Synthesis, Antibacterial and Antifungal Activity of New 3-Aryl-5H-pyrrolo[1,2-a]imidazole and 5H-Imidazo[1,2-a]azepine Quaternary Salts

A series of novel 3-aryl-5H-pyrrolo[1,2-a]imidazole and 5H-imidazo[1,2-a]azepine quaternary salts were synthesized in 58–85% yields via the reaction of 3-aryl-6, 7-dihydro-5H-pyrrolo[1,2-a]imidazoles or 3-aryl-6,7,8,9-tetrahydro-5H-imidazo[1,2-a]azepines and various alkylating reagents. All compounds were characterized by 1H NMR, 13C NMR, and LC-MS. The conducted screening studies of the in vitro antimicrobial activity of the new quaternary salts derivatives established that 15 of the 18 newly synthesized compounds show antibacterial and antifungal activity. Synthesized 3-(3,4-dichlorohenyl)-1-[(4-phenoxyphenylcarbamoyl)-methyl]-6,7-dihydro-5H-pyrrolo[1,2-a]imidazol-1-ium chloride 6c possessed a broad activity spectrum towards Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Acinetobacter baumannii, and Cryptococcus neoformans, with a high hemolytic activity against human red blood cells and cytotoxicity against HEK-293. However, compound 6c is characterized by a low in vivo toxicity in mice (LD50 > 2000 mg/kg).

Assisted by Hydrogen-Bond Donors Cinchona Quaternary Salts as Privileged Chiral Catalysts for Phase-Transfer Reactions

This review is devoted to the asymmetric phase-transfer reactions with the use of hybrid ammonium <i>Cinchona</i> catalysts supported by hydrogen-bond donor groups. Herein, we present a recent advancement of this type of catalysts in the field of biphasic reaction systems. The main emphasis was put on the advantages of additional functional groups present in the structure of the catalysts, such as: hydroxyl, amide, (thio)urea or squareamide.

Helicity: A Non-Conventional Stereogenic Element for Designing Inherently Chiral Ionic Liquids for Electrochemical Enantiodifferentiation

Configurationally stable 5-aza[6]helicene (1) was envisaged as a promising scaffold for non-conventional ionic liquids (IL)s. It was prepared, purified, and separated into enantiomers by preparative HPLC on a chiral stationary phase. Enantiomerically pure quaternary salts of 1 with appropriate counterions were prepared and fully characterized. N-octyl-5-aza[6]helicenium bis triflimidate (2) was tested in very small quantities as a selector in achiral IL media to perform preliminary electrochemical enantiodifferentiation experiments on the antipodes of two different chiral probes. The new organic salt exhibited outstanding enantioselection performance with respect to these probes, thus opening the way to applications in the enantioselective electroanalysis of relevant bioactive molecules.

Contrasting effect of 1-butanol and 1, 4-butanediol on the triggered micellar self-assemblies of C16-type cationic surfactants

Self-assembly in aqueous solutions of three quaternary salts based C16-type cationic surfactant with different polar head groups and identical carbon alkyl chain viz., cetylpyridinium bromide (CPB), cetyltrimethylammonium tosylate (CTAT), and...

APPLICATION OF IMIDAZOLINES BASED ON TALL OIL FATTY ACIDS AND THEIR QUATERNARY SALTS FOR THE SEPARATION OF THE BINARY NON-AQUEOUS AZEOTROPE SYSTEMS

Методом экстрактивной (в том числе солевой) ректификации с использованием имидазолинов и четвертичных солей на их основе разделены на компоненты неводные двойные азеотропные системы. В качестве разделяющих агентов выбраны: промышленный продукт 1-гидроксиэтил-2-алкенил-2-имидазолин на основе жирных кислот таллового масла, а также его четвертичные соли - хлорид и тетрафторборат 1-гидроксиэтил-2-алкенил-3-бензил-2-имидазолиния. Для разделения были использованы неводные азеотропные системы: ацетон-метанол, метилацетат-метанол, этилацетат-этанол и хлороформ-метанол. Равновесие жидкость-пар в соответствующих тройных системах исследовано в модифицированном приборе Отмера при 101,3 кПа, состав жидкой и паровой фаз определен газохроматографическим методом анализа. Минимальные концентрации (в мольных долях) имидазолина и имидазолиниевых солей для разрушения азеотропов составили 0,156-0,264. Для корреляции экспериментальных данных о парожидкостном равновесии в системах, содержащих имидазолиниевые соли использована электролитная модель NRTL. Средние абсолютные отклонения расчетных данных от экспериментальных значений мольного содержания растворителей в паровой фазе и температуры в системах составили 0,007-0,008 и 0,25-0,35 К, соответственно. The non-aqueous binary azeotrope systems have been separated into components by the method of extractive rectification (and salt rectification) using imidazolines and their quaternary salts. The following were selected as separating agents: industrial product 1-hydroxyethyl-2-alkenyl-2-imidazoline based on tall oil fatty acids, as well as its quaternary salts - chloride and tetrafluoroborate 1-hydroxyethyl-2-alkenyl-3-benzyl-2-imidazolinium. Non-aqueous azeotrope acetone - methanol, methyl acetate - methanol, ethyl acetate - ethanol, and chloroform - methanol systems were used for separation. The vapor-liquid equilibrium in the corresponding ternary systems was investigated in a modified Othmer still at 101.3 kPa, the composition of the liquid and vapor phases was determined by gas chromatographic analysis. The minimum concentrations (in molar fractions) of imidazoline and imidazolinium salts for the azeotrope breaking were 0.156-0.264. The mean absolute deviations between experimental and calculated data for the solvent mole fraction in the vapor phase and temperature in the imidazolinium salt containing systems were 0,007-0,008 and 0,25-0,35 К respectively.

