Structures of sterically hindered p-hydroxystyrylpyridines and acid-base transformations of their quaternary salts

The structures of p-hydroxystyrylpyridines and a number of their new quaternary salts were studied by means of electronic absorption spectra. The reverse transformation of the salts to the corresponding quinonoid compounds was examined as a function of the pH of the medium, and the equilibrium constants were determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1087–1091, August, 1972.     

Reactions of quaternary salts of benzo derivatives of phenazine with nucleophilic reagents

The electronic structures of benzo[a]phenazine and dibenzo[a,c]phenazine have been studied by the MO LCAO method. The reactions of four quaternary salts with oxomethylene compounds and with quaternary salts of nitrogenous heterocycles have been described. The absorption spectra of the dyes obtained are given.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1552–1557, November, 1973.     

取代苄基吡啶类季铵盐的制备及其杀菌活性

采用吡啶或2-氨基吡啶与取代苄基衍生物反应获得3种苄基吡啶类季铵盐．即：溴化苄基吡啶盐（[Bz—Py]Br）,溴化苄基-2-氨基吡啶盐（[Bz-2-NH2Py]Br）和溴化对硝基苄基吡啶盐（[NO2Bzpy]Br]）．通过元素分析,红外光谱和电子喷雾质谱等手段进行了组成分析和结构表征,并以绿脓杆菌和金葡萄球菌为致病菌体测定了3种盐的杀菌活性．实验结果表明,所制备的3种吡啶类季铵盐具有良好的杀菌性能．     

Synthesis and application of novel carbohydrate-based ammonium and triazolium salts

The synthesis of nine new carbohydrate-based quaternary ammonium salts and two new triazolium salts starting from d-glucose has been accomplished. Our synthesis utilized the regio- and stereoselective ring opening reaction of 2,3-anhydro sugars by nucleophilic reagents to afford the key intermediates. In these new types of phase transfer catalysts, the ammonium and triazolium functions are directly attached to the carbohydrate scaffold in different positions (2-, 3-, 6-positions of the sugar). The efficiency of the altrose- and glucose-based quaternary salts were tested in the alkylation of N-(diphenyl) methylene glycine tert-butyl ester with benzyl bromide. To our knowledge this is the first example when sugar-based quaternary ammonium or triazolium salts were used successfully as phase transfer catalysts. The enantiomeric recognition ability of the synthesized salts towards racemic Mosher’s acid silver salt was also investigated by ¹⁹F NMR spectroscopy.     

Reduction of quaternary salts of 3-azafluorene and 3-azafluorenone and their conversion to indenoindolizines

The tetrahydro and hexahydro derivatives with respect to the nitrogen-containing ring were obtained by reduction of 3-azafluorene and 3-azafluorenone methiodides, respectively, with sodium borohydride. Indenoindolizines with linear and angular structures were synthesized from the N-phenacyl quaternary salts of 3-azafluorenones via 1,3-dipolar cycloaddition and by the Chichibabin method. 7-Nitro-3-azafluorenone and 3-azafluorenone N-oxide were obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 252–255, February, 1983.     

含不同季铵盐结构的新型水显影感光树脂

通过不同的三乙胺盐及丙烯酸对环氧酚醛树脂的开环反应,合成了含不同季铵盐及丙烯酸酯基的新型水显影感光树脂。研究了环氧基在不同三乙胺盐开环时的转化率,产物溶解性,感光性及热稳定性等。     

Quaternary salts of quinolybenzimidazoles

The nitrogen atoms of the benzimidazole ring are alkylated initially in the quaternization of 2-(2-quinolyl)benzimidazole, and the nitrogen atom of the quinoline ring is alkylated only after this. Pyridyl- and quinolylbenzimidazoles and their quaternary salts were synthesized in order to study geometrical isomerism in the dihetaryl series. It was concluded that geometrical isomerism cannot occur in the case of the protonated forms or any other quaternary salts of dihetaryls, since as a result of the mutual electron-acceptor effect of the heteroaromatic cations the carbon-carbon bond between them is converted to a single bond, despite the fact that it is a bond between two sp² carbon atoms.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1662–1669, December, 1980.     

Insoluble polystyrene-bound quaternary onium salt catalysts for the synthesis of cyclic carbonates by the reaction of oxiranes with carbon dioxide

The addition reaction of oxiranes ( 26a—e ) with carbon dioxide (CO₂) was performed using insoluble polystyrene beads containing pendant quaternary ammonium or phosphonium salts as catalysts under atmospheric pressure. The reaction of 26a—e with CO₂ proceeded smoothly catalyzed by 1–2 mol % of the polymer-supported quaternary onium salts to give the corresponding cyclic carbonates ( 27a—e ) in high yields at 80–90°C. In this reaction system, the catalytic activity of the polymer-supported quaternary onium salts was strongly affected by the following factors: degree of ring substitution (DRS) of the onium salt residues to the polymer, degree of crosslinking (DC) of the polystyrene beads, chain length of the alkylene spacer between the polymer back-bone and the onium salt, hydrophobicity of the alkyl group on the onium salts, and kind of onium salts. That is, the polymer-supported quaternary phosphonium salts with low DRS and DC and with long alkylene spacer chain were found to have higher catalytic activity than low molecualr weight quaternary onium salts. The above polymer-supported catalysts can easily be separated at the end of a reaction by filtration and can be reused for at least seven runs. It was also found that the rate of reaction was proportional to the products of catalyst concentration and oxirane concentration. © 1993 John Wiley & Sons, Inc.     

