- A CO2-mediated base catalysis approach for the hydration of triple bonds in ionic liquids
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Herein, we report a CO2-mediated base catalysis approach for the activation of triple bonds in ionic liquids (ILs) with anions that can chemically capture CO2 (e.g., azolate, phenolate, and acetate), which can achieve hydration of triple bonds to carbonyl chemicals. It is discovered that the anion-complexed CO2 could abstract one proton from proton resources (e.g., IL cation) and transfer it to the CN or CC bonds via a six-membered ring transition state, thus realizing their hydration. In particular, tetrabutylphosphonium 2-hydroxypyridine shows high efficiency for hydration of nitriles and CC bond-containing compounds under a CO2 atmosphere, affording a series of carbonyl compounds in excellent yields. This catalytic protocol is simple, green, and highly efficient and opens a new way to access carbonyl compounds via triple bond hydration under mild and metal-free conditions.
- Han, Buxing,Ke, Zhengang,Li, Ruipeng,Liu, Zhimin,Tang, Minhao,Wang, Yuepeng,Zeng, Wei,Zhang, Fengtao,Zhao, Yanfei
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supporting information
p. 9870 - 9875
(2021/12/27)
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- One-pot method for the synthesis of 1-aryl-2-aminoalkanol derivatives from the corresponding amides or nitriles
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We have identified a novel one-pot method for the synthesis of β-amino alcohols, which is based on C-H bond hydroxylation at the benzylic α-carbon atom with a subsequent nitrile or amide functional group reduction. This cascade process uses molecular oxygen as an oxidant and sodium bis(2-methoxyethoxy)aluminum hydride as a reductant. The substrate scope was examined on 30 entries and, although the respective products were provided in moderate yields only, the above simple protocol may serve as a direct and powerful entry to the sterically congested 1,2-amino alcohols that are difficult to prepare by other routes. The plausible mechanistic rationale for the observed results is given and the reaction was applied to a synthesis of a potentially bioactive target. This journal is
- Bobal, Pavel,Otevrel, Jan,Svestka, David
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p. 25029 - 25045
(2020/07/14)
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- [18F]MALEIMIDE-BASED GLYCOGEN SYNTHASE KINASE-3BETA LIGANDS FOR POSITRON EMISSION TOMOGRAPHY IMAGING AND RADIOSYNTHESIS METHOD
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The present invention provides a compound having the structure: (Formula I), and a method of inhibiting Glycogen synthase kinase-3 β (GSK-3β) in a subject comprising administering to the subject said compound, so as to thereby inhibit the GSK-3β in the subject.
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Page/Page column 68
(2018/08/03)
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
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Paragraph 0138; 0139; 0140; 0151; 0152
(2018/05/07)
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- Synthesis method of 2-thienylmethylamine
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The invention relates to a synthesis method of 2-thienylmethylamine. According to the method, raw materials of 2-acetylthiophene, ethyl alcohol, concentrated ammonia water and sulphur powder take a reaction under the condition of 0.08 to 2.00 MPa to produce the 2-thienylacetamide; the 2-thienylacetamide and sodium hypochlorite or sodium hypobromite are prepared into 2-thienylmethylamine through Hofmann degradation under the effect of liquid caustic soda. The synthesis method has the advantages that the raw materials can be easily obtained; the process is simple and controllable; the maneuverability is high; the purity of the prepared finished product is high; the yield is high.
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Paragraph 0004; 0012; 0015; 0018; 0021
(2017/08/28)
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- Phosphinous Acid-Assisted Hydration of Nitriles: Understanding the Controversial Reactivity of Osmium and Ruthenium Catalysts
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The synthesis and catalytic behavior of the osmium(II) complexes [OsCl2(η6-p-cymene)(PR2OH)] [R=Me (2 a), Ph (2 b), OMe (2 c), OPh (2 d)] in nitrile hydration reactions is presented. Among them, the best catalytic results were obtained with the phosphinous acid derivative [OsCl2(η6-p-cymene)(PMe2OH)] (2 a), which selectively provided the desired primary amides in excellent yields and short times at 80 °C, employing directly water as solvent, and without the assistance of any basic additive (TOF values up to 200 h?1). The process was successful with aromatic, heteroaromatic, aliphatic, and α,β-unsaturated organonitriles, and showed a high functional group tolerance. Indeed, complex 2 a represents the most active and versatile osmium-based catalyst for the hydration of nitriles reported so far in the literature. In addition, it exhibits a catalytic performance similar to that of its ruthenium analogue [RuCl2(η6-p-cymene)(PMe2OH)] (4). However, when compared to 4, the osmium complex 2 a turned out to be faster in the hydration of less-reactive aliphatic nitriles, whereas the opposite trend was generally observed with aromatic substrates. DFT calculations suggest that these differences in reactivity are mainly related to the ring strain associated with the key intermediate in the catalytic cycle, that is, a five-membered metallacyclic species generated by intramolecular addition of the hydroxyl group of the phosphinous acid ligand to the metal-coordinated nitrile.
