- Generation of a Mn(IV)-Peroxo or Mn(III)-Oxo-Mn(III) Species upon Oxygenation of Mono- and Binuclear Thiolate-Ligated Mn(II) Complexes
-
A thiolate-bridged binuclear complex [PPN]2[(MnII(TMSPS3))2] (1, PPN = bis(triphenylphosphine)iminium and TMSPS3H3 = (2,2′,2″-trimercapto-3,3′,3″-tris(trimethylsilyl)triphenylphosphine)), prepared from the reaction of MnCl2/[PPN]Cl and Li3[TMSPS3], converts into a mononuclear complex [PPN][MnII(TMSPS3)(DABCO)] (2) in the presence of excess amounts of DABCO (DABCO = 1,4-diazabicyclo[2.2.2]octane). Variable temperature studies of solution containing 1 and DABCO by UV-vis spectroscopy indicate that 1 and 2 exist in significant amounts in equilibrium and mononuclear 2 is favored at low temperature. Treatment of 1 or 2 with the monomeric O2-side-on-bound [PPN][MnIV(O2)(TMSPS3)] (3) produces the mono-oxo-bridged dimer [PPN]2[(MnIII(TMSPS3))2(μ-O)] (4). The electrochemistry of 1 and 2 reveals anodic peak(s) for a MnIII/MnII redox couple at shifted potentials against Fc/Fc+, indicating that both complexes can be oxidized by dioxygen. The O2 activation mediated by 1 and 2 is investigated in both solution and the solid state. Microcrystals of 2 rapidly react with air or dry O2 to generate the Mn(IV)-peroxo 3 in high yield, revealing a solid-to-solid transformation and two-electron reduction of O2. Oxygenation of 1 or 2 in solution, however, is affected by diffusion and transient concentration of dioxygen in the two different substrates, leading to generation of 3 and 4 in variable ratios.
- Lee, Chien-Ming,Wu, Wun-Yan,Chiang, Ming-Hsi,Bohle, D. Scott,Lee, Gene-Hsiang
-
-
Read Online
- Degradation of Organic Cations under Alkaline Conditions
-
Understanding the degradation mechanisms of organic cations under basic conditions is extremely important for the development of durable alkaline energy conversion devices. Cations are key functional groups in alkaline anion exchange membranes (AAEMs), and AAEMs are critical components to conduct hydroxide anions in alkaline fuel cells. Previously, we have established a standard protocol to evaluate cation alkaline stability within KOH/CD3OH solution at 80 °C. Herein, we are using the protocol to compare 26 model compounds, including benzylammonium, tetraalkylammonium, spirocyclicammonium, imidazolium, benzimidazolium, triazolium, pyridinium, guanidinium, and phosphonium cations. The goal is not only to evaluate their degradation rate, but also to identify their degradation pathways and lead to the advancement of cations with improved alkaline stabilities.
- You, Wei,Hugar, Kristina M.,Selhorst, Ryan C.,Treichel, Megan,Peltier, Cheyenne R.,Noonan, Kevin J. T.,Coates, Geoffrey W.
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supporting information
p. 254 - 263
(2020/12/23)
-
- Synthesis method of triethylene diamine
-
The invention relates to a synthesis method of triethylene diamine, and solves the technical problems of high cost or certain risk of raw materials, no environmental protection, complex synthesis process, low product yield and the like in the existing production process. The synthesis method comprises the following steps: (1) adding oxalic acid diester into a reaction bottle, dissolving piperazinewith a solvent in advance, adding a catalyst, dropwise adding piperazine dissolved with the solvent at the reaction temperature of 30-80 DEG C, stirring for 1-2 hours, filtering, washing an obtainedfilter cake with the solvent, and drying to obtain an intermediate product, namely dioxytriethylene diamine; (2) adding the dioxytriethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding a solvent until the dioxytriethylene diamine is completely dissolved, adding a catalyst, tightly covering a kettle cover, sealing, heating to 150-200 DEG C, introducing hydrogen into a high-pressure valve until the pressure reaches 2-10MPa, and continuously introducing hydrogen to maintain the pressure in the reaction process to obtain a triethylene diamine crude product; and (3) carrying out post-treatment to obtain the final product triethylene diamine. The method is applied to synthesis of triethylene diamine.
