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Terms modified by CF3

  • cf3 group
  • cf3 groups

  • Selected Abstracts

    Linear Coinage Metal Complexes Stabilized by a Group 13 Metalloid Ligand

    Ganesan Prabusankar
    Abstract The synthesis and structural characterization of the linear, cationic complex [{(DDP)Ga}2Cu][OTf]·2C6H5F (2, Tf = O2SCF3) stabilized by the monodentate, gallium-based ligand Ga(DDP) (DDP = [HC{(CMe)N(2,6- iPr2C6H3)}2],), as well as NMR spectroscopic evidence for the formation of the corresponding silver compound [{(DDP)Ga}2Ag][Al(hfip)4] (3, hfip = [OC(H)(CF3)2]), are reported. The remarkable steric properties of this gallium-based ligand permit the stabilization of 2, which exhibits an unusual linear geometry and a coordination number of two. [source]

    Molecular Motion and Performance Enhancement of BORAZAN Fluorescent Dyes

    Tyler J. Morin
    Abstract The preparation of three 2,6-dipyrazolyl-4-X-anilines, H(pz2AnX) (X = p -CF3, Cl, tBu) using CuI-catalyzed amination is described. Subsequent reactions of H(pz2AnX) with triphenylboron proceeds with benzene elimination to give the corresponding Ph2B(pz2AnX) compounds in high yields. The Ph2B(pz2AnX) are more highly emissive in the solid state than the previously reported BORAZAN fluorophores, Ph2B(pzAnX), their monopyrazolyl counterparts. As with the Ph2B(pzAnX), the color of emission in Ph2B(pz2AnX) can be tuned simply by varying the para -aniline substituent where the emission of Ph2B(pz2AnX) is red-shifted relative to the corresponding Ph2B(pzAnX) derivatives. The electronic properties were studied by cyclic voltammetry and electronic absorption/emission spectroscopy as well as by density functional calculations (B3LYP/6-31G*). The di-pyrazolyl derivatives exhibit greater stability toward solvolysis and higher photoluminescent quantum yields (despite the red-shift in emission) compared to their monopyrazolyl counterparts presumably due to kinetic stabilization of the chromophore imparted by the second pyrazolyl ligand. For Ph2B(pz2AnX), evidence for intramolecular motion of the diphenylboryl moiety traversing both pyrazolyl groups was detected by variable temperature 1H NMR spectroscopy. The rate increases with increasing electron-donor abilities of the para -aniline substituent.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

    Stable Platinum(0) Catalysts for Catalytic Hydrosilylation of Styrene and Synthesis of [Pt(Ar-bian)(,2 -alkene)] Complexes

    Jeroen W. Sprengers
    Abstract The use of alkenes and bidentate N-ligands in the platinum(0)-catalyzed hydrosilylation of styrene with triethylsilane has been evaluated. A number of bidentate N-ligands, phen, bpy, dafo, and phenyl-bian, were tested at various reaction temperatures using in situ formed catalysts with [Pt(nbe)3] as a precursor. The main conclusions are: (i) ligands, such as phen, which form stable platinum(0) complexes, give lower catalytic activities compared to the ligands which form less stable complexes; (ii) a small ligand effect is observed with dafo and phenyl-bian compared to [Pt(nbe)3], the precursor complex, displaying the lability of these ligands. The complex [Pt(nbe)3], that only has labile alkene ligands, is an active catalyst at low temperatures. At higher temperatures, the catalyst is no longer stable and a decrease in yield is observed. Several novel complexes have been synthesized: [Pt(m,m -(CF3)2 -C6H3 -bian)(tcne)], [Pt(m,m -(CF3)2 -C6H3 -bian)(ma)], [Pt(p -MeO-C6H4 -bian)(ma)], [Pt(p -MeO-C6H4 -bian)(dmfu)] and [Pt(phenyl-bian)(dmfu)]. Whereas the two [Pt(Ar-bian)(ma)] complexes are intrinsically more active than the two [Pt(Ar-bian)(dmfu)] complexes, the latter are much more stable, i.e. the nature of the alkene in these complexes is an important factor in determining their catalytic behavior. Compared to [Pt(Me-nq)(nbe)2], the two [Pt(Ar-bian)(dmfu)] complexes are much more stable resulting in significantly higher overall yields. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]

    Designing Ionic Liquids: 1-Butyl-3-Methylimidazolium Cations with Substituted Tetraphenylborate Counterions

    Joep van den Broeke
    Abstract The hydrophobic, low melting, 1-butyl-3-methylimidazolium (BMIm) salts [BMIm][BPh4] (1), [BMIm][B(C6H4Me-4)4] (2), [BMIm][B{C6H4(CF3)-4}4] (3), [BMIm][B{C6H3(CF3)2 -3,5}4] (4), [BMIm][B{C6H4(C6F13)-4}4] (5), [BMIm][B{C6H4(SiMe3)-4}4] (6), [BMIm][B(C6H4{SiMe2(CH2CH2CF3)}-4)4] (7), [BMIm][B{C6H4(SiMe2C8H17}-4}4] (8) and [BMIm][B(C6H4{SiMe2(CH2CH2C6F13)}-4)4] (9) have been prepared. Systematic variation of the substituents on the tetraphenylborate anion allowed an assessment of their influence on the physical properties of the imidazolium salts. Structural investigations using NMR and IR spectroscopy, combined with single crystal X-ray structure determinations for 2, 3, 5 and 6, revealed hydrogen-bonding interactions between the imidazolium ring protons and the borate anion, both in the solid state and in solution. These interactions are weakened upon the introduction of electron-withdrawing substituents in the anion and follow the order 3,5-(CF3)2 < ,C6F13 < ,CF3 < ,SiMe2CH2CH2C6F13 < ,SiMe2CH2CH2CF3 < ,H < ,Me < ,SiMe3. The melting points of the salts depend primarily on the bulk of the lipophilic substituents, and decrease with increasing size. Bulky lipophilic substituents dramatically enhance the solubility of the imidazolium borates 8 and 9 in hexane and reduce their relative polarity. These unique properties make imidazolium borates 8 and 9 interesting as amphiphilic ionic liquids with low polarity. Attempts to crystallise 7 resulted in decomposition. A single-crystal X-ray structure determination of the product, isolated in 6% yield, showed that a carbene,tris[4-{dimethyl(3,3,3-trifluoropropyl)silyl}phenyl]borane adduct was formed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]

