Preparing Alicyclic Acids By Carbonylation Patents (Class 562/497)
  • Patent number: 8058472
    Abstract: The present invention concerns a new efficient method for the selective transformation, under mild conditions and in aqueous medium, of gaseous (ethane, propane and n-butane) and liquid (n-pentane, n-hexane, cyclopentane and cyclohexane) alkanes into carboxylic acids bearing one more carbon atom, characterized by a single-pot low-temperature (25-60° C.) reaction of the alkane with carbon monoxide in water/acetonitrile liquid medium, either in the absence or in the presence of a metal catalyst, in systems containing also an oxidant (a peroxodisulphate salt).
    Type: Grant
    Filed: January 17, 2008
    Date of Patent: November 15, 2011
    Assignee: Instituto Superior Tecnico
    Inventors: Armando Pombeiro, Marina Kirillova, Alexander Kirillov, Jose Armando Silva, Joao Frausto Da Silva
  • Publication number: 20110218342
    Abstract: Disclosed are ?-amino acids that are unsubstituted in the ? position; that are substituted in the ? position with an aryl group; that are substituted in the ? position with an aryl group; that bear two substituents in the ? position; and/or that are substituted in the ? and ? positions with groups which, together with the carbon atoms at the ? and ? positions, form a ring. Also disclosed are methods for making the above-mentioned ?-amino acids and other ?-amino acids which involve providing an ?,?-unsaturated imide; converting the ?,?-unsaturated imide to a 2-substituted-isoxazolidin-5-one; and converting the 2-substituted-isoxazolidin-5-one to a ?-amino acid.
    Type: Application
    Filed: July 21, 2004
    Publication date: September 8, 2011
    Inventors: Mukund P. Sibi, Craig P. Jasperse, Prabagaran Narayanasamy, Sandeep R. Ghorpade
  • Patent number: 7820849
    Abstract: A process is provided, in particular a continuous process for the carbonylation of butadiene by reacting the butadiene with carbon monoxide and a hydroxyl group-containing compound in the presence of a palladium catalyst system in a reaction zone to form a reaction mixture, said catalyst system comprising (a) a source of palladium cations, (b) a mono-, bi- or multidentate phosphine ligand, containing at least one phosphorus atom which is directly bound to two or three aliphatic carbon atoms, as process ligand to produce a palladium-phosphine ligand complex catalyst, and (c) a source of anions, said process ligand (b) containing the moiety shown in formula (I), wherein A1 and A2 each represent an aliphatic carbon atom which can be connected to one or more aliphatic or aromatic carbon atoms or both A1 and A2 are part of an at least 5-membered ring including the phosphorus atom, and X represents an aliphatic or aromatic carbon atom which can be connected to one or more aliphatic or aromatic carbon atoms or X
    Type: Grant
    Filed: June 28, 2004
    Date of Patent: October 26, 2010
    Assignee: DSM IP Assets B.V.
    Inventors: Otto Erik Sielcken, Imre Toth, Henricus Anna Christiaan Baur
  • Publication number: 20070179314
    Abstract: The compound, bicyclo[4.3.0]nonane-3(4),7(8)-dicarboxylic acid and to a process for its preparation, wherein bicyclo[4.3.0]nona-3,7-diene is reacted with synthesis gas in an homogeneous organic phase in the presence of transition metal compounds of Group VIII of the Periodic Table containing complex-bound organophosphorus compounds, and of excess organophosphorus compound, at temperatures of 70 to 160° C. and pressures of 5 to 35 MPa, and the 3(4),7(8)-bisformylbicyclo[4.3.0]nonane thus obtained is oxidized, or is first hydrogenated to 3(4),7(8)-dihydroxymethylbicyclo[4.3.0]nonane and the diol thus obtained is reacted in an alkali melt.
    Type: Application
    Filed: January 25, 2007
    Publication date: August 2, 2007
    Inventors: Helmut Springer, Paolo Bavaj
  • Patent number: 7227034
    Abstract: Forming a 4-aminobiphenyl derivative arylamine compound, includes (i) providing a first disubstituted 4-aminobiphenyl compound; (ii) optionally formylating the first disubstituted 4-aminobiphenyl compound to form a bisformyl substituted compound where the first disubstituted 4-aminobiphenyl compound is not a bisformyl substituted compound; (iii) acidifying the bisformyl substituted compound to convert formyl functional groups into acid functional groups to form an acidified compound; and (iv) hydrogenating the acidified compound to saturate at least one unsaturated double bonds in the acidified compound.
    Type: Grant
    Filed: November 22, 2004
    Date of Patent: June 5, 2007
    Assignee: Xerox Corporation
    Inventors: Timothy P. Bender, Jennifer A. Coggan
  • Patent number: 7186858
    Abstract: The present invention provides a safe, convenient and efficient method for producing carboxylic acid by a reaction of alicyclic alcohol with an aqueous hydrogen peroxide to thereby obtain carboxylic acid in high yield from alicyclic alcohol or alicyclic ketone under mild reaction conditions, wherein the reaction operation is simple and easy, a step for removing solvent after completion of the reaction is not necessary and influence and toxicity upon the environment and human body are markedly small. In order to provide it, an oily alicyclic alcohol is allowed to react with an aqueous hydrogen peroxide in the presence of a catalyst containing a metal compound belonging to Group 6 of the Periodic Table in a heterogeneous solution system.
