169170-03-0Relevant articles and documents
Redox-neutral decarboxylative photocyclization of anthranilic acids
Huang, Huawen,Deng, Kun,Deng, Guo-Jun
, p. 8243 - 8247 (2020/12/29)
A mild metal-, catalyst-, and oxidant-free photoredox neutral system has been found to efficiently enable intramolecular decarboxylative cyclization of anthranilic acids. This facile protocol provides an alternative method for the synthesis of carbazoles. Mechanistic studies reveal a key photoinduced 6π-electrocyclization process and formic acid was released as the sole byproduct.
Substrate-Controlled Selectivity Switch in the Three-Component Coupling Involving Arynes, Aromatic Tertiary Amines, and CO2
Bhojgude, Sachin Suresh,Roy, Tony,Gonnade, Rajesh G.,Biju, Akkattu T.
, p. 5424 - 5427 (2016/11/04)
The transition-metal-free multicomponent coupling involving arynes, aromatic tertiary amines, and CO2 is reported. The reaction exhibits switchable selectivity depending on the electronic nature of the aromatic amines used. With amines bearing electron-releasing/neutral groups as the nucleophilic trigger, the reaction afforded 2-arylamino benzoates via a nitrogen to oxygen alkyl group migration. Employing electron-deficient amines in the reaction furnished 2-aminoaryl benzoates proceeding via the aryl to aryl amino group migration resembling a Smiles rearrangement.
PhI(OAc)2-mediated intramolecular oxidative aryl-aldehyde C sp 2-C sp 2 bond formation: Metal-free synthesis of acridone derivatives
Zheng, Zisheng,Dian, Longyang,Yuan, Yucheng,Zhang-Negrerie, Daisy,Du, Yunfei,Zhao, Kang
, p. 7451 - 7458 (2014/09/17)
A metal-free protocol for direct aryl-aldehyde Csp2-Csp 2 bond formation via a PhI(OAc)2-mediated intramolecular cross-dehydrogenative coupling (CDC) of various 2-(N-arylamino)aldehydes was developed. The novel methodology requires no need of preactivation of the aldehyde group, is applicable to a large variety of functionalized substrates, and most of all provides a convenient approach to the construction of biologically important acridone derivatives.
TRANSITION-METAL-FREE N-ARYLATION OF TERTIARY AMINES USING ARYNES
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Paragraph 0029; 0040, (2015/01/16)
The present invention relates to transition-metal-free process for the synthesis of tertiary arylamines comprises coupling reaction between arynes and N,N-dimethyl aniline compounds in presence of 18-crown-6, KF and THF.
Construction of 1,4-benzodiazepine skeleton from 2-(arylamino)benzamides through PhI(OAc)2-mediated oxidative C-N bond formation
Li, Xuming,Yang, Liu,Zhang, Xiang,Zhang-Negrerie, Daisy,Du, Yunfei,Zhao, Kang
, p. 955 - 962 (2014/03/21)
New compounds involving the biologically important 1,4-benzodiazepine skeleton were conveniently constructed from 2-(arylamino)benzamides through PhI(OAc)2-mediated oxidative C-N bond formation. The attractive features of this new synthetic strategy include mild reaction conditions, the heavy-metal-free characteristic of the oxidative coupling process, and the flexibility to tolerate a broad scope of substrates.
Employing arynes in transition-metal-free monoarylation of aromatic tertiary amines
Bhojgude, Sachin Suresh,Kaicharla, Trinadh,Biju, Akkattu T.
supporting information, p. 5452 - 5455 (2013/11/19)
The highly monoselective N-arylation of aromatic tertiary amines using a transition-metal-free approach using arynes has been developed. The reaction afforded functionalized diaryl amines in moderate to excellent yield. High levels of functional group compatibility especially with halogen containing substrates, dyes and donor-acceptor systems, and high yields of products are the notable features of the present reaction.
