- Probing the compound I-like reactivity of a bare high-valent oxo iron porphyrin complex: The oxidation of tertiary amines
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The mechanisms of oxidative N-dealkylation of amines by heme enzymes including peroxidases and cytochromes P450 and by functional models for the active Compound I species have long been studied. A debated issue has concerned in particular the character of the primary step initiating the oxidation sequence, either a hydrogen atom transfer (HAT) or an electron transfer (ET) event, facing problems such as the possible contribution of multiple oxidants and complex environmental effects. In the present study, an oxo iron(IV) porphyrin radical cation intermediate 1, [(TPFPP)?+Fe IV=O]+ (TPFPP = meso-tetrakis (pentafluorophenyl) porphinato dianion), functional model of Compound I, has been produced as a bare species. The gas-phase reaction with amines (A) studied by ESI-FT-ICR mass spectrometry has revealed for the first time the elementary steps and the ionic intermediates involved in the oxidative activation. Ionic products are formed involving ET (A?+, the amine radical cation), formal hydride transfer (HT) from the amine ([A(-H)]+, an iminium ion), and oxygen atom transfer (OAT) to the amine (A(O), likely a carbinolamine product), whereas an ionic product involving a net initial HAT event is never observed. The reaction appears to be initiated by an ET event for the majority of the tested amines which included tertiary aliphatic and aromatic amines as well as a cyclic and a secondary amine. For a series of N,N-dimethylanilines the reaction efficiency for the ET activated pathways was found to correlate with the ionization energy of the amine. A stepwise pathway accounts for the C-H bond activation resulting in the formal HT product, namely a primary ET process forming A?+, which is deprotonated at the α-C-H bond forming an N-methyl-N-arylaminomethyl radical, A(-H)?, readily oxidized to the iminium ion, [A(-H)]+. The kinetic isotope effect (KIE) for proton transfer (PT) increases as the acidity of the amine radical cation increases and the PT reaction to the base, the ferryl group of (TPFPP)FeIV=O, approaches thermoneutrality. The ET reaction displayed by 1 with gaseous N,N-dimethylaniline finds a counterpart in the ET reactivity of FeO+, reportedly a potent oxidant in the gas phase, and with the barrierless ET process for a model (P)?+FeIV=O species (where P is the porphine dianion) as found by theoretical calculations. Finally, the remarkable OAT reactivity of 1 with C6F 5N(CH3)2 may hint to a mechanism along a route of diverse spin multiplicity.
- Chiavarino, Barbara,Cipollini, Romano,Crestoni, Maria Elisa,Fornarini, Simonetta,Lanucara, Francesco,Lapi, Andrea
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- Structure and dynamic behavior of phosphine gold(I)-coordinated enamines: Characterization of α-metalated iminium ions
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Cationic gold(I) enamine complexes with the (t-Bu)2(o-biphenyl) phosphine ligand were isolated and characterized by NMR spectroscopy and X-ray crystallography. The complexes display highly distorted coordination modes that are consistent with characterization as α-metalated iminium ions. The barrier to rotation around the formal enamine C-C double bond has been measured in a geminally disubstituted enamine complex, and it is comparable to the barrier to C-C single-bond rotation in electronically restricted alkanes. With additional substitution on the enamine double bond, the complexes remain highly distorted, and the reaction of a mixture of E and Z enamines results in formation of a stereochemically pure gold complex. A survey of binding constants reveals enamines to be significantly stronger donors than any alkenes examined to date, and in the case of a geminally disubstituted enamine, the coordination is stronger even than that of triethylamine. The high stability drives the isomerization of an internal enamine complex generated from an intramolecular hydroamination reaction, to the exocyclic double-bond isomer.
- Sriram, Madhavi,Zhu, Yuyang,Camp, Andrew M.,Day, Cynthia S.,Jones, Amanda C.
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- Solvent influence on the thermodynamics for hydride transfer from bis(diphosphine) complexes of nickel
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The thermodynamic hydricity of a metal hydride can vary considerably between solvents. This parameter can be used to determine the favourability of a hydride-transfer reaction, such as the reaction between a metal hydride and CO2 to produce formate. Because the hydricities of these species do not vary consistently between solvents, reactions that are thermodynamically unfavourable in one solvent can be favourable in others. The hydricity of a water-soluble, bis-phosphine nickel hydride complex was compared to the hydricity of formate in water and in acetonitrile. Formate is a better hydride donor than [HNi(dmpe)2]+ by 7 kcal mol-1 in acetonitrile, and no hydride transfer from [HNi(dmpe)2]+ to CO2 occurs in this solvent. The hydricity of [HNi(dmpe)2]+ is greatly improved in water relative to acetonitrile, in that reduction of CO2 to formate by [HNi(dmpe)2]+ was found to be thermodynamically downhill by 8 kcal mol-1. Catalysis for the hydrogenation of CO2 was pursued, but the regeneration of [HNi(dmpe)2] under catalytic conditions was unfavourable. However, the present results demonstrate that the solvent dependence of thermodynamic parameters such as hydricity and acidity can be exploited in order to produce systems with balanced or favourable overall thermodynamics. This approach should be advantageous for the design of future water-soluble catalysts.
- Connelly Robinson, Samantha J.,Zall, Christopher M.,Miller, Deanna L.,Linehan, John C.,Appel, Aaron M.
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- Absolute rate constants for some reactions of the triethylamineboryl radical and the borane radical anion
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Laser flash photolysis (LFP) of dj-tert-butyl peroxide or dicumyl peroxide at ambient temperatures in the presence of Et3N→BH3 or BH4- generated the title radicals which were found to have broad, featureless absorptions in the visible region. Rate constants for H-atom abstraction from Et3N→BH3 by cumyloxyl radicals show a small solvent dependence, e.g. 12 × 107 and 2.2 × 107 dm3 mol-1 s-1 in isooctane and acetonitrile, respectively. Rate constants for halogen atom abstraction by Et3N→BH2. and BH3.- from a number of chlorides and bromides were determined by LFP and by competitive kinetics, e.g., for Et3N→BH2. + CCl4/PhCH2Cl/CH3(CH2)2Cl, k = 4.4 × 109/1.1 × 107/5.1 × 105 dm3 mol-1 s-1 and for BH3.- + CCl4/PhCH2Cl, k = 2.0 × 109/3.0 × 107 dm3 mol-1 s-1. Rates of addition of Et3N→BH2. to 1-and 1,1-substituted olefins increase dramatically as the electron affinity of the olefin increases, confirming the nucleophilic character of amine-boryl radicals. A comparison of the present results with literature data for the addition of olefins of four nucleophilic carbon-centered radicals proves that Et3N→BH2. is by far the most nucleophilic radical for which kinetic data are available. A few rate constants for abstraction of hydrogen from electron-deficient carbon by Et3N→BH2. are also reported.
