PROCESS FOR PD-CATALYZED HYDROXYCARBONYLATION OF DIISOBUTENE: ACETIC ACID/DIISOBUTENE RATIO

Process for Pd-catalyzed hydroxycarbonylation of diisobutene:acetic acid/diisobutene ratio. 2. Process according to claim 1 ,wherein the compound in process step b) is selected from:{'sub': 2', '2', '2', '2', '2', '3', '2, 'PdCl, PdBr, Pd(acac), Pd(dba)(dba=dibenzylideneacetone), PdCl(CHCN).'}3. Process according to claim 1 ,wherein the acetic acid is added in an amount in the range from 6 mol to 7 mol of acetic acid per mole of diisobutene.4. Process according to claim 1 ,wherein the reaction mixture is heated to a temperature in the range from 80° C. to 160° C. in process step f).5. Process according to claim 1 ,wherein the CO is fed in in process step e) such that the reaction proceeds under a CO pressure in the range from 10 bar to 40 bar.6. Process according to claim 1 ,wherein the process comprises the additional process step g):g) addition of sulfuric acid. The invention relates to a process for Pd-catalyzed hydroxycarbonylation of diisobutene:acetic acid/diisobutene ratio.Carboxylic acids including propionic acid, adipic acid and fatty acids are used in the preparation of polymers, pharmaceuticals, solvents and food additives. The routes leading to carboxylic acids generally include the oxidation of hydrocarbons, alcohols or aldehydes, the oxidative cleavage of olefins by ozonolysis, the hydrolysis of triglycerides, nitriles, esters or amides, the carboxylation of Grignard or organolithium reagents, and the halogenation and subsequent hydrolysis of methyl ketones in the haloform reaction.The hydrocarboxylation of olefins is a highly promising and environmentally-friendly method for obtaining carboxylic acids. Acetic acid is produced by carbonylation of methanol, which is carried out with iodide. In the Koch reaction, the addition of water and carbon monoxide to alkenes is catalyzed by strong bases. This method is effective with alkenes that form secondary and tertiary carbocations, e.g. isobutylene to pivalic acid. The hydrocarboxylation occurring with the ...

BUTYL-BRIDGED DIPHOSPHINE LIGANDS FOR ALKOXYCARBONYLATION

The invention relates to compounds of formula (I) 2. Compound according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 3', '20, 'where at least two of the R, R, R, Rradicals are a —(C-C)-heteroaryl radical.'}3. Compound according to claim 1 ,{'sup': 1', '3, 'sub': 3', '20, 'where the Rand Rradicals are each a —(C-C)-heteroaryl radical.'}4. Compound according to claim 1 ,{'sup': 1', '3, 'sub': 3', '20, 'where the Rand Rradicals are each a —(C-C)-heteroaryl radical;'}{'sup': 2', '4, 'sub': 1', '12', '3', '12', '3', '12', '6', '20, 'and Rand Rare each independently selected from —(C-C)-alkyl, —(C-C)-cycloalkyl, —(C-C)-heterocycloalkyl, —(C-C)-aryl.'}5. Compound according to claim 1 ,{'sup': 1', '3, 'sub': 3', '20, 'where the Rand Rradicals are each a —(C-C)-heteroaryl radical;'}{'sup': 2', '4, 'sub': 1', '12, 'and Rand Rare each a —(C-C)-alkyl radical.'}6. Compound according to claim 1 ,{'sup': 1', '2', '3', '4, 'where R, R, R, R, if they are a heteroaryl radical, are each independently selected from furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, furazanyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzofuranyl, indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl.'}8. Complex comprising Pd and a compound according to .10. Process according to claim 9 ,wherein the ethylenically unsaturated compound comprises 2 to 30 carbon atoms and optionally one or more functional groups selected from carboxyl, thiocarboxyl, sulpho, sulphinyl, carboxylic anhydride, imide, carboxylic ester, sulphonic ester, carbamoyl, sulphamoyl, cyano, carbonyl, carbonothioyl, hydroxyl, sulphhydryl, amino, ether, thioether, aryl, heteroaryl or silyl groups and/or halogen substituents.11. Process according to claim 9 ,wherein the ethylenically unsaturated compound is selected from ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene ...

