Identification of sulphur heterocycles in coal tar and pitch

Burchill, Paul; Herod, Alan A.; Pritchard, Ernest

doi:10.1016/s0021-9673(00)87247-7

Cited by 45 publications

(18 citation statements)

References 17 publications

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“…Using a very polar cyanopropyl stationary phase for GC analysis with an AED, Andersson and Schmid (1) detected naphtho [1,2-b] [2,3-b]thiophene, the two other three-ring polycyclic aromatic sulfur heterocycles with the chemical formula C 12 H 8 S, were also detected. The coelution of dibenzothiophene with naphtho [1,2-b]thiophene is consistent with earlier reports of Burchill et al (6,7) that only three chromatographic peaks of the chemical formula C 12 H 8 S were detected by GC-MS analysis of coal tar and anthracene oil for the four possible isomers that contain a thiophene ring condensed with two benzene rings. Thus, naphthothiophenes are among the condensed thiophenes present in fossil fuels and their derivatives.…”

supporting

confidence: 91%

“…In addition to benzo-and dibenzothiophenes, other polycyclic aromatic sulfur heterocycles have been identified by gas chromatography (GC) analyses of solvent-refined coal liquids, coal tars, anthracene oils, shale oils, and higher-boiling-point petroleum fractions using a sulfur-selective flame photometric detector (FPD) or an atomic emission detector (AED) and GC-mass spectrometry (GC-MS). The compounds identified include benzonaphthothiophenes, phenanthrothiophenes, dinaphthothiophenes, benzophenanthrothiophenes, and other compounds containing two to four benzene rings condensed with one or two thiophene rings (6,7,12,39,44,59).…”

mentioning

confidence: 99%

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Bacterial transformations of naphthothiophenes

Kropp¹,

Andersson²,

Fedorak³

1997

Appl Environ Microbiol

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Naphthothiophenes are minor components of fossil fuels, and they can enter the environment from oil spills. Naphtho[2,1-b]thiophene, naphtho[2,3-b]thiophene, and 1-methylnaphtho[2,1-b]thiophene were synthesized and used in biodegradation studies with 1-methylnaphthalene (1-MN)-degrading Pseudomonas strains W1, F, and BT1. Cultures were incubated with one of the naphthothiophenes with or without 1-MN, acidified, and extracted with CH 2 Cl 2. The extracts were analyzed by gas chromatography with flame photometric and mass detectors to characterize sulfur-containing metabolites and with an atomic emission detector for quantification. Only strain W1 was able to grow on naphtho[2,1-b]thiophene, but strains F and BT1 cometabolized this compound if 1-MN was present. 1-MN was required by all three strains to metabolize naphtho[2,3-b]thiophene, which was more resistant to biodegradation than the [2,1-b] isomer. Two metabolites of naphtho [2,1-b]thiophene were purified, analyzed by 1 H nuclear magnetic resonance spectroscopy, and found to be 4-hydroxybenzothiophene-5-carboxylic acid (metabolite I) and 5-hydroxybenzothiophene-4-carboxylic acid (metabolite II). In cultures of strain W1 grown for 7 days on 52 mol of naphtho[2,1-b]thiophene, >84% of the substrate was degraded and metabolites I and II accounted for 19 and 9%, respectively, of the original amount of naphtho[2,1-b]thiophene. When 1-MN was present, strain W1 degraded >97% of the naphtho[2,1-b]thiophene and similar amounts of metabolite II were produced, but metabolite I did not accumulate. 1-MN was shown to promote the further degradation of metabolite I, but not of metabolite II, by strain W1. Thus, 1-MN enhanced the biodegradation of naphtho[2,1-b]thiophene. Approximately 70% of the 1-methylnaphtho [2,1-b]thiophene added to cultures of strain W1 with 1-MN was recovered as 4-hydroxy-3-methylbenzothiophene-5-carboxylic acid, the 3-methyl analog of metabolite I. The methyl substitution hindered further metabolism of 3-methyl-metabolite I even in the presence of 1-MN. Cometabolism of naphtho[2,3-b]thiophene yielded two products that were tentatively identified as 5-hydroxybenzothiophene-6-carboxylic and 6-hydroxybenzothiophene-5-carboxylic acids.

