Alkylation Or Dealkylation Process Patents (Class 546/349)
  • Patent number: 9012632
    Abstract: Provided is a method whereby a heteroaromatic ring aryl can be very rapidly methylated at a high yield. In an N-alkyl-2-pyrrolidinone, a heteroaromatic ring aryltrialkylstannan is cross-coupled with methyl iodide in the presence of a palladium complex, a phosphine ligand, a cuprous halide, a carbonic acid salt and/or an alkali metal fluoride to thereby rapidly methylate the heteroaromatic ring aryl. (Formula shows a case wherein the heteroaromatic ring aryl is a pyridyl group.
    Type: Grant
    Filed: December 25, 2009
    Date of Patent: April 21, 2015
    Assignee: Riken
    Inventors: Masaaki Suzuki, Hisashi Doi, Hiroko Koyama
  • Publication number: 20110263849
    Abstract: Provided is a method whereby a heteroaromatic ring aryl can be very rapidly methylated at a high yield. In an N-alkyl-2-pyrrolidinone, a heteroaromatic ring aryltrialkylstannan is cross-coupled with methyl iodide in the presence of a palladium complex, a phosphine ligand, a cuprous halide, a carbonic acid salt and/or an alkali metal fluoride to thereby rapidly methylate the heteroaromatic ring aryl. (Formula shows a case wherein the heteroaromatic ring aryl is a pyridyl group.
    Type: Application
    Filed: December 25, 2009
    Publication date: October 27, 2011
    Inventors: Masaaki Suzuki, Hisashi Doi, Hiroko Koyama
  • Patent number: 7432268
    Abstract: There are disclosed compounds of the formula (I): prodrugs thereof, or pharmaceutically acceptable salts of the compounds or of said prodrugs which are useful as inhibitors of Type 3 17?-Hydroxysteroid Dehydrogenase. Also disclosed are pharmaceutical compositions containing said compounds and their use for the treatment or prevention of androgen dependent diseases.
    Type: Grant
    Filed: November 14, 2005
    Date of Patent: October 7, 2008
    Assignee: Schering Corporation
    Inventors: Timothy Guzi, Kamil Paruch, Alan Mallams, Jocelyn D. Rivera, Ronald J. Doll, Viyyoor M. Girijavallabhan, Jonathan A. Pachter, Yi-Tsung Liu, Anil K. Saksena
  • Patent number: 7041856
    Abstract: There are disclosed a process for producing a coupling compound of formula (1): (Y—)(n?1)R1—R2—(R1)(n??1),??(1) wherein R1 and R2 independently represent a substituted or unsubstituted aryl group, which process is characterized by reacting an unsaturated organic compound of formula (2): n?(R1X1n)??(2) wherein n, n?, and R1 are the same as defined above, and X1 is the same or different and independently represents a leaving group and bonded with a sp2 carbon atom of R1 group, with a boron compound of formula (3): m{R2(BX22)n?}??(3) wherein R2 and n? are the same as defined above, X2 represents a hydroxy group, an alkoxy group, in the presence of a catalyst containing (A) a nickel compound, and (B) a nitrogen-containing cyclic compound, and the catalyst.
    Type: Grant
    Filed: October 22, 2002
    Date of Patent: May 9, 2006
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Tamon Itahashi, Takashi Kamikawa
  • Patent number: 7026478
    Abstract: A process for the production of compounds Ar—R1 by means of a cross-coupling reaction of an organometallic reagent R1-M with an aromatic or heteroaromatic substrate Ar—X catalyzed by one or several iron salts or iron complexes as catalysts or pre-catalysts, present homogeneously or heterogeneously in the reaction mixture. This new invention exhibits substantial advantages over established cross coupling methodology using palladium- or nickel complexes as the catalysts. Most notable aspects are the fact that (i) expensive and/or toxic nobel metal catalysts are replaced by cheap, stable, commercially available and toxicologically benign iron salts or iron complexes as the catalysts or pre-catalysts, (ii) commercially attractive aryl chlorides as well as various aryl sulfonates can be used as starting materials, (iii) the reaction can be performed under “ligand-free” conditons, and (iv) the reaction times are usually very short.