- González-Fernández, Rebeca,Crochet, Pascale,Cadierno, Victorio,Menéndez, M. Isabel,López, Ramón
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p. 15210 - 15221
(2017/10/12)
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- Development of [18F]Maleimide-Based Glycogen Synthase Kinase-3β Ligands for Positron Emission Tomography Imaging
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Dysregulation of glycogen synthase kinase-3β (GSK-3β) is implicated in the pathogenesis of neurodegenerative and psychiatric disorders. Thus, development of GSK-3β radiotracers for positron emission tomography (PET) imaging is of paramount importance, because such a noninvasive imaging technique would allow better understanding of the link between the activity of GSK-3β and central nervous system disorders in living organisms, and it would enable early detection of the enzyme’s aberrant activity. Herein, we report the synthesis and biological evaluation of a series of fluorine-substituted maleimide derivatives that are high-affinity GSK-3β inhibitors. Radiosynthesis of a potential GSK-3β tracer [18F]10a is achieved. Preliminary in vivo PET imaging studies in rodents show moderate brain uptake, although no saturable binding was observed in the brain. Further refinement of the lead scaffold to develop potent [18F]-labeled GSK-3 radiotracers for PET imaging of the central nervous system is warranted.
- Hu, Kongzhen,Patnaik, Debasis,Collier, Thomas Lee,Lee, Katarzyna N.,Gao, Han,Swoyer, Matthew R.,Rotstein, Benjamin H.,Krishnan, Hema S.,Liang, Steven H.,Wang, Jin,Yan, Zhiqiang,Hooker, Jacob M.,Vasdev, Neil,Haggarty, Stephen J.,Ngai, Ming-Yu
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p. 287 - 292
(2017/03/17)
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- Chlorophosphines as auxiliary ligands in ruthenium-catalyzed nitrile hydration reactions: Application to the preparation of β-ketoamides
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The catalytic hydration of nitriles into amides, in water under neutral conditions, has been studied using a series of arene-ruthenium(ii) complexes containing commercially available chlorophosphines as auxiliary ligands, i.e. compounds [RuCl2(η6-p-cymene)(PR2Cl)] (R = aryl, heteroaryl or alkyl group). In the reaction medium, the coordinated chlorophosphines readily undergo hydrolysis to generate the corresponding phosphinous acids PR2OH, which are well-known "cooperative" ligands for this catalytic transformation. Among the complexes employed, best results were obtained with [RuCl2(η6-p-cymene){P(4-C6H4F)2Cl}]. Performing the catalytic reactions at 40 °C with 2 mol% of this complex, a large variety of organonitriles could be selectively converted into the corresponding primary amides in high yields and relatively short times. The application of [RuCl2(η6-p-cymene){P(4-C6H4F)2Cl}] in the preparation of synthetically useful β-ketoamides is also presented.
- González-Fernández, Rebeca,González-Liste, Pedro J.,Borge, Javier,Crochet, Pascale,Cadierno, Victorio
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p. 4398 - 4409
(2016/07/06)
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- Supported Gold Nanoparticles-Catalyzed Microwave-Assisted Hydration of Nitriles to Amides under Base-Free Conditions
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Polystyrene-supported gold (Au@PS) nanoparticles were synthesized by the reduction deposition approach and well characterized by UV-visible, XRD, TEM, SAED, EDX, and XPS studies. The Au@PS was applied as catalyst for the hydration of nitriles to amides in water under microwave irradiation. Several functionalized aromatic, heterocyclic and aliphatic nitriles were found to be active for synthesis of the corresponding amides where no activation of water by base, ligand and support is needed. Easy recovery, negligible leaching and recyclability for up to eight runs are added advantages of the catalyst under water-mediated reaction conditions. (Figure presented.).
