Synthesis,spectroscopy, electrochemistry,and molecular structure of tetrakis{(E)-2-((pyridin-2-ylimino)methyl)phenolato}(hydroxido)0.5(nitrato)1.5-tetracopper(II) nitrate hydroxide

Abstract

Reaction between (E)-2-((pyridin-2-ylimino)methyl)phenol (HL) and copper(II) nitrate provides tetrakis{(E)-2-((pyridin-2-ylimino)methyl)phenolato}(hydroxido)_0.5(nitrato)_1.5-tetracopper(II) nitrate hydroxide, [(CuL)₄(NO₃)_1.5(OH)_0.5](NO₃)(OH) (1 (a) J. Miao, Z. Zhao, H. Chen, D. Wang, Y. Nie. Acta Cryst., E65, m904 (2009); (b) A. Castineiras, J.A. Castro, M.L. Duran, J.A. Garcia-Vazquez, A. Macias, J. Romero, A. Sousa. Polyhedron, 8, 2543 (1989); (c) I.S. Vasil'chenko, A.S. Antsyshkina, D.A. Garnovskii, G.G. Sadikov, M.A. Porai-Koshits, S.G. Sigeikin, A.D. Garnovskii. Koord. Khimiya, 20, 824 (1994).[Crossref], [Web of Science ®] , [Google Scholar], [Google Scholar], [Google Scholar]). ESI-mass spectra show the ion peaks for the dinuclear species at m/z 565 for [(CuL)₂(HCO₂)]⁺ and 521 for [(CuL)₂+H]⁺ and the mononuclear species at m/z 260 for [(CuL)]⁺. Vibrational spectra show very strong bands at 1604/1546?cm^?1 for ν(C?=?N/C?=?C) and at 1384, 1351?cm^?1 for ν(NO₃^–). Cyclic voltammograms demonstrate an irreversible redox processes for the Cu(II)/Cu(I) and Cu(I)/Cu(0) couples in acetonitrile. X-ray molecular structure determination explores the formation of a cationic tetranuclear copper(II)-complex, in which a deprotonated ligand molecule chelates to one copper ion with the phenolate-O and imino-N atoms. In addition, a phenolate-O atom bridges between two neighboring copper ions and a pyridine-N atom coordinates to a third copper ion, so that each ligand bridges among three copper ions in a κ²N,O:κO:κN' coordination sphere. Thus, the four copper ions and four chelating-bridging ligands assemble primarily into a cationic [(CuL)₄]⁴⁺ complex. The two copper ions are further coordinated by either a nitrate anion (75% occupancy) or a hydroxide anion (25% occupancy) and form the core of a tetranuclear [(CuL)₄(NO₃)_1.5(OH)_0.5]²⁺ cation.     

New N-Substituted (E)-4-Arylidene Isoquinoline-1,3-dione Derivatives: NMR Spectroscopic Investigation and Antibacterial Activity

Abstract

New N-substituted 4-arylidene-isoquinoline-1,3-dione derivatives were obtained as one geometrical isomer by aldol condensation of the appropriate aldehyde and the corresponding N-substituted homophthalimides. The structural elucidation of compounds 3a–h was established by infrared and NMR spectroscopy including ¹ Dimmock , J. R. ; Wong , M. L. C. Bioactivities and potential uses in drug design of acyclic α,β-unsaturated ketones . Can. J. Pharm. Sci. 1976 , 11 , 35 – 53 .[Web of Science ®] , [Google Scholar]H, ¹³ Perjési , P. ; Szabó , D. ; Batta , G. ; Földesi , A. The stereochemistry of reaction of 2-benzylidenecyclohexanone with dithiocarbamic acid . Tetrahedron Lett. 1987 , 28 , 571 . [Google Scholar]C, CH CORR, and distortionless enhancement by polarization transfer measurements. Compounds 3d–h were evaluated for their antibacterial activity against some strains of bacteria using the disc diffusion method and microdilution tests.     

Synthesis of Cyclotriphosphazenes Containing Cyanostilbenes with Different Terminal Substituents

Abstract

The synthesis and mesomorphic properties of a class of cyclotriphosphazenes containing cyanostilbene groups with different terminal substituents (-H, -CH₃, -OCH₃, -CN) are described. All the resulting compounds are characterized by ¹ Barberá , J. ; Bardají , M. ; Jiménez , J. ; Laguna , A. ; Martínez , M. P. ; Oriol , L. ; Serrano , J. L. ; Zaragozano , I. Columnar mesomorphic organizations in cyclotriphosphazenes . J. Am. Chem. Soc. 2005 , 127 , 8994 – 9002 .[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]H, ¹³ An , B.-K. ; Lee , D.-S. ; Lee , J.-S. ; Park , Y.-S. ; Song , H.-S. ; Park , S.-Y. Stongly fluorescent organogel system comprising fibrillar self-assembly of a trifluoromethyl-based cyanostilbene derivative . J. Am. Chem. Soc. 2004 , 126 , 10232 – 10233 .[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]C, and ³¹P NMR, matrix-assisted laser desorption/ionization time of flight, and elemental analysis. The thermal behaviors of cyclotriphosphazene derivatives are studied by the means of differential scanning calorimetry and polarizing optical microscopy. Nematic phases are observed in cyclotriphosphazenes with terminal substituents (-CH₃, -OCH₃, -CN).     

