CH2Cl2

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Terms modified by CH2Cl2

  • ch2cl2 solution

  • Selected Abstracts


    Dual Luminescent Dinuclear Gold(I) Complexes of Terpyridyl-Functionalized Alkyne Ligands and Their Efficient Sensitization of EuIII and YbIII Luminescence

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2010
    Xiu-Ling Li
    Abstract Reaction of (tpyC6H4C,CAu)n {tpyC6H4C,CH = 4,-(4-ethynylphenyl)-2,2,:6,,2,-terpyridine} with diphosphane ligands Ph2P(CH2)xPPh2 (x = 2 dppe, 3 dppp, 4 dppb, 5 dpppen, 6 dpph) in CH2Cl2 afforded the corresponding dual luminescent binuclear gold(I) complexes [(tpyC6H4C,CAu)2(,-dppe)] (1), [(tpyC6H4C,CAu)2(, - dppp)] (2), [(tpyC6H4C,CAu)2(,-dppb)] (3), [(tpyC6H4C,CAu)2(,-dpppen)] (4), [(tpyC6H4C,CAu)2(,-dpph)] (5). Crystal structural analysis of complexes 12CH2Cl2 and 22CH2Cl2 show that the terpyridine moieties are free of coordination in these gold(I)-acetylide-phosphane complexes. Spectrophotometric titration between complex 1 and [Eu(tta)3] (Htta = 2-thenoyltrifluoroacetone) or [Yb(hfac)3(H2O)2] (Hhfac = hexafluoroacetylacetone) gave a 2:1 ratio between Ln(,-diketonate)3 (Ln = Eu, Yb) units and the complex 1 moiety, indicating the formation of Au2Ln2 complexes. Both the luminescence titrations and the luminescence quantum yields of Au2Ln2 (Ln = Eu, Yb) solutions show that the energy transfer occurs efficiently from the binuclear gold(I) antennas 1,5 to EuIII and YbIII centers, and all complexes 1,5 are good energy donors for sensitization of visible and NIR luminescence of EuIII and YbIII ions. [source]


    Gold(I) Complexes of P,N Ligands and Their Catalytic Activity

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 7 2010
    Chosu Khin
    Abstract Gold(I) complexes were readily prepared by reaction of the respective ligands with (Me2S)AuCl in CH2Cl2. Complexes of formula LAuCl {L = diphenyl(2-pyridyl)phosphane (PPh2Py), (R)-(+)-4-[(2)-(diphenylphosphanyl)-1-naphthyl]- N -[(R)-1-phenylethyl]-1-phthalazinamine (PINAP)} were obtained when a 1:1 molar ratio of ligand to starting gold precursor was used. When a 2:1 ratio of ligand to gold precursor was used with PPh2Py or MandyPhos as ligands, complexes of the type L2AuCl were obtained. All complexes were fully characterized, and single-crystal X-ray structures could be determined for four complexes. Chloride ions were removed by reaction with silver salts, such as AgNTf2, AgOTf and AgBF4, for the use of these complexes as catalysts. After the catalytic reaction with alkynes and alcohols in acetonitrile, a unique trinuclear gold(I) complex derived from [(PPh2Py)Au]BF4 could be characterized by X-ray structural analysis, showing a mode of catalyst deactivation. [source]


    Molecular Iodine Stabilization in an Extended NI,IN Assembly

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 24 2009
    Francesco Isaia
    Abstract The adduct [bis(quinoxaline)-2,2,,3,3,-disulfideI2], (Q2S2I2), (1) can be easily synthesised from the reaction of Q2S2 and I2 in CH2Cl2 or, in the absence of any solvent, through diffusion of I2 vapours at 60 C. X-ray diffraction analysis shows the presence of an extended NI,IN assembly in which each I2 molecule links a Q2S2 molecule at both ends through a nitrogen atom to form a polymeric species; the d(I,I) and d(N,I) bond lengths confirm a very weak nitrogen,iodine interaction at the base of the NI,IN assembly. DFT calculations provide optimised distances for the NI and I,I bonds and explanation for the zigzag chain formation: the mPW1PW functional and the B3LYP hybrid functional with a variety of basis sets for the I atomic species [CRENBL, LANL2DZ, LANL2DZ(d,p), LANL08(d), SBKJC, SBKJC polarised-LFK and Stuttgart RLC] have been tested. Compound 1 proved stable up to nearly 100 C, and the stability is to be mainly attributed to the lattice energy of its polymeric structure then to donor,acceptor stabilisation. The facile insertion of molecular iodine into the Q2S2 network makes this compound an interesting iodine sponge, suitable for I2 storage; moreover, Q2S2 can easily collect and release I2(g) by a temperature-controlled process (60 and 97 C, respectively). ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]


