Peroxynitrogen: A Study of Nitrogen/Oxygen Heterocycles with
            <scp>N</scp>
            
            <scp>O</scp>
            and
            <scp>O</scp>
            
            <scp>O</scp>
            or
            <scp>N</scp>
            
            <scp>O</scp>
            
            <scp>O</scp>
            Bonding

Slayden, Suzanne W.; Greer, Alexander; Liebman, Joel F.

doi:10.1002/9780470682531.pat0516

Cited by 3 publications

(7 citation statements)

References 128 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…CHCl 3 contains trace ethanol as a stabilizer, which was not removed. The results were reproducible and nearly identical in either CHCl 3 or CH 3 ] that was synthesized as described previously. 7 Computational Methods.…”

Section: Methodssupporting

confidence: 52%

“…Despite the decades-long interest in N-nitrosamine organic chemistry and toxicity, 1,2 no photochemical O-atom exchange process with molecular oxygen has been reported. One paper 3 speculated that an O-atom exchange between singlet oxygen ( 1 O 2 ) and N-nitrosamine would proceed by a 1,2,3,4trioxazetidine intermediate (cycloNO 3 species) (Scheme 1).…”

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Mechanism of Photochemical O-Atom Exchange in Nitrosamines with Molecular Oxygen

et al. 2015

Self Cite

View full text Add to dashboard Cite

The detection of an oxygen-atom photoexchange process of N-nitrosamines is reported. The photolysis of four nitrosamines (N-nitrosodiphenylamine 1, N-nitroso-N-methylaniline 2, N-butyl-N-(4-hydroxybutyl)nitrosamine 3, and N-nitrosodiethylamine 4) with ultraviolet light was examined in an (18)O2-enriched atmosphere in solution. HPLC/MS and HPLC-MS/MS data show that (18)O-labeled nitrosamines were generated for 1 and 2. In contrast, nitrosamines 3 and 4 do not exchange the (18)O label and instead decomposed to amines and/or imines under the conditions. For 1 and 2, the (18)O atom was found not to be introduced by moisture or by singlet oxygen [(18)((1)O2 (1)Δg)] produced thermally by (18)O-(18)O labeled endoperoxide of N,N'-di(2,3-hydroxypropyl)-1,4-naphthalene dipropanamide (DHPN(18)O2) or by visible-light sensitization. A density functional theory study of the structures and energetics of peroxy intermediates arising from reaction of nitrosamines with O2 is also presented. A reversible head-to-tail dimerization of the O-nitrooxide to the 1,2,3,5,6,7-hexaoxadiazocane (30 kcal/mol barrier) with extrusion of O═(18)O accounts for exchange of the oxygen atom label. The unimolecular cyclization of O-nitrooxide to 1,2,3,4-trioxazetidine (46 kcal/mol barrier) followed by a retro [2 + 2] reaction is an alternative, but higher energy process. Both pathways would require the photoexcitation of the nitrooxide.

show abstract

Section: Methodssupporting

confidence: 52%

Section: ■ Introductionmentioning

confidence: 99%

Mechanism of Photochemical O-Atom Exchange in Nitrosamines with Molecular Oxygen

et al. 2015

Self Cite

View full text Add to dashboard Cite

show abstract

“… and so must be “approximated.” There are no species at all with measured enthalpies of formation with either –O–O–N– or –O–N–N– functionalities should we sensibly ignore multiply bonded species such as peroxynitrites and azoxy compounds (for a review of the thermochemistry of hydroxylamine derivatives and a survey of cyclic species with the –O–O–N– functionality see Refs. and respectively). Said differently, while ∆ f H 0 ( 4 ) = C–(N)(O)(H) 2 + N–(N)(O)(C) + O–(O)(N) + O–(O)(C) + N–(N)(H) 2 + ring correction, but the group increments C–(N)(O)(H) 2 , O–(O)(N) and N–(N)(O)(C) and the ring correction must be derived de novo for the current study.…”