    Type: Grant
    Filed: July 24, 2003
    Date of Patent: March 6, 2007
    Assignee: National Institute of Advanced Industrial Science and Technology
    Inventors: Kazuhiko Sato, Youko Usui
  • Patent number: 7151192
    Abstract: A manufacturing process for the preparation of ?,?-branched alkane carboxylic acids, by reacting a mono-olefin or a precursor thereof, with carbon monoxide in the presence of a strong acid catalyst characterized in that the starting olefin is a dimmer C8 or trimer C12 derived from n-butene, which predominantly comprise 2-butene, that the acid catalyst is composed of BF3/H3PO4 in a molar ratio of BF3:H3PO4 in the range of from 0.5:1.0 to 5.0:1.0, or of CF3SO 3H, that the weight ratio of the catalyst relative to the mono-olefin is in the range of from 1:1 to 10:1, that the reaction is carried out at a temperature in the range of from 60 to 140° C., and with an initial water content in the catalyst system in the range of from 8 to 25 wt %; and vinyl esters and glycidyl esters derived from said carboxylic acids.
    Type: Grant
    Filed: July 2, 2002
    Date of Patent: December 19, 2006
    Assignee: Hexion Specialty Chemicals, Inc.
    Inventors: Hendrik Stichter, Leonardus Petrus, Hans Arie Stil
  • Patent number: 7145041
    Abstract: The invention relates to a method for catalytically oxidizing unsaturated hydrocarbons to form oxidation products, and to the production of saturated alcohols, ketones, aldehydes or carboxylic acids by subsequently hydrogenating the oxidation product. A compound of formula (I) is used as a catalyst during oxidizing in which: R1, R2=H, an aliphatic or aromatic alkoxy radical, carboxyl radical, alkoxycarbonyl radical or hydrocarbon radical, each having 1 to 20 carbon atoms, SO3H, NH2, OH, F, Cl, Br, I and/or NO2, whereby R1 and R2 signify identical or different radicals or R1 and R2 can be coupled to one another via a covalent bond, with Q1, Q2=the same or different, C, CH, N; X, Z=C, S or CH2; Y=O or OH; k=0, 1 or 2; 1=0, 1 or 2; m=1 to 100 in the presence of a radical initiator. Peroxy compounds or azo compounds can be used as radical initiators. Preferred substrates are cyclic aliphatic or aromatic compounds.
    Type: Grant
    Filed: June 12, 2002
    Date of Patent: December 5, 2006
    Assignee: Degussa AG
    Inventors: Adolf Kuehnle, Carsten Jost, Roger Arthur Sheldon, Sandrine M. M. Chatel, Isabella W. C. E. Arends
  • Patent number: 7115782
    Abstract: There is provided a process for producing an aromatic compound by Friedel-Crafts reaction product, which comprises reacting an aromatic compound with an ester compound in the presence of a heteropolyacid-containing solid acid catalyst.
    Type: Grant
    Filed: May 15, 2003
    Date of Patent: October 3, 2006
    Assignee: Showa Denko K.K.
    Inventors: Toshio Okuhara, Tetsuo Nakajo
  • Patent number: 6858753
    Abstract: The present invention provides an improved process for the production of carboxylic acids by the carbonylation of alcohol. The process involves contacting an alcohol with carbon monoxide in the presence of a nickel compound, a heterocyclic organic compound and an iodide promoter to produce the corresponding carboxylic acid. The improvement relates to the use of heterocyclic organic compound as a promoter containing at least two heteroatoms of which at least one is selected independently from S or N, which provides an inexpensive and stable catalyst system.
    Type: Grant
    Filed: March 14, 2002
    Date of Patent: February 22, 2005
    Assignee: Council of Scientific and Industrial Research
    Inventors: Raghunath Vitthal Chaudhari, Sunil Shankar Joshi, Ashutosh Anant Kelkar, Sunil Sadashiv Divekar
  • Patent number: 6852893
    Abstract: The invention relates to a method for oxidizing substrates such as hydrocarbons, waxes or soot. The method involves the use of a compound of formula (I) in which: R1 and R2 represent H, an aliphatic or aromatic alkoxy radical, carboxyl radical, alkoxycarbonyl radical or hydrocarbon radical, each having 1 to 20 hydrocarbon atoms, SO3H, NH2, OH, F, Cl, Br, I and/or NO2, whereby R1 and R2 designate identical or different radicals or R1 and R2 can be linked to one another via a covalent bonding; Q1 and Q2 represent C, CH, N, CR5, each being the same or different; X and Z represent C, S, CH2, each being the same or different; Y represents O and OH; k=0, 1, 2; l=0, 1, 2; m=1 to 3, and; R5 represents one of the meanings of R1. Said compound is used as a catalyst in the presence of a radical initiator, whereby the molar ratio of the catalyst to the hydrocarbon is less than 10 mol %. Peroxy compounds or azo compounds can be used as the radical initiator. Preferred substrates are aliphatic or aromatic hydrocarbons.
