两种新型卟啉吡啶季铵盐的合成

合成了两种新型卟啉吡啶季铵盐:溴化5-[4-N-(对硝基)苄铵基吡啶基]-10,15,20-三(4-N吡啶基)卟啉和氯化5-[4-N-(对甲氧基)苄铵基吡啶基]-10,15,20-三(4-N-吡啶基)卟啉.这两种化合物尚未见文献报道,它们的结构分别由紫外可见光谱、红外光谱、核磁共振谱、质谱、元素分析得到确证.     

An efficient ultrasonic-assisted synthesis of imidazolium and pyridinium salts based on the Zincke reaction

A mild and efficient method has been developed using ultrasound irradiation for the synthesis of imidazolium and pyridinium salts based on the Zincke reaction. Tertiary nitrogen nucleophiles such as pyridines and imidazoles can be alkylated with primary amine by simply using their ammonium form Zincke salts. In almost all cases, a clear yield increase results and a dramatic reduction of the reaction time accompanied by an improved quality of the products occurs.     

ESR spectroscopic studies of alkylammonium,pyridinium and arsonium solid salts of C 60 −

The synthesis of a series of new solid salts of the monoanion of C₆₀ using a variety of countercations, e.g., tetraalkylammonium, pyridinium and tetraalkylarsonium cations, and their initial characterization by ESR spectroscopy are reported. Both the size of the countercation and the solvent used in the synthesis of the C₆₀ monoanion salts have been found to affect the ESR spectral characteristics of the resulting salts. For example, for countercations less than 10 Å in diameter, the ESR spectral linewidths decrease as the countercation diameter decreases. In a similar manner, those salts believed to be solvent free display narrower ESR spectral linewidths and somewhat largerg-values than those in which solvent is believed to be incorporated in the crystal structure of the salt in question. Finally, ESR spectroscopy was used to show that exposure of the salts reported herein to ambient atmosphere leads to a decrease in the original ESR signal and an increase of a sharp (i.e., narrow line) signal which is superimposed on the original broad line.     

Photochromic behavior of several new synthesized dyes via Zincke salts

Synthesis of several ‘dyes’, analogs of retinal imine visual pigment via nucleophilic attack of some secondary amines to pyridinium salts following precyclic ring‐opening reaction, is discussed. The photochromic properties of these dyes have been studied by UV‐Vis spectroscopy under irradiation of UV light. Copyright © 2009 John Wiley & Sons, Ltd.     

Photophysical Behaviour of Novel Quaternary Pyrenoyl Salts and Their Sensitivity Towards Bile Salt Micellization

The present work describes the synthesis and characterization of pyrene derivatives, N-(1-Pyrenoylmethyl) pyridinium bromide (PM-PB) and N-(1-Pyrenoylmethyl)-N,N,N-triethylammonium bromide (PM-TAB). The photophysical behavior of these molecules has been studied in various protic and aprotic solvents. Using steady state fluorescence intensity, fluorescence anisotropy and dynamic fluorescence lifetime studies, the sensitivity of these molecules towards the micellization process of bile salts has been monitored. These derivatives have been effectively used in estimating critical micellar concentration (CMC) of bile salt, sodium deoxycholate (NaDC).

     

C-13 and H-1 NMR Study of Alkyl and Aryl-Substituted 1-(4′-Dimethylaminobenzylideneamino)pyridinium Perchlorates

C-13 and H-1 NMR spectra of some 1-(4′-dimethylaminobenzylideneamino)pyridinium perchlorates show that the angle of twist of the pyridine ring in unsubstituted, 1, and 2-alkyl substituted compounds 2–5 is comparable. However, it is considerably increased in 2,6-dialkyl derivatives. As seen from the spectral data, pyridine and phenyl rings in 2,6-diphenyl derivative 15 are not coplanar. The effect of 4-alkyl substituent is of hyperconjugative chacter. In general, the amount of the positive charge at C-4 in 2,6-dialkyl substituted salts is higher as compared to 2-monosubstituted compounds.     