    Toward an Allosteric Metallated Container

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2009
    Helga Szelke
    Abstract Polytopic ligands L1 and L2 in which three 2,2,-bipyridine units are linked to a central tris(pyrid-2-yl)amine (L1) or tris(pyrid-2-yl)methanol (L2) moiety by alkyl spacers were prepared by multistep organic syntheses. The parent tris(pyrid-2-yl)-type ligands were shown to be modest-to-good chelators for Zn2+ and Cu2+ ions in solution, and bi- and tridentate N-coordination was confirmed by crystal structures of CuII and RuII complexes, respectively. FeII and RuII smoothly form stable, cage-like 1:1 complexes with L1 and L2, in which the metal ion is coordinated to the tris(bpy) site of the ligands. The vacant tris(pyrid-2-yl) site of these complexes is, however, a poor donor site for Zn2+ and Cu2+ ions. In addition, FeII modulates the coordination behaviour of the tris(pyrid-2-yl) site toward Zn2+: Whereas tris(5-methylpyrid-2-yl)amine forms a 2:1 complex with Zn2+ in CH2Cl2, [Fe(L1)]2+ forms a 1:1 Zn complex. Spectrophotometric titrations suggest that [Fe(L2)]2+ forms a polynuclear Zn2+ complex in CH2Cl2, possibly involving bridging coordination of the alcohol OH group, which contrasts the smooth formation of a 2:1 complex of the parent tris(pyrid-2-yl)-type ligand with Zn. FeII might therefore be considered as an allosteric effector, which modulates the metal binding properties of the second tris(pyrid-2-yl) site of L1 and L2. Contrary to expectation, Zn2+ and Cu2+ appear to associate weakly with donor atoms directed toward the exterior of the cage-like complexes [Fe(Ln)]2+ and [Ru(L1)]2+, rather than locating in the interior of the container by tripodal coordination to the tris(pyrid-2-yl) site.( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]


    Uncommon Solvent Effect in Oxidative Addition of MeI to a New Dinuclear Platinum Complex Containing a Platina(II)cyclopentane Moiety

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 32 2008
    S. Jafar Hoseini
    Abstract The reaction of the known complex cis,cis -[Me2Pta(,-dppm)(,-SMe2)Ptb,CH2(CH2)2CcH2(Ptb,Cc)] [dppm = bis(diphenylphosphanyl)methane] with phthalazine (NN) proceeded by replacement of the labile bridging SMe2 ligand with the bidentate N-donor ligand NN to give cis,cis -[Me2Pta(,-dppm)(,-NN)Ptb,CH2(CH2)2CcH2(Ptb,Cc)] (1) as a pale red solid in good yield. The complex was fully characterized by multinuclear (1H, 31P, 195Pt) NMR spectroscopy. The subsequent reaction of complex 1 with excess MeI gave the colorless diplatinum(IV) complex [Me3Pta(,-dppm)(,-I)2Ptb{CH2(CH2)2CcH2(Ptb,Cc)}Me], in which the bridging NN ligand is replaced by bridging iodido ligands. The reddish color of complex 1, which is due to a metal-to-ligand charge transfer (MLCT) band in the visible region, was used to monitor its reaction with MeI in the solvents acetone, CH2Cl2, and benzene. The kinetic data revealed that the reactions in nonpolar benzene or slightly polar CH2Cl2 proceeded in two steps, each following a common SN2 mechanism. In the first step, MeI attacked the platina(II)cyclopentane center rather than the dimethylplatinum(II) center, because the first center is more electron-rich than the second center. In the more polar acetone, the reaction proceeded similarly, with the exception that each step was accompanied by a solvolytic reaction, which was suggested to be responsible for the unusually slower reaction rate in acetone than in benzene or CH2Cl2. Consistently, the reaction rate in the highly polar solvent CH3CN was too slow for any meaningful measurement.( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]


    Monocyclopentadienyl Phenoxido,Amino and Phenoxido,Amido Titanium Complexes: Synthesis, Characterisation, and Reactivity of Asymmetric Metal Centre Derivatives

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 29 2008
    Giuseppe Alesso
    Abstract Reduction of phenol,imine derivatives R,N=CH(3,5-R2C6H2 -2-OH) (R = tBu; R, = C6H51a, p -MeC6H41b, Cy 1c, tBu 1d, 2,6-Me2C6H31e; R = H; R, = p -MeC6H41f; Cy = cyclohexyl) with MBH4 (M = Li, Na) or AlLiH4 in ethyl ether or thf at room temperature affords the phenol,amine compounds R,NHCH2(3,5-R2C6H2 -2-OH) 2a,c and 2e,f. The N -R-[2,4-di- tert -butyl]benzo-1-oxa-3-azine species (R = tBu 2d1, 2,6-Me2C6H32e1) are obtained by Mannich reaction of 2,4-di- tert -butylphenol with RNH2 in refluxing methanol. Intermediate 2d1 is converted in ethanol at room temperature into N - tert -butyl[2-hydroxy-3,5-di- tert -butyl]benzylamine (2d), whereas 2e is not obtained from 2e1 by using this procedure.N -alkyl,N - tert -butyl[2-hydroxy-3,5-di- tert -butyl]benzylaminecompounds tBuN(R)CH2(3,5- tBu2C6H2 -2-OH) (R = Me 2g, Et 2h, nPr 2i, CH2Ph 2j) are also prepared by the appropriate synthetic method. Treatment of 2a,c with 1 equiv. of TiCpCl3 in the presence of 2.5 equiv. of NEt3 in hexane at room temperature gives the monocyclopentadienyl phenoxido,amido monochloride complexes TiCp[R,NCH2(3,5- tBu2C6H2 -2-O)]Cl (R, = C6H53a, R, = p -MeC6H43b, R, = Cy 3c). The analogous complex Ti(,5 -C5H4SiMe2Cl)[C6H5NCH2(3,5- tBu2C6H2 -2-O)]Cl (4a) results from the reaction of 2a with Ti(,5 -C5H4SiMe2Cl)Cl3. Nevertheless, 2d reacts with TiCpCl3 in hexane in the presence of NEt3 at room temperature yielding the monocyclopentadienyl phenoxido dichloride compound TiCp[tBuNHCH2(3,5- tBu2C6H2 -2-O)]Cl2 (5), whereas in ethyl ether and in the absence of NEt3 adduct 5HCl is obtained, which is further converted into TiCp[tBuNCH2(3,5- tBu2C6H2 -2-O)]Cl (3d) by addition of a NEt3/ethyl ether solution. The reaction of TiCpCl3 with 2a in the presence of 2.5 equiv. of NEt3 in a polar solvent (thf, CH2Cl2 or toluene) at room temperature affords TiCp[Ph(H)NCH2(3,5- tBu2C6H2 -2-O)]Cl (6a) as a mixture of two stereoisomers. All the reported compounds were characterised by the usual analytical and spectroscopic methods and the molecular structures of 2a, 2d, 2e and 3d were determined by X-ray diffraction analysis from suitable single crystals. Preliminary studies of catalytic activity for ethylene polymerisation by using solid methylaluminoxane as cocatalyst were performed.( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]


