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3-Substituted-6-Aryl Pyridines As Ligands of C5a Receptors

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(19) & (11) EP 1 565 452 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07D 401/06 (2006.01) C07D 405/12 (2006.01) 04.04.2012 Bulletin 2012/14 C07D 413/04 (2006.01) (21) Application number: 03768799.3 (86) International application number: PCT/US2003/035694 (22) Date of filing: 07.11.2003 (87) International publication number: WO 2004/043925 (27.05.2004 Gazette 2004/22) (54) 3-SUBSTITUTED-6-ARYL PYRIDINES AS LIGANDS OF C5A RECEPTORS 3-SUBSTITUIERTE-6-ARYL- PYRIDIN DERIVATE ALS LIGANDEN FÜR C5A-REZEPTOREN 6-ARYL PYRIDINES SUBSTITUEES EN POSITION 3 EN TANT QUE LIGANDS DES RECEPTEURS C5A (84) Designated Contracting States: (74) Representative: Adam, Holger et al AT BE BG CH CY CZ DE DK EE ES FI FR GB GR Kraus & Weisert HU IE IT LI LU MC NL PT RO SE SI SK TR Patent- und Rechtsanwälte Thomas-Wimmer-Ring 15 (30) Priority: 08.11.2002 US 425281 P 80539 München (DE) (43) Date of publication of application: (56) References cited: 24.08.2005 Bulletin 2005/34 EP-A- 0 338 504 EP-A- 1 308 438 WO-A-02/49993 WO-A-99/31062 (73) Proprietor: Novartis International Pharmaceutical Ltd. • PATENT ABSTRACTS OF JAPAN vol. 2000, no. Hamilton (BM) 11, 3 January 2001 (2001-01-03) & JP 2000 226372 A (NIPPON SODA CO LTD), 15 August 2000 (72) Inventors: (2000-08-15) • HUTCHISON, Alan • ROBL J A ET AL: "PHOSPHORUS-CONTAINING Madison, CT 06443 (US) INHIBITORS OF HMG-COA REDUCTASE. 2. • YUAN, Jun SYNTHESISAND BIOLOGICAL ACTIVITIES OF A Guilford, CT 06437 (US) SERIES OF SUBSTITUTED PYRIDINES • LEE, Kyungae CONTAINING A HYDROXYPHOSPHINYL" Newton, MA 02459 (US) JOURNAL OF MEDICINAL CHEMISTRY, • MAYNARD, George AMERICAN CHEMICAL SOCIETY. Clinton, CT 06413 (US) WASHINGTON, US, vol. 34, no. 9, 1991, pages • CHENARD, Bertrand, L. 2804-2815, XP002922111 ISSN: 0022-2623 Waterford, CT 06385 (US) • DATABASE CHEMABS [Online] CHEMICAL • LIU, Nian ABSTRACTS SERVICE, COLUMBUS, OHIO, US; Edison, NJ 08837 (US) retrieved from STN Database accession no. •GUO,Qin 121:57290 XP002276374 & JOURNAL OF THE Waterford, CT 06385 (US) CHEMICAL SOCIETY, PERKIN TRANSACTIONS • GUO, Zihong 1 - ORGANIC AND BIO-ORGANIC CHEMISTRY, Southbury, CT 06488 (US) vol. 6, 1994, pages 739-751, • HRNCIAR, Peter Hamden, CT 06518 (US) Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 1 565 452 B1 Printed by Jouve, 75001 PARIS (FR) (Cont. next page) EP 1 565 452 B1 • DATABASE BEILSTEIN BEILSTEIN INSTITUTE • DATABASE BEILSTEIN BEILSTEIN INSTITUTE FORORGANIC CHEMISTRY, FRANKFURT-MAIN, FORORGANIC CHEMISTRY, FRANKFURT-MAIN, DE; Database accession no. BRN:6806495 DE; Database accession no. BRN:6803593 XP002276375 & JOURNAL OF CHEMICAL XP002276380 & JOURNAL OF CHEMICAL SOCIETYPERKIN TRANSACTIONS 1, vol. 6, 1994, SOCIETYPERKIN TRANSACTIONS 1, vol. 6, 1994, pages 739-752, pages 739-752, • DATABASE BEILSTEIN BEILSTEIN INSTITUTE • DATABASE BEILSTEIN BEILSTEIN INSTITUTE FORORGANIC CHEMISTRY, FRANKFURT-MAIN, FORORGANIC CHEMISTRY, FRANKFURT-MAIN, DE; Database accession no. BRN:8976300 DE; Database accession no. BRN:6504050 XP002276376 & JOURNAL OF CHEMICAL XP002276381 & J.CHEM.SOC.CHEM.COMM., vol. SOCIETY DALTON TRANSACTIONS, vol. 18, 14, 1982, page 777 2001, pages 2641-2648, • CAMPOS P J ET AL: "A Versatile Synthesis of • DATABASE BEILSTEIN BEILSTEIN INSTITUTE Pyrrolo-, Furo- and Thienopyridines via FORORGANIC CHEMISTRY, FRANKFURT-MAIN, Photocyclization of 3-Amino-2-alkene Imines in DE; Database accession no. BRN:788991 an Acid Medium" TETRAHEDRON, ELSEVIER