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Paragraph 0031; 0033-0036; 0038-0041; 0043-0046; 0048-0051
(2020/09/16)
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- METHOD FOR PRODUCING PIPERAZINE AND TRIETHYLENEDIAMINE
-
PROBLEM TO BE SOLVED: To provide a method for producing piperazine and triethylenediamine in combination, making it possible to provide piperazine with high selectivity and high yields. SOLUTION: Under a basic condition with pH of 8 or more, pentasil type zeolite subjected to ion exchange with alkali metal salt, and one or more amine react with each other, under a condition of 50 wt.% or more substrate concentration. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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-
Paragraph 0055; 0056; 0057; 0058
(2017/07/19)
-
- METHOD FOR PRODUCING BICYCLIC AMINE COMPOUND
-
PROBLEM TO BE SOLVED: To provide a stable production method for a bicyclic amine compound that inhibits the generation of by-products in the production of a bicyclic amine. SOLUTION: The present invention provides a method for producing a bicyclic amine compound which employs a catalyst comprising an inorganic support and an alkali metal phosphate, and further comprising alkaline earth metal hydroxide and/or hydroxyapatite in an amount of 1.5 wt.% or more and less than 15 wt.% relative to the inorganic support. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPO&INPIT
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Paragraph 0047; 0054
(2017/11/15)
-
- Hetero Face-to-Face Porphyrin Array with Cooperative Effects of Coordination and Host–Guest Complexation
-
We successfully synthesized a hetero face-to-face porphyrin array composed of ZnTPP and RuTPP(DABCO)2 (TPP: 5, 10, 15, 20-tetraphenylporphyrin, DABCO: 1,4-diazabi-cyclo[2.2.2]octane) in 2:1 molar ratio. A cyclic Zn porphyrin dimer (ZnCP) was also used as the host molecule for the Ru porphyrin. In the latter, the Ru-DABCO bonding in RuTPP(DABCO)2 was stabilized by the host-guest complexation. Reaction progress kinetic analysis of the ligand substitution reaction of RuTPP(DABCO)2 and that in ZnCP revealed the stabilization mechanism of the Ru-DABCO bonding. Photoinduced electron transfer (PET) from the Zn porphyrin to the Ru porphyrin was observed in the porphyrin array. The host-guest stabilization of unstable complex for construction of a donor—acceptor–donor structure is expected to be a new method for an artificial photosynthesis.
- Chiba, Yusuke,Liu, Maning,Tachibana, Yasuhiro,Fujihara, Tetsuaki,Tsuji, Yasushi,Terao, Jun
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supporting information
p. 1900 - 1904
(2017/08/10)
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- MANUFACTURING METHOD OF PIPERAZINE AND TRIETHYLENE DIAMINE
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PROBLEM TO BE SOLVED: To provide a manufacturing method of piperazine and triethylene diamine, in which piperazine is obtained more selectively and at a higher yield. SOLUTION: Ethylene diamines and steam-treated ZSM-5 type zeolite are brought into contact to make react. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0047; 0048; 0049
(2017/10/07)
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- The method of manufacturing the amine compound Bicylic
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PROBLEM TO BE SOLVED: To provide a method for simply obtaining a bicyclic amine compound at high yield and for suppressing by-product tar contents that may obstruct the continuous production. SOLUTION: The compound indicated by a formula (1) is subjected to intramolecular dehydration in a gas phase under the presence of a solid catalyst to produce the bicyclic amine compound indicated by a formula (2). In the formula (1), R1-R8each independently represents a hydrogen atom, a 1-4C alkyl group, a hydroxy group, a hydroxymethyl group or a 1-4C alkoxy group; X represents a carbon atom or a nitrogen atom; and Y represents a hydrogen atom, an alkyl group, a hydroxy group or a 1-4C hydroxyalkyl group. In the formula (2), R1-R8, X and Y are defined in the same manner as above. COPYRIGHT: (C)2012,JPOandINPIT
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Paragraph 0058-0060; 0062
(2017/04/19)
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- METHOD FOR PRODUCING PIPERAZINE AND TRIETHYLENEDIAMINE
-
PROBLEM TO BE SOLVED: To provide a joint production method of piperazine and triethylenediamine capable of obtaining piperazine more selectively and also at a high yield. SOLUTION: Diethylenetriamine and at least one kind of amine selected from the group consisting of ethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and their alkylated bodies are mixed, the mixture is contacted with ZSM-5 type zeolite in which the ion exchange rate in the alkali metal salt is 50% or higher, and reaction is caused. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0091; 0092
(2017/05/26)
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- METHOD FOR PRODUCING PIPERAZINE AND TRIETHYLENE DIAMINE
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PROBLEM TO BE SOLVED: To provide a method for producing piperazine and triethylene diamine that allows piperazine to be obtained selectively with high yields. SOLUTION: At least one amine selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and their alkylate is brought into contact with zeolite having BEA structure for a reaction. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0046-0063
(2018/10/17)
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- Synthesis of piperazine and method of triethylene diamine
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The invention discloses a method for synthesizing piperazidine and triethylenediamine. The method aims to solve the problems of low efficiency and need for expensive high-vacuum rectifiers in the process of converting ethanolamine into piperazidine and triethylenediamine in the prior art. The method comprises the following steps: mixing and gasifying ethanolamine and ammonia, and carrying out amination reaction in a fixed-bed reactor R by using a catalyst A (using a mesoporous-microporous composite molecular sieve MOR/MCM-41 as a support) and a catalyst B (using a mesoporous-microporous composite molecular sieve ZSM-5 MCM-41 as a support); carrying out rectification separation on the reactor outlet product in a rectification tower T1 to distil off unconverted ammonia, piperazidine and triethylenediamine from the tower top, and circulating unreacted ethanolamine and amination byproduct obtained from the tower bottom to the inlet of the fixed-bed reactor R to continue reaction; and sending the top fraction of the rectification tower T1 into a rectification tower T2, and separating to obtain the piperazidine and triethylenediamine. The method is used for synthesizing piperazidine and triethylenediamine.
