Intramolecular photocyclization of N-[(2-haloaryl)methyl]pyridinium and n-(arylmethyl)-2-halopyridinium salts

Various N-[(2-haloaryl)methyl]pyridinium, N-(arylmethyl)-2-halopyridinium and N-(2-halobenzyl)iso-quinolinium salts have been synthesized and their intramolecular photocyclization reactions studied. Upon irradiation the aqueous solution of N-[(2-haloaryl)methyl]pyridinium, and N-arylmethyl-2-halopyridinium salts 1, 2 were cyclized to give isoindolium salts. In contrast to the pyridinium salts 1, 2 , the aqueous solution of N-(2-halobenzyl)isoquinolinium salts 3 appear not to undergo photocyclization. N-Benzyl-2-chloropyridinium salts 1c is more reactive than N-(2-chlorobenzyl)pyridinium salt 1a in the photocyclization. N-(2-Chlorobenzyl)-2-chloropyridinium salt 1d is three times more reactive than 1c . A mechanism of π-complex formation of the halogen moiety of the pyridinium ring with the phenyl ring is suggested for the reactive pyridinium salt. The triplet energy of the isoquinolinium salts 3 is tool low to photocyclize.     

Two Energetic Salts based on 5,5′‐Bitetrazole‐1,1′‐diolate: Syntheses,Characterization, and Properties

Two salts based on 1H,1′H‐5,5′‐bitetrazole‐1,1′‐diolate (BTO) anion with pyrazole ( 1 ) and imidazole ( 2 ) cations were synthesized with metathesis reactions. Structural characterization was accomplished for them by using the element analysis, Fourier transform infrared spectroscopy (FT‐IR), NMR and mass spectrum, and X‐ray single crystal diffraction. Thermal analysis for the title salts were determined by means of differential scanning calorimetry (DSC) and thermogravimetry‐derivative thermogravimetry (TG‐DTG) as well as the calculation of non‐isothermal kinetic parameters. Consequently, both salts shown acceptable thermal stabilities as the decomposition temperatures were over 200 °C. The enthalpies of formation were calculated for these salts using the measured combustion energies with a result of 70.6 kJ · mol^–1 for 1 and –47.8 kJ · mol^–1 for 2 , respectively. Impact and friction sensitivities were also tested and the results indicated that these salts both have low sensitivities (>40 J, 120 N). The title energetic salts possess acceptable performance, they can therefore be applied in the field of energetic materials.     

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.     

Reaction of 1‐benzoselenopyrylium salts with grignard reagents: Formation of 2,4‐disubstituted selenochromenes and their conversion into the corresponding 1‐benzoselenopyrylium salts

Treatment of 2‐tert‐butyl‐1‐benzoselenopyrylium salts 1A and 2‐phenyl‐1‐benzoselenopyrylium salts 1B with an alkyl(phenyl)magnesium halide resulted in nucleophilic addition at the C‐4 position to give the corresponding 2,4‐disubstituted 4H‐selenochromenes 2A and 2B in good yields, respectively. The obtained selenochromenes 2 were then easily converted into the 4‐substituted 2‐tert‐butyl‐1‐benzoselenopyrylium salts 6A by treatment with triphenylcarbenium tetrafluoroborate in high yields. The 4‐substituted 2‐phenyl derivatives 6B were also obtained in a similar manner. The reaction of the unsubstituted 1‐benzoselenopy‐rylium salt 1C with an alkylmagnesium halide is also described.     

Sels de N-alcoxyquinoléinium et de N-alcoxyisoquinoléinium porteurs d'une fonction ester dans leur chaine alcoxyle: Synthèse et réactivité vis-a-vis des ions cyanure

Reaction of ethyal α-bromoisobutyrate on quinoline 1-oxide and isoquinoline 2-oxide in the presence of silver perchlorate leads to the corresponding N-alkoxyl salts 1 and 2 . On treatment with potassium cyanide, these salts are converted into 2-cyanoquinoline and 1-cyanoise-quinoline according to mode B of the Katritzky' s classification concerning the reaction of nucliophiles on N-alkoxypyridinium salts. When the reaction of cyanide ions were performed on salt 1 at 0° in aqueous solution the dihydro aromatic 4 was isolated. This result confirms the addition-elimination mechanism of the reaction studied.     

Nucleophilic addition to substituted 1H-4,5-dihydroimidazolium salts

1H-4,5-Dihydroimidazolium salts 1 react readily with nucleophilic reagents originating cyclic products which may be stable or become transformed into acyclic compounds maintaining the structural ethylenediamine unit. With methylmagnesium iodide compound 1e affords the expected imidazolidine, but in the case of substituted 1-aryl-3-methyl-2-phenyl salts 1b-d the N-aryl-N′-methylethylenediamines 3b-d and acetophenone ( 4 ) were isolated, the process representing the transfer of the C-2 unit to a nucleophilic carbon. With alkaline cyanides salts 1 react efficiently affording α,α-diaminonitriles 5 . In these compounds the cyano group may be readily substituted by nucleophiles (hydroxyl anion, species with nucleophilic carbon and reagents that act by hydride ion transfer), in a way similar to the salts but with better yields.     