    Dicopper(II) Complexes with the Enantiomers of a Bidentate Chiral Reduced Schiff Base: Inclusion of Chlorinated Solvents and Chiral Recognition of1,2-Dichloroethane Rotamers in the Crystal Lattice

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2006
    Vamsee Krishna Muppidi
    Abstract Bisphenoxo-bridged dicopper(II) complexes [Cu2Ln2Cl2] {1 (n = 1) and 2 (n = 2)} with the N,O-donor reduced Schiff bases N -(2-hydroxybenzyl)-(R)-,-methylbenzylamine (HL1) and N -(2-hydroxybenzyl)-(S)-,-methylbenzylamine (HL2) have been synthesised and characterised. In both 1 and 2, the bidentate chiral ligands coordinate the metal centres through the secondary amine N atom and the bridging phenolate O atom. The chloride ion occupies the fourth coordination site and completes a slightly distorted square-planar NO2Cl environment around each copper(II) centre. Magnetic susceptibility measurements in the solid state suggest a strong antiferromagnetic interaction between the metal centres in both complexes. Both 1 and 2 readily form 1:1 host-guest compounds with chlorinated solvents such as CH2Cl2, CHCl3 and Cl(CH2)2Cl. All the host-guest compounds crystallise in noncentrosymmetric space groups. 1CH2Cl2 and 2CH2Cl2 crystallise in the P21 space group while 1CHCl3, 2CHCl3, 1Cl(CH2)2Cl and 2Cl(CH2)2Cl crystallise in the P212121 space group. In these inclusion crystals, the C,HCl interactions between the guest and the host molecules are primarily responsible for enclatheration of the chloroalkane molecules. In the case of CH2Cl2, one of its Cl atoms acts as the acceptor. On the other hand, for CHCl3 and Cl(CH2)2Cl, the metal coordinated Cl atom of the host complex acts as the acceptor. The structures of 1(P)-Cl(CH2)2Cl and 2(M)-Cl(CH2)2Cl provide rare examples for chiral recognition of the right handed (P) and the left handed (M) gauche forms of Cl(CH2)2Cl in molecular assemblies. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]


    Synthesis, Structure and Spectroscopic Properties of Novel9,10-Bis{[6-(diphenylphosphanyl)-2-pyridylmethyl]propylaminomethyl}anthracene-Bridged Group 11 Metal (M = CuI and AgI) Dinuclear Complexes

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2005
    Hu Xu
    Abstract Dinuclear complexes [M2(,-BPNNAn)]X2 (M = CuI, X = ClO4,1, X = BF4,2; M = AgI, X = BF4,3, X = ClO4,4) have been prepared by treating 9,10-bis{[6-(diphenylphosphanyl)-2-pyridylmethyl]propylaminomethyl}anthracene (BPNNAn) with M(CH3CN)4X in CH2Cl2. The structures of complexes 1, 2 and 3 have been determined by single-crystal X-ray diffraction studies. In the complexes, BPNNAn acts as a chelating ligand and two metal ions riding on two bridgehead carbon atoms in the anthracene group leads to the deformation of the anthracenyl ring. The Cu,Arene charge transfer interaction is observed from the nonfluorescent emission of Cu complex 1, while the Ag complex 3 exhibits dual emission at high concentrations in a CH2Cl2 solution. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]


    Synthesis of (1,2,4-Oxadiazole)palladium(II) Complexes by [2 + 3] Cycloaddition of Nitrile Oxides to Organonitriles in the Presence of PdCl2