    Synthesis of Some Trifluoromethylated Cyclodextrin Derivatives and Analysis of Their Properties as Artificial Glycosidases and Oxidases

    Jeannette Bjerre
    Abstract Cyclodextrin derivatives containing trifluoromethyl groups at C6 of the A and D rings were synthesized for the purpose of creating artificial enzymes. The compounds were synthesized by perbenzylation of ,-cyclodextrin followed by selective A,D-debenzylation according to Sina˙. Subsequent oxidation to dialdehyde with Dess,Martin periodinane followed by addition of CF3 by using Arduengo carbene and TMSCF3 led to the C6 -bistrifluoromethylated alcohols. These were either deprotected by hydrogenolysis or subjected to another round of oxidation to provide the corresponding ketones that were deprotected. The trifluoromethylated alcohols were found to be weak artificial enzymes catalysing hydrolysis of nitrophenyl glycosides at neutral pH with a kcat/kuncat of up to 56. It is proposed that this catalysis is analogues to the catalysis performed by related cyanohydrins. The trifluoro ketones were likewise weak articial enzymes catalysing oxidation of amines to nitro derivatives or alcohols to ketones with a kcat/kuncat of up to 133. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

    Preparation, Crystallographic Characterization, and Theoretical Study of C70(CF3)14,

    Alexey A. Goryunkov
    Abstract Five C70(CF3)14 isomers have been isolated chromatographically from the mixture produced in the ampoule reaction between C70 and CF3I at 390 °C. Molecular structures of four isomers have been determined in a single-crystal X-ray diffraction study. A quantum chemical survey of the theoretically possible isomers demonstrated that the structures obtained are energetically favorable but that there is probably no full thermodynamic control in the trifluoromethylation process.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

    A One-Pot Synthesis of Doubly Unsaturated Trifluoromethyl Amines:Easy Access to CF3 -Substituted Piperidines

    Guillaume Magueur
    Abstract A straightforward route to trifluoromethyl analogs of piperidines is described. These syntheses involve a Barbier-type allylation reaction of trifluoroacetaldimines, followed by N -allylation (one-pot), and ring-closing metathesis. An efficient asymmetric version is also reported (>98,% de). Functionalized heterobicyclic compounds can also be obtained by a Pauson,Khand reaction. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

    Surface-Transfer Doping of Organic Semiconductors Using Functionalized Self-Assembled Monolayers,

    W. Chen
    Abstract Controlling charge doping in organic semiconductors represents one of the key challenges in organic electronics that needs to be solved in order to optimize charge transport in organic devices. Charge transfer or charge separation at the molecule/substrate interface can be used to dope the semiconductor (substrate) surface or the active molecular layers close to the interface, and this process is referred to as surface-transfer doping. By modifying the Au(111) substrate with self-assembled monolayers (SAMs) of aromatic thiols with strong electron-withdrawing trifluoromethyl (CF3) functional groups, significant electron transfer from the active organic layers (copper(II) phthalocyanine; CuPc) to the underlying CF3 -SAM near the interface is clearly observed by synchrotron photoemission spectroscopy. The electron transfer at the CuPc/CF3 -SAM interface leads to an electron accumulation layer in CF3 -SAM and a depletion layer in CuPc, thereby achieving p-type doping of the CuPc layers close to the interface. In contrast, methyl (CH3)-terminated SAMs do not display significant electron transfer behavior at the CuPc/CH3 -SAM interface, suggesting that these effects can be generalized to other organic-SAM interfaces. Angular-dependent near-edge X-ray absorption fine structure (NEXAFS) measurements reveal that CuPc molecules adopt a standing-up configuration on both SAMs, suggesting that interface charge transfer has a negligible effect on the molecular orientation of CuPc on various SAMs. [source]

    NMR-Solution Structures and Affinities for the Human Somatostatin G-Protein-Coupled Receptors hsst1,5 of CF3 Derivatives of Sandostatin® (Octreotide)

    Dieter Seebach
    Abstract The previously reported (Helv. Chim. Acta2008, 91, 2035) derivatives of octreotide (1) with a (CF3)-Trp substitution, i.e., 3, and with open-chain structures, i.e., 2, 4, and 5, have been tested for their affinities to hsst1,5 receptors and subjected to a detailed NMR analysis. Their affinities vary from 15,nM to 5,,M, as compared to 0.6,nM to 0.8,,M for octreotide itself (Table,1). This decreased bioactivity may have had to be expected for the open-chain compounds 4 and 5; possible reasons for this decrease in the case of CF3 derivative of octreotide, 3, are discussed. NMR Analysis (Tables,2 and 3) provides evidence for increased dynamics of all new derivatives 2,5. The dynamics of the octreotide molecule 1 was analyzed by (natural-abundance) longitudinal 13C-T1 -relaxation time measurements (Table,4), from which the conclusion is drawn that the backbone of the macrocycle is rather rigid on the time scale of this method. [source]

