- Nanotubular structures through templateless electropolymerization using thieno[3,4-b]thiophene derivatives with different substituents and water content
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Here, we report a strategy to prepare controllable nanotubular structures using a templateless electropolymerization process in organic solvent (CH2Cl2) and without surfactant. We use thieno [3,4-b]thiophene derivatives with various substituents including hydrocarbon chains, fluorocarbon chains and aromatic groups of various size. The influence of the water content (CH2Cl2 + H2O) in also studied in order to release in-situ a higher amount of gas bubbles (O2 and/or H2). The best results are obtained with the pyrene substituent, which lead to highly densely packed nanotubular structures while the water content allows to highly increase their porosity, changing the resulting surface morphology from tree-like to coral-like structure. This is probably due to both high π-stacking interaction of pyrene and its polymerization capacity in the same potential range. This change also induces an increase in surface hydrophilicity because the water highly penetrates these porous structures. Moreover, both the poly (thieno [3,4-b]thiophene) polymers and the substituents participate to the film fluorescence while the nanostructures seem to amplify their intensity. Such surfaces are extremely interesting for potential applications in sensors or in water harvesting systems.
- Sane, Omar,Diouf, Alioune,Pan, Miaobo,Morán Cruz, Gabriela,Savina,Méallet-Renault, Rachel,Dieng, Samba Yandé,Amigoni,Guittard, Frédéric,Darmanin, Thierry
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Read Online
- New Series of Potent Allosteric Inhibitors of Deoxyhypusine Synthase
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Deoxyhypusine synthase (DHPS) is the primary enzyme responsible for the hypusine modification and, thereby, activation of the eukaryotic translation initiation factor 5A (eIF5A), which is key in regulating the protein translation processes associated with tumor proliferation. Although DHPS inhibitors could be a promising therapeutic option for treating cancer, only a few studies reported druglike compounds with this inhibition property. Thus, in this work, we designed and synthesized a new chemical series possessing fused ring scaffolds designed from high-throughput screening hit compounds, discovering a 5,6-dihydrothieno[2,3-c]pyridine derivative (26d) with potent inhibitory activity; furthermore, the X-ray crystallographic analysis of the DHPS complex with 26d demonstrated a distinct allosteric binding mode compared to a previously reported inhibitor. These findings could be significantly useful in the functional analysis of conformational changes in DHPS as well as the structure-based design of allosteric inhibitors.
- Tanaka, Yuta,Kurasawa, Osamu,Yokota, Akihiro,Klein, Michael G.,Saito, Bunnai,Matsumoto, Shigemitsu,Okaniwa, Masanori,Ambrus-Aikelin, Geza,Uchiyama, Noriko,Morishita, Daisuke,Kimura, Hiromichi,Imamura, Shinichi
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supporting information
p. 1645 - 1652
(2020/09/15)
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- Isomerizing thieno[3,4-: B] thiophene-based near-infrared non-fullerene acceptors towards efficient organic solar cells
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With the rapid growth in the requirement for emerging photovoltaic technology like semitransparent solar cells applied for integrated smart windows, there is an urgent need to develop near-infrared (NIR) non-fullerene acceptors (NFAs). To address this issue, thieno[3,4-b]thiophene (TT), which has a stable quinoid structure to minimize the energy difference between two resonance structures corresponding to the band gap, is introduced into the push-pull molecular architecture as a bridge unit to narrow the band gap of the derived acceptors. Due to the different linkage positions (4-or 6-position) of asymmetric TT, these acceptors are classified into two types of isomers, namely 4TIC, 4T4F, 6TIC and 6T4F, of which all have strong absorption in the NIR range. By incorporation with polymer donor PTB7-Th, the devices based on 6-position isomers exhibit superior photovoltaic performance, wherein a champion device based on 6T4F is obtained with a power conversion efficiency of 10.74%. With detailed investigations on inherent optoelectronic properties as well as structural and morphological variation, this performance diversity induced by isomerism is determined by the evident difference in the packing order, which will impact the charge mobility and fill factor. This work presents a class of high-performance NIR acceptors in which the regioisomeric backbone will significantly impact the optoelectronic properties.