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Paragraph 0030-0032
(2017/03/08)
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- Introduction of a novel nanosized N-sulfonated Br?nsted acidic catalyst for the promotion of the synthesis of polyhydroquinoline derivatives via Hantzsch condensation under solvent-free conditions
-
In this research 4,4′-(butane-1,4-diyl)bis(1-sulfo-1,4-diazabicyclo[2.2.2]octane-1,4-diium)tetrachloride (NS-C4(DABCO-SO3H)2)·4Cl) as a new nano sized N-sulfonic acid was prepared and characterized using different types of methods including FT-IR, 1H NMR, 13C NMR, mass, XRD, TGA, SEM and AFM analysis. After the characterization of this reagent, it was efficiently used for the promotion of the one-pot synthesis of hexahydroquinolines via one-pot four-component condensation of aryl aldehydes, 1,3-cyclohexadione derivatives, β-ketoesters and ammonium acetate under solvent-free conditions. The procedure gave the products in excellent yields in short reaction times and good to high yields. Also this catalyst can be reused several times without loss of its catalytic activity.
- Goli-Jolodar, Omid,Shirini, Farhad,Seddighi, Mohadeseh
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p. 26026 - 26037
(2016/03/25)
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- METHOD OF PRODUCING BICYCLIC AMINE COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for efficiently producing a bicyclic amine compound having a long catalytic activity life. SOLUTION: There is provided a method for producing a bicyclic amine compound represented by formula (2) using an inorganic oxide represented by formula (1) as a catalyst. AaMbNcPdOe (1) [A is a metal; M is an alkali metal; N is an alkaline earth metal; P is phosphorus; O is oxygen; subscripts a to e are molar numbers of each element; b/a=0.001 to 0.3; c/a=0.001 to 0.1; d/a=0.001 to 0.3; e is a value determined by the bonding state of each atom] [R1 to R8 each independently represents H, an alkyl group having 1-4 carbon atoms, a hydroxymethyl group or an alkoxy group having 1-4 carbon atoms; X represents a carbon atom or a nitrogen atom; and Y represents H, an alkyl group having 1-4 carbon atoms, a hydroxyl group or a hydroxyalkyl group having 1-4 carbon atoms.] SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0057; 0064; 0065
(2017/04/22)
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- METHOD OF PRODUCING BICYCLIC AMINE COMPOUND
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PROBLEM TO BE SOLVED: To provide a method of efficiently producing a bicyclic amine compound while improving a color tone of it. SOLUTION: A method of producing a bicyclic amine compound includes a reaction step in which the formula (1) is made to react in a gas phase in the presence of a solid catalyst such as an inorganic oxide and a metal phosphoric acid, to produce a bicyclic amine compound of the formula (2), and a distillation step. COPYRIGHT: (C)2015,JPOandINPIT
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-
Paragraph 0051-0054
(2018/02/27)
-
- Laser flash photolysis study of the photochemistry of 4,5-diaza-9-fluorenone
-
The triplet excited state of 4,5-diaza-9-fluorenone (1) shows absorption maxima at 410 and 470 nm and a lifetime of 3 μs, in acetonitrile. Its intersystem crossing quantum yield was determined using 9-fluorenone as a secondary standard and a value of 0.41 ± 0.01 was obtained. The reactivity of the triplet excited state of 1 towards several quenchers, in acetonitrile, was investigated employing the laser flash photolysis technique quenching rate constants ranging from 7.9 × 104 M-1 s-1 (2-propanol) to 1.0 × 1010 M-1 s-1 (triethylamine) were obtained. From the quenching rate constants obtained one can conclude that 4,5-diaza-9-fluorenone has a ππ? triplet excited state. A Hammett plot for the quenching rate constants of triplet 1 by phenols containing polar substituents against σ + gave a reaction constant ρ of -1.54 ± 0.10, which demonstrates the electrophilic character of the 4,5-diaza-9-fluorenone triplet excited state.