- Sheeller, Brad,Ingold, Keith U.
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- Reactions of diethylamine and ethylene catalyzed by PtII or Pt0 - Transalkylation vs. hydroamination
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PtBr2/nBu4PBr (without solvent) or K 2PtCl4/NaBr (in water) have been shown to efficiently catalyze the hydroamination of ethylene by aniline and are poor catalysts for the hydroamination of ethylene by diethylamine. A DFT study on the hydroamination mechanism indicates that the energetic span of the C 2H4/Et2NH catalytic cycle is close to that of the C2H4/PhNH2 cycle. The poor performance is attributed to rapid catalyst degradation with reduction to metallic platinum. Pt0, on the other hand, catalyzes a transalkylation process, partially transforming Et2NH into Et3N, EtNH2 and NH3. This process is inhibited by C2H4. Mechanistic considerations for the Pt0-catalyzed transalkylation process are presented. Copyright
- Dub, Pavel A.,Bethegnies, Aurelien,Poli, Rinaldo
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- Validated HPLC and stability-indicating densitometric chromatographic methods for simultaneous determination of camylofin dihydrochloride and paracetamol in their binary mixture
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Two accurate, sensitive, precise and selective HPLC and stability-indicating TLC methods were developed for the simultaneous determination of camylofin-2HCl and paracetamol. Forced acid, alkali and oxidative degradation of camylofin-2HCl?were tried where complete degradation was achieved using 5?N HCl. HPLC method was developed to determine the mixture of the two drugs using Zorbax NH2 column and a mobile phase of 0.5percent triethylamine and pH 3.0 adjusted with 0.1percent phosphoric acid and methanol (70:30 v/v) over concentration ranges of 3–90 and 10–95?μg/mL for camylofin-2HCl and paracetamol, respectively.TLC method was used for the separation of camylofin from its acid degradate and paracetamol using chloroform–methanol–acetone–conc. ammonia (8:2:2:0.1, by volume) as developing system and band scanning at 254 nm over concentration ranges of 5–40?μg/band for camylofin-2HCl and 0.1–0.5?μg/band for paracetamol. The validation of two methods was carried out according to ICH guideline. Accuracy ranged between 98.47 and 100.67percent for the two methods with acceptable precision RSDpercent ranging between 0.66 and 1.47percent.
- Abdel Razeq, Sawsan A.,Khalil, Israa A.,Mohammd, Samah A.
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- Production of hcooh/net3 adducts by co2/h2 incorporation into neat NEt3
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Chemical Equaction Presented Adding HCOOH to NEt3 gives a biphasic system of amine and an adduct with a molar acid/amine ratio (AAR) of 1.33. In the presence of a suitable catalyst, CO2/H 2 (1:1) acts as HCOOH if both amine and 1.33-adduct phases are present. For example, at 4O°C and 120 bar, neat amine, doped with both 1.33 adduct and catalyst, is quantitatively converted into 1.78 adduct, which is distilled as an azeotrope with AAR = 2.35.
- Preti, Debora,Squarcialupi, Sergio,Fachinetti, Giuseppe
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- Soluble polymer-supported synthesis of tertiary amines
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The synthesis of tertiary amines on a modified soluble polymer, poly(ethylene glycol) (PEG), is described. The PEG-bound quaternary intermediates were assembled via Michael addition reaction, followed by alkylation. Cleavage from the soluble polymer support was induced by insoluble weak basic resin, to afford the target tertiary amines in excellent purity.
- Chen, Zuxing,Yang, Guichun,Zhang, Zhaojun
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- Effects of metal particle size in gas-phase hydrogenation of acetonitrile over silica-supported platinum catalysts
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The gas-phase hydrogenation of acetonitrile was studied with silica-supported platinum catalysts of which the degrees of metal dispersion were widely changed by reduction conditions. The activities were found to decrease gradually during the course of reaction for all the catalysts examined. The initial rate of reaction increased with an increase in the degree of platinum dispersion, D. Triethylamine was the only main product irrespective of D and period of reaction time. The initial turnover frequency, TOF0, was shown to be smaller for larger D values. This dependence of TOF0 on D was explained by the electronic state of the surface of the platinum particles and the state of acetonitrile molecules adsorbed on them on the basis of X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy measurements. The surface layer of smaller particles is more favorable for the adsorption of acetonitrile. The acetonitrile is adsorbed by platinum with the electron lone pair of nitrogen in the antibonding orbital, but electron back-donation does not takes place. As a result, the C≡N bonds of acetonitrile adsorbed on smaller particles are stronger and more difficult to hydrogenate.
- Arai, Masahiko,Takada, Yoshiomi,Nishiyama, Yoshiyuki
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- CIDEP Study of Durosemiquinone Radical in Various Solvents
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F-pair polarization and triplet mechanism (TM) polarization of durosemiquinone radical produced by light irradiation of duroquinone-phenol systems were discriminated at 260 K in a simple way based on the analysis of the enhancement factors in the steady-state method with intermittent light irradiation.Both polarizations are not so sensitive to viscosity or polarity of solvents.TM enhancement factor is nearly constant (-0.8) in wide range of viscosity (2.5-25 cP, 1 cP=0.001 Pa s).F-pair polarization is suppressed in some extent by halogenated solvents while TM polarization is not affected by such solvents.
