Investigation of the structure and thermolysis of quaternary salts of 2-alkyl- and 2-arylamino derivatives of thiazolines

2-Arylamino derivatives of 5-methylthiazoline react with alkyl iodides to give quaternary salts with primarily an exocyclic orientation of the C=N bond, while the C=N bond is localized in the: ring in the corresponding salts of 2-alkylamino derivatives of thiazoline. The decomposition of these salts leads to the corresponding 2-arylaminothiazolidines and 2-alkylaminothiazolines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 917–920, July, 1981.     

Extraction of Zinc and Copper with Acetylenic Quaternary Ammonium Salts

Extraction of zinc(II) and copper(II) from HCl solutions with solutions of mono- and dialkynyl-substituted quaternary ammonium halides in chloroform and toluene is more efficient than the extraction with saturated quaternary ammonium salts and occurs by different mechanism. The dependences of the metal distribution factors on the HCl concentration have two maxima whose positions (absolute and relative) and relative intensities depend on the particular extractant, metal, and diluent.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 5, 2005, pp. 712–718.Original Russian Text Copyright © 2005 by Andreev, Tunina, Remizova.     

Synthesis of fluoro-substituted symmetrical dialkylaminotriazines under interphase-catalysis conditions

The reaction of chloro derivatives of symmetrical dialkylaminotriazines with potassium fluoride in the presence of catalytic amounts of crown ethers or quaternary ammonium salts leads to the formation of the corresponding fluoro derivatives in high yields. The structure of the catalyst and the nucleophilicity of the solvent affect the yields of the fluoro derivatives of the symmetrical dialkylaminotriazines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1370–1372, October, 1990.     

Secondary ion mass spectra of organic cationic dyestuffs

Rules for the behavior under fast atom bombardment (FAB) have been established for 15 cationic dyes — quaternary ammonium salts of heterocyclic amines and heterocycles containing quaternary nitrogen atoms with aliphatic substituents. Intense peaks corresponding to the molecular mass of the cationic part of the dyes [M-Hal]⁺ are observed in the spectra of all the derivatives. Fragmentation of the azodyes is determined by the azo group and the heterocyle. The base peaks in the case of compounds containing a quaternary nitrogen atom with aliphatic substituents correspond to the ammonium ion and a fragment of amine type. The results obtained can be used to identify dyes of unknown structure from their secondary ion mass spectra (SIMS).DeceasedTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, 1411–1417, October, 1992     

Reaction of quinazoline derivatives with quaternary salts of heterocyclic bases

The formation of carbocyanine and styryl dyes from quinazoline derivatives and quaternary salts of heterocyclic bases was detected. The intermediate compounds were separated and mechanisms of the reactions were proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 662–670, May, 1992.     

Substitution and elimination reactions of poly(epichlorohydrin) and poly(2-chloroethyl vinyl ether) using phase transfer catalysis

The reactions of poly(epichlorohydrin) (PECH) and poly(2-chloroethyl vinyl ether) (PCEVE) with various reagents were investigated using phase transfer catalyst (PTC) such as tetra-n-butylammonium bromide (TBAB), 18-crown-6 (CR6), and dicyclohexyl-18-crown-6 (DCHC) is a solid—liquid two-phase system. Although the reactions of these polymers hardly occurred without PTC in nonpolar solvents such as toluene and diglyme under mild conditions, the addition of PTC caused the reactions to proceed smoothly under the same conditions. In addition, the reactions of PECH and PCEVE with a strong base such as potassium hydroxide proceeded selectively through β-elimination reaction to produce the polymers with pendant vinyl groups. These results suggested this method is useful for the syntheses of functional polymers. On the other hand, it turned out that quaternary ammonium salts such as TBAB have higher catalytic activity than crown ethers such as CRG and DCHE in these reactions. Furthermore, the catalytic activity of quaternary ammonium salts was strongly influenced by their chain length and the structure of the polymers.     

