Heterocyclic-based nitrodicyanomethanide and dinitrocyanomethanide salts: a family of new energetic ionic liquids

Twelve novel energetic salts 1a-f and 2a-f with nitrodicyanomethanide and dinitrocyanomethanide anions paired with 1,5-diamino-4-methyltetrazolium, 1,4-dimethyl-5-aminotetrazolium 1,4,5-trimethyltetrazolium, 1-methyl-4-amino-1,2,4-triazolium, 1,4-dimethyltriazolium, and 1,3-dimethylimidazolium have been prepared through metathesis reactions of equivalent silver(I) salts with corresponding iodide salts in acetonitrile. Key physical properties, such as melting point, thermal stability and density, were measured. The relationship between their structures and these properties was determined. The structures of 1,5-diamino-4-methyltetrazolium-based salts 1a and 2a were further confirmed by single-crystal X-ray analysis. The densities and standard enthalpies of formation for these energetic salts were calculated. All of the salts possess higher enthalpies of formation than the nitrate analogues.     

Reaction of 4-ethoxychromylium salts with some amines

The reactions of 4-ethoxychromylium salts with some amines were studied. It was shown that o-hydroxyarylpyrazoles and chromone phenylhydrazones, respectively, are formed by the reaction of these salts with hydrazine and phenylhydrazine. The action of primary aromatic amines leads to replacement of the 4-ethoxy group by a 4-arylamino group, while the reaction of the 4-ethoxychromylium salts with N,N-diethylaniline gives 4-ethoxy-4-diethylaminoflavylium salts.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1112–1114, August, 1971.     

4-(Azulen-1-yl) six-membered heteroaromatics substituted in 2- and 6- positions with 2-(2-furyl)vinyl, 2-(2-thienyl)vinyl or 2-(3-thienyl)vinyl moieties

The synthesis of pyrylium and pyridinium salts and pyridines with azulene-1-yl moieties in position 4 and two 2-heteroarylvinyl groups in positions 2 and 6 was accomplished. The pyrylium salts were obtained starting from pyranones and pyridines could be prepared from these salts by treating them with ammonium acetate. The general procedures for the synthesis of pyridinium salts, which occur with good results in less delocalized electronic systems, do not take place when applied to the above obtained pyrylium salts. Therefore, as starting material 4-(azulen-1-yl)-1-(n-butyl)-2,6-dimethylpyridinium perchlorate was used, which was condensed with heteroarylcarboxaldehydes. These compounds were completely characterized and some of their spectra were discussed. Their interaction with some metal ions was revealed, observing an affinity better than in the case of simple azulenepyridines. In the last part of the paper are presented redox potentials for several pyrylium salts and pyridines in comparison with those of the nonvinylogated derivatives.     

2-Styryl-4H-1,3-benzoxazin-4-onium salts

A method was developed for the synthesis of 2-styryl-4H-1,3-benzoxazin-4-onium salts by condensation of 2-alkylbenzoxazinonium salts with aromatic aldehydes. It is shown that these same compounds are formed by acid condensation of salicylamides, salicylnitrile, or salicylaldoxime with aromatic aldehydes in acetic anhydride. The hydrolysis and alcoholysis of the synthesized salts were studied.     

Synthesis,characterization and theoretical study of 2-azido-4- nitroimidazole-based energetic salts

The 2-azido-4-nitroimidazole-based energetic salts were synthesized in a simple and straightforward manner. The structures of these new salts were determined by IR, 1H NMR and 13C NMR spectroscopy and elemental analysis. These salts also exhibited high positive enthalpies of formation, high nitrogen content, and moderate detonation properties.     

Carboranylpyrans and carboranylpyrylium salts

Relatively difficult-to-oxidize 4-carboranylpyrans were obtained by the action of (phenyl-o-carboranyl)lithium on 2,6-disubstituted pyrylium salts. The conversion of the 4-carboranyl-pyrans to the corresponding 4-carboranylpyrylium salts is achieved by the action of a one-electron oxidizing agent-tris(p-bromophenyl)aminium hexachloroantimonate. The 4-(o-car-boranyl)pyrylium salts readily undergo one-electron electrochemical reduction. It is assumed that the first step in dehydrogenation of the pyrans is one-electron transfer.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1172–1175, September 1977.     

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.     