- Kanemoto, Akihiko,Niizuma, Sigeya,Konishi, Siro,Kokubun, Hiroshi
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- High-Mobility Ions in Cyclohexane. A Transient Absorption Study
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Transient absorption kinetics in radiolysis of N2O-saturated cyclohexane has been studied (0.1 - 100 ns; 300 - 800 nm).The spectra indicate the involvement of at least three cations (ions I, II, and III), only one of them having abnormally high mobility.Ion II is probably the cyclohexene radical cation, and ion III might be the dimer olefin ion.These two ions absorb as much as ion I at 450 - 500 nm.While ion II and ion III are scavenged by ethanol and triethylamine with a rate constant of ca. 1E10 mol-1 dm3 s-1, the scavenging of ion I proceeds with rate constants of ca. 9E10 and 2.3E11 mol-1 dm3 s-1, respectively.The spectrum of ion I is similar to the spectrum of the radical cation of cyclohexane isolated in low-temperature matrices.We were not able to observe the absorption from ion I at delay times longer than 50 ns.A corresponding fast growth of the absorption from solute radical cations of pyrene and perylene was observed.The data (simulated using continuum-diffusion and Monte Carlo approaches) indicate that the scavenging constant is ca. 4E11 mol-1 dm3 s-1; the lifetime of the precursor of the aromatic radical cations is ca. 30 ns.This short lifetime cannot be explained by a reaction with radiolytic products or by homogeneous recombination, and it seems to be incompatible with identification of the long-lived high-mobility ions observed in conductivity experiments as the radical cation of cyclohexane.A mechanism in which the mobile radical cation is in equilibrium with a normally-diffusing ion is examined in an attempt to resolve this conundrum.
- Shkrob, I. A.,Sauer, M. C.,Trifunac, A. D.
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- Studies on nitroaromatic compounds. Part 8. A kinetic and spectroscopic study of the reaction of di- and tri-ethylamine with 1,5-dimethyl-2,4,8- trinitronaphthalene
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The reaction of 1,5-dimethyl-2,4,8-trinitronaphthalene with diethylamine and triethylamine in DMSO and in DMSO-MeOH solvent systems has been studied. 1H N.m.r. investigations have shown that a benzyl type anion is formed due to hydrogen abstraction from the 1-methyl group of the nitroaromatic compound. Kinetic and thermodynamic data for the systems have been determined. The results are explained in terms of the difference in solvation of the two amines and the charged products and the difference in solvating ability of the solvent media used. The effect of added triethylammoniun chloride on the reaction of 1,5-dimethyl-2,4,8-trinitronaphthalene with triethylamine in DMSO has been studied and the change in kinetics is attributed to ion association between the added salt and the charged products.
- Buckley, Eric,Everard, John E.,Wells, Clifford H. J.
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- Ionic hydrogen bonds in bioenergetics. 4. Interaction energies of acetylcholine with aromatic and polar molecules
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The binding energies of the quaternary ions (CH3)4N+ and acetylcholine (ACh) to neutral molecules have been measured by pulsed high-pressure mass spectrometry and calculated ab initio, to model interactions in the acetylcholine receptor channel. Binding energies to C6H6 and C6H5CH3 are similar to those to H2O (33-42 kJ/mol (8-10 kcal/mol)), but are weaker than those to polar organic ligands such as CH3CO2CH3 (50-63 kJ/mol (12-15 kcal/mol)) and to amides (up to 84 kJ/mol (20 kcal/mol)). These data suggest that aromatic residues that line the groove leading to the ACh receptor site may provide stabilization comparable to water, and therefore allow entry from the aqueous environment, yet do not bind ACh as strongly as polar protein groups, and therefore allow transit, without trapping, to the receptor site. Four of the five distinct ACh conformers located computationally are stabilized by internal C-H...O hydrogen bonds involving the quaternary ammonium group, which is supported by the thermochemistry of the protonated analogue, CH3CO2CH2CH2N-(CH3) 2H+, and by the measured bonding energy between models of the ACh end groups, (CH3)4N+ and CH3CO2CH3. Each conformer forms a number of stable complexes with water or benzene. Several possible roles for an ACh conformational change upon entry into the channel are discussed, including partial compensation for the loss of bulk solvation. An additional role for the aromatic environment is also suggested, namely lowering the energy barrier to the formation of the active all-trans ACh rotamer required at the receptor site.
- Deakyne, Carol A.,Meot-Ner, Michael
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- Zirconium-hydride-catalyzed site-selective hydroboration of amides for the synthesis of amines: Mechanism, scope, and application
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Developing mild and efficient catalytic methods for the selective synthesis of amines is a longstanding research objective. In this respect, catalytic deoxygenative amide reduction has proven to be promising but challenging, as this approach necessitates selective C–O bond cleavage. Herein, we report the selective hydroboration of primary, secondary, and tertiary amides at room temperature catalyzed by an earth-abundant-metal catalyst, Zr-H, for accessing diverse amines. Various readily reducible functional groups, such as esters, alkynes, and alkenes, were well tolerated. Furthermore, the methodology was extended to the synthesis of bio- and drug-derived amines. Detailed mechanistic studies revealed a reaction pathway entailing aldehyde and amido complex formation via an unusual C–N bond cleavage-reformation process, followed by C–O bond cleavage.
- Han, Bo,Jiao, Haijun,Wu, Lipeng,Zhang, Jiong
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p. 2059 - 2067
(2021/09/02)
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- PHENYLPYRAZOLE COMPOUND AND METHOD FOR CONTROLLING PLANT DISEASE
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The present invention provides a method for controlling a plant disease which comprises applying a compound represented by formula (I) [wherein Z represents a C1-C6 chain hydrocarbon group and the like, R1 and R2 are identical to or different from each other and represent a hydrogen atom or a fluorine atom, and R3, R4, R5, R6 and R7 are identical to or different from each other and represent a C1-C6 chain hydrocarbon group and the like] to a plant or a soil, which has excellent control efficacies against plant diseases.
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- A Lewis Base Nucleofugality Parameter, NFB, and Its Application in an Analysis of MIDA-Boronate Hydrolysis Kinetics
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The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured. Parameterization of these rates has enabled the development of a nucleofugality scale (NFB), shown to quantify and predict the leaving group ability of a range of other Lewis bases. Additivity observed across a number of series R′3-nRnX (X = P, N; R′ = aryl, alkyl) has allowed the formulation of related substituent parameters (nfPB, nfAB), providing a means of calculating NFB values for a range of Lewis bases that extends far beyond those experimentally derived. The utility of the nucleofugality parameter is explored by the correlation of the substituent parameter nfPB with the hydrolyses rates of a series of alkyl and aryl MIDA boronates under neutral conditions. This has allowed the identification of MIDA boronates with heteroatoms proximal to the reacting center, showing unusual kinetic lability or stability to hydrolysis.
- García-Domínguez, Andrés,Gonzalez, Jorge A.,Leach, Andrew G.,Lloyd-Jones, Guy C.,Nichol, Gary S.,Taylor, Nicholas P.
