The Preparation of Nitrosyl Perfluoroacylates from Perfluoro Acid Anhydrides and Dinitrogen Trioxide

Rice, D. E.; Crawford, G. H.

doi:10.1021/jo01038a516

Cited by 7 publications

(6 citation statements)

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“…[38] When the substrate is added into N 2 O 3 solution, the disappearance of the color could sometimes mark the endpoint of the reaction. [11,81]…”

Section: Preparation Of N 2 O 3 Solutionsmentioning

confidence: 99%

“…Liquid N 2 O 3 condensed from the equimolar mixture of NO(g) and NO 2 (g) [127] was added slowly with anhydride 9. [81] The color change of the reaction mixture from blue to amber or yellow indicates the endpoint of the reaction (Eq. 37).…”

Section: O-nitrosationmentioning

confidence: 99%

“…37). [81] Nitrosyl perfluoroacylates (10) were isolated by distillation under reduced pressure (10 a-b) or by evaporation (10 c).…”

Section: O-nitrosationmentioning

confidence: 99%

“…The color change of the reaction mixture from blue to amber or yellow indicates the endpoint of the reaction (Eq. 37) [81] . Nitrosyl perfluoroacylates ( 10 ) were isolated by distillation under reduced pressure ( 10 a ‐ b ) or by evaporation ( 10 c ).…”

Section: Reactions With Organic Compoundsmentioning

confidence: 99%

“…Generally, polar solvents stabilize N 2 O 3 by solvation, exhibiting the blue color of N 2 O 3 ; apoler solvents do not solvate N 2 O 3 well, so the solution therein is green, a mixed color of N 2 O 3 (blue) and NO 2 (reddish brown) [38] . When the substrate is added into N 2 O 3 solution, the disappearance of the color could sometimes mark the endpoint of the reaction [11,81] …”

Section: Preparation Of N2o3mentioning

confidence: 99%

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Preparation of Dinitrogen Trioxide for Organic Synthesis: A Phase Equilibrium Approach

Chen,

Monbaliu

2024

Chemistry A European J

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Dinitrogen trioxide (N2O3) is a potent nitrosating agent featured with high reactivity and appealing atom economy. Because of its instability and the entanglement of chemical and phase equilibria, N2O3 has rarely been utilized in organic synthesis as a stock reagent with well‐defined composition. In this review, the preparations of pure N2O3 and its concentrated solution (> 0.1 M) are discussed from the aspect of phase equilibrium. Understanding the physical and chemical characteristics of N2O3, along with how reaction parameters (temperature, pressure, molar ratio) interact, plays a crucial role in managing the concentration of N2O3 in the liquid phase. This control holds practical significance in achieving quantitative reactions.

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“…[38] When the substrate is added into N 2 O 3 solution, the disappearance of the color could sometimes mark the endpoint of the reaction. [11,81]…”

Section: Preparation Of N 2 O 3 Solutionsmentioning

confidence: 99%

Section: O-nitrosationmentioning

confidence: 99%

“…37). [81] Nitrosyl perfluoroacylates (10) were isolated by distillation under reduced pressure (10 a-b) or by evaporation (10 c).…”

Section: O-nitrosationmentioning

confidence: 99%

Section: Reactions With Organic Compoundsmentioning

confidence: 99%

Section: Preparation Of N2o3mentioning

confidence: 99%

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Preparation of Dinitrogen Trioxide for Organic Synthesis: A Phase Equilibrium Approach

Chen,

Monbaliu

2024

Chemistry A European J

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The acyl hypohalites

Tanner

Bunce

1972

PATAI'S Chemistry of Functional Groups

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Investigation of N‐carbamoylamino acid nitrosation by {NO + O₂} in the solid‐gas phase. Effects of NO_x speciation and kinetic evidence for a multiple‐stage process

Lagrille¹,

Taillades²,

Boiteau³

et al. 2007

J of Physical Organic Chem

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Nitrosation of N‐carbamoylamino acids (CAA) by gaseous NO + O2, an interesting synthetic pathway to amino acid N‐carboxyanhydrides (NCA), alternative to the phosgene route, was investigated on N‐carbamoyl‐valine either in acetonitrile suspension or solventless conditions, and compared to the classical nitrosating system NaNO2 + CF3COOH (TFA), the latter being quite less efficient in terms of either rate, stoichiometric demand, or further tractability of the product. The rate and efficiency of the NO + O2 reaction mainly depends on the O2/NO ratio. Evaluation of the contribution of various nitrosating species (N2O3, N2O4, HNO2) through stoichiometric balance showed the reaction to be effected mostly by N2O3 for O2/NO ratios below 0.3, and by N2O4 for O2/NO ratios above 0.4. The relative contribution of (subsequently formed) HNO2 always remains minor. Differential scanning calorimetry (DSC) monitoring of the reaction in the solid phase by either HNO2 (from NaNO2 + TFA), gaseous N2O4 or gaseous N2O3, provides the associated rate constants (ca. 0.1, 2 and 108 s−1 at 25°C, respectively), showing that N2O3 is by far the most reactive of these nitrosating species. From the DSC measurement, the latent heat of fusion of N2O3, 2.74 kJ · mol−1 at −105 °C is also obtained for the first time. The kinetics was investigated under solventless conditions at 0°C, by either quenching experiments or less tedious, rough calorimetric techniques. Auto‐accelerated, parabolic‐shaped kinetics was observed in the first half of the reaction course, together with substantial heat release (temperature increase of ca. 20°C within 1–2 min in a 20‐mg sample), followed by pseudo‐zero‐order kinetics after a sudden, important decrease in apparent rate. This kinetic break is possibly due to the transition between the initial solid‐gas system and a solid‐liquid‐gas system resulting from water formation. Overall rate constants increased with parameters such as the specific surface of the solid, the O2/NO ratio, or the presence of moisture (or equivalently the hydrophilicity of the involved CAA), however without precise relationship, while the last two parameters may directly correlate to the increasing acidity of the medium. Copyright © 2007 John Wiley & Sons, Ltd.

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The Preparation of Nitrosyl Perfluoroacylates from Perfluoro Acid Anhydrides and Dinitrogen Trioxide

Cited by 7 publications

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Preparation of Dinitrogen Trioxide for Organic Synthesis: A Phase Equilibrium Approach

Preparation of Dinitrogen Trioxide for Organic Synthesis: A Phase Equilibrium Approach

The acyl hypohalites

Investigation of N‐carbamoylamino acid nitrosation by {NO + O₂} in the solid‐gas phase. Effects of NO_x speciation and kinetic evidence for a multiple‐stage process

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The Preparation of Nitrosyl Perfluoroacylates from Perfluoro Acid Anhydrides and Dinitrogen Trioxide

Cited by 7 publications

References 0 publications

Preparation of Dinitrogen Trioxide for Organic Synthesis: A Phase Equilibrium Approach

Preparation of Dinitrogen Trioxide for Organic Synthesis: A Phase Equilibrium Approach

The acyl hypohalites

Investigation of N‐carbamoylamino acid nitrosation by {NO + O2} in the solid‐gas phase. Effects of NOx speciation and kinetic evidence for a multiple‐stage process

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Product

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Investigation of N‐carbamoylamino acid nitrosation by {NO + O₂} in the solid‐gas phase. Effects of NO_x speciation and kinetic evidence for a multiple‐stage process