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2005
    Nadezhda A. Bokach
    Abstract The reaction between the nitrile oxides 2,4,6-R3C6H2CNO (R = Me, OMe) and trans -[PdCl2(RCN)2], or RCN (R = Me, Et, CH2CN, NMe2, Ph) in the presence of PdCl2, proceeded smoothly under mild conditions and allowed the isolation of the 1,2,4-oxadiazole complexes trans -[PdCl2{Na=C(R)-ON=Cb(C6H2R3)(Na,Cb)}2] (1,8) in 40,85,% yields. In CH2Cl2, the reaction between 2,4,6-R3C6H2CNO and [PdCl2(MeCN)2] furnishes [PdCl2(ONCC6H2R3)2] (9 and 10), which are the first representatives of metal compounds where nitrile oxides act as ligands. The 1,2,4-oxadiazole complexes 1,8 were characterized by elemental analysis, FAB mass spectrometry, and IR, 1H and 13C{1H} NMR spectroscopy, while 2, 3, 7, and 8 were additionally characterized by X-ray crystallography. The liberation of the heterocyclic species from 1,8 was successfully performed by substitution reaction either with 1,2-bis(diphenylphosphanyl)ethane or with an excess amount of Na2S7H2O in MeOH; the liberated 1,2,4-oxadiazoles (11,18) were characterized by positive-ion FAB mass spectrometry and 1H and 13C{1H} NMR spectroscopy. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]


    Mono- and Dimetallic Cyano Complexes with {Mo(,3 -allyl)(CO)2(N,N)} Fragments

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 6 2003
    Julio Prez
    Abstract Treatment of [MoCl(,3 -allyl)(CO)2(phen)] with NaCN in CH2Cl2/MeOH afforded [Mo(CN)(,3 -allyl)(CO)2(phen)] [allyl = C3H5 (1a); 2-MeC3H4 (1b)] as the sole products (no products of cyanide attack on the allyl group were detected). Treatment of 1a,b with [Mo(OTf)(,3 -C3H5)(CO)2(phen)] and NaBAr,4 in CH2Cl2 yielded the compounds [{Mo(,3allyl)(CO)2(phen)}(,-CN){Mo(,3 -C3H5)(CO)2(phen)}]BAr,4 (2a,b). Analogous treatment of 1a with fac -[M(OTf)(CO)3(bipy)] (M = Mn, Re) and NaBAr,4 resulted in the synthesis of [{Mo(,3 -C3H5)(CO)2(phen)}(,-CN){M(CO)3(bipy)}]BAr,4 (3, 4), in which the C and N atoms of the cyano bridge are bonded to Mo and M (M = Mn, Re), respectively. The linkage isomer of 4 (C and N atoms of the cyano group bonded to Re and Mo, respectively) (6) was prepared by treatment of [Re(CN)(CO)3(bipy)] (5) with [Mo(OTf)(,3 -C3H5)(CO)2(phen)] and NaBAr,4. Compounds 1a, 2b, 3, and 6 were characterized by X-ray diffraction. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]


    Synthesis, Crystal Structure, and Photoluminescent Properties of a Tetracarbonyl(naphthyridylcarbamoyl)rhenium(I) Complex and a Highly Emissive Tetracarbonyl(naphthyridylamido)rhenium(I) Complex

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2003
    Jing-Lin Zuo
    Abstract The reactions of Re(CO)5X (X = Cl, Br) with 7-amino-2,4-dimethyl-1,8-naphthyridine (H2L1) and 7-[2-(6-chloropyridyl)amino]-2,4-dimethyl-1,8-naphthyridine (HL2) in the presence of tBuOK afforded the ,1 -naphthyridylcarbamoyl complex [Re(CO)4(HL1CO)] (1) and the naphthyridylamido complex [Re(CO)4(L2)] (2), respectively. The structures of HL2, 1CHCl3, 1HL32CH2Cl2 [HL3 = (7-chloronaphthyridyl)(5,7-dimethylnaphthyridyl)amine], and 2 have been determined by X-ray crystallography. Complex 1 displays a weak emission at 453 nm in an EtOH/MeOH (1:4, v/v) glassy solution at 77 K; complex 2 exhibits an intense (quantum yield: 0.22 in CH2Cl2) and long-lived emission (46 ,s in CH2Cl2), with a solvent-sensitive ,max, in degassed solutions at room temperature. ( Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2003) [source]


    Synthesis of Oligosaccharide Mimetics with Glycoaminoxy Acids

    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 34 2009
    Yanchun Gong
    Abstract From readily available di- O -isopropylidene- D -glucose, a D -ribofuranoid glycoaminoxy acid and its tBu ester have been efficiently prepared as a new family of sugar building blocks by introducing the phthalimido aminoxy group by a Mitsunobu reaction. We found that the tBu ester can be selectively deprotected with 13.7,% TFA in CH2Cl2 at 0 C in the presence of the 1,2- O -isopropylidene acetal. This selective deprotection has made possible the synthesis of homo-oligomers of glycoaminoxy acids (up to six sugar units) as a novel type of oligosaccharide mimetics. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]


    Silylene/Oxazolidinone Double-Locked Sialic Acid Building Blocks for Efficient Sialylation Reactions in Dichloromethane

    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 25 2009
    Shinya Hanashima
    Abstract We describe efficient sialylation reactions in CH2Cl2 with the use of silylene/oxazolidinone double-locked sialic acid building blocks. The building blocks were synthesized from 4,5-oxazolidinone-protected phenylthiosialoside. In sialylation reactions towards primary and relatively reactive secondary hydroxy groups on the galactosides, the double-locked building blocks provided desired coupling products in good yields with excellent ,-selectivities. In the sialylation reaction with the C3-OH of the galactoside, the double-locked building blocks expressed significantly better ,-selectivity in comparison with the results obtained by using the oxazolidinone-locked building block. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]