PROCESS FOR ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS USING BENZENE-BASED DIPHOSPHINE LIGANDS AND ALUMINIUM TRIFLATE

Process for alkoxycarbonylation of ethylenically unsaturated compounds using benzene-based diphosphine ligands and aluminium triflate.

PROCESS FOR PD-CATALYZED HYDROXYCARBONYLATION OF DIISOBUTENE: EFFECT OF SOLVENT

Process for Pd-catalyzed hydroxycarbonylation of diisobutene: Effect of solvent

PROCESS FOR PHOTOCATALYTIC ACCEPTOR-FREE DEHYDROGENATION OF HYDROCARBAZOLES AND HYDROINDOLES

A process for the photocatalytic acceptor-free dehydrogenation of hydrocarbazoles and hydroindoles is provided, wherein a hydrocarbazole or hydroindole is irradiated in the presence of a catalyst that is a rhodium complex containing organic phosphorus(III) compounds as ligands. 1. A process for dehydrogenation of a hydrocarbazole or a hydroindole , comprising:irradiating the hydrocarbazole or hydroindole in a reaction mixture comprising a rhodium complex to remove hydrogen from the hydrocarbazole or hydroindole;whereina hydrogen acceptor is not present, andthe rhodium complex comprises a ligand of an organic phosphorus(III) compound.2. The process according to claim 1 ,wherein a hydrocarbazole is dehydrogenated, andthe hydrocarbazole is at least one of dodecahydro-N-ethylcarbazole and dodecahydro-N-methylcarbazole.3. The process according to claim 1 ,wherein the reaction mixture further comprises a Lewis base.4. The process according to claim 3 ,wherein the Lewis base is an organic amine.5. The process according to claim 3 ,wherein the Lewis base is a heterocyclic amine.6. The process according to claim 3 ,wherein the Lewis base is at least one selected from the group consisting of a bipyridine, bathocuproin and phenanthroline.7. The process according to claim 6 ,wherein the Lewis base is a bipyridine and is 2,2-bipyridine and/or 4,4-bipyridine.8. The process according to claim 6 ,wherein the Lewis base is bathocuproin or phenanthroline.9. The process according to claim 1 ,{'sub': '2', 'wherein the reaction is conducted in the presence of CO.'}10. The process according to claim 1 ,wherein the irradiation is conducted with light of wavelength 320 nm to 500 nm.11. The process according to claim 1 ,wherein a temperature of the dehydrogenation is from 45° C. to 120° C.12. The process according to claim 1 , {'br': None, 'sup': '1', 'sub': '2', 'Rh(L)(CO)X\u2003\u2003(I)'}, 'wherein the rhodium complex is of formula (I)wherein{'sup': '1', 'sub': 1', '5', '3, 'Lis P(C- ...

ALKOXYCARBONYLATION OF TRIVINYLCYCLOHEXANE

Process for the alkoxycarbonylation of trivinylcyclohexane. 2. Process according to claim 1 ,wherein the compound (i) is initially charged in process step a).3. Process according to claim 1 ,wherein the compound (ii) is initially charged in process step a).4. Process according to claim 1 ,wherein the alcohol in process step c), besides the oxygen, does not comprise any further heteroatoms and contains no multiple bonds.5. Process according to claim 1 ,wherein the alcohol in process step c) is selected from:{'sup': n', 'n', 'iso', 'n', 'iso', 'n', 'iso', 'n', 'iso', 'n', 'iso', 'n', 'iso, 'methanol, ethanol, butanol, methylpropanol, pentanol, pentanol, 2-methylbutanol, 3-methylbutanol, hexanol, hexanol, heptanol, heptanol, octanol, octanol, 2-ethylhexanol, nonanol, nonanol, decanol, decanol, 2-propylheptanol.'}6. Process according to claim 1 ,wherein the alcohol in process step c) is methanol.7. Process according to claim 1 ,wherein CO is fed in in process step d) up to a pressure in the range from 20 bar to 60 bar.8. Process according to claim 1 ,wherein the heating in process step e) is carried out at a temperature in the range from 90° C. to 130° C.9. Process according to claim 1 ,comprising the additional process step f):f) purifying the triester.10. Process according to claim 9 ,comprising the additional process step g):{'sub': '2', 'g) reacting the purified triester with NaOMe and Hto give the triol.'}11. Process according to claim 10 ,wherein the reaction in process step g) is catalyzed with Ru-MACHO—BH.12. Process according to claim 10 ,{'sub': '2', 'wherein the reaction in process step g) is carried out at a Hpressure in the range of 30 bar to 70 bar.'}13. Process according to claim 10 ,wherein the reaction in process step g) is carried out at a temperature in the range from 80° C. to 120° C. The present invention relates to a process for the alkoxycarbonylation of trivinylcyclohexane.The alkoxycarbonylation of ethylenically unsaturated compounds is a ...