- Kumar, Sandeep,Sharma, Saurabh,Das, Pralay
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supporting information
p. 2889 - 2894
(2016/09/16)
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- Bis(allyl)-ruthenium(IV) complexes with phosphinous acid ligands as catalysts for nitrile hydration reactions
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Several mononuclear ruthenium(iv) complexes with phosphinous acid ligands [RuCl2(η3:η3-C10H16)(PR2OH)] have been synthesized (78-86% yield) by treatment of the dimeric precursor [{RuCl(μ-Cl)(η3:η3-C10H16)}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) with 2 equivalents of different aromatic, heteroaromatic and aliphatic secondary phosphine oxides R2P(O)H. The compounds [RuCl2(η3:η3-C10H16)(PR2OH)] could also be prepared, in similar yields, by hydrolysis of the P-Cl bond in the corresponding chlorophosphine-Ru(iv) derivatives [RuCl2(η3:η3-C10H16)(PR2Cl)]. In addition to NMR and IR data, the X-ray crystal structures of representative examples are discussed. Moreover, the catalytic behaviour of complexes [RuCl2(η3:η3-C10H16)(PR2OH)] has been investigated for the selective hydration of organonitriles in water. The best results were achieved with the complex [RuCl2(η3:η3-C10H16)(PMe2OH)], which proved to be active under mild conditions (60 °C), with low metal loadings (1 mol%), and showing good functional group tolerance.
- Tomás-Mendivil, Eder,Francos, Javier,González-Fernández, Rebeca,González-Liste, Pedro J.,Borge, Javier,Cadierno, Victorio
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p. 13590 - 13603
(2016/09/04)
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- Chemoselective hydration of nitriles to amides using hydrated ionic liquid (IL) tetrabutylammonium hydroxide (TBAH) as a green catalyst
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A transition metal-free process, catalyzed by tetrabutylammonium hydroxide (TBAH), has been developed for the convenient and selective hydration of nitriles to the corresponding amides. The present process converts aromatic, aliphatic, and heteroaromatic nitriles with a wide variety of functional groups into amides. The regioselective hydration of one nitrile moiety in the presence of another nitrile group gives the present protocol high impact.
- Veisi, Hojat,Maleki, Behrooz,Hamelian, Mona,Ashrafi, Samaneh Sedigh
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p. 6365 - 6371
(2015/02/19)
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- An efficient ruthenium(iv) catalyst for the selective hydration of nitriles to amides in water under mild conditions
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A Ru(iv) catalyst able to promote the selective hydration of nitriles to amides in water, at low metal loadings and under mild conditions, is presented. This journal is the Partner Organisations 2014.
- Tomás-Mendivil, Eder,Suárez, Francisco J.,Díez, Josefina,Cadierno, Victorio
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supporting information
p. 9661 - 9664
(2014/08/18)
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- Exploring rhodium(I) complexes [RhCl(COD)(PR3)] (COD = 1,5-cyclooctadiene) as catalysts for nitrile hydration reactions in water: The aminophosphines make the difference
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Several rhodium(I) complexes, [RhCl(COD)(PR3)], containing potentially cooperative phosphine ligands, have been synthesized and evaluated as catalysts for the selective hydration of organonitriles into amides in water. Among the different phosphines screened, those of general composition P(NR 2)3 led to the best results. In particular, complex [RhCl(COD){P(NMe2)3}] was able to promote the selective hydration of a large range of nitriles in water without the assistance of any additive, showing a particularly high activity with heteroaromatic and heteroaliphatic substrates. Employing this catalyst, the antiepileptic drug rufinamide was synthesized in high yield by hydration of 4-cyano-1-(2,6- difluorobenzyl)-1H-1,2,3-triazole. For this particular transformation, complex [RhCl(COD){P(NMe2)3}] resulted more effective than related ruthenium catalysts.