Preparation of alumina supported Mo catalysts from molybdenum blue precursor

Alumina supported Mo catalysts were prepared by adsorption of molybdenum blue (MB) on two alumina supports. Sulfided catalysts were tested in HDN/HDS reactions of pyridine and thiophene and compared with catalysts prepared from ammonium heptamolybdate (AHM). Activities of catalysts prepared from MB were considerably higher in thiophene HDS and pyridine hydrogenation and lower in C–N bond hydrogenolysis.     

Reaction of 2-methylene-3-oxoquinuclidine with nucleophilic reagents

The salts and quaternary derivatives of 2-methylene-3-hydroxyquinuclidine readily add nucleophilic reagents because of the high polarity and polarizability of the carbon-carbon double bond, which are due to the overall electron-acceptor effect of the positively charged nitrogen atom and the carbonyl group. The double bond is substantially deactivated in the base, and the addition of nucleophilic reagents is hindered.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1370–1376, October, 1977.     

Cycloaddition of cyclobutenone and azomethine imine enabled by chiral isothiourea organic catalysts

The addition of an organic catalyst to the ketone moiety of a γ-mono-chloride substituted cyclobutenone destroys its stable, conjugated and nearly planar structure. The C–C bond in the resulting less stable anionic oxy-substituted non-planar intermediate is then activated. The breaking of one C–C single bond leads to a catalyst-bound intermediate that undergoes α-carbon selective reactions with azomethine imines to afford nitrogen-containing heterocyclic compounds with excellent diastereo- and enantio-selectivities. Our organocatalytic approach provides a new reaction pattern for C–C bond activation of cyclobutenones that is unavailable with transition metal catalysis. In addition, the present study with isothioureas as the organocatalysts expands the potential in using organocatalysts for C–C bond breaking and selective reactions.     

Dynamic Covalent Chemistry of Nucleophilic Substitution Component Exchange of Quaternary Ammonium Salts

Dynamic covalent libraries (DCLs) of quaternary ammonium cations were set up by reversible nucleophilic substitution (S_N2′ and S_N2) exchange reactions of ammonium salts and tertiary amines. The reactions were conducted at 60 °C to generate thermodynamically and kinetically controlled mixtures of quaternary ammonium compounds and tertiary amines, and were accelerated by using iodide as a nucleophilic catalyst. Microwave irradiation was used to assist the exchange reaction between the pyridinium salts and pyridine derivatives. Finally, experiments towards the generation of dynamic ionic liquids were performed. The results of this study pave the way for the extension of dynamic combinatorial chemistry to nucleophilic substitution reactions.     

Recyclization of 2-vinylpyridinium quaternary salts

It is shown that in the reaction of 2-vinylpyridinium quaternary salts with methylammonium sulfite under isomerization recyclization conditions a water molecule adds initially to the double bond of the vinyl substituents, after which the resulting carbinols undergo recyclization to N-alkylaniline derivatives. The reaction is accompanied by a parallel process involving dealkylation of the pyridine ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 229–232, February, 1982.     

Binol quinone methides as bisalkylating and DNA cross-linking agents

The photogeneration and detection of new binol quinone methides undergoing mono- and bisalkylation of free nucleophiles was investigated by product distribution analysis and laser flash photolysis in water solution using binol quaternary ammonium derivatives 2 and 12 as photoactivated precursors. The alkylation processes of N and S nucleophiles are strongly competitive with the hydration reaction. DNA cross-linking potency of the water-soluble binol quaternary ammonium salt 2 was investigated as a pH function and compared to that of other quaternary ammonium salts capable of benzo-QM (QM = quinone methide) photogeneration by gel electrophoresis. DFT calculations in the gas phase and in water bulk on the binol and benzo quaternary ammonium salts 2 and 4 evidence structural and electrostatic features of the binol derivative which might offer a rationalization of its promising high photo-cross-linking efficiency.     

