- Methyl modified MOF-5: A water stable hydrogen storage material
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Water stable methyl modified MOF-5s have been synthesized via a solvothermal route. Methyl- and 2,5-dimethyl-modified MOF-5s show the same topology and hydrogen uptake capability as that of MOF-5. The H2 uptake capacity of MOF-5, however, drops
- Yang, Jie,Grzech, Anna,Mulder, Fokko M.,Dingemans, Theo J.
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Read Online
- Functionalization of coordination nanochannels for controlling tacticity in radical vinyl polymerization
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Systematic functionalization of porous coordination polymers (PCPs), [Cu2(L)2(ted)]n (where L = dicarboxylates and ted = triethylenediamine), by introducing various substituents onto the component organic ligand, L, was performed to regulate the radical polymerization of methyl methacrylate (MMA) in the nanochannels. The effect of the substituent groups on stereoregularity of the resulting poly(methyl methacrylate) (PMMA) was observed, where the tacticity of the PMMA strongly depended on the number and position of the substituent. In particular, polymerization of MMA in [Cu2(2,5-dimethoxyterephthalate) 2(ted)]n gave PMMA with high isotactic and heterotactic triad fractions, which is one of the most effective systems for changing the tacticity of PMMA in radical polymerization. To understand the mechanism of this drastic stereoregularity change, a variety of experimental and theoretical analyses, such as IR, N2 adsorption, a statics study, and molecular dynamics (MD) calculations, were performed. Accurate MD calculations were helpful to determine the most plausible structures of [Cu2(L) 2(ted)]n and revealed that the specific channel shape of [Cu2(2,5-dimethoxyterephthalate)2(ted)]n induces the large tacticity change of the resulting PMMA.
- Uemura, Takashi,Ono, Yukari,Hijikata, Yuh,Kitagawa, Susumu
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Read Online
- An: In situ approach to functionalize metal-organic frameworks with tertiary aliphatic amino groups
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Metal-catalyzed reductive amination of formyl-containing linkers with N,N-dialkylformamide solvents is concomitant with the solvothermal coordination assembly, leading to novel MOFs functionalized with tertiary aliphatic amino groups. This illustrates a novel one-pot strategy to functionalize MOFs through in situ organic transformation. The UiO-66 MOFs partially functionalized with the amino groups are highly active heterogeneous catalysts for Knoevenagel condensation.
- Xi, Fu-Gui,Sun, Wei,Dong, Zhi-Yun,Yang, Ning-Ning,Gong, Teng,Gao, En-Qing
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supporting information
p. 13177 - 13180
(2020/11/09)
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- Method for preparing 1-oxo-1,3-dihydro-3-hydroxybenzofuran-5-formic acid
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The invention discloses a method for preparing 1-oxo-1,3-dihydro-3-hydroxybenzofuran-5-formic acid. The method disclosed by the invention comprises the following steps: dissolving 2,5-toluene dihalideinto a tetrahydrofuran solution, carrying out a reactio
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Paragraph 0031; 0033; 0035-0036
(2019/11/28)
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- Tandem one-pot CO2 reduction by PMHS and silyloxycarbonylation of aryl/vinyl halides to access carboxylic acids
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The present study discloses the synthesis of aryl/vinyl carboxylic acids from Csp2-bound halides (Cl, Br, I) in a carbonylative path by using silyl formate (from CO2 and hydrosilane) as an instant CO-surrogate. Hydrosilane provides hydride for reduction and its oxidation product silanol serves as a coupling partner. Mono-, di-, and tri-carboxylic acids were obtained from the corresponding aryl/vinyl halides.
- Paridala, Kumaraswamy,Lu, Sheng-Mei,Wang, Meng-Meng,Li, Can
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supporting information
p. 11574 - 11577
(2018/10/31)
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- Synthesis and solvent-free polymerisation of vinyl terephthalate for application as an anode material in organic batteries
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The synthesis and polymerisation of dimethyl 2-vinylterephthalate M1 for possible applications as an anode material in organic secondary batteries are reported. M1 exhibits a vinyl group as a polymerisable unit while the carboxylate moieties serve as cation (Li+, Na+) coordinating sites. The gram-scale synthesis of M1 is described via three different routes in order to evaluate the route with the highest overall yield. Furthermore, different conditions for free radical polymerisation are investigated for obtaining polymer P1 with high molecular weights in order to study the impact of immobilising the carboxylate redox-active centres in a polymer on the charge/discharge cycling stability when used in an organic battery. In order to synthesis suitable materials for battery investigations, P1 was post-functionalised to the corresponding lithium salt P1-Li, which was further electrochemically investigated. Cyclic voltammetry measurements showed for P1-Li redox activity in the range of 0.5-1.2 V vs. Li+/Li which assigns it as a candidate for the anode. Under the present experimental conditions, the galvanostatic measurements of P1-Li exhibited a specific capacity of 64 mA h g1. It is further demonstrated that P1-Li shows an improved cycling stability of 83% discharge capacity remaining after 100 cycles compared to the parent monomer (44%).