    A Practical Method for Selective Cleavage of a tert -Butoxycarbamoyl N -Protective Group from N,N -Diprotected ,-Amino Acid Derivatives Using Montmorillonite K-10,

    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 30 2007
    J. Nicols Hernndez
    Abstract A new, practical, and mild procedure for the selective cleavage of a tert -butoxycarbonyl group (Boc) in N -Boc- N -acyl-diprotected amines is described. When applied to ,-amino acids, complete integrity of the stereochemistry was observed. The use of N,N -di-Boc-,-amino-,- and ,-hydroxy esters provided both ,- and ,-lactones in very good yields. The method is based on the use of Montmorillonite K-10 either in CH2Cl2 at room temperature or in toluene at 65 C and is compatible with the presence of a large range of functional and other protecting groups in the substrates. In most cases virtually pure samples are obtained after filtration and removal of solvents. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]


    N -Functionalization of Azoles through Coupling Reactions with Alkoxydienyl and Alkoxystyryl Boronic Esters

    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 8 2007
    Annamaria Deagostino
    Abstract Alkoxydienyl boronates 1a and 1b and alkoxystyryl boronate 2 have been used in various copper mediated cross-coupling reactions with azoles. A variety of N -alkoxydienyl- and N -styrylazoles have been synthesized under mild conditions. The process utilizes Cu(OAc)2 in the presence of CsF in CH2Cl2 at room temperature. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]


    SN2 Displacement by Bromide Ions in Dichloromethane , The Role of Reverse Micelles

    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 18 2006
    Lucia Brinchi
    Abstract Reverse micellar systems are of interest as reaction media because they are powerful models for biological compartmentalization, enzymatic catalysis and separation of biomolecules. Solutions of ionic surfactants in apolar solvents may contain reverse micelles, but they may also contain ion pairs, or small clusters, with waters of hydration. We studied the bimolecular reaction in CH2Cl2 solutions of cationic tetraalkylammonium bromide salts (onium salts), such as cetyltrimethylammonium bromide (CTABr), cetyltripropylammonium bromide (CTPABr) and tetra- n -butylammonium bromide (TBABr). Methylnaphthalene-2-sulfonate (,-MeONs), its 6-sulfonate derivative (,-MeONsS,) as the 2,6-lutidinium salt and methyl-5- N,N,N,trimethylammonium naphthalene-1-sulfonate (,-MeONsNT+) as the trifluoromethanesulfonate salt react with Br, in CH2Cl2. First-order rate constants, kobs, increase linearly and similarly for the three substrates with increasing concentrations of the onium salts. Reactions are faster with TBABr than they are with CTPABr and CTABr, and the reactivity of the three substrates is in the order: ,-MeONsNT+ >> ,-MeONsS, > ,-MeONs. The reactions are inhibited by the addition of H2O, but CTABr tolerates H2O in large excess. At [H2O]/[CTABr] = w0 , 6, "water-pool" reverse micelles form, and kobs for all three substrates is then independent of w0. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]


    Rational Design of Charge-Neutral, Near-Infrared-Emitting Osmium(II) Complexes and OLED Fabrication

    ADVANCED FUNCTIONAL MATERIALS, Issue 16 2009
    Tsang-Chi Lee
    Abstract A new series of charge neutral Os(II) isoquinolyl triazolate complexes (1,4) with both trans and cis arrangement of phosphine donors are synthesized, and their structural, electrochemical and photophysical properties are established. In sharp contrast to the cis -arranged complexes 2,4, the trans derivative 1, which shows a planar arrangement of chromophoric N -substituted chelates, offers the most effective extended , -delocalization and hence the lowest excited state energy gap. These complexes exhibit phosphorescence with peak wavelengths ranging from 692,805,nm in degassed CH2Cl2 at room temperature. Near-infrared (NIR)-emitting electroluminescent devices employing 6,wt % of 1 (or 4) doped in Alq3 host material are successfully fabricated. The devices incorporating 1 as NIR phosphor exhibit fairly intense emission with a peak wavelength at 814,nm. Forward radiant emittance reaches as high as 65.02,W,cm,2, and a peak EQE of ,1.5% with devices employing Alq3, TPBi and/or TAZ as electron-transporting/exciton-blocking layers. Upon switching to phosphor 4, the electroluminescence blue shifts to 718,nm, while the maximum EQE and radiance increase to 2.7% and 93.26 (,W,cm,2) respectively. Their performances are optimized upon using TAZ as the electron transporting and exciton-blocking material. The OLEDs characterized represent the only NIR-emitting devices fabricated using charge-neutral and volatile Os(II) phosphors via thermal vacuum deposition. [source]


    Chemoselectivity of the Reactions of Diazomethanes with 5-Benzylidene-3-phenylrhodanine

