5579-27-1Relevant academic research and scientific papers
Chlorotrimethylsilane, Hexamethyldisilane, and 1,2-Dimethyl-1,1,2,2-tetraphenyldisilane as Oxidizing Agents in the Conversion of Hydrazines to 2-Tetrazenes. Trimethylsilyl Anion as a Leaving Group
Hwu, Jih Ru,Wang, Naelong,Yung, Richard T.
, p. 1070 - 1073 (1989)
The possibility of the Me3Si- species to be a nucleofuge of a compound containing the NSiMe3 group was investigated.Treatment of hydrazines with 1.1 equiv of Me3SiCl, Me3SiSiMe3, or Ph2MeSiSiMePh2 in the presence of 1.0 equiv of potassium hydride gave the corresponding 2-tetrazenes (R1R2NN=NNR1R2) in fair to good yields.The hydrazines included 1-methyl-1-phenylhydrazine (9), 1-aminopiperidine (10), 1-amino-2,6-dimethylpiperidine (11), 4-aminomorpholine (12), and 1-aminohomopiperidine (13).In these reactions, Me3SiCl, Me3SiSiMe3, and Ph2MeSiSiMePh2 acted as oxidizing agents.Results from control experiments supported the proposed mechanism: silylation of hydrazines gave monosilylhydrazines, decomposition of monosilylhydrazines generated aminonitrenes, and dimerization of aminonitrenes afforded 2-tetrazenes.In the decomposition of monosilylhydrazines, Me3Si- behaved as a leaving group from the NSiMe3 moiety.
SN2 substitution reactions at the amide nitrogen in the anomeric mutagens, N-acyloxy-N-alkoxyamides
Cavanagh, Katie L.,Glover, Stephen A.,Price, Helen L.,Schumacher, Rhiannon R.
scheme or table, p. 700 - 710 (2010/02/16)
N-Acyloxy-N-alkoxyamides 1a are unusual anomeric amides that are pyramidal at the nitrogen because of bis oxyl substitution. Through this configuration, they lose most of their amide character and resemble -haloketones in reactivity. They are susceptible to SN2 reactions at nitrogen, a process that is responsible for their mutagenic behaviour. Kinetic studies have been carried out with the nucleophile N-methylaniline that show that, like SN2 reactions at carbon centres, the rate constant for SN2 displacement of carboxylate is lowered by branching to the nitrogen centre, or bulky groups on the alkoxyl side chain. Branching or bulky groups on the carboxylate leaving group, however, do not impact on the rate of substitution, which is mostly controlled by the pKA of the departing carboxylate group. These results are in line with computed properties for the model reaction of ammonia with N-acetoxy-N-methoxyacetamide but are in contrast to the role of steric effects on their mutagenicity. CSIRO 2009.
Bimolecular Reactions of Mutagenic N-Acetoxy-N-alkoxybenzamides and N-Methylaniline
Campbell, John J.,Glover, Stephen A.
, p. 1661 - 1663 (2007/10/02)
N-Methylaniline reacts bimolecularly with mutagenic N-acetoxy-N-alkoxybenzamides and the resultant N-alkoxy-N-(N-methylanilino)benzamides undergo a novel, concerted rearrangement to alkylbenzoates and 1-methyl-1-phenyldiazene which dimerizes to 1,4-dimethyl-1,4-diphenyl-tetrazene.
THE REACTIONS OF N-BENZOYLPEROXYCARBAMIC ACID WITH AZINES AND IMINES
Paredes, Rodrigo,Bastos, Holger,Montoya, Raul,Chavez, Alba Lucia,Dolbier, William R.,Burkholder, Conrad R.
, p. 6821 - 6830 (2007/10/02)
N-Benzoylperoxycarbamic acid (BPC) was found to react generally with imines and azines to form oxaziridines rather than N-oxides.The imine products were stable, but those found from azines apparently were unstable and converted to ketones or aldehydes plus diazo compounds.
OXIDATION OF HYDRAZINES WITH NITROSOBENZENES
Kano, Kunio,Koga, Masahiro,Anselme, Jean-Pierre
, p. 137 - 144 (2007/10/02)
Nitrosoarenes react with 1,1-disubstituted hydrazines to yield products of direct oxidation and the thermally stable triazene N-oxides.The triazene N-oxides undergo photoinduced fragmentation to yield products which may be rationalized through the interme