- Nauroozi, Djawed,Pejic, Marijana,Schwartz, Pierre-Olivier,Wachtler, Mario,B?uerle, Peter
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p. 111350 - 111357
(2016/12/03)
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- Cerium-based metal organic frameworks with UiO-66 architecture: Synthesis, properties and redox catalytic activity
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A series of nine Ce(IV)-based metal organic frameworks with the UiO-66 structure containing linker molecules of different sizes and functionalities were obtained under mild synthesis conditions and short reaction times. Thermal and chemical stabilities were determined and a Ce-UiO-66-BDC/TEMPO system was successfully employed for the aerobic oxidation of benzyl alcohol.
- Lammert, Martin,Wharmby, Michael T.,Smolders, Simon,Bueken, Bart,Lieb, Alexandra,Lomachenko, Kirill A.,De Vos, Dirk,Stock, Norbert
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supporting information
p. 12578 - 12581
(2015/08/06)
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- Inclusion complex containing epoxy resin composition for semiconductor encapsulation
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The invention is an epoxy resin composition for sealing a semiconductor, including (A) an epoxy resin and (B) a clathrate complex. The clathrate complex is one of (b1) an aromatic carboxylic acid compound, and (b2) at least one imidazole compound represented by formula (II): wherein R2 represents a hydrogen atom, C1-C10 alkyl group, phenyl group, benzyl group or cyanoethyl group, and R3 to R5 represent a hydrogen atom, nitro group, halogen atom, C1-C20 alkyl group, phenyl group, benzyl group, hydroxymethyl group or C1-C20 acyl group. The composition has improved storage stability, retains flowability when sealing, and achieves an effective curing rate applicable for sealing delicate semiconductors.
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- Single- and mixed-linker Cr-MIL-101 derivatives: A high-throughput investigation
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New single- and mixed-linker Cr-MIL-101 derivatives bearing different functional groups have been synthesized. The influence of the reaction parameters, such as metal source (CrO3, CrCl3, and Cr(NO3)3·9H2O) or linker composition, on product formation have been investigated using high-throughput methods. Highly crystalline Cr-MIL-101 materials were obtained with CrCl3 as the metal source with either 2-bromoterephthalic (TA-Br) or 2-nitroterephthalic (TA-NO2) acid as one of the mixed-linker components. On the basis of these results, numerous new mixed-linker Cr-MIL-101 derivatives containing -NH2, -NO2, -H, -SO3H, -Br, -OH, -CH 3, and -COOH have been synthesized. The use of TA-NH2 and TA-OH were shown, under the same reaction conditions, to lead to decarboxylation and the formation of 3-amino- and 3-hydroxybenzoic acid, respectively. Furthermore, we were also able to directly synthesize single-linker Cr-MIL-101-X derivatives with X = F, Cl, Br, CH3. Postsynthetic modification was used to selectively reduce the mixed-linker compound Cr-MIL-101-Br-NO 2 to Cr-MIL-101-Br-NH2. To establish the successful incorporation of the linker molecules and possible decomposition of certain starting materials, 1H NMR spectra of dissolved reaction products were recorded.
- Lammert, Martin,Bernt, Stephan,Vermoortele, Frederik,De Vos, Dirk E.,Stock, Norbert
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supporting information
p. 8521 - 8528
(2013/09/02)
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- PROCESS FOR PRODUCING AROMATIC POLYCARBOXYLIC ACID
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A process for producing an aromatic polycarboxylic acid in which all alkyl groups are converted into carboxyl groups in a high yield by decreasing a residual amount of an intermediate product is provided. The process comprises oxygen-oxidizing an aromatic compound having a plurality of alkyl groups (e.g., durene) in the presence of a catalyst containing a cyclic imino unit having an N—OR group (wherein R represents a hydrogen atom or a protecting group for a hydroxyl group) and a transition metal co-catalyst (e.g., a cobalt compound, a manganese compound, and a zirconium compound) under heating in a lower-temperature zone and a higher-temperature zone to produce an aromatic polycarboxylic acid in which a plurality of alkyl groups are oxidized into carboxyl groups. In an initial stage of the reaction, the reaction may be conducted in a first lower-temperature zone (a reaction temperature of 60 to 120° C. and a second lower-temperature zone (an intermediate temperature zone) (a reaction temperature of 100 to 140° C.); and then, in a latter stage of the reaction, the reaction may be conducted in a higher-temperature zone (a reaction temperature of 110 to 150° C.).