    Type: Grant
    Filed: March 22, 2001
    Date of Patent: February 8, 2005
    Assignee: Creavis Gesellschaft fuer Technologie and Innovation mbH
    Inventors: Adolf Kühnle, Mark Duda, Carsten Jost, Guido Fries, Jochen Kirchhoff, Thomas Schiffer, Roger Arthur Sheldon, Sasidharan Manickam, Isabella W. C. E. Arends
  • Patent number: 6521783
    Abstract: This invention relates in part to a processes for the conversion of a feedstock stream comprising carbon monoxide and hydrogen to a product stream comprising at least one of an ester, acid, acid anhydride and mixtures thereof. This invention also relates in part to processes for converting an alcohol and/or ether feedstock to oxygenated products, e.g., esters, acids, acid anhydrides and mixtures thereof. The processes and catalysts are especially suitable for the production of acetic acid and methyl acetate from a synthesis gas feedstock or from an alcohol and/or ether feedstock.
    Type: Grant
    Filed: July 10, 2000
    Date of Patent: February 18, 2003
    Assignee: Union Carbide Chemicals & Plastics Technology Corporation
    Inventors: Richard William Wegman, David McNeill Somerville, Barry Brent Fish, Raymond Edwin Rooks, Chinsoo Stephen Lee, Paul Frank Bryan, William J. Bartley, David Michael Anthony Minahan, Fungau Ho
  • Publication number: 20020177733
    Abstract: Production of cyclic aliphatic acids and esters are achieved in high yield via carbonylation of a cyclic olefin with carbon monoxide in the presence of catalyst.
    Type: Application
    Filed: March 28, 2001
    Publication date: November 28, 2002
    Inventor: Ramzi Saleh
  • Patent number: 6420304
    Abstract: The invention relates to a polymer-supported carbonylation catalyst and its use in a process for preparing organic carboxylic acid or anhydride having n+1 carbon atoms. The invention relates also to a process for preparing organic carboxylic acid or anhydride having n+1 carbon atoms by carbonylating with monoxide, in the presence of the above-mentioned carbonylation catalyst, on alcohols having n carbon atoms, ethers having 2n carbon atoms or esters formed from said alcohols and acids. In particular, the invention relates to a process for preparing acetic acid by carbonylating methanol with carbon monooxide in the presence of said carbonylation catalyst. By using said carbonylation catalyst, the temperature for carbonylation can be lowered to about 160° C. with a reaction rate better than that of a traditional process, while the tendency of catalyst precipitation in the course of carbonylation can be improved also.
    Type: Grant
    Filed: April 20, 2000
    Date of Patent: July 16, 2002
    Assignee: China Petrochemical Development Corporation
    Inventors: Chia-Jung Tsai, Yao-Lung Liu, Hsi-Chin Tsai
  • Publication number: 20010007911
    Abstract: The invention relates to a process for preparing N-acylglycine derivatives of the formula (III) 1
    Type: Application
    Filed: July 7, 1999
    Publication date: July 12, 2001
    Inventors: HOLGER GEISSLER, SANDRA BOGDANOVIC, MATTHIAS BELLER, MARKUS ECKERT, FRANK VOLLMULLER
  • Patent number: 6169201
    Abstract: Process for the preparation of N-acetyl protected amino acids of Formula I by amido carbonylation utilizing carbon monoxide, nitrile, and an aldehyde in the presence of a metal catalyst.
    Type: Grant
    Filed: May 13, 1999
    Date of Patent: January 2, 2001
    Assignee: Degussa-Huels AG
    Inventors: Matthias Beller, Markus Eckert, Wahed Moradi
  • Patent number: 6011171
    Abstract: The present invention provides a process for synthesizing tertiary carboxylic acids or the esters thereof having one or two more carbon atoms than the raw material has, comprising reacting in a strong acid (e.g., sulfuric acid, sulfuric acid-phosphoric acid, hydrogen fluoride, fluorosulfuric acid, boron trifluoride.water complex and trifluoromethanesulfonic acid) a raw material compound (i.e., olefin, alcohol, diene, diol or saturated hydrocarbon) with carbon monoxide in the presence of a specific metal carbonyl catalyst (i.e., platinum carbonyl catalyst, palladium carbonyl catalyst and gold dicarbonyl catalyst).The metal carbonyl catalyst is formed by reacting in a strong acid at least one specific metal compounds (e.g., platinum compound such as platinum (II, IV) oxide, platinum (II, IV) hydroxide, a platinum powder, etc.; palladium compound such as palladium (II, III, IV) oxide, palladium (II) hydroxide, palladium (II) sulfate, palladium (II) carboxylate, a palladium powder, etc.
