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Acetophenone
Kinds of Acetophenone Terms modified by Acetophenone Selected AbstractsFirst Authentication of Kostanecki's Triketone and Multimolecular Reaction of Aromatic Aldehydes with AcetophenoneHELVETICA CHIMICA ACTA, Issue 6 2009Zixing Shan Abstract A double-component, multimolecular reaction between acetophenone and aromatic aldehydes was achieved under catalysis by the solid-base mixture NaOH/K2CO3, and Kostanecki's triketone, supposed to exist for more than 110 years, was successfully separated for the first time as an accompaniment of a pentane-1,5-dione or a 1,2,3,4,5-pentasubstituted cyclohexanol (Scheme,1) and authenticated by spectroscopic and single-crystal X-ray diffraction analysis. Thus, the multimolecular-reaction mechanism of the formation of 1,2,3,4,5-pentasubstituted cyclohexanols from 1-phenylalkan-1-ones and aromatic aldehydes was fully validated based on the results (Scheme,3). [source] Synthesis of Ruthenium Hydride Complexes Containing beta-Aminophosphine Ligands Derived from Amino Acids and their use in the H2 -Hydrogenation of Ketones and IminesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4 2005Kamaluddin Abdur-Rashid Abstract The new complexes RuHCl(PPh2CH2CHRNH2)2 and RuHCl(PPh2CH2CHRNH2)(R- binap), R=H (Pgly), R=Me [(R)-Pala] were prepared by the substitution of the PPh3 ligands in RuHCl(PPh3)3 or RuHCl(PPh3)[(R)-binap] with beta-aminophosphines derived from amino acids. The complex trans -RuHCl(Pgly)[(R)-binap] has been characterized by X-ray crystallography. The complex trans -RuHCl[(S)-Ppro]2 where (S)-Ppro is derived from proline was also prepared and characterized by X-ray crystallography. These were used as catalyst precursors in the presence of a base (KOPr- i or KOBu- t) for the hydrogenation of various ketones and imines to the respective alcohols and amines with H2 gas (1,11 atm) at room temperature. Acetophenone was hydrogenated to (S)-1-phenylethanol in low ee (up to 40%) when catalyzed by the enantiomerically pure complexes. These complexes are especially active in the hydrogenation of sterically congested and electronically deactivated ketones and imines and are selective for the hydrogenation of CO bonds over CC bonds. [source] ChemInform Abstract: One-Pot Synthesis of Phenacyl Esters from Acetophenone, [Bmim]Br3, and Potassium Salts of Carboxylic Acids under Solvent-Free Conditions.CHEMINFORM, Issue 32 2009Zhang-Gao Le Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: A New Class of Acetophenone-Based Cinchona Alkaloids as Phase-Transfer Catalysts: Application to the Enantioselective Synthesis of ,-Amino Acids.CHEMINFORM, Issue 14 2008Jian Lv Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Asymmetric Reduction of Acetophenone and Propiophenone by NaAl(IPTOLate)H2 Combined with Enantiomeric Enrichment of the Reaction Product as an Inclusion Complex with IPTOL.CHEMINFORM, Issue 10 2004M. G. Vinogradov Abstract For Abstract see ChemInform Abstract in Full Text. [source] Synthesis of Chiral Phosphorus Reagents and Their Catalytic Activity in Asymmetric Borane Reduction of N-Phenyl Imine of Acetophenone.CHEMINFORM, Issue 51 2003Kangying Li Abstract For Abstract see ChemInform Abstract in Full Text. [source] Hydrido-Osmium(II), -Osmium(IV) and-Osmium(VI) Complexes with Functionalized Phosphanes as Ligands,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 35 2009Birgit Richter Abstract Reaction of five-coordinate [OsHCl(CO)(PiPr3)2] (1) with the chelating phosphane iPr2PCH2CO2Me gave six-coordinate [OsHCl(CO)(PiPr3){,2(P,O)- iPr2PCH2C(=O)OMe}] (2), which upon treatment with CO and O2 afforded the 1:1 adducts [OsHCl(CO)(L)(PiPr3){,(P)- iPr2PCH2CO2Me}] (3, 4) by partial opening of the chelate ring. The vinyl complex [OsCl(CH=CHPh)(CO)(PiPr3){,2(P,O)- iPr2PCH2C(=O)OMe}] (5) was obtained from 2 and PhC,CH by insertion of the alkyne into the Os,H bond. Reaction of 2 with sodium acetate led to metathesis of the anionic ligands and formation of [OsH(,2 -O2CCH3)(CO)(PiPr3){,(P)- iPr2PCH2CO2Me}] (6). Osmium(VI) compounds [OsH6(PiPr2R)2] with R = CH2CH2OMe (12), CH2CO2Me (13) and CH2CO2Et (14), and [OsH6(PiPr3){,(P)- iPr2PCH2CH2NMe2}] (16) were prepared from osmium(IV) precursors and shown to rapidly react with O2 and primary alcohols. Exploratory studies revealed that the catalytic activity of the hexahydrido complexes in the hydrogen transfer reaction from 2-propanol to cyclohexanone and acetophenone depends on the type of the functionalized phosphane and is best for R = CH2CH2OMe. