Racemization, Resolution, Or Inversion Of Configuration Processes For Optically Active Compounds Patents (Class 558/354)
  • Patent number: 9596857
    Abstract: The present invention is directed to a novel insecticidal composition comprising bifenthrin and a cyano-pyrethroid which exhibit an unexpected increase in insecticidal activity as compared to the insecticidal activity of the individual components. The present invention is also directed to a novel insecticidal composition comprising bifenthrin and a cyano-pyrethroid in admixture with at least one agriculturally acceptable extender or adjuvant.
    Type: Grant
    Filed: March 19, 2015
    Date of Patent: March 21, 2017
    Assignee: FMC Corporation
    Inventors: Robert M. Herrick, Mark Walmsley, Charles A. Staetz, Hui S. Yang, D. Craig Heim, Hylsa Garcia, Nancy Hilton
  • Patent number: 9107416
    Abstract: The present invention is directed to novel insecticidal and/or miticidal compositions comprising bifenthrin and a cyano-pyrethroid. The compositions exhibit an unexpected increase in insecticidal activity as compared to the insecticidal activity of the individual components.
    Type: Grant
    Filed: December 21, 2006
    Date of Patent: August 18, 2015
    Assignee: FMC Corporation
    Inventors: Robert M. Herrick, Mark Walmsley, Charles A. Staetz, Nancy Hilton, Hui S. Yang, D. Craig Heim, Hylsa Garcia
  • Patent number: 8536365
    Abstract: Process for the optical resolution of the compound of formula (I): by chiral chromatography. Application in the synthesis of ivabradine, of its addition salts with a pharmaceutically acceptable acid and of their hydrates.
    Type: Grant
    Filed: August 24, 2009
    Date of Patent: September 17, 2013
    Assignee: Les Laboratoires Servier
    Inventors: Jean-Michel Lerestif, Jean-Pierre Lecouve, Daniel Dron, Eric Gojon, Maryse Phan
  • Patent number: 8349344
    Abstract: The present invention is directed to novel insecticidal compositions comprising bifenthrin and enriched cypermethrin, the compositions are physically stable when diluted with water.
    Type: Grant
    Filed: March 12, 2012
    Date of Patent: January 8, 2013
    Assignee: FMC Corporation
    Inventors: Charles A. Staetz, Hui S. Yang, Hylsa Garcia
  • Patent number: 8304252
    Abstract: The present invention is directed to a regio-and stereoselective bioconversion of selected aliphatic dinitriles into corresponding cyanocarboxylic acids. More particularly, the present invention provides methods for the conversion of 2-isobutyl-succinonitrile into (S)-3 cyano-5-methylhexanoic acid, which is a useful intermediate in the synthesis of (S)-3(aminomethyl)-5-methylhexanoic acid (pregabalin). Pregabalin can be used for treating certain cerebral diseases, for example, in the treatment and prevention of seizure disorders, pain, and psychotic disorders.
    Type: Grant
    Filed: April 20, 2010
    Date of Patent: November 6, 2012
    Assignee: Pfizer Inc.
    Inventors: Michael P. Burns, Justin K. Weaver, John Wing Wong
  • Patent number: 8153145
    Abstract: The present invention is directed to novel insecticidal compositions comprising bifenthrin and enriched cypermethrin, the compositions are physically stable when diluted with water.
    Type: Grant
    Filed: December 21, 2006
    Date of Patent: April 10, 2012
    Assignee: FMC Corporation
    Inventors: Charles A. Staetz, Hui S. Yang, Hylsa Garcia
  • Patent number: 7803962
    Abstract: A new process is described for the resolution of racemic verapamil, which allows the desired enantiomer to be obtained in high yields and with high enantiomeric purity. The process uses optically active 2,3-bis[(2-fluorobenzoyl)oxy]butanedioic acid as the resolving agent, and a water/dimethylformamide or water/acetonitrile or water/methanol mixture, as the reaction solvent.
    Type: Grant
    Filed: June 3, 2008
    Date of Patent: September 28, 2010
    Assignee: Cosma S.p.A.
    Inventors: Chiara Bertolotti, Massimiliano Lussana, Enrica Pizzatti, Enrico Vigano', Ernesto Landonio
  • Publication number: 20100204503
    Abstract: The present invention is directed to a regio- and stereoselective bioconversion of selected aliphatic dinitriles into corresponding cyanocarboxylic acids. More particularly, the present invention provides methods for the conversion of 2-isobutyl-succinonitrile into (S)-3 cyano-5-methylhexanoic acid, which is a useful intermediate in the synthesis of (S)-3(aminomethyl)-5-methylhexanoic acid (pregabalin). Pregabalin can be used for treating certain cerebral diseases, for example, in the treatment and prevention of seizure disorders, pain, and psychotic disorders.
    Type: Application
    Filed: April 20, 2010
    Publication date: August 12, 2010
    Inventors: Michael P. Burns, Justin K. Weaver, John Wing Wong
  • Publication number: 20100056778
    Abstract: Process for the optical resolution of the compound of formula (I): by chiral chromatography. Application in the synthesis of ivabradine, of its addition salts with a pharmaceutically acceptable acid and of their hydrates.