    Type: Grant
    Filed: November 4, 1997
    Date of Patent: January 4, 2000
    Assignee: Jiro Hiraishi, Director-General, Agency of Industrial Science and Technology
    Inventors: Qiang Xu, Yoshie Souma
  • Patent number: 5952522
    Abstract: A process is disclosed for the carbonylation of acetylenically unsaturated compounds by reaction with carbon monoxide and a co-reactant in the presence of a catalyst system based on: (a) a source of platinum; (b) a bidentate ligand of the formula R.sup.1 R.sup.2 M.sup.1 -R-M.sup.2 R.sup.3 R.sup.4, wherein M.sup.1 and M.sup.2 independently are P, As or Sb, R represents a bivalent substituted or non-substituted bridging group containing from 1 to 5 atoms in the bridge, R.sup.1 and R.sup.2 together are a substituted or non-substituted bivalent group whereby the two free valencies are linked to M.sup.1, and R.sup.3 and R.sup.4 together are a substituted or non-substituted bivalent group whereby the two free valencies are linked to M.sup.2 or R.sup.3 and R.sup.4 independently are substituted or non-substituted hydrocarbyl groups; and (c) a source of anions.
    Type: Grant
    Filed: December 18, 1996
    Date of Patent: September 14, 1999
    Assignee: Shell Oil Company
    Inventors: Eit Drent, Willem Wabe Jager
  • Patent number: 5814193
    Abstract: A process for the purification of a C.sub.2 to C.sub.4 carboxylic acid and/or an anhydride thereof having halide impurities, which process comprises the steps of (a) exposing the impure acid and/or anhydride to electromagnetic radiation under conditions of intensity, wavelength and temperature, and for a time, sufficient to convert at least a portion of the halide impurities to lower--and/or higher-boiling halide components and (b) separating the lower--and/or higher-boiling halide components formed in step (a) from the C.sub.2 to C.sub.4 carboxylic acid and/or anhydride. Also, a process for the purification of a C.sub.2 to C.sub.
    Type: Grant
    Filed: August 9, 1996
    Date of Patent: September 29, 1998
    Assignee: BP Chemicals Limited
    Inventor: Barry Crowe
  • Patent number: 5808147
    Abstract: The present invention relates to certain purine nucleoside analogues containing a carbocyclic ring in place of the sugar residue, salts, esters and pharmaceutically acceptable derivatives thereof, processes for their preparation, pharmaceutical formulations containing them and to the use of such compounds in therapy, particularly the treatment or prophylaxis of certain viral infections.
    Type: Grant
    Filed: November 7, 1997
    Date of Patent: September 15, 1998
    Assignee: Glaxo Wellcome Inc.
    Inventors: Susan Mary Daluge, Douglas Alan Livingston
  • Patent number: 5710323
    Abstract: A process for producing a monocarboxylic acid and/or a dicarboxylic acid by the reaction of a starting compound selected from among saturated hydrocarbons, .alpha.-olefins of 6 to 20 carbon atoms, saturated monocarboxylic acids and esters of the acids either with both of carbon monoxide and water at the same time or first with carbon monoxide and then with water, wherein the reaction of the starting compound either with both of carbon monoxide and water or with carbon monoxide alone is conducted in a strong acid solution containing a trifluoromethane-sulfonic acid catalyst and an alcohol and/or an olefin of 3 to 5 carbon atoms.
    Type: Grant
    Filed: March 27, 1997
    Date of Patent: January 20, 1998
    Assignee: Idemitsu Petrochemical Co., Ltd.
    Inventors: Ryoichi Okuda, Tadashi Kato, Yoshio Okada
  • Patent number: 5463137
    Abstract: A propylene stream which contains propane as an impurity is contacted with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst thereby producing a product stream containing butyraldehyde and/or n-butyl alcohol, unreacted propylene and propane. A gas mixture containing propylene and propane is separated from the product stream and subjected to adsorption at a temperature of 0.degree. to 250.degree. C. in a bed of adsorbent which selectively adsorbs propylene, thereby adsorbing substantially all of the propylene from the gas mixture. The propylene is desorbed from the adsorbent and recycled to the reaction zone. The process is operated on a low per pass conversion with recycle of unreacted propylene. In the system of the invention the propylene adsorption unit may be upstream or downstream of the hydroformylation reactor.
    Type: Grant
    Filed: April 22, 1994
    Date of Patent: October 31, 1995
    Assignee: The BOC Group, Inc.
    Inventors: Ramakrishnan Ramachandran, Loc H. Dao
  • Patent number: 5359122
    Abstract: The preparation of 3-arylacrylic acids and their derivatives I ##STR1## where Ar is aryl which can additionally have substituents which do not react with ketene and are stable under the conditions of the reaction described below, andR.sup.1 is hydrogen, an alkali metal, an alkaline earth metal, ammonium or C.sub.1 -C.sub.20 -alkyl,comprises a first stage in which a dialkyl acetal of an aromatic aldehyde of the formula II ##STR2## where R.sup.2 is C.sub.1 -C.sub.4 -alkyl, is reacted with ketene of the formula CH.sub.2 .dbd.C.dbd.O in the presence of catalytic amounts of a protic or Lewis acid to give a 3-arylpropionic acid derivative of the formula III ##STR3## and a second stage in which this intermediate III is reacted in the presence of acid or base and, in the case where R.sup.1 is C.sub.1 -C.sub.20 -alkyl, additionally with a C.sub.1 -C.sub.20 -alkanol to give the final product I.