- Kong, Lingwei,Liu, Feng,Shan, Tong,Zhang, Yi,Zhang, Zeqi,Zhong, Hongliang,Zhu, Lei
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supporting information
p. 4357 - 4364
(2020/04/15)
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- DINAPHTHOTHIOPHENE COMPOUNDS
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The present invention generally relates to various dinaphthothiophene compounds and processes for preparing these compounds.
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Paragraph 0050; 0051
(2019/01/04)
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- Synthesis of Unsymmetric Monosubstituted and Disubstituted Dinaphthothiophenes
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Dinaphthothiophenes (DNTs) are a class of compounds with potential uses in organic semiconductors and the synthesis of unsymmetric catalysts. Symmetrical or asymmetrical addition of functional groups to the DNT structure may be desired for steric bulk in binaphthyl catalyst synthesis or tuning the electronic properties of semiconductors. Thus, versatility of functional group addition is a great asset in DNT synthesis. Until now, no versatile and concise methods for the synthesis of unsymmetrically substituted DNTs have been reported. Herein, we report three synthetic routes for the creation of three different classes of DNTs. Each route involves the successive addition of two functionalized styryl groups to a thiophene ring, followed by a photocyclization to form the desired asymmetric DNT. Various novel unsymmetrically monosubstituted and disubstituted dinaphtho[2,1-b:1′,2′-d]thiophenes, dinaphtho[1,2-b:1′,2′-d]thiophenes, and dinaphtho[1,2-b:2′,1′-d]thiophenes were synthesized from 2-bromothiophene,2,4-dibromothiophene, and 3,4-dibromothiophene in three or four steps. These methods can be used to synthesize a wide variety of unsymmetrically functionalized DNTs.
- Throgmorton, John C.,Chintala, Satyanarayana M.,McCulla, Ryan D.
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supporting information
p. 3682 - 3688
(2017/10/09)
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- Oligothiophene-Bridged Conjugated Covalent Organic Frameworks
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Two-dimensional covalent organic frameworks (2D-COFs) are crystalline, porous materials comprising aligned columns of π-stacked building blocks. With a view toward the application of these materials in organic electronics and optoelectronics, the construction of oligothiophene-based COFs would be highly desirable. The realization of such materials, however, has remained a challenge, in particular with respect to laterally conjugated imine-linked COFs. We have developed a new building block design employing an asymmetric modification on an otherwise symmetric backbone that allows us to construct a series of highly crystalline quaterthiophene-derived COFs with tunable electronic properties. Studying the optical response of these materials, we have observed for the first time the formation of a charge transfer state between the COF subunits across the imine bond. We believe that our new building block design provides a general strategy for the construction of well-ordered COFs from various extended building blocks, thus greatly expanding the range of applicable molecules.
- Keller, Niklas,Bessinger, Derya,Reuter, Stephan,Calik, Mona,Ascherl, Laura,Hanusch, Fabian C.,Auras, Florian,Bein, Thomas
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supporting information
p. 8194 - 8199
(2017/06/27)
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- A Computational and Experimental Study of Thieno[3,4-b]thiophene as a Proaromatic π-Bridge in Dye-Sensitized Solar Cells
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Four D-π-A dyes (D=donor, A=accpetor) based on a 3,4-thienothiophene π-bridge were synthesized for use in dye-sensitized solar cells (DSCs). The proaromatic building block 3,4-thienothiophene is incorporated to stabilize dye excited-state oxidation potentials. This lowering of the excited-state energy levels allows for deeper absorption into the NIR region with relatively low molecular weight dyes. The influence of proaromatic functionality is probed through a computational analysis of optimized bond lengths and nucleus independent chemical shifts (NICS) for both the ground- and excited- states. To avoid a necessary lowering of the TiO2 semiconductor conduction band (CB) to promote efficient dye-TiO2 electron injection, strong donor functionalities based on triaryl- and diarylamines are employed in the dye designs to raise both the ground- and excited-state oxidation potentials of the dyes. Solubility, aggregation, and TiO2 surface protection are addressed by examining an ethylhexyl alkyl chain in comparison to a simple ethyl chain on the 3,4-thienothiophene bridge. Power conversion efficiencies of up to 7.8 % are observed.
