scholarly journals Synthesis, structure and reactivity of oxalyl di(4-methylimidazole)

2019 ◽  
Vol 59 (7) ◽  
pp. 122-127
Author(s):  
Pyotr P. Purygin ◽  
◽  
Alina V. Shargalo ◽  
Konstantin V. Milyutin ◽  
Yury P. Zarubin ◽  
...  
Keyword(s):  
Biological Activity ◽  
Functional Groups ◽  
1H Nmr ◽  
Chemical Shifts ◽  
Thermodynamic Characteristics ◽  
Step Method ◽  
Absorption Bands ◽  
Kinetics Of Hydrolysis ◽  
Kinetics Of ◽  
Urological Diseases

The article describes a two-step method for the synthesis of oxalyl di(4-methylimidazole) from 4(5)-methylimidazole through 1-trimethyl-4-methylimidazole followed by interaction with oxalyl chloride; the yield of the final product is 89%. The kinetics of hydrolysis, alcoholysis, and aminolysis of oxalyl di(4-methylimidazole) in acetonitrile – water (9 : 1), acetonitrile – methanol (9 : 1), acetonitrile – diethylamine (9 : 1) at 25 °C was studied. To study the thermodynamic features of the reactions to obtain this compound in the Spartan’14 1.1.4 program, a number of thermodynamic characteristics were determined that determine the spontaneous and exothermic nature of the process. The data obtained make it possible to select the optimal conditions for the synthesis of oxalyl di(4-methylimidazole) and to draw a conclusion about its low stability in media containing nucleophiles. Possible conformers were found for the oxalyl di(4-methylimidazole) molecule in the Molecular Operating Environment 2014.0901 program, for which nucleophilic susceptibility surfaces were calculated in the SCIGRESS Modeling 3.1.4 program. It was shown that the most reactive conformers in which carbonyl groups are minimally screened by fragments of 4-methylimidazole. The structure of oxalyl di(4-methylimidazole) was confirmed by IR and 1H NMR spectroscopy. Characteristic absorption bands were found in the IR spectra, confirming the presence of the corresponding functional groups in the structure of the compound, and proton signals with characteristic chemical shifts for the corresponding functional groups were detected in 1H NMR spectra. In the PASS Professional 2007 program, the most probable types of biological activity of the test compound were predicted. The most significant types of biological activity are in relation to urological diseases, antiseborrheic effect, stimulator of renal function, stimulator of leukopoiesis.

scholarly journals Synthesis of 1,1'-oxalyldibenzotriazole, study of the kinetic and thermodynamic features of its hydrolysis and prediction of biological activity

2019 ◽  
Vol 59 (7) ◽  
pp. 17-23
Author(s):  
Pyotr P. Purygin ◽  
◽  
Konstantin V. Milyutin ◽  
Yury P. Zarubin ◽  
Olga B. Grigoryeva ◽  
...  
Keyword(s):  
Biological Activity ◽  
1H Nmr Spectroscopy ◽  
Oxalyl Chloride ◽  
Thermodynamic Characteristics ◽  
Renal Diseases ◽  
Optimal Conditions ◽  
Operating Environment ◽  
Step Method ◽  
Kinetics Of Hydrolysis ◽  
Kinetics Of

The article describes a two-step method for the synthesis of 1,1'-oxalyl dibenzotriazole (bis(1H-benzotriazol-1-yl)ethane-1,2-dione) from benzotriazole via 1-trimethylsilylbenzotriazole, followed by reaction with oxalyl chloride; the yield of the final product is 87%. The kinetics of hydrolysis, alcoholysis and aminolysis of 1,1'-oxalyldibenzotriazole was studied in the systems acetonitrile – water (9 : 1), acetonitrile – methanol (9 : 1), acetonitrile – diethylamine (9 : 1) at 25 °C, and also by the equation Arrhenius values of the activation energy in the reactions of hydrolysis, alcoholysis, and aminolysis of 1,1'-oxalyl dibenzotriazole were calculated. To study the thermodynamic features of the reactions of obtaining this compound in the Spartan’14 1.1.4 program, a number of thermodynamic characteristics were calculated, determining the spontaneous and exothermic nature of the process. For the 1,1'-oxalyl dibenzotriazole molecule, possible conformers were found in the Molecular Operating Environment 2014.0901 software, for which the surfaces of nucleophilic susceptibility were calculated in the SCIGRESS Modeling 3.1.4 software. The structure of 1,1'-oxalyl dibenzotriazole was confirmed by IR and 1H NMR spectroscopy. The program PASS Professional 2007 predicted the most likely types of biological activity of the studied compounds. The most significant types of biological activity are in relation to renal diseases, anti-neurotoxic, anti-acid, anti-inflammatory. The obtained data allow us to choose the optimal conditions for the synthesis of 1,1’-oxalyl dibenzotriazole and to conclude that it is low stability in nucleophilic-containing media.