Saturated heterocycles. 176 Synthesis and steric structure of quaternary azeto[2,1-a]isoquinoline stereoisomers

Starting from 1-substituted azeto[2,1-a]isoquinoline diastereomers, a number of quaternary salts were prepared. The reactions leading to the quaternary salts were stereospecific, independently of the configuration at C-1, resulting in diastereomers. The steric structures of the new compounds were proved by nmr spectroscopy.     

Synthesis and liquid crystal properties of new banana-shaped cinnamoyl derivatives

Three new achiral five-ring banana-shaped homologous series have been synthesized and their liquid crystalline properties studied by polarizing microscopy, differential scanning calorimetry, and electro-otpical analysis. The compounds consist of two identical mesogenic structures of bis (alkoxycinnamoyloxybenzoates) linked on a different central ring (unsubstituted or methyl-substituted). The length of the terminal alkoxy groups was varied from heptyloxy to dodecyloxy; the hexadecyloxy group was also included in the study. It was found that the polymorphism of compounds can be strongly dependent upon molecular structure in this class of compound. In particular, substituents on the central ring may exert a significant effect on the type of mesophase observed.     

Synthesis and liquid crystal properties of new banana-shaped cinnamoyl derivatives

Three new achiral five-ring banana-shaped homologous series have been synthesized and their liquid crystalline properties studied by polarizing microscopy, differential scanning calorimetry, and electro-otpical analysis. The compounds consist of two identical mesogenic structures of bis (alkoxycinnamoyloxybenzoates) linked on a different central ring (unsubstituted or methyl-substituted). The length of the terminal alkoxy groups was varied from heptyloxy to dodecyloxy; the hexadecyloxy group was also included in the study. It was found that the polymorphism of compounds can be strongly dependent upon molecular structure in this class of compound. In particular, substituents on the central ring may exert a significant effect on the type of mesophase observed.     

Synthesis of benzimidazole derivatives

New bases and quaternary salts — 2-methylbenzimidazole derivatives — containing 2-pyridyl residues as a substituent in various positions of the benzimidazole ring were synthesized. Benzimidazolium salts of a new type with hetaryl groups attached to both nitrogen atoms were obtained. Imidacyanines were synthesized from the quaternary salts of pyridyl-substituted 2-methylbenzimidazoles, and the chief light-absorption maxima of these dyes were determined.See [1] for communication IVTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 687–690, May, 1972.     

The stereochemistry of quaternary N-methyl sparteinium cations, their derivatives, stereoisomers and analogues : Part II. Molecular and crystal structure, and IR spectra of methiodide and methperchlorate of 2-oxosparteine

The crystal and molecular structures of two quarternary salts of 2-oxosparteine (II), the methiodide (IICH⁺₃ • I⁻) and the methperchlorate (IICH⁺₃ • ClO⁻₄) have been determined on the basis of X-ray and IR data. The studies were performed by analogy to previously investigated quaternary salts of sparteine (I), the methiodide (ICH⁺₃ • I⁻) and the methperchlorate (ICH⁺₃ • ClO⁻₄). As expected, the configurations and conformations of cationic parts within the two pairs of quaternary salts are identical, except for the structure of their A/B fragments, which in ICH⁺₃ cations have the character of tertiary amines, but in IICH⁺₃ that of lactams.

On the basis of accumulated X-ray and IR data the similarities and differences in the modes of interaction of perchlorate and iodide anions with quaternary cations, and especially with their N⁺---CH₃ groups are discussed. In this discussion are also included the methiodide and methperchlorate of -isosparteine: IIICH⁺₃ • X⁻ (X⁻ = I⁻ or ClO⁻₄) where N⁺---CH₃ groups are cisoidally oriented to the basic nitrogen atoms. The most interesting observations are as follows: (i) When N⁺---CH₃ groups are easily accessible for direct quasi hydrogen bonding interactions with counter anions and when other positive charged groups, for instance lactam groups, are absent in quaternary cations, perchlorate anions interact more strongly than the iodide anions and in consequence introduce conformational changes into the ring with N⁺---CH₃ group as well as into further rings. (ii) Perchlorate and iodide anions interact with N⁺---CH₃ groups similarly and very weakly if at all, when the N⁺---CH₃ groups are for steric reasons inaccessible to counter anions or when in quaternary cations there are additional groups which attract the counter anions electrostatically. The last mechanism operates in both quaternary salts of 2-oxosparteine and this is the reason why their monocrystals are isosteric and IR spectra almost identical. (iii) The sterically hindered N⁺---CD₃ groups in both IIICD⁺₃ • X⁻ salts give rise in their IR spectra to two doubles of sharp, well resolved bands which indicate the presence of two different rotamers stabilized by two modes of weak intramolecular hydrogen bonds with basic N atoms. (iv) In IIICH⁺₃ • X⁻ and IIICD⁺₃ • X⁻ salts the perchlorate and iodide anions do not interact at all with the rotating and vibrating N⁺---CH₃ (N⁺---CD₃) group but the structures of these salts are not isosteric since the perchlorate anions interact more strongly than iodide anions with the A/B fragment of the IIICH⁺₃ cations. This is visible from the shapes and intensities of the so-called “trans” band in the IR spectra of both salts.     