Synthesis of Functionalized Tetrahydrofurans from Hydroxy Sulfinyl Dienes

Hydroxy sulfinyl dienes yielded functionalized tetrahydrofurans through nucleophilic and metal-catalyzed epoxidations.[1] Fernández de la Pradilla, R., Manzano, P., Montero, C., Priego, J., Martínez-Ripoll, M. and Martínez-Cruz, L. A. 2003. J. Org. Chem., 68: 7755–7767.  [Google Scholar] Effective oxirane cleavage has been achieved in these systems and a formal synthesis of (?)-Kumausallene is reported.     

Facile and Convenient Synthesis of Pyrazole,Pyridine, Pyridazine,Pyrazolo[3,4-b]pyridine,and Pyrazolo[5,1-c][1,2,4]triazine Derivatives

Abstract

A convenient synthesis of a series of pyrazole, pyridine, pyridinethione, pyridazine, pyrazolo[3,4-b]pyridine, imidazo[1,2-a]pyrimidine, and pyrazolo[5,1-c][1 Kumar , R. 5-(1-Substituted)alkyl pyrimidine nucleosides as antiviral (herpes) agents . Curr. Med. Chem. 2004 , 11 , 2749 – 2766 . [Google Scholar] 2 Holy , A. ; Günter , J. ; Dvoráková , H. ; Masojídková , M. ; Andrei , G. ; Snoeck , R. ; Balzarini , J. ; De Clercq , E. Structure–antiviral activity relationship in the series of pyrimidine and purine N-[2-(2-phosphonomethoxy)ethyl] nucleotide analogues, 1: Derivatives substituted at the carbon atoms of the base . J. Med. Chem. 1999 , 42 , 2064 – 2086 . [Google Scholar] 4 Brandes , W. ; Daum , W. ; Krauss , P. Fungicidal oxime ethers. Ger. Patent 2,623,847, 1977; Chem. Abstr . 1978 , 88 , 120822h . [Google Scholar]]triazine derivatives incorporating a pyrimidine moiety, via the reactions of the versatile, readily accessible 3-oxo-N-(pyrimid-2-yl)butanamide with the appropriate reagents, is described.     

Heterocyclic polycatenar liquid crystals

We report the synthesis of polycatenar liquid crystals incorporating 2,5‐disubstituted 1 O’Neill, M. and Kelly, S. M. 2003. Adv. Mater., 15: 1135[Crossref], [Web of Science ®] , [Google Scholar] 3 Catry, C., van der Auweraer, M., de Schryver, F. C., Bengs, H., Häussling, K., Karthaus, O. and Ringsdorf, H. 1993. Makromol. Chem., 194: 2985[Crossref] , [Google Scholar] 4 Adam, D., Schumacher, P., Simmerer, J., Häussling, K., Siemensmeier, K., Etzbach, K. H., Ringsdorf, H. and Haarer, D. 1994. Nature., 371: 141[Crossref], [Web of Science ®] , [Google Scholar]‐oxadiazole and 1 O’Neill, M. and Kelly, S. M. 2003. Adv. Mater., 15: 1135[Crossref], [Web of Science ®] , [Google Scholar] 3 Catry, C., van der Auweraer, M., de Schryver, F. C., Bengs, H., Häussling, K., Karthaus, O. and Ringsdorf, H. 1993. Makromol. Chem., 194: 2985[Crossref] , [Google Scholar] 4 Adam, D., Schumacher, P., Simmerer, J., Häussling, K., Siemensmeier, K., Etzbach, K. H., Ringsdorf, H. and Haarer, D. 1994. Nature., 371: 141[Crossref], [Web of Science ®] , [Google Scholar]‐thiadiazole rings joined by a combination of carbon–carbon single and double bonds (–CH = CH–). The ratio of the aromatic core to the aliphatic chains was varied systematically by changing the number of the aliphatic chains, from two to six, and their length, from short to very long, i.e. from methoxy to hexadecyloxy. The shape anisotropy of the core was varied by exchanging the oxygen atom in the 1 O’Neill, M. and Kelly, S. M. 2003. Adv. Mater., 15: 1135[Crossref], [Web of Science ®] , [Google Scholar] 3 Catry, C., van der Auweraer, M., de Schryver, F. C., Bengs, H., Häussling, K., Karthaus, O. and Ringsdorf, H. 1993. Makromol. Chem., 194: 2985[Crossref] , [Google Scholar] 4 Adam, D., Schumacher, P., Simmerer, J., Häussling, K., Siemensmeier, K., Etzbach, K. H., Ringsdorf, H. and Haarer, D. 1994. Nature., 371: 141[Crossref], [Web of Science ®] , [Google Scholar]‐oxadiazole for a sulfur atom to form the corresponding 1 O’Neill, M. and Kelly, S. M. 2003. Adv. Mater., 15: 1135[Crossref], [Web of Science ®] , [Google Scholar] 3 Catry, C., van der Auweraer, M., de Schryver, F. C., Bengs, H., Häussling, K., Karthaus, O. and Ringsdorf, H. 1993. Makromol. Chem., 194: 2985[Crossref] , [Google Scholar] 4 Adam, D., Schumacher, P., Simmerer, J., Häussling, K., Siemensmeier, K., Etzbach, K. H., Ringsdorf, H. and Haarer, D. 1994. Nature., 371: 141[Crossref], [Web of Science ®] , [Google Scholar]‐thiadiazole ring with a smaller deviation from coaxiality of the bonds in the 2,5‐positions. The shape anisotropy of the core was increased by the presence of an additional phenylenevinylene unit in a series of tetracatenar oxadiazoles. We report the synthesis, physical properties and polymerization of a polycatenar reactive mesogen in a columnar phase to form a polycatenar polymer network.     