scholarly journals Synthesis of malonyldi(1,2,4-triazole), the study of the kinetic and thermodynamic features of its hydrolysis and prediction of biological activity

2019 ◽  
Vol 57 (1) ◽  
pp. 41-49
Author(s):  
Pyotr P. Purygin ◽  
◽  
Maria V. Evstegneeva ◽  
Roman V. Shafigulin ◽  
Yury P. Zarubin ◽  
...  
Keyword(s):  
Biological Activity ◽  
Water System ◽  
Thermodynamic Characteristics ◽  
Heat Of Formation ◽  
Step Method ◽  
Stable Conformer ◽  
Anti Oxidant ◽  
Layer Chromatography ◽  
Kinetics Of ◽  
Hydrolysis Of

This article describes a two-step method for the synthesis of malondyl (1,2,4-triazole) (1,3-di (1H-1,2,4-triazol-1-yl)propane-1,3-dione) of 1,2,4-triazole through 1-trimethylsilyl-1,2,4-triazole, followed by reaction with malonyl chloride; the yield of the final product is 85%. The kinetics of hydrolysis of malonyldi(1,2,4-triazole) in the acetonitrile – water system (9:1) at 25 °C and 35 °C was studied, and the activation energy of the hydrolysis of malonyldi(1,2,4-triazole). To study the thermodynamic features of the reactions of obtaining this compound in the Spartan’14 1.1.4 program, a number of thermodynamic characteristics were calculated, which determine the spontaneous and exothermic nature of the process. For the molecule malonyldi(1,2,4-triazole), the most and least stable conformers were found in the program Molecular Operating Environment 2009.10, for which the surfaces of nucleophilic susceptibility were calculated in the program SCIGRESS Modeling 3.1.4. It was shown that the most stable conformer of the malonyldi(1,2,4-triazole) molecule should have the highest reactivity in reactions with different nucleophiles and the lowest value of the heat of formation. In this case, the nucleophilic susceptibility of carbonyl carbon atoms is different, despite the symmetry of the structure of the molecules malonyldi(1,2,4-triazole), which suggests a stepwise interaction of malonyldi(1,2,4-triazole) with nucleophiles. The structure of malonyldi(1,2,4-triazole) was confirmed by IR, 1H NMR spectroscopy, individuality – by thin-layer chromatography. The proposed mechanism for the hydrolysis of malonyldi(1,2,4-triazole) is described. The program PASS Professional 2007 predicted the most likely types of biological activity of the studied compounds. The most significant types of biological activity are anti-diabetic, anti-ulcer, anti-ischemic, anti-oxidant. The obtained data allow us to choose the optimal conditions for the synthesis of malonyldi(1,2,4-triazole) and to conclude that it is highly hydrolytically stable in an aqueous acetonitrile medium.

scholarly journals Synthesis and study of the reactivity of 1,1'-oxalyl di(2-methylimidazole) in reactions with N-nucleophiles

2020 ◽  
Vol 64 (10) ◽  
pp. 136-145
Author(s):  
Pyotr P. Purygin ◽  
◽  
Viktoriya D. Fedotova ◽  
Vitaly Yu. Alekseev ◽  
Yury P. Zarubin ◽  
...  
Keyword(s):  
Carboxylic Acids ◽  
Functional Groups ◽  
1H Nmr ◽  
Oxalyl Chloride ◽  
Chemical Shifts ◽  
Crystalline Substance ◽  
Reaction Products ◽  
Absorption Bands ◽  
Oncological Diseases ◽  
Pass Online