    Structures of the Reactive Intermediates in Organocatalysis with Diarylprolinol Ethers


    Abstract Structures of the reactive intermediates (enamines and iminium ions) of organocatalysis with diarylprolinol derivatives have been determined. To this end, diarylprolinol methyl and silyl ethers, 1, and aldehydes, PhCH2CHO, tBuCH2CHO, PhCH=CHCHO, are condensed to the corresponding enamines, A and 3 (Scheme,2), and cinnamoylidene iminium salts, B and 4 (Scheme,3). These are isolated and fully characterized by melting/decomposition points, [,]D, elemental analysis, IR and NMR spectroscopy, and high-resolution mass spectrometry (HR-MS). Salts with BF4, PF6, SbF6, and the weakly coordinating Al[OC(CF3)3]4 anion were prepared. X-Ray crystal structures of an enamine and of six iminium salts have been obtained and are described herein (Figs.,2 and 4,8, and Tables,2 and 7) and in a previous preliminary communication (Helv. Chim. Acta2008, 91, 1999). According to the NMR spectra (in CDCl3, (D6)DMSO, (D6)acetone, or CD3OD; Table,1), the major isomers 4 of the iminium salts have (E)-configuration of the exocyclic NC(1,) bond, but there are up to 11% of the (Z)-isomer present in these solutions (Fig.,1). In all crystal structures, the iminium ions have (E)-configuration, and the conformation around the exocyclic N-CC-O bond is synclinal-exo (cf.C and L), with one of the phenyl groups over the pyrrolidine ring, and the RO group over the , -system. One of the meta -substituents (Me in 4b, CF3 in 4c and 4e) on a 3,5-disubstituted phenyl group is also located in the space above the , -system. DFT Calculations at various levels of theory (Tables,3,6) confirm that the experimentally determined structures (cf. Fig.,10) are by far (up to 8.3,kcal/mol) the most stable ones. Implications of the results with respect to the mechanism of organocatalysis by diarylprolinol derivatives are discussed. [source]

    Are Oxazolidinones Really Unproductive, Parasitic Species in Proline Catalysis?

    Experiments Pointing to an Alternative View, Thoughts
    Abstract The N,O-acetal and N,O-ketal derivatives (oxazolidinones) formed from proline, and aldehydes or ketones are well-known today, and they are detectable in reaction mixtures involving proline catalysis, where they have been considered ,parasitic dead ends'. We disclose results of experiments performed in the early 1970's, and we describe more recent findings about the isolation, characterization, and reactions of the oxazolidinone derived from proline and cyclohexanone. This oxazolidinone reacts (THF, room temperature) with the electrophiles , -nitrostyrene and chloral (=trichloroacetaldehyde), to give the Michael and aldol adduct, respectively, after aqueous workup (Scheme,5). The reactions occur even at ,75° when catalyzed with bases such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or EtN(i-Pr)2 (DIPEA) (10%; Table,1). It is shown by NMR (Figs.,1 and 3) and IR analysis (Figs.,2 and 4) that the primarily detectable product (before hydrolysis) of the reaction with the nitro-olefin is again an oxazolidinone. When dissolved in hydroxylic solvents such as MeOH, ,hexafluoroisopropanol' ((CF3)2CHOH; HFIP), AcOH, CF3COOH, or in LiBr-saturated THF, the ring of the oxazolidinone from cyclohexanone and proline opens up to the corresponding iminium ion (Tables,2,4), and when treated with strong bases such as DBU (in (D8)THF) the enamino-carboxylate derived from proline and cyclohexanone is formed (Scheme,8). Thus, the two hitherto putative participants (iminium ion and enamine) of the catalytic cycle (Scheme,9) have been characterized for the first time. The commonly accepted mechanism of the stereoselective C,C- or C,X-bond-forming step (i.e., A,D) of this cycle is discussed and challenged by thoughts about an alternative model with a pivotal role of oxazolidinones in the regio- and diastereoselective formation of the intermediate enamino acid (by elimination) and in the subsequent reaction with an electrophile (by trans -addition with lactonization; Schemes,11,14). The stereochemical bias between endo - and exo -space of the bicyclo[3.3.0]octane-type oxazolidinone structure (Figs.,5 and 6) is considered to possibly be decisive for the stereochemical course of events. Finally, the remarkable consistency, with which the diastereotopic Re -face of the double bond of pyrrolidino-enamines (derived from proline) is attacked by electrophiles (Schemes,1 and 15), and the likewise consistent reversal to the Si -face with bulky (Aryl)2C-substituents on the pyrrolidine ring (Scheme,16) are discussed by invoking stereoelectronic assistance from the lone pair of pyramidalized enamine N-atoms. [source]

    Insertion Reactions of 1,2-Disubstituted Olefins with an , -Diimine Palladium(II) Complex