    Type: Grant
    Filed: May 10, 2002
    Date of Patent: April 11, 2006
    Assignee: Studiengesellschaft Kohle mbH
    Inventors: Alois Fürstner, Andreas Leitner, María Méndez
  • Patent number: 6911451
    Abstract: Phenylalanine derivatives of formula (1) are described: wherein L1 is a linker atom or group; X1 is a group selected from —N(R3)CO—, —N(R3)SO2—, —N(R3)C(O)O— or —N(R3)CON(R3a)—; and R is a carboxylic acid or a derivative thereof. The compounds are able to inhibit the binding of a 4 integrins to their ligands and are of use in the prophylaxis and treatment of diseases or disorders involving inflammation.
    Type: Grant
    Filed: June 4, 1999
    Date of Patent: June 28, 2005
    Assignee: Celltech R&D Limited
    Inventors: John Robert Porter, John Clifford Head, Graham John Warrellow, Sarah Catherine Archibald
  • Patent number: 6642273
    Abstract: An unsaturated derivative at the 4-position of 6-tert-butyl-1,1-dimethylindane corresponding to the following formula: in which: X represents: a divalent radical of formula: and Y represents a divalent radical of following formula: R1 represents —CH3, —(CH2)p—OR4, —(CH2)p—COR5 or —S(O)t—R6, p being 0, 1, 2 or 3, t being 0, 1 or 2, R4 represents H, lower alkyl, —COR7, aryl, aralkyl, mono- or polyhydroxyalkyl, or a polyether radical, R5 represents H, lower alkyl, —OR8 or R6 represents H or lower alkyl, R7 represents lower alkyl, R8 represents H, alkyl, alkenyl, alkynyl, aryl, aralkyl, mono- or polyhydroxyalkyl, a sugar residue selected from the group consisting of residues deriving from glucose, galactose, mannose and glucuronic acid or an amino acid residue deriving from lysine, glycine and aspartic acid, r′ and r″, which are identical or different, represent H, low
    Type: Grant
    Filed: August 9, 2002
    Date of Patent: November 4, 2003
    Assignee: Galderma Research & Development
    Inventors: Angel De Lera, Beatriz Dominguez
  • Patent number: 6635645
    Abstract: The invention relates to 2,5-diazabicyclo[2.2.1]heptane derivatives, to pharmaceutical compositions containing them, and to methods for the treatment or prevention of disorders associated with a dysfunction of the nicotinic receptors utilizing them.
    Type: Grant
    Filed: August 16, 2001
    Date of Patent: October 21, 2003
    Assignee: Sanofi-Synthelabo
    Inventors: Alistair Lochead, Samir Jegham, Alain Nedelec, Jean Jeunesse, Frédéric Galli, Luc Even
  • Patent number: 6630510
    Abstract: This invention relates to novel substituted succinic acid metallo-&bgr;-lactamase inhibitors which are useful potentiators of &bgr;-lactam antibiotics. Accordingly, the present invention provides a method of treating bacterial infections in animals or humans which comprises administering, together with a b-lactam antibiotic, a therapeutically effective amount of a compound of formula I: including pharmaceutically acceptable salts, prodrugs, anhydrides, and solvates thereof.
    Type: Grant
    Filed: October 26, 2000
    Date of Patent: October 7, 2003
    Assignee: Merck & Co., Inc.
    Inventors: James M. Balkovec, Mark L. Greenlee, Steven H. Olson, Gregory P. Rouen
  • Publication number: 20030162950
    Abstract: There are disclosed a process for producing a coupling compound of formula (1):
    Type: Application
    Filed: October 22, 2002
    Publication date: August 28, 2003
    Inventors: Tamon Itahashi, Takashi Kamikawa
  • Publication number: 20030109713
    Abstract: A process for producing organic substituted aromatic or heteroaromatic compounds including biaryl and biheteroaryl compounds in a two-step reaction. In the first step, the aromatic or heteroaromatic compound is borylated in a reaction comprising a borane or diborane reagent (any boron reagent where the boron reagent contains a B—H, B—B or B—Si bond) and an iridium or rhodium catalytic complex. In the second step, a metal catalyst catalyzes the formation of the organic substituted aromatic or heteroaromatic compound from the borylated compound and an electrophile such as an aryl or organic halide, triflate (OSO2CF3), or nonaflate (OSO2C4F9). The steps in the process can be performed in a single reaction vessel or in separate reaction vessels. The present invention also provides a process for synthesis of complex polyphenylenes starting from halogenated aromatic compounds.
