Flow nuclear magnetic resonance study of the dehydration of the tetrahedral intermediate resulting from the addition of hydroxylamine to acetaldehyde

Cocivera, Michael; Fyfe, C. A.; Effio, Adan; Vaish, Shiv P.; Chen, Holger E.

doi:10.1021/ja00422a049

Cited by 32 publications

(11 citation statements)

References 2 publications

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“…We note that many carbinolamines formed from carbonyl-amine reactions are relatively long-lived with laboratory studies indicating a slow reverse reaction, with the carbinolamine intermediates remaining stable for several hours even in solution. 45,46 Hence given the abundance of organics with carbonyl functional groups and their importance in secondary aerosol growth, the current findings have important implication for atmospheric chemistry. In particular, our results suggest that as atmospheric carbonyl compounds become more oxygenated, their addition reactions will occur with greater efficiency and with a larger range of amines.…”

Section: Introductionmentioning

confidence: 81%

Oxygenate-Induced Tuning of Aldehyde-Amine Reactivity and Its Atmospheric Implications

et al. 2017

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Atmospheric aerosols often contain a significant fraction of carbon-nitrogen functionality, which makes gas-phase aldehyde-amine chemistries an important source of nitrogen containing compounds in aerosols. Here we use high-level ab initio calculations to examine the key determinants of amine (ammonia, methylamine, and dimethylamine) addition onto three different aldehydes (acetaldehyde, glycolaldehyde, and 2-hydroperoxy acetaldehyde), with each reaction being catalyzed by a single water molecule. The model aldehydes reflect different degrees of oxygenation at a site adjacent to the carbonyl moiety, the α-site, and represent typical oxygenates that can arise from atmospheric oxidation especially under conditions where the concentration of NO is low. Our results show that the reaction barrier is influenced not only by the nature of the amine but also by the nature of the aldehyde. We find that, for a given amine, the reaction barrier decreases with increasing oxygenation of the aldehyde. This observed trend in barrier height can be explained through a distortion/interaction analysis, which reveals a gradual increase in internal hydrogen bonding interactions upon increased oxygenation, which, in turn, impacts the reaction barrier. Further, the calculations reveal that the reactions of methylamine and dimethylamine with the oxygenated aldehydes are barrierless under catalysis by a single water molecule. As a result, we expect these addition reactions to be energetically feasible under atmospheric conditions. The present findings have important implications for atmospheric chemistry as amine-aldehyde addition reactions can facilitate aerosol growth by providing low-energy neutral pathways for the formation of larger, less volatile compounds, from readily available smaller components.

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Section: Introductionmentioning

confidence: 81%

Oxygenate-Induced Tuning of Aldehyde-Amine Reactivity and Its Atmospheric Implications

et al. 2017

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“…We note that many carbinolamines have been observed to behave as long-lived intermediates, and laboratory studies of several carbonyl-amine reactions have revealed a slow reverse reaction, with the carbinolamine remaining stable for several hours even in solution. 75,76 Hence, under atmospheric conditions, the hydrogen atoms associated with the terminal methyl groups of the carbinolamine, such as that generated by the DMA + H 2 CO + H 2 O reaction, can provide reaction sites amenable to rapid attack by atmospheric OH radicals. The attack by OH followed by the subsequent reaction of the newly formed radical centers with atmospheric O 2 and NO, as shown in eq 5, can then lead to the formation of additional new carbonyl sites.…”

Section: The Journal Of Physical Chemistry Amentioning

confidence: 99%

Dimethylamine Addition to Formaldehyde Catalyzed by a Single Water Molecule: A Facile Route for Atmospheric Carbinolamine Formation and Potential Promoter of Aerosol Growth

et al. 2015

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We use ab initio calculations to investigate the energetics and kinetics associated with carbinolamine formation resulting from the addition of dimethylamine to formaldehyde catalyzed by a single water molecule. Further, we compare the energetics for this reaction with that for the analogous reactions involving methylamine and ammonia separately. We find that the reaction barrier for the addition of these nitrogen-containing molecules onto formaldehyde decreases along the series ammonia, methylamine, and dimethylamine. Hence, starting with ammonia, the reaction barrier can be "tuned" by the substitution of an alkyl group in place of a hydrogen atom. The reaction involving dimethylamine has the lowest barrier with the transition state being 5.4 kcal/mol below the (CH3)2NH + H2CO + H2O separated reactants. This activation energy is significantly lower than that for the bare reaction occurring without water, H2CO + (CH3)2NH, which has a barrier of 20.1 kcal/mol. The negative barrier associated with the single-water molecule catalyzed reaction of dimethylamine with H2CO to form the carbinolamine (CH3)2NCH2OH suggests that this reaction should be energetically feasible under atmospheric conditions. This is confirmed by rate calculations which suggest that the reaction will be facile even in the gas phase. As amines and oxidized organics containing carbonyl functional groups are common components of secondary organic aerosols, the present finding has important implications for understanding how larger, less volatile organic compounds can be generated in the atmosphere by combining readily available smaller components as required for promoting aerosol growth.

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“…The presence of carbinolamine compounds is not wholly unexpected as they are the intermediate compounds to imine formation via reactions between carbonyl compounds and primary or secondary amines. These compounds have been observed as intermediates in other carbonyl-amine reactions and have been shown to have a slow reverse reaction, remaining stable in solution for up to 24 h (Cheung et al, 2005;Cocivera et al, 1976;Pedersen et al, 1999).…”

Section: Mass Spectrum Interpretationmentioning

confidence: 99%

Secondary organic aerosol formation from primary aliphatic amines with NO<sub>3</sub> radical

Malloy

Warren

et al. 2009

Atmos. Chem. Phys.

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Abstract. Primary aliphatic amines are an important class of nitrogen containing compounds emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with O 3 and NO 3 have been investigated. Very little aerosol formation is observed in the presence of O 3 only. However, after addition of NO, and by extension NO 3 , large aerosol mass yields (∼44% for butylamine) are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO 2 in the total signal (<1% for all amines tested) as detected by an aerosol mass spectrometer (AMS). We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities with elevated nighttime PM loadings, when significant levels of NO 3 exist.

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Flow nuclear magnetic resonance study of the dehydration of the tetrahedral intermediate resulting from the addition of hydroxylamine to acetaldehyde

Cited by 32 publications

References 2 publications

Oxygenate-Induced Tuning of Aldehyde-Amine Reactivity and Its Atmospheric Implications

Oxygenate-Induced Tuning of Aldehyde-Amine Reactivity and Its Atmospheric Implications

Dimethylamine Addition to Formaldehyde Catalyzed by a Single Water Molecule: A Facile Route for Atmospheric Carbinolamine Formation and Potential Promoter of Aerosol Growth

Secondary organic aerosol formation from primary aliphatic amines with NO<sub>3</sub> radical

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Flow nuclear magnetic resonance study of the dehydration of the tetrahedral intermediate resulting from the addition of hydroxylamine to acetaldehyde

Cited by 32 publications

References 2 publications

Oxygenate-Induced Tuning of Aldehyde-Amine Reactivity and Its Atmospheric Implications

Oxygenate-Induced Tuning of Aldehyde-Amine Reactivity and Its Atmospheric Implications

Dimethylamine Addition to Formaldehyde Catalyzed by a Single Water Molecule: A Facile Route for Atmospheric Carbinolamine Formation and Potential Promoter of Aerosol Growth

Secondary organic aerosol formation from primary aliphatic amines with NO&lt;sub&gt;3&lt;/sub&gt; radical

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Secondary organic aerosol formation from primary aliphatic amines with NO<sub>3</sub> radical