Section: Resultsmentioning

confidence: 88%

Theoretical Study of the Reaction Formalhydrazone with Singlet Oxygen. Fragmentation of the C=N Bond, Ene Reaction and Other Processes

Rudshteyn

Castillo

Ghogare

et al. 2013

Photochem & Photobiology

Self Cite

View full text Add to dashboard Cite

Photobiologic and synthetic versatility of hydrazones has not yet been established with 1O2 as a route to commonly encountered nitrosamines. Thus, to determine whether the “parent” reaction of formalhydrazone and 1O2 leads to facile C=N bond cleavage and resulting nitrosamine formation, we have carried out CCSD(T)//DFT calculations and analyzed the energetics of the oxidation pathways. A [2 + 2] pathway occurs via diradicals and formation of 3-amino-1,2,3-dioxazetidine in a 16 kcal/mol process. Reversible addition or physical quenching of 1O2 occurs either on the formalhydrazone carbon for triplet diradicals at 2–3 kcal/mol, or on the nitrogen (N(3)) atom forming zwitterions at ~15 kcal/mol, although the quenching channel by charge-transfer interaction was not computed. The computations also predict a facile conversion of formalhydrazone and 1O2 to hydroperoxymethyl diazene in a low-barrier ‘ene’ process, but no 2-amino-oxaziridine-O-oxide (perepoxide-like) intermediate was found. A Benson-like analysis (group increment calculations) on the closed shell species are in accord with the quantum chemical results.

show abstract

“…It is suggested that this thermal reaction might proceed via corresponding nitroso oxide or directly 100,101 . (5) Inui and colleagues attempted to detect dioxaziridine by IR spectroscopy upon photolysis of 4-nitrophenyl azide in a xenon matrix doped with oxygen at 50 K 94 . The formation of cis-and trans-isomers of the corresponding nitroso oxide was registered.…”

Section: Study Of Mechanism Of Transformations Of Nitroso Oxides In Lmentioning

confidence: 99%

“…At the present time, there are several reviews devoted to organic azides 1, 2 , dioxygen species XO 2 3, 4 , and nitrogen-oxygen heterocyclic compounds 5 , in which some attention was paid to nitroso oxides. They possess very interesting properties, significant progress in the study of which was achieved in recent years.…”

Section: Introductionmentioning

confidence: 99%

The chemistry of nitroso oxides

Chainikova

Khursan

Safiullin

2014

Patai's Chemistry of Functional Groups

View full text Add to dashboard Cite

Nitroso oxides (RNOO) are the isoelectronic analogs of carbonyl oxides (R 2 COO) and ozone (O 3 ) and, as well as these species, possess a three‐centered 4π‐electron system, which determines their chemical properties and reactivity unusual for a family of peroxides. The review is focused on the chemistry of the parent nitroso oxide (HNOO) and its aromatic analogs (ArNOO). The structure, spectral properties, methods for generation, reactivity and mechanisms of various transformations of these species both in the gas and condensed media are discussed in detail. An aromatic substituent significantly stabilizes the π‐system of nitroso oxide. The typical reactions of nitroso oxides are O‐transfer to an appropriate substrate or [3+2]‐cycloaddition to unsaturated bonds. Special attention was paid to the redox isomerization of arylnitroso oxides with ring cleavage that leads to the formation of diene nitrile oxides.

show abstract

Peroxynitrogen: A Study of Nitrogen/Oxygen Heterocycles with N  O and O  O or N  O  O Bonding

Cited by 3 publications

References 128 publications

Mechanism of Photochemical O-Atom Exchange in Nitrosamines with Molecular Oxygen

Mechanism of Photochemical O-Atom Exchange in Nitrosamines with Molecular Oxygen

Theoretical Study of the Reaction Formalhydrazone with Singlet Oxygen. Fragmentation of the C=N Bond, Ene Reaction and Other Processes

The chemistry of nitroso oxides

Contact Info

Product

Resources

About