Determination of Micro Quantities of the C<sub>1</sub>-C<sub>4</sub> Primary and Secondary Amines by Electron Affinity Detection.

Day, Edgar W.; Gołab, T; Koons, J R

doi:10.1021/ac60240a024

Cited by 42 publications

(14 citation statements)

References 30 publications

(12 reference statements)

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“…61 The hydrazones were also prepared by a literature method. 62 Other compounds: N-ethyl-N-methyl-4-nitrosoaniline 22, 63 N-ethyl-N-methyl-2-nitroaniline 23, 64 N-ethyl-N-methyl-2,4-dinitroaniline 18, 65 N-ethyl-N-methyl-4chloro-2-nitroaniline 33. 66…”

Section: Synthesismentioning

confidence: 99%

The mechanistic origin of regiochemical changes in the nitrosative N-dealkylation of N,N-dialkyl aromatic amines

Teuten

Loeppky

2005

Org. Biomol. Chem.

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The regioselectivity of the nitrous acid mediated dealkylation of 4-substituted-N-ethyl-N-methylanilines is a function of the acidity of the reaction mixture. At high acidity deethylation predominates, whereas demethylation is the predominant reaction in nitrosamine formation at pH 2 and above. In some cases the regioselectivity of nitrosative dealkylation changes as the run proceeds. Through the use of the corresponding 4-nitroaniline as the primary substrate, CIDNP, kinetics, kinetic deuterium isotope effects and other transformations involving nitrosations with NO2 or NOBF4 in aprotic solvents, a new mechanism of tertiary amine nitrosation has been deduced and proposed to explain regioselective deethylation. The mechanism involves the oxidation of the substrate to the amine radical cation by NO+. This is followed by the abstraction of a hydrogen atom from the carbon adjacent to the amine nitrogen by NO2 to produce an iminium ion which reacts further to produce the corresponding aldehyde and the nitrosamine. Depending upon the acidity, this process competes with three other mechanistic pathways, two of which give the nitrosamine through the iminium ion, and one leads to the formation of C-nitro compounds. The competing pathways to nitrosamine formation involve NOH elimination from a nitrosammonium ion and deprotonation of the radical cation to give an alpha-amino radical which rapidly oxidized to the iminium ion. Predominant, but not highly regioselective demethylation occurs by these pathways. Nitro compound formation principally arises from the reaction of NO2 with the radical cation followed by deprotonation, but also occurs by para C-nitrosation followed by oxidation.

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Section: Synthesismentioning

confidence: 99%

The mechanistic origin of regiochemical changes in the nitrosative N-dealkylation of N,N-dialkyl aromatic amines

Teuten

Loeppky

2005

Org. Biomol. Chem.

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“…2,6-Dinitrofluorobenzene (DNFB) (Eastman Organic Chemicals, Rochester, NY) was used as received. Di-n-propyl-2,6dinitroaniline (DPA-DNFB) and n-propyl-2,6-dinitroaniline (NPA-DNFB) were synthesized by the method of Day et al (1966). Potassium ferrioxalate was prepared according to the method of Hatchard and Parker (1956).…”

Section: Acknowledgmentmentioning

confidence: 99%

“…The analyses for NPA and DPA were performed on the aqueous photolysis solutions using a method similar to that developed by Day et al (1966). A 10.0-mL portion of each solution was placed in a 125-mL boiling flask.…”

Section: Acknowledgmentmentioning

confidence: 99%

Photolysis of N-nitrosodi-n-propylamine in water

Saunders¹,

Mosier²

1980

J. Agric. Food Chem.

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“…The reagents used in these derivatizations have the disadvantage of reacting with water, which limits their applicability to organic solvent extracts of amines. Direct derivatization of amines in water with reagents such as o-phthaladehyde (12), dinitrofluorobenzene (13,14), and 2-methoxy-2,4-diphenyl-3(277)-furanone (15) have been reported. These direct methods lack one or more of the following desirable features: sensitivity, selectivity for primary amines, and chromatographic resolution.…”

mentioning

confidence: 99%

Gas chromatography/mass spectrometry determination of water-soluble primary amines as their pentafluorobenzaldehyde imines

Avery¹,

Junk²

1985

Anal. Chem.

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Primary aliphatic amines present at trace levels In water samples were converted to Imine derivatives using pentafluorobenzaldehyde. The derivatives were extracted Into hexane and measured by combined hlgh-resolutlon gas chromatography/mass spectrometry using multiple Ion monitoring. The detection limit of this method for determining amines was 10 ppb for 0.5-mL samples of tap, river, and oil shale process waters.

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Determination of Micro Quantities of the C₁-C₄ Primary and Secondary Amines by Electron Affinity Detection.

Cited by 42 publications

References 30 publications

The mechanistic origin of regiochemical changes in the nitrosative N-dealkylation of N,N-dialkyl aromatic amines

The mechanistic origin of regiochemical changes in the nitrosative N-dealkylation of N,N-dialkyl aromatic amines

Photolysis of N-nitrosodi-n-propylamine in water

Gas chromatography/mass spectrometry determination of water-soluble primary amines as their pentafluorobenzaldehyde imines

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Determination of Micro Quantities of the C1-C4 Primary and Secondary Amines by Electron Affinity Detection.

Cited by 42 publications

References 30 publications

The mechanistic origin of regiochemical changes in the nitrosative N-dealkylation of N,N-dialkyl aromatic amines

The mechanistic origin of regiochemical changes in the nitrosative N-dealkylation of N,N-dialkyl aromatic amines

Photolysis of N-nitrosodi-n-propylamine in water

Gas chromatography/mass spectrometry determination of water-soluble primary amines as their pentafluorobenzaldehyde imines

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Determination of Micro Quantities of the C₁-C₄ Primary and Secondary Amines by Electron Affinity Detection.