    Carla Carfagna
    Abstract The migratory insertions of cis or trans olefins CH(X)CH(Me) (X,=,Ph, Br, or Et) into the metal,acyl bond of the complex [Pd(Me)(CO)(iPr2dab)]+ [B{3,5-(CF3)2C6H3}4], (1) (iPr2dab,=,1,4-diisopropyl-1,4-diazabuta-1,3-diene,=,N,N, -(ethane-1,2-diylidene)bis[1-methylethanamine]) are described (Scheme,1). The resulting five-membered palladacycles were characterized by NMR spectroscopy and X-ray analysis. Experimental data reveal some important aspects concerning the regio- and stereochemistry of the insertion process. In particular, the presence of a Ph or Br substituent at the alkene leads to the formation of highly regiospecific products. Moreover, in all cases, the geometry of the substituents in the formed palladacycle was the same as in the starting olefin, as a consequence of a cis addition of the Pd,acyl fragment to the CC bond. Reaction with CO and MeOH of the five-membered complex derived from trans-, -methylstyrene (=,[(1E)-prop-1-enyl]benzene) insertion, yielded the 2,3-substituted , -keto ester 9 with an (2RS,3SR)-configuration (Scheme,3). [source]

    Thermally Induced Reversible Phase Transformations Accompanied by Emission Switching Between Different Colors of Two Aromatic-Amine Compounds

    ADVANCED MATERIALS, Issue 31 2009
    Yunfeng Zhao
    Thermally driven reversible emission switching between different colors and solid-phase transformation are investigated for two aromatic-amine compounds bearing trifluoromethyl (CF3) groups. The phase-dependent emission properties are attributed to the different molecular packing properties and changeable molecular geometry for different solid phases (see figure). [source]

    Kinetic and mechanistic investigation into the influence of chelate substituents on the substitution reactions of platinum(II) terpyridine complexes

    Deogratius Jaganyi
    The substitution kinetics of the complexes [Pt{4,-(o -CH3 -Ph)-terpy} Cl]SbF6 (CH3PhPtCl(Sb)), [Pt{4,-(o -CH3 -Ph)-terpy}Cl]CF3SO3 (CH3PhPtCl(CF)), [Pt(4,-Ph-terpy)Cl]SbF6 (PhPtCl), [Pt(terpy)Cl]Cl·2H2O (PtCl), [Pt{4,-(o -Cl-Ph)-terpy}Cl]SbF6 (ClPhPtCl), and [Pt{4,-(o -CF3 -Ph)-terpy}Cl]SbF6 (CF3PhPtCl), where terpy is 2,2,:6,,2,-terpyridine, with the nucleophiles thiourea (TU), N,N,-dimethylthiourea (DMTU), and N,N,N,,N,-tetramethylthiourea (TMTU) were investigated in methanol as a solvent. The substitution reactions of the chloride displacement from the metal complexes by the nucleophiles were investigated as a function of nucleophile concentration and temperature under pseudo-first-order conditions using the stopped-flow technique. The reactions followed the simple rate law kobs = k2[Nu]. The results indicate that the introduction of substituents in the ortho position of the phenyl group on the ancillary ring of the terpy unit does influence the extent of ,-backbonding in the terpy ring. This controls the electrophilicity of the platinum center, which in turn controls the lability of the chloro-leaving group. The strength of the electron-donating or -withdrawing ability of the substituents correlates with the reactivity of the complexes. Electron-donating substituents decrease the rate of substitution, whereas electron-withdrawing substituents increase the rate of substitution. This was supported by DFT calculations at the B3LYP/LACVP+** level of theory, which showed that most of the electron density of the HOMO is concentrated on the phenyl ligand rather than on the metal center in the case of the strongest electron-withdrawing substituent in CF3PhPtCl. The opposite was found to be true with the strongest electron-donating substituent in CH3PhPtCl. Thiourea was found to be the best nucleophile with N,N,N,,N,-tetramethylthiourea being the weakest due to steric effects. The temperature dependence studies support an associative mode of activation. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 808,818, 2008 [source]

    CF3CH(ONO)CF3: Synthesis, IR spectrum, and use as OH radical source for kinetic and mechanistic studies

    M. P. Sulbaek Andersen
    The synthesis, IR spectrum, and first-principles characterization of CF3CH(ONO)CF3 as well as its use as an OH radical source in kinetic and mechanistic studies are reported. CF3CH(ONO)CF3 exists in two conformers corresponding to rotation about the RCONO bond. The more prevalent trans conformer accounts for the prominent IR absorption features at frequencies (cm,1) of 1766 (NO stretch), 1302, 1210, and 1119 (CF stretches), and 761 (ONO bend); the cis conformer contributes a number of distinct weaker features. CF3CH(ONO)CF3 was readily photolyzed using fluorescent blacklamps to generate CF3C(O)CF3 and, by implication, OH radicals in 100% yield. CF3CH(ONO)CF3 photolysis is a convenient source of OH radicals in the studies of the yields of CO, CO2, HCHO, and HC(O)OH products which can be difficult to measure using more conventional OH radical sources (e.g., CH3ONO photolysis). CF3CH(ONO)CF3 photolysis was used to measure k(OH + C2H4)/k(OH + C3H6) = 0.29 ± 0.01 and to establish upper limits of 16 and 6% for the molar yields of CO and HC(O)OH from the reaction of OH radicals with benzene in 700 Torr of air at 296 K. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 159,165, 2003 [source]

    Efficient and Highly Chemoselective Direct Reductive Amination of Aldehydes using the System Silane/Oxorhenium Complexes

