scholarly journals SYNTHESIS OF 1,2,3-TRIAZOLO-QUINOLIZIDINES BASED ON THE QUINOLIZIDINE ALKALOID LUPININE

2021 ◽  
Vol 3 ◽  
pp. 108-118
Author(s):  
Zh.S. Nurmaganbetov ◽  
◽  
O.A. Hurkenov ◽  
S.D. Fazylov ◽  
G.K. Mukusheva ◽  
...  
Keyword(s):  
Chemical Shifts ◽  
Integral Intensity ◽  
13C Nmr Spectroscopy ◽  
Structural Features ◽  
Sodium Ascorbate ◽  
Terminal Acetylene ◽  
1H And 13C Nmr ◽  
One Dimensional ◽  
Acetylene Group ◽  
Hydroxymethylene Group

The modification of the quinolysin alkaloid lupinine was carried out with the intro-duction of 1,2,3-triazolyl substituents for the hydroxymethylene group in the C-1 position of the quinolysin backbone. The reaction of lupinine with methanesulfochloride in the presence of triethylamine smoothly led to lupinine methanesulfonate, whose further reaction with sodium azide in DMFA led to lupinilazide. 1,3-Dipolar [4+2]-cycloaddition of the resulting azide to alkynes produced more stable 1,2,3-triazole compounds. The interaction of lupinilazide with 2-ethinylpyridine and with alcohols containing a terminal acetylene group (propargyl alcohol, 2-methylbut-3-in -2-ol or hex-5-in -1-ol) proceeded smoothly in the DMFA medium. The reactions were carried out in the presence of an aqueous solution of CuSO4 and sodium ascorbate in DMFA and allowed the corresponding 4-substituted (1S,9aR)-1H-1,2,3-triazol-1-yl to be synthesized with good yields)methyl)octahydro-1H-quinolysins. The results of studying the structural features of synthesized compounds by 1H - and 13C - NMR spectroscopy, as well as data from the two-dimensional COSY (1H-1H) and HMQC (1H-13C) spectra are presented. The values of chemical shifts, multiplicity and integral intensity of 1H and 13C signals in one-dimensional NMR spectra are determined. In the spectra of all synthesized new quinolizi-dinotriazoles, there is a peak of the fragmentary C10H17N ion (150-151 cu), corresponding to the cleavage of the molecule by the C-10 atom of the quinolizidine backbone.

scholarly journals The Solvent Effect on Composition and Dimensionality of Mercury(II) Complexes with Picolinic Acid

Molecules ◽  
2021 ◽  
Vol 26 (16) ◽  
pp. 5002
Author(s):  
Željka Soldin ◽  
Boris-Marko Kukovec ◽  
Dubravka Matković-Čalogović ◽  
Zora Popović
Keyword(s):  
Coordination Compounds ◽  
Picolinic Acid ◽  
Chloride Ion ◽  
13C Nmr Spectroscopy ◽  
Thermal Methods ◽  
1H And 13C Nmr ◽  
Coordination Environment ◽  
One Dimensional ◽  
X Ray ◽  
Different Types

Three new mercury(II) coordination compounds, {[HgCl(pic)]}n (1), [HgCl(pic)(picH)] (2), and [HgBr(pic)(picH)] (3) (picH = pyridine-2-carboxylic acid, picolinic acid) were prepared by reactions of the corresponding mercury(II) halides and picolinic acid in an aqueous (1) or alcohol–methanol or ethanol (2 and 3) solutions. Two different types of coordination compounds were obtained depending on the solvent used. The crystal structures were determined by the single-crystal X-ray structural analysis. Compound 1 is a one-dimensional (1-D) coordination polymer with mercury(II) ions bridged by chelating and bridging N,O,O′-picolinate ions. Each mercury(II) ion is four-coordinated with a bidentate picolinate ion, a carboxylate O atom from the symmetry-related picolinate ion and with a chloride ion; the resulting coordination environment can be described as a highly distorted tetrahedron. Compounds 2 and 3 are isostructural mononuclear coordination compounds, each mercury(II) ion being coordinated with the respective halide ion, N,O-bidentate picolinate ion, and N,O-bidentate picolinic acid in a highly distorted square-pyramidal coordination environment. Compounds 1–3 were characterized by IR spectroscopy, PXRD, and thermal methods (TGA/DSC) in the solid state and by 1H and 13C NMR spectroscopy in the DMSO solution.