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supporting information
(2022/01/04)
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- Catalytic Deoxygenation of Amine and Pyridine N-Oxides Using Rhodium PCcarbeneP Pincer Complexes
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Rhodium PCcarbeneP pincer complexes 1-L (L = PPh3, PPh2(C6F5), PCy3) readily facilitate deoxygenation of amine and pyridine N-oxides. The resulting complexes exhibit δ2-C= O coordination of the resulting keto POP pincer ligand. These δ2-Ca? O linkages in the metalloepoxide complexes are readily reduced by isopropyl alcohol and various benzylic alcohols. Thus, efficient catalytic deoxygenation of amine and pyridine N-oxides is possible using complexes 1-L and isopropyl alcohol. This represents a pioneering example of PCcarbeneP pincer complexes being used as catalysts for catalytic deoxygenation.
- Tinnermann, Hendrik,Sung, Simon,Cala, Beatrice A.,Gill, Hashir J.,Young, Rowan D.
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p. 797 - 803
(2020/03/13)
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- Electroactivated alkylation of amines with alcohols: Via both direct and indirect borrowing hydrogen mechanisms
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A green, efficient N-alkylation of amines with simple alcohols has been achieved in aqueous solution via an electrochemical version of the so-called "borrowing hydrogen methodology". Catalyzed by Ru on activated carbon cloth (Ru/ACC), the reaction works well with methanol, and with primary and secondary alcohols. Alkylation can be accomplished by either of two different electrocatalytic processes: (1) in an undivided cell, alcohol (present in excess) is oxidized at the Ru/ACC anode; the aldehyde or ketone product condenses with the amine; and the resulting imine is reduced at an ACC cathode, combining with protons released by the oxidation. This process consumes stoichiometric quantities of current. (2) In a membrane-divided cell, the current-activated Ru/ACC cathode effects direct C-H activation of the alcohol; the resulting carbonyl species, either free or still surface-adsorbed, condenses with amine to form imine and is reduced as in (1). These alcohol activation processes can alkylate primary and secondary aliphatic amines, as well as ammonia itself at 25-70 °C and ambient pressure.
- Appiagyei, Benjamin,Bhatia, Souful,Keeney, Gabriela L.,Dolmetsch, Troy,Jackson, James E.
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supporting information
p. 860 - 869
(2020/02/21)
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- Characteristics of Si-Y mixed oxide supported nickel catalysts for the reductive amination of ethanol to ethylamines
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Si-Y mixed oxide synthesis was achieved via Si dissolution from a Pyrex reactor during the synthesis of yttrium hydroxide by the precipitation method at pH 10 and an aging temperature of 100 ℃. The Ni/SY mixed oxide catalysts with 5–25 wt% Ni contents were synthesized using an incipient wetness impregnation method. The characterization of the calcined Ni/SY oxide catalysts was performed using N2-sorption, X-ray diffraction, H2-temperature programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), and ethanol-TPD. The reaction parameters such as reaction temperature and the partial pressures of ethanol, NH3, and H2 were varied in the reductive amination reaction, and the catalytic activities for the production of monoethylamine, diethylamine, triethylamine, and acetonitrile as main products were compared. The 10 wt% Ni/SY oxide catalyst containing 11 wt% Si showed the maximum activity, and the presence and absence of H2 and NH3 had a great effect on the conversion and selectivities. The stability after 110 h on stream was observed to be 2.5% less than the initial activity. The cause of this deactivation is the formation of nickel carbonitride, as confirmed by XPS and temperature programmed oxidation (TPO) measurements. On the basis of a detailed proposed reaction mechanism, reaction rates were determined, and the kinetic parameters were estimated by fitting the experimental data obtained under a variety of conditions. Our kinetic model showed that the temperature and the partial pressures of ethanol and hydrogen significantly influenced the conversion, whereas the partial pressure of ammonia had little influence because the imine partial pressure rapidly reached saturation.
- Jeong, Ye-Seul,Woo, Yesol,Park, Myung-June,Shin, Chae-Ho
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p. 287 - 297
(2019/10/14)
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- Method of preparation of ethylamine or acetonitrile by reductive amination of ethanol
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The present invention relates to a catalyst for manufacturing ethylamine and a method for manufacturing the same. More specifically, the present invention relates to: a nickel-supported catalyst for manufacturing ethylamine or acetonitrile which has impregnated nickel on a supporter as a catalyst capable of efficiently manufacturing ethylamine or acetonitrile at a normal pressure or lower by reacting ethanol with ammonia, a method for manufacturing the same, and a method for manufacturing ethylamine using the same.COPYRIGHT KIPO 2019
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Paragraph 0095-0099; 0107; 0144
(2019/06/22)
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- Selective Synthesis of Secondary and Tertiary Amines by Reductive N-Alkylation of Nitriles and N-Alkylation of Amines and Ammonium Formate Catalyzed by Ruthenium Complex
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A new ruthenium catalytic system for the syntheses of secondary and tertiary amines via reductive N-alkylation of nitriles and N-alkylation of primary amines is proposed. Isomeric complexes 8 catalyze transfer hydrogenation and N-alkylation of nitriles in ethanol to give secondary amines. Unsymmetrical secondary amines can be produced by N-alkylation of primary amines with alcohols via the borrowing hydrogen methodology. Aliphatic amines were obtained with excellent yields, while only moderate conversions were observed for anilines. Based on kinetic and mechanistic studies, it is suggested that the rate determining step is the hydrogenation of intermediate imine to amine. Finally, ammonium formate was applied as the amination reagent for alcohols in the presence of ruthenium catalyst 8. Secondary amines were obtained from primary alcohols within 24 hours at 100 °C, and tertiary amines can be produced after prolonged heating. Secondary alcohols can only be converted to secondary amines with moderate yield. Based on mechanistic studies, the process is suggested to proceed through an ammonium alkoxy carbonate intermediate, where carbonate acts as an efficient leaving group.
- Alshakova, Iryna D.,Nikonov, Georgii I.
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p. 5370 - 5378
(2019/06/14)
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- AUTOTAXIN INHIBITORS AND USES THEREOF
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Described herein are methods and compositions for the treatment of conditions, diseases, or disorders associated with autotaxin activity. The methods and compositions disclosed herein include the use of at least one autotaxin inhibitor compound.
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- Is water a suitable solvent for the catalytic amination of alcohols?