    Sara C. A. Sousa
    Abstract This work reports a novel method for direct reductive amination of aldehydes with silanes catalyzed by several high-valent oxorhenium(V) and oxorhenium(VII) complexes. The catalytic system PhSiH3/ReIO2(PPh3)2 (2.5,mol%) was very efficient for the synthesis of secondary amines and highly chemoselective, tolerating a wide range of functional groups such as NO2, CF3, SO2R, CO2R, F, Cl, Br, I, CN, OH, OCH3, SCH3, NCOR, and double bonds. This novel method was also employed in the synthesis of tertiary amines with moderate yields. [source]

    Extremely Efficient Cross-Coupling of Benzylic Halides with Aryltitanium Tris(isopropoxide) Catalyzed by Low Loadings of a Simple Palladium(II) Acetate/Tris(p -tolyl)phosphine System

    Chi-Ren Chen
    Abstract Highly efficient coupling reactions of benzylic bromides or chlorides with aryltitanium tris(isopropoxide) [ArTi(O- i- Pr)3] catalyzed by a simple palladium(II) acetate/tris(p -tolyl)phosphine [Pd(OAc)2/ P(p -tolyl)3] system are reported. The coupling reactions proceed in general at room temperature employing low catalyst loadings of 0.02 to 0.2,mol%, affording coupling products in excellent yields of up to 99%. For benzylic bromides bearing strong electron-withdrawing cyano (CN) or trifluoromethyl (CF3) substituents, the reactions require a higher catalyst loading of 1,mol%, or the reactions are carried out at 60,°C. The catalytic system also tolerates (1-bromoethyl)benzene bearing ,-hydrogen atoms while using a catalyst loading of 1,mol% to afford the coupling product in a 70% yield. [source]

    Substituent effects on O,H and S,H bond dissociation enthalpies of disubstituted phenols and thiophenols

    Daniel J. V. A. dos Santos
    Abstract The O,H and S,H homolytic bond dissociation enthalpies of a set of disubstituted phenols and thiophenols (NH2, OH, CH3, Cl, CF3, and NO2) have been computed by a density functional theory procedure with the 6-311++G(d,p) basis set. A very good agreement between our results and available experimental ones is observed. The effect of substituents on structure, charges and BDEs are investigated and their correlation with Hammett parameters is studied. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source]

    A generalized exo -anomeric effect.

    Substituent, solvent effects on the conformational equilibria of 2-(arylseleno)cyclohexanones
    The effects of substitution and solvent on the conformational equilibria of 2-[(4-R-substituted-phenyl)seleno]cyclohexanones are described. The conformational equilibria were determined by comparison of the linewidths of the H-2 resonances in the 1H NMR spectra of the conformationally averaged systems with those of the anancomeric (highly biased) 4-isopropyl-2-substituted cyclohexanones. The substituent (R = NMe2, OMe, Me, H, F, Cl, CF3, NO2) and solvent ((CD3)2CO, CD3CN, CD2Cl2, CDCl3) effects are discussed in terms of electrostatic effects and the possible stabilizing orbital interactions. The values of Keq (axial-equatorial) increase as the substituent becomes more electron withdrawing, in agreement with the dominance of nSe , ,*C=O or ,C-Se , ,*C=O orbital interactions in the axial conformers. The increase in the proportion of the equatorial isomers in more polar solvents for a given substituent suggests a damping of the dipolar interactions in the equatorial isomers. However, the proportion of the equatorial isomers in a given solvent increases as the substituent becomes more electron withdrawing, indicating that electrostatic interactions do not dominate in controlling the conformational equilibria. Analysis of the equilibrium data by means of a dual substituent parameter approach indicates the best correlation with ,I and ,+R substituent constants in CD2Cl2 and with ,I and ,°R substituent constants in CD3CN, with similar sensitivities to the resonance and polar effects. The correlations are interpreted in terms of accommodation of effective positive charge on the selenium atom in the axial isomers in CD2Cl2, and a lesser sensitivity to the buildup of positive charge in the more polar solvent CD3CN. Comparison of the IR ,CO -stretching frequencies for the axial and equatorial ArSe-substituted anancomeric systems (R = NO2, NMe2) indicates a higher stretching frequency for the NO2 -substituted isomers. In the case of the NMe2 -substituted compounds, ,CO appears at a higher frequency in the equatorial isomer, whereas in the case of the NO2 -substituted compounds, ,CO is less sensitive to the axial or equatorial orientation of the substituent. The results are consistent with the operation of nse , ,*c=0 or ,C-Se , ,*C=O orbital interactions in the axial isomers. The JC2-H2 values in the axially-substituted anancomeric isomers are of greater magnitude than those in the equatorially-substituted isomers, which is also consistent with the operation of the orbital interactions described above. There is, however, no marked substituent effect on the JC2,H2 values within the series of axial or equatorial isomers. We argue that this does not support the dominance of ,C-Se , ,*C=O orbital interactions. Examination of crystal structures reported in the literature for related compounds indicates a particular gauche orientation about the C2,Se bond, which lends further support to the operation of an nSe , ,*C=O orbital interaction. We suggest that the latter interaction is a manifestation of a generalized exo -anomeric effect. [source]

    Enhanced Hydrogenation Activity and Recycling of Cationic Rhodium Diphosphine Complexes through the Use of Highly Fluorous and Weakly-Coordinating Tetraphenylborate Anions