    Type: Grant
    Filed: February 8, 1994
    Date of Patent: October 25, 1994
    Assignee: BASF Aktiengesellschaft
    Inventors: Michael Huellmann, Josef Gnad, Rainer Becker
  • Patent number: 5347048
    Abstract: A process for producing (.+-.)-2,2,2,5a-tetramethyl-1-(carboxymethyl)-2-hydroxydecalin, comprising the steps of allowing a carbonate of dihydro-.beta.-vinyl-ionol to react with carbon monoxide in the presence of a palladium catalyst to form .beta.-monocyclohomofarnesic acid, cyclizing said .beta.-monocyclohomofarnesic acid in the presence of an acid catalyst to form (.+-.)-norambreinolid, and hydrolyzing said (.+-.)-norambreinolide to form (.+-.)-2,5,5,8a-tetramethyl-1-(carboxymethyl)-2-hydroxydecalin.
    Type: Grant
    Filed: September 7, 1993
    Date of Patent: September 13, 1994
    Assignee: Kuraray Co., Ltd.
    Inventors: Goro Asanuma, Yoshin Tamai
  • Patent number: 5292928
    Abstract: In a process for reacting a low molecular weight hydroxy compound with a carboxylic acid halide, a small amount of the acid halide is introduced into the reaction vessel and the remainder of the acid halide and the hydroxy compound are added gradually in an approximately stoichiometric ratio. The hydrogen halide formed is thus prevented from dissolving in the reaction medium. The heat of reaction to be dissipated is negligible.
    Type: Grant
    Filed: July 31, 1992
    Date of Patent: March 8, 1994
    Assignee: Hoechst Aktiengesellschaft
    Inventor: Karlheinz Miltenberger
  • Patent number: 5290955
    Abstract: (-)-2,5,5,8a-Tetramethyl-1-(carboxymethyl)-2-hydroxydecalin is subjected to lactonization by dehydration to form decahydro-3a,6,6,9a-tetramethyl(3a.alpha.,5a.beta.,9a.alpha.,9b.beta.)-(+) -naphtho[2,1-b]furan-2(1H)-one, which is then reduced with a metal hydride to convert it into (-)-2,5,5,8a-tetramethyl-1-(carboxymethyl)-2-hydroxydecalin, followed by dehydrative cyclization to give L-ambrox.The (-)-2,5,5,8a-tetramethyl-1-(carboxymethyl)-2-hydroxydecalin is produced from its racemic mixture. The resolution is performed using a 1-(aryl)ethylamine. The starting material for the synthesis is beta-ionone.
    Type: Grant
    Filed: December 23, 1992
    Date of Patent: March 1, 1994
    Assignee: Kuraray Co., Ltd.
    Inventors: Goro Asanuma, Yoshin Tamai
  • Patent number: 5235119
    Abstract: An efficient direct functionalization of nitrocubanes has been achieved by irradiation of a solution in an oxalyl halide to yield halogenated and halocarbonylated derivatives of nitrocubanes.
    Type: Grant
    Filed: October 1, 1992
    Date of Patent: August 10, 1993
    Assignee: The United States of America as represented by the Secretary of the Army
    Inventor: Abdollah Bashir-Hashemi
  • Patent number: 5214221
    Abstract: An efficient direct functionalization of nitrocubanes has been achieved by rradiation of a solution in an oxalyl halide to yield halogenated and halocarbonylated derivatives of nitrocubanes.
    Type: Grant
    Filed: October 1, 1992
    Date of Patent: May 25, 1993
    Assignee: The United States of America as represented by the Secretary of the Army
    Inventor: Abdollah Bashir-Hashemi
  • Patent number: 5179224
    Abstract: Disclosed herein is a process for preparing a corresponding cinnamate ester by reacting a styrene compound, carbon monoxide, an alcohol and oxygen by the use of (1) metallic palladium or a compound thereof, (2) a copper compound, (3) a compound of at least one metal selected from Groups 4A, 5A, 7A, 8A (the iron group only) and 2B in the Periodic Table and (4) a halogen compound as a catalyst which comprises treating the catalyst components recovered from the reaction liquid after completion of the reaction with an oxidizing agent in the presence of an organic acid to regenerate their catalytic activity, using the resulting catalyst components again in the reaction as a catalyst and repeating the foregoing procedure.The regenerated catalyst is recovered in catalytic activity to the extent of that of a fresh catalyst and thus gives a high reaction performance in the subsequent reaction. Thus, the catalyst containing expensive metal can be used circulatively.