ω-Iodoalkyl(methyl)malonate Esters

Abstract

ω-Iodoalkyl(methyl)malonate esters have potential utility in the bioconjugate chemistry of steroids. A representative set of these esters with a variety of protecting groups and alkyl groups has been prepared. The compounds offer a range of elution values on silica, as well as several convenient deprotection options.

ω-Bromoalkyl(methyl)malonate esters are precursors of chalcogenobarbiturates, which, in radiolabeled form, may be useful as brain imaging agents.[1] Grigsby, R.A., Irgolic, K.J. and Knapp, F.F. 1983. Synthesis and spectral properties of diethyl organylchalcogenoalkyl(alkyl)malonates and 5-alkyl-5-(organylchalcogenoalkyl)barbiturates. J. Organomet. Chem., 259: 171–181.  [Google Scholar] Recently, we have become interested in the analogous ω-iodoalkyl(methyl)malonate esters because of their possible utility in the bioconjugate chemistry of steroids. It is known that steroids can be conjugated to platinum through a malonate moiety.[2] Gandolfi, O., Apfelbaum, H.C., Migron, Y. and Blum, J. 1989. Syntheses of cis-dichlorodiammineplatinum analogs having steroidal hormones bound to the metal atom via malonato bridges. Inorg. Chim. Acta, 161: 113–123.  [Google Scholar] Such platinated steroids are significant because of their potential as tissue-selective antitumor agents.     

Synthesis and Characterization of a New Dioxime and Its Heterotrinuclear BF2 + Capped Complexes

ω‐Isonitrosoacetophenone 1 Uçan, H. ? and Mirzao?lu, R. 1990. Synth. React. Inorg. Met.‐Org. Chem., 20: 437[Taylor & Francis Online], [Web of Science ®] , [Google Scholar], phenylglyoxime 2 Burakevich, J. V., Lore, A. M. and Volpp, G. P. 1971. J. Org. Chem., 36: 1[Crossref], [Web of Science ®] , [Google Scholar], chlorophenylglyoxime 1 Uçan, H. ? and Mirzao?lu, R. 1990. Synth. React. Inorg. Met.‐Org. Chem., 20: 437[Taylor & Francis Online], [Web of Science ®] , [Google Scholar], dopaminophenylglyoxime 3 Uysal, ?., Co?kun, A., Koç, Z. E., Uçan, M. and Uçan, H. ?. 2007. R. J. Coord. Chem., 33: 351–357. [Crossref] , [Google Scholar] and [(salen/saloph)Fe]₂O 4 Kopel, P., Sindelar, Z. and Klicka, R. 1998. Trans. Met. Chem., 23: 139[Web of Science ®] , [Google Scholar] have been synthesized as described in the literature procedure. [Fe(III)(salen/saloph)dopaminophenylglyoxime)] (starting complexes) have been synthesized from dopaminophenylglyoxime and tetradentate schiff bases which contain dinuclear Fe(III) oxygen‐bridges N,N′‐bis(salicylidene)ethylenediamine (salenH₂) and bis(salicylidene)‐o‐phenylenediamine (salophH₂). The new heterotrinuclear complexes have been obtained from starting complexes and Co(II), Ni(II), Cu(II) salts. Then, heterotrinuclear vic‐dioxime complexes containing BF₂ ⁺ capped have been synthesized. The complexes have been characterized as low‐spin distorted octahedral Fe(III) bridged by o‐hydroxyphenolic groups. The o‐hydroxyphenolic groups play a role as bridges for weak antiferromagnetic intramolecular exchange. The structure of dioxime and its complexes were identified by using elemental analysis, ICP‐AES, ¹H‐NMR and IR spectral data.     