P-Chirogenic phosphonium salts: preparation and use in Rh-catalyzed asymmetric hydrogenation of enamides

P-Chirogenic trialkylphosphonium salts were prepared from the corresponding free phosphines by treatment with a strong acid (HBF₄ or HOTf). No racemization of the phosphonium salts occurred in methanol or water even at considerably high temperature. The salts were conveniently used in rhodium-catalyzed asymmetric hydrogenation of enamides.     

二苯胺重氮盐在乙醇中的光、热分解动力学

二苯胺-4-重氮盐与甲醛的缩聚产物-重氮树脂是制备阴图PS版最重要的感光剂,用它制备阴图PS版已有很多专利^[1-7],但二苯胺重氮盐(包括有类似结构的咔唑重氮盐)光、热分解,文献上还未见有报导。     

Reactions of 2- and 4-methylpyrylium salts with ethyl orthoformate

Under mild conditions 2- and 4-methylpyrylium salts react with ethyl orthoformate to give their β-ethoxyvinyl derivatives. Symmetrical and unsymmetrical cyanine dyes were synthesized by heating the latter with 2- and 4-methylpyrylium salts or N-methylquinaldinium perchlorate. The pyrylocyanines react with perchloric acid to give bispyrylium salts, and they are converted to the corresponding pyridine bases by the action of ammonium acetate.     

Facilitated transport of salts by neutral anion carriers

Partitioning of ions from water to the membrane solvent (NPOE) can be quantified by Gibbs free energies of transfer, deltaG(tr,NPOE)(ion). These were derived from transport studies of lipophilic salts through supported liquid membranes (SLMs) in the absence of the carrier. Partition coefficients Kp for various salts can now be calculated. The neutral anion receptors uranyl sal(oph)enes 1-5 transport Cl- and H2PO4- as tetrapropylammonium salts. The transport is diffusion-limited and can be described by two transport parameters Dm and K(ex). From the extraction constants K(ex) and the partition coefficients Kp of the transported salts, the association constants Ka of the anion receptors for Cl- and H2PO4- in NPOE were determined. Competitive transport with carriers 3 and 4 of NPr4H2PO4 and NPr4Cl demonstrated highly selective transport of H2PO4- even in the presence of excess of Cl-.     

Crystal structures and physicochemical properties of mixed salts of ammonium nitrate and sulfate

Mixed salts (NH₄)₂SO₄·2NH₄NO₃ (1) and (NH₄)₂SO₄·3NH₄NO₃ (2) were synthesized and studied by X-ray diffraction analysis. The unit cell parameters of these salts were determined and their crystal structures were solved. The thermal stability of the salts was studied by differential scanning calorimetry and thermogravimetric analysis. The temperatures and enthalpies of incongruent melting of compounds 1 and 2 were determined. The enthalpies of formation from the constituent salts were estimated.     

Synthesis of 4H-1,3-benzoxazin-4-onium salts and 4-H-1,3-benzoxazin-4-ones

Salicylamide and its substituted derivatives react with aliphatic carboxylic acid anhydrides and perchloric acid to give 4H-1,3-benzoxazin-4-onium salts. These same compounds were obtained by acidic cyclization of O- and N-acylsalicylamides. The synthesized salts are converted to 2-substituted 4H-1,3-benzoxazin-4-ones by the action of triethylamine and are hydrolyzed by water to N-acylsalicylamides. The probable reaction scheme is examined.     

Studies on tellurium-containing heterocycles. Part 20. Reactions of 2-benzoselenopyrylium salts and 2-benzotelluropyrylium salts with nucleophiles: formation of 1-functionalized 1H-isoselenochromenes and 1H-isotellurochromenes

The reactions of the 2-benzoselenopyrylium (1A) and 2-benzotelluropyrylium cations (1B) with a variety of nucleophiles have been investigated. LiAlH(4), sodium alkoxide (NaOMe, NaOi-Pr and NaOt-Bu), diethylamine, n-butylamine and acetone reacted with 1 to give the 1H-isochromenes (2) and the corresponding 1-substituted products (4-9) under mild conditions in almost good to high yields. The 1-alkyl(phenyl)isoselenochromenes (10-13) and 1-benzylisochromenes (18A, 18B), which were produced by the reaction of the salts 1 with Grignard reagents, were converted to the corresponding 1,3-disubstituted 2-benzopyrylium salts (14-17, 19) by treatment with triphenylcarbenium tetrafluoroborate (Ph(3)C(+) BF(4)(-)), respectively. The 1-benzylselenopyrylium salts (19A) and 1-benzyltelluropyrylium salts (19B) exist in the solvent as an equilibrium mixture of the salts (19) and the corresponding (Z)-benzylidene compounds (20).     

