Kinetics of the hydroxylation of N-picryl-4-[4-(dimethylamino)styryl]pyridinium salts by molecular oxygen in acetonitrile

The reactions of N-picryl-4-[4-(dimethylamino)styryl]pyridinium salts with molecular oxygen in the presence of 4-[4-(dimethylamino)styryl]pyridine (DASP) in acetonitrile proceeds with the formation of DASP picrate. The reactions are first-order relative to the salt cation, molecular oxygen, and the catalyst (DASP). L. M. Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine, 70 R, Lyuksemburg ul., Donetsk 340114, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 34, No. 5, pp. 286–289, September–October, 1998.     

Kinetics and mechanism of the reaction of 1-benzoyloxy-4-[4-(dimethylamino)styryl]pyridinium tetrafluoborate with trimethyl-benzylammonium chloride in acetonitrile

The reaction of 1-benzoyloxy-4-[4-(dimethylamino)styryl]pyridinium tetrafluoborate with trimethylbenzylammonium chloride in acetonitrile takes place with the formation of an ion pair of 1-benzoyloxy-4-[4-(dimethylamino)styryl]pyridinium chloride, the slow decomposition of which to the σ adduct is rate-determining. The equilibrium constants of the individual steps of formation of ions from the ionogens PhCOCl and DASPO are determined. L. M. Litvinenko Institute of Physical Organic Chemistry and Carbon Chemistry, National Academy of Sciences of Ukraine, 70 Lyuksemburg ul., Donetsk 341114, Ukraine. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 34, No. 3, pp. 148–152, May–June, 1998.     

Kinetic and thermodynamic interpretation of the reversible reaction of 2,4,6-trinitrochlorobenzene with 4-[4-(dimethylamino)styryl]pyridine in acetonitrile

The energetic and activation parameters for the reversible reaction of 2,4,6-trinitrochlorobenzene with 4-[4-(dimethylamino)styryl]pyridine in acetonitrile were determined. The rate constants for the forward and reverse reactions were found to be equal at 300 K. L. M. Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine, R. Lyuksemburg St., 340114 Donetsk. Ukraine. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 33, No. 3, pp. 149–152, May–June, 1997.     

Indoor 222Rn concentrations and the corresponding lung cancer risk in Celein region, west of Al Khums, Libya

Paramagnetic products stabilized in both 4,4′(5′)-di-(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6) and its solution in 1-octanol upon low temperature (77 K) X-rays irradiation were studied by ESR spectroscopy. Macrocyclic –O–ĊH–CH₂– radicals and acyclic O = C(H)–ĊH–O– radicals were found as main radiolysis products in neat DtBuCH18C6. Fraction of acyclic radicals resulting from the macrocycle cleavage was about 50%. No radical products resulted from t-Bu and cyclohexyl fragments were observed. It was concluded that the primary events were essentially concerned with ionization of the polyether moiety. Irradiation of frozen DtBuCH18C6 solutions in 1-octanol resulted in formation of radicals both from crown ether and alcohol.     

A new binucleating macrocycle incorporating exocyclic oxime groups and its polynuclear complexes

A new binucleating macrocycle incorporating four exocyclic oxime groups, 6,6′-methylene-bis[1,12–di(hydroximino)-2,3;9,10–dibenzo-1,11–diaza-4,8–dithiacyclotridecane] (LH4) has been synthesized, its mononuclear CoIII and hetropolynuclear CoIII-PdII complexes have been prepared. LH4 and its metal complexes have been characterized by elemental analysis, 1H- and 13C-n.m.r., i.r. and mass spectral studies. The elemental analysis, stoichiometry and the spectroscopic data of the mononuclear CoIII complex indicate that the CoIII ions are coordinated by the oxime nitrogen atoms (C=N); PdII ions in the latter complex are coordinated through diaza-dithia moiety on the macrocycle. The mononuclear CoIII complex of LH4 has a 1:1 metal:ligand ratio. All spectral data support the proposed structure of LH4 and its complexes. This revised version was published online in June 2006 with corrections to the Cover Date.     

Mechanism of the Reaction of Picryl Iodide with 4-[4-(Dimethylamino)styryl]pyridine

We have used semiempirical calculations (PM3, MNDOd) to show that the parabolic dependence of the rate constants (k_obs, s⁻¹) on the picryl iodide (PicI) concentration in the reaction of quaternization of 4-[4-(dimethylamino)styryl]pyridine (DASP) in acetonitrile is due to formation of an inactive σ_1,3 adduct from DASP and PicI. Formation of the σ_1,1 adduct is the rate-limiting step of the S_NAr substitution. __________ Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 41, No. 4, pp. 242–246, July–August, 2005.     