Investigation of novel monopodal and dipodal oxy-Schiff base triazine from cyanuric chloride: Structural and antimicrobial studies

During the last few years, the potential of s-triazine derivatives in agrochemical and medicinal properties have been subjected to investigation. s-Triazine derivatives have received great attention due to their significant antimicrobial, antibacterial, antifungal, anti-HIV, anticancer, and a wide array of other biological activities. The present study reported a method for achieving Dipodal systems formed by reaction 2,4,6-trichloro-1,3,5-triazine and 4-hydroxybenzaldehyde, 2-aminophenol. Herein, we reported the synthesis of a dialdehyde and its Schiff base as a new template. The reaction of cyanuric chloride with 1 equiv. methanol and 2 equiv. of p-hydroxybenzaldehyde gave the desired dialdehyde. The dialdehyde was then reacted with 2-aminophenolto afford the corresponding multidirectional oxy-Schiff base triazines. The structures of the compounds were identified by FT-IR,¹H-NMR and elemental analysis. Their antimicrobial activities were performed by using the broth microdilution method in DMSO: Phosphate Buffered Saline (PBS) against eight bacteria strain and one yeast strain. The results of the test were compared with gentamicin. It has been determined that 2,4-Bis(2-hydroxyphenylimino-4'-formylphenoxy)-6-methoxy-1,3,5-triazine (3) Padalkar, V. S., Gupta, V. D., Phatangare, K. R., Patil, V. S., Umape, P. G., Sekar, N. J. (2014) Saudi. Chem. Soc., 18, 262–268.[Crossref], [Web of Science ®] , [Google Scholar] (2DP2AF) and 2-(2-hydroxyphenylimino-4'-formylphenoxy)-4-(4'-formylphenoxy)-6-methoxy-1,3,5-triazine (2) Raval, J. P., Rai, A. R., Patel, N. H., Patel, H. V., Patel, P. S. (2009) Int. J. Chem. Tech. Res., 1, 616–620. [Google Scholar] (1DP2AF) have significant antibacterial and antifungal activity against Enterococcus faecalis and Candida albicans and these effects were close to the control antibiotic used. Ent. faecalis was the most sensitive strain against both two tested chemicals. It was determined that our chemicals have similar antifungal capacity when compared to gentamicin.     

Bivalent Organophosphorus Compounds—Synthesis and Acetylcholinesterase Inhibitory Activity

Abstract

A series of novel symmetric S,S′-2,2′-(ethane-1,2-diylbis(azanediyl)) bis(2-oxoethane-2,1-diyl) O,O,O′,O′-tetraethyl diphosphorodithioate derivatives (12) was designed and synthesized based on the cluster effect and the multiple binding sites of acetylcholinesterase (AChE). The structures of all the newly synthesized title compounds were characterized by ¹ Choi, S. K. Synthetic Multivalent Molecules: Concepts and Biomedical Application, 20–21. New Jersey: John Wiley & Sons, Inc. 2004, chapter 1 [Google Scholar]H and ¹³ Tang, H., Zhao, L. Z., Zhao, H. T., Huang, S. L., Zhong, S. M., Qin, J. K., Chen, Z. F., Huang, Z. S. and Liang, H. 2011. Euro. J. Med. Chem., 46: 4970–4979. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar]C NMR as well as elemental analyses. Their inhibitory activities against AChE were tested, and compound 12b exhibited the best activity (6.60-fold higher than ethion). The results suggested that the compound would bind to the catalytic center and the narrow gorge of the AChE simultaneously.

Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional table.     

Ethylene spacer-linked bis-acetamidopyridine for dicarboxylic acid recognition and polymeric new wave-like anti-perpendicular arrangement of a host–guest in the solid state