This article describes the synthesis of 1,1'-oxalyl di(2-methylimidazole), which was obtained in two stages. At the first stage of the synthesis, 1-trimethylsilyl-2-methylimidazole and oxalyl chloride were obtained. At the second stage of the synthesis, the target product was obtained by reacting 1-trimethylsilyl-2-methylimidazole with oxalyl chloride. The product was a dark crystalline substance, the yield of the final product was 83%. The structure of 1,1'-oxalyl di(2-methylimidazole) was confirmed by IR and 1H NMR spectroscopy. In the IR spectra, characteristic absorption bands were found, confirming the presence of the corresponding functional groups in the structure of the compound, in the 1H NMR spectrum, proton signals with characteristic chemical shifts for the corresponding functional groups were found. The PASS online software predicted the types of biological activity of the compound under study. The most probable possibilities of application in the treatment of urological diseases, diabetes mellitus, staphylococcal, oncological diseases, antiaggregatory action. For the 1,1'-oxalyl di(2-methylimidazole) molecule, 6 conformers were found, which were three pairs of enantioconformers in the Molecular Operating Environment 2009.10 software, for which the electrostatic potential, nucleophilic and electrophilic susceptibility surfaces were calculated in the SCIGRESS Modeling 3.1.4 software. It was shown that the interaction with nucleophilic reagents is most typical for the 1,1'-oxalyl di(2-methylimidazole) molecule. Calculations of the potential energy of the conformers of 1,1'-oxalyl di(2-methylimidazole) molecules have been carried out. Using 1,1'-oxalyl di(2-methylimidazole), the syntheses of acetanilide, benzanilide and diethylformamide were carried out. These syntheses were carried out in order to test the reactivity and the possibility of amide-type bond formation upon activation of the carboxyl group in carboxylic acids. The reactions were carried out in one stage without isolation of the intermediate 2-methylimidazolide of the corresponding carboxylic acid. In this case, the proposed reaction mechanism should be two-stage. Possible structures of reactants, transition states, and reaction products in the interaction of 1,1'-oxalyl di(2-methylimidazole) with carboxylic acids and amines have been calculated by methods of computational chemistry.

scholarly journals Isothermal and non-isothermal kinetics of hydrolysis of 1-[2-(2- pentyloxyphenylcarbamoyloxy)-(2-methoxymethyl)-ethyl]- perhydroazepinium chloride (BK 129)

2013 ◽  
Vol 60 (2) ◽  
pp. 43-48
Author(s):  
Stankovičová M. ◽  
Bezáková Ž. ◽  
Beňo P. ◽  
Húšťavová P.
Keyword(s):  
Biological Activity ◽  
Alkaline Hydrolysis ◽  
Functional Group ◽  
Isothermal Kinetics ◽  
Basic Part ◽  
Buffer Solutions ◽  
Kinetics Of Hydrolysis ◽  
Short Time ◽  
Kinetics Of ◽  
Hydrolysis Of

Abstract The substance BK 129 - 1-[2-(2-pentyloxyphenylcarbamoyloxy)-(2-methoxymethyl)-ethyl]-perhydroazepinium chloride was prepared in terms of influence of the connecting chain between the carbamate functional group and the basic part of molecule on biological activity. Such a structural feature is important with regard to its stability. In this work we determined the rate constants of alkaline hydrolysis of this compound at increased temperature under isothermal and non-isothermal conditions. The hydrolysis was also performed in buffer solutions with the purpose of evaluating its stability. Non-isothermal tests of stability enable to reduce the number of analyses. The necessary data for stability of compound are in this way achieved in a short time.

Relativistic and Dynamic effects are needed to correctly model the 1H NMR Chemical Shifts of an Iridium Polyhydride Cluster

2020 ◽  
Author(s):  
Abril C. Castro ◽  
David Balcells ◽  
Michal Repisky ◽  
Trygve Helgaker ◽  
Michele Cascella
Keyword(s):  
1H Nmr ◽  
Chemical Shifts ◽  
Dynamic Effects ◽  
Nmr Chemical Shifts

Broad Assessment of Bioactivity of a Collection of Spiroindane Pyrrolidines Through “Cell Painting”

2020 ◽  
Author(s):  
Zarko Boskovic ◽  
Manvendra Singh ◽  
Zachary Pearson ◽  
Nathan Garza
Keyword(s):  
Biological Activity ◽  
Small Molecules ◽  
Functional Groups ◽  
Organelle Morphology

A collection of small molecules has been synthesized by composing photo-cycloaddition, C-H functionalization, and N-capping strategies. Multidimensional biological fingerprints of molecules comprising this collection have been recorded as changes in cell and organelle morphology. This untargeted, phenotypic approach allowed for a broad assessment of biological activity to be determined. Reproducibility and the magnitude of measured fingerprints revealed activity of several treatments. Reactive functional groups, such as imines, dominated the observed activity. Two non-reactive candidate compounds with distinct bioactivity fingerprints were identified, as well.