Electrochemically driven organic monolayer formation on silicon surfaces using alkylammonium and alkylphosphonium reagents

The functionalization of silicon surfaces with organic monolayers, bound through Si–C bonds, is an area of wide interest due to the technological promise of organosilicon hybrid devices, but also to investigate fundamental surface reactivity. In this paper, the use of alkylammonium and alkylphosphonium cations as sources of organic moieties to bind to hydrogen-terminated flat and porous silicon is demonstrated. Tetraalkylammonium, tetraalkyl/arylphosphonium reagents, and alkyl pyridinium salts can be utilized, but trialkylammonium salts cannot as they yield substantial surface oxidation. Under electrochemical conditions, either potentiostatic or galvanostatic modes, alkyl groups derived from the ammonium or phosphonium salts are grafted to the silicon surface and are bound through Si–C bonds. Covalent attachment of the organic monolayers to the surface was demonstrated by XPS, AFM scribing, and FTIR. The mechanism may proceed via reduction of the ammonium salt yielding alkyl radicals, R, which may be reduced to R⁻ and attack surface Si–Si bonds, leading to Si–C bonds, or the formation of silyl anions (≡Si⁻) under the cathodic conditions followed by nucleophilic attack on the trialkylammonium cation.     

Dihydropyridines in MCRs. Tandem processes leading to modular tetrahydroquinoline systems with up to 6 diversity elements

An efficient, modular method for the synthesis of highly substituted tetrahydroquinoline systems is described. The Lewis acid catalyzed interaction of dihydropyridines with glyoxalate and anilines affords the heterocyclic parent systems in good yields. Tandem one-pot processes allow the incorporation of additional components: a preliminary nucleophilic attack on pyridinium salts generates the reactive dihydropyridine in situ, and subsequent electrophilic reactions on the secondary amine complete the assembly of the final targets, which have up to 6 diversity points.     

Solvolytic reactivity of pyridinium ions

The leaving group abilities of pyridine, 4‐methylpyridine, and 4‐chloropyridine in S_N1 solvolytic reactions have been determined by analyzing the rate constants of X,Y‐substituted benzhydrylpyridinium salts obtained in various solvents. By applying the linear free energy relationship equation, log k = s_f (E_f + N_f), the nucleofuge specific parameters of 4‐substituted pyridine have been extracted. Because of solvation in the reactant ground state, the reactivity (nucleofugality, N_f) of a given pyridine decreases as the polarity of the solvent increases. High slope parameters (s_f > 1) may be due to the spread of the energy levels of the benzhydrylium ion/pyridine pair intermediates in comparison to benzhydrylium ion/chloride pairs (s_f ≈ 1). Because of slow heterolysis step of pyridinium salts in various solvents, some are stable under normal conditions. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and Characterization of New Y-shaped Fluorophores with an Imidazole Core

Four new y-shaped fluorophores of 4- {4,5-[2,2'-Bis(2,4,6-trimethoxyphenyl)vinyl]-1-H-imidazole-2-yl}benzonitrile 1a, 2-phenyl-{4,5-[2,2'-Bis(2,4,6-trimethoxyphenyl)vinyl]-1-H-imidazole} 1b, 2- (9-anthryl)-{4,5-[2,2'-Bis(2,4,6-trimethoxyphenyl)vinyl] }-1-H-imidazole 1c and 2- (4-nitrophenyl) - {4,5-[2,2'-Bis(2,4,6-trimethoxyphenyl)vinyl] -1-H-imidazole 1d which bear an imidazole core, were synthesized for the first time via intermediate 1,6-Bis(2,4,6-trimethoxyphenyl)hexa-1,5-diene-3,4-dion with different aldehydes. The structures of the new derivatives were confirmed by (1)H NMR, (13)C NMR and FT-IR. The optical properties such as absorption and emission maxima, Stokes' shift and quantum yield values were investigated in solvents of toluene, tetrahydrofuran and acetonitrile. The products show intense emission maxima in the range of 440-630?nm. The imidazole derivatives exhibited excellent photostabilities.     