- Tomas-Mendivil, Eder,Garcia-Alvarez, Rocio,Vidal, Cristian,Crochet, Pascale,Cadierno, Victorio
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p. 1901 - 1910
(2014/06/24)
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- An efficient hydration of nitriles to amides in aqueous media by hydrotalcite-clay supported nickel nanoparticles
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Hydrotalcite-clay supported nickel nanoparticles catalyze hydration of nitriles to amides in aqueous media. This Ni NPs/HT system is efficient for the synthesis of a diverse range of amides and affords the expected products with good yields in aqueous media. The synthesized nickel nanoparticles are characterized by UV-DRS, powder XRD, SEM and HRTEM. The catalyst is reused at least three times and a plausible mechanism is proposed. This fast, simple, effective and environmentally benign heterogeneous protocol provides a safer alternative to hazardous, corrosive and more polluting conventional catalysts.
- Subramanian, Thirumeni,Pitchumani, Kasi
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p. 109 - 113
(2013/01/15)
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- Arene-ruthenium(II) complexes containing inexpensive tris(dimethylamino) phosphine: Highly efficient catalysts for the selective hydration of nitriles into amides
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The catalytic hydration of nitriles into amides, in water under neutral conditions, has been studied using a series of arene-ruthenium(II) derivatives containing the commercially available and inexpensive ligand tris(dimethylamino)phosphine. Among them, best results were obtained with the complex [RuCl2(η6-C6Me6) {P(NMe2)3}], which selectively provided the desired amides in excellent yields and short times (TOF values up to 11 400 h-1). The process was operative with both aromatic, heteroaromatic, aliphatic, and α,β-unsaturated organonitriles and showed a high functional group tolerance. The stability of [RuCl2(η6-C 6Me6){P(NMe2)3}] in water was evaluated, observing its progressive decomposition into the less-active dimethylamine-ruthenium(II) complex [RuCl2(η6-C 6Me6)(NHMe2)] by hydrolysis of the coordinated P(NMe2)3 ligand. The X-ray crystal structure determination of the toluene complex [RuCl2(η6-C6H 5Me){P(NMe2)3}] is also included.
- Garcia-Alvarez, Rocio,Diez, Josefina,Crochet, Pascale,Cadierno, Victorio
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experimental part
p. 5442 - 5451
(2011/12/13)
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- Arene-ruthenium(II) complexes containing amino-phosphine ligands as catalysts for nitrile hydration reactions
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Three different series of novel mononuclear arene-ruthenium(II) complexes containing amino-phosphine ligands, namely, [RuCl2{κ 1(P)-2-Ph2PC6H4CH 2NHR}(η6-arene)], [RuCl2{κ 1(P)-3-Ph2PC6H4CH 2NHR}(η6-arene)], and [RuCl2{κ 1(P)-4-Ph2PC6H4CH 2NHR}(η6-arene)] (arene = C6H6, p-cymene, 1,3,5-C6H3Me3, C6Me 6; R = iPr, tBu; all combinations), have been synthesized and fully characterized. These readily accessible species are efficient catalysts for the selective hydration of organonitriles into amides under challenging reaction conditions, i.e., pure aqueous medium in the absence of any cocatalyst, being much more active than their corresponding nonfunctionalized triphenylphosphine counterparts [RuCl2(PPh 3)(η6-arene)]. The results obtained in this study indicate that the (amino-phosphine)ruthenium(II) complexes operate through a "bifunctional catalysis" mechanism in which the ruthenium center acts as a Lewis acid, activating the nitrile molecule, and the P-donor ligand acts as a Brnsted base, the pendant amino group generating the real nucleophile of the hydration process, i.e., the OH- group.
- Garcia-Alvarez, Rocio,Diez, Josefina,Crochet, Pascale,Cadierno, Victorio
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experimental part
p. 3955 - 3965
(2010/12/25)
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- Biotransformation of nitriles using the solvent-tolerant nitrile hydratase from Rhodopseudomonas palustris CGA009
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A study has been carried out into the biocatalytic hydration of nitriles using the nitrile hydratase enzyme from Rhodopseudomonas palustris CGA009. It has been shown that this nitrile hydratase can hydrate aliphatic, aromatic and heterocyclic nitriles under very mild conditions, in mixtures of pH 7 buffer and a range of organic solvents, often with excellent chemoselectivity. The major determinant of hydration occurring is the degree of steric hindrance around the nitrile moiety and/or size of the substrates.