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The catalytic conversion of biomass and biogenic platform chemicals typically requires the use of solvents. Water is present already in the raw materials and in most cases a suitable solvent for the typically highly polar substrates. Hence, the development of novel catalytic routes for further processing would profit from the optimization of the reaction conditions in the aqueous phase mainly for energetic reasons by avoiding the initial water separation. Herein, we report the amination of biogenic alcohols in aqueous solutions using solid Ru-based catalysts and ammonia as a reactant. The influence of different support materials and bimetallic catalysts is investigated for the amination of isomannide as a biogenic diol. Most importantly, the transferability of the reaction conditions to various other primary and secondary alcohols is successfully proved. Hence, water appears to be a suitable solvent for the sustainable production of biogenic amines and offers great potential for further process development.
- Niemeier, Johannes,Engel, Rebecca V.,Rose, Marcus
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supporting information
p. 2839 - 2845
(2017/07/24)
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- Ruthenium-catalyzed deaminative redistribution of primary and secondary amines
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A ruthenium-hydride complex, [Ru(H)(Cl)(CO)(PCy3)2], was found to be active in the highly selective redistribution of primary and secondary amines bearing an α-hydrogen atom. This new deaminative coupling of amines enables the highly selective synthesis of secondary amines from primary amines and of tertiary amines from secondary amines with the evolution of ammonia. A preliminary mechanistic view of this novel reaction based on catalytic experiments using NMR methods confirms the synthetic observations.
- Kostera,Wyrzykiewicz,Pawlu?,Marciniec
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supporting information
p. 11552 - 11555
(2017/09/18)
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- Photochemical Activation of Tertiary Amines for Applications in Studying Cell Physiology
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Representative tertiary amines were linked to the 8-cyano-7-hydroxyquinolinyl (CyHQ) photoremovable protecting group (PPG) to create photoactivatable forms suitable for use in studying cell physiology. The photoactivation of tamoxifen and 4-hydroxytamoxifen, which can be used to activate Cre recombinase and CRISPR-Cas9 gene editing, demonstrated that highly efficient release of bioactive molecules could be achieved through one- and two-photon excitation (1PE and 2PE). CyHQ-protected anilines underwent a photoaza-Claisen rearrangement instead of releasing amines. Time-resolved spectroscopic studies revealed that photorelease of the tertiary amines was extremely fast, occurring from a singlet excited state of CyHQ on the 70 ps time scale.
- Asad, Naeem,Deodato, Davide,Lan, Xin,Widegren, Magnus B.,Phillips, David Lee,Du, Lili,Dore, Timothy M.
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supporting information
p. 12591 - 12600
(2017/09/23)
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- USE OF NITROGEN COMPOUNDS QUATERNISED WITH ALKYLENE OXIDE AND HYDROCARBYL-SUBSTITUTED POLYCARBOXYLIC ACID AS ADDITIVES IN FUELS AND LUBRICANTS
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The invention relates to the use of quaternized nitrogen compounds as a fuel and lubricant additive or kerosene additive, such as in particular as a detergent additive, for decreasing or preventing deposits in the injection systems of direct-injection diesel engines, in particular in common rail injection systems, for decreasing the fuel consumption of direct-injection diesel engines, in particular of diesel engines having common rail injection systems, and for minimizing the power loss in direct-injection diesel engines, in particular in diesel engines having common rail injection systems; the invention further relates to the use as an additive for petrol, in particular for operation of DISI engines.
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- 4-Hydroxyphenacyl Ammonium Salts: A Photoremovable Protecting Group for Amines in Aqueous Solutions
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Irradiation of N-protected p-hydroxyphenacyl (pHP) ammonium caged derivatives at 313 nm releases primary and secondary amines or ammonia in nearly quantitative yields via the photo-Favorskii reaction when conducted in acidic or neutral aqueous buffered media. The reaction efficiencies are strongly dependent on the pH with the most efficient and highest yields obtained when the pH of the media maintains the ammonium and p-hydroxyl groups as their conjugate acids. For example, the overall quantum yields of simple secondary amines release are 0.5 at acidic pH from 3.9 to 6.6 dropping to 0.1 at neutral pH 7.0 and 0.01 at pH 8.4. Speciation studies provide an acid-base profile that helps define the scope and limitations of the reaction. When the pKa of the ammonium group is lower than that of the phenolic hydroxyl group, as is the case for the α-amino-protected amino acids, the more acidic ammonium ion deprotonates as the media pH is changed from acidic toward neutral or basic, thus diminishing the leaving group ability of the amino group. This, in turn, lowers the propensity for the photo-Favorskii rearrangement reaction to occur and opens the reaction pathway to alternative competing photoreduction process.
- Bownik, Iwona,?ebej, Peter,Literák, Jaromír,Heger, Dominik,?imek, Zdeněk,Givens, Richard S.,Klán, Petr
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p. 9713 - 9721
(2015/10/12)
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- METHOD FOR PREPARING DIALKYL CARBONATE
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Disclosed is a method for preparing a dialkyl carbonate, in which a dialkyl carbonate such as dimethyl carbonate is economically prepared in an environmentally-friendly manner at a higher yield while reducing generation of a by-product. The method for preparing the dialkyl carbonate includes reacting urea, an alkyl carbamate having 1 to 3 carbon atoms, or a mixture thereof with a monovalent alcohol having 1 to 3 carbon atoms in the presence of a room temperature ionic liquid and a catalyst including a salt of a transition metal or a rare earth metal.
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Paragraph 0095; 0102
(2014/03/24)
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- METHOD FOR PREPARING DIALKYL CARBONATE
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Disclosed is a method for preparing a dialkyl carbonate, in which a dialkyl carbonate such as dimethyl carbonate is economically prepared in an environmentally-friendly manner at a higher yield while reducing generation of a by-product. The method for preparing the dialkyl carbonate includes reacting urea, an alkyl carbamate having 1 to 3 carbon atoms, or a mixture thereof with a monovalent alcohol having 1 to 3 carbon atoms in the presence of a room temperature ionic liquid and a catalyst including a salt of a transition metal or a rare earth metal.