Synthesis and characterization of tetraphenylphosphonium salts of N-phosphorylated thioureas and bis-thioureas

Russian Chemical Bulletin - Tetraphenylphosphonium salts of N-phosphorylated thioureas and bio-thioureas were synthesized by the reactions of their sodium salts with PPh4Br in 96% aqueous EtOH. The...     

Studies of imidazo[4, 5-f]quinoline

The UV absorption spectra of imidazo[4, 5-f]quinoline and its quaternary salts were examined. The causes of the development of luminescence in solutions of the quaternary salts of imidazo[4, 5-f]quinoline were elucidated.For part I, see [6].     

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.     

取代二苯胺重氮盐、重氮树脂合成及光、热分解性质

二苯胺型重氮树脂是阴图PS版最重要的感光剂^[1],关于它的应用已有许多专利^{[2 5]}.作为一种预涂感光版,阴图PS版的贮存期要求在一年以上,从而对作为感光剂的重氮树脂的热稳定性有较高的要求,希望其热分解温度尽量高一些并能在潮热气候下性质稳定.一般来说,二苯胺重氮盐的苯环上带取代基时,有利这些性质的改善,如3-甲氧基二苯胺-4-重氮盐树脂就是一个例子,它已获得广泛的应用^[6,7].     

Effects of electrolytes on the configuration change of cobalt(II)-halide complexes in chloroform/water reverse micelle systems.

The effects of various salts and HClO4 on the configuration change of cobalt(II)-halide complexes in CHCl3/CTAC or CTAB/H2O reverse micelle systems were examined at 25 degrees C by means of spectrophotometry, where CTAC and CTAB represent cetyltrimethylammonium chloride and bromide, respectively. The formation of the [CoCl4]> or [CoBr4]2- species of the tetrahedral configuration from [Co(H2O)6]2+ of the octahedral configuration in the reverse micelles was greatly promoted not only by a decrease in the W value (W = [H2O]/[surfactant]), but also, at a constant W value (e.g., W = 2.0), by the addition of relatively low concentrations of salts or the acid (e.g., 4.0 mol dm(-3) in the aqueous phase or 4.0 x 10(-2) mol dm(-3) in the whole reverse micelle system). The effects of perchlorate salts increased as Na+ < or = Li+ approximately H+ < Sr2+ < Ca2+ < Mg2+. Non-metallic salts, various tetraalkylammonium (R4N+) salts at lower concentrations, gave minor effects. The enhanced effects of metal salts on the configuration change of the cobalt(II)-halide complexes were interpreted by a further distortion of the hydrogen-bonded structure of the water in a "water pool" in the presence of salts of even relatively low concentrations. A conformation change with increasing temperature was also attributed to a further distortion of the water structure. An almost completed formation of [CoBr4]2- as well as [CoCl4]2- was attained in the reverse micelles at a low W value of 0.69 containing LiClO4 or HClO4. A partial transfer of the [CoX4]2- species from a "water pool" into the CHCl3 phase by the addition of the metal salts may be suspected. An examination of cobalt(II)-bromide complexes in dichloromethane/CTAB/H2O at W = 1.3 - 5.55 justified all the arguments concerning the chloroform systems. The Raman spectra of D2O containing concentrated LiBr and LiClO4 have supplied conclusive evidence that the hydrogen-bonded structure of the bulk water is completely distorted by extremely concentrated salts.     

Synthesis and properties of 3-formyl-4H-pyrans

The Vilsmeier formylation of 4H-pyrans afforded 3-formyl-4H-pyrans. These were converted to 3-formylpyrylium salts, from which pyridine or pyridine salts with an aldehyde group at C₍₃₎ were obtained. The reaction between 3-formyl-4-allyl-4H-pyran and methyltrifluoromethanesulfonate proceeded via a Koop rearrangement.Translated from Khimiya Geterotsiklicheskii Soedinenii, No. 5, pp. 603–607, May, 1990.