Synthesis and properties of salts of 2-substituted derivatives of 1, 6-dimethyl-7-chloro-1, 6-diazaphenalenium salts,III

A series of 2-substituted 1,6-diazaphenalene derivatives, the subsequent alkylation of which give 1,6-dimethyl-2-R-7-chloro-1,6-diazaphenalenium salts, was obtained by cyclization of acyl derivatives of 5-amino- and 5-methylamino-8-chlorolepidines. A study of the absorption spectra of the salts attests to the fact that, as in cyanine dyes, electron-donor substituents heighten the color, while electron-acceptor substituents deepen it.See [1] for communication II.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1391–1395, October, 1972.     

Base-assisted one-pot synthesis of N,N',N"-triaryltriazatriangulenium dyes: enhanced fluorescence efficiency by steric constraints

In this paper we report the first synthesis of cationic N,N',N"-triaryltriazatriangulenium dyes (Ar(3)-TATA(+)). Previously, only alkyl-substituted triazatriangulenium derivatives (R(3)-TATA(+)) were known, a consequence of the low reactivity of anilines in the aromatic nucleophilic substitution reaction leading to the formation of the TATA(+) core. The synthesis of Ar(3)-TATA(+) was achieved by heating the tris(2,6-dimethoxyphenyl)methylium ion (DMP(3)C(+)) in various anilines in the presence of NaH. In the solvent-free reaction all three aryl substituents could be introduced despite the low reactivity of the anilines. The symmetric Ar(3)-TATA(+) derivatives with Ar = phenyl (2), 4-methoxyphenyl (3), and 4-bromophenyl (4) were synthesized. Single crystal structures of 2 and 4 were obtained as BF(4)(-) salts, where torsional angles larger than 80° were observed between the TATA(+) chromophore and the aryl substituents. The photophysical properties were studied in solution and in thin films. The results show that the Ar(3)-TATA(+) dyes have a surprising 3-fold increase in fluorescence quantum yields when compared to the parent alkyl-substituted R(3)-TATA(+) salts. With a high quantum yield (>50%) and emission in the red (λ(fl) = 560 nm) the Ar(3)-TATA(+) dyes represent a promising new addition to the family of superstable cationic triangulenium dyes. Additionally, the synthesized tribromo derivative 4 is shown to be a potential triagonal synthon for polymers and other macromolecules.     

Secondary ion mass spectra of organic cationic dyestuffs

Rules for the behavior under fast atom bombardment (FAB) have been established for 15 cationic dyes — quaternary ammonium salts of heterocyclic amines and heterocycles containing quaternary nitrogen atoms with aliphatic substituents. Intense peaks corresponding to the molecular mass of the cationic part of the dyes [M-Hal]⁺ are observed in the spectra of all the derivatives. Fragmentation of the azodyes is determined by the azo group and the heterocyle. The base peaks in the case of compounds containing a quaternary nitrogen atom with aliphatic substituents correspond to the ammonium ion and a fragment of amine type. The results obtained can be used to identify dyes of unknown structure from their secondary ion mass spectra (SIMS).DeceasedTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, 1411–1417, October, 1992     

Radical C?H Arylation of the BODIPY Core with Aryldiazonium Salts: Synthesis of Highly Fluorescent Red‐Shifted Dyes

We describe herein the first radical C H arylation of BODIPY dyes. This novel, general, one‐step synthetic procedure uses ferrocene to generate aryl radical species from aryldiazonium salts and allows the straightforward synthesis of brightly fluorescent (Φ>0.85) 3,5‐diarylated and 3‐monoarylated boron dipyrrins in up to 86 % yield for a broad range of aryl substituents. In this way, new and complex dyes with red‐shifted spectra can be easily prepared.     

Radical CH Arylation of the BODIPY Core with Aryldiazonium Salts: Synthesis of Highly Fluorescent Red‐Shifted Dyes

We describe herein the first radical C? H arylation of BODIPY dyes. This novel, general, one‐step synthetic procedure uses ferrocene to generate aryl radical species from aryldiazonium salts and allows the straightforward synthesis of brightly fluorescent (Φ>0.85) 3,5‐diarylated and 3‐monoarylated boron dipyrrins in up to 86 % yield for a broad range of aryl substituents. In this way, new and complex dyes with red‐shifted spectra can be easily prepared.     

