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.     

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.     

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.     

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.     

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.     

Synthesis of New α-Heterocyclic α-Aminophosphonates

α-heterocyclic α-aminophosphonates were obtained in good yields by N-of several nitrogen heterocycles with α-azido-α-aminophosphonate 1. ¹ Elachqar, A., El Hallaoui, A., Roumestant, M. L. and Viallefont, Ph. 1994. Synthetic Comm, 24: 1279 [CSA][Taylor & Francis Online], [Web of Science ®] , [Google Scholar]     

[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.     

Dicopper complex of p-tert -butylcalix8arene bearing acylhydrazone pendant domains

A dicopper complex of p-tert-butylcalix8 Atwood, JL, Barbour, LJ, Hardie, MJ and Raston, CL. 2001. Coord. Chem. Rev., 222: 3[Crossref], [Web of Science ®] , [Google Scholar]arene bearing eight salicylaldehyde acylhydrazone domains was prepared and its single crystal structure determined, in which only four acylhydrazone domains act as monoanionic tridentate planar chelators to coordinate to two copper ions.     

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.     

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.     

Synthesis,Structural, and Antibacterial Studies of Some Transition Metal Complexes Derived from Thiosemicarbazone and Semicarbazone

A series of metal complexes of Pd(II), Pt(II), Rh(III), Ir(III), and Ru(III) with thiosemicarbazone and semicarbazone of 2-acetyl thiophene have been synthesized. Their structures were determined on the basis of elemental analyses; molar conductance; magnetic susceptibility measurements; and IR, ¹ H NMR, and electronic spectral studies. On the basis of molar conductance, the complexes may be formulated as [M(L)₂]Cl₂ and [M′(L)₂Cl₂]Cl [where M = Pd(II), Pt(II) and M′ = Rh(III), Ir(III), and Ru(III)] due to their 1:2 and 1:1 electrolytic nature. On the basis of IR, ¹ West, D. X., Liberta, A. E., Padhye, S. B., Chikate, R. C., Sonawane, P. B. V., Kumbhar, A. S. and Yerande, R. G. 1993. Coord. Chem. Rev., 123: 49[Crossref], [Web of Science ®] , [Google Scholar]H NMR, and electronic spectral studies, an octahedral geometry has been assigned for Rh(III), Ir(III), and Ru(III), while square planar geometry has been assigned for the Pd(II) and Pt(II) complexes. The synthesized ligands and their complexes have been screened for bactericidal activity against several bacterial species (i.e., B. macerans, A. aureus, E. coli), and it is shown that the metal complexes act as more active antimicrobial agents than the uncomplexed ligands from which they derive.     

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.     

The Effect of the Electron Density Distribution of Guest on the Entropy Change During Complex Formation of Calix[6]arene Hexasulfonate Host with ortho- and para-cresols as Guests

The π–π interaction-based inclusion complexation of calix[6 Danil de Namor, A. F., Cleverly, R. M. and Zapata-Ormachea, M. L. 1998. Chem. Rev., 98: 2495[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]]arene hexasulfonate as host with neutral aromatic guest molecules was studied in aqueous media. To vary the distribution of electron density on the guest's aromatic rings, the phenol parent compound was substituted in the para- or ortho- positions with CH₃ group. To study the interaction between calixarene and the guests, PL, DSC and quantum-chemical methods were used. The results indicate 1:1 stoichiometry of the formed host-guest complexes. Although the enthalpy change during complex formation of calixarene with p- or o-cresol are the same, the Gibbs free energy change is significantly higher in the case of calixarene—o-cresol complexes. This property is due to the unexpected entropy change during the complex formation. Using molecular dynamic calculations, a guest-induced redistribution of the electron density on the calixarene rings, followed by the restructuring of the solvent molecules was identified as a background of this unexpected entropy change at molecular level.     

SYNTHESIS OF HIGHLY SUBSTITUTED 1,6-NAPHTHYRIDINES: A REINVESTIGATION

ABSTRACT

A reinvestigation of the recently described method of synthesis of highly substituted 1,6-naphthyridines was carried out. It was found out that the reaction of chalcones with malononitrile catalysed by pyrrolidine afforded the mixture of four products both when thermal as well as microwave heating was used. The claimed[1] Murugan, P., Raghukumar, V. and Ramakrishnan, V.T. 1999. Synth. Commun., 29: 3881–3386. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar] 1,6-naphthyridines formation were exceptions.     

