614-00-6Relevant articles and documents
Nitrosothiosulphate Ion (S2O3NO-) as a Nitrosating Species
Bryant, Tracey,Williams, D. Lyn H.,Ali, M. Hoshair H.,Stedman, Geoffrey
, p. 193 - 196 (1986)
Analysis of rate data obtained for the nitrosation of N-methylaniline in the presence of thiosulphate ion indicates that the nitrosothiosulphate ion is formed and that it acts as a nitrosating species.The bimolecular rate constant for reaction in water at 25 deg C is evaluated as 1.2E4 l mol-1 s-1 from the variation of the observed rate constant with and also as 1.2E4 l mol-1 s-1 from the variation of the observed rate constant with .Results are also reported, for comparison purposes, for the corresponding reactions of nitrosyl bromide and nitrosyl thiocyanate.Nitrosyl bromide (in its reaction with N-methylaniline) is more reactive than the nitrosothiosulphate ion by a factor of ca. 4E-5, and nitrosyl thocyanate is more reactive than the nitrosothiosulphate ion by a factor of ca.1.5E-4.There is also kinetic evidence of nitrosation by the nitrosothiosulphate ion of methanol, hydrazine, and a thiol.The decomposition of S2O3NO(-) follows the rate law -d/dt=k1+k22.This is interpreted in terms of two concurrent reaction pathways, the first involving the formation of the radical anion S2O3-. in a rate-limiting homolysis (followed by rapid dimerisation) and the second a bimolecular reaction of two S2O3NO(-) ions homolysis (followed by rapid dimrisation) and the second a bimolecular reaction of two S2O3NO(-) ions with concurrent S-N bond fission and S-S bond formation yielding the tetrathionate ion S4O6(2-).
Kinetic Studies on the Formation of N-Nitroso Compounds IX. Nitrosyl Acetate as a Nitrosating Agent
Casado, Julio,Castro, Albino,Mosquera, Manuel,Prieto, M. Flor Rodriguez,Tato, Jose Vazquez
, p. 669 - 682 (1984)
A study of the nitrosation of N-methylaniline and piperazine by nitrous acid in acetate buffer supports a mechanism covering both reactions, whose effective pathway depends on the relationship between the concentrations of nitrite ion, acetate ion, and nitrosatable substrate.In the case of N-methylaniline the only nitrosating agent is nitrosyl acetate, whereas in the nitrosation of piperazine the nitrous acidium ion and dinitrogen trioxide are also involved.The results obtained seem to show that nitrosation by nitrosyl acetate is diffusion controlled.On this assumpti on, the equilibrium constant of the reaction AcOH + HNO2 AcONO + H2O has been estimated from kinetic measurements as approximately 1.4*E-8 M-1.This means that the concentration of nitrosyl acetate in the medium must be extremely small, which explains the virtual impossibility of detecting it in aqueous solution except by kinetic methods. - (Keywords: Acetate buffer; Kinetics of nitrosation; Nitroso compounds; Nitrosyl acetate)
One-Pot Tandem ortho-Naphthoquinone-Catalyzed Aerobic Nitrosation of N-Alkylanilines and Rh(III)-Catalyzed C-H Functionalization Sequence to Indole and Aniline Derivatives
Si, Tengda,Kim, Hun Young,Oh, Kyungsoo
, p. 1152 - 1163 (2021/01/14)
The nitroso group served as a traceless directing group for the C-H functionalization of N-alkylanilines, ultimately removed after functioning either as an internal oxidant or under subsequent reducing conditions. The unique ability of o-NQ catalysts to aerobically oxidize the N-alkylanilines without using solvents and stoichiometric amounts of oxidants has rendered the new opportunity to develop the telescoped catalyst systems without a need for directly handling the hazardous N-nitroso compounds.
Three-Component Couplings among Heteroarenes, Difluorocyclopropenes, and Water via C-H Activation
Liu, Xuexin,Chen, Jian,Yang, Chunyan,Wu, Zhouping,Li, Zhiyang,Shi, Yuesen,Huang, Tianle,Yang, Zhongzhen,Wu, Yong
supporting information, p. 6831 - 6835 (2021/09/08)
Three-component couplings have been realized for efficiently constructing various nitrogen-containing skeletons via C-H activation, where difluorocyclopropenes have been first identified as coupling partners. Many substrates including sp2 and sp3 C-H substrates were well tolerated, furnishing the corresponding products in good yields. Furthermore, a catalyst-dependent reaction was also developed, enabling divergent construction of two different frameworks. The application value of these reactions was demonstrated in gram-scale experiments with as little as 1 mol % catalyst.
