DOCSLIB.ORG

(12) Patent Application Publication (10) Pub. No.: US 2005/0104233 A1 Kato Et Al

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
(12) Patent Application Publication (10) Pub. No.: US 2005/0104233 A1 Kato Et Al US 2005O104233A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2005/0104233 A1 Kato et al. (43) Pub. Date: May 19, 2005 (54) METHOD OF SUBSTITUENT (30) Foreign Application Priority Data INTRODUCTION THROUGH HALOGEN-METAL, EXCHANGE REACTION May 31, 2002 (JP)...................................... 2002-16O759 (76) Inventors: Shinji Kato, Aichi (JP); Nobuaki Publication Classification Nonoyama, Aichi (JP); Toshiaki Mase, Aichi (JP) (51) Int. Cl." ................................. C07F 1/02; CO7F 3/04 (52) U.S. Cl. ................................. 260/665 G; 260/665 R Correspondence Address: (57) ABSTRACT WENDEROTH, LIND & PONACK, L.L.P. 2033 K STREET N. W. A method of exchanging a halogen atom of a halide, which SUTE 800 has a group containing an acidic proton and in which one or WASHINGTON, DC 20006-1021 (US) more halogen atom(s) is/are Substituted on a carbon atom of the carbon-carbon double bond, with a metal atom by (21) Appl. No.: 10/514,935 halogen-metal-exchange reaction and introducing an elec trophilic reagent into the carbon atom to which the metal (22) PCT Filed: May 27, 2003 atom is attached. The above method is an industrially excellent method of introducing a Substituent by halogen (86) PCT No.: PCT/JP03/06624 metal eXchange reaction. US 2005/0104233 A1 May 19, 2005 METHOD OF SUBSTITUENT INTRODUCTION eXchange reaction. As a result, they found that a halide THROUGH HALOGEN-METAL, EXCHANGE which has a Substituent containing an acidic proton can be REACTION employed as a starting material without protection of the Substituent, and the condition of extreme low temperature TECHNICAL FIELD (-78 C.) can be avoided when a halide, which has a 0001. The present invention is useful in the field of fine Substituent containing an acidic proton and in which the chemicals. Such as pharmaceuticals, agricultural chemicals, carbon atom(s) of the carbon-carbon double bond is/are perfumes and the like. In more detail, the present invention Substituted by one or more halogen(s), as a starting material relates to a method of introducing a Substituent to a produc is reacted with a magnesium halide compound, a magnesium tion intermediate for a compound which is useful in the field compound, or a mixture thereof, and Subsequently reacted of pharmaceuticals and the like, and a novel production with a lithium compound and then with an electrophilic method which is advantageous for the production. reagent. The present inventors carried out further Studies on the basis of those findings, and finally completed the present BACKGROUND ART invention. 0002 Some of the compounds produced by a method of 0008 Namely, the present invention relates to: introducing a Substituent by halogen-metal eXchange reac tion according to the present invention are useful as a 0009 (1) A method of exchanging a halogenatom of production intermediate for the compound which is useful as a halide with a metal atom by halogen-metal a neuropeptide Y receptor antagonist disclosed, for example, eXchange reaction and introducing an electrophilic in WO 01/14376. reagent into a carbon atom to which the metal atom is attached, which comprises reacting a halide which 0003) A method of introducing a substituent by halogen has a group containing an acidic proton and in which metal eXchange reaction has often been utilized in the one or more halogen atom(s) is/are Substituted on a production of intermediates for pharmaceuticals, including carbon atom of the carbon-carbon double bond, with the aforementioned compounds. a magnesium halide represented by the formula (I): 0004 Known methods of introducing a substituent by halogen-metal eXchange reaction are disclosed in, for example, ACCOUNTS OF CHEMICAL RESEARCH, vol. I 15, p. 300-305, 1982, William E. parham et al., JOURNAL OF ORGANIC CHEMISTRY, vol.39, p. 2051-2053, 1974, William E. parham et al. and JOURNAL OF ORGANIC CHEMISTRY, vol. 41, p. 2628-2633, 1976, William E. Parham et al., however, those production methods disclosed in Said literatures are carried out under an extreme cold 0010) (wherein R is a hydrocarbon group, and X is a condition (-78° C). In the industrial production, setting halogen atom), or a magnesium compound represented by Such an extreme cold condition requires a particular cooling System, thus Said production methods are inefficient and not the formula (II): desirable for the industrial production. 