    Type: Application
    Filed: August 24, 2009
    Publication date: March 4, 2010
    Inventors: Jean-Michel Lerestif, Jean-Pierre Lecouve, Daniel Dron, Eric Gojon, Maryse Phan
  • Publication number: 20080306296
    Abstract: A new process is described for the resolution of racemic verapamil, which allows the desired enantiomer to be obtained in high yields and with high enantiomeric purity. The process uses optically active 2,3-bis[(2-fluorobenzoyl)oxy]butanedioic acid as the resolving agent, and a water/dimethylformamide or water/acetonitrile or water/methanol mixture, as the reaction solvent.
    Type: Application
    Filed: June 3, 2008
    Publication date: December 11, 2008
    Inventors: Chiara Bertolotti, Massimiliano Lussana, Enrica Pizzatti, Enrico Vigano, Ernesto Landonio
  • Patent number: 7301044
    Abstract: A process and intermediates for producing 3-amino nitrites. The process involves resolving an enantiomeric mixture of chiral 3-amino nitrites in the presence of a chiral acid in a solvent system to produce a chiral 3-amino nitrile salt. The process may further comprise a recrystalizing step, wherein an enantiomerically enriched 3-amino nitrile salt is produced. The process may further comprise a salt exchanging step, wherein another acid is added to the chiral 3-amino nitrile salt or the enantiomerically enriched 3-amino nitrile salt to produce another 3-amino nitrile salt.
    Type: Grant
    Filed: September 21, 2004
    Date of Patent: November 27, 2007
    Assignee: Pfizer Inc.
    Inventors: David Robert Allen, Crystal A Achenbach-McCarthy
  • Patent number: 7022869
    Abstract: Methods of synthesizing pure enantiomers of acylanalides such as Casodex® (bicalutamide) and its derivatives utilizing a compound having a ring structure that, when opened, provides a substituent having the structure of Formula I: wherein R1 is alkyl or haloalkyl having up to 4 carbons; R2 is alkyl having up to 6 carbon atoms; and R3 is CH2OR4 where R4 is hydrogen or benzyl, C(O)CH3, or C(O)OR5 where R5 is hydrogen or alkyl; are disclosed.
    Type: Grant
    Filed: May 23, 2003
    Date of Patent: April 4, 2006
    Assignee: Nobex Corporation
    Inventor: Nnochiri Nkem Ekwuribe
  • Patent number: 6730803
    Abstract: The &bgr;-keto ester compound, &bgr;-hydroxy acid compound and acetonide form of a 1,3-diol derivative of the formulas (I), (V) and (VIII) wherein each symbol is as defined in the specification, are useful as a synthetic intermediate for an epothilone derivative being developed as a pharmaceutical agent having an antitumor activity.
    Type: Grant
    Filed: September 30, 2002
    Date of Patent: May 4, 2004
    Assignee: Sumika Fine Chemicals Co., Ltd.
    Inventors: Mitsuhiro Iwasaki, Kiyoshi Sugi, Hideto Miyamoto, Nobushige Itaya
  • Patent number: 6583306
    Abstract: Methods of synthesizing pure enantiomers of acylanalides such as Casodex® (bicalutamide) and its derivatives utilizing a compound having a ring structure that, when opened, provides a substituent having the structure of Formula I: wherein R1 is alkyl or haloalkyl having up to 4 carbons; R2 is alkyl having up to 6 carbon atoms; and R3 is CH2OR4 where R4 is hydrogen or benzyl, C(O)CH3, or C(O)OR5 where R5 is hydrogen or alkyl; are disclosed. Methods of synthesizing acylanalides such as Casodex® (bicalutamide) and/or derivatives thereof from a starting material of citramalic acid are also provided.
    Type: Grant
    Filed: October 18, 2000
    Date of Patent: June 24, 2003
    Assignee: Nobex Corporation
    Inventor: Nnochiri Nkem Ekwuribe
  • Patent number: 6465684
    Abstract: A diastereomer complex obtained via a process for the separation of enantiomers is disclosed, wherein separation can be rapidly effected such that enantiomers are obtained with high e.e. values. The process permits the separation of mixtures of enantiomers in which more than one resolving agent is used, of which at least one resolving agent is optically active, and which yields a diastereomer complex containing at least two resolving agents in optically active form. The process provides for, inter alia, a diastereomer complex having at least three compounds of which at least two compounds are resolving agents in optically active form, and at least one compound is an enantiomer in optically active form. Also provided is a diastereomer complex having at least three compounds of which at least one compound is a resolving agent in optically active form, and at least two compounds which are enantiomers in optically active form.
    Type: Grant
    Filed: February 16, 2001
    Date of Patent: October 15, 2002
    Assignee: DSM N.V.