Crown ether styryl dyes

A novel styryl dye containing benzodithia-18-crown-6 andN-(4-sulfobutyl)benzothiazolium fragments was synthesized. The complex formation of thecis-isomers of several photochromic styryl dyes containing dithia-15(18)-crown-5(6) fragments with Hg²⁺ and Mg²⁺ ions was studied. The stability constants of the complexes with Mg²⁺ and the relative stability constants of the complexes with Hg²⁺ (with respect to benzo-1,10-dithia-18-crown-6 ether) were measured. The fact that the stability constant increases 11-fold on going from thetrans- to the correspondingcis-isomer was attributed to the formation of an anion-“capped” complex. For Part 22, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2213–2220, December, 1997.     

Synthesis of a new conjugated 2,2′-(1,4-phenylenedivinylene)bis-quinoxaline and a series of styryl derivatives of quinoxaline and quinoline as promising electro- and photoluminescent materials

A new poly(p-phenylenedivinylene) oligomer 2,2'-(1,4-phenylenedivinylene)bisquinoxaline, a promising candidate in organic electroluminescent devices, was synthesised via a Knoevenagel condensation reaction of 2-methylquinoxaline with 1,4-benzenedicarbaldehyde. The same synthetic strategy was applied to obtain substituted styryl dyes, derivatives of quinoxaline, whereas styryl derivatives of quinoline were prepared by "Anil Synthesis". The considered dyes are of interest as fluorescence emitting materials. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 95–100, January, 2009.     

Oxidation of 2-(thiazol-2-yl)acrylonitrile derivatives with an H<Subscript>2</Subscript>O<Subscript>2</Subscript>—KOH system: Convenient route to new oxirane-2-carboxamides

An efficient procedure was developed for the synthesis of previously unknown 3-aryl(styryl)-2-(4-arylthiazol-2-yl)oxirane-2-carboxamides and 2-(4-arylthiazol-2-yl)-1-oxaspiro[2.5]octane-2-carboxamides based on treatment of (E)-3-aryl-2-(4-arylthiazol-2-yl)acrylonitriles and cyclohexylidene(4-arylthiazol-2-yl)acetonitriles with an H₂O₂—KOH system in EtOH. Oxidation of (E)-3-(4-chlorophenyl)-2-(4-phenylthiazol-2-yl)acrylonitrile with an H₂O₂—AcOH system affords 3-(4-chlorophenyl)-2-(4-phenylthiazol-2-yl)oxirane-2-carbonitrile in 55% yield. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2319–2322, October, 2005.     

Synthesis and condensation reactions of the boron difluoride complex with 3-acetyl-4-hydroxy-1-methyl-2-quinolone

A reaction of 3-acetyl-4-hydroxy-1-methyl-2-quinolone with boron trifluoride etherate gave its boron difluoride complex. Condensation of this complex with various carbonyl compounds afforded new 2-quinolone derivatives (polymethine and styryl dyes) that intensely absorb in the visible region of the spectrum and show effective fluorescence. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1701–1706, August, 2008.     

Simple synthesis of a terpenophenol—chlorin conjugate with an amide bond

A terpenophenol with a butylaminomethyl group was synthesized and conjugated to a chlorin macrocycle through formation of an amide bond without using activating reagents. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 561–563, November–December, 2007.     

Effect of arrangement of the styryl fragment on the optical properties and complexation of mono-and bis(styryl)-substituted <Emphasis Type="Italic">N</Emphasis>-methylpyridinium perchlorates containing benzo-15-crown-5 ether moieties

Using ¹H NMR spectroscopy and steady-state and time-resolved electronic spectroscopy, the optical properties of mono-and bis(styryl)pyridinium perchlorates and their complexes with Mg²⁺, Ba²⁺ cations were studied. The stability constants of the complexes were determined using spectrophotometric titration. The formation of inclusion complexes for Mg²⁺ and sandwich type complexes for Ba²⁺ results in fluorescence enhancement and increases the lifetimes of the excited states of the initial bis-styryl ligands. The variation of position of the styryl fragment in the pyridinium aromatic ring gives rise to photochromic crown ethers with different optical and photophysical characteristics and is also an easy route to bis(crown-ethers) of symmetrical and unsymmetrical structure. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2092–2100, November, 2007.     

Synthesis and luminescence behavior of inorganic–organic hybrid materials covalently bound with pyran-containing dyes

A DCM derivative, namely 4-Dicyanomethylene-2-methyl-6-{[4′-(N-hydroxyethyl-N-methyl)amino]styryl}-4H-pyran (DCMH), has been synthesized and covalently incorporated into the inorganic silica network as pendants via a sol–gel process. Molecular structures of the resultants are confirmed by elemental analysis, ¹H NMR, DSC, TGA, FTIR and UV–Vis spectroscopy. Photoluminescence (PL) spectra shows that the emission of DCMH peaked at 625 nm is almost completely quenched in DMF solution with a concentration of 1 × 10⁻⁴ mol/L, however, in hybrid films, the PL intensity enhances obviously with increasing DCMH concentration even at the high loading content of 40 mol%. All the hybrid films exhibit PL emission around 646–650 nm and the peak position reveal little dependence on the concentration of dye, suggesting they can be used as red emissive materials in light-emitting diodes. The relationship between fluorescence lifetime and dye concentration is also investigated by time-resolved PL measurements.     