Orientation of the methoxyl group in cis- and trans-2-methoxy-4-methyl-1,3-dioxanes and related compounds as inferred by 1H and 13C nmr spectroscopy. The significance of the "exo-anomeric" effect

1982 ◽  
Vol 60 (9) ◽  
pp. 1067-1072 ◽  
Author(s):  
Vanga S. Rao
Keyword(s):  
Dynamic Equilibrium ◽  
Chemical Shifts ◽  
13C Nmr Spectroscopy ◽  
Methoxyl Group ◽  
Anomeric Effect ◽  
1H And 13C Nmr ◽  
Nuclear Overhauser ◽  
Cis And Trans ◽  
In Cis ◽  
Related Compounds

Carbon-13 chemical shifts and 13C—1H couplings are reported for some substituted 2-methoxy-1,3-dioxanes and related tetrahydropyran derivatives. These data, together with nuclear Overhauser enhancement experiments, provided evidence for a favored orientation of the methoxyl group. From an analysis of the 13C chemical shifts and the magnitude of vicinal 13C—1H coupling between —OCH3 and H-2, a possible dynamic-equilibrium orientation for the methoxyl group is proposed, and an evaluation of the significance of a "generalized exo-anomeric effect" is presented.

scholarly journals SYNTHESIS OF PROPERTIES N-METHYL-2-(PYRID-4-YL)-3,4-FULLEROPYRROLIDINE

2020 ◽  
Vol 2 (440) ◽  
pp. 62-68
Author(s):  
S.D. Fazylov ◽  
O.A. Nurkenov ◽  
A.E. Arinova ◽  
T.M. Seilkhanov ◽  
A.M. Gazaliev ◽  
...  
Keyword(s):  
13C Nmr ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Wide Spectrum ◽  
13C Nmr Spectroscopy ◽  
Fullerene C60 ◽  
Water Soluble ◽  
1H And 13C Nmr ◽  
Integrated Intensity ◽  
Pharmacophore Group

The article is devoted to the reactions of [2+3] cycloaddition of pyridine-4-aldehyde to fullerene C60, as well as to the preparation of its water-soluble from of the resulting reaction product N-methyl-2-(pyrid-4-yl)-3,4-fulleropyrrolidine. A literature review of organic compounds containing the pyrrolidine cycle was carried out. It is noted that such compounds have a wide spectrum of biological activity and are part of many drugs of both natural and synthetic origin. In this regard, an interesting “pharmacophore” group is the pyridine cycle, which is part of about 5% of all known drugs. The reaction of pyridin-4-aldehyde with fullerene C60 was carried out in the presence of sarcosine under the conditions of the Prato reaction. The reaction mechanism of 1,2-dipolar cycloaddition, leading to fulleropyrrolidine, is described. The water-soluble complex fulleropyrrolidinas with poly-N-vinylpyrrolidone was obtained. The structures of the synthesized compounds were studied by IR, UV, 1H and 13C NMR spectroscopy, as well as by the date of two-dimensional spectra of COSY (1H-1H) and HMQC (1H-13H). The values of chemical shifts, multiplicity and integrated intensity of 1H and 13C NMR signals in one-dimensional NMR spectra were determined. Using spectra in the formats COSY (1H-1H) and HMQC (1H-13C) homo- and heteronuclear interaction were established, confirming the structure of the studied compounds. Key words: fullerene C60, sarcosine, pyridine-4-aldehyde, fulleropyrrolidines, Prato reaction, NMR spectra.

scholarly journals Synthesis, structural and conformational study of selected N-substituted phthalimides

2005 ◽  
Vol 3 (4) ◽  
pp. 683-704 ◽  
Author(s):  
Isabel Iriepa ◽  
F. Javier Villasante ◽  
Enrique Gálvez ◽  
Antonio Herrera ◽  
Angel Sánchez ◽  
...  
Keyword(s):  
Double Resonance ◽  
13C Nmr Spectroscopy ◽  
Two Dimensional ◽  
X Ray Diffraction ◽  
1H And 13C Nmr ◽  
Conformational Studies ◽  
One Dimensional ◽  
X Ray ◽  
Nmr Techniques ◽  
New Compounds