Effect of Aromatic System Expansion on Crystal Structures of 1,2,5-Thia- and 1,2,5-Selenadiazoles and Their Quaternary Salts: Synthesis, Structure, and Spectroscopic Properties

Rational manipulation of secondary bonding interactions is a crucial factor in the construction of new chalcogenadiazole-based materials. This article reports detailed experimental studies on phenanthro[9,10-c][1,2,5]chalcogenadiazolium and 2,1,3-benzochalcogenadiazolium salts and their precursors. The compounds were synthesized, characterized employing NMR and UV-Vis spectroscopy. TD-DFT calculations were also performed. The influence of the size of the aromatic system on the molecular motifs formed by the compounds in the solid state has been studied by means of single-crystal X-ray diffraction. In case of the salts, the nature of an anion was also taken into consideration. The results show that cyclic [E···N]2 supramolecular synthon connects neighboring molecules of phenanthro[9,10-c][1,2,5]chalcogenadiazoles, with a relatively large aromatic system, in dimers regardless of the chalcogen atom in the molecule. Both N-methyl-2,1,3-benzothiadiazolium and N-methylphenanthro[9,10-c][1,2,5]chalcogenadiazolium cations have a strong affinity for triflate and iodide anions, therefore the formation of S···N or Se···N secondary bonding interactions is observed only in two out of the eight quaternary salts. Less coordinating anions must be used to enable the building blocks studied to form cyclic [E···N]2 synthons. Moreover, for two of the triflate salts, which are isostructural, a new supramolecular motif has been observed.

Orthoamide und Iminiumsalze, IIC. Darstellung von N-(ω-Ammonioalkyl)-N,N′,N′,N″,N″-peralkylierten Guanidiniumsalzen und N-(ω-Aminoalkyl)-N′,N′,N″,N″-tetramethylguanidinen

N,N,N′,N′-Tetraalkylchlorformamidiniumchlorides 1a, b react with ω-dimethylaminoalkylamines 19, 20 to give mixtures of N-(ω-dimethylammonioalkyl)-guanidinium salts 12, 13 and N-(ω-dimethylaminoalkyl)-guanidinium salts 21, 22. These mixtures are transformed to mixtures of the ureas 15, 17 and N-(ω-dimethylaminoalkyl)-guanidines 23, 25 on treatment with aqueous sodium hydroxide. The reaction of N-(3-dimethylammoniopropyl)-guanidin 25a with dimethylsulfate in a molar ratio of 1:1 delivers a mixture of the N-(3-dimethylaminopropyl)-N,N,N′,N′,N″,N″-pentamethyl-guanidinium salt 29a and the N-(3-dimethylammoniopropyl)-N,N′,N′,N″,N″-pentamethyl-guanidinium-bis (methylsulfate) 33a. The action of dimethylsulfate on the guanidines 23a, 25a in a molar ratio of 2:1 affords the bisquarternary salts 32a, 33a. Alkylating reagents as methyliodide, benzylbromide, allylbromide and chloroacetonitrile attack N-(2-dimethylaminoethyl)-N′,N′,N″,N″-tetraethylguanidine (23b) in a molar ratio of 1:1 cleanly at the dimethylaminoethylgroup to give the ammonium salts 30a–d. As a strong base the guanidine 23b dehydrochlorinates β-Chlorpropionitrile and chloroacetone under formation of the guanidinium salt 21c. In contrast to this the reaction of ethyl bromoacetate with the N-(2-dimethylaminoethyl)guanidine 23b occurs at the guanidinogroup giving the guanidinium salt 28c. The methylation of the guanidinium chlorides 21a, 22a with dimethyl sulfate affords the bis-quaternary salts 35b, 36b with mixed anions. From the heterocyclic guanidines 14, 16 and the alkylating reagents benzylbromide and ethyl bromoacetate the heterocyclic guanidinium salts 37a, b, 39a, b can be obtained. The reactions with ethyl chloroformiate proceed in an analogous way giving the guanidinium salts 37c, 39c. The N-alkyl-N,N,N′,N′-tetramethyl-(3-ureidopropyl)guanidinium salts 41a, b can be prepared from the N′,N′,N″,N″-tetramethyl-N′′-(3-ureidopropyl) guanidine 17a and the alkylating compounds dimethyl sulfate and benzyl bromide. Several compounds obtained that way were transformed to the corresponding tetraphenyloborates and bis(tetraphenylborates), respectively.

4,15-Dimethyl-7,12-diazoniatricyclo[10.4.0.02,7]hexadeca-1(12),2,4,6,13,15-hexaene dibromide monohydrate

The title compound, C16H20N2 2+·2Br−·H2O (1) is a member of the class of compounds called viologens. Viologens are quaternary salts of dipyridyls and are especially useful as redox indicators as a result of their large negative one-electron reduction potentials. Compound 1 consists of a dication composed of a pair of 4-methylpyridine rings mutually joined at the 2-position, with a dihedral angle between the pyridine rings of 62.35 (4)°. In addition, the rings are tethered via the pyridine nitrogen atoms by a tetramethylene bridge. Charge balance is provided by a pair of bromide anions, which are hydrogen bonded to a single water molecule [D O...Br = 3.3670 (15) and 3.3856 (15) Å]. The crystal structure of 1, details of an improved synthesis, and a full analysis of its NMR spectra are presented.