Unexpected reactions of [60]fullerene involving tertiary amines and insight into the reaction mechanisms

Thermal reactions of [60]fullerene with amino acid ester hydrochlorides and triethylamine in o-dichlorobenzene at reflux afforded pyrrolidinofullerene derivatives containing the CH(3)CH moiety and originating from triethylamine through an unusual C-N bond cleavage. Detailed investigation of these thermal reactions resulted in the discovery of unprecedented reactions between C(60) and tertiary amines and of reactions of C(60) with tertiary amines and aldehydes, giving cyclopentafullerene derivatives with high stereoselectivity. Plausible reaction mechanisms for the product formation involving the uncommon C-N bond cleavage of tertiary amines were proposed on the basis of extensive experimental results.     

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.     

Inhibitory activity of fluorine-containing quaternary ammonium salts comprising an N-methylpiperazinyl moiety

New fluorine-containing quaternary ammonium salts comprising an N-methylpiperazinyl moiety, which exhibited a high inhibiting capacity against hydrochloric acid corrosion of low-carbon steel, were synthesized. The polarization-resistance method was applied to determine the uniform corrosion rate of steel-3 in relation to the structure and concentration of the fluorine-containing substituents in the salts. It was found that the structure of the fluorine-containing moiety of the quaternary ammonium salts does not significantly influence the corrosion processes.     

Formation of a C–C double bond from two aliphatic carbons. Multiple C–H activations in an iridium pincer complex

The search for novel, atom-economic methods for the formation of C–C bonds is of crucial importance in synthetic chemistry. Especially attractive are reactions where C–C bonds are formed through C–H activation, but the coupling of unactivated, alkane-type C_sp³–H bonds remains an unsolved challenge. Here, we report iridium-mediated intramolecular coupling reactions involving up to four unactivated C_sp³–H bonds to give carbon–carbon double bonds under the extrusion of dihydrogen. The reaction described herein is completely reversible and the direction can be controlled by altering the reaction conditions. With a hydrogen acceptor present a C–C double bond is formed, while reacting under dihydrogen pressure leads to the reverse process, with some of the steps representing net C_sp³–C_sp³ bond cleavage. Mechanistic investigations revealed a conceptually-novel overall reactivity pattern where insertion or deinsertion of an Ir carbene moiety, formed via double C–H activation, into an Ir–C bond is responsible for the key C–C bond formation and cleavage steps.     

The Effect of Onium Salt Additives on the Diels-Alder Reactions of a 1-Phenyl-1,2-dihydrophosphinine Oxide under Microwave Conditions

The microwave absorbing ability of toluene is increased in the presence of a slight amount (2–4 mg/3 mL) of quaternary ammonium or phosphonium salts. These additives somewhat accelerated the Diels-Alder reaction of 1-phenyl-1,2-dihydrophosphinine oxide 1 with N-phenylmaleimide and maleic acid anhydride to afford phosphabicyclo[2.2.2]octene derivatives.     

Heterocyclic analogs of pleiadiene. 57. Reactions of aceperimidylenes with some nucleophiles

N-Substituted aceperimidylenes were subjected for the first time to a recyclization reaction (the action of aroyl chlorides in the presence of triethylamine). As a result, their 2-aryl and 2-styryl derivatives were obtained in good yields. The reactions of the N-substituted aceperimidylenes and their quaternary salts with some other nucleophiles were studied.See [1] for Communication 56.Translated from Khimiya Geterosiklicheskikh Soedinenii, No. 3, pp. 372–377, March, 1985.     

Modification of the sesquiterpene lactone arteannuin B and antimicrobial activities of the products obtained

A number of amino derivatives have been synthesized from the sesquiterpene lactone arteannuin B, and quaternary salts have been obtained from them with alkyl halides. The results are given of a study of the antimicrobial activities of the modified derivatives.Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 714–717, September–October, 1997.     

Determination of the dissociation energy of the C-At bond in substituted astatobenzenes

The dissociation energy of C–At bond /D_C–At/ in a number of astatobenzene derivatives has been determined by pyrolytic method. The values of D_C–At for the astatoaromatic compounds investigated have been found to be independent of the substituents and their relative position in the astatoaromatic system.Dedicated to Prof. V.D. Nefedov on the occasion of his 70th birhtday