    Type: Application
    Filed: July 12, 2002
    Publication date: June 12, 2003
    Applicant: Board of Trustees operating Michigan State University
    Inventors: Milton R. Smith, III, Robert E. Maleczka
  • Publication number: 20030050500
    Abstract: The present invention encompasses a process for preparing arylolefins by reacting one or more arylamines with one or more organic nitrites, in the presence of one or more olefins which bear at least one hydrogen atom on the double bond and in the presence of acid and in the presence of palladium or one or more palladium compounds.
    Type: Application
    Filed: August 12, 2002
    Publication date: March 13, 2003
    Inventors: Markus Eckert, Albert Schnatterer, Walter Lange
  • Publication number: 20020183516
    Abstract: Improved methods for generating a —C—C— bond by cross-coupling of a transferable group with an acceptor group. The transferable group is a substituent of an organosilicon nucleophile and the acceptor group is provided as an organic electrophile. The reaction is catalyzed by a Group 10 transition metal complex (e.g., Ni, Pt or Pd), particularly by a palladium complex. Certain methods of this invention use improved organosilicon nucleophiles which are readily prepared, can give high product yields and exhibit high stereo selectivity. Methods of this invention employ activating ions such as halides, hydroxide, hydride and silyloxides. In specific embodiments, organosilicon nucleophilic reagents of this invention include siloxanes, particularly cyclic siloxanes. The combination of the cross-coupling reactions of this invention with ring-closing metathesis, hydrosilylation and intramolecular hydrosilylation reactions provide useful synthetic strategies that have wide application.
    Type: Application
    Filed: June 6, 2001
    Publication date: December 5, 2002
    Inventors: Scott E. Denmark, Jun Young Choi, Daniel Wehrli, Zhicai Wu, Luc Neuville, Weitao Pan, Ramzi F. Sweis, Zhigang Wang, Shyh-Ming Yang
  • Patent number: 6245918
    Abstract: Process for the preparation of an ionic compound, Q+A− liquid at less than 150° C., wherein a trialkyloxonium of the anion is reacted with an amine in a hydrocarbon solvent. The aforesaid ionic compound can be used as a solvent in numerous catalytic reactions.
    Type: Grant
    Filed: June 1, 1999
    Date of Patent: June 12, 2001
    Assignee: Institut Francais du Petrole
    Inventors: Hélène Olivier, Frédéric Favre
  • Patent number: 6096894
    Abstract: A method of producing a 2-(p-alkylphenyl)pyridine compound economically, easily and industrially, which comprises adding manganese dioxide and trimethylchlorosilane, or adding manganese chloride to an organic ether solvent, and reacting p-alkylphenylmagnesium halide and 2-halopyridine in the obtained organic ether solvent.
    Type: Grant
    Filed: July 27, 1999
    Date of Patent: August 1, 2000
    Assignee: Sumika Fine Chemicals Co., Ltd.
    Inventors: Kozo Matsui, Yoshihide Umemoto, Kiyoshi Sugi, Tetsuya Shintaku, Nobushige Itaya
  • Patent number: 5763668
    Abstract: Amines are prepared by reacting a mixture obtained in the cracking of mineral oil fractions with ammonia or a primary or secondary amine of the general formula I ##STR1## where R.sup.1 and R.sup.2 are each hydrogen, C.sub.1 -C.sub.20 -alkyl, C.sub.2 -C.sub.20 -alkenyl, C.sub.2 -C.sub.20 -alkynyl, C.sub.3 -C.sub.20 -cycloalkyl, C.sub.4 -C.sub.20 -alkylcycloalkyl, C.sub.4 -C.sub.20 -cycloalkylalkyl, aryl, C.sub.7 --C.sub.20 -alkylaryl or C.sub.7 --C.sub.20 -aralkyl or together are a saturated or unsaturated C.sub.2 -C.sub.12 -alkylene ene chain,at from to C.
    Type: Grant
    Filed: July 3, 1996
    Date of Patent: June 9, 1998
    Assignee: BASF Aktiengesellschaft
    Inventors: Uwe Dingerdissen, Jurgen Herrmann, Karsten Eller
  • Patent number: 5705648
    Abstract: Mepiquat chloride is formed from the reaction between N-methylpiperidine and chloromethane in an anhydrous liquid solvent selected from the group consisting of acetone, methyl ethyl ketone, toluene, tetrahydrofuran, isopropanol, acetonitrile, N,N-dimethylformamide and methylene chloride in the absence of sodium hydroxide. Mepiquat chloride precipitates as a solid of high purity and is recovered under a substantially moisture-free atmosphere.The solid mepiquat chloride can be sealed into a water soluble pouch or into a water soluble encapsulated solid form (e.g., granule, pellet, or briquette) for convenient handling. The pouch contains powdered mepiquat chloride or the encapsulated solid is merely introduced directly into a spray tank or reservoir for application with low human exposure and no containers in contact with the mepiquat chloride that require disposal.Mepiquat chloride is used as a component of a system for growing a number of commodity plants including cotton.
