Oxidation Reactions With Pertrifluoroacetic Acid

Emmons, William D.; Ferris, Arthur F.

doi:10.1021/ja01114a539

Cited by 40 publications

(17 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…9). Therefore, we propose that part of MorNO2 is generated from an electrophilic attack of N 2 O 4 on morpholine in addition to oxidation of MorNO with H 2 O 2 [58].…”

Section: Cleaved Bondmentioning

confidence: 99%

See 1 more Smart Citation

The Reaction of Peroxynitrite with Morpholine (Secondary Amines) Revisited: The Overlooked Hydroxylamine Formation

Kirsch¹,

Korth²,

Wensing³

et al. 2006

Helvetica Chimica Acta

View full text Add to dashboard Cite

In memoriam Hanns FischerThe reaction of peroxynitrite/peroxynitrous acid with morpholine as a model compound for secondary amines is reinvestigated in the absence and presence of carbon dioxide. The concentration-and pHdependent formation of N-nitrosomorpholine and N-nitromorpholine as reported in three previous papers ([25] [26] [14]) is basically confirmed. However, 13 C-NMR spectroscopic product analysis shows that, in the absence of CO 2 , N-hydroxymorpholine is, at pH ! 7, the major product of this reaction, even under anaerobic conditions. The formation of N-hydroxymorpholine has been overlooked in the three cited papers. Additional (ring-opened) oxidation products of morpholine are also detected. The data account for radical pathways for the formation of these products via intermediate morpholinederived aminyl and a-aminoalkyl radicals. This is further supported by EPR-spectrometric detection of morpholine-derived nitroxide radicals, i.e., morpholin-4-yloxy radicals. N-Nitrosomorpholine, however, is very likely formed by electrophilic attack of peroxynitrite-derived N 2 O 4 .15 N-CIDNP Experiments establish that, in the presence of CO 2 , N-nitro-and C-nitromorpholine are generated by radical recombination. The present results are in full accord with a fractional (28 AE 2%) homolytic decay of peroxynitrite/peroxynitrous acid with release of free hydroxyl and nitrogen dioxide radicals.

show abstract

“…9). Therefore, we propose that part of MorNO2 is generated from an electrophilic attack of N 2 O 4 on morpholine in addition to oxidation of MorNO with H 2 O 2 [58].…”

Section: Cleaved Bondmentioning

confidence: 99%

“…(710 AE 20 mM) were prepared as described previously [24]. MorOH and MorNO2 were prepared by standard procedures [63] [58]. All other compounds and solvents were commercially available.…”

Section: Experimental Partmentioning

confidence: 99%

The Reaction of Peroxynitrite with Morpholine (Secondary Amines) Revisited: The Overlooked Hydroxylamine Formation

Kirsch¹,

Korth²,

Wensing³

et al. 2006

Helvetica Chimica Acta

View full text Add to dashboard Cite

show abstract

“…Addition of hydrogen peroxide to the carbonyl group,13,20 followed by in situ epoxidation by trifluoroacetic peracid,21 would afford a mixture of epoxides 22 and 23 . Cyclization of the hydroxyl group of hemi-peroxyketal 23 would provide intermediate tetrahydrofuran 24 22.…”

mentioning

confidence: 99%

Preparation of Bicyclic 1,2,4-Trioxanes from γ,δ-Unsaturated Ketones

2009

View full text Add to dashboard Cite

show abstract

“…It will efficiently bring about the oxidations for which peracids are normally used, such as the Baeyer-Villiger oxidation of ketones to esters [58] and the conversion of alkenes to glycols [59] or, when a buffer is present, to epoxides [60] and nitrosamines to nitramines [56,61]. It will efficiently bring about the oxidations for which peracids are normally used, such as the Baeyer-Villiger oxidation of ketones to esters [58] and the conversion of alkenes to glycols [59] or, when a buffer is present, to epoxides [60] and nitrosamines to nitramines [56,61].…”

Section: Peroxytrifluoroacetic Acidmentioning

confidence: 99%

Functional Compounds Containing Oxygen, Sulphur or Nitrogen and their Derivatives

Chambers

2004

Fluorine in Organic Chemistry

View full text Add to dashboard Cite

This chapter contains only a brief survey of the chemistry of a range of derivatives that are of interest to the organic chemist; further aspects have been discussed in detail and may be referred to elsewhere [1,2]. Because of the extreme electronegativity of fluorine and fluorocarbon groups, the acidities of various functions are increased by introduction of these groups. Some examples are given in Table 8.1: it is clear that fluorocarbon groups have a dramatic effect on the acidities of alcohols and carboxylic acids. Moreover, the CF 3 SO 2 group is one of the most electron-withdrawing groups known [3] and consequently the carbon acid ðCF 3 SO 2 Þ 2 CH 2 is more acidic than trifluoroacetic acid. Also, the sulphonamide ðCF 3 SO 2 Þ 2 NH is a strong acid [4].Conversely, fluorine or fluorocarbon groups have a major effect in reducing the base strength of amines, ethers and carbonyl compounds; for example, 2,2,2-trifluoroethylamine (pK b ¼ 3:3) is ca. 10 5 times less basic than ethylamine. Also, pentafluoropyridine is only protonated in strong acid [6], whereas hexafluoroacetone is not protonated even in superacids [7-9] and perfluorinated tertiary amines and ethers are sufficiently non-basic for them to be used as inert fluids interchangeably with perfluorocarbons.

show abstract

Oxidation Reactions With Pertrifluoroacetic Acid

Cited by 40 publications

References 5 publications

The Reaction of Peroxynitrite with Morpholine (Secondary Amines) Revisited: The Overlooked Hydroxylamine Formation

The Reaction of Peroxynitrite with Morpholine (Secondary Amines) Revisited: The Overlooked Hydroxylamine Formation

Preparation of Bicyclic 1,2,4-Trioxanes from γ,δ-Unsaturated Ketones

Functional Compounds Containing Oxygen, Sulphur or Nitrogen and their Derivatives

Contact Info

Product

Resources

About