In this paper, 1,2-bis(2-acetamido-6-pyridyl)ethane, receptor 1, having an ethylene spacer is reported to recognise dicarboxylic acids. The binding study in the solution phase is carried out using ¹H NMR (1:1) and UV–vis experiments and in the solid phase by single-crystal X-ray analysis. In ¹H NMR, the downfield shifts of specific amide protons of receptor 1 in 1:1 complexes of receptor and guest diacids, and in the UV–vis experiment, the appearance of an isosbestic point as well as significant binding constants are observed, which thus unambiguously support the complexation of receptor 1 with dicarboxylic acids in solution. Receptor 2, simple 2-acetamido-6-methylpyridine, has lower binding constants than receptor 1 due to cooperative binding of two pyridine amide groups with two acid groups of diacids. In the solid phase, the ditopic receptor 1 shows a grid-like polymeric hydrogen-bonded network that changes to a polymeric wave-like 1:1 anti-perpendicular network instead of the syn–syn polymeric 1:1 (Goswami, S.; Dey, S.; Fun, H.-K.; Anjum, S.; Rahman, A.-U. Tetrahedron Lett. 2005 (a) Goswami, S., Ghosh, K. and Dasgupta, S. 2000. J. Org. Chem., 65: 1907–1914. (b) Goswami, S.; Ghosh, K.; Mukherjee, R. Tetrahedron2001, 57, 4987–4993. (c) Goswami, S.; Ghosh, K.; Halder, M. Tetrahedron Lett.1999, 40, 1735–1738. (d) Goswami, S.; Dey, S.; Fun, H.-K.; Anjum, S.; Rahman, A.-U. Tetrahedron Lett.2005, 46, 7187–7191. (e) Goswami, S.; Jana, S.; Dey, S.; Razak, I.A.; Fun, H.-K. Supramol. Chem.2006, 18, 571–574. (f) Goswami, S.; Jana, S.; Fun, H.-K. Cryst. Eng. Comm.2008, 10, 507–517. (g) Goswami, S.; Jana, S.; Dey, S.; Sen, D.; Fun, H.-K.; Chantrapromma, S. Tetrahedron2008,64, 6426–6433. (h) Goswami, S.; Dey, S.; Jana, S. Tetrahedron2008, 64, 6358–6363 [Google Scholar], 46, 7187–7191), anti–anti polymeric 1:1 (Goswami, S.; Jana, S.; Dey, S.; Razak, I.A.; Fun, H.-K. Supramol. Chem. 2006 (a) Goswami, S., Ghosh, K. and Dasgupta, S. 2000. J. Org. Chem., 65: 1907–1914. (b) Goswami, S.; Ghosh, K.; Mukherjee, R. Tetrahedron2001, 57, 4987–4993. (c) Goswami, S.; Ghosh, K.; Halder, M. Tetrahedron Lett.1999, 40, 1735–1738. (d) Goswami, S.; Dey, S.; Fun, H.-K.; Anjum, S.; Rahman, A.-U. Tetrahedron Lett.2005, 46, 7187–7191. (e) Goswami, S.; Jana, S.; Dey, S.; Razak, I.A.; Fun, H.-K. Supramol. Chem.2006, 18, 571–574. (f) Goswami, S.; Jana, S.; Fun, H.-K. Cryst. Eng. Comm.2008, 10, 507–517. (g) Goswami, S.; Jana, S.; Dey, S.; Sen, D.; Fun, H.-K.; Chantrapromma, S. Tetrahedron2008,64, 6426–6433. (h) Goswami, S.; Dey, S.; Jana, S. Tetrahedron2008, 64, 6358–6363 [Google Scholar], 18, 571–574; Goswami, S.; Jana, S.; Fun, H.-K. Cryst. Eng. Comm. 2008, 10, 507–517; Goswami, S.; Jana, S.; Dey, S.; Sen, D.; Fun, H.-K.; Chantrapromma, S. Tetrahedron 2008, 64, 6426–6433), syn–syn 2:2 (Karle, I.L.; Ranganathan, D.; Haridas, V. J. Am. Chem. Soc. 1997 (a) Garcia-Tellado, F., Goswami, S., Chang, S.K., Geib, S.J. and Hamilton, A.D. 1990. J. Am. Chem. Soc., 112: 7393–7394. (b) Geib, S.J.; Vicent, C.; Fan, E.; Hamilton, A.D. Angew. Chem. Int. Ed. Engl.1993, 32, 119–121. (c) Garcia-Tellado, F.; Geib, S.J.; Goswami, S.; Hamilton, A.D. J. Am. Chem. Soc.1991, 113, 9265–9269. (d) Karle, I.L.; Ranganathan, D.; Haridas, V. J. Am. Chem. Soc.1997, 119, 2777–2783. (e) Moore, G.; Papamicaël, C.; Levacher, V.; Bourguignon, J.; Dupas, G. Tetrahedron2004, 60, 4197–4204. (f) Korendovych, I.V.; Cho, M.; Makhlynets, O.V.; Butler, P.L.; Staples, R.J.; Rybak-Akimova, E.V. J. Org. Chem.2008, 73, 4771–4782. (g) Ghosh, K.; Masanta, G.; Fröhlich, R.; Petsalakis, I.D.; Theodorakopoulos, G. J. Phys. Chem. B2009, 113, 7800–7809 [Google Scholar], 119, 2777–2783) or top–bottom-bound 1:1 (Garcia-Tellado, F.; Goswami, S.; Chang, S.K.; Geib, S.J.; Hamilton, A.D. J. Am. Chem. Soc. 1990 (a) Goswami, S., Ghosh, K. and Dasgupta, S. 2000. J. Org. Chem., 65: 1907–1914. (b) Goswami, S.; Ghosh, K.; Mukherjee, R. Tetrahedron2001, 57, 4987–4993. (c) Goswami, S.; Ghosh, K.; Halder, M. Tetrahedron Lett.1999, 40, 1735–1738. (d) Goswami, S.; Dey, S.; Fun, H.-K.; Anjum, S.; Rahman, A.-U. Tetrahedron Lett.2005, 46, 7187–7191. (e) Goswami, S.; Jana, S.; Dey, S.; Razak, I.A.; Fun, H.-K. Supramol. Chem.2006, 18, 571–574. (f) Goswami, S.; Jana, S.; Fun, H.-K. Cryst. Eng. Comm.2008, 10, 507–517. (g) Goswami, S.; Jana, S.; Dey, S.; Sen, D.; Fun, H.-K.; Chantrapromma, S. Tetrahedron2008,64, 6426–6433. (h) Goswami, S.; Dey, S.; Jana, S. Tetrahedron2008, 64, 6358–6363 [Google Scholar], 112, 7393–7394) co-crystals.