Structures and reactivities of benzo-1,2,3-dithiazolium salts and their selenium analogs

A number of benzo-1,2,3-dithiazolium chlorides (I) and their selenium analogs — benzo-1,2,3-thiaselenazolium, benzo-2,1,3-thiaselenazolium, and benzo-1,2,3-diselenazolium salts — were synthesized. The electronic structures and reactivities of the I cation and salts I–IV are discussed on the basis of a quantum-chemical calculation of cation I and the PMR spectra of salts I–IV. Successive substitution of the sulfur atoms in the I cation by selenium atoms, particularly in the 2 position, substantially increases the degree of transfer of positive charge to the condensed benzene ring. The trend of the nucleophilic reactivities of 6-methoxy derivatives of salts I–IV in the reaction with aromatic amines is the same as the trend of the degree of localization of the positive charge in the 6 position.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 912–916, July, 1978.     

Bioluminescence activity of Latia luciferin analogues: replacement of the 2,6,6-trimethylcyclohexene ring onto the methyl-substituted phenyl groups

A series of Latia luciferin analogues having methyl-substituted phenyl groups instead of the natural 2,6,6-trimethylhexene ring was synthesized and their bioluminescence activity were measured. The Latia luciferase was found to be able to moderately recognize the appropriately methyl-substituted phenyl analogues with the same light production kinetics as that of natural luciferin.     

Reaction of 2- and 4- alk oxy - 1 - benzopyrylium salts with methylene bases of heterocyclic cations

2-Alkoxy- and 2-alkylthio-1-benzopyrylium salts condense in the 2 position with methylene bases formed from methyl-substituted heterocyclic onium compounds. The 4-methoxy-1-benzopyrylium salt also reacts primarily in the 2 position, during which the benzopyrylium ring is cleaved. In addition, condensation also takes place in the 4 position with splitting out of the methoxy group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 173–177, February, 1977.     

溴化苄基取代吡啶类季铵盐的制备和抗菌性能

抗菌材料和抗菌制品的研究与应用一直是世界各国研究的重要课题~([1-3]),其中有机抗菌剂占据主要地位.季铵盐是研究比较多的一类有机抗菌剂,它们表现出良好的物理性质,如胶束浓度低,黏弹性好和溶解性强~([4]),同时此类抗菌剂具有强效的抗菌作用~([5]),引起了人们的极大兴趣.季铵盐广泛应用于医药、卫生、食品、饲料工业、农业、纺织、塑料、橡胶、造纸、水处理、油田开采、涂料、日常生活等多种领域~([6-10]).     

Hydrophilic quaternary ammonium type ionic liquids. Systematic study of the relationship among molecular structures, osmotic pressures, and water-solubility

This Letter examines the relationship between the structures of ionic liquids and their water-solubility or osmotic pressure with a number of synthesized quaternary ammonium type ionic liquids and organic salts containing a hydroxyl group as hydrophilic substituted groups on ammonium group cations, and bromide or methylsulfonate as anions. The study found a linear relation between the amount and osmotic pressure of the water-soluble ionic liquids synthesized here, strongly indicating that these water-soluble ionic liquids are perfectly ionized in water like inorganic salts with small diameter ions.     

Phthalocyanines and Related Compounds: XL. Synthesis of β-Diethylaminoethyl-substituted Octa-4,5-carboxyphthalocyanine Tetraimides and Their Quaternary Salts

Cobalt, zinc, hydroxoaluminum, and iron complexes of N,N′,N″,N?-tetrakis(β-diethylaminoethyl) phthalocyanine-2,3 : 9,10 : 16,17 : 23,24-tetrakis(dicarboxamide) were synthesized and were converted into the corresponding water-soluble quaternary salts by treatment with methyl iodide, methyl p-toluenesulfonate, diethyl and dimethyl sulfates, and trimethyl phosphate. The electronic absorption spectra of the quaternary salts indicated their considerable aggregation in aqueous solution; the degree of aggregation decreases in going to solutions in ethanol and disappears in DMSO.     

Reactivity of 4-Methylpyridinium Salts in a New Reaction of Ring Transformation of Pyridine and Isoquinoline Derivatives

Dependence of reactivity on substituents in the pyridine ring of the 4-methylpyridinium salts was studied in intermolecular reaction of ring transformation involving quaternary salts of pyridinium and isoquinolinium promoted by methylammonium sulfite.