PROCESS FOR DOUBLE CARBONYLATION OF ALLYL ETHERS TO CORRESPONDING DIESTERS

The invention relates to a process for doubly carbonylating allyl ethers to the corresponding diesters, wherein a linear or branched allyl ether is reacted with a linear or branched alkanol (alcohol) with supply of CO and in the presence of a catalytic system composed of a palladium complex and at least one organic phosphorus ligand and in the presence of a hydrogen halide selected from HCl, HBr and HI. 1. Process for doubly carbonylating allyl ethers to diesters ,characterized in that a linear or branched allyl ether is reacted with a linear or branched alkanol with supply of CO and in the presence of a catalytic system composed of a palladium complex and at least one organic phosphorus ligand and in the presence of a hydrogen halide selected from HCl, HBr and HI.3. Process according to claim 1 ,{'sub': 1', '10', '4', '20', '7', '11, 'characterized in that the alkanols are compounds of the general formula ROH where R is a C- to C-alkyl, a C- to C-cycloalkyl or a C- to C-aralkyl group.'}4. Process according to claim 1 ,characterized in that the reaction is conducted in the liquid phase at a temperature of 70 to 250° C.5. Process according to claim 1 ,characterized in that reaction is conducted under a pressure of 2 to 100 bar.6. Process according to claim 1 ,characterized in that the palladium complex is formed in situ proceeding from a pre-complex, using, as palladium source, palladium-containing salts and complexes as precursor.7. Process according to claim 6 ,characterized in that the palladium complex is selected from the group comprising Pd acetates, Pd acetonates, Pd halides and Pd halide complexes, and also Pd-halogen-1,5-cyclooctadienes, Pd nitrates and Pd oxide.8. Process according to claim 1 ,characterized in that the phosphine ligands have a mono- or bidentate structure, preferably selected from the group comprisingL1—(9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine),L2—(oxybis(2,1-phenylene))bis(di-tert-butylphosphine),L3—1,2-bis((di-tert- ...

