Preparation and synthetic utility of fluorinated phosphonium salts,bisphosphonium salts and phosphoranium salts

The synthesis and mechanism of formation of phosphonium salts of the type [R₃$\text{P}\text{+}$CFXY]Z^? (where X = F, Cl, Br; Y = Br, Cl; Z = Br, Cl), $\text{bis}$-phosphonium salts of the type [R₃$\text{P}\text{+}$CF₂$\text{P}\text{+}$R₃]2Br^?, and phosphoranium salts of the type [R₃$\text{P}\text{+}$$\text{C}\text{?}$F$\text{P}\text{+}$R₃]X^? (X = Br, Cl) will be presented. The applicability of these substrates in the generation of useful nucleophilic or electrophilic synthetic intermediates will be discussed.     

Dialkyldialkoxyphosphonium salts

Conclusions Dialkyldialkoxyphosphonium halides are stable only in the case of branched alkoxy groups. The stability is explained by the difficulty of attack of the isoalkoxy group by halide anions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 415–417, February, 1971.     

Alkylselenophosphonium salts

Conclusions Methylselenophosphonium salts have been obtained for the first time by the reaction of full amides of phosphoroselenoic and alkylphosphonoselenoic acids with methyl iodide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, p. 169, January, 1969.     

Pyridinium salts

New 4- (benzazol-2-yl)pyridinium salts have been synthesized. Their reduction in a neutral medium with sodium tetrahydroborate has given 2-(1,2,5,6-tetrahydropyridin-4-yl)benzazoles. The catalytic hydrogenation of the latter leads to piperidine derivatives which have also been synthesized by an independent route.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 104–107, January, 1974.     

Dioxolanium salts

A new method was developed for the synthesis of dioxolanium salts by the condensation of 1,2-glycols of the pinacol series with aliphatic acid anhydrides in the presence of perchloric acid. The dioxolanium ring is opened to form monoacylates of the starting pinacols under the influence of water, alcohol, and ammonia. A method was developed for the acetylation of aromatic compounds by dioxolanium salts.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1023–1026, August, 1971.     

Aziridiniminium salts

Stable aziridiniminium salts have been obtained from the reaction of 2-amino-1-azirines with trityl tetrafluoroborate or trimethylsilyl triflate. These new derivatives of α-lactams react with carbanions to give 2-amino-1-aziridines.     

Thienopyrylium salts

The catalytic acylation and subsequent heterocyclization of- and-acetonyl derivatives of thiophene were studied. Mechanisms for the synthesis of thienopyrylium salts, the reaction of which with ammonia leads to the difficult-to-obtain thienopyridines, are proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 320–325, March, 1971.     

Pyranyltriphenylphosphonium salts

The reaction of pyrylium salts having a free or position with triphenylphosphine has given pyranylphosphonium salts. 2,4,6-Trisubstituted pyrylium salts do not react with triphenylphosphine. The properties and IR spectra of the compounds synthesized are discussed.     

Synthesis of mono-amino-functionalised ferrocene, ferrocene salts and ferrocenium salts

A number of mono-amino-functionalised ferrocenes, ferrocene salts and a mono-amino-functionalised ferrocenium salt have been synthesised and characterised. This represents a novel method of accessing these important classes of molecules. In the cases of some of the ferrocene salts, there are some interesting structural features in the solid state. These include N-H...O and N-H...F hydrogen bonds.     

An efficient synthesis of imidazolinium salts using vinyl sulfonium salts

The synthesis of imidazolinium salts from the reaction of formamidines and (2-bromoethyl)diphenylsulfonium triflate is described. A variety of symmetrical and unsymmetrical imidazolinium triflate salts were synthesized in high yield in short reaction times under mild conditions. Aromatic and aliphatic N-substituents work well. The reaction is proposed to proceed via generation of a vinyl sulfonium salt intermediate from the bromoethylsulfonium triflate.     

1,2-dithiolium salts

The reaction of aryl-1,2-dithiol-3-thiones with alkyl iodides and with ICH₂COOH and ICH₂COOC₂H₅ has been studied. This gives 3-alkylithio-S-carboxymethylthio-, and 3-ethoxycarbonylmethylthio-1, 2-dithiolium iodides. Compounds of the first type are formed only with lower unbranched alkyl iodides (CH₃I, C₂H₅I, and n-C₃H₇I), and salts of the last two types were previously unknown.     

α-Ferrocenylcarbonium salts

Conclusions A study was made of the effect of the dimethylamino group, found in the p-position of the benzene ring attached to the carbonium carbon, on the stability and reactivity of-ferrocenylphenylcarbonium salts.To be sure, the title of the paper is arbitrary. As is clear from the formulas given below the structure of the described salts is rather of the ammonium type.Translated from Izvestiya Akademii Nauk SSSR Seriya Khimicheskaya No. 11, pp. 2017–2019, November, 1966.     

Polycyano-anion-based energetic salts

Energetic salts based on polycyano anions and cations with a high nitrogen content tend to have extensive hydrogen bonding and exhibit heats of formation up to DeltaH(f)=1579.1 kJ mol(-1). Based on theoretical calculations, some of the new salts may be considered to be low-energy monopropellants. One of the salts can be used as a precursor to a carbon nitride.     

Liquid azide salts

Ionic liquid azides from azidoethyl, alkyl, and alkenyl substituted derivatives of 1,2,4- and 1,2,3-amino-triazoles were prepared and examined for the first time to investigate their structural and physical properties. All reported salts possess melting points below 100 degrees C. The unique character of these newly discovered ionic liquid azides is based upon the fact that these molecules are not simple protonated salts like previously reported substituted hydrazinium azides. The presence of quaternary nitrogen confers both thermal stability and negligible volatility.     

2-Benzopyrylium salts

The previously unknown oxabenzo[c]phenanthrenium salts were synthesized from -veratryl-naphthol and its acetate.See [1] for communication XVIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 745–747, June, 1976.     

2-Benzopyrylium salts

The interaction of 6,7-dimethoxy-3-(3,4-dimethoxyphenyl)-2-benzopyrylium perchlorate with -aminocarbonyl compounds forms N--aminocarbonyl-substituted isoquinolinium compounds which on treatment with acids are converted into dibenzo [a,g] quinolizinium compounds, one of which is the natural alkaloid dehydronorcoraldine. The products were characterized by the results of elementary analysis and IR, PMR, and UV spectroscopy.For Communication XXXIV, see [1].Scientific-Research Institute of Physical and Organic Chemistry, N. A. Suslov Rostov State University. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 75–80, January–February, 1989.     

Nonaromatic isoxazolinediazonium salts

Diazotization of 3-aminoisoxazolines has given stable, nonaromatic 2-isoxazoline-3-diazonium salts which undergo the azo-coupling reaction. The electronic structures of these diazo- and azo-compounds are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1110–1112, August, 1990.