Sc(OTf)3-catalyzed dehydrogenative cyclization for synthesis of N-methylacridones
Li, Xi-An,Wang, Hong-Li,Yang, Shang-Dong
, p. 1794 - 1797 (2013/05/23)
A novel method has been developed for the synthesis of substituted N-methylacridones from 2-(N-methyl-N-phenylamino)benzaldehydes via dehydrogenative cyclization. This transformation involves two primary processes: the aldehyde first coordinates with Sc(OTf)3 and induces the aromatic electrophilic substitution (SEAr) reaction to form the active intermediate N-methyl-acridin-9-ol, which is then quickly oxidized in situ to afford the acridones. Furthermore, the procedure involved is both environmental friendly and atom efficient; H2O is the only byproduct in this reaction.
Detection of explosives via photolytic cleavage of nitroesters and nitramines
Andrew, Trisha L.,Swager, Timothy M.
experimental part, p. 2976 - 2993 (2011/06/21)
The nitramine-containing explosive RDX and the nitroester-containing explosive PETN are shown to be susceptible to photofragmentation upon exposure to sunlight. Model compounds containing nitroester and nitramine moieties are also shown to fragment upon exposure to UV irradiation. The products of this photofragmentation are reactive, electrophilic NOx species, such as nitrous and nitric acid, nitric oxide, and nitrogen dioxide. N,N-Dimethylaniline is capable of being nitrated by the reactive, electrophilic NOx photofragmentation products of RDX and PETN. A series of 9,9-disubstituted 9,10-dihydroacridines (DHAs) are synthesized from either N-phenylanthranilic acid methyl ester or a diphenylamine derivative and are similarly shown to be rapidly nitrated by the photofragmentation products of RDX and PETN. A new (turn-on) emission signal at 550 nm is observed upon nitration of DHAs due to the generation of fluorescent donor-acceptor chromophores. Using fluorescence spectroscopy, the presence of ca. 1.2 ng of RDX and 320 pg of PETN can be detected by DHA indicators in the solid state upon exposure to sunlight. The nitration of aromatic amines by the photofragmentation products of RDX and PETN is presented as a unique, highly selective detection mechanism for nitroester- and nitramine-containing explosives and DHAs are presented as inexpensive and impermanent fluorogenic indicators for the selective, standoff/remote identification of RDX and PETN.
Thermal decomposition of tert-butyl o-(phenoxy)- and o-(anilino)-phenyliminoxyperacetates
Calestani, Gianluca,Leardini, Rino,McNab, Hamish,Nanni, Daniele,Zanardi, Giuseppe
, p. 1813 - 1824 (2007/10/03)
Some o-phenoxy- and o-anilino-substituted aryliminyl radicals have been generated by thermal decomposition of suitable tert-butyl iminoxyperacetates. The iminyls show no disposition to give 7-membered cyclisation on the phenyl group. In some cases, products have been found that can be rationalised through a 1,6-spirocyclisation of the iminyl radicals followed by homolytic 1,5-migration of the phenyl group from the aminic to the iminic nitrogen: this seems to be the first instance of such a process. Evidence has been found for the formation of imines through hydrogen abstraction by the iminyls; with two o-phenoxy-substituted peresters these imines have been unexpectedly isolated. The reactions have also afforded significant - in some cases major - amounts of other products (acridine, quinazolinone and indole derivatives) presumably deriving from carbon radicals: mechanisms are suggested to account for the formation of these compounds. The structure of the quinazolinone compound has been determined by X-ray crystallographic analysis.
Gas-phase cyclisation reactions of 1-(2-arylaminophenyl)alkaniminyl radicals
Leardini, Rino,McNab, Hamish,Nanni, Daniele,Parsons, Simon,Reed, David,Tenan, Anton G.
, p. 1833 - 1838 (2007/10/03)
Flash vacuum pyrolysis (FVP) of the oxime ethers 9-11 at 650°C (10-2-10-3 Torr) gives products such as the nitrile 17, carbazoles 19 and 20 and acridines 18 and 21 derived from the corresponding iminyl radicals 13-15. The mechanism proposed for the formation of the acridines involves a key hydrogen abstraction by the iminyl of the adjacent N-H atom. When this route is blocked by an N-methyl group, as in 12, alternative cyclisations ensue, yielding the dihydroquinazoline 26 (via another hydrogen abstraction process) and the benzimidazole 25 (via an iminyl-imidoyl interconversion).
