4463-22-3Relevant articles and documents
Catalyst-free generation of acyl radicals induced by visible light in water to construct C-N bonds
Ran, Maogang,He, Jiaxin,Yan, Boyu,Liu, Wenbo,Li, Yi,Fu, Yunfen,Li, Chao-Jun,Yao, Qiuli
supporting information, p. 1970 - 1975 (2021/03/16)
We describe herein a catalyst-free and redox-neutral photochemical strategy for the direct generation of acyl radicals from α-diketones, and its selective conversion of nitrosoarenes to hydroxyamides or amides with AcOH or NaCl as an additive. The reaction was carried out under mild conditions in water with purple LEDs as the light source. A broad scope of substrates was demonstrated. Mechanistic experiments indicate that α-diketones cleave to give acyl radicals, with hydroxyamides being further reduced to amides.
Synthesis of site-specific damaged DNA strands by 8-(acetylarylamino)- 2′-deoxyguanosine adducts and effects on various DNA polymerases
Krueger, Sarah,Meier, Chris
, p. 1158 - 1169 (2013/04/10)
Beside the predominately found 8-(arylamino)-2′-dG, 8-(acetylarylamino) damages within DNA-strands may also play an important role in the induction of chemical carcinogenesis. A synthesis pathway leading to these 8-(acetylarylamino)-dG adducts using different aromatic amines has been optimized. The 8-modified dGs were converted into the corresponding phosphoramidites and site-specifically incorporated into different oligonucleotides leading to DNA strands. Lesion-bearing hybrids of these damaged DNA-strands with complementary oligonucleotides were used to study their melting properties and their circular dichroism spectra. It was shown that no EcoRI restriction took place with the damage inside the cleavage site. Finally, three different DNA polymerases were used for primer extension studies. C8-NAc-Arylamine adducts of 2′-deoxyguanosine with various aromatic amines were synthesized by using cross-coupling reactions and converted into 3′-phosphoramidites. Site-specific damaged NarI-, EcoRI- and 20mer-oligonucleotides were prepared by automated DNA-synthesis. Biophysical properties, restriction endonuclease studies and DNA-polymerase assays were performed. Copyright
N-Arylhydroxamic Acids: Reaction of Nitroso Aromatics with α-Oxo Acids
Sakamoto, Yasuko,Yoshioka, Tadao,Uematsu, Takayoshi
, p. 4449 - 4453 (2007/10/02)
A practical and high-yielding route to N-arylhydroxamic acids from nitroso aromatics and α-oxo acids 1a-d is desctibed.In aqueous and acetic acid containing media, the reactions exhibit second-order reaction kinetics overall.In the aqueous medium, the rate constant (kobsd) for N-phenylacetohydroxamic acid (8b) formation increased with increasing +>, though there were some side pathways involving azoxybenzene formation.In general, kobsd for the reaction in the acetic acid containing medium was about one-tenth of that in HCl at pH 0.6.On a preparative scale, acetic acid is better than HCl, in that both reactants showed sufficient solubilities in acetic acid for a high reaction velocity and no side reaction was detected.With this method, the proximate carcinogens, N-(4-biphenylyl)acetohydroxamic acid (12b) and N-(2-fluorenyl)acetohydroxamic acid (13b), could be easily prepared.Under both conditions, the order of kobsd for the reactions of nitrosobenzene (2) with α-oxo acids 1a-d was glyoxylic (1a) > pyruvic (1b) 2-oxobutyric (1c) > benzoylformic (1d) acid.For the reactions of substituted nitrosobenzenes 3-6 with pyruvic acid (1b), the order of kobsd was p-phenyl (6) > unsubstituted (2) > p-chloro (5) > m-chloro (4) >> o-chloro (3) nitrosobenzene.The negative Hammett reaction constant value obtained indicates that an electron-donating substituent is preferable for the reaction.The reaction mechanism and other factors affecting N-arylhydroxamic acid formation are also descussed.
