Synthesis and properties of novel dialkylaminocarbenium salts

Novel dialkylaminocarbenium salts with metallocomplex counter ions were prepared by the reaction of phosgene with either DMF or tetramethylurea in the presence of metal chlorides. Reactions of organosilicon amides with phosgene gave corresponding carbenium salts, while organosilicon ureas yielded aminoiminocarbenium salts. Dialkylaminochlorocarbenium salts were reduced with hydrosilanes to give dialkylaminocarbenium, salts and can be easily hydrolyzed to afford either amides or ureas. Pathways of the reaction with water and alcohols depend on the nature of reagent and the reaction conditions. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1035–1040, May 1997.     

S-苯并噻吩盐的合成的方法及其反应的研究进展

综述了近年来合成苯并噻吩盐的多种方法,讨论了其存在的优缺点,并详细介绍了S-苯基苯并噻吩盐的[4+2]Diels-Alder反应、加热反应、光解反应以及开环反应,并对其发展前景做出了展望.     

Recyclization reactions of heterocycles XVIII. Synthesis and recyclization of thiazolium and benzothiazolium salts

A number of thiazolium salts were obtained, and their reaction with hydrazine was studied. On reaction with hydrazine the aryl-substituted thiazolium salts are recyclized to dihydro-l, 2, 4-triazines, whereas on reaction with monoalkylhydrazines they are converted to 4H, 5H-1, 2-4-triazinium salts; thiazolium salts are converted to hydrazidohydrazones on reaction with phenylhydrazine. Recyclization to the dihydro-sym-tetrazine system was observed for 2-phenyl-substituted benzothiazolium tosylate.See [1] for communication XVII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 635–640, May, 1976.     

Cycloaddition d'azides aux sels de nitrilium; obtention de sels de tetrazolium et de tetrazolines

The reaction of nitrilium salts with azides allows the synthesis with good yields of 1,4,5-alkyl or -aryl-substituted tetrazolium salts. The mechanism of this reaction is discussed. Reduction or alkylation of these tetrazolium salts leads to the corresponding tri- or tetra-substituted tetrazolines.     

The participation of the anion and alkyl substituent of diaryliodonium salts in photo‐initiated cationic polymerization reactions

The photo‐initiated cationic polymerization (PCP) of epoxides using diaryliodonium salt photoacid generators (PAGs) bearing alkyl groups and anions was investigated. The properties and reactivities of a series of iodonium salts containing various cations and anions were compared in the context of a PCP reaction. The products from the decomposition of the cations of these salts were analyzed using gas chromatography‐mass spectrometry (GC‐MS) spectra. The relationship between the molecular structure of the salts and their reaction mechanism in the PCP reaction was investigated. Based on the results of the investigation, it was concluded that the structures of the cations and anions of theiodonium salts affect the PCP reaction rate, which was controlled by the products from the diaryliodonium salts. As part of an additional investigation, the diaryliodonium salts‐epoxide materials were applied to 254 nm‐photo‐patterning. Copyright © 2006 John Wiley & Sons, Ltd.     

A versatile synthesis of substituted benzimidazolium salts by an amination/ring closure sequence

[reaction: see text]. A new method to produce benzimidazolium salts based on a successive Buchwald-Hartwig amination and ring closure is reported. A variety of different benzimidazolium salts can be prepared using this procedure. Amines that bear an alpha-chiral group undergo the reaction to furnish chiral benzimidazolium salts. The salts that lack a C2 substituent on the heterocycle are readily deprotonated to give nucleophilic carbenes.     

Synthesis and some properties of benzo-1,2,3-thiaselenazolium salts

The reaction of selenious acid on benzo-1,2,3-dithiazolium salts (Herz salts) gives benzo-1,2,3-thiaselenazolium salts, which were previously obtained from o-aminothiophenols. This reaction, which involves exchange of sulfur by selenium in the heteroring, occurs only under conditions in which the products of hydrolysis of the Herz salts —benzo-3H-1,2,3-dithiazole 2-oxides- are in equilibrium with them.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1361–1364, October, 1976.     

Soluble polymer-supported catalysts containing pendant quaternary onium salts for the addition reaction of oxiranes with carbon dioxide

The addition reaction of oxiranes ( 15a-d ) with carbon dioxide (CO₂) was carried out using 1 mol % of soluble polymer-supported quaternary onium salts as catalysts under atmospheric pressure. The reaction of 15a-d with CO₂ proceeded very smoothly to give the corresponding five-membered cyclic carbonates ( 16a-d ) in high yields at 90-100°C. The catalytic activity of the soluble polymer-supported quaternary onium salts was strongly affected by the following factors: kind of reaction solvent, degree of introduction of the pendant onium salt residues in the polymer chain, and type of alkyl group on the onium salts due to the balance between lipophilicity and steric hindrance of the onium salt residue. Furthermore, these soluble polymer-supported quaternary onium salts were found ordinarily to have higher catalytic activity than low molecular weight quaternary onium salts under the same reaction conditions. It was also found that the rate of reaction was proportional both to catalyst concentration and to oxirane concentration. © 1995 John Wiley & Sons, Inc.     