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Page/Page column 14
(2011/04/18)
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- SOLID INORGANIC/ORGANIC HYBRID WITH MODIFIED SURFACE
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The invention relates to solid organometallic hybrids with modified surface. Said solid may be used for example for the encapsulation and vectoring of molecules of interest such as active pharmaceutical agents, compounds of interest in cosmetics and markers, for example, contrast agents. Said solids show good results in terms of loading capacity in medicament agents and in biocompatibility.
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- Functionalization in flexible porous solids: Effects on the pore opening and the host-guest interactions
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The synthesis on the gram scale and characterization of a series of flexible functionalized iron terephthalate MIL-53(Fe) type solids are reported. Chemical groups of various polarities, hydrophilicities, and acidities (-Cl, -Br, -CF3, -CH3, -NH2, -OH, -CO2H) were introduced through the aromatic linker, to systematically modify the pore surface. X-ray powder diffraction (XRPD), molecular simulations, thermogravimetric analyses, and in situ IR and 57Fe Moessbauer spectrometries indicate some similarities with the pristine MIL-53(Fe) solid, with the adoption of the narrow pore form for all solids in both the hydrated and dry forms. Combined XRPD and computational structure determinations allow concluding that the geometry of the pore opening is predominantly correlated with the intraframework interactions rather than the steric hindrance of the substituent. Only (MIL-53(Fe)-(CF3)2) exhibits a nitrogen accessible porosity (SBET ≈ 100 m2 g-1). The adsorption of some liquids leads to pore openings showing some very specific behaviors depending on the guest-MIL-53(Fe) framework interactions, which can be related to the energy difference between the narrow and large pore forms evaluated by molecular simulation.
- Devic, Thomas,Horcajada, Patricia,Serre, Christian,Salles, Fabrice,Maurin, Guillaume,Moulin, Beatrice,Heurtaux, Daniela,Clet, Guillaume,Vimont, Alexandre,Greneche, Jean-Marc,Le Ouay, Benjamin,Moreau, Florian,Magnier, Emmanuel,Filinchuk, Yaroslav,Marrot, Jerome,Lavalley, Jean-Claude,Daturi, Marco,Ferey, Gerard
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supporting information; experimental part
p. 1127 - 1136
(2010/04/01)
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- ORGANIC/INORGANIC HYBRID NANOPARTICULATES MADE FROM IRON CARBOXYLATES
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The invention relates to nanoparticles made from organometallic hybrid materials made from iron carboxylates, used for example as contrast agents. The particles can also be used for the encapsulation and vectoring of molecules of interest such as active3 pharmaceutical agents, cosmetically interesting compounds and markers. Apart from the intrinsic properties thereof for imaging, said nanoparticles give good results in terms of capacity for loading with medicaments and in biocompatibility.
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(2010/08/22)
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- DIPEPTIDYL PEPTIDASE-IV INHIBITORS
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The present invention relates generally to pyrrolidine and thiazolidine DPP-IV inhibitor compounds. The present invention also provides synthetic methods for preparation of such compounds, methods of inhibiting DPP-IV using such compounds and pharmaceutical formulations containing them for treatment of DPP-IV mediated diseases, in particular, Type-2 diabetes.
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Page/Page column 77
(2008/06/13)
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- Aerobic oxidation of trimethylbenzenes catalyzed by N,N′,N″-trihydroxyisocyanuric acid (THICA) as a key catalyst
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The oxidation of trimethylbenzenes was examined with air or O2 using N,N′,N″-trihydroxyisocyanuric acid (THICA) as a key catalyst. Thus, 1,2,3-, 1,2,4-, and 1,3,5-trimethylbenzenes under air (20 atm) in the presence of THICA (5 mol %), Co(OAc)2 (0.5 mol %), Mn(OAc)2, and ZrO(OAc)2 at 150 °C were oxidized to the corresponding benzenetricarboxylic acids in good yields (81-97%). In the aerobic oxidation of 1,2,4-trimethylbenzene by the THICA/Co(II)/Mn(II) system, remarkable acceleration was observed by adding a very small amount of ZrO(OAc)2 to the reaction system to form 1,2,4-benzenetricarboxylic acid in excellent yield (97%). In contrast, no considerable addition effect was observed in the oxidation of 1,3,5-trimethylbenzene. This aerobic oxidation by the present catalytic system provides an economical and environmentally benign direct method to benzenetricarboxylic acids, which are very important polymer materials.