    Broeke, Joep van
    Abstract The effect of the nature of the anion on the performance of ionic rhodium catalysts has received little attention. Herein it is shown that the use of highly fluorous tetraphenylborate anions can enhance catalyst activity in both conventional and fluorous media. For hydrogenation catalysts of the type [Rh(COD)(dppb)][X] {COD=1,5- cis,cis -cyclooctadiene; dppb=1,4-bis(diphenylphosphino)butane; X=BF4, (1a), [BPh4], (1b), [B{C6H4(SiMe3)-4}4], (1c), [B{C6H3(CF3)2 -3,5}4], (1d), [B{C6H4(SiMe2CH2CH2C6F13)-4}4], (1e), [B{C6H4(C6F13)-4}4], (1f) and [B{C6H3(C6F13)2 -3,5}4], (1,g)} the activity towards the hydrogenation of 1-octene in acetone increased in the order 1c <1b <1e <1a <1d ~ 1f <1g with 1g being twice as active as the commonly applied 1a. Despite the fluorophilic character introduced by the substituted tetraarylborate anions, the presence of some perfluoroalkyl-substituents in the cation was still required for achieving high partition coefficients. Therefore, [Rh(COD)(Ar2PCH2CH2PAr2)][X] {Ar=C6H4(SiMe2CH2CH2C6F13)-4, X=[B{C6H3(C6F13)2 -3,5}4], (3f); Ar=C6H4(SiMe(CH2CH2C6F13)2)-4 and X=[B{C6H4(C6F13)-4}4], (2g)} were prepared, which were active in the hydrogenation of 1-octene, 2g even more so than 3f. Both these highly fluorous catalysts could be recycled with 99% efficiency through fluorous biphasic separation, whereas the corresponding BF4, complex of 2g (2a) did not show any affinity for the fluorous phase. [source]

    Fluoropassivation and gelatin sealing of polyester arterial prostheses to skip preclotting and constrain the chronic inflammatory response

    Xingyi Xie
    Abstract Fluoropassivation and gelatin coating have been applied to polyethylene terephthalate (PET) vascular prosthesis to combine the advantages of both polytetrafluoroethylene (PTFE) and PET materials, and to eliminate the preclotting procedure. The morphological, chemical, physical, and mechanical properties of such prostheses were investigated and compared with its original model. Fluoropassivation introduced OCF3, CF3, and CFCF2 structures onto the surface of the polyester fibers. However, the surface fluorine content was only 28,32% compared to the 66% in expanded PTFE (ePTFE) grafts. The fluoropassivation decreased the hydrophilicity, slightly increased the water permeability, and marginally lowered the melting point and the crystallinity of the PET fibers. After gelatin coating, the fluoropassivated and nonfluoropassivated prostheses showed similar surface morphology and chemistry. While gelatin coating eliminated preclotting, it also renders the prostheses slightly stiffer. The original prosthesis had the highest bursting strength (275 N), with the fluoropassivated and gelatin-sealed devices showing similar bursting strength between 210 and 230 N. Fluoropassivation and gelatin coating lowered the retention strength by 23 and 30% on average, respectively. In vitro enzymatic incubation had only marginal effect on the surface fluorine content of the nongelatin-sealed prostheses. However, the gelatin-sealed ones significantly lost their surface fluorine after in vitro enzymatic incubation (by 69,85%) or in vivo 6-month implantation (by 51,60%), showing the lability of the fluoropolymer layer under the hostile biological environment. © 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2010 [source]

    A flexible approach to the design of new potent substance P receptor ligands

    R. Millet
    The development of small-molecule antagonists of the substance-P-preferring tachykinin NK1 receptor offers an excellent opportunity to exploit these molecules as novel therapeutic agents in diverse pathologies such as depression, emesis or asthma. GR71251 has previously been identified as a potent and selective substance-P-receptor antagonist. We have therefore undertaken the synthesis of new pseudopeptidic analogues based on the C-terminal sequence of GR71251. The evaluation of binding affinities toward NK1 and NK2 receptors has enabled us to propose new selective NK1 ligands with high affinity. Structure-activity relationships showed that the Trp-OBzl(CF3)2 moiety is essential for NK1 affinity and that the introduction of building units such as spirolactam, lactam or proline, leading to a constrained peptide, increased selectivity for NK1 receptors. These compounds constitute a useful starting point for new substance P antagonists and represent an attractive lead series for further studies on the design of specific NK1 antagonists. [source]

    Comparative study of electronic structure and optical properties of a series of Pt(II) complexes containing different electron-donating and -withdrawing groups: a DFT study

    Xiao-Na Li
    Abstract We report a quantum-chemistry study of electronic structures and spectral properties of a series of Pt(II) complexes containing different substituents (CH3 (1), OCH3 (2), NO2 (3), CF3 (4), and COOH (5)). 1 and 2 have been previously synthesized in experiment, while 3,5 are artificial complexes that we suggest can be used to investigate the electron-withdrawing effect on charge injection, transport, absorption, and phosphorescence properties. The results reveal that the stronger electron-donating and -withdrawing groups show stronger absorption intensity, while the phosphorescence efficiency is generally higher for complexes containing electron-donating substituents. 1 and 2 are easier for hole injection, while 3,5 are easier for electron injection. The enhanced electron injection abilities of 3,5 will confine more excitons in the light-emitting layer (EML) and may not result in lower electroluminescence (EL) efficiency than 1 and 2. These results suggest that the three artificial complexes may be new emitters in organic light-emitting diodes (OLEDs). Copyright © 2009 John Wiley & Sons, Ltd. [source]