Preparation,Crystal Structure,and Thermal Analysis of Two Energetic Salts Based on Nitro Phenolic Compounds with Diamino‐glyoxine

As a key research objective for environmentally friendly energetic materials, energetic salts without heavy metal have received wide attention. The energetic salts DAG · PA · H₂O ( 1 ) and DAG · TNR · H₂O ( 2 ) were synthesized by using diamino‐glyoxine (DAG) and picric acid (PA) or 2, 4,6‐trinitro‐resorcinol (TNR) as raw materials, and their structures were characterized by elemental analysis, FT‐IR, ¹H NMR, and ¹³C NMR spectroscopy. Single crystals of the title salts were cultured and their structures were determined by X‐ray single‐crystal diffraction. Both salts belong to the triclinic space group P1 with density values of 1.764 and 1.751 g · cm^–3, respectively. The thermal decomposition behaviors of both salts were investigated by differential scanning calorimetry (DSC), the non‐isothermal kinetic parameters and the critical temperature of thermal explosion were calculated. The heats of formation for the salts were also determined through the combustion heats date measured by using the oxygen bomb calorimetry. In addition, the detonation pressure (P) and detonation velocities (D) of the salts were predicted by using the K‐J equations, and their sensitivities towards impact and friction were tested. The results indicated that the title salts have potential applications in the field of energetic materials.     

Synthesis and Reactivity of Unsaturated Bisphosphonium Salts

Abstract

The synthesis of 1, 2 vinylene bisphosphonium salts 1 has now been enlarged to the vinylogous 1, 4-butadienylene bisphosphonium salts 2. The salts 2, a new class of unsaturated disalts, have also been prepared through a two-step isomerisation of acetylenic salts. New aspects of the reactivity of salts 1 and the comparative study of salts 2 (selective cleavage reactions of P-C bonds and reactions with nucleophiles having a mobile hydrogen) are described. This reactivity allows the preparation of new series of phosphonium salts substituted by heteroatomic groups.     

Bridged tetraquaternary salts from N,N'-polyfluoroalkyl-4,4'-bipyridine

4,4'-Bipyridine (1) with excess of polyfluoroalkyl bromide or iodides 2a-d at 100-110 degrees C without solvent gave the monoquaternary salts 3a-d in >90% yields. However, 1 with 2.5 equiv of 2a-c in DMF at 110 degrees C resulted in the diquaternary salts 5a-c in >85% yields. In DMF, 5a-c were obtained in comparable yields when a molar excess of 2a-c reacted with 3a-c. 1,4-Dibromobutane with 3a,b in DMF at 100 degrees C led to the tetraquaternary salts 7a,b in approximately 85% yields. In water or acetone/water as a solvent, salts 3a-d and 5a-c were metathesized with LiN(SO(2)CF(3))(2) and KSO(3)CF(3) to produce monoquaternary ionic liquids 4a-h in >88% yields and diquaternary ionic liquids 6a-f in >86% yields, respectively. Tetraquaternary ionic liquids 8a,b were obtained when LiN(SO(2)CF(3))(2) was reacted with salts 7a,b. These compounds were stable to 340 degrees C as determined by DSC. They are the first N-mono-, N,N'-di-, and N,N,N',N'-tetra-4,4'-polyfluoroalkylbipyridinium quaternary salts and ionic liquids.     

Energetic polymer salts from 1‐vinyl‐1,2,4‐triazole derivatives

Energetic polymers salts from 1‐vinyl‐1,2,4‐triazole derivatives have been synthesized via free radical polymerization of 1‐vinyl‐1,2,4‐triazolium monomer salts or by protonation of poly(1‐vinyl‐1,2,4‐triazole) with inorganic or organic acids. Standard enthalpies of formation of the new monomer salts were calculated using the computationally feasible DFT(B3LYP) and MP2 methods in conjunction with an empirical approach based on densities of salts. Compared with the monomer salts, the polymer salts have good thermal properties with high densities > 1.5 g cm^?3. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2414–2421, 2008     

Thiazolocyanines

Quaternary thiazolium salts with active methylthio groups and 2-thiazolyl and 2-pyridyl residues attached to the nitrogen atom of the thiazole ring were obtained. 2-Methyl-3-(2-pyridyl)-and 2-methyl-3-(2-thiazolyl)thiazolium salts were synthesized by replacement of the methylthio group by a methyl group. Monomethylidynecyanines and nullmethylidyne- and dimethylidynemerocyanines were obtained from salts with active methyl and methylthio groups.See [1] for communication XV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 749–752, June, 1973.     

Polymers by the reaction of bis(pyrylium salts) with diamines: A novel approach to ionene polymers

The following reactions of pyrylium salts with amines are described: (1)bis(pyrylium salts) with amines; (2) diamines with pyrylium salts; and (3) bis(pyrylium salts) with diamines. Both (1) and (2) give bis(pyridinium salts) in high yields, and (3) gives the corresponding polymers which are isolated and characterized. This procedure was applied to cationic bis(pyrylium salts) to give cationic dimers and polymers, and further to zwitterionic bis(pyrylium salts) to yield the corresponding zwitterionic dimers and polymers.     