- Bertoti, Ada R.,Guimar?es, Alexandre K.,Netto-Ferreira, José Carlos
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p. 166 - 171
(2015/02/19)
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- Cyclization of monoethanolamine to aziridine over Cs2O-P 2O5/SiO2
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Several commercially available supports were examined for cyclization of monoethanolamine to aziridine, and SiO2 was found to yield the best results. The obtained results indicated that selectivity of aziridine was mainly influenced by support. The catalysts were characterized by NH3-TPD and XRD. It was found that SiO2 with lower acidity could inhibit the intermolecular condensations, and thus favored the formation of aziridine. The Cs4P2O7 phase was confirmed as the active site in the supported cesium phosphate catalyst. The reaction parameters were also optimized and a yield of 52% aziridine was obtained over 200 h. Thus, a continuous process for the cyclization of monoethanolamine to aziridine has been established. Springer Science+Business Media B.V. 2012.
- Kong, Xiangjin,Wang, Guangyuan,Li, Lei,Sun, Meng,Du, Xiaobao,Chen, Ligong
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p. 1743 - 1750
(2013/02/22)
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- PROCESS FOR PRODUCING HYDROXYALKYLTRIETHYLENEDIAMINE COMPOUND, AND CATALYST COMPOSITION FOR THE PRODUCTION OF POLYURETHANE RESIN USING THE HYDROXYALKYLTRIETHYLENEDIAMINE COMPOUND
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To provide a process for producing a hydroxyalkyltriethylenediamine or hydroxytriethylenediamine simply and in a small number of steps without requiring multistage reaction steps; a novel catalyst composition whereby a polyurethane product can be obtained with good productivity and good moldability without bringing about odor problems or environmental problems; and a process for producing a polyurethane resin using the catalyst composition. For example, a hydroxyalkyltriethylenediamine or hydroxytriethylenediamine is produced by subjecting a mono-substituted dihydroxyalkylpiperazine and/or a di-substituted hydroxyalkylpiperazine to an intramolecular dehydration condensation reaction in the presence of an acid catalyst. Further, for example, a polyurethane resin is produced by using a catalyst composition which comprises a hydroxyalkyltriethylenediamine or hydroxytriethylenediamine (A), and an amine compound (B) having, in its molecule, one or more substituents selected from the group consisting of a hydroxy group, a primary amino group and a secondary amino group, or a tertiary amine compound (C) having a value of [blowing reaction rate constant/gelling reaction rate constant] of at least 0.5.
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Page/Page column 27
(2011/04/18)
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- Intermolecular condensation of ethylenediamine to 1,4-diazabicyclo(2,2,2)octane over H-ZSM-5 catalysts: Effects of Si/Al ratio and crystal size
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The intermolecular condensation of ethylenediamine (EDA) to 1,4-diazabicyclo [2.2.2] octane (DABCO) or triethylenediamine (TEDA) was conducted over H-ZSM-5 catalysts. The effects of reaction parameters, Al content and crystal size on the EDA condensation over H-ZSM-5 have been investigated. The H-ZSM-5 catalyst with a medium Al content (Si/Al = 110) and a small crystal size (ca. 100 nm) showed 99% EDA conversion and afforded a TEDA yield as high as 74% under optimized conditions. The mechanism for the H-ZSM-5-catalyzed condensation of EDA has also been considered. The framework Al-related Br?nsted acid sites were assumed to contribute to selective intermolecular condensation of EDA to TEDA. The primary intermolecular condensation of EDA to piperazine (PIP) took place mainly inside the micropores of the MFI structure, while the secondary condensation of PIP with EDA to TEDA was favored by the acid sites located near the pore entrance and on the external surfaces of crystals.
- Wang, Yong,Guo, Lifang,Ling, Yun,Liu, Yueming,Li, Xiaohong,Wu, Haihong,Wu, Peng
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experimental part
p. 45 - 53
(2010/09/05)
-
- Macrocyclic Compounds As Antiviral Agents
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A class of macrocyclic compounds of formula (I), wherein R1, R3, R4, Ra, Rb, A, Z, Y, X, M, W, n and m are defined herein, that are useful as inhibitors of viral proteases, particularly the hepatitis C virus (HCV) NS3 protease, are provided. Also provided are processes 5 for the synthesis and use of such macrocyclic compounds for treating or preventing HCV infection. Formula (I):
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- Intermolecular condensation of ethylenediamine to 1,4-diazabicyclo[2,2,2]octane over TS-1 catalysts
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The intermolecular condensation of ethylenediamine (EDA) to 1,4-diazabicyclo[2.2.2]octane or triethylenediamine (TEDA) has been carried out over various titanosilicate catalysts. Superior to Ti-MWW, Ti-Beta, Ti-FER, and Ti-MOR, TS-1 showed higher EDA conversion and TEDA selectivity. The effects of reaction parameters, Ti content, and crystal size on the EDA condensation over TS-1 have been investigated. The mechanism for the TS-1-catalyzed condensation of EDA has also been considered. The acid sites, originated from the Si-OH groups adjacent to the "open" Ti sites, were assumed to contribute to the intermolecular condensation of EDA, whereas the Lewis acid sites directly related to Ti(IV) ions were not the true active sites. The primary intermolecular condensation of EDA to 1,4-diazacyclohexane or piperazine (PIP) took place mainly inside the micropores of the MFI structure, while the secondary condensation of PIP with EDA to TEDA was favored by the acid sites located near the pore entrance and on the outer surface of crystals.