Rhodium-catalyzed tandem acylmethylation/annulation ofN-nitrosoanilines with sulfoxonium ylides for the synthesis of substituted indazoleN-oxides
Cui, Xin-F,Huang, Guo-Sh
supporting information, p. 4014 - 4018 (2020/06/09)
An atom-economical protocol for synthesizing indazoleN-oxides from readily availableN-nitrosoanilines and sulfoxonium ylides through the rhodium(iii)-catalyzed C-H activation and cyclization reaction is described here. This protocol employs nitroso as a traceless directing group. The transformation features powerful reactivity, tolerates various functional groups, and proceeds with moderate to good yields under an ambient atmosphere, providing a straightforward approach to access structurally diverse and valuable indazoleN-oxide derivatives. Importantly, this new annulation process represents a hitherto unobserved reactivity pattern for theN-nitroso group.
Rh(iii)-catalyzed, hydrazine-directed C-H functionalization with 1-alkynylcyclobutanols: A new strategy for 1: H -indazoles
Zhang, Lei,Chen, Junyu,Chen, Xiahe,Zheng, Xiangyun,Zhou, Jian,Zhong, Tianshuo,Chen, Zhiwei,Yang, Yun-Fang,Jiang, Xinpeng,She, Yuan-Bin,Yu, Chuanming
supporting information, p. 7415 - 7418 (2020/07/15)
Rh(iii)-catalyzed coupling of phenylhydrazines with 1-alkynylcyclobutanols was realized through a hydrazine-directed C-H functionalization pathway. This [4+1] annulation, based on the cleavage of a Csp-Csp triple bond in alkynylcyclobutanol, provides a new pathway to prepare diverse 1H-indazoles under mild reaction conditions. This journal is
Substrate promiscuity of ortho-naphthoquinone catalyst: Catalytic aerobic amine oxidation protocols to deaminative cross-coupling and n-nitrosation
Kim, Hun Young,Oh, Kyungsoo,Si, Tengda
, p. 9216 - 9221 (2019/10/08)
ortho-Naphthoquinone-based organocatalysts have been identified as versatile aerobic oxidation catalysts. Primary amines were readily cross-coupled with primary nitroalkanes via deaminative pathway to give nitroalkene derivatives in good to excellent yields. Secondary and tertiary amines were inert to ortho-naphthoquinone catalysts; however, secondary nitroalkanes were readily converted by ortho-naphthoquinone catalysts to the corresponding nitrite species that in situ oxidized the amines to the corresponding N-nitroso compounds. Without using harsh oxidants in a stoichiometric amount, the present catalytic aerobic oxidation protocol utilizes the substrate promiscuity feature to provide a facile access to amine oxidation products under mild reaction conditions.
Rhodium(iii)-catalyzed indole synthesis at room temperature using the transient oxidizing directing group strategy
Shang, Yaping,Jonnada, Krishna,Yedage, Subhash Laxman,Tu, Hua,Zhang, Xiaofeng,Lou, Xin,Huang, Shijun,Su, Weiping
supporting information, p. 9547 - 9550 (2019/08/15)
Rh-catalyzed reactions of N-alkyl anilines with internal alkynes at room temperature have been developed using an in situ generated N-nitroso group as a transient oxidizing directing group. Due to mild reaction conditions, this method enabled synthesis of a broad range of N-alkyl indoles, including even two indole-based medicinal compounds. Our work disclosed the feasibility of the transient oxidizing directing group strategy in C-H functionalization reactions, which possesses the potential to enhance overall step-economy and impart new reactivity patterns to substrates.
Synthesis of 2-aminobenzophenones through acylation of anilines with α-oxocarboxylic acids assisted by: Tert -butyl nitrite
Wang, Qianqian,Zhang, Xinying,Fan, Xuesen
, p. 7737 - 7747 (2018/11/02)
In this paper, a regioselective, efficient and convenient synthesis of 2-aminobenzophenones through acylation of anilines with α-oxocarboxylic acids assisted by tert-butyl nitrite is presented. Interestingly, tert-butyl nitrite acts as not only an efficient and mild nitrosation reagent, but also a sustainable oxidant required in the Pd(ii)-catalyzed decarboxylative acylation. Meanwhile, the NO unit turned out to be an easily introduced and readily removable directing group for the regioselective acylation.
Direct Transformation of Arylamines to Aryl Halides via Sodium Nitrite and N-Halosuccinimide
Mukhopadhyay, Sushobhan,Batra, Sanjay
supporting information, p. 14622 - 14626 (2018/09/21)
A one-pot universal approach for transforming arylamines to aryl halides via reaction with sodium nitrite (NaNO2) and N-halosuccinimide (NXS) in DMF at room temperature under metal- and acid-free condition is described. This new protocol that is complementary to the Sandmeyer reaction, is suggested to involve the in situ generation of nitryl halide induce nitrosylation of aryl amine to form the diazo intermediate which is halogenated to furnish the aryl halide.