     

[2]Benzothiophene bent-shaped liquid crystals

New liquid crystalline (LC) compounds containing the [2 Weissflog, W., Nádasi, H., Dunemann, U., Pelzl, G., Diele, S., Eremin, A. and Kresse, H. 2001. J. Mater. Chem., 11: 2748–2758. [Crossref], [Web of Science ®] , [Google Scholar]]benzothiophene chromophore unit have been synthesised and their mesomorphic properties studied. Mesomorphic and fluorescent properties have been modified by various chemical moieties. Among others, terminal fluoroalkyl and/or chiral chains were introduced to stabilise mesophases and support the formation of polar phases. In spite of the bent shape due to the central 1,3-diphenylbenzo[c]thiophene unit, all compounds exhibit phases typical for the rod-like LC: nematic, smectic A and smectic C or their chiral analogues using the chiral (S)-C₂H₅CH(CH₃)(CH₂)₆CO or (S)-C₁₀H₂₁OCH(CH₃)CO chain. The orientational order in the nematic phase was studied by polarised infrared measurements. The fluorescent properties of the studied compounds have been measured and their parameters established.     

Optically active tertiary alcohols by biocatalysis

Initially, chemoenzymatic route to optically active aromatic ring-fused cyclic tertiary alcohols (S)-(–)-1-methyl-1,2,3,4-tetrahydronaphthalen-1-ol-(–)-1b, (S)-(+)-1-methyl-2,3-dihydro-1H-inden-1-ol-(+)-1a has been reported.^[9 Özdemirhan, D.; Sezer, S. Sönmez, Y. Tetrahedron Asymmetry 2008, 19(23), 2717–2720.[Crossref], [Web of Science ®] , [Google Scholar]^] CAL-A (lipase-A from Candida antarctica) was found the best biocatalyst for 1b, CAL-A cross linked enzyme aggregate (CLEA) for 1a, with ee values of 20 and 45% and the esters 2b and 2a with ee values 99 and 71%. Then, cyclopent-2-ene anchored tertiary allyl 1a′, homoallyl 1b′ and homopropargyl 1c alcohols have been enzymaticly resolved in a high ee (up to 90%) with 44, 40, and 43% chemical yield, respectively, cyclohex-2-ene anchored tertiary allyl 3a, homoallyl 3b, and homopropargyl 3c alcohols in high ee (up to 97%) too with 42, 45, and 49% chemical yield in turn. Chiral dienes yield the spirocyclic dihydropyrans through ring-closing methathesis with 74 and 78% chemical yields with 90 and 97% ee. Chiral enynes afford the cyclopentenone pyrans through Pauson–Khand reaction with 80 and 81% chemical yields as single diastereomers as reported subsequently.^[1a (a) Tanyeli, C.; Özdemirhan, D. Tetrahedron Asymmetry 2014, 25(8), 658–666; (b) Gassoline, F.; Britton, R. A.; Mowat, J.; O’shea, P. D.; Davies, I. W. Synlett 2007, 14, 2193–2196; (c) Garcia, C.; Martin, V. S. Curr. Org. Chem. 2006, 10(14), 1849–1889; (d) Fujino, A.; Asano, M.; Yamaguchi, H.; Shirasaka, N.; Sakoda, A.; Ikunaka, M.; Obata, R.; Nishiyama, S.; Sugai, T. Tetrahedron Lett. 2007, 48(6), 979–983.[Crossref], [Web of Science ®] , [Google Scholar]^]     