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Paragraph 0103; 0110
(2014/03/24)
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- Catalytic hydrogenation of amides to amines under mild conditions
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Under (not so much) pressure: A general method for the hydrogenation of tertiary and secondary amides to amines with excellent selectivity using a bimetallic Pd-Re catalyst has been developed. The reaction proceeds under low pressure and comparatively low temperature. This method provides organic chemists with a simple and reliable tool for the synthesis of amines. Copyright
- Stein, Mario,Breit, Bernhard
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supporting information
p. 2231 - 2234
(2013/03/28)
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- Photocatalytic hydrodenitrogenation of aromatic cyanides on TiO2 loaded with Pd nanoparticles
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Photocatalytic hydrodenitrogenation of aromatic cyanides has been carried out on TiO2 loaded with Pd nanoparticles (Pd-TiO2) in the presence of ethanol as a hydrogen source. Photoirradiation of Pd-TiO2 at λ > 300 nm in ethanol containing aromatic cyanides successfully produces the corresponding toluene derivatives and triethylamine with almost quantitative yields. Photoexcited Pd-TiO2 catalysts promote oxidation of ethanol and reduction of protons, producing acetaldehyde and hydrogen atoms on the surface of Pd particles (H-Pd species). Aromatic cyanides undergo hydrodenitrogenation via consecutive reactions involving hydrogenation by the H-Pd species and condensation with aldehydes. The catalytic activity strongly depends on the amount of Pd loaded. The catalyst containing 2 wt% Pd, with a relatively low Schottky barrier height at the Pd-TiO2 heterojunction and a large number of surface Pd atoms, exhibits the highest denitrogenation activity.
- Sugano, Yoshitsune,Fujiwara, Keisuke,Shiraishi, Yasuhiro,Ichikawa, Satoshi,Hirai, Takayuki
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p. 1718 - 1724
(2013/08/23)
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- PROCESS FOR PREPARING FORMIC ACID
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A process for preparing formic acid by hydrogenation of carbon dioxide in the presence of a tertiary amine (I) and a catalyst at a pressure of from 0.2 to 30 MPa abs and a temperature of from 20 to 200° C., wherein the catalyst is a heterogeneous catalyst comprising gold.
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Page/Page column 10-11
(2013/02/28)
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- MCR DENDRIMERS
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The invention relates to a method for producing peptoidic, peptidic and chimeric peptidic-peptoidic dendrimers by multiple iterative multi-component reactions (MCR), in particular Ugi or Passerini multi-component reactions, to compounds produced in this way and to the use thereof.
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Page/Page column
(2013/08/15)
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- The synthesis of N-ethyl-n-butylamine by amines disproportionation
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A synthesis of N-ethyl-n-butylamine with simple separation method in a fixed-bed reactor using CuO-NiO-PtO/γ-Al2O3 as the catalyst was proposed and investigated. The present catalytic system gave high activity and good selectivity, and the reaction conditions such as temperature and liquid hourly space velocity were optimized. Since no water was generated, the protocol proved to be easy to separate, and N-ethyl-n-butylamine was collected at 110 °C by distillation. The yield and the purity were 60.7 and 99.5 %, respectively.
- Xu, Lu-Feng,Huang, Jia-Min,Qian, Chao,Chen, Xin-Zhi,Feng, Lie,Chen, Yun-Bin,He, Chao-Hong
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p. 2697 - 2704
(2013/07/26)
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- An efficient synthesis of tertiary amines from nitriles in aprotic solvents
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Tertiary amines are utilized extensively as non-nucleophilic proton scavengers for a number of organic transformations. Herein we report the efficient syntheses of tertiary alkyl amines from their corresponding alkyl nitriles in the presence of a heterogeneous palladium catalyst and a source of dihydrogen in aprotic solvents. The reaction is atom economic, the conditions are mild, and the isolated yields are virtually quantitative. The degree of amine alkylation shows some solvent dependency; in polar protic solvents such as ethanol or methanol, the reaction affords a mixture of products with the secondary alkyl amine as the major product.
- Shares, Jonathan,Yehl, Jenna,Kowalsick, Amanda,Byers, Philip,Haaf, Michael P.
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experimental part
p. 4426 - 4428
(2012/09/25)
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- A practical and benign synthesis of amines through Pd@mpg-C 3N4 catalyzed reduction of nitriles
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Liquid phase hydrogenation of nitriles is an important method for the production of amines, which find a variety of applications as intermediates in chemical and pharmaceutical industry. In the present work, a highly efficient Pd@mpg-C3N4 catalytic system has been developed for chemoselective reduction of nitriles providing good to excellent conversion with remarkable chemoselectivity (up to 99%) without additives. Compared with homogeneous catalyst systems, the developed protocol is more advantageous due to the use of ambient hydrogen, solvent free and effective catalyst recyclability.
- Li, Yi,Gong, Yutong,Xu, Xuan,Zhang, Pengfei,Li, Haoran,Wang, Yong
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- METHODS FOR PRODUCING POLYASPARTIC ACID PRECURSOR POLYMER AND POLYASPARTIC ACID SALT
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Disclosed are a method for producing a polyaspartic acid precursor polymer by polymerization using at least one kind selected from a product obtained from maleic anhydride and ammonia and, maleamic acid as a monomer, wherein at least part of carboxyl groups in the monomers are a tertiary amine salt; and an industrially inexpensive and simple method for producing a polyaspartic acid salt by treating the polyaspartic acid precursor polymer obtained by this method with a basic aqueous solution.
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- Mild and efficient CO-mediated eliminative deoxygenation of epoxides catalyzed by supported gold nanoparticles
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Supported gold nanoparticles (NPs), which are well-known epoxidation catalysts, were found to be exceptionally active for the selective deoxygenation of epoxides into alkenes using cheap and easily accessible CO and H 2O as the reductant. The Royal Society of Chemistry 2011.
- Ni, Ji,He, Lin,Liu, Yong-Mei,Cao, Yong,He, He-Yong,Fan, Kang-Nian
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supporting information; experimental part
p. 812 - 814
(2011/04/15)
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- PROCESS FOR PREPARING UNSYMMETRIC SECONDARY TERT-BUTYLAMINES IN THE LIQUID PHASE
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The present application relates to a process for preparing unsymmetric secondary tert-butylamines which, as well as the tert-butyl radical, also comprise an alkyl, cycloalkyl or benzyl radical. They are prepared by reacting corresponding aldehydes with tert-butylamine and hydrogen in the presence of hydrogenation catalysts (reductive amination) in the liquid phase.
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Page/Page column 5-6
(2011/10/19)
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- COMPOSITIONS FOR TREATMENT OF CYSTIC FIBROSIS AND OTHER CHRONIC DISEASES
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The present invention relates to pharmaceutical compositions comprising an inhibitor of epithelial sodium channel activity in combination with at least one ABC Transporter modulator compound of Formula A, Formula B, Formula C, or Formula D. The invention also relates to pharmaceutical formulations thereof, and to methods of using such compositions in the treatment of CFTR mediated diseases, particularly cystic fibrosis using the pharmaceutical combination compositions.
