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.     

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.     

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.     

Pentafluorosulfanylnitramide salts

The synthesis and properties of a new class of inorganic salts, named pentafluorosulfanylnitramide salts (or pentafluorosulfanylnitraminic acid salts) [Z+SF5NNO2-], are described. A number of SF5-nitramide salts (Z+SF5NNO2-) were successfully prepared via nucleophilic displacements from carbamates and/or ion exchange techniques, but some salts [M(SF5NNO2)x; M = Li, Mg, Al] decomposed during isolation procedures and appear to be unstable in the solid state. Single-crystal X-ray diffraction was used to fully characterize the Z+SF5NNO2-, and their properties/structures are compared with those of the corresponding dinitramide salts (or dinitraminic acid salts), Z+N(NO2)2-. X-ray crystallography revealed major structural differences between N(NO2)2- and SF5N(NO2)- salts concerning the N-N distances and the angles subtended at the central nitrogen atom. In the N(NO2)2- salts, there are two nonequivalent N-N (average lengths 1.372(2) and 1.354(2) A) distances and an average N-N-N angle of 115.8(3) degrees (falls between sp3 and sp2 hybridization). In the SFsNNO2- salts, the average N-N distance is much shorter, 1.308(9) A, and the average N-N-S angle is 120.0(5) degrees (closely fits sp2 hybridization). The SF5NNO2- salts show a remarkable metrical similarity for the SF5 moiety in all structures, indicating a lack of sensitivity to its steric and electronic environment. This is in marked contrast to N(NO2)2-, where there is a wide variation in conformations adopted by these anions which can be related to their environment.     

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.     

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 synthesis of berberine analogs — substituted dibenzo[a,g]quinolizinium salts — was worked out on the basis of 2-benzopyrylium salts.See [1] for communication XXII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1481–1483, November, 1977.     

3-Bromopyrylium salts

Three new methods have been proposed for the synthesis of 3-bromopyrylium salts. An unsaturated 1,5-diketone is converted into a 3-bromopyrylium salt by allyl bromination and the addition of bromine to the double bond. 3-Bromopyrone, obtained by the bromination of dibenzoylacetone is converted by treatment with Grignard reagents into 3-bromopyrylium salts. Similar compounds have also been synthesized by the pyrylation of aromatic and heterocyclic compounds with 3-bromo-4-chloropyrylium salts obtained from 3-bromopyrone.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 873–877, July, 1973.     

2-Benzopyrylium salts

The previously unknown bis-2-benzopyrylium salts and 2-benzopyrylium salts containing an alkylcarboxy group were synthesized by the acylation of some alkoxy-substituted deoxybenzoins and phenylacetones with dibasic aliphatic acids in polyphosphoric acid. The effect of the structure of the dicarboxylic acid on the structure of the reaction products was followed. The IR spectra of the synthesized salts are presented.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 454–456, April, 1972.See [8] for communication XI.