Search results for "tautomer"
showing 10 items of 141 documents
Annular Tautomerism of 3(5)-Disubstituted-1H-pyrazoles with Ester and Amide Groups
2019
A series of disubstituted 1H-pyrazoles with methyl (1), amino (2), and nitro (3) groups, as well as ester (a) or amide (b) groups in positions 3 and 5 was synthesized, and annular tautomerism was investigated using X-ray, theoretical calculations, NMR, and FT-IR methods. The X-ray experiment in the crystal state showed for the compounds with methyl (1a, 1b) and amino (2b) groups the tautomer with ester or amide groups at position 3 (tautomer 3), but for those with a nitro group (3b, 4), tautomer 5. Similar results were obtained in solution by NMR NOE experiments in CDCl3, DMSO-d6, and CD3OD solvents. However, tautomer equilibrium was observed for 2b in DMSO. The FT-IR spectra in chloroform …
Biomimetic Synthesis of the Apoptosis-Inducing Thiazinoquinone Thiaplidiaquinone A
2012
A concise total synthesis of the apoptosis-inducing, marine metabolite thiaplidiaquinone A is described. The key ring forming steps are both based on biosynthetic considerations and involve the construction of the central benzo[c]chromene quinone unit by an extremely facile oxa-6π-electrocyclic ring closure reaction of an ortho-quinone intermediate, derived by tautomerization of a bis-benzoquinone, readily accessed from two simple phenolic precursors. This is followed by the installation of the 1,4-thiazine-dioxide ring by reaction of the benzo[c]chromene quinone with hypotaurine.
ChemInform Abstract: The Tautomerism of Nitraminopyridines
2010
1H, 13C and 15N NMR data for nitraminopyridines are discussed in terms of tautomeric equilibria in these compounds. The favoured tautomer is determined mainly from 15N NMR spectroscopy. The chemical shift of the nitrogen atom of the nitro group in nitraminopyridines and N-nitroanilines which cannot tautomerize vary from 28·0 to 35·4 ppm in DMSO solution. 3-Nitraminopyridine and 2-nitramino-3- and -5-nitropyridines behave similarly. In the 15N NMR spectra of nitrimino-1-methyldihydropyridines, used as models, an upfield shift of that atom, different from that observed for 2-nitraminopyridine, indicates the significance of the nitrimino tautomer. In contrast, a downfield shift of the ring nit…
The tautomerism of nitraminopyridines
1995
1H, 13C and 15N NMR data for nitraminopyridines are discussed in terms of tautomeric equilibria in these compounds. The favoured tautomer is determined mainly from 15N NMR spectroscopy. The chemical shift of the nitrogen atom of the nitro group in nitraminopyridines and N-nitroanilines which cannot tautomerize vary from 28·0 to 35·4 ppm in DMSO solution. 3-Nitraminopyridine and 2-nitramino-3- and -5-nitropyridines behave similarly. In the 15N NMR spectra of nitrimino-1-methyldihydropyridines, used as models, an upfield shift of that atom, different from that observed for 2-nitraminopyridine, indicates the significance of the nitrimino tautomer. In contrast, a downfield shift of the ring nit…
Proton tautomerism in 2-nitramino-C-nitropyridine derivatives - Experimental and quantum chemical study
2019
Abstract The structures of 2-nitramino-3-nitropyridine and 2-nitramino-5-nitropyridine have been characterized by X-ray diffraction and Density Functional Theory (DFT) studies. In the crystals, both compounds exist as the imino forms. The DFT calculations were performed in order to explore the amino-imino tautomerism of the studied compounds in the gas phase and the influence of solvent polarity on the tautomeric equilibrium. The Harmonic Oscillator Model of Aromaticity index (HOMA) and Nucleus Independent Chemical Shift (NICS) calculated for the pyridine rings of the studied systems, demonstrated a noticeable decrease in aromaticity of the imino forms. This study showed also that the highe…