0005 Recently, a report by Kazuya Kitagawa et al. in II) ANGEWANTE CHEMIE INTERNATIONAL EDITION, vol. 39, p. 2481-2483, and WO 01/57046 also disclosed a method of introducing a Substituent by halogen-metal eXchange reaction in which an extreme cold condition was not necessary. This method of introducing a Substituent by halogen-metal eXchange reaction, however, has a limitation 0.011) (wherein R and R are each independently a that the compound having a halogen atom, which is a hydrocarbon group), or a mixture thereof, followed by Starting material, is not applicable when it includes a Sub Successive reactions with a lithium compound represented Stituent containing an acidic proton. Therefore, in case by the formula (III): where a starting material includes a Substituent containing an acidic proton, it is necessary to protect the Substituent and Li-R III then to remove the protecting group after the reaction, 0012 (wherein R" is a hydrocarbon group), and then with resulting in additional processes, complex proceSS control an electrophilic reagent, and then optionally treating the and reduced yield. Accordingly, Said method is inefficient resulting product with an acid, for the purpose of industrial production. 0013 (2) The method according to the above (1), DISCLOSURE OF THE INVENTION wherein the hydrocarbon group is an alkyl group, an 0006 An object of the present invention is to improve aromatic group or an aralkyl group, problems relating to the known methods of introducing a 0014) (3) The method according to the above (1) or Substituent by halogen-metal-exchange reaction and to pro (2), wherein the halide which has a group containing vide an industrially Superior method of introducing a Sub an acidic proton and in which one or more halogen Stituent by halogen-metal eXchange reaction. atom(s) is/are substituted with the carbon atom of the 0007. The present inventors conducted intensive studies carbon-carbon double bond is a compound repre on a method of introducing a Substituent by halogen-metal sented by the formula (IV): US 2005/0104233 A1 May 19, 2005 pyl magnesium chloride, isopropyl magnesium bro mide, n-butyl magnesium chloride, n-butyl IV magnesium bromide, isobutyl magnesium chloride, X2 phenyl magnesium chloride or phenyl magnesium bromide, and the magnesium compound represented by the formula (II) is dimethylmagnesium, diethyl o-O 3 magnesium, di-n-propylmagnesium, diisopropyl magnesium, di-n-butylmagnesium, diisobutylmag nesium, di-Sec-butylmagnesium, n-butyl(Sec 0015 wherein butyl)magnesium or diphenylmagnesium, 0016 X is a halogen atom; 0025 (7) The method according to any one of the above (1) to (6), wherein the lithium compound 0017 X is a hydrogen atom or a halogen atom; represented by the formula (III) is methyllithium, 0018 n is an integer of 1 to 4; n-butyllithium, sec-butyllithium, tert-butyllithium or 0019 Y is a carboxyl group, a hydroxymethyl phenylithium, group, a hydroxy group, a Sulfamoyl group, a group 0026 (8) The method according to any one of the of the formula: -SOH, a phosphono group, a group above (1) to (7), wherein the electrophilic reagent is of the formula: -NH-Y (wherein Y is a hydro benzaldehyde, methyl iodide, N,N-dimethylforma gen atom, a hydroxy group, an alkyl group, a car mide, 1-benzyl-4-piperidone, 1-tert-butoxycarbonyl boxyl group, an aromatic group, a benzyloxycarbo 4-piperidone, allyl bromide, cyclohexanone, n-hep nyl group, an alkoxycarbonyl group or a tanal, n-hexanal, acetone or methyl ethyl ketone, phenyloxycarbonyl group), a group of the formula: -CO-NH-Y (Y is a hydrogen atom, an alkyl 0027 (9) The method according to the above (1), group or an aromatic group) or a group of the which comprises reacting 2-bromobenzoic acid rep formula: -NH-SO-Y (wherein Y is a hydro resented by the formula: gen atom, an alkyl group or an aromatic group), and 0020 the group represented by the formula: Br COOH 0028 with di-n-butylmagnesium, di-sec-butylmagne sium, n-butyl(Sec-butyl)magnesium, isopropyl magnesium chloride, n-butyl magnesium bromide, or a mixture thereof, 0021 is a divalent homocyclic or heterocyclic group, and followed by Successive reactions with n-butyllithium, and when n is more than 1, each Y may be the same or different, then with a piperidone derivative represented by the for 0022 (4) The method according to the above (2) or mula: (3), wherein the alkyl group is a linear or branched C-C alkyl group, and the aromatic group is phenyl, 1-naphthyl, 2-naphthyl or benzyl, 0023 (5) The method according to any one of the above (1) to (4), wherein the homocyclic or hetero cyclic ring is a benzene ring, a naphthalene ring, an indene ring, an indane ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a 0029 and then treating the product with an acid to give thiophen ring, a furan ring, a pyran ring, an isoben a Spiro compound represented by the formula: Zofuran ring, a pyrrole ring, an imidazole ring, a pyrazole ring, an isothiazole ring, a thiazole ring, an Oxazole ring, an isoxazole ring, aquinoline ring, an isoquinoline ring, a benzofuran ring, an indole ring, an isolindole ring, a phthalazine ring, a quinoxaline ring, a benzimidazole ring, a 1,8-naphthyridine ring, a benzoxazole ring, a benzothiazole ring, a ben Zothiophen ring, a cinnoline ring or a quinazoline ring, 0024 (6) The method according to any one of the above (1) to (5), wherein the magnesium halide represented by the formula (I) is methyl magnesium bromide, methyl magnesium chloride, ethyl magne sium chloride, n-propyl magnesium chloride, isopro US 2005/0104233 A1 May 19, 2005 0030) and 0041.