PROCESS FOR THE ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS WITH MONOPHOSPHINE LIGANDS

The invention relates to a process comprising the following process steps: 2. Process according to claim 1 ,{'sup': '1', 'sub': 1', '12', '6', '20', '3', '12', '3', '20, 'wherein Ris selected from —(C-C)-alkyl, —(C-C)-aryl, —(C-C)-cycloalkyl, —(C-C)-heteroaryl.'}3. Process according to claim 1 ,{'sup': '2', 'sub': 6', '20', '3', '12', '3', '20, 'wherein Ris selected from —(C-C)-aryl, —(C-C)-cycloalkyl, —(C-C)-heteroaryl.'}4. Process according to claim 1 ,{'sup': 1', '2, 'sub': 3', '20, 'wherein Rand R, if they are —(C-C)-heteroaryl, are selected from heteroaryl groups having five to ten ring atoms.'}5. Process according to claim 1 ,{'sup': 1', '2, 'sub': 3', '20, 'wherein Rand R, if they are —(C-C)-heteroaryl, are selected from furyl, thienyl, pyrrolyl, imidazolyl, pyridyl, pyrimidyl, indolyl.'}6. Process according to claim 1 ,{'sup': '3', 'wherein Ris selected from heteroaryl groups having five to ten ring atoms.'}7. Process according to claim 1 ,{'sup': '3', 'wherein Ris selected from furyl, thienyl, pyrrolyl, imidazolyl, pyridyl, pyrimidyl, indolyl.'}8. Process according to claim 1 ,{'sup': 1', '2', '3, 'sub': 1', '12', '6', '20', '6', '20', '1', '12', '6', '20', '1', '12, 'wherein R, Rand Rmay each independently be substituted by one or more substituents selected from —(C-C)-alkyl, —(C-C)-aryl, —(C-C)-aryl-(C-C)-alkyl, —(C-C)-aryl-O—(C-C)-alkyl.'}10. Process according to claim 1 ,wherein the ethylenically unsaturated compound is selected from ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, and mixtures thereof.11. Process according to claim 1 ,wherein the ethylenically unsaturated compound comprises 8 to 12 carbon atoms.12. Process according to claim 1 ,wherein the compound comprising Pd in process step b) is selected from palladium dichloride, palladium(II) ...

BUTYL-BRIDGED DIPHOSPHINE LIGANDS FOR ALKOXYCARBONYLATION

The invention relates to compounds of formula (I) where R 1 , R 2 , R 3 , R 4 are each independently selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 20 )-heteroaryl; at least one of the R 1 , R 2 , R 3 , R 4 radicals is a —(C 3 -C 20 )-heteroaryl radical; and R 1 , R 2 , R 3 , R 4 , if they are —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl or —(C 3 -C 20 )-heteroaryl, may each independently be substituted by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )-cycloalkyl, —S—(C 1 -C 12 )-alkyl, —S—(C 3 -C 12 )-cycloalkyl, —COO—(C 1 -C 12 )-alkyl, —COO—(C 3 -C 12 )-cycloalkyl, —CONH—(C 1 -C 12 )-alkyl, —CONH—(C 3 -C 12 )-cycloalkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 3 -C 12 )-cycloalkyl, —N—[(C 1 -C 12 )-alkyl] 2 , —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl, —(C 3 -C 20 )-heteroaryl-(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl-O-(C 1 -C 12 )-alkyl, —COOH, —OH, —SO 3 H, —NH 2 , halogen; and to the use thereof as ligands in alkoxycarbonylation.

PROCESS FOR THE DIRECT CONVERSION OF ALKENES TO CARBOXYLIC ACIDS

Process for the direct conversion of alkenes to carboxylic acids. 2. Process according to claim 1 ,wherein the substance in process step b) is selected from:{'sub': 2', '2', '2', '2', '2', '3', '2, 'PdCl, PdBr, Pd(acac), Pd(dba)(dba=dibenzylideneacetone), PdCl(CHCN).'}3. Process according to claim 1 ,wherein the process comprises the additional process step e):e) addition of acetic acid.4. Process according to claim 1 ,wherein the process comprises additional process step f):f) addition of water.5. Process according to claim 1 ,wherein the process comprises the additional process step g):g) addition of p-toluenesulfonic acid.6. Process according to claim 1 ,wherein the reaction mixture is heated to a temperature in the range from 80° C. to 160° C. in process step d).7. Process according to claim 1 ,wherein the CO is fed in in process step c) such that the reaction proceeds under a CO pressure in the range from 20 bar to 60 bar, The invention relates to a process for the direct conversion of alkenes to carboxylic acids.Carboxylic acids are used in the preparation of polymers, pharmaceuticals, solvents and food additives. The routes leading to carboxylic acids generally include the oxidation of hydrocarbons, alcohols or aldehydes, the oxidative cleavage of olefins by ozonolysis, the hydrolysis of triglycerides, nitriles, esters or amides, the carboxylation of Grignard or organolithium reagents, and the halogenation and subsequent hydrolysis of methyl ketones in the haloform reaction.The object of the invention was to provide a process with which alkenes can be directly converted to a carboxylic acid.In the context of this application, “direct conversion” is intended to mean that the reaction takes place in one step, i.e. without separation or work-up or similar of an intermediate product.This does not exclude, in the course of the reaction, intermediates forming which are directly converted onward.The object is achieved by a process according to claim .Process ...