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- A mild and efficient rhenium-catalyzed transfer hydrogenation of terminal olefins using alcoholysis of amine-borane adducts as a reducing system
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[ReBr2(NO)(CH3CN)(PTA)2] (PTA = 1, 3, 5-triaza-7-phosphaadamantane) catalyzes the alcoholysis of ammonia-borane and amine-boranes and the catalytic transfer hydrogenations of various terminal olefins. Excellent yields were achieved at 70 °C in isopropanol using tBuOK as a co-catalyst affording TOF values up to 396 h-1.
- Dong, Hailin,Berke, Heinz
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experimental part
p. 1803 - 1808
(2011/06/19)
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- PEPTIDE ANALOGUES
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The present invention relates to compounds of Formula (I) and their pharmaceutically acceptable salts, wherein the substituents are as described herein, and their use in medicine, in particular as opioid agonists
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- Osmium and ruthenium catalysts for dehydrogenation of alcohols
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A series of pincer-type complexes of Os and Ru have been synthesized and investigated in catalytic alcohol dehydrogenation. The hydrides OsHCl(CO)[HN(C2H4PiPr2)2] and OsH2(CO)[HN(C2H4PiPr2)2] possess good air, moisture, and thermal stability and are outstanding versatile dehydrogenation catalysts for primary alcohols for reactions of transfer hydrogenation, dehydrogenative coupling, and amine alkylation.
- Bertoli, Marcello,Choualeb, Aldjia,Lough, Alan J.,Moore, Brandon,Spasyuk, Denis,Gusev, Dmitry G.
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scheme or table
p. 3479 - 3482
(2011/09/20)
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- Method to recover organic tertiary amines from waste sulfuric acid
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The present invention describes a method to recover organic tertiary amines from waste sulfuric acid comprising the following steps: a) reacting i) waste sulfuric acid comprising organic tertiary amines with ii) ammonia in an amount sufficient to obtain a pH of 9.5 or higher and b) separating the organic tertiary amines from the reaction mixture obtained in step a) wherein during the separation the pH of the reaction mixture is adjusted at a pH of 9.5 or higher.
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Page/Page column 6
(2011/11/07)
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- Method to recover organic tertiary amines from waste sulfuric acid employing a plug flow reactor
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The present invention describes a method to recover an organic tertiary amine from waste sulfuric acid comprising the following steps: a) reacting in a plug flow reactor at a pressure ranging from 1.5 to 12 bar i) waste sulfuric acid comprising organic tertiary amines with ii) ammonia; and b) separating the organic tertiary amine from the reaction mixture obtained in step a).
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Page/Page column 6
(2011/11/07)
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- Recoverable polymer-bound homogeneous catalysts for catalytic chain transfer process
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Disclosed herein are novel polymer-tethered ligands, metal complexes comprising these ligands, and the use of these complexes as chain transfer catalysts to control the molecular weight of oligomeric and polymeric materials produced in a radical polymerization process. The materials made by the processes disclosed herein have significantly reduced color, making them suitable for a wide range of color-critical end-uses, including automotive coatings.
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- Bimetallic Ru/Ni supported catalysts for the gas phase hydrogenation of acetonitrile
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A family of bimetallic Ni-Ru catalysts supported on a mesoporous SBA-15 silica was prepared by conventional impregnation method, with constant metal molar loadings, but varying Ni/(Ni + Ru) atomic ratios. The corresponding Ni and Ru monometallic catalysts were also prepared for comparison. These catalysts were characterized by XRD, N2 adsorption-desorption at -196 °C, TEM, XPS, H2-TPR, chemisorption of H2 at r.t., H2-TPD and NH3-TPD techniques. Finally, they were also tested in the hydrogenation of acetonitrile reaction, in the gas phase and at atmospheric pressure. Acetonitrile conversion values depended on the Ni/(Ni + Ru) composition of the bimetallic catalysts. Ru-rich bimetallic catalysts exhibited acetonitrile conversion values higher than that of pure Ni one; thus, although selectivity patterns remained almost unchanged, primary amine yields were increased. These higher conversion values resulted as a consequence of enhanced specific activity of Ni0 atoms, attributable to a strong interaction between both metals, Ni and Ru, likely because NiRu alloy nanoparticles were formed.
- Braos-García,García-Sancho,Infantes-Molina,Rodríguez-Castellón,Jiménez-López
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experimental part
p. 132 - 144
(2010/08/07)
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- Novel carbosilane dendrimers, preparation method thereof and use of same
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Novel carbosilane dendrimers, their preparation and their uses. The dendrimers of the invention have secondary, tertiary and quaternary amino groups at their branch ends. Their possible uses include vehicles for carrying anionic-charged molecules in the blood, such as nucleic acids, among them ODN and RNAi, and other anionic drugs with which they have the capacity of interacting, protecting them from interaction with plasma protein and/or increasing their penetration rate in target cells. In the cases where the bond is long-lasting, the dendrimers of the invention can be used to fix anionic molecules to surfaces. Their uses also include their administration as active ingredients to prevent or treat diseases caused by micro-organisms with whose structure and/or life cycle they interfere.
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- Thermodynamics of halogen bonding in solution: Substituent, structural, and solvent effects
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A detailed study of the thermodynamics of the halogen-bonding interaction in organic solution is presented. 19F NMR titrations are used to determine association constants for the interactions of a variety of Lewis bases with fluorinated iodoalkanes and iodoarenes. Linear free energy relationships for the halogen bond donor ability of substituted iodoperfluoroarenes XC 6F4I are described, demonstrating that both substituent constants (σ) and calculated molecular electrostatic potential surfaces are useful for constructing such relationships. An electrostatic model is, however, limited in its ability to provide correlation with a more comprehensive data set in which both halogen bond donor and acceptor abilities are varied: the ability of computationally derived binding energies to accurately model such data is elucidated. Solvent effects also reveal limitations of a purely electrostatic depiction of halogen bonding and point to important differences between halogen bonding and hydrogen bonding.
- Sarwar, Mohammed G.,Dragisic, Bojan,Salsberg, Lee J.,Gouliaras, Christina,Taylor, Mark S.