XP002276377 & PAK.J.SCI.IND.RES., vol. 19, SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 1976, 55, no. 49, 3 December 1999 (1999-12-03), pages • TRECOURT F ET AL: JOURNAL OF ORGANIC 14079-14088, XP004184726 ISSN: 0040-4020 CHEMISTRY, vol. 61, 1996, pages 1673-1676, • BENNABI S ET AL: "Conjugate propargylation of XP002276372 alpha,beta-unsaturated lactones: a solution via • KATRITZKY A R ET AL: JOURNAL OF ORGANIC 1,4-addition of (Z)-2-ethoxyvinyl anion" CHEMISTRY, vol. 59, 1994, pages 2740-2742, TETRAHEDRON LETTERS, ELSEVIER SCIENCE XP002276373 PUBLISHERS, AMSTERDAM, NL, vol. 41, no. 46, • DATABASE BEILSTEIN BEILSTEIN INSTITUTE 11 November 2000 (2000-11-11), pages FORORGANIC CHEMISTRY, FRANKFURT-MAIN, 8873-8876, XP004236151 ISSN: 0040-4039 DE; Database accession no. BRN:4432438 XP002276378 & JOURNAL OF ORGANIC Remarks: CHEMISTRY, vol. 54, no. 18, 1989, pages Thefile contains technical information submitted after 4275-4277, the application was filed and not included in this • DATABASE BEILSTEIN BEILSTEIN INSTITUTE specification FORORGANIC CHEMISTRY, FRANKFURT-MAIN, DE; Database accession no. BRN:5178911 XP002276379 & JOURNAL OF CHEMICAL SOCIETY PERKIN TRANSACTIONS 1, 1980, pages 2743-2754, 2 EP 1 565 452 B1 Description FIELD OF THE INVENTION 5 [0001] This invention relates generally to 3-substituted-6-aryl pyridines that act as modulators of mammalian comple- ment C5a receptors, and to pharmaceutical compositions as well as packaged pharmaceutical preparations comprising such modulators. The present invention further relates to the use of such modulators in treating a variety of inflammatory and immune system disorders and as probes for the localization of C5a receptors. 10 BACKGROUND OF THE INVENTION [0002] C5a, a 74 amino acid peptide, is generated in the complement cascade by the cleavage of the complement protein C5 by the complement C5 convertase enzyme. C5a has both anaphylatoxice.g. ( , bronchoconstricting and vascular spasmogenic) and chemotactic effects. Therefore, it is active in engendering both the vascular and cellular 15 phases of inflammatory responses. Because it is a plasma protein and, therefore, generally almost instantly available at a site of an inciting stimulus, it is a key mediator in terms of initiating the complex series of events that results in augmentation and amplification of an initial inflammatory stimulus. The anaphylatoxic and chemotactic effects of the C5a peptide are believed to be mediated through its interaction with the C5a receptor (CD88 antigen), a 52 kD membrane bound G-protein coupled receptor (GPCR). C5a is a potent chemoattractant for polymorphonuclear leukocytes, bringing 20 neutrophils, basophils, eosinophils and monocytes to sites of inflammation and/or cellular injury. C5a is one of the most potent chemotactic agents known for a wide variety of inflammatory cell types. C5a also "primes" or prepares neutrophils for various antibacterial functions ( e.g., phagocytosis). Additionally, C5a stimulates the release of inflammatory mediators (e.g., histamines, TNF-α, IL-1, IL-6, IL-8, prostaglandins, and leukotrienes) and the release of lysosomal enzymes and other cytotoxic components from granulocytes. Among its other actions, C5a also promotes the production of activated 25 oxygen radicals and the contraction of smooth muscle. [0003] Considerable experimental evidence implicates increased levels of C5a in a number of autoimmune diseases and inflammatory and related disorders. Agents that block the binding of C5a to its receptor other agents, including inverse