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] 16-Electron (Arene)ruthenium Complexes with Superbasic Bis(imidazolin-2-imine) Ligands and Their Use in Catalytic Transfer HydrogenationEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 29-30 2009Thomas Glöge Abstract The ligands N,N, -bis(1,3,4,5-tetramethylimidazolin-2-ylidene)-1,2-ethanediamine (BLMe) and N,N, -bis(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)-1,2-ethanediamine(BLiPr) react with [(,5 -C5Me5)RuCl]4 to afford cationic 16-electron half-sandwich complexes [(,5 -C5Me5)Ru(BLR)]+ (R = Me, 3; R = iPr, 4), which resist coordination of the chloride counterion because of the strong electron-donating ability of the diimine ligands. Upon reaction with [(,6 -C6H6)RuCl2]2 or [(,6 -C10H14)RuCl2]2, these ligands stabilize dicationic 16-electron benzene and cymene complexes of the type [(,6 -C6H6)Ru(BLR)]2+ (R = Me, 5; R = iPr, 6) and [(,6 -C10H14)Ru(BLR)]2+ (R = Me, 7; R = iPr, 8). The X-ray crystal structure of [5]Cl2 reveals the absence of any direct Ru,Cl interaction, whereas a long Ru,Cl bond, supported by two CH···Cl hydrogen bonds, is observed for [(6)Cl]Cl in the solid state. Treatment of the dichlorides of 6 and 8 with NaBF4 affords [6](BF4)2 and [8](BF4)2, which are composed of individual dications and tetrafluoroborate ions with no direct Ru,F interaction. All complexes catalyze the transfer hydrogenation of acetophenone in boiling 2-propanol. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Mechanistic Insights into Acetophenone Transfer Hydrogenation Catalyzed by Half-Sandwich Ruthenium(II) Complexes Containing 2-(Diphenylphosphanyl)aniline , A Combined Experimental and Theoretical StudyEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2008Alessia Bacchi Abstract Several new half-sandwich ruthenium(II) complexes containing 2-(diphenyphosphanyl)aniline (PNH2) of formula {Ru[(,2P,N)PNH2](p -cymene)Cl}Y [Y = Cl (1a), PF6 (1b), BF4 (1c), BPh4 (1d), TfO (1e)] were synthesized and fully characterized both in solution (1H NMR and 31P{1H} NMR spectroscopy) and in the solid state (FTIR, X-ray analysis on single crystal). Complexes 1a and 1b are active precatalysts in the hydrogen transfer reaction of acetophenone, leading to tof values up to 4440 h,1. In comparison, the {Ru[(,2P,N)PNMe2](p -cymene)Cl}Cl complex leads to a tof value of 100 h,1 under the same catalytic conditions. The mechanism through which the precatalysts operate was deeply explored by high-resolution MS (ESI) and DFT/PCM studies. The results reveal that the complexes containing PNH2 operate through a bifunctional mechanism analogous to that proposed for diamines and amino alcohol ligands. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Water-Soluble Arene Ruthenium Complexes Containing a trans -1,2-Diaminocyclohexane Ligand as Enantioselective Transfer Hydrogenation Catalysts in Aqueous SolutionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2005Jérôme Canivet Abstract The cationic chloro complexes [(arene)Ru(H2N,NH2)Cl]+ (1: arene = C6H6; 2: arene = p -MeC6H4iPr; 3: arene = C6Me6) have been synthesised from the corresponding arene ruthenium dichloride dimers and enantiopure (R,R or S,S) trans -1,2-diaminocyclohexane (H2N,NH2) and isolated as the chloride salts. The compounds are all water-soluble and, in the case of the hexamethylbenzene derivative 3, the aqua complex formed upon hydrolysis [(C6Me6)Ru(H2N,NH2)OH2]2+ (4) could be isolated as the tetrafluoroborate salt. The molecular structures of 3 and 4 have been determined by single-crystal X-ray diffraction analyses of [(C6Me6)Ru(H2N,NH2)Cl]Cl and [(C6Me6)Ru(H2N,NH2)OH2][BF4]2. Treatment of [Ru2(arene)2Cl4] with the monotosylated trans -1,2-diaminocyclohexane derivative (TsHN,NH2) does not yield the expected cationic complexes, analogous to 1,3 but the neutral deprotonated complexes [(arene)Ru(TsN,NH2)Cl] (5: arene = C6H6; 6: arene = p -MeC6H4iPr; 7: arene = C6Me6; 8: arene = C6H5COOMe). Hydrolysis of the chloro complex 7 in aqueous solution gave, upon precipitation of silver chloride, the corresponding monocationic aqua complex [(C6Me6)Ru(TsHN,NH2)(OH2)]+ (9) which was isolated and characterised as its tetrafluoroborate salt. The enantiopure complexes 1,9 have been employed as catalysts for the transfer hydrogenation of acetophenone in aqueous solution using sodium formate and water as a hydrogen source. The best results were obtained (60 °C) with 7, giving a catalytic turnover frequency of 43 h,1 and an enantiomeric excess of 93,%. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Ruthenium Complexes Containing Chiral N-Donor Ligands as Catalysts in Acetophenone Hydrogen Transfer , New Amino Effect on EnantioselectivityEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 21 2005Montserrat Gómez Abstract New p -cymene ruthenium species containing chiral amino alcohols (1,3), primary (4,7) and secondary (8, 9) amino-oxazolines, were tested as catalysts in the hydrogen transfer of acetophenone, using 2-propanol as the hydrogen source. A remarkable effect on the enantioselectivity, but also on the activity, was observed depending on the amino-type oxazoline, Ru/8 and Ru/9 being low active and nonselective catalytic systems, in contrast to their primary counterpart Ru/5. Complexes containing amino-oxazolines (10,12) were prepared and fully characterized, both in solution and in solid state. The X-ray structure was determined for (SRu,RC)- 10. The diastereomeric ratios observed for complexes 10 and 11 were determined by 1H NMR and confirmed by means of structural modeling (semi-empirical PM3(tm) level). DFT theoretical calculations for the transition states involved in the hydrogen transfer process proved the important differences in their relative populations, which could justify the enantioselectivity divergences observed between primary and secondary amino-oxazoline ruthenium systems. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] One-Pot Synthesis of 3-Substituted Isoquinolin-1-(2H)-ones and Fused Isoquinolin-1-(2H)-ones by SRN1 Reactions in DMSOEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 17 2006Javier F. Guastavino Abstract 3-Substituted isoquinolin-1-(2H)-ones and fused isoquinolin-1-(2H)-ones have been obtained by the photostimulated SRN1 reactions of 2-iodobenzamide with the enolates of aromatic (acetophenone, 1-(benzo[d][1,3]dioxol-5-yl)ethanone, 1- and 2-naphthyl methyl ketones, and 2-, 3-, and 4-acetylpyridine), aliphatic (1-adamantyl methyl ketone), and cyclic ketones (1- and 2-indanone, ,- and ,-tetralone, and 1-benzosuberone) in DMSO. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Efficient Routes to Acenaphthylene-Fused Polycyclic Arenes/Heteroarenes and Heterocyclic Fluoranthene AnaloguesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 10 2005Kausik Panda Abstract The acenaphthenone-derived , -oxoketene dithioacetal 2 has been subjected to various [3 + 3] aromatic and heteroaromatic annulation and other heterocyclization reactions previously developed in our laboratory, providing short and efficient routes to a diverse range of known and unknown acenaphtho-annulated linear and angular PAHs, heteroaromatics and five-membered heterocycles in good yields. Thus, benzo- and naphthoannulation of 2 with various allyl and benzyl Grignard reagents afforded substituted fluoranthenes 4a,c and benzo[k]fluoranthene 8, respectively, in good yields. Similarly, the parent benzo[j]fluoranthene 15a and its substituted derivative 16b have been synthesized by base-induced conjugate 1,4-addition of arylacetonitriles to 2, followed by acid-induced cyclization of the conjugate adducts 12a,b to give 13a,b and subsequent further transformations. The adducts obtained by 1,4-addition of anions derived from acetophenone and acenaphthenone were subjected toheterocyclization in the presence of ammonium acetate to give 8-arylacenaphtho[1,2- b]pyridines 18a,b and bis(acenaphtho)-annulated pyridine 20. Heterocyclization of 2 with bifunctional nucleophiles such as 2-picolyllithium and guanidinium nitrate afforded the corresponding acenaphtho[1,2- b]quinolizinium salt 23 and acenaphtho[1,2- d]pyrimidine 24, respectively, in high yields. Finally, acenaphtho[1,2- c]-fused five-membered heterocycles such as 7-(methylthio)acenaphtho[1,2- c]thiophene (25), 7-(methylthio)acenaphtho[1,2- c]furan (27) and 7-(methylthio)acenaphtho[1,2- c]pyrrole-2-carboxylic acid (30) were obtained in good yields by subjection of 2 to Simmons,Smith reaction conditions or by treatment with dimethylsulfonium methylide or glycinate dianion. Some of these newly synthesized PAHs or fused heterocycles were subjected to Raney Ni desulfurization to furnish sulfur-free compounds. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] C-Glycosidations of a 2-Ketohexosyl Bromide with Electrophilic, Radical, and Nucleophilic Anomeric CarbonsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 16 2003Frieder W. Lichtenthaler Abstract The susceptibility of acylated 2-ketohexosyl halides to C-homologation is demonstrated with the easily accessible tri- O -benzoyl-,- D - arabino -hexos-ulosyl bromide 1 as the model compound. C-Glycosidation with an electrophilic anomeric carbon requires prior carbonyl protection, to avoid carbonyl addition by the C-nucleophile, for example, as the cyanohydrin. Silver triflate-promoted reaction with the silylenol ether of acetophenone then efficiently yields the ,-phenacyl product. With thermal (AIBN) or photochemical induction, 1 smoothly generates an anomeric radical , comparatively electrophilic, due to its capto-dative substitution , which exclusively traps hydrogen in the presence of tributyltin and electron-deficient alkenes. With allyltributylstannanes, however, it reacts with high stereoselectivity to afford ,- C -allyl glycosiduloses. The ,-bromoketone functionality in ulosyl bromide 1 is susceptible to Reformatsky conditions: treatment with zinc-copper couple readily generates the 1,2-enolate, a most simple anomeric nucleophile, which effectively adds to aldehydes to give ,- C -hydroxyalkyl glycosiduloses or ,- C -disaccharides (with sugar aldehydes) with a high degree of double stereoselection. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] First Authentication of Kostanecki's Triketone and Multimolecular Reaction of Aromatic Aldehydes with AcetophenoneHELVETICA CHIMICA ACTA, Issue 6 2009Zixing Shan Abstract A double-component, multimolecular reaction between acetophenone and aromatic aldehydes was achieved under catalysis by the solid-base mixture NaOH/K2CO3, and Kostanecki's triketone, supposed to exist for more than 110 years, was successfully separated for the first time as an accompaniment of a pentane-1,5-dione or a 1,2,3,4,5-pentasubstituted cyclohexanol (Scheme,1) and authenticated by spectroscopic and single-crystal X-ray diffraction analysis. Thus, the multimolecular-reaction mechanism of the formation of 1,2,3,4,5-pentasubstituted cyclohexanols from 1-phenylalkan-1-ones and aromatic aldehydes was fully validated based on the results (Scheme,3). [source] Reductions of Benzene Derivatives Whose Benzylic Positions Bear Oxygen Atoms under Mild ConditionsHELVETICA CHIMICA ACTA, Issue 12 2008Abdullah Menzek Abstract Reductions of compounds whose benzylic positions bear O-atoms, such as benzyl alcohol, dibenzyl ether, styrene oxide, benzaldehyde, acetophenone, and benzophenone, to the corresponding non-conjugated dienes were performed by using t -BuOH, Li, and gaseous NH3 in THF at room temperature. In these reductions, it was observed that the functional groups at benzylic positions were reduced first. [source] Claisen,Schmidt Condensation Catalyzed by Metal-Organic FrameworksADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4 2010Amarajothi Dhakshinamoorthy Abstract Metal-organic framework [Fe(BTC) (BTC=1,3,5-benzenetricarboxylic acid)] is a convenient heterogeneous catalyst for the carbon-carbon bond forming reaction in toluene between acetophenone and benzaldehyde to give selectively chalcone in high yield. Fe(BTC) appears as a general catalyst able to synthesize selectively different chalcone derivatives bearing various functionalities. Fe(BTC) could be recycled with no significant loss of catalytic efficiency and crystallinity in subsequent runs. [source] Metal-Free: An Efficient and Selective Catalytic Aerobic Oxidation of Hydrocarbons with Oxime and N -HydroxyphthalimideADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 16 2009Gengxiu Zheng Abstract A non-metal catalytic system consisting of dimethylglyoxime (DMG) and N -hydroxyphthalimide (NHPI) for the selective oxidation