Load more

Recommended publications
  • WO 2015/179628 Al 26 November 2015 (26.11.2015) P O P C T
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2015/179628 Al 26 November 2015 (26.11.2015) P O P C T (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C08F 210/16 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (21) International Application Number: BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, PCT/US20 15/03 1952 DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, 2 1 May 2015 (21 .05.2015) KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, (25) Filing Language: English PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, (26) Publication Language: English SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: 14/284,689 22 May 2014 (22.05.2014) US (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (71) Applicant: CHEVRON PHILLIPS CHEMICAL COM¬ GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, PANY LP [US/US]; 10001 Six Pines Drive, The Wood TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, lands, TX 77380 (US).
    [Show full text]
  • Synthesis and Properties of Diorganomagnesium Compounds
    University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 12-1967 Synthesis and Properties of Diorganomagnesium Compounds Conrad William Kamienski University of Tennessee - Knoxville Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss Part of the Chemistry Commons Recommended Citation Kamienski, Conrad William, "Synthesis and Properties of Diorganomagnesium Compounds. " PhD diss., University of Tennessee, 1967. https://trace.tennessee.edu/utk_graddiss/3077 This Dissertation is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by Conrad William Kamienski entitled "Synthesis and Properties of Diorganomagnesium Compounds." I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the equirr ements for the degree of Doctor of Philosophy, with a major in Chemistry. Jerome F. Eastham, Major Professor We have read this dissertation and recommend its acceptance: Bruce M. Anderson, George K. Schwitzer, David A. Shirley Accepted for the Council: Carolyn R. Hodges Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) Novemb er 27, 1967 To the Graduate Council: I am submitting herewith a dissertation written by Conrad Wiliiam Kamienski entitled "Synthesis and Properties of Diorgano­ magnesium Compounds." I recommend that it be accepted in partial fulfillment of the requirements for the degree of Doctor of Philosophy, with a maj or in Chemistry .
    [Show full text]
  • (12) United States Patent (10) Patent No.: US 6,232,417 B1 Rhodes Et Al
    USOO6232417 B1 (12) United States Patent (10) Patent No.: US 6,232,417 B1 Rhodes et al. (45) Date of Patent: May 15, 2001 (54) PHOTORESIST COMPOSITIONS FOREIGN PATENT DOCUMENTS COMPRISING POLYCYCLIC POLYMERS WITH ACID LABILE PENDANT GROUPS O789278 8/1997 (EP). 0836119 4/1998 (EP). 5297591 11/1993 (JP). (75) Inventors: Larry F Rhodes, Silverlake; Andrew 9230595 9/1997 (JP). Bell, Lakewood; Saikumar Jayaraman, Cuyahoga Falls, OTHER PUBLICATIONS John-Henry Lipian, Broadview Heights; Brian L. Goodall, Akron; J. V. Crivello et al., Chemically Amplified Electron-Beam Photoresists, Chem. Mater, 1996, 8,376-381. it. Shick, Strongsville, all of Louis A. Cappino et al., Novel Carboxylic Acid and Car boxamide Protective Groups Based on the Exceptional Sta (73) Assignee: The B. F. Goodrich Company, bilization of the Cyclopropylmethyl Cation, J. Org. Chem. 1995, 60, 7718. T719. Brecksville,reCKSVIIIe, OH (US)(US Patents wr’sAbstracts of Japan, vol. 018, No. 096 (P-1694), Feb. (*) Notice: Subject to any disclaimer, the term of this 16, 1994. patent is extended or adjusted under 35 Robert G. Gastinger et al., IL-Arene Complexes of Nickel U.S.C. 154(b) by 0 days. (II). Synthesis (from Metal Atoms) of (T-Arene)bis(pen tafluorophenyl)nickel(II). Properties, C-Arene Lability, and (21) Appl. No.: 08/928,573 Chemistry, J. Am. Chem. Soc., 1980, 102, 4959–4966. y - - - 9 (22) Filed: Sep. 12, 1997 Primary Examiner Donald R. Wilson e - as ASSistant Examiner-Caixia Lu (51) Int. Cl." ........................................................ C08F 4/80 (74) Attorney, Agent, or Firm Thoburn T. Dunlap (52) U.S. Cl. .......................... 526/171; 526/283; 526/308;526/309 (57) ABSTRACT (58) Field of Search ....................................