    Type: Grant
    Filed: October 17, 1994
    Date of Patent: January 6, 1998
    Assignee: Micro Flo Co.
    Inventors: Richard U. Clark, James S. Lovell, James C. Thigpen, David William Bristol, John Raymond Tyndall, Albert Roger Frisbee
  • Patent number: 5360911
    Abstract: A novel process is disclosed for producing stilbazolium salts. Said novel process employs a heterocyclic amine catalyst, such as pyrrolidine, an alkylated pyridine salt and a substituted benzaldehyde which unexpectedly results in increased reaction rates and product yields.
    Type: Grant
    Filed: June 17, 1993
    Date of Patent: November 1, 1994
    Assignee: General Electric Company
    Inventors: Eugene P. Boden, Peter D. Phelps, Kevin R. Stewart
  • Patent number: 5290932
    Abstract: Amines of the general formula I ##STR1## where R.sup.1 and R.sup.2 are each C.sub.1 -C.sub.20 -alkyl, C.sub.3 -C.sub.20 -cycloalkyl, C.sub.4 -C.sub.20 -alkylcycloalkyl, C.sub.4 -C.sub.20 -cycloalkylalkyl, aryl, C.sub.7 -C.sub.20 -alkylaryl, C.sub.7 -C.sub.20 -aralkyl or a heterocyclic radical and n is an integer of from 3 to 7, are prepared by a process in which a ketone of the general formula II ##STR2## where R.sup.1 and R.sup.2 have the abovementioned meanings, is reacted with a cyclic amine of the general formula III ##STR3## where n has the abovementioned meanings, in the presence of a zeolite and/or SiO.sub.2 having a zeolite structure and/or a phosphate and/or a phosphate having a zeolite structure as catalysts at from to C. and from 0.01 to 50 bar.
    Type: Grant
    Filed: October 30, 1992
    Date of Patent: March 1, 1994
    Assignee: BASF Aktiengesellschaft
    Inventors: Uwe Dingerdissen, Wolfgang Hoelderich
  • Patent number: 5080719
    Abstract: This invention privdes novel heteroaromatic compounds, and smoking compositions which contain an invention heteroaromatic compound as a flavorant-release additive as illustrated by the following additive structure: ##STR1## Under typical cigarette smoking conditions, 2-isopropylpyrazine and acetophenone are released as pyrolysis products, and enhance the flavor and aroma of the mainstream and sidestream smoke.
    Type: Grant
    Filed: September 24, 1987
    Date of Patent: January 14, 1992
    Assignee: Philip Morris Incorporated
    Inventors: Yoram Houminer, Henry V. Secor, Jeffrey I. Seeman
  • Patent number: 5061805
    Abstract: A process for dealkylating the 2-position on a trisubstituted pyridine derivative having the formula ##STR1## where R.sub.1 is a straight chain alkyl group from about C.sub.2 -C.sub.5 and where R.sub.2 and R.sub.3 are alkyl, aryl or aralkyl groups up to about C.sub.10, comprising the step of reacting said pyridine derivative at reflux with excess sulfur. Of particular note is the preparation of 2,3,5-trimethylpyridine including the initial preparation of its 2-ethyl precursor by the Chichibabin reaction of propionaldehyde and ammonia.
    Type: Grant
    Filed: August 10, 1990
    Date of Patent: October 29, 1991
    Assignee: Reilly Industries, Inc.
    Inventor: Gerald L. Goe
  • Patent number: 4701530
    Abstract: Process for the production of 2,4,6-trimethyl pyridine wherein a carbonyl compound such as acetone is reacted with ammonia in the presence of a condensation catalyst at a temperature in the range from to C. to produce a mixture of products containing 2,2,4,6-tetramethyl-1,2-dihydropyridine which is then purified. The substantially pure dihydropyridine is then contacted with a cracking catalyst at a temperature in the range from to C. to produce 2,4,6-trimethyl pyridine in high yield.
