x2H2O and CuBr2 results in polyhalogenated dibenzodioxins. Besides the chlorinated compounds, bromination stages 1 to 5 are obtained at chlorination levels of 0 to 7 for monobromo-, 0 to 7 for dibromo-, 0 to 4 for tribromo-, 0 to 3 for tetrabromo-, and 0 to 1 for pentabromodibenzodioxin. The 2,3,7,8 position is halogenated preferentially.

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An improved general synthesis of substituted dibenzodioxines by reaction of catechol and substituted 1,2-dichloro- or 2-chloronitro-benzenes with metallic potassium in hexamethylphosphoramide is reported.The yields are generally superior to those in published methods, and in particular the reaction appears the one of choice for the synthesis of both the parent dibenzodioxine and the 1-carboxy derivative.