    [Show full text]
  • Ep 0500944 B1
    Europaisches Patentamt (19) European Patent Office Office europeenpeen des brevets EP 0 500 944 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) intci.e: C08F 10/00, C08F 4/646, of the grant of the patent: C08F 4/647 07.10.1998 Bulletin 1998/41 (86) International application number: (21) Application number: 91913096.3 PCT/JP91/00983 Date of 24.07.1991 (22) filing: (87) International publication number: WO 92/01723 (06.02.1992 Gazette 1992/04) (54) CATALYST FOR ALPHA-OLEFIN POLYMERIZATION AND PRODUCTION OF POLY-ALPHA-OLEFIN THEREWITH KATALYSATOR FUR ALPHA-OLEFIN POLYMERISATION UND HERSTELLUNG VON POLY(ALPHA)OLEFINEN DAMIT CATALYSEUR POUR POLYMERISATION ALPHA-OLEFIN IQUE ET PRODUCTION D'UNE POLY-ALPHA-OLEFINE A LAIDE DE CE CATALYSEUR (84) Designated Contracting States: (72) Inventors: BE DE FR GB IT NL • SUGIMOTO, Ryuichi Takaishi-shi, Osaka 592 (JP) (30) Priority: 24.07.1990 JP 193904/90 • ASANUMA, Tadashi 01.08.1990 J P 202455/90 Takaishi-shi, Osaka 592 (JP) 27.08.1990 JP 222582/90 • IWATANI, Tutomu 02.10.1990 J P 262985/90 Takaishi-shi, Osaka 592 (JP) 13.11.1990 JP 303791/90 • TAKEUCHI, Katsumi 13.11.1990 J P 303792/90 Takaishi-shi, Osaka 592 (JP) 08.02.1991 JP 17371/91 • UCHIDA, Osamu 12.02.1991 JP 18531/91 Takaishi-shi, Osaka 592 (JP) 13.02.1991 JP 19792/91 13.02.1991 JP 19793/91 (74) Representative: 21.02.1991 J P 27058/91 Luderschmidt, Schiller & Partner GbR 13.03.1991 JP 47851/91 Patentanwalte, 13.03.1991 J P 47984/91 Postfach 3929 65029 Wiesbaden (DE) (43) Date of publication of application: 02.09.1992 Bulletin 1992/36 (56) References cited: JP-A- 1 301 704 JP-A- 1 501 950 (60) Divisional application: 98102883.0/0 841 349 JP-A- 1 502 036 JP-A-61 130 314 (73) Proprietor: MITSUI CHEMICALS, INC.