    HELVETICA CHIMICA ACTA, Issue 9 2009
    Martin
    Abstract The reactions of 5-benzylidene-3-phenylrhodanine (2; rhodanine=2-thioxo-1,3-thiazolidin-4-one) with diazomethane (7a) and phenyldiazomethane (7b) occurred chemoselectively at the exocyclic CC bond to give the spirocyclopropane derivatives 9 and, in the case of 7a, also the C -methylated products 8 (Scheme,1). In contrast, diphenyldiazomethane (7c) reacted exclusively with the CS group leading to the 2-(diphenylmethylidene)-1,3-thiazolidine 11via [2+3] cycloaddition and a ,two-fold extrusion reaction'. Treatment of 8 or 9b with an excess of 7a in refluxing CH2Cl2 and in THF at room temperature in the presence of [Rh2(OAc)4], respectively, led to the 1,3-thiazolidine-2,4-diones 15 and 20, respectively, i.e., the products of the hydrolysis of the intermediate thiocarbonyl ylide. On the other hand, the reactions with 7b and 7c in boiling toluene yielded the corresponding 2-methylidene derivatives 16, 21a, and 21b. Finally, the reaction of 11 with 7a occurred exclusively at the electron-poor CC bond, which is conjugated with the CO group. In addition to the spirocyclopropane 23, the C -methylated 22 was formed as a minor product. The structures of the products (Z)- 8, 9a, 9b, 11, and 23 were established by X-ray crystallography. [source]


    Internal Nucleophilic Termination in Acid-Mediated Polyene Cyclizations Part 4,

    HELVETICA CHIMICA ACTA, Issue 12 2005
    Synthetic Access to Tetracyclic Didehydro, Tetradehydro Analogues of ()- Ambrox
    Treatment of the unsaturated bicyclic homoallylic alcohols (E)- and (Z)- 5 and (Z)- and (E)- 10 and allenic alcohol 16 with an excess of ClSO3H in 2-nitropropane or CH2Cl2 at ,,80 afforded, in moderate yields (ca. 30,70%), diastereoisomer mixtures of racemic tetracyclic ethers 12a,c (Table,1) and 17a,b (Table,2), respectively. These kinetically controlled stereospecific transformations are believed to proceed via concerted or nonconcerted pathways (see Schemes,4 and 6) and the results are fully consistent with our earlier work. Representing novel didehydro bridged analogues of known, olfactively active labdane tricyclic ethers, the organoleptic properties of 12a,c and 17a,b are briefly described, especially those of 12c which, in the context of structure,activity studies, is a racemic didehydro analogue of the known ambergris odorant Ambrox. [source]


    The Synthesis, Characterisation, and Reactivity of Some Polydentate Phosphinoamine Ligands with Benzene-1,3-diyl and Pyridine-2,6-diyl Backbones

    HELVETICA CHIMICA ACTA, Issue 10 2003
    Nermin Biricik
    The polydentate phosphinoamines 1,3-{(Ph2P)2N}2C6H4 and 2,6-{(Ph2P)2N}2C5H3N have been prepared in a single step from the reaction of the amines 1,3-(NH2)2C6H4 or 2,6-(NH2)2C5H3N with Ph2PCl in presence of Et3N (1,:,4,:,4 molar ratio) in CH2Cl2. Reaction of 1,3-{(Ph2P)2N}2C6H4 or 2,6-{(Ph2P)2N}2C5H3N with elemental sulfur or selenium in CH2Cl2 affords the corresponding tetrasulfide or tetraselenide, respectively, in good yield. The complexes [1,3-{Mo(CO)4(Ph2P)2N}2(C6H4)] and [2,6-{Mo(CO)4(Ph2P)2N}2(C5H3N)] were prepared from the reaction of these phosphinoamines with [Mo(CO)4(nbd)] (nbd=norbornadiene) in toluene, and the structure of the latter complex has been determined by single-crystal X-ray diffraction analysis. [source]


    Thiiranation of 2,-adamantylidene-9-benzonorbornenylidene using 4,4,-oligothiodimorpholine and brnsted acid

    HETEROATOM CHEMISTRY, Issue 1 2009
    Yoshiaki Sugihara
    On leaving 4,4,-dithiodimorpholine 6 powder undisturbed at room temperature over 10 years, it led to the formation of 4,4,-tetrathiodimorpholine 7. Reactions of 2,-adamantylidene-9-benzonorbornenyidene 1 with 6, 7, and 4,4,-thiodimorpholine 8 and a Brnsted acid in CH2Cl2 at room temperature proceeded to afford the corresponding thiiranes, 2 and 3. The order of reactivity of 4,4,-oligothiodimorpholines combined with a Brnsted acid is 7 > 6 > 8. The thiirane 3 was transformed to 1 and 2 under the reaction conditions. 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:12,18, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20505 [source]


    Reactions of 9,9,-bibenzonorbornenylidene sulfoxides with TMSOTf: Anomalous pinacol-type rearrangement of thiirane 1-Oxides

    HETEROATOM CHEMISTRY, Issue 1 2009
    Yoshiaki Sugihara
    syn-9,9,-Bibenzonorbornenylidene sulfoxide 8b underwent pinacol-type rearrangement to form 9, together with a mixture of thiiranes 4a and 4b by reaction with TMSOTf in CH2Cl2 at room temperature. The rearrangement of anti-sulfoxide 8a proceeded more slowly giving a mixture of 9, 4a, and 4b. 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:29,34, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20507 [source]


    Organic Thin-film Transistors Based on Polythiophene Nanowires Embedded in Insulating Polymer

    ADVANCED MATERIALS, Issue 13 2009
    Longzhen Qiu
    Blending poly(3-hexylthiophene) (P3HT) and amorphous polystyrene (PS) using a marginal solvent (CH2Cl2) with temperature-dependent solubility allows a reduction of the semiconductor content to as low as 3 wt% without considerable degradation of the field-effect electronic properties. Morphological and structural studies reveal that the P3HT molecules in these blends form highly crystalline, interconnected nanofibrillar networks. [source]