    Inventors: Ton R. Vries, Hans Wijnberg, Erik Van Echten, Lumbertus A. Hulshof, Quirinus B. Broxterman
  • Patent number: 6235927
    Abstract: A diastereomer complex obtained via a process for the separation of enantiomers is disclosed, wherein separation can be rapidly effected such that enantiomers are obtained with high e.e. values. The process pets the separation of mixtures of enantiomers in which more than one resolving agent is used, of which at least one resolving agent is optically active, and which yields a diastereomer complex containing at least two resolving agents in optically active form. The process provides for, inter alia, a diastereomer complex having at least three compounds of which at least two compounds are resolving agents in optically active form, and at least one compound is an onantiomer in optically active form. Also provided is a diastereomer complex having at least three compounds of which at lea one compound is a resolving agent in optically active form, and at least two compounds which are enantiomers in optically active form.
    Type: Grant
    Filed: October 22, 1997
    Date of Patent: May 22, 2001
    Assignee: DSM N.V.
    Inventors: Ton R. Vries, Hans Wijnberg, Erik Van Echten, Lumbertus A. Hulshof, Quirinus B. Broxterman
  • Patent number: 6184381
    Abstract: This document describes a novel and practically excellent process for the preparation of optically active compounds, such as optically active alcohols or amines which are useful for various applications, for example, as synthetic intermediates of pharmaceuticals, liquid crystal materials, and reagents for optical resolution, wherein a hydrogen transfer type asymmetric reduction is carried out in the presence of both a transition metal complex and an optically active nitrogen compound or a transition metal complex having an optically active nitrogen compounds as an asymmetric ligand, and a hydrogen-donating organic or inorganic compound.
    Type: Grant
    Filed: September 29, 1998
    Date of Patent: February 6, 2001
    Assignees: Japan Science & Technology Corp., NKK Corp., Takeda Chemical Industries, Asahi Kasei Kogyo Kabushiki Kaisha, Takasago Intl. Corp.
    Inventors: Takao Ikariya, Shohei Hashiguchi, Jun Takehara, Nobuyuki Uematsu, Kazuhiko Matsumura, Ryoji Noyori, Akio Fujii
  • Patent number: 5929279
    Abstract: A process for the preparation of largely isomerically pure .alpha.-bisoximes of the formula IaR.sup.1 O--N.dbd.CR.sup.2 --CR.sup.3 .dbd.N--OR.sup.4 Iawhere the groups R.sup.1 O-- and R.sup.2 on the N.dbd.C bond are cis to one another and where the radicals have the following meanings:R.sup.1 and R.sup.4 are hydrogen or a C-organic radical;R.sup.2 is hydrogen, cyano, nitro, hydroxyl, amino, halogen or an organic radical which can be bonded to the structure directly or via an oxygen, sulfur or nitrogen atom;R.sup.3 is hydrogen, cyano, nitro, hydroxyl, amino, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino or cycloalkyl,from a mixture of the isomers of the a-bisoximes Ia and Ib ##STR1## is described.
    Type: Grant
    Filed: October 7, 1997
    Date of Patent: July 27, 1999
    Assignee: BASF Aktiengesellschaft
    Inventors: Ruth Muller, Remy Benoit, Herbert Bayer, Norbert Gotz, Hubert Sauter
  • Patent number: 5910601
    Abstract: The subject invention concerns a process for preparing a single enantiomer, either R or S, of R'--NH--(CH.sub.2).sub.3 --C(Ar)(CN)--R. The process is particularly useful for preparing verapamil, and analogues thereof, in single enantiomeric form.
    Type: Grant
    Filed: March 27, 1996
    Date of Patent: June 8, 1999
    Assignee: Darwin Discovery Limited
    Inventors: Raymond McCague, Shouming Wang
  • Patent number: 5900503
    Abstract: An optically active cyanohydrin represented by the following general formula (1): ##STR1## wherein each of R1 and R2 is a hydrogen atom or an amino-protecting group, and the configurations relating to the carbon atoms at the *2-position and *3-position are as follows: in the case of the carbon atom at the *2-position being in R-configuration, the carbon atom at the *3-position is in S-configuration, and in the case of the carbon atom at the *2-position being in S-configuration, the carbon atom at the *3-position is in R-configuration, can be efficiently produced by crystallizing one of the optically active cyanohydrins while treating a mixture of cyanohydrin diastereomers in the presence of an amine and an organic solvent to change the configuration relating to the carbon atom at the 2-position and thereby cause isomerization.
    Type: Grant
    Filed: May 11, 1998
    Date of Patent: May 4, 1999
    Assignee: Nippon Kayaku Kabushiki Kaisha
    Inventors: Yoshinobu Miyazawa, Taichi Koshigoe, Kouichi Ohkawa, Jouji Sekine, Shinichiro Saeki
  • Patent number: 5892093
    Abstract: A reproducible process for preparing a substantially single enantiomer (R or S) of 4-cyano-4-(3,4-dimethoxyphenyl)-5-methylhexanoic acid, or an analogue thereof, thereby providing single enantiomer acid for the first time, proceeds by means of a classical salt resolution employing a resolving agent selected from an enantiomer (R or S) of a 1-arylalkylamine and (-)-quinine, and provides novel salts that are readily convertible to verapamil.
