97661-69-3Relevant academic research and scientific papers
Tert-Butyl Nitrite-Mediated Synthesis of N-Nitrosoamides, Carboxylic Acids, Benzocoumarins, and Isocoumarins from Amides
Yedage, Subhash L.,Bhanage, Bhalchandra M.
, p. 5769 - 5781 (2017/06/07)
This work reports tert-butyl nitrite (TBN) as a multitask reagent for (1) the controlled synthesis of N-nitrosoamide from N-alkyl amides, (2) hydrolysis of N-methoxyamides to carboxylic acids, (3) metal- and oxidant-free benzocoumarin synthesis from ortho-aryl-N-methoxyamides via N-H, C-N, and C-H bond activation, and (4) isocoumarin synthesis using Ru(II)/PEG as a recyclable catalytic system via ortho-C-H activation and TBN as an oxygen source. The sequential functional group interconversion of amide to acid has also been examined using IR spectroscopic analysis. Additionally, this methodology is highly advantageous due to short reaction time, gram scale synthesis, and broad substrate scope.
Reaction of N-Aryl- and N-Alkyl-benzimidoyl Chlorides with Silver Nitrate
Iley, Jim,Carvalho, Emilia,Norberto, Fatima,Rosa, Eduarda
, p. 281 - 290 (2007/10/02)
N-Arylbenzimidoyl chlorides, in which the N-aryl group is unsubstituted at the ortho- and para-positions, react with AgNO3 to yield N-(nitroaryl)benzamides, in which the NO2 group resides in the ortho- or para-position.N-Arylbenzimidoyl chlorides, in which the N-aryl ring is 2,4,6-trisubstituted, react with AgNO3 to yield the corresponding N-aryl-N-nitrobenzamides.The formation of both types of product can be explained by the intermediacy of an O-nitro imidate.Spectroscopic and chemical evidence is presented for the formation of this intermediate in the reaction of N-(2,4,6-trisubstituted phenyl)benzimidoyl chlorides with AgNO3.Rearrangement of the O-nitro imidate is unimolecular and intramolecular.The rate of rearrangement is independent of the substituent in the C-aryl ring, but increases with the electon-withdrawing ability of the substituents in the N-aryl ring.A mechanism is proposed in which the imidoyl chloride reacts with AgNO3 to produce first a nitrilium ion which goes on to form an O-nitro imidate that subsequently rearranges via a homolytic cleavage of the O-NO2 bond.The ortho:para ratios of N-(nitroaryl)benzamides obtained in the present work indicate that O-nitro imidates are not responsible for the high 1/2ortho:para ratios sometimes observed in the nitration of anilides.N-Alkylbenzimidoyl chlorides react with AgNO3 to form the corresponding N-nitro- and N-nitrosobenzamides.The mechanism of formation of the N-alkyl-N-nitrobenzamide arises from a pathway analogous to that for N-aryl-N-nitrobenzamides, involving a nitrilium ion that gives rise to an O-nitro imidate.The evidence for the formation of the N-nitrosobenzamide points to an alternative reaction of the imidoyl chloride with AgNO3.One possible mechanism for this reaction is described.