Synthesis of Some N1-(3-Hydroxy-2-pyridyl)benzamides

Benzoxazoles are of special interest because of having various types of biological properties such as antihistaminic, antihelmintic antifungal and antibacterial activities. ¹ Hisano, T., Ichikawa, M., Tsumoto, K. and Tasaki, M. 1982. Chem. Pharm. Bull, 30: 2996 [CSA][Crossref], [Web of Science ®] , [Google Scholar], ² Prudhomme, M., Guyot, J. and Jeminet, G. 1986. J. Antibiotics, 39: 934 [CSA][Crossref], [PubMed], [Web of Science ®] , [Google Scholar], ³ Ersan, S., Nacak, S., Berkem, R. and Özden, T. 1997. Arzneim. Forsch, 47: 963 [CSA][PubMed], [Web of Science ®] , [Google Scholar], ⁴ Sener, E., Yalc?n, ?., Temeiz, Ö., Ören, ?., Ak?n, A. and Ucartürk, N. 1997. Farmaco, 52: 99 [CSA][PubMed] , [Google Scholar], ⁵ Ören, ?., Temiz, Ö., Yalc?n, ?., Sener, E., Ak?n and Ucartürk, N. 1997. Forsch, 47: 1393 [CSA] [Google Scholar], ⁶ Temiz, Ö., Ören, ?., Sener, E., Yalc?n, ?. and Ucartürk, N. 1998. Farmaco, 53: 337 [CSA][CROSSREF][Crossref], [PubMed] , [Google Scholar], ⁷ Yalc?n, ?., Ören, ?., Sener, E., Ak?n, A. and Ucartürk, N. 1992. J. Med. Chem, 27: 401 [CSA][CROSSREF][Crossref], [Web of Science ®] , [Google Scholar], ⁸ Temiz, Ö., Ören, ?. and Altanlar, N. 2002. Farmaco, 57: 175 [CSA][CROSSREF][Crossref], [PubMed] , [Google Scholar], ⁹ Sener, E., Temeiz, Ö., Yalc?n, ?. and Altanlar, N. 2000. Farmaco, 55: 397 [CSA][CROSSREF][Crossref], [PubMed] , [Google Scholar], ¹⁰ Ören, ?., Temiz, Ö., Yalc?n, ?., Sener, E. and Altanlar, N. 1998. Eur. J. Pharm. Sci., 7: 153 [CSA][Crossref], [Web of Science ®] , [Google Scholar] Benzamide derivatives, as the possible metabolites of benzoxazoles, show various types of biological activities. ¹¹ Sener, E., Bingöl, K., Ören, ?., Arpac?, Ö., Yalc?n, K. ?. and Altanlar, N. 2000. Farmaco, 55: 469 [CSA][CROSSREF][Crossref], [PubMed] , [Google Scholar], ¹² Sener, E., Yalc?n, K. ?. and Altanlar, N. 2002. Farmaco, 57: 451 [CSA][CROSSREF][Crossref], [PubMed] , [Google Scholar] Some N-(2-hydroxyphenyl)- benzamides, which showed significant activity compared to phenylacetamides and furamides,11 have been synthesized by treating 2-aminophenol with carboxylic acid chlorides under weak basic solution. ¹¹ Sener, E., Bingöl, K., Ören, ?., Arpac?, Ö., Yalc?n, K. ?. and Altanlar, N. 2000. Farmaco, 55: 469 [CSA][CROSSREF][Crossref], [PubMed] , [Google Scholar], ¹² Sener, E., Yalc?n, K. ?. and Altanlar, N. 2002. Farmaco, 57: 451 [CSA][CROSSREF][Crossref], [PubMed] , [Google Scholar] However, synthesis and especially biological activity of N-(3-hydroxy-2-pyridyl)benzamides were not studied well. Owing to the versatility of benzamides we have extended the reaction of 2-amino-3-pyridinol with different carboxylic acid chlorides in order to preparation of some new benzamide derivatives containing a hydroxypyridyl ring.     

Three-component reactions of phosphorus ylides,thiophenols, and acetyl chloride for the synthesis of (β-thioacrylates)

The facile synthesis of β-thioacrylates has been realized via direct three-component reactions of thiophenols, Wittig reagents, and acetyl chloride. Under transition metal-free conditions, a class of β-thioacrylates have been synthesized with fair to excellent yields via cascade C=C double bond and C(sp² Kano, T.; Shirozu, F.; Akakura, M.; Maruoka, K. J. Am. Chem. Soc. 2012, 134, 16068-16073.[Crossref], [PubMed], [Web of Science ®] , [Google Scholar])-S bond formation.     

New materials derivatives of tetrathiapentalene functionalized by amide groups: Synthesis,characterization, and electrical study

A new series of bis-fused tetrathiafulvalene containing functional groups was synthesized. The synthesis was carried out by using routes involving cross coupling, reduction, and oxidation reactions. The identity of these new donors is confirmed by ¹ Wudl, F.; Smith, G. M.; Hufnagel, E. J. J. Chem. Soc. Chem. Commun. 1970, 21, 1453-1454.[Crossref] , [Google Scholar] H NMR spectroscopy, mass spectrometry, and elemental analysis. We have used the cyclic voltammetry in order to determine the character π-donors of these molecules and to verify the reversibility of the redox process involved. Molecular orbital diagram has been calculated using density-functional calculations. Charge transfer complexes with tetracyanoquinodimethane (TNQ) were prepared by chemical redox reactions.     