- Wang, Yong,Liu, Yueming,Li, Xiaohong,Wu, Haihong,He, Mingyuan,Wu, Peng
-
experimental part
p. 258 - 267
(2011/03/17)
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- Work-Up in the Preparation of High-Purity Triethylenediamine
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The present invention relates to a process for working up triethylenediamine (TEDA) in which TEDA is vaporized and the gaseous TEDA is introduced into a solvent, subsequently crystallized and separated off from this and the mother liquor formed is extracted with an extractant, wherein the raffinate phase obtained after the extraction stage is worked up further by adsorption in which extractant and/or by-products and intermediates present in the raffinate phase are removed therefrom.
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Page/Page column 3-4
(2009/01/24)
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- DABCO and DMAP - Why are they different in organocatalysis?
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(Chemical Equation Presented) What makes a good organocatalyst? DABCO (1,4-diazabicyclo[2.2.2]octane) is a thousandfold better nucleophile (k →) and at the same time a million times better leaving group (k←) than DMAP (4-(dimethylamino)pyridine). This apparent contradiction is resolved by consideration of the intrinsic reaction barriers.
- Baidya, Mahiuddin,Kobayashi, Shinjiro,Brotzel, Frank,Schmidhammer, Uli,Riedle, Eberhard,Mayr, Herbert
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p. 6176 - 6179
(2008/04/05)
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- Decolorization and color stabilization of TEDA-solutions
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Die vorliegende Erfindung bezieht sich auf ein Verfahren zur Herstellung von TEDA-L?sungen mit einem L?sungsmittel aus der Gruppe der mehrwertigen Alkohole und Ether von mehrwertigen Alkoholen. Das Verfahren umfa?t das Einleiten von gasf?rmigem TEDA in das L?sungsmittel und anschlie?endes Behandeln der L?sungen mit einem oder mehreren geeigneten Adsorbentien. Es werden dadurch L?sungen erhalten, die nur geringe Farbzahlen aufweisen und auch bei Lagerung farbzahlstabil sind. Die L?sungen k?nnen als solche in den bevorzugten Anwendungen von TEDA, vorzugsweise der Polyurethan-Herstellung eingesetzt werden.
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- Mechanochemical assembly of hydrogen bonded organic-organometallic solid compounds
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Solvent-free reactions with molecular systems have been exploited to prepare hybrid organic-organometallic solids: grinding of the complex [Fe(η5-C5H4COOH)2] with solid bases B generates quantitatively the corre
- Braga, Dario,Maini, Lucia,Polito, Marco,Mirolo, Laurent,Grepioni, Fabrizia
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p. 2960 - 2961
(2007/10/03)
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- Method for producing triethylenediamines and piperazines
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A method for producing triethylenediamines and piperazines, which comprises contacting an amine compound having a group of the formula (1): wherein each of R1to R4which are independent of one another, is a hydrogen atom or a C1-3alkyl group which may have a substituent, with a catalyst consisting of a crystalline aluminosilicate calcinated at a temperature of from 500 to 950° C. and then contacted with an inorganic acid, and having a molar ratio of silica to alumina of at least 12.
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- Enhanced product selectivity in continuous N-methylation of amino alcohols over solid acid-base catalysts with supercritical methanol
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The unique properties of supercritical fluids can be exploited for fine-tuning product selectivity. Under the conditions listed for the N-methylation of amino alcohols (see scheme) over solid acid-base bifunctional catalysts, the total yield and product selectivity could be improved. Enhanced product selectivity might be attributed to the milder reaction conditions possible with supercritical methanol, as well as the increased concentration of methanol on the catalyst.
- Oku, Tomoharu,Ikariya, Takao
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p. 3476 - 3479
(2007/10/03)
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- Suppository and composition comprising at least one polyethylene glycol
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There is provided a suppository comprising at least one biocompatible polymer, wherein the biocompatible polymer is essentially non-biodegradable, and wherein the suppository essentially does not swell when contacted with an aqueous fluid. The suppository may further comprise a plurality of open cells at least partly separated from one another by an interpenetrating matrix comprising at least one biocompatible polymer in branched or crosslinked form. The plurality of interlinked, open cells are capable of containing an aqueous fluid, and the permeability of the suppository ensures that entry of body fluids into the open cells under practical circumstances occurs essentially without dehydration of mucousal membrane tissue contacting the suppository. The suppository furthermore preferably comprises a controlled release formulation.