Water clusters in supramolecular inclusion hydrates. Crystal structure of decaazatricyclo[28.2.2.213.16]tetratriacontane nanohydrate

Inclusion compounds of solvate water molecules in a crystal matrix are investigated by X-ray diffraction analysis of a macrocyclic polyamine decaazatricyclo[28.2.2.2^13.16]tetratriacontane nanohydrate (I). When included in a crystal, water molecules are bonded by water-water (O-H...O) and water—macrocycle (0-H...N and N-H...O) hydrogen bonds, forming a linear cluster. Translated fromZhurnal Strukturnoi Khimii, Vol. 40, No. 5, pp. 993–1001, September–October, 1999.     

Hydrindacene‐Based Acetylenic Macrocycles with Horizontally and Vertically Ordered Functionality Arrays

The macrocyclization of 2,6‐diethynyl hydrindacenes ( 1 ) with functional groups at mutually perpendicular positions results in the formation of novel macrocycles which, as a result of the hindered rotation of the hydrindacene units, possess directionally persistent peripheral functionalities. The two hydrindacene units in the dimer macrocycle ( 2 ) have been shown to interact electronically through their respective butadiyne moieties, whereas the trimer macrocycle ( 3 ) demonstrates a moderate degree of geometrical flexibility as a result of the five‐membered hydrindacene rings. In addition, these trimer macrocycles contain a central cavity suitably sized for the inclusion of various solvent molecules. These new macrocycles can be further modified by introducing π‐conjugated side groups, such as styryl and thienyl groups, as well as by attaching a variety of peripheral ester groups.     

Macrocycle opening in crown ethers

A method for the synthesis of nitrogen-containing podands from 4′-nitrobenzocrown ethers was developed. It involves nucleophilic regioselective cleavage of the macrocycle upon heating with MeNH₂. For Communication 2 see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 540–543, March, 1997.     

Syntheses and Cyclization Reactions of Bifunctional 1,2-Bis (styryl)benzenes and Some Aza Analogues. Macrocyclic aza compounds. V

The syntheses of the bis (styryl)benzenes 4 and 5 and of the aza analogue 3 are described. Diamine 3 and dialdehyde 5 were cyclized to the 14-membered macrocycles 19 and 27 , respectively. Diamine 4 and glyoxal give the 28-membered macrocycle 28 . The cyclizations are discussed.     

Synthesis,complexation, and <Emphasis Type="Italic">E—Z</Emphasis> photoisomerization of azadithiacrown-containing styryl dyes as new optical sensors for mercury cations

New styryl dyes containing azadithia-15-crown-5 fragments were synthesized. The complexation of these compounds with Ag⁺, Pb²⁺, Cu²⁺, Hg²⁺, and H⁺ cations was studied by ¹H NMR spectroscopy, steady-state, and time-resolved spectroscopy. The stability constants of the complexes were calculated from the spectrophotometric titration data. The photophysical properties and E—Z photoisomerization of styryl dyes and their complexes with mercury and copper(II) cations in acetonitrile were examined. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 495–507, March, 2007. Centre de Physique Moléculaire Optique et Hertzienne-UMR CNRS 5798, Bordeaux University I, 351 Cours de la Libération, 33405 Talence, France.     

Synthesis of conjugates of isobornylphenols and natural chlorins

A series of terpenophenol—chlorin conjugates containing terpenophenol and porphyrin fragments of various structure was synthesized. The terpenophenol fragment was added to the chlorin macrocycle using reactions of the exocyclic ester and the propionate substituent in the 17-position of methylpheophorbide a analogs. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 484–487, September-October, 2008.     

Reactivity of macroheterocycles with respect to sulfamic acid

It has been established, on the basis of the formation of a 1∶1∶1 inclusion compound of 18,19-benz-1,16-diaza-4,7,10,13-tetraoxoeicosa-17,20-dione with sulfamic acid and water from the interaction of 11–20-membered macrocyclic oxyethyleneamides of phthalic acid with sulfamic acid, that 18–20-membered oxyethylene macrocycles containing six oxygen donor atoms in the macrocycle are effective in the formation of “host-guest” complexes. Physicochemical Institute for the Preservation of the Environment and Mankind, Ministry of Education and Ukraine National Academy of Sciences of Ukraine, Odessa 270100. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1571–1573 November, 1997.