    Type: Grant
    Filed: February 7, 1997
    Date of Patent: April 6, 1999
    Assignee: Darwin Discovery Limited
    Inventors: Robin Mark Bannister, Graham Robert Evans, Benjamin Mark Skead
  • Patent number: 5886207
    Abstract: This invention relates to optically active compounds of Flubrocythrinate, their preparations and uses. The insecticidal and miticidal activities of the optically active compounds of the present invention are apparently higher than that of mixture racemic compounds, thus resulting in an increase in rate of utilization as well as a decrease in environmental pollution. Moreover, the process for the preparations of the insecticidal and miticidal agents of the present invention are quite simple, therefore they might have a wide-ranging applications.
    Type: Grant
    Filed: November 17, 1995
    Date of Patent: March 23, 1999
    Assignee: Shanghai Zhongxi Pharmaceutical Co. Ltd.
    Inventors: Guanhe Sun, Weigao Jin, Lin Zuo, Hongyue Xie
  • Patent number: 5821369
    Abstract: A process for the racemization of an enantiomerically-enriched compound of formula (3), comprises treatment of enantiomerically-enriched (3) with a base to obtain anion (4), optionally in protonated form, which is then combined with CH.sub.2 =CH--Y.sup.1 to form racemic (3), ##STR1## wherein Ar=aryl or heteroaryl; Ak=C.sub.1-20 alkyl; X=CN, CO.sub.2 R, CONR.sup.1 R.sup.2, and COR; Y and Y.sup.1 are independently selected from CN, CO.sub.2 R, CONR.sup.1 R.sup.2 and R, R.sub.1 and R.sub.2 are independently selected from H and C.sub.1-20 alkyl; optionally as a salt thereof.This racemization process can be used as part of an efficient synthesis of enantiomerically-enriched verapamil or aminoglutethimide.
    Type: Grant
    Filed: February 7, 1997
    Date of Patent: October 13, 1998
    Assignee: Chiroscience Limited
    Inventor: Raymond McCague
  • Patent number: 5650524
    Abstract: A process for preparing (R)-3-amino-5-methoxychroman is provided. The process comprises the steps of (i) dissolving racemic 3-amino-5-methoxychroman and L(+)tartaric acid in water to form the tartrate salt; (ii) heating the solution until a clear solution is obtained; and (iii) crystallizing the tartrate salt by allowing the solution to cool to room temperature.
    Type: Grant
    Filed: May 26, 1995
    Date of Patent: July 22, 1997
    Assignee: Astra Aktiebolag
    Inventor: Lars-Gunnar Larsson
  • Patent number: 5648386
    Abstract: The invention relates to the separation of enantiomers of cimaterol, (-)-cimaterol, the addition salts thereof and processes for preparing them and their use in pharmaceutical compositions and animal feeds.
    Type: Grant
    Filed: November 29, 1994
    Date of Patent: July 15, 1997
    Assignee: Boehringer Ingelheim Vetmedica GmbH
    Inventors: Wolfgang Resemann, Adolf Durr, Gunther Engelhardt, John Frances Quirke
  • Patent number: 5493047
    Abstract: The invention relates to a method of preparing an optically active cyanohydrin carboxylic acid ester from an optically active cyanohydrin of opposite configuration, wherein said starting cyanohydrin is converted with a carboxylic acid in the presence of a dialkyl azodicarboxylate and a triarylphosphine.The invention also relates to a method of preparing an optically active cyanohydrin of opposite configuration by a subsequent solvolysis of the ester obtained under conservation of the configuration.
    Type: Grant
    Filed: December 6, 1993
    Date of Patent: February 20, 1996
    Assignee: Duphar International Research B.V.
    Inventors: Johannes Brussee, Arne Van Der Gen, Erwin G. J. C. Warmerdam, Chris G. Kruse
  • Patent number: 5457224
    Abstract: A process for the resolution of racemic verapamil which comprises reacting the free base of the compound with optically active dibenzoyltartaric acid or ditoluoyltartaric acid in the molar ratio from 1:1 to 1:2 in a methanol/water mixture in the ratio from 1:1 to 3:1 or acetone/water mixture in the ratio from 0.5:1 to 2:1, separating the mixture of diastereomers obtained in this way by crystallization, and then converting the diastereomers into the free bases and these into their salts, if required, with physiologically tolerated acids.
    Type: Grant
    Filed: June 7, 1994
    Date of Patent: October 10, 1995
    Assignee: Knoll Aktiengesellschaft
    Inventors: Oskar Ehrmann, Herbert Nagel
  • Patent number: 5395957
    Abstract: The invention relates to the separation of enantiomers of cimaterol, (-)-cimaterol, the addition salts thereof and processes for preparing them and their use in pharmaceutical compositions and animal feeds.