AbstractThis paper synthesizes N-substituted phthalimides derived from nitrogen heterocycles as potential 5-HT4 ligands by using the Mitsunobu reaction. Conformational studies of some of the new compounds have been conducted using 1H and 13C-NMR spectroscopy. Proton and carbon resonances were achieved through the application of one-dimensional selective NOE, two-dimensional NMR techniques-homonuclear COSY-45, NOESY and heteronuclear 1H-13C HMQC correlated spectroscopy- and double resonance experiments. The crystal structure of compound 1 was determined by X-ray diffraction.

scholarly journals Synthesis and Structural Features of 3(5)-alkyl(aryl)-5(3)-pyridyl-4-nitroso-1Н-pyrazoles

2021 ◽  
pp. 218-225
Author(s):  
Darya S. Volkova ◽  
Anna S. Kositsyna ◽  
Kukushkin, Alexey A. Kukushkin ◽  
Evgeniy V. Root
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Hydrazine Hydrate ◽  
13C Nmr ◽  
13C Nmr Spectroscopy ◽  
Structural Features ◽  
Alkyl Aryl ◽  
Dicarbonyl Compounds ◽  
1H And 13C Nmr ◽  
Modern Methods

А para-chlorophenyl substituent was firstly obtained into the structure of pyridyl-substituted 4-nitrosopyrazole by cyclocondensation of hydrazine hydrate with the corresponding isonitroso-β-dicarbonyl compounds. The structure of previously unknown 3(5)-(4-chlorophenyl)-5(3)-pyridine-(3(4))-yl-4-nitroso-1H-pyrazoles and previously obtained 3(5)-alkyl(aryl)-5(3)-pyridine-(3(4))-yl-4-nitroso-1H-pyrazoles is proved and studied in detail by modern methods of analysis: mass spectrometry, 1H- and 13C NMR-spectroscopy

scholarly journals Study of glycoluril and its derivatives by 1H and 13C NMR spectroscopy

2020 ◽  
Vol 99 (3) ◽  
pp. 21-37
Author(s):  
S.Yu. Panshina ◽  
◽  
O.V. Ponomarenko ◽  
A.A. Bakibaev ◽  
V.S. Malkov ◽  
...  
Keyword(s):  
Electron Density ◽  
13C Nmr ◽  
Heterocyclic Compounds ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
13C Nmr Spectroscopy ◽  
Reaction Centers ◽  
1H And 13C Nmr ◽  
Spatial Configurations ◽  
Donor Acceptor

Bicyclic bisureas, especially 2,4,6,8-tetraazabicyclo[3.3.0.]octan-3,7-dione (glycoluril), have a special place in chemistry of heterocyclic compounds. The carbamide fragment in glycoluril structure determines the properties of the molecule, which are due to the presence of two reaction centers (NH-groups and C=O-groups) in the molecule. In this work, we analyzed the proton and carbon chemical shifts of glycoluril and its derivatives (86 compounds) in the NMR spectra to reveal the effect of the donor-acceptor substituents on the changes in the electron density in the bicyclic framework from the position of symmetry and asymmetry. A general analysis of the 1H and 13C NMR spectra of glycolurils makes it possible to accurately determine the spatial configurations of molecular symmetry, in the presence of which (σ1 and / or σ2) the enantiotopic hydrogen and carbon atoms of the bicyclic framework are manifested by equivalent signals. Also, according to the 1H and 13C chemical shifts in the NMR spectra, glycolurils with electron-acceptor substituents can be clearly distinguished by the shielding of carbon atoms of C=O-groups, and with electron-donating substituents by the deshielding of CH-CH-carbons, due to the rearrangement of electron density and the occurrence of local paramagnetic contributions owing to anisotropy.

Solid state and solution stereochemistry of crown ethers and models. ortho-Dimethoxydiphenyl ether and related dibenzo-15-crown-5 and tetrabenzo-30-crown-10 ethers as studied by X-ray crystallography and 1H and 13C NMR spectroscopy

1994 ◽  
Vol 72 (5) ◽  
pp. 1218-1224 ◽  
Author(s):  
G. W. Buchanan ◽  
A. Rodrigue ◽  
K. Bourque ◽  
A. C. Chiverton ◽  
I. R. Castleden ◽  
...  
Keyword(s):  
Solid Phase ◽  
Direct Methods ◽  
13C Nmr Spectroscopy ◽  
Structural Features ◽  
X Ray Diffraction ◽  
1H And 13C Nmr ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
C Nmr