Synthesis, structures, and stability of N-donor-stabilized N-silylphosphoranimine cations

A series of DMAP-stabilized (DMAP=4-dimethylaminopyridine) N-silylphosphoranimine cations [DMAPPR(2)==NSiMe(3)](+), bearing R=Cl ([8](+)), Me ([10 a](+)), Me/Ph ([10 b](+)), Ph ([10 c](+)), and OCH(2)CF(3) ([10 d](+)) substituents, have been synthesized from the reactions of the parent phosphoranimines Cl(3)P==NSiMe(3) (3) and XR(2)P==NSiMe(3) (X=Cl (9), Br (11); R=Me (9 a and 11 a), Me/Ph (9 b and 11 b), Ph (9 c and 11 c), and OCH(2)CF(3) (9 d and 11 d)) with DMAP and silver salts as halide abstractors. Reactions in the absence of silver salts yield the corresponding cations, with halide counterions. The stability of the salts is highly dependent on the phosphoranimine substituent and the nature of the counteranion, such that electron-withdrawing substituents and non-coordinating anions yield the most stable salts. X-ray structural determination of the cations reveal extremely short phosphoranimine P--N bond lengths for the cations [8](+) and [10 d](+) (1.47-1.49 A) in which electron-withdrawing substituents are present and a longer phosphoranimine P--N length for the cation [10 a](+) (1.53 A) in which electron-donating substituents are present. Very wide bond angles at nitrogen are observed for the salts containing the cation [10 d](+) (158-166 degrees ) and indicate significant sp hybridization at the nitrogen centre.     

Near-infrared fluorescent probes: synthesis and spectroscopic investigations of a few amphiphilic squaraine dyes

With the objective of developing near-infrared fluorescence probes for biological applications, a few squaraine dyes 3a-d, containing amphiphilic substituents, were synthesized and their photophysical properties have been investigated in the presence and absence of the organized media. These dyes exhibited absorption in the range 630-650 nm, with significant absorption coefficients (epsilon = 1-3 x 10(5) M(-1) cm(-1)) in the aqueous medium. The fluorescence spectra of these dyes showed emission maximum from 660 to 675 nm, depending on the nature of substituents. The fluorescence quantum yields were in the range from 0.15 to 0.21 in ethanol, but 10 times lower values were observed (phi(f) = 0.01-0.02) in the aqueous medium. In the presence of micelles such as cetyltrimethylammonium bromide, sodium dodecyl sulfate, and Triton X-100, these dyes showed negligible changes in their absorption properties, whereas a significant enhancement (5-10-folds) in their fluorescence yields was observed. Picosecond time-resolved studies indicated that these dyes show single-exponential decay in ethanol and ethanol-water mixtures; however, they exhibit biexponential decay with longer lifetimes in the presence of the micellar media. The results indicate that these novel amphiphilic squaraine dyes 3a-d, which exhibit favorable photophysical properties, good solubility in the aqueous medium, and interact efficiently with micelles, can have potential biological applications as near-infrared fluorescence sensors.     

Synthesis of novel quinaldine-based squaraine dyes: effect of substituents and role of electronic factors

[reaction: see text] Condensation of squaric acid with quinaldinium salts containing electron-donating substituents gave only the semisquaraines. However, with salts possessing electronegative and electron-withdrawing groups, the squaraine dyes were isolated in quantitative yields. The semisquaraines formed undergo condensation with highly nucleophilic salts yielding the unsymmetrical squaraine dyes. These results demonstrate the role of electronic factors and provide valuable information for the design of efficient squaraine-based sensitizers that can have potential applications in photodynamic therapy.     

Quino-4-cyanines with carbonyl-containing substituents

6-Carbonyl-substituted lepidines and their quaternary salts were synthesized. Quino-4-cyanines were obtained from them. The introduction of carbonyl-containing substituents substantially deepens the color of the dyes obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 943–947, July, 1984.     