agonists, which modulate signal transduction associated with C5a-receptor interactions, can inhibit the patho- genic events, including chemotaxis, associated with anaphylatoxin activity contributing to such inflammatory and au- 30 toimmune conditions. The present invention provides such agents, and has further related advantages. [0004] Among the prior art, WO 02/49993 A describes modulators of mammalian complement C5a receptors for treating a variety of inflammatory and immune system disorders, where the compounds include an imidazole core. [0005] Furthermore, EP 1 398 438 A discloses compounds having a urea core, which show a C5a receptor antagonistic action and are useful as an agent for the prophylaxis or treatment of diseases or syndromes due to inflammation caused 35 by C5a. SUMMARY OF THE INVENTION [0006] The present invention provides compounds that modulate, and preferably inhibit, C5a receptor activation and/or 40 C5a receptor-mediated signal transduction. Such C5a receptor modulators are preferably high affinity C5a receptor ligands and act as antagonists (e.g., inverse agonists) of complement C5a receptors, such as human C5a receptors. According to one aspect, C5a receptor modulators provided herein are 3-substituted-6-aryl pyridines of Formula I or a pharmaceutically acceptable form thereof: 45 50 wherein: 55 Ar is 2,6-diethylphenyl; A is NR4R5; R1 is chosen from: 3 EP 1 565 452 B1 (i) hydrogen, halogen, amino, and cyano; and (ii) C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C1-C6alkoxy, C1-C4haloalkyl, C1-C4haloalkoxy, mono- and di-(C1-C6alkyl)ainino, (C3-C7cycloalkyl)C0-C4alkyl, (3- to 7-membered heterocycloalkyl)C0-C4alkyl and -S(On)C1-C4alkyl, each of which is substituted with from 0 to 4 substituents independently chosen from Rx; 5 R2 is halogen, cyano or XRy; R3 is hydrogen, halogen, hydroxy, amino, cyano,1-C 4alkyl,C C2-C4alkenyl, C2-C4alkynyl, C1-C4alkoxy, C1-C2haloalkyl, C1-C2haloalkoxy, mono- or di-(C1-C4alkyl)amino or - S(On)C1-C4alkyl; 10 with the proviso that at least one of R1, R2 and R3 is not hydrogen; R4 is: (i) C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, (C3-C7cycloalkyl)C0-C4alkyl, mono- or di-(C1-C4alkylamino)C0- 15 C4alkyl,
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    Durham E-Theses Studies on the organic chemistry of boron Livingstone, J.G. How to cite: Livingstone, J.G. (1961) Studies on the organic chemistry of boron, Durham theses, Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/9111/ Use policy The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that: • a full bibliographic reference is made to the original source • a link is made to the metadata record in Durham E-Theses • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders. Please consult the full Durham E-Theses policy for further details. Academic Support Oce, Durham University, University Oce, Old Elvet, Durham DH1 3HP e-mail: [email protected] Tel: +44 0191 334 6107 http://etheses.dur.ac.uk (11 ft u 4 SIAO rsi ^> V 3^NVJ-i3>Vc)V3 Nl 39IMVH3 0 6> CM 5 li 70 7D 0 0> 6 ID 8 79 730 Uoi 0 STUDIES ON THE ORGANIC CHEMISTRY OF BORON BY J. Gr« LIVINGSTONE A dissertation submitted for the Degree of Doctor of Philosophy in the Durham Colleges of the University of Durham. 1961 CONTENTS Page Acknowledgments (1) Memorandum (II) Summary (Ill) FART I Introduction Page Organor-Derivatives of Boric Acid I Trialkyl- and Triaryl Boranes 8 Mixed Trialkyl and Aryl-Alkylboranes 40 Cyclic Boranes 43 Boronic Acids and Esters 46 Borinic Acids and Esters 54 Boroxines 62 Alkyl- and Aryl- Dihaloboranes 65 Dialkyl.