- Brogdon, Phillip,Giordano, Fabrizio,Puneky, George A.,Dass, Amala,Zakeeruddin, Shaik M.,Nazeeruddin, Mohammad Khaja,Gr?tzel, Michael,Tschumper, Gregory S.,Delcamp, Jared H.
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supporting information
p. 694 - 703
(2016/01/12)
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- PYRROLOTRIAZINE INHIBITORS OF IRAK4 ACTIVITY
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The present invention relates to pyrrolotriazine inhibitors of IRAK4 of formula (I) and provides compositions comprising such inhibitors, as well as methods therewith for treating IRAK4-mediated or -associated conditions or diseases.
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Page/Page column 43; 44
(2016/09/26)
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- PYRAZOLOPYRIMIDINE INHIBITORS OF IRAK4 ACTIVITY
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The present invention relates to pyrazolopyrimidine inhibitors of IRAK4 of formula (I) and provides compositions comprising such inhibitors, as well as methods therewith for treating IRAK4-mediated or -associated conditions or diseases.
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Page/Page column 65
(2016/09/26)
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- THIENOPYRAZINE INHIBITORS OF IRAK4 ACTIVITY
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The present invention relates to thienopyrazine inhibitors of IRAK4 of formula (I) and provides compositions comprising such inhibitors, as well as methods therewith for treating IRAK4-mediated or -associated conditions or diseases.
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Page/Page column 38
(2016/09/26)
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- PYRROLOPYRIDAZINE INHIBITORS OF IRAK4 ACTIVITY
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The present invention relates to pyrrolopyridazine inhibitors of IRAK4 of formula (I) and provides compositions comprising such inhibitors, as well as methods therewith for treating IRAK4-mediated or -associated conditions or diseases.
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Page/Page column 42
(2016/09/26)
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- Low band-gap polymers based on easily synthesized thioester-substituted thieno[3,4-b]thiophene for polymer solar cells
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A new acceptor S-alkyl thieno[3,4-b]thiophene-2-carbothioate-based acceptor (TTS) was firstly developed via easy of synthesis and applied in the construction of donor-acceptor (D-A) type conjugated polymers, by replacing the alkyl chain of ketone-substituted thieno[3,4-b]thiophene with an alkylthio side chain. Then, two new TTS-based polymers PBDTT-TTSO and PBDTT-TTSE were synthesized by Stille coupling reaction. The TTS acceptor moieties made the polymers exhibit a lower band gap (~1.5 eV) and appropriate HOMO and LUMO energy levels relative to the fullerene acceptors, which could make the polymers perform well in photovoltaic devices. Solar cells were fabricated with the structure ITO/PEDOT:PSS/polymer:PC71BM/Ca/Al. The polymer PBDTT-TTSO device exhibits a power conversion efficiency (PCE) of 4.7% with an open circuit voltage (VOC) of 0.68 V, a short circuit current density (JSC) of 12.7 mA cm-2, and a fill factor (FF) of 54.6% while the PBDTT-TTSE device yields a higher PCE of 5.8% with a VOC of 0.70 V, a JSC of 14.6 mA cm-2, and a FF of 56.7%. The results indicate that thioester-substituted thieno[3,4-b]thiophene (TTS) is a promising building block for further design of high performance photovoltaic polymers.
- Zhu, Dangqiang,Sun, Liang,Bao, Xichang,Wen, Shuguang,Han, Liangliang,Gu, Chuantao,Guo, Jing,Yang, Renqiang
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p. 62336 - 62342
(2015/08/11)
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- Exploitation of an additional hydrophobic pocket of σ1 receptors: Late-stage diverse modifications of spirocyclic thiophenes by C-H bond functionalization
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The hypothesis that the σ1 receptor will tolerate an additional aryl moiety in position 1 of the spirocyclic system was based on spirocyclic pyrazole derivatives, pharmacophore models of σ1 receptor ligands and DFT calculations. The strategy of introducing the aryl residue at the final step of the synthesis allowed the preparation of a large set of diverse ligands for the exploitation of the hydrophobic pocket of the σ1 receptor protein. The catalyst system PdCl 2/2,2′-bipyridyl/Ag2CO3 is able to introduce various aryl groups onto the α-positions of spirocyclic thiophene derivatives 5 and 6 to afford the target aryl-appended spirocyclic thiophenes 3 and 4. Although the σ1 affinity of the 1-phenyl substituted spirocyclic thiophenes 3a and 4a is slightly reduced compared with the σ1 affinity of the non-arylated compounds 5 and 6, both compounds represent very potent σ1 receptor ligands (3a: K i = 4.5 nM; 4a: Ki = 1.0 nM). This result indicates that an aryl moiety in position 1 is well tolerated by the σ1 receptor protein. The substitution pattern of the additional phenyl moiety has only weak effects on the σ1 affinity. Even ligands 3f and 4h with extended naphthyl residue show high σ1 affinity. However, decrease of σ1 affinity by extension of the π-system to a biphenylyl substituent (4j: Ki = 30 nM) indicates that the biphenylyl residue is too large for the primary hydrophobic binding pocket of the σ1 receptor. The Royal Society of Chemistry 2011.