    Type: Grant
    Filed: October 1, 1991
    Date of Patent: January 12, 1993
    Assignee: Mitsui Toatsu Chemicals, Incorporated
    Inventors: Usaji Takaki, Yoshihiro Yamamoto, Toshio Matsuhisa, Isamu Sudo, Shinobu Aoki
  • Patent number: 5158921
    Abstract: A catalyst system, which containsa) a source of a group VIII metal, andb) a phosphine of general formula: ##STR1## in which R.sup.1, R.sup.2 and R.sup.3 are independently selected from an optionally substituted aryl group and a group of general formula: ##STR2## wherein eachh of A, X, Y and Z is independently selected from a nitrogen atom, a CH group and a group of formula CR wherein R represents a hydroxyl group, an amino group, an amido group, a cyano group, an aryl group, an aryloxy group, a halogen atom, an optionally substituted hydrocarbyl group or an optionally substituted hydrocarbyloxy group, it also being possible for two adjacent CR groups to form a ring, provided that at least one of R.sup.1, R.sup.2 and R.sup.3 represents a group of formula (II) in which at least one of A and Z represents a group of formula CR; or an acid addition salt thereof.Also disclosed is the use of the catalyst system in the selective carbonylation of unsaturated hydrocarbons.
    Type: Grant
    Filed: February 28, 1990
    Date of Patent: October 27, 1992
    Assignee: Shell Oil Company
    Inventors: Eit Drent, Petrus H. M. Budzelaar, Willem W. Jager
  • Patent number: 5149868
    Abstract: A process for the carbonylation of olefinically or alkynically unsaturated compounds with carbon monoxide in the presence of water and a catalyst, wherein the catalyst is based ona) a palladium compound,b) a phosphine general formula PR.sup.1 R.sup.2 R.sup.3, wherein R.sup.1, R.sup.2 and R.sup.3 are the same or different each represent an alkyl, cycloalkyl or aryl group, at least one of which carries a substituent selected from the group consisting of a sulphonic acid, phosphonic acid and carboxylic acid groups, or a salt thereof, andc) an anion of an acid having a pK.sub.a <3 (measured in water at 18.degree. C.) except hydrohalogenic acids,and wherein the reaction medium is at least initally a multiphase liquid reaction medium.
    Type: Grant
    Filed: March 19, 1991
    Date of Patent: September 22, 1992
    Assignee: Shell Oil Company
    Inventor: Eit Drent
  • Patent number: 5145987
    Abstract: A process is disclosed for preparing cyclohexane tricarboxylic acids and esters thereof comprising contacting carbon monoxide, cis-1,2,3,6-tetrahydrophthalic acid anhydride and water or a lower alkanol at elevated pressure and temperature and in the presence of a palladium complex and an ether solvent wherein the selectivity to cis-1,2-trans-4-cyclohexane tricarboxylic acids and esters thereof is greater than that obtained in the absence of the ether solvent.
    Type: Grant
    Filed: May 22, 1991
    Date of Patent: September 8, 1992
    Assignee: The Dow Chemical Company
    Inventor: David C. Molzahn
  • Patent number: 5081292
    Abstract: .beta., .gamma.-Unsaturated carboxylic acids, e.g., 3-hexene-1,6-dioic acid, are selectively prepared by carbonylating (with carbon monoxide) an allyl alcohol, e.g., a butenediol, at an elevated temperature and under superatmospheric pressure, in the presence of a catalytically effective amount of a palladium-based catalyst and at least one quaternary onium chloride of one of the Group VB elements nitrogen or phosphorus, such element being tetracoordinated via carbon atoms and with the proviso that such nitrogen atom may be coordinated to two pentavalent phosphorus atoms.
    Type: Grant
    Filed: April 30, 1990
    Date of Patent: January 14, 1992
    Assignee: Rhone-Poulenc Chimie
    Inventors: Philippe Denis, Jean Jenck, Robert Perron
  • Patent number: 5041642
    Abstract: .beta.,.gamma.-Unsaturated carboxylic acids are facilely prepared by carbonylating a conjugated diene with carbon monoxide in the presence of (i) water, (ii) a halogenated hydracid, (iii) a palladium catalyst comprising palladium metal or supported palladium metal, a palladium oxide, or a complex salt of palladium, the anion coordinated to the palladium cation of which comprising a hard or borderline base, and (iv) a quaternary onium salt of nitrogen, phosphorus or arsenic, said N, P or As being tetra-coordinated to a carbon atom, the anion of which comprising a hard or borderline base.
    Type: Grant
    Filed: December 30, 1985
    Date of Patent: August 20, 1991
    Assignee: Rhone-Poulenc Chimie de Base
    Inventor: Jean Jenck
  • Patent number: 4981619
    Abstract: A process for preparing alpha-hydroxycarboxylic acids. An organic halide is reacted with carbon monoxide and a hydrogen donor compound, in the presence of a carbonylation catalyst and an inorganic base, at a temperature of at least 90.degree. C.
    Type: Grant
    Filed: November 28, 1986
    Date of Patent: January 1, 1991
    Assignee: Rhone Poulenc Specialities Chimiques
    Inventor: Bernard Besson
  • Patent number: 4960926
    Abstract: Process for the carbonylation of olefinically unsaturated compounds with carbon monoxide in the presence of a hydroxyl-group-containing compound, a palladium catalyst, an organic phosphine, an acid with a pKa value <2, with the exception of halogen acids and carboxylic acids as promoter, and a catlayst stabilizer selected from the group consisting of compounds of the general formula; ##STR1## wherein X represents an element of group Va with a valency greater than 3, selected from P. As or Sb, where Y represents an element of group VIa, selected from O, S or Se, and where either a, b and c are 0 or 1, where R.sub.4, R.sub.5 and R.sub.6 are the same or different and represent hydrocarbon groups, or a and b=0 and c=0 or 1 and R.sub.4 and R.sub.5 together with X form a heterocyclic group, or a, b and c=0 and R.sub.4, R.sub.5 R.sub.6 together with X form a heterocyclic group, compounds of the general formula: ##STR2## wherein R.sub.7 is a hydrocarbon group and where R.sub.8 and R.sub.