Experimental and theoretical push-pull Chemo- and regioselectivity in 1,3-Dipolar cycloaddition reactions: the case of benzotriazepin-5-one with mesi…
2007
A novel heterocyclic compound 3-mesityl-5-methyl-4,5,11,11a-tetrahydro-6H-[1,2,4]oxadiazolo [5,4-b][1,3,4]benzotriazepin-6-one 4 has been synthesised by a 1,3 dipolar cycloaddition (13DC) reaction of 1,3,4-benzotriazepin-5-one 1 with mesitylnitrile oxide 3. The reaction, beside its synthetic interest, has shown to be completely chemo- and regioselective. The structure of the compound was determined by X-ray crystallography and analysed by spectral methods (NMR and mass spectrometry). The molecular mechanism for the reaction has been studied using quantum mechanical calculations at the B3LYP/6-31G* theory level. Two mechanisms are possible for the formation of the cycloadduct 4. The first on…
The azide/tetrazole equilibrium: an investigation in the series of furo- and thieno[2,3-e]tetrazolo[3,2-d]pyrimidine derivatives
2016
Abstract Starting from 7(8)-chlorofuro(thieno)[3,2- d ]pyrimidines 1 , the corresponding 7(8)-hydrazinofuro(thieno)[3,2- d ]pyrimidines 2 were obtained by reaction with hydrazine. By treatment with nitrous acid, compounds 2 gave fused furo- and thieno[2,3- e ]tetrazolo[1,5- c ]pyrimidines 3 T and 4 T in excellent yields, which in solution exist in equilibrium with 7(8)-azidofuro(thieno)[3,2- d ]pyrimidines 3 A and 4 A . Compounds 3 T / 3 A and 4 T / 4 A represent useful substrates for investigating the azide/tetrazole equilibrium: it has been examined as a function of solvent, temperature, and their structure. We have observed that, in solution, in both 3 and 4 the equilibrium was strongly …
1,4-Benzoquinones with Styryl Substituents
2002
2-Styryl-1,4-benzoquinone (1) and compounds 2 and 3 containing 1 as a substructure all proved to be highly reactive towards thermal or photochemical [4π + 2π] cyclodimerization reactions. Chemo-, regio- and stereoselective processes lead to dimers (compounds 1−10), which can undergo secondary reactions consisting of the addition of nucleophiles combined with a twofold keto-enol tautomerism (10 ⇄ 12). An alternative process is dehydrogenation/oxidation followed by an intramolecular [4π + 2π] cycloaddition (10 ⇄ 11). The same selective [4π + 2π] cyclodimerization can be observed in solution upon irradiation (e.g., 1a ⇄ 10a), in contrast to irradiation in the crystalline state which yields a […
Syntheses with organoboranes. Part 14: Enolization–aldolization of conjugated cyclohexenones via dienolborinates
2002
Abstract Enolization of cyclohex-2-enone ( 1 ), 3-methyl- ( 2 ), 3,5-dimethyl- ( 3 ), 3,5,5-trimethyl- ( 4 ), and 3,4,5,5-tetramethylcyclohex-2-enone ( 5 ) with chlorodicyclohexylborane proceeds by deprotonation at the 6-position. Aldolization of the dienolborinates with benzaldehyde, and acetaldehyde, provides the corresponding anti aldols with 87–95% selectivity. Ketones 4 and 5 undergo competitive deprotonation at the 3-methyl group and aldolization at the 2-position. In contrast, lithium dienolates derived from 4 and 5 gave syn aldols with 95% selectivity.
Preparation and Structure of Diexo-Oxanorbornane-fused 1,3-Heterocycles
2004
Via the reaction of diexo-oxanorbornanedicarboxylic anhydride with toluene, the diexo-aroylcarboxylic acid (3a) was prepared, which exists partly as the tautomeric lactol (3b). With bifunctional reagents, 3a yields fused heterocycles containing three-six rings. Thus, alkylenediamines result in imidazole- and 1,3-diazepine-fused oxygen- bridged isoindolones (6a,b), alkanolamines form the oxazole- and 1,3-oxazine-fused oxanorbornene derivatives (7a-c), and o-phenylenediamine undergoes cyclization to furnish the condensed benzimidazole (8). The reaction of 3a with diexo- aminonorbornanecarbohydrazide yields a pyrimidopyridazine containing six condensed rings (9). In a similar reaction with die…