  • Synthesis and Reactions Of

    Synthesis and Reactions Of

    SYNTHESIS AND REACTIONS OF HETEROSUBSTITUTED N-HETEROCYCLIC CARBENE-BORANES by Everett William Merling B.S., Xavier University, 2009 Submitted to the Graduate Faculty of the Kenneth P. Dietrich School of Arts and Sciences in partial fulfillment of the requirements for the degree of Doctor of Philosophy University of Pittsburgh 2015 UNIVERSITY OF PITTSBURGH DIETRICH SCHOOL OF ARTS AND SCIENCES This dissertation was presented by Everett William Merling It was defended on April 10, 2015 and approved by Professor Theodore Cohen, Department of Chemistry Professor Scott Nelson, Department of Chemistry Professor Yadong Wang, Department of Bioengineering Committee Chair: Professor Dennis P. Curran, Department of Chemistry ii Copyright © by Everett William Merling 2015 iii SYNTHESIS AND REACTIONS OF HETEROSUBSTITUTED N-HETEROCYCLIC CARBENE-BORANES Everett William Merling, PhD University of Pittsburgh, 2015 Carbene-boranes 1,3-bis-(2,6-diisopropylphenyl)imidazol-2-ylidene borane (dipp-Imd- BH3) and 1,3-dimethylimidazol-2-ylidene borane (diMe-Imd-BH3) were treated with various electrophiles to compare reactivity of carbene-borane with nucleophilicity values of carbene- borane (dipp-Imd-BH3 = 9.55 N, diMe-Imd-BH3 = 11.88 N). Compounds with electrophilicity values greater –15 E reacted rapidly with carbene-borane, but compounds with electrophilicity values less than –15 E reacted slowly or not at all with carbene-borane. Hydroboration complexes were isolated from the reactions of diMe-Imd-BH3 with benzylidenemalononitrile and 2-ethylidenemalononitrile. Overall the reactivity of carbene-borane matched predictions based on nucleophilicity and electrophilicity values. Carbene-boranes were also treated with acid halides and halogens to form halogenated carbene-boranes. Iodination occurs most rapidly followed by bromination and then chlorination.
  • Physical Properties of Chemicals in PAC Revision 27 Listing

    Physical Properties of Chemicals in PAC Revision 27 Listing

    LLNL-TR-625492 Physical Properties of Chemicals in PAC Revision 27 Listing M. A. Johnson March 8, 2013 Disclaimer This document was prepared as an account of work sponsored by an agency of the United States government. Neither the United States government nor Lawrence Livermore National Security, LLC, nor any of their employees makes any warranty, expressed or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States government or Lawrence Livermore National Security, LLC. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States government or Lawrence Livermore National Security, LLC, and shall not be used for advertising or product endorsement purposes. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. Physical Properties of Chemicals in PAC Revision 27 Listing 1 Purpose The purpose of this chemical physical property listing is to provide data required to apply the DOE SCAPA Protective Action Criteria (PAC) values to calculation of the LLNL Quantity (Q) Value thresholds for facility chemical hazard classification. This chemical physical property listing based on the DOE SCAPA Protective Action Criteria (PAC) Revision 27 listing Identifies: 1. Physical state at 25°C (i.e.