280-57-9Relevant articles and documents
Generation of a Mn(IV)-Peroxo or Mn(III)-Oxo-Mn(III) Species upon Oxygenation of Mono- and Binuclear Thiolate-Ligated Mn(II) Complexes
Lee, Chien-Ming,Wu, Wun-Yan,Chiang, Ming-Hsi,Bohle, D. Scott,Lee, Gene-Hsiang
, p. 10559 - 10569 (2017)
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.
Degradation of Organic Cations under Alkaline Conditions
You, Wei,Hugar, Kristina M.,Selhorst, Ryan C.,Treichel, Megan,Peltier, Cheyenne R.,Noonan, Kevin J. T.,Coates, Geoffrey W.
supporting information, p. 254 - 263 (2020/12/23)
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.
Synthesis method of triethylene diamine
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Paragraph 0031; 0033-0036; 0038-0041; 0043-0046; 0048-0051, (2020/09/16)
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.
METHOD FOR PRODUCING PIPERAZINE AND TRIETHYLENEDIAMINE
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Paragraph 0055; 0056; 0057; 0058, (2017/07/19)
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
METHOD FOR PRODUCING BICYCLIC AMINE COMPOUND
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Paragraph 0047; 0054, (2017/11/15)
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
Hetero Face-to-Face Porphyrin Array with Cooperative Effects of Coordination and Host–Guest Complexation
Chiba, Yusuke,Liu, Maning,Tachibana, Yasuhiro,Fujihara, Tetsuaki,Tsuji, Yasushi,Terao, Jun
supporting information, p. 1900 - 1904 (2017/08/10)
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.
MANUFACTURING METHOD OF PIPERAZINE AND TRIETHYLENE DIAMINE
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Paragraph 0047; 0048; 0049, (2017/10/07)
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
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
Goli-Jolodar, Omid,Shirini, Farhad,Seddighi, Mohadeseh
, p. 26026 - 26037 (2016/03/25)
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.
METHOD OF PRODUCING BICYCLIC AMINE COMPOUND
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Paragraph 0057; 0064; 0065, (2017/04/22)
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
The method of manufacturing the amine compound Bicylic
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Paragraph 0058-0060; 0062, (2017/04/19)
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
