The Reaction of Disubstituted Nitrosamines with Lithium Aluminum Hydride<sup>1</sup>

Hanna, Calvin; Schueler, F. W.

doi:10.1021/ja01134a507

Cited by 12 publications

(2 citation statements)

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“…Catalytic hydrogenation was of interest for industrial purposes, and Pd/C, Pt/C, and Rh/C all yield the corresponding hydrazines, although the yield of 27 is strongly dependent on reaction conditions and the identity of 1 . , The yield of 27 by catalytic hydrogenation is improved by the inclusion of a salt (e.g., NH 4 OAc, CaCl 2 ) in the reaction mixture . Hydride reduction using LAH generally provides fair to good yields of 1,1-dialkyl or 1,1-alkylaryl 27 , ,− but diarylnitrosamines are easily over-reduced to give the parent amine and ammonia unless the reaction conditions are carefully controlled . Reduction of 1 can be effected with sodium metal in either absolute ethanol or ethanol in liquid ammonia, but the yield is lower than with LAH for many substrates .…”

Section: Reactions Of Nitrosamines In the Ground Statementioning

confidence: 99%

An Organic Chemist’s Guide to N-Nitrosamines: Their Structure, Reactivity, and Role as Contaminants

2021

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N-Nitrosamines are a class of compounds notorious both for the potent carcinogenicity of many of its members and for their widespread occurrence throughout the human environment, from air and water to our diets and drugs. Considerable effort has been dedicated to understanding Nnitrosamines as contaminants, and methods for their prevention, remediation, and detection are ongoing challenges. Understanding the chemistry of N-nitrosamines will be key to addressing these challenges. To facilitate such understanding, we focus in this Perspective on the structure, reactivity, and synthetic applications of N-nitrosamines with an emphasis on alkyl N-nitrosamines. The role of Nnitrosamines as water contaminants and the methods for their detection are also discussed.N-Nitrosamines (or simply "nitrosamines") are a class of compounds sharing the general structure 1 (Chart 1), where

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Section: Reactions Of Nitrosamines In the Ground Statementioning

confidence: 99%

An Organic Chemist’s Guide to N-Nitrosamines: Their Structure, Reactivity, and Role as Contaminants

2021

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“…Several methods are possible for its reduction [2][3][4][5][6][7][8][9][10][11][12]. Nevertheless, it must be handled with a lot of precaution because of its highly carcinogenic properties, which complicates synthesis on an industrial scale.…”

Section: )mentioning

confidence: 99%

Kinetics of the oxidation of N-aminopiperidine with chloramine

Darwich

Elkhatib²,

Steinhäuser³

et al. 2009

Kinet Catal

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The kinetics of the oxidation of N-aminopiperidine with chloramine was studied at different temperatures, with variable concentrations of the two reactants and at a pH ranging between 12 and 13.5. The reaction showed to be involving two steps: the first corresponded to the formation of a diazene intermediate, the second to the evolution of this intermediate into numerous compounds within a complex reactional chain. The rate law of the first step was determined by the Ostwald method and 2 found to be first order with respect to each reactant. The rate constant was determined at pH = 12.89 and T = 25°C: k 2 = 1.15 × 10 5 exp(-39/RT) M -1 s -1 (E 2 in kJ mol -1 )With decreasing pH value, the first step exhibited acid catalysis phenomena, and diazene was converted into azopiperidine particularly faster. This created overlapping UV-absorptions between chloramine and azopiperidine, also observed in HPLC. GC/MS analyses were used to identify some of the numerous by-products formed. Their proportions are dependent of both pH and the reactants' concentrations ratio. A reaction mechanism taking this relationship into account, was suggested.

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Chlorine‐Atom Transfer Reactions between Chloramine (=Chloramide) and Piperidine: Kinetic Reactivity and Characterization in a Raschig Medium

Darwich

Elkhatib²,

Steinhäuser

et al. 2009

Helvetica Chimica Acta

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The kinetics of the Cl-transfer reaction between chloramine (1) and piperidine (2) in a Raschig medium (8 < pH < 9) was studied at various temperatures, with variable concentrations of the two reactants. The influence of the pH on the interaction of 1 and 2 was examined at a pH ranging between 8.25 and 12.89. The Cl-transfer reaction resulted in the formation of 1-chloropiperidine (3), which, in the presence of NaOH, underwent a dehydrohalogenation leading to an endocyclic imine derivative: 2,3,4,5-tetrahydropyridine (4). The kinetics of the dehydrohalogenation was also studied at different temperatures, with variable concentrations of 3 and NaOH. Kinetic and thermodynamic parameters were determined for the Cl-transfer and dehydrohalogenation reactions. Both 3 and 4 were prepared according to efficient synthetic routes; they were isolated, purified, and characterized by elemental analysis, IR, 1 H-and 13 C-NMR, and MS. Their thermal stabilities were evaluated by differential scanning calorimetry (DSC), and their absorption coefficients at various wavelengths were determined experimentally by UV spectrophotometry.

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The Reaction of Disubstituted Nitrosamines with Lithium Aluminum Hydride¹

Cited by 12 publications

References 0 publications

An Organic Chemist’s Guide to N-Nitrosamines: Their Structure, Reactivity, and Role as Contaminants

An Organic Chemist’s Guide to N-Nitrosamines: Their Structure, Reactivity, and Role as Contaminants

Kinetics of the oxidation of N-aminopiperidine with chloramine

Chlorine‐Atom Transfer Reactions between Chloramine (=Chloramide) and Piperidine: Kinetic Reactivity and Characterization in a Raschig Medium

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The Reaction of Disubstituted Nitrosamines with Lithium Aluminum Hydride1

Cited by 12 publications

References 0 publications

An Organic Chemist’s Guide to N-Nitrosamines: Their Structure, Reactivity, and Role as Contaminants

An Organic Chemist’s Guide to N-Nitrosamines: Their Structure, Reactivity, and Role as Contaminants

Kinetics of the oxidation of N-aminopiperidine with chloramine

Chlorine‐Atom Transfer Reactions between Chloramine (=Chloramide) and Piperidine: Kinetic Reactivity and Characterization in a Raschig Medium

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The Reaction of Disubstituted Nitrosamines with Lithium Aluminum Hydride¹