    A Methyl Tricyanoethylenecarboxylate-Based Room-Temperature Magnet,

    ADVANCED MATERIALS, Issue 20 2007
    I. Pokhodnya
    A room-temperature magnet of V[MeTCEC]20.6(CH2Cl2) composition (MeTCEC,=,methyl tricyanoethylenecarboxylate) is formed by the reaction of MeTCEC and V(CO)6 (see figure). Analysis of the magnetization indicates a less disordered structure of V[MeTCEC]20.6(CH2Cl2) with respect to similarly synthesized V[TCNE]x0.34(CH2Cl2), presumably because of the much slower reaction of MeTCEC and V(CO)6. [source]


    Solution and Thin-Film Aggregation Studies of Octasubstituted Dendritic Phthalocyanines

    ISRAEL JOURNAL OF CHEMISTRY, Issue 1 2009
    Casey A. Kernag
    The synthesis and solution and thin-film characterization of eight octasubstituted dendritic phthalocyanines (Pcs) and their zinc complexes are reported. The Pc chromophore was substituted in the 2,3,9,10,16,17,23,24-positions with three generations of benzylaryl ether dendrons with either a benzyl (3a-3c) or 3,5-di- t -butylbenzyl periphery (3d-3f). Visible spectra in solution (CH2Cl2 -EtOH mixtures, toluene, THF, dioxane, acetone, and EtOAc) indicated a varying degree of chromophore aggregation that depended on solvent, dendrimer generation, and whether the Pc was metallated. Variable-concentration visible spectroscopic studies were analyzed using a nonlinear least-squares fitting procedure giving Kd values. These values further quantitated the observations that the t -butyl-substituted den-drimers 3d-3f were all less prone to aggregation in solution than the unsubstituted dendrimers 3a-3c, with a monotonic decrease in Kd across the series 3a , 3b , 3c , 3d , 3e , 3f. Second-generation t -butyl-substituted dendrimer 3f showed little to no aggregation in all solvents studied. Thin-film studies indicated that the largest members of the two dendrimer groups, third-generation 3c and second-generation 3f, were largely monomeric as evidenced by split Q-bands, similar to that seen in dilute CH2Cl2 solution when deposited via spin-coating onto glass slides. The metallated zinc Pcs 4a-4f all exhibited significantly less tendency toward aggregation in both solution and thin-films than their unmetallated analogues. [source]


    Syntheses and Properties of Fluorous Quaternary Phosphonium Salts that Bear Four Ponytails; New Candidates for Phase Transfer Catalysts and Ionic Liquids

    ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 12-13 2006
    Charlotte Emnet
    Abstract The fluorous tertiary phosphine [Rf6(CH2)2]3P [Rfn=CF3(CF2)n,1] and excess PhCH2Br, CH3(CH2)3OSO2CF3, or Rf6(CH2)2OSO2CF3 react (CF3C6H5, 45,110,C) to give the phosphonium salts (PhCH2)[Rf6(CH2)2]3P+ Br, (2, 71,%), [CH3(CH2)3][Rf6(CH2)2]3P+ CF3SO3, (3, 65,%), or [Rf6(CH2)2]4P+ CF3SO3, (4, 83,%). The phosphines [Rf6(CH2)2]2[Rf8(CH2)2]P and [Rf8(CH2)2]3P are similarly elaborated with Rf6(CH2)2I, Rf8(CH2)2I, or Rf8(CH2)2Br (DMF, 115,C) to [Rf8(CH2)2]4- x[Rf6(CH2)2]xP+ I, (x=3, 7; 2, 8; 1, 9; 0, 10) or [Rf8(CH2)2]4P+ Br, (80,60,%). The salts exhibit melting points between 110,C and 43,C, with lower values favored by less symmetrical cations, Rf6 segments, and triflate and bromide anions. Solubilities decrease in the solvent sequence CF3C6F5 (all salts at least moderately soluble, room temperature)>acetone>THF>CF3C6H5>CF3C6F11>CH3C6H5, Et2O, CH2Cl2, hexane (all salts insoluble at elevated temperatures); some appreciably increase upon heating. Partition coefficients are very biased towards fluorous phases (>93:<7). The salts can be quite efficient at extracting picrate from water into CF3C6F5 (97,86,% for 2, 4, 9, 10) or CF3C6H5 (85,66,% for 2 - 4), demonstrating their potential for phase transfer catalysis. A CF3C6F5 solution of Rf8(CH2)3I and aqueous NaCl react at 100,C in the presence (but not the absence) of 9 to give Rf8(CH2)3Cl. [source]


