Synthesis of Seven Trimethyldibenzothiophenes

Andersson, Jan T.; Schräder, Wolfgang; Traulsen, Fridtjof; Werlich, Sabine

doi:10.1080/10406630108033066

Cited by 5 publications

(5 citation statements)

References 10 publications

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“…-6 1,2-dimethyladamantane Mass spectral interpretation, ; mass spectral comparison, ; GC elution order, , , ; previous assignment of NA in OSPW and comparison of retention position and mass spectra with reference NA, , , Hall and Douglas (1981), Philp (1985), Chicarelli et al (1988); previous evidence of terpenoid NA in oil sands, , Azevedo et al (1992) and NIST MS library; previous assignment of monoaromatic terpenoid NA in tasmanite, dbt-I Sulphurcontaining tricyclic diaromatic -18 4-isobutyldibenzothiophene Comparison of retention position with synthetic reference hydrocarbon, Wilde (2015); mass spectral interpretation and mass spectral comparison, Andersson et al (2001), Bobinger et al (1999), (Andersson and Schade, 2004), Li et al (2014); previous assignment of NA (Porter, 1985), (Hawthone and Porter, 1968) and NIST MS library…”

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confidence: 99%

Naphthenic acids in oil sands process waters: Identification by conversion of the acids or esters to hydrocarbons

Wilde

Rowland

2018

Organic Geochemistry

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Concerns over the toxicity associated with 'naphthenic' acids (NA) within oil produced waters and oil sands process waters (OSPW), whether justified or not, have increased the need for the structural elucidation of NA. Certainly, oil sands mining operations, such as those in Alberta, Canada, result in the production of large volumes of OSPW contaminated with NA. Monitoring NA, predicting the toxicities and accounting for the toxicity of residual NA after clean-up treatments, have all been hindered by the lack of NA identifications.Recently, a method involving the conversion of the esters of petroleum NA to the corresponding hydrocarbons before analysis by comprehensive two-dimensional gas chromatography-mass spectrometry (GC×GC-MS), resulted in the most comprehensive study of bicyclic NA from petroleum to date. Here, we present results of the analysis by GC×GC-MS of NA extracted from OSPW after conversion of the acids or ester derivatives to the corresponding hydrocarbons. The identifications presented include novel alicyclic, aromatic and sulphur-containing hydrocarbons and thus, by inference, of the corresponding acids. This supports and significantly extends, previous identifications of OSPW NA as their methyl esters and can now be used to better inform environmental monitoring programs and toxicity studies.

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confidence: 99%

Naphthenic acids in oil sands process waters: Identification by conversion of the acids or esters to hydrocarbons

Wilde

Rowland

2018

Organic Geochemistry

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“…All chemicals were of analytical reagent grade. Standards not commercially available were synthesized in our laboratories. − Some PASHs are known to be carcinogenic and should be handled with care …”

Section: Methodsmentioning

confidence: 99%

“…A variety of standard compounds was used within this study. The compounds were either purchased (dibenzothiophene (DBT), 4-methylDBT, 4,6-dimethylDBT) or synthesized in our laboratories according to straightforward procedures (1-, 2-methyl and 3-methylDBT, 4,6-diethylDBT, 1,2,3,4-tetrahydroDBT, 4-methyltetrahydroDBT). − For CE-analysis, 2.0 mg of each PASH was dissolved in 2 mL of 1,2-dichloroethane, 100 μL of methyl iodide was added, and the vial wrapped with aluminum foil to exclude light (Figure S1). Sixty mg of silver tetrafluoroborate was added, and the mixture was stirred overnight.…”