    [Show full text]
  • Heterogeneous Single-Site Catalysts for Olefin Polymerization
    Chem. Rev. 2000, 100, 1347−1376 1347 Heterogeneous Single-Site Catalysts for Olefin Polymerization Gregory G. Hlatky* Equistar Chemicals, LP, Equistar Technology Center 11530 Northlake Drive, Cincinnati, Ohio 45249 Received August 30, 1999 Contents I. Introduction 1347 II. Source Materials 1348 III. Supported Catalysts Activated by 1348 Trialkylaluminums IV. Supported Catalysts Activated by Alumoxanes 1349 A. Supported Alumoxanes 1350 B. Supported Metal Complexes 1350 C. Supporting Metal Complex−MAO Solutions 1352 D. Influence of Hydroxyl Groups 1352 E. Prepolymerization of Supported Catalysts 1353 V. Alumoxane-Free Supported Single-Site Catalysts 1354 VI. Supported Catalysts without Cocatalysts 1356 VII. Chemically Tethered Metal Complexes 1356 Gregory Hlatky was born in 1956 near Philadelphia, PA. He received his VIII. Chemically Tethered Activators 1361 B.S. degree in 1978 from Rider University, studying chemistry and history, A. Alumoxanes 1361 and his Ph.D. degree in 1983 from Yale University, where he worked under Robert Crabtree. After postdoctoral research at the University of B. Boron Activators 1362 Cambridge with Sir Jack Lewis and Brian Johnson, he joined Exxon IX. Supported Group 3 and Lanthanide Single-Site 1364 Chemical Company in 1984 at the Baytown Polymers Center in Baytown, Catalysts TX. In 1996 he moved to Lyondell Petrochemical Company, now part of X. Supported Group 5 Single-Site Catalysts 1365 Equistar Chemicals, LP. His research interests are in inorganic and XI. Supported Group 6 Single-Site Catalysts 1365 organometallic complexes for homogeneous catalysis, intellectual property analysis, and chemical information. Otherwise he helps his wife breed, XII. Supported Late-Transition Metal Single-Site 1366 raise, and show Borzoi (Russian Wolfhounds) under the kennel name Catalysts Soyara.
    [Show full text]
  • Acetic Acid Toxic
    Chemical Waste Name or Mixtures: Listed Characteristic Additional Info Disposal Notes (-)-B- bromodiisopropinocampheyl (-)-DIP-Bromide Non Hazardous None liquid: sanitary sewer/ solid: trash borane (-)-B- chlorodiisopropinocampheylb (-)-DIP-Chloride Non Hazardous None liquid: sanitary sewer/ solid: trash orane [(-)-2-(2,4,55,7-tetranitro-9- fluorenyodeneaminooxy)pro (-)-TAPA Non Hazardous None liquid: sanitary sewer/ solid: trash pionic acid] (+)-B- bromodiisopropinocampheyl (+)-DIP-Bromide Non Hazardous None liquid: sanitary sewer/ solid: trash borane (+)-B- chlorodiisopropinocampheylb (+)-DIP-Chloride Non Hazardous None liquid: sanitary sewer/ solid: trash orane [(+)-2-(2,4,55,7-tetranitro-9- fluorenylideneaminooxy)prop (+)-TAPA Non Hazardous None liquid: sanitary sewer/ solid: trash ionic acid] (2,4,5-Trichlorophenoxy) Acetic Acid Toxic None EHS NA (2,4-Dichlorophenoxy) Acetic Acid Toxic None EHS NA trans-8,trans-10-dodecadien- (E,E)-8,10-DDDA Non Hazardous None liquid: sanitary sewer/ solid: trash 1-ol trans-8,trans-10-dodecadien- (E,E)-8,10-DDDOL Non Hazardous None liquid: sanitary sewer/ solid: trash 1-yl acetate trans-7,cis-9-dodecadien-yl (E,Z)-7,9-DDDA Non Hazardous None liquid: sanitary sewer/ solid: trash acetate (Hydroxypropyl)methyl Cellulose Non Hazardous None liquid: sanitary sewer/ solid: trash NA ammonium phosphate (NH4)2HPO4 Non Hazardous None liquid: sanitary sewer/ solid: trash (dibasic) (NH4)2SO4 Non Hazardous None liquid: sanitary sewer/ solid: trash ammonium sulfate ammonium phosphate (NH4)3PO4 Non Hazardous None
