The Synthesis of 2,5-Diarylthiophenes

Campaigne, E.; Foye, William O.

doi:10.1021/jo50010a023

Cited by 84 publications

(33 citation statements)

References 7 publications

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“…In volcanic gases, production of CS 2 may occur through sulfonation processes involving compounds typical of magmatic degassing (SO 2 and CO 2 ), as well as gases from secondary gas‐water‐rock interactions (H 2 S and CH 4 ) [ Petherbridge et al , 2002]. Among the various catalytic processes able to synthesize thiophenes [ Southward et al , 1998; Tomov et al , 2000; Li et al , 2008], ring closure of dienes, known as Paal–Knorr synthesis, through addition of H 2 S in presence of H + and metals [ Campaigne and Foye , 1952], is to be considered the most reliable genetic mechanism in active volcanoes that are rich in these catalysts [ Tassi et al , 2010a]. Similarly, ring closure of oxygenated alkenes may represent the main genetic mechanism for furans, which are the most abundant fraction of oxygenated species (Table 2).…”

Section: Discussionmentioning

confidence: 99%

Geogenic and atmospheric sources for volatile organic compounds in fumarolic emissions from Mt. Etna and Vulcano Island (Sicily, Italy)

et al. 2012

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In this paper, fluid source(s) and processes controlling the chemical composition of volatile organic compounds (VOCs) in gas discharges from Mt. Etna and Vulcano Island (Sicily, Italy) were investigated. The main composition of the Etnean and Volcano gas emissions is produced by mixing, to various degrees, of magmatic and hydrothermal components. VOCs are dominated by alkanes, alkenes and aromatics, with minor, though significant, concentrations of O‐, S‐ and Cl(F)‐substituted compounds. The main mechanism for the production of alkanes is likely related to pyrolysis of organic‐matter‐bearing sediments that interact with the ascending magmatic fluids. Alkanes are then converted to alkene and aromatic compounds via catalytic reactions (dehydrogenation and dehydroaromatization, respectively). Nevertheless, an abiogenic origin for the light hydrocarbons cannot be ruled out. Oxidative processes of hydrocarbons at relatively high temperatures and oxidizing conditions, typical of these volcanic‐hydrothermal fluids, may explain the production of alcohols, esters, aldehydes, as well as O‐ and S‐bearing heterocycles. By comparing the concentrations of hydrochlorofluorocarbons (HCFCs) in the fumarolic discharges with respect to those of background air, it is possible to highlight that they have a geogenic origin likely due to halogenation of both methane and alkenes. Finally, chlorofluorocarbon (CFC) abundances appear to be consistent with background air, although the strong air contamination that affects the Mt. Etna fumaroles may mask a possible geogenic contribution for these compounds. On the other hand, no CFCs were detected in the Vulcano gases, which are characterized by low air contribution. Nevertheless, a geogenic source for these compounds cannot be excluded on the basis of the present data.

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Section: Discussionmentioning

confidence: 99%

Geogenic and atmospheric sources for volatile organic compounds in fumarolic emissions from Mt. Etna and Vulcano Island (Sicily, Italy)

et al. 2012

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“…Etna (Italy). Synthesis of thiophenes may also proceed via ring closure of dienes (Paal-Knorr process) through the addition of H 2 S in presence of H + and metals (Campaigne and Foye, 1952), the latter being typically abundant in a hydrothermal environment. Production of non-aromatic S-bearing organics, such as CS 2 , may occur through sulfonation processes involving hydrothermal-magmatic compounds (SO 2 , H 2 S, CH 4 and CO 2 ) (Petherbridge et al, 2002;Rushdi and Simoneit, 2005;Schulte, 2010).…”

Section: S-bearing Compoundsmentioning

confidence: 99%

Volatile organic compounds (VOCs) in soil gases from Solfatara crater (Campi Flegrei, southern Italy): Geogenic source(s) vs. biogeochemical processes

Tassi

Venturi

Cabassi

et al. 2015

Applied Geochemistry

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“…The thiophene Paal-Knorr synthesis involves the reaction of 1,4-diketones with H 2 S as sulphurising agent [57]. Generally speaking, in gases from natural fluid discharges, the most reliable genetic mechanism for the formation of thiophene is through the addition of H 2 S to dienes in the presence of H + and metal catalysts (Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

Origin and Distribution of Thiophenes and Furans in Gas Discharges from Active Volcanoes and Geothermal Systems

Tassi

Montegrossi

Capecchiacci

et al. 2010

IJMS

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The composition of non-methane organic volatile compounds (VOCs) determined in 139 thermal gas discharges from 18 different geothermal and volcanic systems in Italy and Latin America, consists of C2–C20 species pertaining to the alkanes, alkenes, aromatics and O-, S- and N-bearing classes of compounds. Thiophenes and mono-aromatics, especially the methylated species, are strongly enriched in fluids emissions related to hydrothermal systems. Addition of hydrogen sulphide to dienes and electrophilic methylation involving halogenated radicals may be invoked for the formation of these species. On the contrary, the formation of furans, with the only exception of C4H8O, seems to be favoured at oxidizing conditions and relatively high temperatures, although mechanisms similar to those hypothesized for the production of thiophenes can be suggested. Such thermodynamic features are typical of fluid reservoirs feeding high-temperature thermal discharges of volcanoes characterised by strong degassing activity, which are likely affected by conspicuous contribution from a magmatic source. The composition of heteroaromatics in fluids naturally discharged from active volcanoes and geothermal areas can then be considered largely dependent on the interplay between hydrothermal vs. magmatic contributions. This implies that they can be used as useful geochemical tools to be successfully applied in both volcanic monitoring and geothermal prospection.

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The Synthesis of 2,5-Diarylthiophenes

Cited by 84 publications

References 7 publications

Geogenic and atmospheric sources for volatile organic compounds in fumarolic emissions from Mt. Etna and Vulcano Island (Sicily, Italy)

Geogenic and atmospheric sources for volatile organic compounds in fumarolic emissions from Mt. Etna and Vulcano Island (Sicily, Italy)

Volatile organic compounds (VOCs) in soil gases from Solfatara crater (Campi Flegrei, southern Italy): Geogenic source(s) vs. biogeochemical processes

Origin and Distribution of Thiophenes and Furans in Gas Discharges from Active Volcanoes and Geothermal Systems

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