Section: Methodsmentioning

confidence: 99%

Desulfurized Fuels from Athabasca Bitumen and Their Polycyclic Aromatic Sulfur Heterocycles. Analysis Based on Capillary Electrophoresis Coupled with TOF MS

et al. 2012

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Polycyclic Aromatic Sulfur Heterocycles (PASHs) are undesirable compounds in fuels and refined petroleumbased products. Capillary electrophoresis (CE) was investigated as an alternative to analyze the preisolated PASHs from partially desulfurized materials derived from Athabasca, Canada, bitumen. The sample complexity is considerably reduced by this preisolation by ligand exchange chromatography on a Pd(II) containing phase and subsequent ionization of the neutral PASHs through S-methylation to impart electrophoretic mobility. The PASH components are separated and characterized using CE with a time-of-flight mass spectrometer (TOF MS) as detector. An additional major advantage of the CE separation is that the drawbacks of HPLC (limited separation efficiency) and GC (volatility limitations) for separations of high molecular weight compounds can be circumvented. CE was demonstrated to be a highly efficient method in the separation of PASHs and up to 200,000 theoretical plates were obtained. The practicability of the method was shown by an extensive qualitative analysis of the PASH fraction of a hydrotreated middle distillate and a hydrotreated heavy gas oil. Additional information on the sample composition like the identity of parent ring systems, the alkyl substitution, and hydrogenated products from the hydrodesulfurization was gained through the use of CE-TOF MS and measuring standard PASHs expected to be present. The results are compared with GC-MS and high-resolution Orbitrap measurements of the same samples.

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“…Seven alkylated DBTs with alkyl side chains adjacent to the sulfur atom (see Table ) were synthesized for the first time using suitably adapted literature methods . In Table , the starting materials for each compound are also listed.…”

Section: Methodsmentioning

confidence: 99%

“…On the basis of the knowledge that compounds substituted in the 4 and 6 positions are more likely to survive the HDS, we concentrated our efforts on such isomers that are now also commercially available . Previously, all monomethyl-, dimethyl-, and ethyldibenzothiophenes have been synthesized, but rather few representatives of higher alkylated DBTs are known. , The speciation of several C 3 -, C 4 -, and C 5 -DBTs in a diesel fuel hydrodesulfurized to either 76 or 13 ppm aromatic sulfur is thus described for the first time, with the aim to establish whether a common substitution motif is detectable in higher alkylated refractory DBTs.…”

Section: Introductionmentioning

confidence: 99%

Speciation of Alkylated Dibenzothiophenes in a Deeply Desulfurized Diesel Fuel

Schade

Andersson

2006

Energy Fuels

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A diesel fuel desulfurized to 76 and 13 ppm sulfur in the aromatic fraction was analyzed with the objective of performing a speciation of the polycyclic aromatic sulfur heterocycles present. This provides information of importance to catalyst and process development. The analysis was based on selectively separating the sulfur from the non-sulfur aromatic compounds on a Pd II -containing liquid chromatographic phase, followed by identification and quantification using gas chromatography with mass-selective and sulfur-selective atomic emission detection. Several newly synthesized alkyldibenzothiophenes (mainly C 3 -and C 4 DBTs) could be quantified, and isomers with up to six alkyl carbon atoms could be detected in the diesel fuel. Besides confirmation that substituents in the 4 position of a dibenzothiophene lead to low rates of hydrodesulfurization (HDS), it is reported for the first time that a methyl group in the 1 position can also lead to a lower reactivity under HDS conditions, allowing such compounds to accumulate in the deeply desulfurized products. It is suggested that the nonplanarity of the aromatic system in such compounds is associated with this phenomenon.

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Synthesis of Seven Trimethyldibenzothiophenes

Abstract: Trimethyldibenzothiophenes are ubiquitous in fossil fuels. The analysis of them demands access to reference compounds. The synthesis and spectral properties of seven trimethyldibenzothiophenes that have been shown to occur in crude oil are described here.

Cited by 5 publications

References 10 publications

Naphthenic acids in oil sands process waters: Identification by conversion of the acids or esters to hydrocarbons

Naphthenic acids in oil sands process waters: Identification by conversion of the acids or esters to hydrocarbons

Desulfurized Fuels from Athabasca Bitumen and Their Polycyclic Aromatic Sulfur Heterocycles. Analysis Based on Capillary Electrophoresis Coupled with TOF MS

Speciation of Alkylated Dibenzothiophenes in a Deeply Desulfurized Diesel Fuel

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