    Computational study of stereoelectronic effects in fluorinated alkylamines,

    Joseph J. Urban
    Abstract A systematic evaluation of the stereoelectronic effects in a series of fluorinated amine compounds has been carried out. A variety of computational methods have been employed, including molecular mechanics, semi-empirical, density functional and ab initio methods. An analysis of the natural bond orbital populations has been carried out and the effect of solvent was considered via the polarized continuum model (PCM). The results indicate a preference for conformations that result in an anti-periplanar arrangement between the nitrogen lone pair and the CX bond (XF or CF3). There are variations in geometry and natural bond orbital population, with conformation that are consistent with a stereoelectronic effect whereby electron density from the nitrogen lone pair is delocalized into the CX ,* orbital. Similar results are obtained for trifluoromethyl methylamines, although the magnitude of the stereoelectronic effect is attenuated resulting in greater expected conformational diversity for these compounds. The PCM results suggest that these preferences should persist in solution. Comparison among the computational methods used reveals that there is good agreement among the ab initio and density functional methods (at the HF/6-31,+,G(d), MP2/6-31,+,G(d), MP2/6-311,+,G(2d,p) and B3LYP/6-31,+,G(d) levels) and these methods agree well with the available experimental data for ethylmethylamine. Published in 2005 by John Wiley & Sons, Ltd. [source]

    N -Isopropyl enols of carboxylic acid amides,

    Yi Xiong Lei
    Abstract Eight N -isopropyl compounds of the formal structure YY,CHCONHPr- i (6), Y,Y,,=,CO2Me, CO2CH2CF3, CN; YY,,=,Meldrum,s acid residue; Y,=,CO2Me, Y,,=,CO2CH2CF3, CN; Y,=,CO2CH2CF3, CO2CH(CF3)2, Y,,=,CN, and the N - t -butyl derivative of Meldrum's acid were prepared and their structures were investigated in the solid state and in solution. The x-ray diffraction data indicate that in the solid state the structure is that of the amide 6, when Y,=,Y,,=,CO2Me, whereas when Y,=,CO2Me, Y,,=,CN or YY,,=,Meldrum,s acid residue the structure is that of the enol (5) YY,C=C(OH)NHPr- i. The solid-state 13C spectra indicate structure 6 when Y,=,CO2Me, Y,,=,CO2R, R,=,Me, CH2CF3 and an enol structure for the other compounds studied. 1H, 13C and when available 19F NMR spectra showed that the enol/amide composition in solution is structure and solvent dependent, in analogy with the previously investigated N -Ph analogs. The percentage of enol (and KEnol) decrease in the order of solvents CCl4,>,CDCl3,>,THF- d8,>,CD3CN,>,DMSO- d6, DMF- d7. For Y,Y, the percentage of enol increases when the number of fluorine atoms in R of the CO2R increases, when CN replaces a CO2R group or for the cyclic Meldrum's acid derivative. Both E - and Z -enols were observed when Y,,,Y,, mostly at low temperature. The ,(OH) values increase with increased polarity of the medium and with increased strength of the hydrogen bonds in which they are involved. In THF- d8 and DMF- d7 the Z -enol/E -enol and the amide/enol ratios increase with increase in temperature. A main conclusion from the work is that the percentage of the enol increases, but not drastically, when the N -substituent is changed from Ph to i -Pr. Copyright © 2003 John Wiley & Sons, Ltd. [source]

    Cyclopolymerization of perfluoroisopropenyl vinylacetate

    Hirotada Fujiwara
    Abstract To develop the polymerization exploiting the interconversion of fluorinated carbon radical to hydrocarbon radical, the radical cyclopolymerization of perfluoroisopropenyl vinylacetate [CF2C(CF3)OCOCH2CHCH2] (FIA) was investigated to afford a polymer possessing mainly five-membered ring structure with bimodal molecular weight distribution having 1 × 105 as the higher molecular weight. This may be the first example wherein the cyclopolymerization between usual allyl group and fluorinated vinyl group is performed. The degree of cyclization was between 70 and 80% determined by 19F NMR of as-polymerized products. The polymer preparation from perfluoroisopropenyl group, which shows scarce homopolymerization reactivity was accomplished. The mechanism that the addition of hydrocarbon radical to perfluoroisopropenyl group to produce fluorinated carbon radical followed by the intramolecular addition reaction onto allyl group to form five-membered ring is proposed. The hydrolysis of the FIA polymer afforded a polymer possessing hydrophobic fluoroalkyl group with hydrophilic hydroxyl and carboxylic acid groups. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3220,3232, 2006 [source]

    Ethylene/,-olefin copolymerization with bis(,-enaminoketonato) titanium complexes activated with modified methylaluminoxane

    Li-Ming Tang
    Abstract Copolymerizations of ethylene with ,-olefins (i.e., 1-hexene, 1-octene, allylbenzene, and 4-phenyl-1-butene) using the bis(,-enaminoketonato) titanium complexes [(Ph)NC(R2)CHC(R1)O]2TiCl2 (1a: R1 = CF3, R2 = CH3; 1b: R1 = Ph, R2 = CF3; and 1c: R1 = t -Bu, R2 = CF3), activated with modified methylaluminoxane as a cocatalyst, have been investigated. The catalyst activity, comonomer incorporation, and molecular weight, and molecular weight distribution of the polymers produced can be controlled over a wide range by the variation of the catalyst structure, ,-olefin, and reaction parameters such as the comonomer feed concentration. The substituents R1 and R2 of the ligands affect considerably both the catalyst activity and comonomer incorporation. Precatalyst 1a exhibits high catalytic activity and produces high-molecular-weight copolymers with high ,-olefin insertion. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6323,6330, 2005 [source]