- Meyer, Christina,Neue, Benedikt,Schepmann, Dirk,Yanagisawa, Shuichi,Yamaguchi, Junichiro,Wuerthwein, Ernst-Ulrich,Itami, Kenichiro,Wuensch, Bernhard
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experimental part
p. 8016 - 8029
(2012/01/04)
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- NIR-absorbing poly(thieno[3,4-b]thiophene-2-carboxylic acid) as a polymer dye for dye-sensitized solar cells
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Thieno[3,4-b]thiophene-2-carboxylic acid (TTHC) was newly synthesized and poly(thieno[3,4-b]thiophene-2-carboxylic acid) (PTTHC), showing NIR absorption with a low band gap of 1.0 eV, was prepared by chemical or electrochemical polymerization. Vis-NIR spectroscopic studies on PTTHC adsorption revealed that the presence of pendant carboxylic groups on a polymer chain is important to obtain highly sensitized TiO2. The extent of PTTHC adsorption showed proportional increases as raising the adsorption temperatures, reaching saturation at the amount equivalent to a monolayer formation (this does not mean PTTHC monolayer coverage on TiO2). Sequential treatments of TiO2 revealed that the polymer can be adsorbed on N3-adsorbed TiO2 without desorbing N3. The amounts of PTTHC adsorbed on N3-adsorbed TiO2 with increasing adsorption temperatures implied that only a small fraction of polymer chains is involved in anchoring with most chain segments remaining unbound to TiO2. The dye adsorption behaviors were further studied by FTIR, EDX, and TGA. Finally, PTTHC was applied for the preparation of panchromatic dye-sensitized solar cells. The power conversion efficiency (η) of 1.2% for PTTHC-adsorbed TiO2 was increased to 4.3% after N3 adsorption on PTTHC-adsorbed TiO2. Similar enhancement of η was observed after PTTHC treatment on N3-adsorbed TiO2.
- Saji, Viswanathan S.,Zong, KyuKwan,Pyo, Myoungho
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experimental part
p. 81 - 87
(2010/11/05)
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- Nitrogen containing heterocyclic compounds and medicines containing the same
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Compounds represented by the following general formula: (wherein X1, X2, X3 and X4 each independently represent a single bond, C1-6 alkylene, etc.; A2 represents optionally substituted phenyl, etc.; A1 represents an optionally substituted 5- to 7-membered heterocyclic group containing —C(═Q1)— (wherein Q1 represents oxygen, sulfur or ═N—R11 (wherein R11 represents hydrogen or C1-6 alkyl)) and nitrogen, etc.; and Z1 represents piperidin-diyl, etc.), salts thereof and hydrates of the foregoing.
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- 4(SPIROPIPERIDINYL)METHYL SUBSTITUTED PYRROLIDINES AS MODULATORS OF CHEMOKINE RECEPTOR ACTIVITY
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3-Substituted pyrrolidines having a spiropiperidinylmethyl substituent on the 4-position of the ring are useful as modulators of chemokine receptor activity. In particular, these compounds are useful as modulators of the chemokine receptors CCR-3 and/or CCR-5.