of hydrocarbons with dioxygen is described. The synergistic effect of DMG and NHPI ensures its efficient catalytic ability: 82.1% conversion of ethylbenzene with 94.9% selectivity for acetophenone could be obtained at 80,°C under 0.3,MPa of dioxygen in 10,h. Several hydrocarbons were efficiently oxidized to their corresponding oxygenated products under mild conditions. [source] Productive Asymmetric Styrene Epoxidation Based on a Next Generation Electroenzymatic MethodologyADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 14-15 2009Reto Ruinatscha Abstract We have established a novel and scalable methodology for the productive coupling of redox enzymes to reductive electrochemical cofactor regeneration relying on efficient mass transfer of the cofactor to the electron-delivering cathode. Proof of concept is provided by styrene monooxygenase (StyA) catalyzing the asymmetric (S)-epoxidation of styrene with high enantiomeric excess, space-time yields, and current efficiencies. Highly porous reticulated vitreous carbon electrodes, maximized in volumetric surface area, were employed in a flow-through mode to rapidly regenerate the consumed FADH2 cofactor required for StyA activity. A systematic investigation of the parameters determining cofactor mass transfer revealed that low FAD concentrations and high flow rates enabled the continuous synthesis of the product (S)-styrene oxide at high rates, while at the same time the accumulation of the side-products acetophenone and phenylacetaldehyde was minimized. At 10,,M FAD and a flow rate of 150,mL,min,1, an average space-time yield of 0.35,g,L,1,h,1 could be achieved during 2,h with a final (S)-styrene oxide yield of 75.2%. At two-fold lower aeration rates, the electroenzymatic reaction could be sustained for 12,h, albeit at the expense of lower (59%) overall space-time yields. Under these conditions, as much as 20.5% of the utilized current could be channeled into (S)-styrene oxide formation. In comparison with state-of-the-art electroenzymatic methodologies for the same conversion, (S)-styrene oxide synthesis could be improved up to 150-fold with respect to both reaction time and space-time yield. These productivities constitute the most efficient reaction reported for asymmetric in vitro epoxidations of styrene. [source] Chiral Polyamino Alcohols via Hydroaminomethylation: A New Class of Polyamines for Dendritic Cores and Ligand PrecursorsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 13 2009Muhammad Afzal Subhani Abstract In this contribution, the synthesis of a new class of chiral polyamino alcohols (PAA) via a two-step hydroaminomethylation/hydrolysis procedure is reported. The chiral polyamines are obtained by hydroaminomethylation of N -olefinic oxazolidinones with different amines in first step followed by hydrolysis of the resulting polyamines to give the chiral PAA in the second step. The dendritic chiral PAA (Mw=1300,1400,g,mol,1) are also synthesized efficiently through a multifold hydroaminomethylation/hydrolysis procedure. Furthermore, chiral PAA are investigated as ligands in ruthenium-catalyzed asymmetric hydrogen transfer reduction of acetophenone to 1-phenyl alcohol. [source] Primary Amine-Thioureas based on tert -Butyl Esters of Natural Amino Acids as Organocatalysts for the Michael ReactionADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2009Christoforos Abstract A new class of primary amine-thioureas based on tert -butyl esters of (S)-,-amino acids and (1S,2S)-diphenylethylenediamine was synthesized and their activity as catalysts in Michael additions was evaluated. Derivatives based on di- tert -butyl aspartate and tert -butyl O - tert -butyl threoninate provided the product of the reaction between trans- ,-nitrostyrene and acetone in quantitative yield and high enantioselectivity (87,91% ee). All the thioureas based on tert -butyl esters of amino acids catalyzed the reaction of nitroolefins with acetophenone with high enantioselectivity (92,98% ee). Thus, low-cost, commercially available tert -butyl esters of natural amino acids are very important chiral building blocks for the construction of novel chiral thioureas able to catalyze asymmetric Michael additions with high enantioselectivity. [source] Immobilisation of the BINAP Ligand on