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- Amine catalyst for producing polyurethane and polyisocyanurate
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An amine catalyst-for production of a polyurethane and a polyisocyanurate is provided which comprises a quaternary ammonium compound represented by General Formula (1): where R1 to R6 are independently a linear or branched saturated hydrocarbon group of 1 to 4 carbon atoms; R7 and R8 are independently a linear or branched, saturated or unsaturated hydrocarbon group of 2 to 12 carbon atoms; n is a number of 0 to 3 provided that at n=o any one of R1, R2 and R3, and R5 and/or R6 may be linked together to form a heterocycle, or at n=1, 2, or 3, R5 or R6 and R4 may be linked together to form a heterocycle; A is a carbonate group or an organic acid group; and X is number of 1 to 2. The catalyst has high activity in formation of polyurethane foams and polyisocyanurate foams, having less odor, and producing foams of high fire retardance, having high curability, high retarding effect, and low corrosiveness.
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- Oxidation catalyst and oxidation process using the same
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In the presence of (1) an oxidation catalyst comprising a crystalline complex of manganese with an N,N′-disalicylidenediamine (e.g., N,N′-disalicylidene C2-8alkylenediamines and N,N′-disalicylidene C6-12arylenediamines), or (2) an oxidation catalyst comprising the above complex and a basic nitrogen-containing compound, a substrate (e.g., β-isophorone or a derivative thereof) is oxidized with molecular oxygen to produce a corresponding oxide (e.g., ketoisophorone). Ketoisophorone can be obtained from β-isophorone with high conversion and high selectivity.
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- Process for the preparation and uses of derivatives of esters of alpha -methylene- beta -hydroxy acids
-
A process for the preparation of derivatives of halo-but-2-enoic acids and esters high in 2-ene content, several of which are novel. The esters and their derivatives are useful as promoters for the polymerization of ethylene or the copolymerization of ethylene with alpha -olefins and, optionally, nonconjugated polyenes. The promoters can also be combined with transition metal compounds, e.g., vanadium, to form combination promoter-catalyst compounds.
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- Oxidation catalytic system and process for producing ketoisophorone using the same
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In the presence of a catalytic system comprising a cyclic base and a complex of a transition metal with an N,N'-disalicylidenediamine, ketoisophorone or a derivative thereof is produced by oxidizing beta -isophorone or a derivative thereof with molecular oxygen with controlling the water content of a reaction system to 1% by weight or less at the initial stage of the reaction. Moreover, the above catalytic system further comprises a basic nitrogen-containing compound. The complex may be an N,N'-disalicylidene C2-5 alkylenediamine complex with manganese, iron, cobalt, copper, or vanadium. The cyclic base may be an alicyclic or aromtaic compound having at least two nitrogen atoms. As the basic nitrogen-containing compound, a Schiff base such as an imino compound and an anil compound can be used. The proportion of the nitrogen-containing compound to the complex is about 0.1/1 to 20/1 (molar ratio). With the above oxydation catalytic system, there can be obtained ketoisophorone and derivatives thereof with high efficiency.
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-
- Excited state interactions of thiopyrylium salts
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The photophysics and photochemistry of thiopyrylium salts have been investigated by UV-VIS absorption spectroscopy and nanosecond laser absorption spectroscopy. The effect of substituents of the heterocycle on the photophysical properties was analysed. Dissociation of peroxidic compounds photosensitized by these salts was studied. The interaction with monomers and many other additives has also been investigated. A mechanism is proposed for the initiation of acrylic photopolymerization reactions.
- Morlet-Savary,Parret,Fouassier,Inomata,Matsumoto
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p. 745 - 752
(2007/10/03)
-
- Photochemical mechanisms responsible for the versatile application of naphthalimides and naphthaldiimides in biological systems
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Despite the number and variety of their biological applications, the mechanisms of action of the photoactive naphthalenic imides have not yet been fully elucidated. In order to provide mechanistic insight, the photochemistry of several N-substituted 1,8-naphthalimides (NT) and 1,4,5,8-naphthaldiimides (NDI) has been studied using absorption and fluorescence spectroscopy and by laser flash photolysis (λ(exc) = 355 nm). The lowest singlet state (S1) is mainly ππ* in nature for NI whereas nπ* character predominates for the NDI. This difference exerts a profound effect on subsequent reaction mechanisms: upon irradiation, only the NDI molecules can undergo intramolecular γ hydrogen abstraction. In the case of NP-III, a bishydroperoxy NDI derivative, this photoprocess (Φ = 0.03) leads to concomitant formation of an oxygen-centered radical (ε = 21,600 M-1 cm-1 at 465 nm in acetonitrile) and release of the hydroxyl radical (.OH). All the compounds studied produce the triplet state (in acetonitrile, ε(T) ~ 10,500-11,500 M-1 cm-1 at 470 nm for NI and 485 nm for NDI). The quantum yield of intersystem crossing was determined to be close to unity except where intramolecular γ hydrogen abstraction was possible (Φ(isc) 0.8 for NI and > 0.5 for NDI). In the absence of quenchers, the triplet states react with the ground-state of starting material via electron-transfer with a high rate constant [k = (4-6) x 109 and 5 x 108 M-1 s-1 for NDI and NI, respectively] to give the radical anion and radical cation of the corresponding naphthalenic derivative. The high reactivity of the triplet states toward electron donors such as DABCO and their low ability for hydrogen abstraction are typical of a ππ* configuration. These mechanistic photochemistry results are discussed with regard to the photobiological effects observed for these compounds and show that the actual reaction leading to biological damage will depend on the microenvironment of the naphthalenic molecule.