    Type: Grant
    Filed: December 14, 1993
    Date of Patent: March 7, 1995
    Assignee: Boehringer Ingelheim Vetmedica GmbH
    Inventors: Wolfgang Resemann, Adolf Durr, Gunther Engelhardt, John F. Quirke
  • Patent number: 5334744
    Abstract: A process for obtaining an isomer of a compound of general formulaR--CH(CN)--R' (I)wherein each of R and R' may be any organic radical linked directly or through a heteroatom to the carbon atom bearing the cyano group provided that at least one of R and R' comprises at least one resolved chiral center which is stable under the conditions of the process, or a racemic modification comprising the isomer and its enantiomer, which comprises the step of treating the epimer of the isomer, or the racemate comprising the epimer and the enantiomer of the epimer, in solution in a polar organic solvent, or in slurry in a polar organic liquid diluent in which the epimer or the racemate is partially soluble, with a source of cyanide ions, in the absence of a base, the isomer, or the racemic modification comprising the isomer and its enantiomer, being less soluble in the solvent or diluent than the epimer of the isomer, or the racemate comprising the epimer of the isomer and the enantiomer of the epimer, respectively.
    Type: Grant
    Filed: December 23, 1992
    Date of Patent: August 2, 1994
    Assignee: Zeneca Ltd.
    Inventors: Ernest S. Cleugh, David J. Milner
  • Patent number: 5312957
    Abstract: The invention provides a process for enantioselective hydrocyanation of aromatic vinyl compounds which produces nonracemic mixtures of chiral, arylpropionitriles; novel carbohydrate phosphorus and nickel catalyst compositions; and optically pure (S)-(-)-2-(6-methoxy-2-naphthalene)propionitrile.
    Type: Grant
    Filed: October 15, 1992
    Date of Patent: May 17, 1994
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: Albert L. Casalnuovo, Thaliyil V. Rajanbabu, Lawrence W. Gosser, Ronald J. McKinney, Nugent, Jr. William A.
  • Patent number: 5278338
    Abstract: A method for racemizing an optically active carboxylic acid, or ester thereof, of the formula: ##STR1## where R.sub.1 is hydrogen, hydroxy, halo, cyano, C.sub.1 to C.sub.6 linear or branched alkoxy, amino or substituted amino or the group ##STR2## is nitrile; R.sub.2, R.sub.3 and R.sub.4 are different and are hydrogen or C.sub.1 to C.sub.6 linear or branched alkyl, C.sub.1 to C.sub.6 linear or branched haloalkyl, aralkyl, cycloalkyl, alkyl substituted cycloalkyl, C.sub.6 to C.sub.10 aryl, C.sub.1 to C.sub.6 linear or branched alkoxy, C.sub.6 to C.sub.10 aryloxy, C.sub.1 to C.sub.6 alkylthio, C.sub.3 to C.sub.8 cycloalkylthio, C.sub.6 to C.sub.10 arylthio, C.sub.6 to C.sub.10 arylcarbonyl, C.sub.4 to C.sub.8 cycloalkenyl, trifluoromethyl, halo, C.sub.4 to C.sub.5 heteroaryl, C.sub.10 to C.sub.14 aryl, or biphenyl unsubstituted or substituted with methyl or halo, comprising heating said optically active carboxylic acid or ester thereof in the presence of water at a temperature of from about 40.degree. C.
    Type: Grant
    Filed: November 4, 1992
    Date of Patent: January 11, 1994
    Assignee: Ethyl Corporation
    Inventor: Rhonda L. Trace
  • Patent number: 5241087
    Abstract: A method of enantiomerically enriching chiral cyanohydrins is disclosed that involves selective cleavage of the unwanted enantiomer into its cleavage products HCN and the corresponding aldehyde or ketone by use of an enantioselective dehydrocyanation catalyst, coupled with simultaneous removal of at least one of the dehydrocyanation products.
    Type: Grant
    Filed: March 9, 1992
    Date of Patent: August 31, 1993
    Assignee: Bend Research, Inc.
    Inventor: Paul van Eikeren
  • Patent number: 5200561
    Abstract: Disclosed is a process for producing an optically active amine represented by the formula (IV) ##STR1## wherein R.sub.7 and R.sub.8 each denote an alkyl group, aryl group or aralkyl group, providing that they do not denote the same group at the same time, and * indicates an asymmetric carbon atom, which comprises reacting an asymmetric reducing agent obtained from (1) an optically active amine derivative represented by the formula (I) ##STR2## wherein R.sub.1 denotes an alkyl group, aryl group or aralkyl group; R.sub.2 denotes a hydrogen atom, alkyl group or aralkyl group; R.sub.3 denotes an aryl group or a substituent represented by the formula (II) ##STR3## wherein R.sub.4 and R.sub.5 each denote a hydrogen atom, aryl group or aralkyl group, and * is as defined above, (2) a metal borohydride and (3) sulfuric acid, with either the syn-isomer or the anti-isomer of an oxime derivative represented by the formula (III) or with a mixture rich in either one of the two isomers ##STR4## wherein R.sub.