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supporting

confidence: 91%

mentioning

confidence: 99%

Bacterial transformations of naphthothiophenes

Kropp¹,

Andersson²,

Fedorak³

1997

Appl Environ Microbiol

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“…The exact structures of these hydrocarbon compounds, which are beyond the range of normal GC/MS, cannot be determined by heated-probe mass spectrometry alone and are liable to be complex mixtures of isomers. The identities of components in these spectra are based on previous work with pitch and hydrogenated coalliquids using packed and capillary columns with accurate mass measurement, [26][27][28] a high-temperature column 29 and from thin-layer chromatographic fractions studied by heated-probe mass spectrometry. 30 The major components are known from these and other 31,32 studies, and the names given above are intended to indicate likely structures for the molecular ions observed.…”

Section: Boiling-point Distributionsmentioning

confidence: 99%

Structural Features of Large Molecular Mass Material in Coal-Derived Liquids: Catalytic Hydrocracking of the Pyridine-Insoluble Fraction of a Coal-Tar Pitch

Begon

Islas

Lázaro

et al. 2000

Eur J Mass Spectrom (Chichester)

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The pyridine-insoluble fraction of a coal-tar pitch has been catalytically hydrocracked. The starting sample contained no material that could be observed by gas chromatography/mass spectrometry (GC/MS) or by heated-probe mass spectrometry. The aim of the study was to generate structural information on this narrow cut of large-molecular-mass material, which consisted mainly of compounds boiling above 450°C. A much broader boiling-point distribution was found for hydrocracked products; evidence from all analytical techniques used (size-exclusion chromatography, UV-fluorescence spectroscopy and heated-probe mass spectrometry) indicated a significant reduction of the molecular mass range. A wide variety of aromatic groups was identified in hydrocracked products by heated-probe mass spectrometry, ranging from phenanthrene ( m/z 178) to beyond dibenzocoronene ( m/z 400). Ions corresponding to alkyl ( m/z 43, 57, 71 and 85) and alkenyl groups ( m/z 41, 55, 69 and 83) were detected. The results reflect the ability of the hydrocracking process to cleave bonds within large pitch molecules, releasing the structural units which form the molecules. The structure of the original pyridine-insoluble material may thus be seen as a series of aromatic groups linked by short bridges or small groups, but with some longer aliphatic bridges (C12 and C17) as shown by pyrolysis-GC/MS. Clearly, some molecular species were reduced in mass but still lay above the range of detection by heated-probe mass spectrometry and could not be identified. Although the extent to which large polycyclic aromatic entities themselves have been cracked (or otherwise reduced to smaller polycyclic aromatic groups) cannot be quantitatively discerned from the present data, the hydrocracking of isolated fractions of intractable coal-derived material appears to offer a useful method for probing their structural features.

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“…Analyses using gas chromatography-mass spectrometry (GC-MS) have demonstrated the presence of C2-benzothiophenes in crude oils (Fedorak & Westlake 1983;Westlake 1983;Williams et al 1986), shale oils (Willey et al 1981;Andersson 1992) and coal tar (Burchill et al 1982). These may be ethylbenzothiophenes or dimethylbenzothiophenes, which have the same molecular weight and are difficult to distinguish by GC-MS analysis.…”

Section: Introductionmentioning

confidence: 99%

Transformations of six isomers of dimethylbenzothiophene by three Pseudomonas strains

Kropp¹,

Saftic²,

Andersson³

et al. 1996

Biodegradation

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Dimethylbenzothiophenes are among the sulfur heterocycles in petroleum that are known to be degraded by microbial activity. Six of the 15 possible isomers of dimethylbenzothiophene were synthesized and used in bio-transformation studies with three Pseudomonas isolates that oxidize a variety of condensed thiophenes including methylbenzothiophenes and methyldibenzothiophenes. The isomers of dimethylbenzothiophene were chosen to have a variety of substitution patterns: both methyl groups on the thiophene ring (the 2,3-isomer); a methyl group on each of the rings (the 2,7-, 3,5-and 3,7-isomers); and both methyl groups on the benzene ring (the 4,6-and 4,7-isomers). Each isolate was grown on 1-methylnaphthalene or glucose in the presence of one of the dimethylbenzothiophenes and culture extracts were analyzed to identify nearly 30 sulfur-containing metabolites in total. Sulfoxides and sulfones were commonly found metabolites in culture extracts from the 2,3-, 2,7- and 3,7-isomers, whereas 2,3-diones, 3(2H)-ones and 2(3H)-ones were formed from the 4,6- and 4,7-isomers. High-molecular-weight products, some of which were tentatively identified as tetramethylbenzo[b]naphtho[1,2-d]thiophenes, were detected in the extracts of cultures incubated with 4,6- or 4,7-dimethylbenzothiophene. The methyl groups of all of the isomers, except 4,6-, were oxidized to give hydroxymethyl-methylbenzothiophenes and methylbenzothiophene-carboxylic acids, and these were the only products detected from the oxidation of 3,5-dimethylbenzothiophene.

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Identification of sulphur heterocycles in coal tar and pitch

Cited by 45 publications

References 17 publications

Bacterial transformations of naphthothiophenes

Bacterial transformations of naphthothiophenes

Structural Features of Large Molecular Mass Material in Coal-Derived Liquids: Catalytic Hydrocracking of the Pyridine-Insoluble Fraction of a Coal-Tar Pitch

Transformations of six isomers of dimethylbenzothiophene by three Pseudomonas strains

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