Oxidations of amines. IV. Oxidative fragmentation

Dennis, William E.; Hull, Larry A.; Rosenblatt, David H.

doi:10.1021/jo01287a012

Cited by 78 publications

(56 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Relief of strain energy contained within the hexaazaisowurtzitane framework and formation of the resonance-stabilized imidazolinium ion provides the driving force for the oxidative cleavage of C(1)-C(7) bond. The similar type of Grob fragmentation was also observed in the reaction of triethylenediamine with either ClO 2 or HOCl [8]. In oxidative dealkylation of tertiary amine, the intermediate iminium cation, which are generally believed to be the key intermediates, is hydrolyzed more or less rapidly, in aqueous solution, with the formation of the corresponding secondary amine [7].…”

Section: Resultsmentioning

confidence: 79%

“…It has been reported that 1,2-diamine radical cations undergo rapid C-C bond fragmentation to form an α-amino radical and an iminium ion [6], and iminium salts are generally believed to be the key intermediates during the oxidation of tertiary amines [7]. The readily oxidative cleavage of 1 must arise from the through-bond interaction between N(2), N(6), N (8) and N(12) atoms, which stabilizes the intermediate-like transition state relative to the ground state. Relief of strain energy contained within the hexaazaisowurtzitane framework and formation of the resonance-stabilized imidazolinium ion provides the driving force for the oxidative cleavage of C(1)-C(7) bond.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Novel Carbon-Carbon Bond Oxidative Cleavage of Hexabenzylhexaazaisowurtzitane by n-BuONO and (NH4)2Ce(NO3)6

et al. 1999

View full text Add to dashboard Cite

show abstract

Section: Resultsmentioning

confidence: 79%

Section: Resultsmentioning

confidence: 99%

Novel Carbon-Carbon Bond Oxidative Cleavage of Hexabenzylhexaazaisowurtzitane by n-BuONO and (NH4)2Ce(NO3)6

et al. 1999

View full text Add to dashboard Cite

show abstract

“…Both electron and hydrogen abstraction mechanisms have been suggested in studies on monoamine without oxygen present (Audeh and Smith, 1970;Hull et al, 1969a;Hull et al, 1967) resulting in aldehyde and ammonia or alkylamine through carbon-nitrogen scission. Dennis suggested that β-amino and β-hydroxyamines instead started with a carbon-carbon cleavage, in the end giving formaldehyde and ammonia for MEA (Dennis et al, 1967). In addition Nicolet showed that DEA was split to 4 moles of formic acid and 1 mole of ammonia using periodic acid (Nicolet and Shinn, 1939).…”

Section: Other Aminesmentioning

confidence: 99%

Oxidative degradation of amines using a closed batch system

Vevelstad

Grimstvedt

Einbu

et al. 2013

International Journal of Greenhouse Gas Control

View full text Add to dashboard Cite

Oxidative degradation experiments on five amines and two amino acids were performed in a new closed setup at atmospheric pressure. For most of the amines/amino acids significant degradation was not present under these conditions, except for MEA and MMEA. The degradation compounds found seem to follow the same patterns as described in literature. Volatile compounds as ammonia and alkylamine play an important role in understanding the initial degradation mechanisms. For MMEA, methylamine and ammonia were found in the same order of magnitude. Oxygen stochiometry of the degradation compounds could not be explained by initial air in the system. Oxygen in some of the degradation compounds could come from oxygen diffusing into the system as seen from proposed model and/or water reacting with iminium giving aldehyde and amine/ammonia. Temperature and dissolved metal seemed to influence oxygen and degradation rate for the MEA experiments.

show abstract

“…8 Therefore, it is expected that both imines 4A and 4B undergo hydrolysis to give the expected products with free amino and aldehyde functionality. It is also known that imines can undergo trimerization process View Article Online resulting in cyclic products, 56 and in the protic solvent the equilibrium between trimers and monomers is promoted.…”

Section: 55mentioning

confidence: 99%

Base-catalyzed reactions of environmentally relevant N-chloro-piperidines. A quantum-chemical study

2011

View full text Add to dashboard Cite

Electronic structure methods have been applied to calculate the gas and aqueous phase reaction energies for base-induced rearrangements of N-chloropiperidine, N-chloro-3-(hydroxymethyl)piperidine, and N-chloro-4-(4-fluorophenyl)-3-(hydroxymethyl)piperidine. These derivatives have been selected as representative models for studying the chemical fate of environmentally relevant chloramines. The performance of different computational methods (MP2, MP4, QCISD, B3LYP and B2PLYP) for calculating the thermochemistry of rearrangement reactions was assessed. The latter method produces energies similar to those obtained at G3B3(+) level, which themselves have been tested against experimental results. Experimental energy barriers and enthalpies for ring inversion, nitrogen inversion and dehydrochlorination reactions in N-chloropiperidine have been accurately reproduced when solvent effects have been included. It was also found that the combined use of continuum solvation models (e.g. CPCM) and explicit consideration of a single water molecule is sufficient to properly describe the water-assisted rearrangement of N-chlorinated compounds in basic media. In the case of N-chloro-4-(4-fluorophenyl)-3-(hydroxymethyl)piperidine, which represents the chlorinated metabolite of the antidepressant paroxetine, several different reactions (intramolecular addition, substitution, and elimination reactions) have been investigated. Transition state structures for these processes have been located together with minimum energy structures of conceivable products. Imine 4A is predicted to be the most stable reaction product, closely followed by imine 4B and oxazinane 8, while formation of isoxazolidine 7 is much less favourable. Calculated reaction barriers in aqueous solution are quite similar for all four processes, the lowest barrier being predicted for the formation of imine 4A.

show abstract

Oxidations of amines. IV. Oxidative fragmentation

Cited by 78 publications

References 0 publications

Novel Carbon-Carbon Bond Oxidative Cleavage of Hexabenzylhexaazaisowurtzitane by n-BuONO and (NH4)2Ce(NO3)6

Novel Carbon-Carbon Bond Oxidative Cleavage of Hexabenzylhexaazaisowurtzitane by n-BuONO and (NH4)2Ce(NO3)6

Oxidative degradation of amines using a closed batch system

Base-catalyzed reactions of environmentally relevant N-chloro-piperidines. A quantum-chemical study

Contact Info

Product

Resources

About