    Type: Grant
    Filed: July 27, 1989
    Date of Patent: October 2, 1990
    Assignee: Shell Oil Company
    Inventor: Eit Drent
  • Patent number: 4894188
    Abstract: Fatty acid and their derivatives are simply produced by reacting an olefin, carbon monoxide and water or reacting an alcohol or its derivative and carbon monoxide in the presence of a hydrogen fluoride catalyst and thermally decomposing the resulting reaction product in the presence of a lower hydrocarbon or a lower halogenated hydrocarbon.
    Type: Grant
    Filed: February 13, 1985
    Date of Patent: January 16, 1990
    Assignee: Mitsubishi Gas Chemical Company, Inc.
    Inventors: Takehiko Takahashi, Makoto Takagawa, Tomiyoshi Furuta, Toshio Hidaka, Kazuo Takada
  • Patent number: 4739109
    Abstract: Process for the carbonylation of an acetylenically unsaturated compound with CO in the presence of an alcohol and/or water and of a catalyst formed by combining a Pd(II) compound, an organic phosphine and a protonic acid, with the exception of hydrohalogenic acids.
    Type: Grant
    Filed: November 27, 1985
    Date of Patent: April 19, 1988
    Assignee: Shell Oil Company
    Inventor: Eit Drent
  • Patent number: 4739107
    Abstract: Process for the preparation of dicarboxylate esters by reacting an optionally substituted ethylenically unsaturated hydrocarbon having two carbon atoms less than said dicarboxylic acid, CO and an alcohol in the presence of a Group VIII noble metal or a compound thereof, a quinone and optionally, a redox agent and molecular oxygen.
    Type: Grant
    Filed: January 12, 1987
    Date of Patent: April 19, 1988
    Assignee: Shell Oil Company
    Inventor: Eit Drent
  • Patent number: 4733006
    Abstract: The present invention provides for an improved process wherein an olefin, an alcohol, or an ester, halide or ether derivative of said alcohol is reacted with carbon monoxide in a liquid phase in the presence of a catalyst system that contains (a) a rhodium component, and (b) and iodine or bromine component. By passing at least a portion of the liquid reaction mass from the reaction zone to a separation zone of substantially lower CO partial pressure, at least a portion of the carbonylation products, as well as unreacted carbon monoxide, inert gases and unreacted olefin, alcohol or alcohol derivatives are vaporized and can be withdrawn from the separation zone. Precipitation of the rhodium catalyst under carbon monoxide deficient conditions is prevented or retarded by addition to the carbon monoxide deficient zones of the system of a catalyst stabilizer which is a germanium (IV) compound, an alkali metal compound, and mixtures thereof.
    Type: Grant
    Filed: August 18, 1983
    Date of Patent: March 22, 1988
    Assignee: Monsanto Company
    Inventors: Thomas C. Singleton, Frank E. Paulik
  • Patent number: 4691047
    Abstract: A process for the carbonylation of a conjugated diene with CO and an alcohol or water in the presence of an aprotic solvent is carried out in the presence of a dissolved catalytic system prepared by combining a Pd(II) compound, at least 5 mol of a triarylphosphine per gram atom of Pd and at least 1 mol of HC1 per gram atom of trivalent P.
    Type: Grant
    Filed: March 26, 1986
    Date of Patent: September 1, 1987
    Assignee: Shell Oil Company
    Inventor: Eit Drent
  • Patent number: 4681707
    Abstract: Carboxylic acid esters are produced by reacting an unsaturated hydrocarbon, for example an olefin or an alkyne, with carbon monoxide and an alcohol in the presence of a protonic acid and as catalyst (a) at least one of the metals palladium, rhodium, ruthenium, iridium and cobalt, and (b) copper. In a modification of the invention carboxylic acids are produced by omitting the alcohol reactant and replacing it with water in an amount up to 8 mole equivalents based on the unsaturated hydrocarbon and a solvent other than an alochol, for example tetrahydrofuran.
    Type: Grant
    Filed: April 23, 1984
    Date of Patent: July 21, 1987
    Assignee: The British Petroleum Company p.l.c.
    Inventors: Howard Alper, Bertrand Despeyroux, David J. H. Smith, James B. Woell
  • Patent number: 4665213
    Abstract: Carboxylic acid esters are produced by reacting an olefinic hydrocarbon with an ester of formic acid in the presence of both carbon monoxide and oxygen at a temperature of up to 200.degree. and a pressure of up to 300 bar in the presence of water, typically in an amount of from 0.01 to 5% w/w, a source of protons, which is preferably a mineral acid or a tectometallosilicate in the hydrogen form, and as catalyst (a) a source of palladium, and (b) a source of copper.