- Black, Gary W.,Gregson, Thomas,McPake, Christopher B.,Perry, Justin J.,Zhang, Meng
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experimental part
p. 1639 - 1641
(2010/05/19)
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- Selective ruthenium-catalyzed hydration of nitriles to amides in pure aqueous medium under neutral conditions
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A study was conducted to demonstrate that water-soluble ruthenium(II) complexes can be used as catalysts for the hydration of nitriles in pure aqueous media and under neutral conditions. The hydration of benzonitrile was investigated as a model reaction and the ruthenium precursor was added to a 0.33M aqueous solution of benzonitrile at 100°C, while the reaction was monitored by gas chromatography. All the complexes checked, were found to be active and selective catalysts in the hydration process, providing benzamide as a specific reaction product. The most relevant results were obtained by using ruthenium complexes, bearing a nitrogen-containing ligand, which led to appropriate production of benzamide. The most effective ruthenium complex was found to be an efficient catalyst for the selective hydration of a large number of other nitriles.
- Cadierno, Victorio,Francos, Javier,Gimeno, Jose
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scheme or table
p. 6601 - 6605
(2009/07/10)
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- Aryl-indolyl maleimides as inhibitors of CaMKIIδ. Part 1: SAR of the aryl region
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A family of aryl-substituted maleimides was prepared and studied for their activity against calmodulin dependant kinase. Inhibitory activities against the enzyme ranged from 34 nM to >20 μM and were dependant upon both the nature of the aryl group and the hydrogen bond donating potential of the maleimide ring. Key interactions with the kinase ATP site and hinge region were found to be consistent with homology modeling predictions.
- Levy, Daniel E.,Wang, Dan-Xiong,Lu, Qing,Chen, Zheng,Perumattam, John,Xu, Yong-jin,Liclican, Albert,Higaki, Jeffrey,Dong, Hanmin,Laney, Maureen,Mavunkel, Babu,Dugar, Sundeep
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p. 2390 - 2394
(2008/09/21)
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- Lactam metalloprotease inhibitors
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The present application describes novel lactams and derivatives thereof of formula I: or pharmaceutically acceptable salt forms thereof, wherein rings ring B is a 4-8 membered cyclic amide containing from 0-3 additional heteroatoms selected from N, O, and S, which are useful as metalloprotease inhibitors.
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- Substituted arylalkynyl-and heteroarylalkynl-N-hydroxyurea inhibitors of leukotriene biosynthesis
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The invention relates to compounds having activity to inhibit lipoxygenase enzyme activity, to pharmaceutical compositions comprising these compounds, and to a medical method of treating. More particularly, this invention concerns certain substituted arylalkynyl- and ((heteroaryl)alkynyl)-N-hydroxy-ureas which inhibit leukotriene biosynthesis, to pharmaceutical compositions of these compounds and to a method of inhibiting leukotriene biosynthesis.
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- Substituted aryl- and heteroarylalkenyl-N-hydroxyurea inhibitors of leukotriene biosynthesis
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Compounds of the structure STR1 wherein Z is selected from optionally substituted thienyl, thiazolyl, oxazolyl and furyl are potent inhibitors of lipoxygenase enzymes and thus inhibit the biosynthesis of leukotrienes. These compounds are useful in the treatment or amelioration of allergic and inflammatory disease states.
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- Preparation of 2-(2-thienyl) ethylamine and synthesis of thieno [3,2-C] pyridine derivatives therefrom
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Compounds of the formulae:and wherein:, R1, R2, R3 and R4 are independently hydrogen, lower alkyl of one to six carbon atoms, aryl or substituted aryl;, are advantageously converted to isocyanurate compounds, 2-(2-thienyl)ethylamine compounds and thieno[3,2-c]pyridine derivatives and the pharmaceutically acceptable salts thereof, particularly ticlopidine hydrochloride.
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- Aminomethylarylmethylpenicillin derivatives
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6-(Aminomethyl substituted phenyl- and thienylacetamido)-penicillanic acid and esters, and synthetic methods for the preparation thereof.
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