    [Show full text]
  • Controlled and Living Polymerizations: Methods and Materials
    Controlled and Living Polymerizations Methods and Materials Edited by Axel H.E. Muller¨ and Krzysztof Matyjaszewski Controlled and Living Polymerizations Edited by Axel H.E. Muller¨ and Krzysztof Matyjaszewski Further Reading Severn,J.R.,Chadwick,J.C.(eds.) Elias, H.-G. Tailor-Made Polymers Macromolecules Via Immobilization of Alpha-Olefin Volume 4: Applications of Polymers Polymerization Catalysts 2009 2008 Hardcover Hardcover ISBN: 978-3-527-31175-0 ISBN: 978-3-527-31782-0 Matyjaszewski, K., Gnanou, Y., Leibler, L. (eds.) Dubois, P., Coulembier, O., Raquez, J.-M. (eds.) Macromolecular Engineering Precise Synthesis, Materials Properties, Handbook of Ring-Opening Applications Polymerization 2007 2009 Hardcover Hardcover ISBN: 978-3-527-31446-1 ISBN: 978-3-527-31953-4 Hadziioannou, G., Malliaras, G. G. (eds.) Barner-Kowollik, C. (ed.) Semiconducting Polymers Handbook of RAFT Chemistry, Physics and Engineering Polymerization 2007 2008 Hardcover Hardcover ISBN: 978-3-527-31271-9 ISBN: 978-3-527-31924-4 Vogtle¨ F., Richardt, G., Werner, N. Elias, H.-G. Dendrimer Chemistry Macromolecules Concepts, Syntheses, Properties, Applications Volume 2: Industrial Polymers and Syntheses 2009 2007 Softcover Hardcover ISBN: 978-3-527-32066-0 ISBN: 978-3-527-31173-6 Elias, H.-G. Macromolecules Volume 3: Physical Structures and Properties 2007 Hardcover ISBN: 978-3-527-31174-3 Controlled and Living Polymerizations Methods and Materials Edited by Axel H.E. Muller¨ and Krzysztof Matyjaszewski The Editors All books published by Wiley-VCH are carefully produced. Nevertheless, authors, Prof.AxelH.E.M¨uller editors, and publisher do not warrant the Universitat¨ Bayreuth information contained in these books, Makromolekulare Chemie II including this book, to be free of errors.
    [Show full text]
  • United States Patent (10) Patent No.: US 8,609,574 B2 Rhodes Et Al
    USOO8609574B2 (12) United States Patent (10) Patent No.: US 8,609,574 B2 Rhodes et al. (45) Date of Patent: Dec. 17, 2013 (54) INSITU OLEFIN POLYMERIZATION 7,456,329 B2 11/2008 Wu et al. CATALYST SYSTEM 7,459,510 B2 12/2008 Lin et al. 2005/0090383 A1* 4/2005 Thiele et al. .................. 502f152 2006/0287544 A1 12/2006 Amoroso et al. (75) Inventors: Larry F. Rhodes, Silver Lake, OH (US); 2008/0125555 A1 5/2008 Matsunaga et al. Luis Francisco Martin, Zaragoza (ES); Andrew Bell, Lakewood, OH (US) FOREIGN PATENT DOCUMENTS (73) Assignee: Promerus LLC, Brecksville, OH (US) WO 2006.004376 1, 2006 (*) Notice: Subject to any disclaimer, the term of this OTHER PUBLICATIONS patent is extended or adjusted under 35 I.C. Appleby, “The Hazards of M-Trifluoromethyl U.S.C. 154(b) by 287 days. phenylmagnesium Bromide Preparation.” Chemistry & Industry, London, United Kingdom, Issue 4, 1971. (21) Appl. No.: 12/428,936 Yoshiharu Inoue, “Useful Synthetic Routes to Pure exo-5-Vinyl-2- norbornene and endo-5-Vinyl-2-norbornene.” The Chemical Society (22) Filed: Apr. 23, 2009 of Japan, vol. 6, No. 5, 1987. Eric J. Moore, et al., “Metal Fluoride Stability.” Chemical & Engi (65) Prior Publication Data neering News, vol. 75, Issue 11, 1997. Terunobu Maeda, et al., “Rearrangement of 5-Vinyl-2-norbornene to US 2009/027O247 A1 Oct. 29, 2009 3a,4,7,7a-Tetrahydroindene.” Nippon Kagaku Kaishi, No. 8, 1974. Shaw-Tao Lin, et al. “Synthesis of (n^6-Arene)NIR2 and CoR2 O O (R=o-Bound Halosilanes and Haloarenes) by (Aliyl) 2Ni/HR Reac Related U.S.
