Denitrocyclisation in the synthesis of dibenzothiazepinones

Smirnov, Alexander; Kalandadze, Levan S.; Sakharov, Vladimir N.; Dorogov, M. V.

doi:10.1070/mc2006v016n05abeh002393

Cited by 8 publications

(6 citation statements)

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“…1 H NMR and 2D correlation spectra NOESY 1 Н 1 H for 5% solutions of the samples in DMSO d 6 were recorded on a Bruker MSL 300 spectrometer at the Institute of chemogenomic prob lems of the Ushinsky Yaroslavl State Pedagogical University.…”

Section: Methodsmentioning

confidence: 99%

“…Therefore, the reactive benzenethiolate site is produced, which enters denitrocyclisation reaction resulting in the pyridobenzothi azepine system 9a-g. Ealier, we have shown that K 2 CO 3 is more effective as the base in comparison with such deprotonating agents as sodium hydride, sodium amide, and potassium tert butoxide. 6 Figures 1 and 2 represent NOESY 1 Н 1 Н spectra of compounds 9a and 9d. The spectra contain no cross peaks in the region that is characteristic of the interaction of the protons of the NCH 3 group (δ 3.57) for 9a and the NCH(CH 3 ) 2 group (δ 4.89, 1.65, 1.17) for 9d with the aromatic proton of the pyridine ring (δ 8.00 and 8.01, respectively, C(4)H).…”

mentioning

confidence: 99%

“…1- 4 Previously, we have shown 5 that the use of intramolec ular nucleophlic aromatic substitution of a nitro group (denitrocyclisation reaction) is one of the promising meth ods to obtain wide range of tricyclic systems with the gen eral formula 1 and their derivatives. [6][7][8][9][10] In the present work, we applied this approach to the synthesis of insufficiently studied pyrido [3,2 b] [1,4] benzothiazepin 10(11H) one derivatives (Scheme 1), which have previously been obtained by photochemical rearrangement of pyridylbenzoylisothiazolones. 11 2 Chloro 3 nitropyridine (2) readily undergoes nu cleophilic aromatic substitution with thiosalicylic acid (3) (both starting compounds are commercially available) re sulting in 2 (3 nitropyridin 2 ylsulfanyl)benzoic acid (4).…”

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confidence: 99%

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Synthesis of N-substituted pyrido[3,2-b][1,4]benzothiazepin-(11H)-one derivatives by denitrocyclisation reaction

et al. 2009

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Section: Methodsmentioning

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Synthesis of N-substituted pyrido[3,2-b][1,4]benzothiazepin-(11H)-one derivatives by denitrocyclisation reaction

et al. 2009

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“…Thus, reaction 16 of the intermediate (2) with a strong base in DMF results in the substitution of a nitro group by the amide function to yield a dibenzothiazepinone derivative (3). Nucleophilic addition across the double bond of 2,4,6-trinitrostyrene may occur with thiophenol, aniline, and aliphatic amines.…”

Section: The S N Ar Mechanismmentioning

confidence: 99%

Nucleophilic Aromatic Substitution

Crampton

2010

Organic Reaction Mechanisms · 2006

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There has been a study of the dediazoniation of 4-nitrobenzenediazonium ions in methanol-water mixtures under acidic conditions using kinetic, spectrophotometric, and chromatographic methods. Two decomposition routes were identified: an ionic pathway yielding nitrophenol and nitroanisole, and a radical pathway involving transient diazo ethers which undergo homolytic fragmentation giving nitrobenzene or 4,4 -dinitrobiphenyl. 1 Catalysis by the Cu(I)-Cu(II)-1,10-phenanthroline system has been reported in the reaction of arenediazonium salts with potassium thiocyanate to yield aryl thiocyanates. 2 Bis(trifluoromethanesulfonyl)amide anions (Tf 2 N − ) are usually considered to have very low nucleophilic reactivity. However, in imidazolium ionic liquids this anion has been shown to have higher reactivity than bromide ions in heterolytic dediazoniation reactions. 3 It has been shown that displacement of the iodo substituent in 4-iodo-1,1,2,2,9,9,10, 10-octafluoro[2.2]paracyclophane by arenethiolates or by stabilized enolates occurs by the radical chain S RN 1 mechanism. The reaction occurs in DMF with photochemical stimulation. 4 The S N Ar MechanismThere has been a review of relationships between activation parameters and mechanisms for biomolecular reactions in solution, including both nucleophilic substitutions and additions. 5 Several studies have been reported involving substitutions by amine nucleophiles where both electronic and steric effects may be important. Kinetic studies of the reactions of 2,4-dinitrophenyl 2,4,6-trinitrophenyl ether (1) with ring-substituted 175

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“…26 We found that the use of intramolecular nucleophilic aromatic substitution of a nitro group (denitrocyclisation 27 ) for constructing a tricyclic system is a promising method for the synthesis of dibenzo[b,f] [1,4]thiazepin-11(10H)-one derivatives. [28][29][30] A distinctive feature of this approach is that not only the phenol nucleophilic centre but also the amide one are involved in the reaction.…”

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confidence: 99%