Dendrimers and Hyperbranched Polymers: Dependence of the Catalytic Properties on the Linker UnitADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4 2009Jutta Abstract A series of immobilised Carbo-BINAP ligands has been synthesised using poly(propylene imine) (PPI) dendrimers as soluble supports. They contain up to 64 BINAP ligands at their periphery without an additional linking unit. Despite the high steric requirements of the ligand, all dendrimers could be completely functionalised, resulting in the immobilised systems in good yields. Furthermore, the immobilisation strategy that worked out for the fixation of AMINAP ligands with additional linking units as well as of Carbo-BINAP ligands without additional linking units on dendrimers has thus been extended to less regularly hyperbranched poly(ethylene imines) (PEI) as soluble supports. In that way it has been possible to attach on average 9, 26, and 138 Glutaroyl-AMINAP or Carbo-BINAP ligands to PEIs of different molecular weights. The catalytic properties of these systems in the copper-catalysed hydrosilylation of acetophenone were investigated. The dendritic PPI-bound Carbo-BINAP ligands displayed a strong dependence of enantioselectivity and activity on the generation of the dendrimer. For the Carbo-BINAP and Glutaroyl-AMINAP ligands immobilised on the hyperbranched polymers, however, activities and enantioselectivities comparable to those of the mononuclear catalysts were found. The macromolecular, immobilised BINAP ligands could be recycled several times without any observable loss of activity or enantioselectivity. [source] Discrete versus In Situ -Generated Aluminum-Salen Catalysts in Enantioselective Cyanosilylation of Ketones: Role of Achiral LigandsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 5 2008Ali Alaaeddine Abstract The monometallic species {Salen}AlX (X=Me, 2a,b; X=Cl, 4a,b; O- i- Pr, 5a,b) and open bimetallic species {Salen}[AlMe2]2 (3a,b) that result from binary combinations between an aluminum precursor [trimethylaluminum, dimethylaluminum chloride, aluminum tris(isopropoxide)] and a diprotio {Salen}H2 pro-ligand 1a,b (a=1R,2R -cyclohexyl-salen; b=1R,2R -diphenylethylene-salen) have been isolated. The crystal structures of 3b, 4b and of ,-oxo species [{diphenylethylene-salen}Al]2O (6b) are reported. The discrete species 2,5a,b have been individually evaluated in the asymmetric cyanosilylation of acetophenone. It is shown that, in several cases, these discrete catalysts display dramatically different performances than the catalyst systems in situ -generated from the binary combinations. The influence of the achiral ligand X on both the enantioselectivity and activity of the cyanosilylation reaction has been investigated, resulting in the definition of a highly active and productive hexafluoro-2-propoxide-based catalyst for a variety of aryl alkyl ketones (TON up to 470, TOF up to 140,h,1 at ,20,°C for acetophenone). [source] Investigation on Aggregate Formation of Ionic LiquidsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2005Sandra Dorbritz Abstract Understanding the behavior of ionic liquids on the molecular level is essential for explaining solubilizing or reaction processes, including catalytic reactions in ionic liquids or with ionic liquids as co-solvent. Using mass spectrometry techniques it is possible to characterize their aggregate formation behavior, which depends on the used solvent. With increasing polarity of the solvent and decreasing ionic liquid concentration, the size of the formed aggregates decreases. From conductivity measurement curves "critical aggregate concentrations" were calculated, which confirm the results of mass spectrometry measurements. Addition of ionic liquids increases the solubility of acetophenone in water. This effect can be explained by the aggregate formation ability of ionic liquids. The findings can be used to explain the outstanding solubility and solvation properties of ionic liquids. [source] Iron-Catalyzed Oxidation of Cycloalkanes and Alkylarenes with Hydrogen PeroxideADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 5 2005Chiara Pavan Abstract An iron-catalyzed process for the oxidation of saturated hydrocarbons (cycloalkanes and alkylarenes) to alcohols and ketones with aqueous H2O2 in