One-pot synthesis of 1,3,6,8-tetraazapyrenes

Aksenov, A. V.; Lyakhovnenko, A. S.; Perlova, T. S.; Аксенова, И. В.

doi:10.1007/s10593-011-0856-3

Cited by 8 publications

(3 citation statements)

References 4 publications

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“…8 Several innovative approaches towards TAPy scaffolds were also developed (Scheme 2). These methods involved one-pot double nitration of perimidines followed by zinc-assisted reductive cyclo-condensation with formic acid (method E), 9 and various peri-annulation cascades triggered by the Schmidt reaction of 6(7)-acylperimidines 8 (Scheme 2) (method F). 10 We also demonstrated that nitroalkanes 10 react with polyphosphoric acid (PPA) to form highly stabilized aci form 11, which can serve as electrophilic component in highly selective Nef-like processes involving various carbon-11 and nitrogen-based nucleophiles 12 (Scheme 3).…”

Section: Resultsmentioning

confidence: 99%

Dual role of polyphosphoric acid-activated nitroalkanes in oxidative peri-annulations: efficient synthesis of 1,3,6,8-tetraazapyrenes

et al. 2017

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Section: Resultsmentioning

confidence: 99%

Dual role of polyphosphoric acid-activated nitroalkanes in oxidative peri-annulations: efficient synthesis of 1,3,6,8-tetraazapyrenes

et al. 2017

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“…Traditionally, they are performed with mixture of nitric and sulfuric acids, which is not environmental friendly and often provides poor selectivity. Various clean nitration approaches [1][2][3] have therefore been explored in order to avoid these insufficient. Since the end of last century, with more and more recognition of room temperature ionic liquids (TSILs), a growing interests have also been witnessed in ionic liquids as solvents or catalysts for aromatic nitration.…”

Section: Introductionmentioning

confidence: 99%

Reusable and Efficient Polystryrene-supported Acidic Ionic Liquid Catalyst for Mononitration of Aromatic Compounds

Li¹,

Ling²,

Liu³

et al. 2012

Bulletin of the Korean Chemical Society

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“…Yield 0.139 g (63%); mp > 300ºC (mp > 300ºC [3]). The 1 H NMR spectrum is similar to that reported in the study [3].…”

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Three-component reaction of acetyl-perimidines with sodium azide and nitrite in polyphosphoric acid

Аксенов

Lyakhovnenko

Spicin

et al. 2011

Chem Heterocycl Comp

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We have previously developed a method for the synthesis of 1H-1,5,7-triazacyclopenta[c,d]phenalenes based on a successive Schmidt reaction of the acetylperimidines 1a,b and cyclization of the intermediate acetamidoperimidines 2a,b [1]. Bearing in mind that a nitroso group is an aza analog of a carbonyl group we decided to develop a method for the peri annelation of a pyrazole ring to azaphenalenes using a tandem transformation: Schmidt reaction -nitrosation -heterocyclization.It was found that the reaction of the acetylperimidines 1a,b, NaN 3 , and NaNO 2 in polyphosphoric acid (PPA) led to the previously unknown 1,2,5,7-tetraazacyclopenta[c,d]phenalenes 4a,b in 18-21% yield based on the acetylperimidines and to the N-oxide of compounds 5a,b. Without separation, the latter were converted to the 1,3,6,8-tetraazapyrenes 6a,b in yields of 63-65%, also based on the starting perimidines 1a,b.It is likely that the Schmidt reaction of ketones 1a,b forms the acetamides 2a,b which give the intermediate compounds 3a,b via nitrosation. The latter are converted to the 1,2,5,7-tetraazacyclopenta[c,d]-phenalenes 4a,b as a result of attack of the nitrogen atom of the acetamide group or form the N-oxides of the 1,3,6,8-tetraazapyrenes 5a,b through attack of the nitrogen atom of the nitrosyl at the carbonyl group.1 H NMR spectra were taken on a Bruker WP-200 (200 MHz) instrument using DMSO-d 6 with TMS as internal standard. Monitoring of the reaction course and the purity of the compounds synthesized were carried out on Silufol UV-254 plates in the solvent system ethyl acetate-ethanol (1:1). The PPA with an 86% P 2 O 5 content was prepared by the method [2].Synthesis of 1,2,5,7-Tetraazacyclopenta[c,d]phenalenes 4a,b and 1,3,6,8-Tetraazapyrenes 6a,b (General Method). The corresponding acetylperimidine 1a,b (1 mmol), NaN 3 (0.07 g, 1.07 mmol), and NaNO 2 (0.1 g, 1.45 mmol) in PPA (2-3 g) were heated for 1 h at 55-60ºC and then for 7 h at 70-80ºC. The reaction mixture was treated with water (50 ml) and basified with 25% ammonia solution to pH 8-9. The mother liquor was extracted with hot benzene (550 ml). The solvent was evaporated to give the 1,2,5,7-tetraazacyclopenta[c,d]-phenalenes 4a,b which were purified by recrystallization from benzene. The aqueous solution remaining after the extraction was refluxed for 2 h with zinc dust (0.128 g, 2 mmol) and then extracted with butanol (350 ml) to give the 1,3,6,8-tetraazapyrenes 6a,b which were purified by recrystallization from ethanol.

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One-pot synthesis of 1,3,6,8-tetraazapyrenes

Cited by 8 publications

References 4 publications

Dual role of polyphosphoric acid-activated nitroalkanes in oxidative peri-annulations: efficient synthesis of 1,3,6,8-tetraazapyrenes

Dual role of polyphosphoric acid-activated nitroalkanes in oxidative peri-annulations: efficient synthesis of 1,3,6,8-tetraazapyrenes

Reusable and Efficient Polystryrene-supported Acidic Ionic Liquid Catalyst for Mononitration of Aromatic Compounds

Three-component reaction of acetyl-perimidines with sodium azide and nitrite in polyphosphoric acid

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