Synthesis and spectral-generational characteristics of pentamethylidynecyanine dyes from 1-methyl-3-arylbenzo[f]quinolinium salts

Pentamethylidynecyanine dyes were synthesized by the reaction of 1-methyl-3-(R-phenyl)benzo[f]quinolinium quarternary salts with 1,3,3-triethoxy-1-propene, Pentamethylidynecyanines substituted in the meso position of the polymethine chain were obtained by condensation of these salts with 1-anilino-2-methyl-3-dimethoxy-1-propene hydrobromide. The spectral and generational characteristics of the dyes were determined. It was shown that the presence of a phenyl group in the benzo-[f]quinoline ring of the dyes gives rise to a bathochromic shift of the absorption and generation maxima. The investigated dyes have high generation efficiencies that lie in the 20–30% range and in the 940–1010 nm spectral range.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1523–1527, November, 1982.     

(Aza)dithiafulvalenes as π-electron donors

(Aza)1,2- and 1,4-dithiafulvalenes are more difficult to oxidize than tetrathiafulvalenes. Depending on substituents, (aza)dithiafulvalenes react with tetracyano-p-quinodimethane (TCNQ) either in a 1:1 or 2:3 ratio to form heterofulvalenium 7,7,8,8-tetracyano-p-quinodimethanides. The electrical conductivity of these salts strongly depends on substituents. The conductivities of alkylthiofulvalene-TCNQ salts are much higher than those of phenyl-substituted derivatives.     

A comparison of linear optical properties and redox properties in chalcogenopyrylium dyes bearing ortho-substituted aryl substituents and tert-butyl substituents

A series of thiapyrylium pentamethine dyes (4 and 12-15) bearing 2,2'-di-tert-butyl-6,6'-diphenyl, 2,2'-di-tert-butyl-6,6'-bis(2,6-dimethylphenyl), 2,2'-di-tert-butyl-6,6'-bis(2-methylphenyl), 2,2',6,6'-tetrakis(2,6-dimethylphenyl), and 2,2',6,6'-tetrakis(2-methylphenyl) substituents, respectively, were prepared and their linear optical properties and electrochemical redox properties were measured and compared to thiapyrylium pentamethine dyes 3 and 5. The tert-butyl and 2,6-dimethylphenyl substituents give nearly identical chromophores with respect to values of lambda(max), molar extinction coefficients (epsilon), bandwidths at half-height (nu(1/2)), and lack of absorption in the visible spectrum. The 2-methylphenyl substituent imparts linear optical properties that are intermediate between those of the tert-butyl and phenyl substituents. The 2,6-dimethylphenyl and 2-methylphenyl substituents impart greater oxidative stability based on anodic shifts in oxidation potential.     

Synthesis and Antimicrobial Activity of New Dialkyl(diaryl)-2-(5-chloro-2-hydroxyphenyl)-2-(phenylethenyl)pentylphosphonium Salts

New dialkyl(diaryl)-2-(5-chloro-2-hydroxyphenyl)-2-(phenylethenyl)pentylphosphonium salts bearing various substituents at the phosphorus atom were synthesized. Antimicrobial activity of the salts obtained was estimated. Derivatives with 2-methoxyphenyl substituents at the phosphorus atom are most active against grampositive bacteria. Herewith, dibenzyl-substituted phosphonium derivatives possess the best antifungal activity.     

Researches on synthetic dyes

1-Aryl-5, 6-benzolepidinium salts condense with p-dimethylaminobenzaldehyde to give the corresponding quinostyryl dyes. The effects of various substituents at the para position of the N-phenyl group at the quinoline ring on the absorption spectra of the dyes synthesized are investigated. Steric hindrance in the molecules of the dyes is postulated.     

