Dicyclohexanecarbonylsulphate: a precursor of cyclohexyloxocarbenium ions

Montoneri, Enzo; Giuffré, L.; Cassago, M.; Tempesti, E.; Fornaroli, M.

doi:10.1139/v77-053

Cited by 5 publications

(2 citation statements)

References 9 publications

(14 reference statements)

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“…13. 5 Hz] which indicates the presence of the two ortho protons with respect to the P 0 3 H 2 group. Since the para structure is ruled out by 'H and 3C n.m.r.…”

Section: 4' 14gmentioning

confidence: 99%

Organosulphur phosphorus acid compounds. Part 1. m-Sulphophenylphosphonic acid

Montoneri¹,

Gallazzi²,

Grassi³

1989

J. Chem. Soc., Dalton Trans.

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“…13. 5 Hz] which indicates the presence of the two ortho protons with respect to the P 0 3 H 2 group. Since the para structure is ruled out by 'H and 3C n.m.r.…”

Section: 4' 14gmentioning

confidence: 99%

Organosulphur phosphorus acid compounds. Part 1. m-Sulphophenylphosphonic acid

Montoneri¹,

Gallazzi²,

Grassi³

1989

J. Chem. Soc., Dalton Trans.

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“…The sodium salt of the methyl derivative, Na + CH 3 COOSO 3 – , was first prepared in 1921, and a synthesis of the protonated species (CH 3 COOSO 2 OH) in nonaqueous solution has been given . Other reports indicate that the parent acid is unstable with respect to rearrangement or decomposition, at least in the solvent systems studied. , Infrared spectra of 1:1 mixtures of cyclohexanecarboxylic anhydride and SO 3 in liquid SO 2 reveal a related compound, dicyclohexanecarbonyl sulfate (RCOO–SO 2 –OCOR) as the predominant species, and the keto–enol equilibrium involving acetic sulfuric anhydride in liquid SO 2 has been investigated . A number of related systems have also been mentioned briefly in other works, − but to the best of our knowledge, little or no additional spectroscopic characterization of any gas phase carboxylic sulfuric anhydride beyond the microwave work noted above has been reported.…”

Section: Introductionmentioning

confidence: 99%

Carboxylic Sulfuric Anhydrides

et al. 2019

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Carboxylic acids react with sulfur trioxide to form carboxylic sulfuric anhydrides, RCOOSO 2 OH. In this article, new supersonic jet microwave spectra are presented for the anhydride derived from propiolic acid (HCCCOOH), and recent work on a series of carboxylic sulfuric anhydrides is reviewed. For the propiolic acid derivative, computed minimumenergy structures are reported for both the anhydride ( H C C C O O S O 2 O H ) a n d i t s p r e c u r s o r c o m p l e x (HCCCOOH−SO 3 ), and additional CCSD(T)/CBS(D-T)// M06-2X/6-311++G(3df,3pd) calculations indicate that, after zero-point energy corrections, the barrier to anhydride formation is effectively zero. These results are similar to those for other carboxylic sulfuric anhydrides studied and are consistent with their rapid production under supersonic jet conditions. Carboxylic sulfuric anhydrides, as a class, have not been widely characterized in the chemical literature and thus their study represents a new feature of the chemistry of sulfur oxides and oxyacids. As such, structural and energetic features of the carboxylic sulfuric anhydrides derived from formic, acetic, acrylic, trifluoroacetic, propiolic, pinic, and benzoic acids are compared. Computed vibrational frequencies are provided as Supporting Information and should be useful for possible future observation by infrared and/or Raman spectroscopy. Statistical thermodynamics is used to estimate the equilibrium constants for the formation reactions at a series of temperatures, and the results indicate values ranging from ∼10 4 atm −1 for formic acid at 288 K to over 10 11 atm −1 for benzoic acid at 217 K. We speculate that carboxylic sulfuric anhydrides could be active species in the Earth's atmosphere and atmospheric concentrations have, therefore, been estimated assuming an equilibrium state. These estimates are subject to significant uncertainties in the atmospheric SO 3 and carboxylic acid concentrations but may be as high as 10 7 molecules/cm 3 in some locations. Related calculations suggest that equilibrium anhydride concentrations may exceed those of the sulfuric acid precursors SO 3 −H 2 O and SO 3 −(H 2 O) 2 by several orders of magnitude. Kinetic modeling will ultimately be necessary to fully assess the role, if any, of carboxylic sulfuric anhydrides in atmospheric processes.

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The application of the reaction calorimetry to investigate reactions involving unstable compounds

Maggiorotti

1992

Journal of Thermal Analysis

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The RC1 calorimeter revealed itself a suitable instrument to obtain information about safety and mechanisms involved in the reaction between eyclohexaneearboxylic acid (AEB) and oleum. A previous hypothesis about the existence of an unstable intermediate was confirmed and its heat of formation was calculated. The heat of sulphonation related to undesirable by-products production and the heat of protonation of AEB with H2SO4 were also evaluated. Therefore, it was possible to distinguish the reactions involved in the process and, through their thermal behaviour, to determine the limit conditions to avoid the by-products formation.

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Dicyclohexanecarbonylsulphate: a precursor of cyclohexyloxocarbenium ions

Cited by 5 publications

References 9 publications

Organosulphur phosphorus acid compounds. Part 1. m-Sulphophenylphosphonic acid

Organosulphur phosphorus acid compounds. Part 1. m-Sulphophenylphosphonic acid

Carboxylic Sulfuric Anhydrides

The application of the reaction calorimetry to investigate reactions involving unstable compounds

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