- Hirai, Naruhisa,Tatsukawa, Yoshinobu,Kameda, Michiko,Sakaguchi, Satoshi,Ishii, Yasutaka
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p. 6695 - 6699
(2007/10/03)
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- ALKYL CARBOXYLATE SALTS AS SOLVENTS FOR HENKEL-RELATED PROCESSES
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Disclosed is the use of one or more molten salts or a mixture thereof for use as a reaction medium in a process for the preparation of an aromatic diacid which comprises heating an alkali metal salt of an aromatic monocarboxylic acid or asymmetrical aromatic dicarboxylic acid under pressure with carbon dioxide gas in the presence of a catalyst at suitable reaction conditions. The molten salt reaction medium provides advantages in a disproportionation reaction to produce, for example, purified terephthalic acid. In another aspect of the invention, novel methylated diacids are produced.
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Page/Page column 6-7
(2008/06/13)
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- Minor groove DNA binders as antimicrobial agents. 1. Pyrrole tetraamides are potent antibacterials against vancomycin resistant Enteroccoci and methicillin resistant Staphylococcus aureus
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A new series of short pyrrole tetraamides are described whose submicromolar DNA binding affinity is an essential component for their strong antibacterial activity. This class of compounds is related to the linked bis-netropsins and bis-distamycins, but here, only one amino-pyrrole-carboxamide unit and an amidine tail is connected to either side of a central dicarboxylic acid linker. The highest degree of DNA binding, measured by compound-induced changes in UV melting temperatures of an AT-rich DNA oligomer, was observed for flat, aromatic linkers with no inherent bent, i.e., terephthalic acid or 1,4-pyridine-dicarboxylic acid. However, the antibacterial activity is critically linked to the size of the N-alkyl substiutent of the pyrrole unit. None of the tetraamides with the commonly used methyl-pyrrole showed antibacterial activity. Isoamyl- or cyclopropylmethylene-substituted dipyrrole derivatives have the minimum inhibitory concentrations in the submicromolar range. In vitro toxicity against human T-cells was studied for all compounds. The degree to which compounds inhibited cell growth was neither directly correlated to DNA binding affinity nor directly correlated to antibacterial activity but seemed to depend strongly on the nature of the N-alkyl pyrrole substituents.
- Dyatkina, Natalia B.,Roberts, Christopher D.,Keicher, Jesse D.,Dai, Yuqin,Nadherny, Joshua P.,Zhang, Wentao,Schmitz, Uli,Kongpachith, Ana,Fung, Kevin,Novikov, Alexander A.,Lou, Lillian,Velligan, Mark,Khorlin, Alexander A.,Chen, Ming S.
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p. 805 - 817
(2007/10/03)
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- Process for introducing a carboxyl group to an aromatic carboxylic acid or a derivative thereof
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Disclosed is a process for introducing a carboxyl group to an aromatic carboxylic acid or a derivative thereof, which comprises reacting a starting aromatic carboxylic acid, such as a benzoic acid, a biphenylcarboxylic acid, a naphthalenecarboxylic acid, a diphenylcarboxylic acid, or a derivative thereof, with a carbon tetrahalide in the presence of a cyclodextrin and an alkali metal hydroxide, thereby introducing a carboxyl group to the aromatic ring of the starting aromatic carboxylic acid or the derivative thereof in substitution for a hydrogen atom bonded thereto. By the process of the present invention, a desired aromatic polycarboxylic acid or a derivative thereof can be easily obtained with high selectivity.
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- Substituent Effects on Hydrogenation of Aromatic Rings: Hydrogenation vs. Hydrogenolysis in Cyclic Analogues of Benzyl Ethers.
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Carbalkoxy substituents are shown to retard the hydrogenation of aromatic rings over Rh/C catalyst.Hydrogenolysis predominates with acyclic (benzyloxy)acetates over this catalyst, but both hydrogenation and hydrogenolysis become sluggish with 2-isochroman-4-ones (1).However, phthalides may be cleanly hydrogenated in moderate to excellent yields without significant hydrogenolysis.Placing a benzyl ether in a ring system appears to greatly retard hydrogenolysis relative to the acyclic analogues.
- Anzalone, Luigi,Hirsch, Jerry A.
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p. 2128 - 2133
(2007/10/02)
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