    Type: Grant
    Filed: October 7, 1991
    Date of Patent: April 6, 1993
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Naoto Konya, Yukio Yoneyoshi, Yoji Sakito, Shinji Nishii, Gohfu Suzukamo, Hiroko Sakane
  • Patent number: 5153349
    Abstract: The invention relates to a process for the preparation of such isomer mixtures of cypermethrine of the Formula (I) ##STR1## wherein carbon atoms indicated by 1, 3 and .alpha. stand for a chiral carbon atom and the wavy line indicates cis or trans configuration related to the cyclopropane ring--which contains out of the theoretically possible 8-isomers of cypermethrine at least 95% of 1RtransS and 1StransR (Ib) isomer pair or only a mixture of 1RcisC and 1ScisR (Ia) and the isomer pair (Ib) of the ratio (Ia):(Ib)=55:45-25:75 by asymmetric transformation of second order performed in the presence of an amine base and solvent from a starting cypermethrine isomer mixture which contains next to the isomer pair (Ib) cis and other trans isomers or the isomer pair Ia+Ib at an undesired ratio.
    Type: Grant
    Filed: October 19, 1990
    Date of Patent: October 6, 1992
    Assignee: Chinoin Gyogyszer- es Vegyeszeti Termekek Gyara Rt.
    Inventors: Sandor Zoltan, Gyorgy Hidasi, Bela Bertok, Istavan Szekely, Janis Hajimichael, Sandor Botar, Lajos Nagy, Eva Somfai, Istvan Lak, Andras Rapi, Antal Gajary, Agnes Hegedus, Maria Tary
  • Patent number: 5128497
    Abstract: Crystalline pyrethroid isomers or enantiomer pairs are converted to more pesticidally active isomers by contacting a hydrocarbon slurry of the starting isomers with an epimerization agent selected from the group consisting of 1,1,3,3-tetramethylguanidine and 1,8-diazabicyclo[5.4.0]undec-7-ene, agitating the slurry while maintaining a temperature effective for conversion, and recovering the resulting isomers. The process typically is effective for enriching cypermethrin, and cyfluthrin.
    Type: Grant
    Filed: January 3, 1990
    Date of Patent: July 7, 1992
    Assignee: FMC Corporation
    Inventor: John W. Ager
  • Patent number: 5110976
    Abstract: A process is disclosed for preparing a synergistic, crystalline product consisting of solely enantiomer pair 1RCisS and 1SCisR and enantiomer pair 1RTransS and 1STransR of cypermethrin in a 3:7 to 5:5 crystalline mixture, which comprises the steps of: (a) epimerizing an oily melt or a saturated solution of enantiomer pair 1RCisS and 1SCisR and enantiomer pair 1RTransS and 1STransR in a ratio other than 3:7 to 5:5, or a mixture of enantiomer pair 1RCisS and 1SCisR, enantiomer pair 1RTransS and 1STransR together with enantiomer pair 1RCisR and 1SCisS and enantiomer pair 1RTransR and 1STransS, said saturated solution including a protic or apolar, aprotic inert organic solvent by treating said oily melt or saturated solution with an organic or inorganic base at a temperature of -15.degree. C. to 30.degree. C.
    Type: Grant
    Filed: May 7, 1991
    Date of Patent: May 5, 1992
    Assignee: Chinoin Gyogyszer es Vegyeszeti Termekek Gyara Rt.
    Inventors: Gyorgy Hidasi, Istvan Szekely, Bela Bertok, Sandor Zoltan, Lajos Nagy, Antal Gajari, Eva Somfai, Agnes Hegedus, Laszlo Pap, Rudolf Soos, Erzsebet Radvany, Sandor Botar, Tamas Szabolcsi
  • Patent number: 5015764
    Abstract: A process for the separation of a racemic mixture of certain aliphatic carboxylic acids or esters thereof is disclosed. The process comprises (i) forming a salt solution comprising said racemic mixture of a C.sub.1 to C.sub.6 linear or branched aliphatic carboxylic acid and an organic or inorganic base (ii) treating said salt solution with one-half molar equivalent of a chiral organic nitrogenous base having a base strength no stronger than said organic or inorganic base (iii) precipitating from the reaction solution formed in step (ii) the less soluble diastereomeric salt and (iv) separating said precipitated diastereomeric salt.
    Type: Grant
    Filed: June 18, 1990
    Date of Patent: May 14, 1991
    Assignee: Ethyl Corporation
    Inventors: Thanikavelu Manimaran, Fred J. Impastato
  • Patent number: 5011995
    Abstract: Asymmetric hydrogenation of prochiral N-aliphatic ketimines to give optically active secondary amines at a temperature from -20.degree. to 80.degree. C., a hydrogen pressure of 10.sup.5 to 10.sup.7 Pa, with the addition of catalytic amounts of an iridium compound of the formula III or IIIa[XIrYZ] (III)or[XIrY].sup..sym. A.sup..crclbar. (IIIa)in which X is two olefin ligands or a diene ligand, Y is a chiral diphosphine the secondary phosphine group of which are attached through 2-4 C atoms and which, together with the Ir atom, forms a 5-membered, 6-membered or 7-membered ring, or Y is a chiral diphosphinite the phosphinite groups of which are attached via 2 C atoms and which, together with the Ir atom, forms a 7-membered ring, Z is Cl, Br or I and A.sup.- is the anion of an oxygen acid or complex acid, and, if appropriate, with the addition of an ammonium chloride, bromide or iodide or an alkali metal chloride, bromide or iodide.