Direct polycondensation of nylon salts by polyphosphates and imidazole

Direct polycondensation of various nylon salts (salts of dicarboxylic acid and diamine) took place under mild conditions in the formation of polyamide in the presence of polyphosphates and organic bases. Among organic bases imidazole was the best in terms of polymer yields. The reactivity of the polyphosphates was arranged in following order: pyrophosphate ? tripolyphosphate > tetrapolyphosphate. Otimum reaction conditions were investigated in terms of solvents, temperatures, and concentration of monomers. A reaction mechanism was proposed for the phosphorylation reaction, due to polyphosphates, which led to the direct polycondensation of nylon salts.     

Acyclic selenoiminium salts: isolation,first structural characterization,and reactions

[reaction: see text] A variety of selenoiminium salts were obtained by reacting the corresponding selenoamides with methyl triflate at room temperature for 30 s. All of the salts were stable under air. The structures of the selenoiminium salts were determined by X-ray molecular analysis. An aromatic selenoiminium salt reacted with BuLi (3 equiv) to give two types of ketones. In a reaction with LiAlH(4)/Te, the selenoiminium salts were converted to telluroamides.     

Synthesis and properties of 1-methylthiopropargylammonium salts and their use as key precursors to sulfur-containing enediynes

1-methylthiopropargylammonium salts were synthesized in a highly efficient manner by reaction of alkynyl S,N-acetals with methyl triflate. Reactions of the 1-methylthiopropargylammonium salts with Grignard reagents gave propargyl sulfides or allenyl sulfides, whereas the reaction with organocopper reagents led to exclusive formation of allenyl sulfides regardless of the nature of substituents on the acetylenic carbon. The salts undergo self-dimerization reactions when treated with organolithium and lithium amide bases.     

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.     

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。     

Some new derivatives of pyridyl- and quinolylphosphonic acids

Diamides and amido esters were obtained by the reaction of pyridine and quinoline N-oxide salts with phosphorous acid amido esters, and pyridyl- and quinolylphosphonic acid esters were obtained by reaction of the N-oxide salts with sodium dialkylphosphites.     

Reactions of N-alkylazinium cations. Reaction of acridinium salts with enamines

The reaction pyridinium N-methylazinium salts and their benzo analogs — quinolinium, isoquinolinium, and acridinium ions — with enamines was investigated. Acridanyl-substituted enamines, their iminium salts, and the corresponding ketones were obtained by reaction of the N-methylacridinium salts with the enamines in dimethyl sulfoxide at room temperature. The quinolinium and isoquinolinium salts have lower activities; the N-methylpyridinium cation does not react at all under the indicated conditions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 666–669, May, 1979.     

Aminopentadiene imines from zincke salts of 3-alkylpyridines. Application to a synthesis of pyridinium salts from amino acids

The reaction of Zincke salts with primary amines to give pyridinium salts generally requires rather elevated temperature to go to completion (50-100 degrees C). It is shown that the addition of 1 equiv of a secondary amine allows formation, at ambient temperature, of intermediate aminopentadiene imine salts which can be isolated and were found to cyclize in acidic medium to give pyridinium salts at temperatures which do not exceed 50 degrees C. If this process has a tendency to give lower yields of pyridinium salt than the standard Zincke procedure, it can be advantageous in some cases, as illustrated by the synthesis of pyridinium salts from amino acids, a challenging reaction which does not work starting from Zincke salt in the absence of diethylamine. More generally, the reaction can be extended to primary amines featuring polar functions, as exemplified by a pyridinium salt synthesis (75 degrees C) in 55% yield from l-carnosine.     

季铵盐固相催化使聚氯乙烯脱HCl

 通过将季铵盐与聚氯乙烯(PVC)混溶成膜,使其在固相脱HCl,研究了催化剂对PVC脱HCl反应速度和产物结构的影响以及固相反应与温度、时间的关系.发现在催化性能上下基铵盐比乙基铵盐好得多,根据实验结果提出了季铵盐通过分解成叔胺实现催化的机理.     

Features of the reaction of 2,3-dihalopropanoic acids with pyridines and nucleophilic addition to <Emphasis Type="Italic">N</Emphasis>-vinylpyridinium salts

The example of vinylpyridinium salts to establish for the first time the possibility of nucleophilic addition to the vinyl group in quaternary ammonium salts, which provides evidence against the concept that such reactions involve d orbitals. The nucleophilic addition reaction was accomplished with triphenylphosphine and pyridine. In the latter case, the suggested reaction scheme was confirmed by the observation of the Wittig reaction under the action of carbon dioxide and the Stevens reaggangement involving the double bond of the pyridinium ring and migrating 2-phosphonioethyl group. Procedures for preparing the starting vinylpyridinium salts. Reaction schemes were siggested.     

季铵盐固相催化使聚氯乙烯脱HCl

通过将季铵盐与聚氯乙烯(PVC)混溶成膜,使其在固相脱HCl,研究了催化剂对PVC脱HCl反应速度和产物结构的影响以及固相反应与温度、时间的关系.发现在催化性能上下基铵盐比乙基铵盐好得多,根据实验结果提出了季铵盐通过分解成叔胺实现催化的机理.     

Reactions of 4-ethoxyflavylium, 4-ethoxychromylium,and 4-ethoxyfurochromylium salts with several amines

The reactions of 4-ethoxyflavylium, 4-ethoxychromylium, and 4-ethoxyfurochromylium salts in acidic media with several acids were investigated. In the reaction with hydrazine the furochromylium salt forms pyrazole, whereas both α,β-substituted benzopyrylium salts are converted to azines. The reaction of hydroxylamine with the flavylium salt gives a flavone oxime, whereas the reaction with the furochromylium salt gives an isoxazolylbenzofuranol.