acetonitrile at room temperature is reported. Addition of a carboxylic acid increases the selectivity towards the ketone formation. Best results were obtained with ethylbenzene as substrate and acetic acid as additive, affording acetophenone as the main product. [source] Synthesis of polymer-supported metal-ion complexes and evaluation of their catalytic activitiesJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2008K. C. Gupta Abstract Polymer-supported transition-metal-ion complexes of the N,N,-bis(o -hydroxy acetophenone) propylenediamine (HPPn) Schiff base were prepared by the complexation of iron(III), cobalt(II), and nickel(II) ions on a polymer-anchored N,N,-bis(5-amino- o -hydroxy acetophenone) propylenediamine Schiff base. The complexation of iron(III), cobalt(II), and nickel(II) ions on the polymer-anchored HPPn Schiff base was 83.44, 82.92, and 89.58 wt%, respectively, whereas the unsupported HPPn Schiff base showed 82.29, 81.18, and 87.29 wt % complexation of these metal ions. The iron(III) ion complexes of the HPPn Schiff base showed octahedral geometry, whereas the cobalt(II) and nickel(II) ion complexes were square planar in shape, as suggested by spectral and magnetic measurements. The thermal stability of the HPPn Schiff base increased with the complexation of metal ions, as evidenced by thermogravimetric analysis. The HPPn Schiff base showed a weight loss of 51.0 wt % at 500°C, but its iron(III), cobalt(II), and nickel(II) ion complexes showed weight losses of 27.0, 35.0, and 44.7 wt % at the same temperature. The catalytic activity of the unsupported and supported metal-ion complexes was analyzed by the study of the oxidation of phenol and epoxidation of cyclohexene in the presence of hydrogen peroxide. The supported HPPn Schiff base complexes of iron(III) ions showed a 73.0 wt % maximum conversion of phenol and 90.6 wt % epoxidation of cyclohexene, but unsupported complexes of iron(III) ions showed 63.8 wt % conversion of phenol and 83.2 wt % epoxidation of cyclohexene. The product selectivity for catechol (CTL) and epoxy cyclohexane (ECH) was 93.1 wt % and 98.1 wt % with the supported HPPn Schiff base complexes of iron(III) ions, but it was low with the supported Schiff base complexes of cobalt(II) and nickel(II) ions. The selectivity for CTL and ECH varied with the molar ratio of the metal ions but remained unaffected by the molar ratio of hydrogen peroxide to the substrate. The energy of activation for the epoxidation of cyclohexene and oxidation of phenol with the polymer-supported Schiff base complexes of iron(III) ions was 10.0 and 12.7 kJ/mol, respectively, but it was found to be higher with the supported HPPn Schiff base complexes of cobalt(II) and nickel(II) ions and with the unsupported HPPn Schiff base complexes of iron(III), cobalt(II), and nickel(II) ions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008 [source] Modeling the phase behavior of ternary systems ionic liquid + organic + CO2 with a Group Contribution Equation of StateAICHE JOURNAL, Issue 5 2009Eliane Kühne Abstract This work presents the results of the use of a Group Contribution Equation of State (GC-EOS) to model experimental data obtained for ternary systems of the type bmim[BF4] + organic solute + CO2 with four different organic compounds, namely acetophenone, 1-phenylethanol, 4-isobutylacetophenone, and 1-(4-isobutylphenyl)-ethanol. Our results show that the GC-EOS is able to qualitatively predict not only L+V,L but also L1+L2,L phase transitions. As the two two-phase boundaries L+V and L1+L2 of the experimentally found three-phase region L1+L2+V almost coincide with the saturated vapor pressure curve of pure CO2, the phase transitions L+V,L1+L2+V and L1+L2+V,L1+L2 have been represented as this vapor-pressure curve by the model. The average absolute deviations between experimental and predicted values for all phase transitions have been found to be very satisfactory. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Decomposition of monochlorobiphenyl isomers in supercritical water in the presence of methanolAICHE JOURNAL, Issue 7 2004Gheorghe Anitescu Abstract Comprehensive studies of monochlorobiphenyl (MCB) decomposition in supercritical water in the presence of methanol and other cosolvents, both with and without oxygen, are being conducted to understand the reaction kinetics and pathways of individual PCB isomers and to determine the structure,reactivity relationships. In the present study the disappearance rate of MCBs, delivered in an isothermal plug-flow tubular reactor as methanolic solutions, is investigated at 25 MPa and temperatures of 673, 723, and 773 K. Experiments are conducted at nominal MCB feed concentrations of 1,100 ,mol/L (reaction conditions) using MCB/MeOH and H2O2/H2O solutions (1,3 g/L and 0,10 wt. %, respectively). Molar conversions of these isomers vary from 3% (2-CB, 773 K, 2 s) to 30% (4-CB, 773 K, 46 s) without oxygen (SCWT) and from 1% (2-CB, 673 K, 3.8 s) to 97% (4-CB, 773 K, 24.5 s) with oxygen (SCWO). For SCWT the overall conversion follows apparent first order, whereas for SCWO the conversion is second order. The regressed data lead to Arrhenius parameters of frequency factor and activation energy with values of 1020.5,1021.3 s,1 and 320,331 kJ/mol for SCWT and 1024.1,1024.8 s,1 (mol/L),1 and 281,292 kJ/mol for SCWO, respectively. The reactivity of the MCB isomers increases in the order 2-MCB < 3-MCB < 4-MCB. The positively identified reaction products by GC-MSD and GC-FID/ECD/TCD analyses are mainly biphenyl, open-ring biphenyl compounds such as acetophenone and benzaldehydes, and mineral products (CO, CO2, and HCl). More studies are in progress regarding the role of the second solvent on reaction rates and reaction mechanisms and pathways. © 2004 American Institute of Chemical Engineers AIChE J, 50: 1536,1544, 2004 [source] Tunnelling corrections in hydrogen abstractions by excited-state ketonesJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 7 2010Monica Barroso Abstract Hydrogen abstraction from 1-phenylethanol by triplet acetophenone occurs from both CH and OH bonds. The reaction path of the Interacting-State Model (ISM) is used with the Transition-State Theory (TST) and the semiclassical correction for tunnelling (ISM/scTST) to help rationalizing the experimental kinetic results and elucidate the mechanisms of these reactions. The weak exothermicity of the abstraction from the strong OH bond is compensated by electronic effects, hydrogen bonding and tunnelling, and is competitive with the more exothermic abstraction from the ,-CH bond of 1-phenylethanol. The alkoxy radical formed upon abstraction from OH reacts within the solvent cage and the primary product of this reaction is 1-phenylethenol. The corresponding kinetic isotope effect is ca. 3 and is entirely consistent with a tunnelling correction ca. 9 for H abstraction. We therefore demonstrate that the tunnelling correction is the major contributor to the kinetic isotope effect. Copyright © 2010 John Wiley & Sons, Ltd. [source] A remarkable difference in the deprotonation steps of the Friedel,Crafts acylation and alkylation reactionsJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 11 2009Shinichi Yamabe Abstract Friedel,Crafts acylation and alkylation reactions were investigated using density functional theory calculations. The reaction systems studied were (benzene,+,acetyl chloride,+,Al2Cl6 (or AlCl3)) and (benzene,+,2-chloropropane,+,Al2Cl6). In the acylation reaction, the acylium ion intermediate is reached either via a MeC(Cl)OAl2Cl6 complex or via direct Cl transfer: MeC(O)ClAl2Cl6,,,MeCO,+Al2Cl. The ion adds to benzene electrophilically to form a Wheland intermediate containing a strong CHCl hydrogen bond, which leads to deprotonation and the subsequent formation of acetophenone. The resulting HClAl2Cl6 fragment is subjected to a nucleophilic attack by the carbonyl oxygen of the acetophenone, and recovery of the Al2Cl6 bridge is unlikely. Attack of the Al2Cl6 moiety by MeC(Cl)O gives the complex MeC(Cl)O,AlCl3, whose reactivity toward acylation is similar to that of the MeC(Cl)O,Al2Cl6 complex. In the alkylation reaction, deprotonation does not take place, but rather a [1,2] H-shift from the Wheland intermediate. The resulting , -protonated cumene undergoes deprotonation, with subsequent recovery of the Al2Cl6 bridge. In addition, the Al2Cl6 -catalyzed isomerization of the n -propyl to the isopropyl cation was found to be a dyotropic shift. Copyright © 2009 John Wiley & Sons, Ltd. [source] | ||||||||||||||||||||||||||||||||||