    Type: Grant
    Filed: July 19, 1988
    Date of Patent: April 30, 1991
    Assignee: Ciba-Geigy Corporation
    Inventors: Benoit Pugin, Gerardo Ramos, Felix Spindler
  • Patent number: 4997970
    Abstract: Crystallizable pyrethroid isomers or enantiomer pairs are converted to more pesticidally active isomers by contacting a hydrocarbon slurry of the starting isomers with a base and a catalyst, the catalyst being substantially soluble in the slurry and selected from a quaternary ammonium compound, a quaternary phosphonium compound and a crown ether, agitating the slurry while maintaining a temperature effective for conversion, and recovering the resulting isomers. The tendency to form benzoin ester by-product is reduced by including in the slurry a weak base, an aldehyde scavenger such as a metabisulfite, and/or a tetraalkyl (C.sub.1 -C.sub.5) ammonium halide catalyst dissolved in an aprotic solvent such as an organic nitrile. The process typically is effective for enriching cypermethrin, cyfluthrin and (cyano (3-phenoxyphenyl)methyl 3-(2,2-dibromoethenyl)-2,2-dimethylcyclopropanecarboxylate in the more active species.
    Type: Grant
    Filed: May 23, 1988
    Date of Patent: March 5, 1991
    Assignee: FMC Corporation
    Inventor: John W. Ager, Jr.
  • Patent number: 4962223
    Abstract: New process for the synthesis of the levodopa, L-(-)-2-amino-3-(3,4-dihydyphenyl)propionic acid, drug used in the treatment of the Parkinson's disease. The process consists in resolving with d-camphorsulfonic acid, or with a salt thereof, the d,l-2-amino-3-(3,4-dimethoxyphenyl)propionitrile, obtained from the 3,4-dimethoxyphenylacetaldehyde, and in the subsequent hydrolysis and demethylation, by means of concentrated solutions of haloid acids, of the d-2-amino-3-(3,4-dimethoxyphenyl)propionitrile and of salts thereof.
    Type: Grant
    Filed: July 3, 1989
    Date of Patent: October 9, 1990
    Assignee: Ministero dell'Universita e delle Ricerca Scientifica e Tecnologica
    Inventors: Vincenzo Cannata, Giancarlo Tamerlani, Mauro Morotti
  • Patent number: 4910309
    Abstract: The optical purity of an optically active 2-(4-aryloxyphenoxy)propionic acid is enriched by formation of the hydrate of the enantiomer in excess and its removal from solution.
    Type: Grant
    Filed: July 8, 1988
    Date of Patent: March 20, 1990
    Assignee: The Dow Chemical Company
    Inventors: Larry D. Kershner, Jimmy J. Tai
  • Patent number: 4853477
    Abstract: A process for the separation of mutually diastereomeric forms of a cyclopropanecarboxylic acid ester of the formula ##STR1## in which R.sup.1 represents hydrogen or halogen,R.sup.2 represents hydrogen or halogen,R.sup.4 represents hydrogen, Cn, --C.dbd.CH or CH.sub.3,R.sup.5 represents hydrogen or halogen, andR.sup.6 represents hydrogen or halogen,comprising reacting such ester in a first stage with about half or an equal molar amount of a second compound of the formula ##STR2## in which R.sup.7, R.sup.8 and R.sup.9 represent hydrogen or methyl, or, together with the C atom to which they are bound and with the adjacent C atoms of the basic structure form a fused 6-membered ring,R.sup.10 represents hydrogen, methyl, ethyl, halogen, amino, methylamino or dimethylamino, andR.sup.
    Type: Grant
    Filed: August 20, 1987
    Date of Patent: August 1, 1989
    Assignee: Bayer Aktiengesellschaft
    Inventors: Rainer Fuchs, Wilhelm Stendel
  • Patent number: 4782174
    Abstract: A process for the preparation of a mixture principally comprising the(b) 1R-3R-.alpha.S+1S-3S-.alpha. and(d) 1R-3S-.alpha.S+1S-3R-.alpha.Renantiomers of the compound .alpha.-cyano-3-phenoxy-4-fluorobenzyl permethrate, comprising dissolving a mixture of all 8 stereoisomers of the compound .alpha.-cyano-3-phenoxy-4-fluorobenzyl permethrate in an alcohol having 2 to 4 carbon atoms, adding a secondary or tertiary alkyl amine having 2-6 carbon atoms in each alkyl moiety and allowing the mass to crystallize, whereby the desired mixture of enantiomers b) and d) crystallizes out of the solution.