Symmetry breaking at the phase transitions in ferroelectric pyridinium salts

The phase transitions in ferroelectric pyridinium tetrafluoroborate (PyBF₄) and pyridinium perchlorate (PyClO₄) have been characterized by structural studies. The continuous ferroelectric phase transition at 238.7 K in PyBF₄ appears to be a unique case for multiaxial ferroelectrics, while the first order phase transition in PyClO₄ at 248 K is consistent with the Landau theorem for deducing the character of phase transitions from symmetry considerations. The phase transition in both materials is caused by ordering of the pyridinium cation as well as tetrahedral anions.     

Theoretical study on second hyperpolarizability for cationic pyridine derivatives

The molecular second hyperpolarizabilities γ of cationic 3- or 4-substituted pyridine derivatives have been investigated. The γ values are calculated by an ab initio molecular orbital (MO) method at correlated levels including CCSD(T). The magnitude of γ for the pyridinium cation is shown to be smaller than that of pyridine. It is found that γ for the pyridinium cation changes dramatically with substitution, whereas γ for neutral pyridine does not show such large substituent effects. This remarkable substituent effect on γ of cationic pyridine derivatives is one of the special features of cationic species.     

2,4,6-三甲基-1,3,5-苯三甲醛的合成与表征

以均三甲苯为初始原料,经氯甲基化、改进的Sommelet反应两步合成了目标产物2,4,6-三甲基-1,3,5-苯三甲醛。利用1H NMR、13C NMR等手段对各步所得产物的结构进行了表征,分析数据证实目标产物为2,4,6-三甲基-1,3,5-苯三甲醛。以均三甲苯计,两步反应的总收率为77.7%。     

三氯异氰尿酸红外光谱测绘方法探讨

本文对ＫＢｒ压片法、ＫＣｌ压片法以及萨特勒图谱采用的，糊剂法所绘制的三氯异氰尿酸的红外光谱进行了分析、对照。ＫＣｌ压片法克服了溶剂的影响，简单、直观地体现了物质的精细结构。同时，将三氯异氰尿酸分别与ＫＣｌ、ＫＢｒ研磨，和三氯异氰尿酸纯品进行了紫外－可见吸收光谱对照。实验发现，与ＫＢｒ研磨的三氯异氰尿酸和纯品的吸收峰有差异，而与ＫＣｌ研磨后的三氯异氰尿酸和纯品一致，说明结构未发生变化。因此，认为ＫＣｌ压片法是绘制三氯异氰尿酸红外光谱较好的方法。     

Herstellung des Arzneimittels Hexamethylmelamin mit deuteriertem Seitenstück

Treatment of N,N,N′,N′,N″-Pentamethyl-1,3,5-triazin-2,4,6-triamin with butyllithium and trideuteroiodomethane give N,N,N′,N′,N″-Pentamethyl-N″-(trideuteromethyl)-1,3,5-triazin-2,4,6-triamin, a deuterated analogue of the anticancer drug hexamethylmelamine, in high yield.     

Third harmonic generation in copolymer films with optically nonlinear N-substituted 4-nitroazobenzene in the side and main polymer chains

The third-order nonlinear optical susceptibility χ⁽³⁾(3ω; ω, ω, ω) of two types of copolymer films containing optically nonlinear N-substituted nitroazobenzene in the side (methacrylic series copolymers) and main (copolyimidoamido esters) polymer chains is investigated using the third harmonic generation method at a wavelength of 1.064 μm. __________ Translated from Fizika Tverdogo Tela, Vol. 44, No. 2, 2002, pp. 379–382. Original Russian Text Copyright ? 2002 by Lebedeva, Loretsyan, Ivanova, Romashkova, Lukoshkin, Kudryavtsev.     

Electron-nuclear spin transitions in free phosphonyl radicals detected via CIDNP

Electron-nuclear spin transitions in short-lived phosphonyl radicals have been investigated experimentally by nuclear magnetic resonance detection of nuclear polarization in diamagnetic reaction products in low magnetic fields (15–80 mT) for³¹P-centered radicals formed in laser photolysis of (2,4,6-trimethylbenzoyl)diphenylphosphine oxide and 2,4,6-trimethylbenzoylphosphonic acid dimethyl ester. A theoretical model on the basis of the numerical solution of the kinetic equation for the density matrix of a radical with one nonzero hyperfine coupling constant has been employed to study the main peculiarities of this effect and to account for the data quantitatively.     