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supporting information; scheme or table
p. 1646 - 1653
(2010/04/04)
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- Proton donor acceptor interactions of disubstituted thiovioluric acids with amines bases
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The stability constants of hydrogen bonded ion pair or proton transfer complex formation of N,N'-dimethyl thiovioluric acid [DMTVA], N,N'- di-o-tolyl thiovioluric acid [DOTTVA], N,N'-di-m-tolyl thiovioluric acid [DMTTVA] and N,N'-di-p-tolyl thiovioluric acid [DPTTVA] with methyl amine, dimethyl amine, trimethyl amine, ethyl amine, diethyl amine, triethyl amine, n-butyl amine, dibutyl amine and tributyl amine have been determined spectroscopically in 95% (v/v) ethanol. The composition of the complexes is determined in solution potentiometrically and spectrophotometrically and substantiated by the element analysis and IR spectra of the isolated complexes. The stabilities of the thiovioluric acid-amine complexes have been correlated with the base strength of amines. The correlation between the mode of enolization in the acids and the structure of the proton transfer complex is discussed. The variation in proton transfer constants of acids has been explained on the basis of the changes in the distribution of electron density in the ring.
- Singh,Rani, Babita,Deep, Sorabh Singh
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experimental part
p. 4781 - 4786
(2010/12/18)
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- Determination of basic strength of aliphatic amines through ion pair formation in some ionic liquid solutions
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(Chemical Equation Presented) To have an evaluation of the basic strength of aliphatic amines in ionic liquid solution, the stability constants relevant to the formation of amine/p-nitrophenol ion pairs were determined in different ionic liquids at 298 K.
- D'Anna, Francesca,Vitale, Paola,Noto, Renato
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experimental part
p. 6224 - 6230
(2009/12/08)
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- Effect of surface composition on the catalytic performance of molybdenum phosphide catalysts in the hydrogenation of acetonitrile
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A series of molybdenum phosphide catalysts with initial Mo/P ratios varying in a narrow range of 0.90-1.10 was prepared by temperature-programmed reaction; characterized by X-ray diffraction, BET, elemental analysis, X-ray photoelectron spectroscopy, and CO chemisorption measurements; and tested for the hydrogenation of acetonitrile at different pressures (0.1-1.0 MPa) and temperatures (473-513 K). The catalysts exhibited attractive catalytic activity, especially at a H2 pressure above 0.2 MPa. The surface composition of the MoP catalysts could be fine-tuned by the initial Mo/P ratio, which consequently led to different surface properties (e.g., CO uptakes) and catalytic behaviors. Catalysts with high initial Mo amount gave high selectivity to the primary amine, ethylamine, whereas those with high initial P amount created more condensed amines, diethylamine and triethylamine.
- Yang, Pengfei,Jiang, Zongxuan,Ying, Pinliang,Li, Can
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- New aspects for heterogeneous cobalt-catalyzed hydroamination of ethanol
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Gas-phase hydroamination of ethanol and ammonia over supported cobalt on silica catalysts was investigated at 103 kPa. Besides the desired products, mono-, di- and triethylamine, acetonitrile, diethylimine, and hydrocarbons (methane, ethene, ethane, propane, and propene) were identified as byproducts. The formation of hydrocarbons was found to depend on the cobalt loading of the catalyst and on the pretreatment of the catalyst. Guaranteeing a sufficient reduction of the cobalt catalyst allows a reduction in the selectivity of hydrocarbons from 25 to 10 mol% at a constant conversion of 90%. In addition, rapid deactivation of the catalyst was observed in the absence of hydrogen. The deactivation was ascribed to the interaction of ammonia with the catalyst and is largely reversible. Carbonaceous species are present on the spent catalyst, as shown by temperature-programmed reduction. These species are thought to be responsible for a slow deactivation in the presence of hydrogen.
- Rausch,van Steen,Roessner
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p. 111 - 118
(2008/09/16)
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- Pharmaceutical Compositions Comprising Nitrogen-Containing Fused Ring Coumpounds
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[Problems] The present invention provides pharmaceutical composition which is effective for the prophylaxis or treatment of pathology showing involvement of uric acid (hyperuricemia, gouty tophus, acute gout arthritis, chronic gout arthritis, gouty kidney, urolithiasis, renal function disorder, coronary arterial disease, ischemic heart disease and the like) and the like, and is superior in the time-course stability and dissolution property (disintegration property). [Solving Means] The pharmaceutical composition of the present invention is a pharmaceutical composition comprising a nitrogen-containing fused ring compound represented by the following formula [1] or a pharmaceutically acceptable salt thereof, and one or more pharmaceutically acceptable additives, wherein the nitrogen-containing fused ring compound or a pharmaceutically acceptable salt thereof is not in contact with a basic additive: wherein each symbol is as described in the specification.
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- METHOD FOR PRODUCING AN ETHYLAMINE
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The invention relates to a method for producing an ethylamine by reacting ethanol with ammonia, with a primary amine or with a secondary amine in the presence of hydrogen or of a heterogeneous hydrogenation/dehydrogenation catalyst, during which a biochemically or biologically produced ethanol (bioethanol) is used. The catalyst contains one or more metals of group VIII and/or IB of the periodic table and after activation with hydrogen, has a CO absorption capacity of > 100 ?mol CO/g of catalyst.
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Page/Page column 13-14
(2008/06/13)
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- Process for obtaining amines by reduction of amides
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Disclosed is a process for the preparation of primary, secondary and tertiary amines via a catalytic hydrogenation of unsubstituted, N-substituted, and N,N-disubstituted amides. The amide is led, together with an auxiliary amine, in vaporised form in a hydrogen containing gas flow over the catalyst. The process can be carried out at relatively low pressures, between 2 and 50 bars, using typical hydrogenation catalysts like CuCr-type catalysts. The amine is obtained with high yield and high selectivity. The process can be carried out in a continuous fixed bed reactor.
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Page/Page column 5
(2008/06/13)
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- PROCESS FOR OBTAINING AMINES BY REDUCTION OF AMIDES
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Disclosed is a process for the preparation of primary, secondary and tertiary amines via a catalytic hydrogenation of unsubstituted, N- substituted, and N,N- disubstituted amides. The amide is led, together with an auxiliary amine, in vaporised form in a hydrogen containing gas flow over the catalyst. The process can be carried out at relatively low pressures, between 2 and 50 bars, using typical hydrogenation catalysts like CuCr-type catalysts. The amine is obtained with high yield and high selectivity. The process can be carried out in a continuous fixed bed reactor.
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Page/Page column 13-14
(2008/06/13)
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