The reactivity of pyridine towards sulphuric acid at elevated temperatures

Hertog, H. J. den; Plas, H. C. Van Der; Buurman, D. J.

doi:10.1002/recl.19580771010

Cited by 20 publications

(3 citation statements)

References 15 publications

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“…By contrast, alcohols are protonated to oxonium derivatives, but these are relatively unstable and prone to rearrangement such as dehydration. Thus, a wide range of amines stably dissolve in CSA as ammonium salts [ 37 , 38 , 39 ], and pyridines and pyrimidines are only sulfonated by oleum or CSA at temperatures above 150 °C [ 40 , 41 , 42 ]. Polyaromatic hydrocarbons and their quinones in general form stable solutions in CSA as colored, protonated species [ 43 , 44 ], unlike solution in octane (which solutions are uncolored) or water (where they do not dissolve).…”

Section: Background On Csa As a Potential Solvent For Lifementioning

confidence: 99%

Evaluating Alternatives to Water as Solvents for Life: The Example of Sulfuric Acid

Bains

Petkowski

Zhan

et al. 2021

Life

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The chemistry of life requires a solvent, which for life on Earth is water. Several alternative solvents have been suggested, but there is little quantitative analysis of their suitability as solvents for life. To support a novel (non-terrestrial) biochemistry, a solvent must be able to form a stable solution of a diverse set of small molecules and polymers, but must not dissolve all molecules. Here, we analyze the potential of concentrated sulfuric acid (CSA) as a solvent for biochemistry. As CSA is a highly effective solvent but a reactive substance, we focused our analysis on the stability of chemicals in sulfuric acid, using a model built from a database of kinetics of reaction of molecules with CSA. We consider the sulfuric acid clouds of Venus as a test case for this approach. The large majority of terrestrial biochemicals have half-lives of less than a second at any altitude in Venus’s clouds, but three sets of human-synthesized chemicals are more stable, with average half-lives of days to weeks at the conditions around 60 km altitude on Venus. We show that sufficient chemical structural and functional diversity may be available among those stable chemicals for life that uses concentrated sulfuric acid as a solvent to be plausible. However, analysis of meteoritic chemicals and possible abiotic synthetic paths suggests that postulated paths to the origin of life on Earth are unlikely to operate in CSA. We conclude that, contrary to expectation, sulfuric acid is an interesting candidate solvent for life, but further work is needed to identify a plausible route for life to originate in it.

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Section: Background On Csa As a Potential Solvent For Lifementioning

confidence: 99%

Evaluating Alternatives to Water as Solvents for Life: The Example of Sulfuric Acid

Bains

Petkowski

Zhan

et al. 2021

Life

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“…A range of reagents can sulfonate other groups and can sulfonate phenyl at lower temperatures [2], but this chemistry is not relevant to the chemistry of sulfuric acid itself. Thus, groups that are less stable to solvolysis than phenyl rings will be attacked and degraded before they are sulfonated (e.g., furan rings), and nitrogen-containing aromatics are resistant to any sulfuric acid chemistry and can only be sulfonated by more potent sulfonating agents, such as "oleum" (solutions of SO 3 in pure sulfuric acid) [22,23].…”

Section: Inference Of Unmeasured Kinetic Parameters For Sulfonation Rmentioning

confidence: 99%

A Data Resource for Sulfuric Acid Reactivity of Organic Chemicals

Bains

Petkowski

Seager

2021

Data

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We describe a dataset of the quantitative reactivity of organic chemicals with concentrated sulfuric acid. As well as being a key industrial chemical, sulfuric acid is of environmental and planetary importance. In the absence of measured reaction kinetics, the reaction rate of a chemical with sulfuric acid can be estimated from the reaction rate of structurally related chemicals. To allow an approximate prediction, we have collected 589 sets of kinetic data on the reaction of organic chemicals with sulfuric acid from 262 literature sources and used a functional group-based approach to build a model of how the functional groups would react in any sulfuric acid concentration from 60–100%, and between −20 °C and 100 °C. The data set provides the original reference data and kinetic measurements, parameters, intermediate computation steps, and a set of first-order rate constants for the functional groups across the range of conditions −20 °C–100 °C and 60–100% sulfuric acid. The dataset will be useful for a range of studies in chemistry and atmospheric sciences where the reaction rate of a chemical with sulfuric acid is needed but has not been measured.

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“…To create robust multidentate N x ligands, sulfonation of picolyl pendant arms is an attractive prospect. Attempts to directly introduce sulfonate groups into unactivated/unsubstituted pyridines and derivatives go back more than 80 years, and the resulting methodologies require harsh conditions. − They are thus unsuitable for the synthesis of complex multidentate ligands.…”

mentioning

confidence: 99%

Multiple Sulfonation of Picolyl-Based Complexes Rendering Them Highly Water-Compatible

2020

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Multidentate ligands chosen for the complexation of hard metals frequently exhibit negative charges, which consequently elicits Coulombic compensation of the metal-ion charge. However, ligands favored by soft metal ions are neutral, which prevents the chemist from obtaining electroneutral complexes, let alone ones with a negative total charge. Here, we report on an efficient synthetic method to decorate picolyl-displaying coordination compounds with multiple sulfonate units at their periphery. We further describe rare anionic versions of three standard complexes that have only been characterized as cationic so far. Our sulfonated complexes show extensive water solubility, which confers these species with great potential for broad application in the biomedical arena.

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The reactivity of pyridine towards sulphuric acid at elevated temperatures

Cited by 20 publications

References 15 publications

Evaluating Alternatives to Water as Solvents for Life: The Example of Sulfuric Acid

Evaluating Alternatives to Water as Solvents for Life: The Example of Sulfuric Acid

A Data Resource for Sulfuric Acid Reactivity of Organic Chemicals

Multiple Sulfonation of Picolyl-Based Complexes Rendering Them Highly Water-Compatible

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