Study of the P-T phase diagram of pyridinium perchlorate by X-ray diffraction and Raman spectroscopy

The crystal structure and vibrational spectra of deuterated pyridinium perchlorate (d ₅PyH)ClO₄ (C₅D₅NHClO₄) are studied by means of neutron diffraction in ambient conditions, X-ray diffraction at high pressures up to 3.5 GPa in the temperature range 297–420 K, and Raman spectroscopy at high pressures up to 5.7 GPa. Deuterated pyridinium perchlorate at ambient conditions has rhombohedral structure with the R3m symmetry (paraelectric phase I). Over the pressure range of 0.5–1.2 GPa, the phase II with monoclinic symmetry Cm exists. At pressure P ～ 1.2 GPa, the phase transition to monoclinic phase III with the Pm symmetry is observed at ambient temperature. The lattice parameters, unit cell volume, and frequencies of internal vibrational modes as functions of pressure are obtained for different phases of deuterated pyridinium perchlorate. The P-T phase diagram of (d ₅PyH)ClO₄ over the extended pressure and temperature range is discussed.     

多氯甲基芳烃的合成与表征

以甲苯、乙苯、异丙苯、间二甲苯和均三甲苯为原料,在由路易斯酸、有机酸和无机酸所组成的新型复合催化剂协同催化下,经多氯甲基化反应制备了2,4,6-三(氯甲基)甲苯、2,4,6-三(氯甲基)乙苯、2,4,6-三(氯甲基)异丙苯、2,4,6-三(氯甲基)间二甲苯和2,4,6-三(氯甲基)均三甲苯.利用IR、1H NMR、13C NMR等手段对所合成产物的结构进行了表征,在优化反应条件下,5种产物的收率分别可达 24.5％、31.7％、15.3％、78.1％和89.6％.     

The ESI CAD fragmentations of protonated 2,4,6-tris(benzylamino)- and tris(benzyloxy)-1,3,5-triazines involve benzyl-benzyl interactions: a DFT study

The electrospray ionization collisionally activated dissociation (CAD) mass spectra of protonated 2,4,6-tris(benzylamino)-1,3,5-triazine (1) and 2,4,6-tris(benzyloxy)-1,3,5-triazine (6) show abundant product ion of m/z 181 (C(14) H(13)(+)). The likely structure for C(14) H(13)(+) is α-[2-methylphenyl]benzyl cation, indicating that one of the benzyl groups must migrate to another prior to dissociation of the protonated molecule. The collision energy is high for the 'N' analog (1) but low for the 'O' analog (6) indicating that the fragmentation processes of 1 requires high energy. The other major fragmentations are [M?+?H-toluene](+) and [M?+?H-benzene](+) for compounds 1 and 6, respectively. The protonated 2,4,6-tris(4-methylbenzylamino)-1,3,5-triazine (4) exhibits competitive eliminations of p-xylene and 3,6-dimethylenecyclohexa-1,4-diene. Moreover, protonated 2,4,6-tris(1-phenylethylamino)-1,3,5-triazine (5) dissociates via three successive losses of styrene. Density functional theory (DFT) calculations indicate that an ion/neutral complex (INC) between benzyl cation and the rest of the molecule is unstable, but the protonated molecules of 1 and 6 rearrange to an intermediate by the migration of a benzyl group to the ring 'N'. Subsequent shift of a second benzyl group generates an INC for the protonated molecule of 1 and its product ions can be explained from this intermediate. The shift of a second benzyl group to the ring carbon of the first benzyl group followed by an H-shift from ring carbon to 'O' generates the key intermediate for the formation of the ion of m/z 181 from the protonated molecule of 6. The proposed mechanisms are supported by high resolution mass spectrometry data, deuterium-labeling and CAD experiments combined with DFT calculations.