Dual Bodipy fluorophores linked by polyethyleneglycol spacers

Several Bodipy dyes were synthesized with various substituents designed to potentially interact with adventurous cations including protons. Among the different synthetic strategies, protection of the amino group by a BOC appears efficient for the substitution of the fluoro groups on the boron by Grignard reagents. Single alkylation on the amino-Bodipy compounds by a polyethyleneglycol chain bearing an alkyne end group is feasible using a biphasic strategy. Linkage of a blue dye on the alkyne fragment is promoted by palladium(0) and it provides novel dual donor-acceptor dyes. Fluorescence of the monoalkylated amino dyes is heavily quenched but restored by protonation or interaction with Fe(II) salts. Very efficient energy transfer from the donor (energy input at 20,000 cm⁻¹) to the acceptor (energy output at 15,100 cm⁻¹) is quantitative and not distance dependent.     

Syntheses and characterization of unsymmetric dicationic salts incorporating imidazolium and triazolium functionalities

A series of both imidazolium- and triazolium-based unsymmetric dicationic salts with alkyl and polyfluoroalkyl substituents were prepared and characterized. Most of them can be classified as ionic liquids (MP < 100 degrees C). Key physical properties, such as melting point, thermal stability, density, and solubility in common solvents were determined and were compared with those of the related monocationic imidazolium- or triazolium-based salts. The effects of anions and substituents bonded to the triazolium and imidazolium cations on these properties were examined. 1-(3-Butyl-imidazolium-1-yl)methylene-(4-butyl-1,2,4-triazolium diiodide) (2d), the precursor of 1-(3-butylimidazolium-1-yl)methylene-(4-butyl-1,2,4-triazolium) bi[bis(trifluoromethanesulfonyl)amide] (3d), reacted with Pd(OAc)(2) at 120 degrees C to generate a binuclear palladium(II) dicarbene complex. The palladium(II) complex was characterized by single-crystal X-ray diffraction analysis and was used as a catalyst precursor for palladium-catalyzed Heck cross-coupling reactions in 3d. Preliminary results show that 3d could serve as both the solvent and catalyst support in the catalytic reactions.     

Condensation of 2-(3,4-methylenedioxyphenyl)-5,6-benzolepidine methiodide with aromatic aldehydes

2-(3,4-Methylenedioxyphenyl)-5,6-benzolepidine methiodide enters into condensation with aromatic aldehydes in absolute alcohol in the presence of piperidine to give styryl dyes. The effect of various substituents in the styryl residue on the position of the absorption maxima of the dyes was studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 689–690, May, 1973.     

Regioselective Synthesis of 1,2,3,4-Tetrasubstituted Arenes by Vicinal Functionalization of Arynes Derived from Aryl(Mes)iodonium Salts**

Herein, the synthesis of 1,2,3,4-tetrasubstituted benzenoid rings, motifs found in pharmaceutical, agrochemical, and natural products, is described.^[1] In the past, the regioselective syntheses of such compounds have been a significant challenge. This work reports a method using substituted arynes derived from aryl(Mes)iodonium salts to access a range of densely functionalized 1,2,3,4-tetrasubstituted benzenoid rings. Significantly, it was found that halide substituents are compatible under these conditions, enabling post-synthetic elaboration via palladium-catalyzed coupling. This concise strategy is predicated on two regioselective events: 1) ortho- deprotonation of aryl(Mes)iodonium salts to generate a substituted aryne intermediate, and 2) regioselective trapping of said arynes, thereby improving previously reported reaction conditions to generate arynes at room temperature and in shorter reaction times. Density functional theory (DFT) computations and linear free energy relationship (LFER) analysis suggest the regioselectivity of deprotonation is influenced by both proximal and distal ring substituents on the aryne precursor. A competition experiment further reveals the role of arene substituents on relative reactivity of aryl(Mes)iodoniums as aryne precursors.     

Preparation of pyrylium salts from 2-phenyl-5H-phenaleno [ 1,9-bc] pyran-5-one

The preparation of 2-phenyl-5H-phenaleno[ 1,9-bc]pyran-5-one ( 7 ) is described. Compound 7 undergoes reactions typical of pyrones and was therefore a useful intermediate for the preparation of pyrylium salts. Several pyrylium dyes were prepared from 7 and the long-wavelength absorptions of these dyes were compared with those of the corresponding flavylium dyes.