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- 4-[(4-(CARBOXYETHYL) PIPERIDINYL) METHYL] PYRROLIDINES AS MODULATORS OF CHEMOKINE RECEPTOR ACTIVITY
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3-Substituted pyrrolidines having a 4-carboxypiperidinylmethyl substituent on the 4-position of the ring are useful as modulators of chemokine receptor activity. In particular, these compounds are useful as modulators of the chemokine receptors CCR-3 and/or CCR-5.
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- Fused pyridine derivatives
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The present provides a condensed pyridine compound (I) represented by the following formula: (wherein, R2represents ring A represents benzene ring, pyridine ring, thiophene ring or furan ring; and B represents its pharmaceutically acceptable salt or hydrates thereof, which is a clinically useful medicament having a serotonin antagonism, in particular, that for treating, ameliorating or preventing spastic paralysis or central muscle relaxants for ameliorating myotonia.
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- Inhibition of Src kinase activity by 4-anilino-7-thienyl-3-quinolinecarbonitriles.
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Based on a screening lead from a yeast-based assay to identify Src family kinase inhibitors, a series of 4-anilino-7-thienyl-3-quinolinecarbonitriles was prepared. When the thiophene ring was substituted with a water-solubilizing group in a 2,5-, 3,5- or 2,4-pattern, potent inhibition of Src kinase activity was observed.
- Boschelli, Diane H,Wang, Daniel Y,Ye, Fei,Yamashita, Ayako,Zhang, Nan,Powell, Dennis,Weber, Jennifer,Boschelli, Frank
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p. 2011 - 2014
(2007/10/03)
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- Phosphorylamides, their preparation and use
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A phosphorylamide derivative represented by the general formula (I): STR1 wherein R represents an amino group that may be substituted, or a salt thereof, possesses potent antibacterial activity against Helicobacter bacterium, especially Helicobacter pylori, and is useful for prevention or treatment of digestive diseases caused by Helicobacter bacterium, solely or in combination with an antacid or an acid secretion inhibitor.
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- Synthesis of Thieno--, -- and --thiophenes and Thieno--, -- and --thienopyrimidin-7(6H)-ones Starting from Thiophene
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3-Bromo-, 3,5-dibromo- and 3,4,5-tribromo-2-thienyllithium have been prepared by bromine ->lithium exchange and converted into a number of thiophene derivatives, including the corresponding 2-carbaldehydes.The aldehydes have been converted into the corresponding thiophene-2-carbonitriles.Metallation of 2,5-dibromo- or 2,4,5-tribromo-thiophene with LDA occured at a vacant 3-position but the resulting 3-lithiated thiophenes rearranged (mechanism discussed) to 3,5-dibromo- and 3,4,5-tribromo-2-thienyllithium, which were quenched with various electrophiles.Attempts to dilithiate 2,5-dibromothiophene with LDA were unsuccessful. 3,4-Dibromo-2,5-dilithiothiophene was prepared from 2,3,4,5-tetrabromothiophene but it failed to yield the 2,5-dicarbaldehyde with N,N-dimethylformamide.The title thienothiophenes were prepared by reaction of a 3-bromothiophene-2-carbaldehyde, a 2-bromothiophene-3-carbaldehyde (prepared by bromination of a thiophene-3-carbaldehyde) or a 4-bromothiophene-3-carbaldehyde, or a corresponding nitrile, with ethyl 2-sulfanylacetate or 2-sulfanylacetamide.Thienothiophenes carrying an o-aminocarboxamide substitution pattern gave the title thienothienopyrimidinones with triethyl orthoformate.
- Hawkins, David W.,Iddon, Brian,Longthorne, Darren S.,Rosyk, Peter J.
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p. 2735 - 2744
(2007/10/02)
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- UREA BASED LIPOXYGENASE INHIBITING COMPOUNDS
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Substituted phenyl, naphthyl, and thienyl N-hydroxy urea compounds form a class of potent inhibitors of 5-and 12-lipoxygenase and are thus useful compounds in the treatment of inflammatory disease states where leukotrienes and other products of lipoxygenase enzyme activity are implicated.
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- Hypoglycemic 5-substituted oxazolidine-2,4-diones
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Hypoglycemic 5-furyl and 5-thienyl derivatives of oxazolidine-2,4-dione and the pharmaceutically-acceptable salts thereof; certain 3-acylated derivatives thereof; and intermediates useful in the preparation of said compounds.
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