    Type: Grant
    Filed: October 1, 1986
    Date of Patent: October 20, 1987
    Assignee: The Dow Chemical Company
    Inventors: Loren L. Swearingen, Randy J. LaTulip
  • Patent number: 4658032
    Abstract: Process for producing 2,3,5-collidine and/or 2,3,5,6-tetramethylpyridine which is characterized by reacting 3,5-lutidine as the starting material with an aliphatic alcohol having 1 to 4 carbon atoms, in the presence of a catalyst for hydrogenation at a temperature of C. or higher.The above-mentioned 2,3,5-collidine and/or 2,3,5,6-tetramethylpyridine are important compounds as intermediates for synthesizing various pharmaceutical chemicals.
    Type: Grant
    Filed: July 10, 1985
    Date of Patent: April 14, 1987
    Assignee: Koei Chemical Co., Ltd.
    Inventor: Mitsuharu Yamaji
  • Patent number: 4656299
    Abstract: A complex of an electron-attracting group-substituted .eta..sup.5 -cyclopentadienylcobalt with a polyene or an acetylene for use as a catalyst, for example, for the synthesis of a substituted pyridine from an alkyne and a nitrile.
    Type: Grant
    Filed: January 13, 1986
    Date of Patent: April 7, 1987
    Assignees: Denki Kagaku Kogyo Kabushiki Kaisha, Rikagaku Kenkyusyo
    Inventors: Chiyuki Fujii, Seiichi Watanabe
  • Patent number: 4294968
    Abstract: The catalytic method of preparing .alpha.-picoline from 5-oxohexanenitrile is improved by using as the catalyst carbon-supported palladium.
    Type: Grant
    Filed: July 7, 1980
    Date of Patent: October 13, 1981
    Assignee: The Dow Chemical Company
    Inventors: Frederick C. Stone, Gary G. Schupska
  • Patent number: 4220785
    Abstract: This invention relates to substituted pyridines prepared by reacting aldehydes, amines, lower carboxylic acids such as acetic acid in the presence of oxygen. The N-substituted pyridinium salts formed can be converted to pyridines by thermal dealkylation.
    Type: Grant
    Filed: August 25, 1978
    Date of Patent: September 2, 1980
    Assignee: Petrolite Corporation
    Inventors: Bernardus A. Oude Alink, Neil E. S. Thompson
  • Patent number: 4189585
    Abstract: A process for preparing pyridine with 2,6 lutidine as by-product, by catalytic demethylation of .alpha.-picoline in the gaseous phase with steam is disclosed wherein the demethylation step is conducted at a temperature of C. using a metallic hydrogenation catalyst at a contact time of about 0.5 to 15 seconds. Pyridine is a known important organic base with many uses, such as denaturant for alcohols and solvent in the rubber and paint industries.
    Type: Grant
    Filed: April 21, 1978
    Date of Patent: February 19, 1980
    Assignee: Stamicarbon, B.V.
    Inventors: Egidius J. M. Verheijen, Nicolaas L. G. Duys
  • Patent number: 4186148
    Abstract: 3,7-Dimethyl-2,6-octadienylamine derivatives are produced by reacting isoprene with a secondary amine in the presence of a catalyst prepared by reacting a secondary amine, a conjugated diene and/or a polycyclic aromatic compound, a lithium salt and sodium and/or potassium metal.
    Type: Grant
    Filed: May 3, 1978
    Date of Patent: January 29, 1980
    Assignee: Nissan Chemical Industries Limited
    Inventors: Atsuo Murata, Shuji Tsuchiya, Akihiro Konno, Jun Uchida
  • Patent number: 4179580
    Abstract: A process for increasing the reaction rate of condensation reactions which occur between non-conjugated non-aromatic olefinically unsaturated hydrocarbons and active hydrogen-containing organic compounds in the presence of alkali metal comprising carrying out the reaction in the presence of titanium metal.
    Type: Grant
    Filed: May 11, 1978
    Date of Patent: December 18, 1979
    Assignee: Phillips Petroleum Company
    Inventor: Raymond L. Cobb
  • Patent number: 4138488
    Abstract: Disclosed herein are substituted diphenylmethyl picolinic acids, pharmaceutically acceptable salts, amides and esters thereof. The compounds disclosed are useful as topical anti-acne agents.
    Type: Grant
    Filed: January 10, 1977
    Date of Patent: February 6, 1979
    Assignee: Schering Corporation
    Inventors: Margaret H. Sherlock, Heide Roebke