    Acyclic diene metathesis polymerization of 2,5-dialkyl-1,4-divinylbenzene with molybdenum or ruthenium catalysts: Factors affecting the precise synthesis of defect-free, high-molecular-weight trans -poly(p -phenylene vinylene)s

    Kotohiro Nomura
    Abstract Factors affecting the syntheses of high-molecular-weight poly(2,5-dialkyl-1,4-phenylene vinylene) by the acyclic diene metathesis polymerization of 2,5-dialkyl-1,4-divinylbenzenes [alkyl = n -octyl (2) and 2-ethylhexyl (3)] with a molybdenum or ruthenium catalyst were explored. The polymerizations of 2 by Mo(N -2,6-Me2C6H3) (CHMe2 Ph)[OCMe(CF3)2]2 at 25 °C was completed with both a high initial monomer concentration and reduced pressure, affording poly(p -phenylene vinylene)s with low polydispersity index values (number-average molecular weight = 3.3,3.65 × 103 by gel permeation chromatography vs polystyrene standards, weight-average molecular weight/number-average molecular weight = 1.1,1.2), but the polymerization of 3 was not completed under the same conditions. The synthesis of structurally regular (all- trans), defect-free, high-molecular-weight 2-ethylhexyl substituted poly(p -phenylene vinylene)s [poly3; degree of monomer repeating unit (DPn) = ca. 16,70 by 1H NMR] with unimodal molecular weight distributions (number-average molecular weight = 8.30,36.3 × 103 by gel permeation chromatography, weight-average molecular weight/number-average molecular weight = 1.6,2.1) and with defined polymer chain ends (as a vinyl group, CHCH2) was achieved when Ru(CHPh)(Cl)2(IMesH2)(PCy3) or Ru(CH-2-OiPr-C6H4)(Cl)2(IMesH2) [IMesH2 = 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene] was employed as a catalyst at 50 °C. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6166,6177, 2005 [source]

    Effects of diamines and their fluorinated groups on the color lightness and preparation of organosoluble aromatic polyimides from 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]-hexafluoropropane

    Chin-Ping Yang
    Abstract To investigate the position and amount of the CF3 group affecting the coloration of polyimides (PIs), we prepared 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane (2) with four CF3 groups with 2-chloro-5-nitrobenzotrifluoride and 2,2-bis(4-hydroxyphenol)hexafluoropropane. A series of soluble and light-colored fluorinated PIs (5) were synthesized from 2 and various aromatic dianhydrides (3a,3f). 5a,5f had inherent viscosities ranging from 0.80 to 1.19 dL/g and were soluble in amide polar solvents and even in less polar solvents. The glass-transition temperatures of 5 were 221,265 °C, and the 10% weight-loss temperatures were above 493 °C. Their films had cutoff wavelengths between 343 and 390 nm, b* values (a yellowness index) ranging from 5 to 41, dielectric constants of 2.68,3.01 (1 MHz), and moisture absorptions of 0.03,0.29 wt %. In a comparison of the PI series 6,8 based on 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]propane, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane, we found that the CF3 group close to the imide group was more effective in lowering the color; this means that CF3 of 5, 7, and 8f was more effective than that of 6c. The color intensity of the four PI series was lowered in the following order: 5 > 7 > 6 > 8. The PI 5f, synthesized from diamine 2 and 4,4,-hexafluoroisopropylidenediphthalic anhydride, had six CF3 groups in a repeated segment, so it exhibited the lightest color among the four series. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 922,938, 2003 [source]

    Theoretical investigation on multinuclear NMR chemical shifts of some tris(trifluoromethyl)boron complexes

    Jun Zhang
    Abstract Tris(trifluoromethyl)boron complexes have unusual properties and may find applications in many fields of chemistry, biology, and physics. To gain insight into their NMR properties, the isotropic 11B, 13C, and 19F NMR chemical shifts of a series of tris(trifluoromethyl)boron complexes were systematically studied using the gauge-included atomic orbitals (GIAO) method at the levels of B3LYP/6-31 + G(d,p)//B3LYP/6-31G* and B3LYP/6-311 + G(d,p)//B3LYP/6-311 + G(d,p). Solvent effects were taken into account by polarizable continuum models (PCM). The calculated results were compared with the experimental values. The reason that the structurally inequivalent fluorine atoms in a specific species give a same chemical shift in experimental measurements is attributed to the fast rotation of CF3 group around the BC(F3) bond because of the low energy barrier. The calculated 11B, 13C(F3), and 19F chemical shifts are in good agreement with the experimental measurements, while the deviations of calculated 13C(X, X = O, N) chemical shifts are slightly large. For the latter, the average absolute deviations of the results from B3LYP/6-311 + G(d,p)//B3LYP/6-311 + G(d,p) are smaller than those from B3LYP/6-31 + G(d,p)//B3LYP/6-31G*, and the inclusion of PCM reduces the deviation values. The calculated 19F and 11B chemical shieldings of (CF3)3BCO are greatly dependent on the optimized structures, while the influence of structural parameters on the calculated 13C chemical shieldings is minor. Copyright © 2009 John Wiley & Sons, Ltd. [source]