Solid phase 45.3 MHz 13C NMR spectra of ortho-dimethoxydiphenyl ether, 1, dibenzo[b,e]-15-crown-5- ether, 2, and tetrabenzo[b,e,q,t]-30-crown-10 ether, 3, have been obtained. Chemical shift trends are discussed in terms of the asymmetric units and structural features available from X-ray crystallographic data. Comparison with solution 13C spectra are made. The crystal structures of 1 and 3 were determined by X-ray diffraction at room temperature. 1 crystallizes in space group P21/a with a = 13.366(1), b = 8.230(1), c = 12.303(1) Å, β = 116.63(1)°, Z = 4. 3 crystallizes in space group P21/c with a = 7.903(1), b = 26.337(2), c = 7.852(1) Å, β = 97.28(1)°, Z = 2. The structures were solved by direct methods and refined by full-matrix least squares to residuals of 0.055 using 1727 reflections for 1 and of 0.042 using 2590 reflections for 3.

scholarly journals Synthesis and structure of thiourea derivatives of functionally substituted pyridines

2021 ◽  
Vol 101 (1) ◽  
pp. 4-11
Author(s):  
O.A. Nurkenov ◽  
◽  
S.D. Fazylov ◽  
T.M. Seilkhanov ◽  
Zh. Nurmaganbetov ◽  
...  
Keyword(s):  
Chemical Shifts ◽  
13C Nmr Spectroscopy ◽  
Potassium Thiocyanate ◽  
Thiourea Derivatives ◽  
1H And 13C Nmr ◽  
Pyridine Moiety ◽  
Substituted Pyridines ◽  
Pharmacologically Active ◽  
Derivatives Of

The article presents data on the synthesis and study of the structure of thiourea derivatives of functionally substituted pyridines. New thiourea derivatives containing a pharmacologically active pyridine moiety in their structure were obtained. As the starting synton, 2-amino-5-bromopyridine, 2-amino-3-hydroxypyridine and 2-aminomethylpyridine were selected. It was shown that the interaction of 2-amino-5-bromopyridine, 2-amino-3-hydroxypyridine and 2-aminomethylpyridine with ethyl and phenylisothiocyanates in ethanol leads to the formation of the corresponding pyridine-containing thioureas. The synthesis of the initial isothiocyanates was carriedout in situ from the corresponding acidic chlorides (benzoyl chloride and p-brombenzoyl chloride) by heating them with potassium thiocyanate in acetone. The structure of the synthe-sized compounds was studied by 1H and 13C NMR spectroscopy, as well as by the data of two-dimensional spectra of COSY (1H-1H) and HMQC (1H-13C). The values of chemical shifts, multiplicity, and integrated in-tensity of 1H and 13C signals in one-dimensional NMR spectra were determined. Using spectra in the formats COSY (1Н-1Н) and HMQC (1Н-13С), homo-and heteronuclear interactions were established, confirming the structure of the studied compounds.

Structure of the exudate gum from Meryta sinclairii

2020 ◽  
Author(s):  
Ian Sims ◽  
Richard Furneaux
Keyword(s):  
Average Molecular Weight ◽  
Gum Arabic ◽  
Arabinogalactan Protein ◽  
Weight Average Molecular Weight ◽  
1H And 13C Nmr ◽  
One Dimensional ◽  
Linkage Analyses ◽  
Yariv Reagent ◽  
Native Tree ◽  
High Level

A gum that exudes from the wounded trunk of the New Zealand native tree Meryta sinclairii has been isolated. The gum was completely precipitated by the β-glucosyl Yariv reagent and was thus determined to be an arabinogalactan-protein (AGP). It contained >95% w/w carbohydrate and only 2% w/w protein with a high level of hydroxyproline. SEC-MALLS showed that the gum had a weight-average molecular weight of 4.45×106Da compared with 6.02×105Da for gum arabic. Constituent sugar and linkage analyses were consistent with polymers comprised of a highly branched backbone of 1,3-linked galactopyranosyl (Galp) residues, with side-chains made up of arabinofuranose- (Araf) containing oligosaccharides, terminated variously by rhamnopyranosyl (Rhap), arabinopyranosyl (Arap), Galp and glucuronopyranosyl (GlcpA) residues. Analysis by one-dimensional and two-dimensional 1H and 13C NMR experiments confirmed the linkage analyses. The structure of the gum is discussed in comparison with the structure of gum arabic and other AGPs. © 2003 Elsevier Science Ltd. All rights reserved.

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