13463-94-0Relevant articles and documents
Oxidation of N-4-chlorophenyl-N′-hydroxyguanidine to N-(4-chlorophenyl)urea and nitric oxide by photoexcited iron porphyrins
Maldotti, Andrea,Molinari, Alessandra,Vitali, Irene,Ganzaroli, Elena,Battioni, Pierrette,Mathieu, Delphine,Mansuy, Daniel
, p. 3127 - 3135 (2004)
Photochemical excitation (λ > 350 nm) of chloro[meso-tetrakis(2, 6-dichlorophenyl)porphyrin]iron(III) [FeIII(TDCPP)Cl] and chloro[meso-tetra(α,α,α,α-pivalamidophenyl)porphyrin] -iron(III) [FeIII(TpivPP)Cl] induces the oxidation of coordinated N-(4-chlorophenyl)-N′-hydroxyguanidine (1) by molecular oxygen, to give iminoxyl radicals and the FeII(O2) [or Fe III(O2.)] adduct. This complex can be accumulated in significant amounts using [FeIII(TpivPP)Cl]. The primary photoproducts give rise to secondary reactions that lead to the formation of N-4-chlorophenyl)urea (2) as the main end-product of 1. The conversion of 1 into 2 is accompanied by the formation of NO, as revealed both by an ESR spin-trapping technique and in the form of its stable end-products NO2- and NO3-. The presence of 1-methyl imidazole (1-MeIm) coordinated in axial position has a significant positive effect on the photoinduced production of 2 and NO from the hydroxyguanidine 1. The observation that radical scavengers inhibit the photooxidation process strongly supports the possibility that the reaction pathway resembles a radical-type autoxidation mechanism, where the very fast reaction of O2 with the ferrous porphyrin in the presence of the photo-generated iminoxyl radical should yield an iron-peroxo intermediate as precursor of the urea 2 and NO. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
CF3SO2Na as a Bifunctional Reagent: Electrochemical Trifluoromethylation of Alkenes Accompanied by SO2 Insertion to Access Trifluoromethylated Cyclic N-Sulfonylimines
He, Zeying,Jiao, Lingcong,Li, Zheng,Liao, Wei-Wei,Sun, Yunhai,Wei, Zhonglin
supporting information, p. 7266 - 7270 (2020/03/23)
An unprecedented electrochemical trifluoromethylation/SO2 insertion/cyclization process has been achieved in an undivided cell in an atom-economic fashion. The protocol relies on tandem cyclization of N-cyanamide alkenes by using Langlois’ reagent as a source of both CF3 and SO2 under direct anodically oxidative conditions, in which two C?C bonds, two C?X bonds (N?S and S?C), and two rings were formed in a single operation. This transformation enabled efficient construction of various trifluoromethylated cyclic N-sulfonylimines from readily accessible materials.
A cascade process for directly converting nitriles (RCN) to cyanamides (RNHCN) via SO2F2-activated Tiemann rearrangement
Zhang, Guofu,Zhao, Yiyong,Ding, Chengrong
, p. 7684 - 7688 (2019/08/30)
A simple, mild and practical process for the direct conversion of nitriles to cyanamides was newly discovered and exhibited a wide substrate scope as well as great functional group-tolerability (36 examples). In this efficient strategy, the in situ generated amidoximes obtained from the reaction of nitriles with hydroxylamine subsequently underwent Tiemann rearrangement, producing the corresponding cyanamides with great isolated yields under SO2F2. Additionally, the control experiments reportedly shed light on the tentative mechanism involved in the formation and elimination of the key intermediate: a sulfonyl ester.