Synthesis and Biological Evaluation of Various New Substituted 1,3,4-oxadiazole-2-thiols

2008 ◽  
Vol 59 (4) ◽  
Author(s):  
Gabriela Laura Almajan ◽  
Stefania Felicia Barbuceanu ◽  
Ioana Saramet ◽  
Mihaela Dinu ◽  
Cristian Vasile Doicin ◽  
...  
Keyword(s):  
Biological Activity ◽  
Plant Growth ◽  
1H Nmr ◽  
Elemental Analysis ◽  
13C Nmr ◽  
Biological Evaluation ◽  
Ethyl Chloroacetate ◽  
Low Concentrations ◽  
Synthesis And Biological Evaluation

5-[4-(4X-phenylsulfonyl)phenyl]-1,3,4-oxadiazole-2-thiols, X=H, Cl, Br, reacted with ethyl chloroacetate to give S-alkylated compounds. Aminomethylation of the thione form of oxadiazoles yielded N(3)-derivatives. All the products have been characterized by elemental analysis, IR, 1H-NMR and 13C-NMR. The plant-growth regulating effects of the title compounds were examined. From the biological activity results, we found that most compounds showed weak stimulatory activities at low concentrations.

Synthesis, Conformational Analysis, Infrared, Raman and UV-Visible Spectra of Novel Schiff Bases compiled with DFT Calculations

2020 ◽  
Vol 23 (7) ◽  
pp. 568-586
Author(s):  
Samy M. Ahmed ◽  
Ibrahim A. Shaaban ◽  
Elsayed H. El-Mossalamy ◽  
Tarek A. Mohamed
Keyword(s):  
Schiff Bases ◽  
1H Nmr ◽  
Electronic Absorption Spectra ◽  
Chemical Shifts ◽  
Basis Set ◽  
Oh Groups ◽  
Vibrational Assignments ◽  
Cartesian Coordinate ◽  
Surface Scan ◽  
Ir And Raman

Objective: Two novel Schiff bases named, 2-((2-Hydroxybenzylidene)amino)-4,5,6,7- tetrahydrobenzo[b] thiophene-3-carbonitrile (BESB1) and 2-((Furan-2-ylmethylene)amino)-4,5,6, 7-tetrahydro-benzo[b]thiophene-3-carbonitrile (BESB2) were synthesized. Methods: The structures were characterized based on CHN elemental analysis, mid-infrared (400– 4000 cm-1), Raman (100-4000 cm-1), 1H NMR, mass and UV-Vis spectroscopic measurements. In addition, quantum mechanical calculations using DFT-B3LYP method at 6-31G(d) basis set were carried out for both Schiff bases. Initially, we have carried out complete geometry optimizations followed by frequency calculations for the proposed conformational isomers; BESB1 (A–E) and BESB2 (F–J) based on the orientations of both CN and OH groups against the azomethine lonepair (NLP) in addition to the 3D assumption. Results: The computational outcomes favor conformer A for BESB1 in which the C≡N and OH moieties are cis towards the NLP while conformer G is preferred for BESB2 (the C≡N/furan-O are cis/trans towards the NLP) which was found consistent with the results of relaxed potential energy surface scan. Aided by normal coordinate analysis of the Cartesian coordinate displacements, we have suggested reliable vibrational assignments for all observed IR and Raman bands. Moreover, the electronic absorption spectra for the favored conformers were predicted in DMSO solution using TD-B3LYP/6-31G(d) calculations. Similarly, the 1H NMR chemical shifts were also estimated using GIAO approach implementing PCM including solvent effects (DMSO-d6). Conclusion: Proper interpretations of the observed electronic transition, chemical shifts, IR and Raman bands were presented in this study.

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