- Aveline, Béatrice M.,Matsugo, Seiichi,Redmond, Robert W.
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p. 11785 - 11795
(2007/10/03)
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- Quinolone- and naphthyridonecarboxylic acid derivatives
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Disclosed are new quinolone- and naphthyridonecarboxyclic acid derivatives of the formula: STR1 wherein T represents a radical of the formula: STR2 and the other radicals are as disclosed herein, for example, the compound 7-(3a-amino-1,2,3,7a-tetrahydro-isoindol-2-yl)-1-cyclopropyl-6-fluoro-1,4-dihydro-8-methoxy-4-oxo-3-quinolinecarboxyclic acid, their salts, antibacterial compositions containing them, processes for their preparation, and methods of using them to combat bacterial infections. Disclosed also are intermediates useful in said processes of preparation.
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- DNA gyrase inhibitors and pharmaceutical preparations therefor
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Bicyclic derivatives of the formula STR1 wherein X1, X2, R1, R2, R3, R4, R5, R6, R7a, R7b, and R8 are as defined in the specification. These compounds are antimicrobially active.
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- Linear dicarbonylation of difunctionalized butenes
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Difunctional butenes are linearly dicarbonylated into 3-hexene-1,6-dioic acid or alkyl diesters thereof, well suited for the ultimate production of, e.g., adipic acid, by reacting such difunctional butene with carbon monoxide and, if appropriate, an alcohol, at an elevated temperature under superatmospheric pressure, in the presence of at least one source of hydrogen chloride and a catalytically effective amount of palladium, at least a portion of which palladium being in the zero oxidation state, as well as a quaternary onium chloride of nitrogen or phosphorus, the nitrogen or phosphorus atom being tetracoordinated to carbon atoms, with the proviso that the nitrogen atom may be coordinated to two pentavalent phosphorus atoms.
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- Catalytic Synthesis Of Aziridine From 1,2-Diaminoethane
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The contact conversion of 1,2-diaminoethane over a tungsten trioxide catalyst at 240-580 deg C has been studied by an impulse chromatographic method.The basic reaction path under these conditions is unimolecular deaminocyclization to give aziridine (31-35percent).Piperazine and triethylenediamine, products of bi- and trimolecular deaminocyclization, are present as products.The deamination process is accompanied by coupled dehydrogenation and hydrogenolysis reactions.Addition of the acid anhydrides SiO2, P2O5 and B2O3 to the catalyst increases its activity but has onlyanegligible affect on the activation energy of the process.
- Anderson, A. A.,Simonyan, S. P.,Shimanskaya, M. V.
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p. 1134 - 1141
(2007/10/02)
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- Process for the stereochemical inversion of (2S,3S)-2-amino-3-phenyl-1,3-propanediols into their (2R,3R) enantiomers
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A four step process for transforming (2S,3S)-2-amino-3-phenyl-1,3-propanediols into their (2R,3R)-enantiomers is described. The final compounds are useful intermediates for the synthesis of antibiotics like Chloramphenicol, Thiamphenicol and Florfenicol. The starting products generally are discard products in the synthesis of said antibiotics.
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- Process for preparation of fluoromethyl-substituted dihydropyridine carbodithioates
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A process for dehydration of a 4-(lower alkyl)-2,6-bis(trifluoromethyl)-2,6-bis(hydroxy)-piperidine-3,5-dicarboxylic acid thioesters and esters.
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- Process for preparation of fluoromethyl-substituted pyridine carbodithioates
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A process for dehydrofluorination of a 2,6-(bis) trifluoromethyl-dihydropyridine-3,5-dicarbothioic acid ester.
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- The Reactions of Amine, Polyamine and Amino Alcohol Corrosion Inhibitors in Water at High Temperatures
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A stainless steel reactor has been used to investigate the reactions of mono-, di-, tri- and tetraamines, amino alcohols and amino ethers in degassed aqueous solution at 240-300 deg C.The predominant reactions involved nucleophilic substitutions, where the amino nitrogen acts as the nucleophile, and not solvolyses.With α,ω-diamines, cyclic and bicyclic amines were formed by inter- or intra-molecular processes.Amino alcohols react by displacement of the hydroxy rather than the amino group.The material balance deficit, however, was generally significant, and it issuggested that the missing materials are polyamines arising from polymerisation that competes with cyclisation.The major product from 1,2-diaminoethane and related polyaminoethanes and ethanolamines is diazabicyclooctane.The kinetics of some of the cyclisations were studied.Reactions of α,ω-diamines and 5-aminopentan-1-ol are first order in reactant.Conversion of 1,4-diaminobutane to pyrrolidine occurs with high selectivity at 240 deg C; in contrast the reactions of the less reactive compounds were less selective, probably due to the formation of polymeric materials.The relative reactivity of the substrates is discussed in detail.