    Polymerization of linseed oil with phenolic resins

    JOURNAL OF APPLIED POLYMER SCIENCE, Issue 2 2010
    Gkhan ayl
    Abstract In this study, linseed oil was directly polymerized with different oil soluble resoles. p- Ethyl (PEP), p-tertiary butyl (PTB), p-tertiary octyl (PTO), and p- phenyl (PPP) phenols were separately reacted with formaldehyde to give linseed oil soluble resoles. These were then reacted with linseed oil to give transparent rubbery polymers. A model reaction was performed with methyl oleate and PTB phenol resole to clarify the reaction mechanism. Reaction products were characterized with 1H-NMR and IR techniques. Spectral examination of the model reaction showed that polymerization reaction proceeded via ene reaction of the quinone methide formed at the end group of the resole with the allylic positions of the fatty ester. Rubbery polymers were obtained with linseed oil using 10 to 40% of the different resoles. Hard, load bearing and tough materials were obtained at 40% phenolic resin loading. Mechanical properties of the materials were characterized by dynamic mechanical analyzer (DMA) and stress,strain tests. The best mechanical and thermal properties were obtained with PEP resole which showed a storage modulus of 350 MPa and a tan , peak at 65C. Storage moduli of 275, 250, and 30 were obtained for PPP, PTB, and PTO resoles-linseed oil polymers, respectively. At the same phenolic resin loading, elongation at break and swelling ratios in CH2Cl2 increased with the longer alkyl substitution on the resole resins. The highest thermal stability was observed by PEP resole,linseed oil polymer which has a 5% weight loss temperature of 340C as determined by TGA. The lowest thermal stability was observed for PTB resole-linseed oil polymer at 220C. 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source]


    ,O -Acyl isopeptide method' for peptide synthesis: Solvent effects in the synthesis of A,1,42 isopeptide using ,O -acyl isodipeptide unit'

    JOURNAL OF PEPTIDE SCIENCE, Issue 12 2007
    Atsuhiko Taniguchi
    Abstract ,O -Acyl isopeptide method' is an efficient synthetic method for peptides. We designed ,O -acyl isodipeptide units', Boc-Ser/Thr(Fmoc-Xaa)-OH, as important building blocks to enable routine use of the O -acyl isopeptide method. In the synthesis of an A,1,42 isopeptide using O -acyl isodipeptide unit Boc,Ser(Fmoc,Gly),OH, a side reaction, resulting in the deletion of Ser26 in the O -acyl isopeptide structure, was noticed during coupling of the unit. We observed that the side reaction occurred during the activation step and was solvent-dependent. In DMF or NMP, an intramolecular side reaction, originating from the activated species of the unit, occurred during the activation step. In non-polar solvents such as CHCl3 or CH2Cl2, the side reaction was less likely to occur. Using CH2Cl2 as solvent in coupling the unit, the target A,1,42 isopeptide was synthesized with almost no major side reaction. Copyright 2007 European Peptide Society and John Wiley & Sons, Ltd. [source]


    Solution, solid phase and computational structures of apicidin and its backbone-reduced analogs

    JOURNAL OF PEPTIDE SCIENCE, Issue 6 2006
    Michael Kranz
    Abstract The recently isolated broad-spectrum antiparasitic apicidin (1) is one of the few naturally occurring cyclic tetrapeptides (CTP). Depending on the solvent, the backbone of 1 exhibits two ,-turns (in CH2Cl2) or a ,-turn (in DMSO), differing solely in the rotation of the plane of one of the amide bonds. In the X-ray crystal structure, the peptidic COs and NHs are on opposite sides of the backbone plane, giving rise to infinite stacks of cyclotetrapeptides connected by three intermolecular hydrogen bonds between the backbones. Conformational searches (Amber force field) on a truncated model system of 1 confirm all three backbone conformations to be low-energy states. The previously synthesized analogs of 1 containing a reduced amide bond exhibit the same backbone conformation as 1 in DMSO, which is confirmed further by the X-ray crystal structure of a model system of the desoxy analogs of 1. This similarity helps in explaining why the desoxy analogs retain some of the antiprotozoal activities of apicidin. The backbone-reduction approach designed to facilitate the cyclization step of the acyclic precursors of the CTPs seems to retain the conformational preferences of the parent peptide backbone. Copyright 2005 European Peptide Society and John Wiley & Sons, Ltd. [source]


    Antinociceptive properties of coumarins, steroid and dihydrostyryl-2-pyrones from Polygala sabulosa (Polygalaceae) in mice

    JOURNAL OF PHARMACY AND PHARMACOLOGY: AN INTERNATI ONAL JOURNAL OF PHARMACEUTICAL SCIENCE, Issue 1 2006
    Juliana V. Ardenghi
    We have investigated the possible antinociceptive action of the extract, fractions and pure compounds obtained from the whole plant Polygala sabulosa A. W. Bennett (Polygalaceae) in acetic acid-induced visceral pain in mice. Intraperitoneal injection of animals with the hydroalcoholic extract and fractions (CH2Cl2, EtOAc, n -BuOH, aqueous fraction) (1,100 mg kg,1) caused a dose-related and significant inhibition of the acetic acid-induced visceral nociceptive response. The CH2Cl2, EtOAc and n -BuOH fractions were more potent than the hydroalcoholic extract and aqueous fraction. The isolated compounds dihydrostyryl-2-pyrones (1, 2, 3), styryl-2-pyrone (7), ,-spinasterol (9), scopoletin (10) and two esters of the coumarin (scopoletin) obtained semisynthetically, acetylscopoletin (10a) and benzoylscopoletin (10b) (0.001,10 mg kg,1), exhibited significant and dose-related antinociceptive effects against acetic acid-induced visceral pain. The results distinguished, for the first time, the extract, fractions and pure compounds obtained from P. sabulosa that produced marked antinociception against the acetic acid-induced visceral nociceptive response, supporting the ethnomedical use of P. sabulosa. [source]