    Type: Grant
    Filed: June 16, 1986
    Date of Patent: November 1, 1988
    Assignee: Bayer Aktiengesellschaft
    Inventors: Rainer Fuchs, Andreas Wittig
  • Patent number: 4749809
    Abstract: The present invention relates to an optically active borane complex represented by the general formula, ##STR1## wherein R.sup.1 represents an aryl group, R.sup.2 represents an alkyl group and a mark * means an asymmetric carbon, and a method for producing optically active alcohol derivatives by the reduction of prochiral ketones with said borane complex. The optically active alcohol derivative is useful for fungicides, herbicides or plant growth regulators.
    Type: Grant
    Filed: July 1, 1985
    Date of Patent: June 7, 1988
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Yukio Yoneyoshi, Gohfu Suzukamo, Kazuhiko Hamada, Toshio Nishioka
  • Patent number: 4733001
    Abstract: A method for preparing a mixture of stereoisomers of .alpha.-cyano-3-phenoxybenzyl isovalerate ester derivatives, which is rich is an enantiomer pair of a compound having an (S)-configuration on both the acid and alcohol moieties and an enantiomer thereof having an (R)-configuration on both the acid and alcohol moieties.
    Type: Grant
    Filed: May 28, 1981
    Date of Patent: March 22, 1988
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Yukio Suzuki, Masahiro Hayashi, Kenzi Takuma
  • Patent number: 4732999
    Abstract: Process for the production of optically-active di-[3-chloro-2-oxy-propyltrimethylammonium]-tartrate. Racemic 3-chloro-2-oxy-propyltrimethylammonium-chloride is converted by racemate resolution with optically-active tartaric acid into the optically-active di-[3-chloro-2-oxy-propyltrimethylammonium]-tartrate. Such optically-active tartrate compound is dissociated in tartaric acid to optically-active 3-chloro-2-oxy-propyltrimethylammonium-chloride and the latter is converted with inorganic cyanides. From the product, the production of optically-active carnitine nitrile chloride can be achieved.
    Type: Grant
    Filed: June 24, 1986
    Date of Patent: March 22, 1988
    Assignee: Lonza Ltd.
    Inventors: Leander Tenud, Jacques Gosteli
  • Patent number: 4723033
    Abstract: This invention concerns a new process of preparing optically active .alpha.-arylalkanoic acids and their precursors. These .alpha.-arylalkanoic acids, esters, amides, nitriles, oxazolines and metal salts are stereoselectively prepared by forming the metal or metal halide of the corresponding acid, ester, amide, oxazoline, nitrile, or metal salt and treating the compound so prepared with an aryl halide in the presence of a chiral (optically active) transition metal catalyst of the formula (LL*)QZT wherein Q is a transition metal selected from palladium and nickel; Z and T are independently halogen; and LL* is a chiral tertiary diphosphine compound capable of acting as a bidentate ligand with Q to form a 5-membered ring, optionally in the presence of a dipolar aprotic solvent or mixtures thereof, for a time sufficient to form the corresponding optically active .alpha.
    Type: Grant
    Filed: March 7, 1986
    Date of Patent: February 2, 1988
    Assignee: Syntex Pharmaceuticals International Ltd.
    Inventor: Gary W. Erickson
  • Patent number: 4701542
    Abstract: A process for the resolution of hemiacetal compounds of the formula ##STR1## wherein A is a hydrocarbon chain containing 1 to 16 groups, the said chain optionally containing at least one heteroatom, at least one unsaturation, the assembly of the group constituting the chain may be a mono- or polycyclic system including a spiro or endosystem and the assembly of chain A and the carbon atoms attached thereto can contain at least one chiral atom or the hemiacetal moiety thereto which can present a chirality due to the dissymetric spatial configuration of the molecule and Y is selected from the group consisting of hydrogen, alkyl of 1 to 18 carbon atoms optionally substituted, --CY.sub.3 ' and the .beta.,.gamma.
    Type: Grant
    Filed: March 31, 1986
    Date of Patent: October 20, 1987
    Assignee: Roussel Uclaf
    Inventors: Jean Tessier, Jean-Pierre Demoute
  • Patent number: 4683324
    Abstract: The invention is a process for the selective and concomitant resolution-racemization-resolution of certain substituted, racemic amino nitriles via their respective tartrate salts. The invention further relates to certain resolved (optically active) amino amides prepared from said amino nitriles, and to the herbicidal substituted oxo-imidazolinyl nicotinic acids and 3-quinoline carboxylic acids prepared therefrom.
    Type: Grant
    Filed: May 25, 1982
    Date of Patent: July 28, 1987
    Assignee: American Cyanamid Company
    Inventors: William H. Gastrock, Peter J. Wepplo
  • Patent number: RE35230
    Abstract: A method of enantiomerically enriching chiral cyanohydrins is disclosed that involves selective cleavage of the unwanted enantiomer into its cleavage products HCN and the corresponding aldehyde or ketone by use of an enantioselective dehydrocyanation catalyst, coupled with simultaneous removal of at least one of the dehydrocyanation products.
    Type: Grant
    Filed: February 7, 1994
    Date of Patent: May 7, 1996
    Assignee: Bend Research, Inc.
    Inventor: Paul van Eikeren