- Smith, John R. Lindsay,Smart, Alison U.,Twigg, Martyn V.
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p. 939 - 947
(2007/10/02)
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- A flash photolysis study of the oxidation of aliphatic amines by phosphate radical
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Rate constants for the reaction of the phosphate radical (PO42-) with various aliphatic amines have been measured by flash kinetic spectrophotometry.Phosphate radical can react with aliphatic amines by hydrogen atom abstraction or electron transfer, the general reactivity order being tertiary secondary primary.For tertiary amines, a good correlation has been obtained when the logarithm of rate constants are plotted against the oxidation peak potentials of the amines, providing clear evidence for an electron transfer mechanism.In the case of tertiary amines, electron transfer from the nitrogen takes place.The identification of aminium cation radicals in the case of cyclic tertiary amines like, 1,4-diazabicyclooctane (DABCO) and 1,3,6,8-tetraazatricyclododecane (TATCD) provides additional proof for electron transfer.Primary and secondary amines get oxidized mainly by hydrogen atom abstraction as shown by the poor correlation with Taft substituent constants, but electron transfer cannot be completely ruled out.In the case of t-butylamine, electron transfer takes place and t-butylalcohol has been identified as the end product.
- Subramanian, P,Rajaram, J,Ramarkrishnan, V,Kuriacose, J C
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p. 913 - 919
(2007/10/02)
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- Process for preparation of fluoromethyl-substituted piperidine carbodithioates
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Described herein is a process for dehydrohalogenation of substituted dihydropyridine dicarbothioate compounds.
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- Process for preparation of fluoromethyl-substituted pyridine dicarboxylates
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Described herein is a process for preparation of substituted pyridine dicarboxylate compounds.
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- Process for the stereochemical inversion of (2S,3S)-2-amino-3-phenyl-1,3-propanediols into their (2R,3R) enantiomers
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A four step process for transforming (2S,3S)-2-amino-3-phenyl-1,3--propanediols into their (2R,3R)-enantiomers is described. The final compounds are useful intermediates for the synthesis of antibiotics like Chloramphenicol, Thiamphenicol and Florfenicol. The starting products generally are discard products in the syn-thesis of said antibiotics.
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- Process for preparation of fluoromethyl-substituted piperidine carbodithioates
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Described herein is a process for preparation of substituted piperidine dicarbothioate compounds.
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- Fluorinated triethylenediamine as an oxygen transport agent
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Fluorinated triethylenediamine compounds such as perfluorotriethylenediamine and the novel compounds undecafluorotriethylenediamine and decafluorotriethylenediamine, prepared by indirect fluorination of triethylenediamine by passing triethylenediamine over, e.g., cobalt trifluoride (CoF3), is useful as a material capable of carrying oxygen in an aqueous emulsion for lifesaving a patient suffering from massive hemorrhage and for preserving internal organs in transplantation. The compounds undergo rapid biological elimination due to their low molecular weight.
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- THE NUCLEOPHILIC ATTACK OF A VINYL-HALO-PHOSPHINE BY A TERTIARY AMINE: A NEW ACCESS TO PHOSPHAALKENES
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The reaction of DABCO with (2,4,6-tris-tertiobutylphenyl)(vinyl) halo phosphine (X=Cl, Br) yields the corresponding 1-(2,4,6-tris-tertiobutylphenyl)-2-ammoniomethyl phosphaethene via a SN2'-like attack at the vinylic CH2.
- Mercier, F,Mathey, F.
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p. 5269 - 5270
(2007/10/02)
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- Preparation of silane and amine alanes
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Process for the preparation of silane and a tertiary amine alane, said process comprising reacting: (a) an alkali metal aluminum tetrahydride having the formula MAlH4, wherein M is an alkali metal selected from the class consisting of lithium, sodium and potassium, (b) silicon tetrachloride, and (c) a complexing tertiary amine, such that the molar proportion of (a) to (b) to (c) is about 4:1:4. In this process, NaAlH4 and triethylamine are preferred reactants. The amine alane product can be reacted with additional silicon halide to prepare additional silane. This step can be conducted utilizing amine alane in the reaction mixture produced by the process above, and is preferably conducted using SiF4 as the silicon tetrahalide to produce AlF3 as a co-product. Both AlF3 and silane are valuable articles of commerce.
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