Construction of C2-Spirocyclopropyl-Indolin-3-Ones through Base-Promoted [2+1] Annulation Reaction of Indolin-3-ones with Bromosulfonium Salts

A simple base-promoted [2+1] annulation of indolin-3-ones and bromosulfonium salts has been developed in this article. This strategy uses simple and easily prepared indolin-3-ones 1 as C1 synthons and bromosulfonium salts 2 as C2 synthons under mild reaction conditions, and 33 examples of C2-spirocyclopropyl-indolin-3-ones were obtained with up to 99 % yield and >20 : 1 dr.     

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.     

Reactions of 1-alkylbenzimidazolium 3-imines with acetylenic compounds and benzaldehyde

1-Alkyl-3-aminobenzimidazolium salts react with dimethyl acetylenedicarboxylate or dibenzoylacelylene in the presence of base to produce unusual 1:1 adducts, 1-(2′-alkylaminophenyl)-pyrazole derivatives. Treatment of the 3-amino salts with benzaldehyde in the presence of alkali gives benzaldehyde 2-(N,N-acylalkylamino)phenylhydrazones. The same hydrazones are obtained by alkaline treatment of 1 -alkyl-3-benzaliminobenzimidazolium salts, which are prepared from the 3-amino salts and benzaldehyde.     

4‐(Azulen‐1‐yl) six‐membered heteroaromatics substituted with thiophen‐2‐yl or furan‐2‐yl moieties in 2 and 6 positions

Pyranylium perchlorates with azulen‐1‐yl moiety in 4‐position and thiophen‐2‐yl or furan‐2‐yl in 2 and 6‐positions were obtained by the substitution of 4‐chloro corresponding salts with azulenes. The pyranylium salts are used as starting materials for the synthesis of pyridine and pyridinium salts. The products were characterized and for pyridines pKa was spectroscopically determined. Several attempts were made for pyridine complexation with metal cations as Hg²⁺ or Ag⁺. J. Heterocyclic Chem., (2011).     

A Simple Route to New N(3)-Substituted 5-Aryl-2-(dialkylamino)-1,3-oxazolium Salts and N(1)-Substituted 4-Aryl-2-(dialkylamino)-1H-imidazoles

In the reaction of N,N-dialkyl-dichloromethaniminium chlorides 11 with 2-aminoacetophenones 12 , a general and simple route to heretofore unknown 5-aryl-substituted 2-(dialkylamino)-1,3-oxazolium salts 13 and 5-aryl-substituted 2-(dialkylamino)oxazoles 14 was found. From the 2-(dialkylamino)-1,3-oxazoles 14 , the corresponding oxazolium salts 13 were obtained after alkylation with (MeO)₂SO₂. The new oxazolium salts 13 were converted to 1-substituted 4-aryl-2-(dialkylamino)-1H-imidazoles 9 by treatment with NH₄OAc. The possible use of these 1H-imidazoles as dye educts was explored. Analytical data, as well as AM1 calculations, reveal some remarkable differences between the structures of the neutral imidazoles 9 and their positively charged oxazolium precursors 13 .     

Preparation of 1‐X‐2, 2‐Difluoroethenylxenon(II) Tetrafluoroborates [CF2=CXXe][BF4]

The new type of alkenylxenon(II) salts [CF₂=CXXe] [BF₄] (X = H, Cl, CF₃) was prepared by reacting the corresponding alkenyldifluoroboranes CF₂=CXBF₂ with XeF₂ in 1, 1, 1, 3, 3‐pentafluoropropane (PFP) at —60 °C. The alkenylxenon(II) salts were characterised by multinuclear NMR spectroscopy. The influence of the substituent X at C‐1 on the stability of alkenylxenon(II) salts is discussed. Additionally the preparation of the potassium alkenyltrifluoroborate salts K [CF₂=CXBF₃] and their transformation into the boranes CF₂=CXBF₂ by fluoride abstraction in PFP is reported.     

New Low‐Molecular‐Mass Gelators Based on L‐Lysine: Amphiphilic Gelators and Water‐Soluble Organogelators

The new L ‐lysine alkali‐metal salts 1 – 5 (M⁺=Na⁺ and K⁺) with different alkyl groups at the N^α‐position were easily synthesized, and their hydro‐ and organogelation properties were investigated. All compounds were H₂O‐soluble, and some salts, especially the potassium salts, functioned as a hydrogenator that could gel water below 2 wt‐%. These salts also had organogelation abilities for many organic solvents.     

Thermogravimetric characteristics of some salts of violuric acid and 1,3-dimethylviouric acid

The thermolysis curves of the various salts of violuric acid and 1,3-dimethylvioluric acid with sodium and potassium are described. These salts form hydrates in all cases. 1,3-Dimethylvioluric acid forms 1 : 1 salts with sodium or potassium; violuric acid may form either 1 : 1 or 1 : 2 salts with these metals.