    Type: Grant
    Filed: August 25, 1986
    Date of Patent: May 12, 1987
    Assignee: The British Petroleum Company p.l.c.
    Inventors: Howard Alper, David J. H. Smith
  • Patent number: 4664851
    Abstract: Process for the co-production of carboxylic acids of the general formula R.sup.1 --COOH and R.sup.2 --COOH and carboxylic acid esters of the general formula R.sup.1 --COOCH.sub.2 R.sup.2 and R.sup.2 --COOCH.sub.2 R.sup.1 from carboxylic acid esters of the general formula R.sup.1 --COOR.sup.2 and/or ethers of the general formula R.sup.3 OR.sup.4 (R.sup.1, R.sup.2, R.sup.3, R.sup.4 representing (substituted) alkyl or (substituted) aryl, alkaryl or aralkyl, R.sup.1 also representing H), carbon monoxide and hydrogen at elevated temperature and pressure in the presence of a ruthenium compound, a further Group VIII metal compound, and a compound R.sup.5 Hal or R.sup.5 COHal where R.sup.5 has one of the meanings given for R.sup.2 and Hal is iodine or bromine, the reaction mixture being substantially free from other transistion metal or Group II metal iodides or bromides, and containing a trivalent nitrogen compound containing a group ##STR1## (X=O or S), such as an amide, a carbamate, a urea or a derivative thereof.
    Type: Grant
    Filed: July 19, 1982
    Date of Patent: May 12, 1987
    Assignee: Shell Oil Company
    Inventor: Eit Drent
  • Patent number: 4661296
    Abstract: In the preparation of a carboxylic acid by the carbonylation of an olefin in the presence of hydrofluoric acid catalyst, the hydrofluoric acid is isolated from the carboxylic acid by means of an ion-permeable membrane and the thus-isolated hydrofluoric acid can be recycled to again catalyze the carbonylation reaction.
    Type: Grant
    Filed: September 13, 1982
    Date of Patent: April 28, 1987
    Assignee: Ashland Oil, Inc.
    Inventors: Dace Grote, Bhupendra C. Trivedi, Thomas O. Mason
  • Patent number: 4659518
    Abstract: A carboxylic acid, such as acetic acid, is prepared by carbonylation of a hydrocarbyl alcohol, such as methanol, by the use of a molybdenum-nickel or tungsten-nickel co-catalyst in the presence of a promoter comprising an organo-phosphorus compound or an organo-nitrogen compound wherein the phosphorus and nitrogen are trivalent and in the presence of an iodide.
    Type: Grant
    Filed: December 24, 1980
    Date of Patent: April 21, 1987
    Assignee: The Halcon SD Group, Inc.
    Inventor: Nabil Rizkalla
  • Patent number: 4658053
    Abstract: A process for the production of an ester comprises reacting an olefin with carbon monoxide, hydrogen and another ester at elevated temperature and pressure in the presence of a catalyst comprising (1) a rhodium source, (2) a ruthenium source, and (3) cobalt or zinc iodide. The product ester comprises the acid group of the ester used as reactant esterified with a hydrocarbyl group derived from the olefin, hydrogen and carbon monoxide.
    Type: Grant
    Filed: February 25, 1985
    Date of Patent: April 14, 1987
    Assignee: BP Chemicals Limited
    Inventor: Michael J. Green
  • Patent number: 4656307
    Abstract: According to the invention a derivative of brendane is provided. The derivative of brendane is represented by the general formula of: ##STR1## wherein R is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R.sup.1 to R.sup.3 each represent a hydrogen atom or a methyl group. The brendane derivative is prepared by reacting an alkenylnorbornene of the general formula of: ##STR2## wherein R.sup.1 to R.sup.3 each represent a hydrogen atom or a methyl group, with carbon monoxide and an alcohol or water in the presence of a catalyst of Group VIII metal compound of the periodic table.
    Type: Grant
    Filed: July 15, 1985
    Date of Patent: April 7, 1987
    Assignee: Nippon Oil Co., Ltd.
    Inventors: Yoshihiro Kobori, Tetsuya Takezono
  • Patent number: 4628113
    Abstract: A process for the preparation of carboxylic acids, alcohols, aldehydes or the secondary products thereof which comprises reacting an alcohol having from one to about twenty carbon atoms with hydrogen and carbon monoxide in the presence of a heterogeneous sulfided catalyst comprising cobalt in admixture with a co-catalyst selected from the elements of Groups V-B, VI-B and the Actinide series of the Periodic Table.
    Type: Grant
    Filed: June 30, 1982
    Date of Patent: December 9, 1986
    Assignee: Chevron Research Company
    Inventor: Steven P. Current
  • Patent number: 4625055
    Abstract: A carboxylic acid, such as propionic acid, is prepared by carbonylation of an olefin, such as ethylene in the presence of water by the use of a molybdenum-nickel-alkali metal, tungsten-nickel alkali metal, or chromium-nickel-alkali metal co-catalyst in the presence of a halide.
    Type: Grant
    Filed: June 3, 1985
    Date of Patent: November 25, 1986
    Assignee: The Halcon SD Group, Inc.
    Inventor: Nabil Rizkalla