Sonochemical synthesis of a new nano-scale 1D copper organic coordination polymer; thermal and spectroscopic characterizations

Single crystal of a new one-dimensional copper organic coordination polymer, 1D-CuOCP, [Cu(HL)NO₃]_n (1) Miyasaka, H., Saitoh, A., Abe, S. (2007) Coord. Chem. Rev., 251(21): 2622–2664.[Crossref], [Web of Science ®] , [Google Scholar] (H₂L = [2-[1-(2-hydroxy-propylimino)-ethyl]-phenol]) and its nanostructure, have been synthesized by slow evaporation of methanol solution of compound (1) Miyasaka, H., Saitoh, A., Abe, S. (2007) Coord. Chem. Rev., 251(21): 2622–2664.[Crossref], [Web of Science ®] , [Google Scholar] and sonochemical process respectively. Nanostructure of the complex was characterized by X-ray powder diffraction (XRD), FT-IR spectroscopy and scanning electron microscopy (SEM) and the structure of compound 1 was determined by single-crystal X-ray diffraction. Thermal stability of compound 1 in its nanosize form has also been studied by thermal gravimetric analysis (TGA). The effect of concentration of initial reagents on size and morphology of nanostructured compound 1 has been examined. The brightness of this study is to use the nanostructure of 1D-CuOCP as precursor to prepare single phase CuO nanoparticles via a solid-state decomposition procedure. Characterization methods confirmed that CuO nanoparticles with an average diameter of 40 nm were obtained from direct calcination of the precursor at 500°C under air.     

DFT calculations,microsynthesis and characterization of isopropyl methylphosphonoselenofluoridate [sarin-Se]

Abstract

Isopropyl methylphosphonoselenofluoridate (sarin-Se) was synthesized in order to determine its analytical data and to compare them as well as its reactivity parameters with those of sarin. After synthesis, sarin-Se was characterized using ¹ Mesilaakso, M. In: Mesilaakso, M. (Ed.), Introduction, Chemical Weapons Convention Analysis, Sample Collection, Preparation and Analytical Methods, Wiley, Chichester, 2005.[Crossref] , [Google Scholar]H, ¹³ Rayman, M. P.; Infante, H. G.; Sargent, M. Food-Chain Selenium and Human Health: spotlight on Speciation. Br. J. Nutr. 2008, 100, 238–253.[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]?C and ³¹P NMR spectroscopy and high resolution mass spectrometry (HRMS). ¹ Mesilaakso, M. In: Mesilaakso, M. (Ed.), Introduction, Chemical Weapons Convention Analysis, Sample Collection, Preparation and Analytical Methods, Wiley, Chichester, 2005.[Crossref] , [Google Scholar]H and ¹³ Rayman, M. P.; Infante, H. G.; Sargent, M. Food-Chain Selenium and Human Health: spotlight on Speciation. Br. J. Nutr. 2008, 100, 238–253.[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]?C NMR chemical shifts were also calculated using density functional theory (DFT) and compared with experimental data, showing a close agreement. Electrophilicity indices of sarin and sarin-Se were calculated at B3LYP/6-31++G (2d, 2p) level of theory. HOMO-LUMO analysis provides a basis to explain electrophilic nature of sarin-Se and sarin, which are almost similar. Based on calculated data, ³¹P NMR chemical shift and the reactivity of sarin-Se towards some enzymes such as acetylcholinesterase and albumin were explained.     

Solvent-free synthesis of novel 2,10-dichoro-12-trichloromethyl-6-substituted xanthato-12H-dibenzo[d,g] [1,3,2] dioxaphosphocin-6-sulfides

Abstract

2,10-Dichloro-12-trichloromethyl-6-substituted xanthato-12H-dibenzo[d,g] [1,3,2] dioxaphosphocin-6-sulfides (2a–l) with the eight-membered phosphorus and oxygen heterocyclic ring were synthesized by reacting equimolar quantities of alcohols, carbon disulfide, and 2,6,10-trichloromethyl-12H-dibenzo[d,g][1,3,2] dioxaphosphocin-6-sulfide 1 Ananda Kumar , K. ; Kuasturaiah , M. ; Suresh Reddy , C. ; Berlin , K.D. J. Heterocyclic Chem . 2003 , 40 , 345 – 351 .[Crossref], [Web of Science ®] , [Google Scholar] in the presence of dimethylaminopyridine (DMAP). The structures of the products were confirmed by IR, ¹H, ¹³C, ³¹P-NMR, and mass spectral analyses.     

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]^]