Atom Transfer Radical Polymerization of Methyl Methacrylate High Efficiently Initiated by Azo-containing Iniferter

Two novel azo-containing iniferters, (4,4′-(diazene-1,2-diyl) bis(4,1-phenylene) bis(2-(diethylca-rbamothioylthio)-2-methylpropanoate (BDCMP) and 4-((4-bromophenyl)diazenyl)phenyl-2-(diethylcarbamothioylthio)-2-methylpropanoate (PDCMP) were synthesized and used successfully as the initiators for atom transfer radical polymerization of methyl methacrylate (MMA). The kinetic plots were first order and the molecular weights of the polymers with narrow molecular weight distributions increased with the monomer conversions. Furthermore, the results showed that the apparent initiation efficiencies (f was close to 0.90 defined as M _n(th)/M _n(GPC)) of BDCMP and PDCMP were both higher than that (f was lower than 0.5) of 2-N,N-(diethylamino)dithiocarboyl-isobutyrate (EDCIB), which was reported previously by us (14 Zhang, W., Zhu, X. L., Cheng, Z. P. and Zhu, J. 2007. J. Appl. Polym. Sci., 106: 230–7. [Crossref] , [Google Scholar]). The obtained mono- and bi-functional PMMAs containing azo and N,N-diethyldithiocarbamate (DC) groups were confirmed by ¹H-NMR and ultraviolet absorption spectra, respectively. The block copolymer, poly (methyl methacrylate)-b-polystyrene (PMMA-b-PS), was also successfully prepared via the ATRP chain-extension experiment using the obtained PMMA as a macroinitiator.     

Chloro complexes of cobalt(II) in aprotic solvents: stability and structural modifications due to solvent effect

Cobalt(II) chloro complexes were studied in aprotic solvents, namely, dimethylsulfoxide (DMSO), dimethylformamide (DMF), and propylene carbonate (PC). The measurements were performed spectrophotometrically in UV–visible–IR region at 25°C and at constant ionic strength: I = 1 mol L^?1 in DMSO and DMF, and 0.1 mol L^?1 in PC. Different models were tested and the model 1 Elleb, M, Meullemeestre, J, Schwing, MJ and Vierling, F. 1980. Inorg. Chem., 19: 2699[Crossref], [Web of Science ®] , [Google Scholar], 2 Elleb, M, Meullemeestre, J, Schwing, MJ and Vierling, F. 1982. Inorg. Chem., 21: 1477[Crossref], [Web of Science ®] , [Google Scholar], 3 Khan, MA, Meullemeestre, J, Schwing, MJ and Vierling, F. 1983. Polyhedron, 2: 459[Crossref], [Web of Science ®] , [Google Scholar], 4 Amuli, C, Meullemeestre, J, Schwing, MJ and Vierling, F. 1983. Inorg. Chem., 22: 3567[Crossref], [Web of Science ®] , [Google Scholar], i.e., that of four mononuclear successive complexes was retained. Stability constants of the identified complexes were determined and they increase inversely with the Gutmann's donor number of the solvents. Calculated electronic spectra are reported and the effect of solvents on the spectral properties are discussed. The symmetry of tetrachlorocobaltate is strictly T_d.     

Host (nanopores of zeolite-Y)/guest (Co(II)-azamacrocyclic complexes) nanocomposite materials: synthesis,characterization and catalytic epoxidation of styrene with molecular oxygen

A series of Co(II) azamacrocyclic complexes, 12 Brunel, D, Bellocq, N, Sutra, P, Cauvel, A, Lasperas, M, Moreau, P, Di Renzo, F, Galarneau, A and Fajula, F. 1998. Coord. Chem. Rev., 178–180: 1085[Crossref], [Web of Science ®] , [Google Scholar]aneN₄, 14 De Vos, DE, Dams, M, Sels, BF and Jacobs, PA. 2002. Chem. Rev., 102: 3615[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]aneN₄, Bzo₂ 12 Brunel, D, Bellocq, N, Sutra, P, Cauvel, A, Lasperas, M, Moreau, P, Di Renzo, F, Galarneau, A and Fajula, F. 1998. Coord. Chem. Rev., 178–180: 1085[Crossref], [Web of Science ®] , [Google Scholar]aneN₄ and Bzo₂ 14 De Vos, DE, Dams, M, Sels, BF and Jacobs, PA. 2002. Chem. Rev., 102: 3615[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]aneN₄, have been encapsulated in the nanocavity of zeolite-Y by a one pot template condensation reaction. Co(II) complexes with azamacrocyclic ligands were entrapped in the nanocavity of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of [bis(diamine)cobalt(II)], [Co(N–N)₂]-NaY, in the supercages of the zeolite, and (ii) in situ condensation of the cobalt(II) precursor complex with diethyloxalate. The new host/guest nanocomposite materials (HGNM) have been characterized by FTIR, DRS and UV-Vis spectroscopic techniques, XRD and elemental analysis, as well as nitrogen adsorption. These complexes (neat and HGNM) were used for epoxidation of styrene with O₂ as oxidant in different solvents. Electronic spectra of the reaction mixture indicated oxidation proceeds through a free radical mechanism.