    [Show full text]
  • HYCHEM LABORATORIES Fulfilling Your Research
    HYCHEM LABORATORIES fulfilling your research Regd. Office: S.V.R. SADAN, SRT – 31, JawaharNagar, Road No. 5, Chikkadpally, Hyderabad-500020. Phone: 27618702, 27601017, 27601240, 27654582 Fax: +91-40- 27663598 Web: www.hychemlabs.com Email: [email protected] TIN No: 28568201946 (V) – CST No: 28568201946 (C) OUR RANGE OF MANUFACTURING & SUPPLY OF CHEMICALS & REAGENTS LIST PRODUCTS CATALOGUE Cat. No. Product Name Cas No. Cap HAS3000 Allylmegnesium bromide-20% (in Diethylether) 1730-25-2 100ml HAS3000 Allylmegnesium bromide-20% (in Diethylether) 1730-25-2 250ml HAS3000 Allylmegnesium bromide-20% (in Diethylether) 1730-25-2 500ml HAS3000 Allylmegnesium bromide-20% (in Diethylether) 1730-25-2 1000ml HSA3001 Allyl magnesium chloride 1.0 M in diethyl ether 2622--05-1 100ml HAS3001 Allyl magnesium chloride 1.0 M in diethyl ether 2622--05-1 250ml HSA3001 Allyl magnesium chloride 1.0 M in diethyl ether 2622--05-1 500ml HSA3001 Allyl magnesium chloride 1.0 M in diethyl ether 2622--05-1 1000ml HSA3002 Allyl tri-n-butyl tin (97%) 24850-33-7 50gm HSA3002 Allyl tri-n-butyl tin (97%) 24850-33-7 100gm HSA3002 Allyl tri-n-butyl tin (97%) 24850-33-7 250gm HSA3002 Allyl tri-n-butyl tin (97%) 24850-33-7 500gm HSA3002 Allyl tri-n-butyl tin (97%) 24850-33-7 1000gm HSA3003 Ammona sol. 2.0 M in THF 7664-41-7 100ml HSA3003 Ammonia sol. 2.0 M in THF 7664-41-7 250ml HSA3003 Ammonia sol. 2.0 M in THF 7664-41-7 500ml HSA3003 Ammonia sol. 2.0 M in THF 7664-41-7 1000ml HSB3100 Benzylmagnesium chloride 2.0 (in THF) 6921-34-2 100ml HSB3100 Benzylmagnesium chloride 2.0
    [Show full text]
  • FULL PAPER Zinc- and Tin-Mediated CC Coupling Reactions of Metalated
    FULL PAPER Zinc- and Tin-Mediated C2C Coupling Reactions of Metalated (2-Pyridylmethyl)(trialkylsilyl)amines 2 Mechanistic, NMR Spectroscopic, and Structural Studies Matthias Westerhausen,*[a] Tobias Bollwein,[a] Nikolaos Makropoulos,[a] Stefan Schneiderbauer,[a][‡] Max Suter,[a][‡] Heinrich Nöth,[a][‡] Peter Mayer,[a][‡] Holger Piotrowski,[a][‡] Kurt Polborn,[b][‡] and Arno Pfitzner[c][‡] Keywords: Amides / C2C coupling / Magnesium / Metalations / Metallacycles / Pyridyl ligands / Tin / Zinc The zincation of (2-pyridylmethyl)(triisopropylsilyl)amine (1) tyldimethylsilyl)(2-pyridylmethyl)amide (9). This compound gives dimeric methylzinc (2-pyridylmethyl)(triisopropylsilyl)- also undergoes an intramolecular metalation reaction, which amide (2). Further addition of dimethylzinc to a toluene solu- results in the loss of the aromaticity of the pyridyl substituent tion of 2 at raised temperatures yields the C−C coupling and the formation of (tetrahydrofuran)magnesium 2-(tert- product [1,2-dipyridyl-1,2-bis(triisopropylsilylamido)ethane]- butyldimethylsilylamidomethylidene)-1-azacyclohexa-3,5- bis(methylzinc) (3). Heating of molten 2, or UV irradiation of dien-1-ide (10). The metalation of 1 with tin(II) bis[bis(trime- 2, results in the formation of 3 and zinc bis[(2-pyridylmethyl)- thylsilyl)amide] yields [bis(trimethylsilyl)amido]tin(II) (2-pyr- (triisopropylsilyl)amide] (4). The reaction between the zinc idylmethyl)(triisopropylsilyl)amide (11). The elimination of dihalide complexes of 1 [5a (X = Cl) and 5b (X = Br)] and tin metal occurs even at room temperature, and the C−C methyllithium yields the C−C coupling product 3 and the het- coupling product [1,2-dipyridyl-1,2-bis(triisopropylsilylami- eroleptic complex 2, observed by NMR spectroscopy. During do)ethane]tin(II) (12) is formed.
    [Show full text]