PLATINUM COMPLEXES HAVING 1,2-SUBSTITUTED BENZYL-BASED DIPHOSPHINE LIGANDS FOR THE CATALYSIS OF THE ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

Platinum complexes having 1,2-substituted benzyl-based diphosphine ligands for the catalysis of the alkoxycarbonylation of ethylenically unsaturated compounds. 2. Complex according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 6', '20, 'wherein at least two of the R, R, R, Rradicals are a —(C-C)-heteroaryl radical having at least six ring atoms.'}3. Complex according to claim 1 ,{'sup': 1', '3, 'sub': 6', '20, 'wherein the Rand Rradicals are each a —(C-C)-heteroaryl radical having at least six ring atoms.'}4. Complex according to claim 1 ,{'sup': 1', '3, 'wherein the Rand Rradicals are each 2-pyridyl.'}5. Complex according to claim 1 ,{'sup': 2', '4, 'sub': 1', '12, 'wherein Rand Rare —(C-C)-alkyl.'}6. Complex according to claim 1 ,{'sup': 2', '4, 'wherein Rand Rare tert-butyl.'}9. Process according to claim 8 ,wherein the ethylenically unsaturated compound is selected from: ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, or mixtures thereof.10. Process according to claim 8 ,wherein the alcohol in process step c) is selected from: methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, tert-butanol, 3-pentanol, cyclohexanol, phenol.11. Process according to claim 8 ,wherein the alcohol in process step c) is methanol.12. Process according to claim 8 ,{'sub': 2', '2', '2', '2', '2', '2', '3', '2', '2', '2, 'wherein the substance comprising Pt is selected from: platinum dichloride (PtCl), platinum(II) acetylacetonate [Pt(acac)], platinum(II) acetate [Pt(OAc)], dichloro(1,5-cyclooctadiene)platinum(II) [Pt(cod)Cl], bis(dibenzylideneacetone)platinum [Pt(dba)], bis(acetonitrile)dichloroplatinum(II) [Pt(CHCN)Cl], (cinnamyl)platinum dichloride [Pt(cinnamyl)Cl].'}13. Process according to claim 8 ,{'sub': 2', '2', '2, 'wherein the substance comprising Pt is ...

METHOXYCARBONYLATION WITH FORMIC ACID AS CO SOURCE

Process for methoxycarbonylation with formic acid as the CO source. 2. Process according to claim 1 ,wherein no CO gas is supplied to the reaction mixture,3. Process according to claim 1 ,wherein HCOOH serves as the only CO source for the reaction,4. Process according to claims 1 ,wherein the compound in process step b) is selected from:{'sub': 2', '2', '3', '3', '2', '2', '3', '2, 'Pd(acac), PdCl, Pd(dba)*CHCl (dba=dibenzylideneacetone), Pd(OAc), Pd(TFA), Pd(CHCN)Cl.'}5. Process according to claim 1 ,wherein the process comprises additional process step f):f) addition of an acid.6. Process according to claim 5 ,{'sub': 2', '4', '3', '3', '3', '3, 'wherein the acid is selected from: HSO, CHSOH, CFSOH, PTSA.'}7. Process according to claim 1 ,wherein the MeOH/HCOOH ratio based on the employed volume is in the range from 1.5:0.5 to 1.2:0.8.8. Process according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 1', '12', '1', '12', '4', '14', '4', '14', '1', '12', '1', '12', '3', '14', '3', '14', '2, 'wherein R, R, R, Rare each independently selected from: —(C-C)-alkyl, —O—(C-C)-alkyl, —(C-C)-aryl, —O—(C-C)-aryl, cycloalkyl, —(C-C)-heteroalkyl, —O—(C-C)-heteroalkyl, —(C-C)-heteroaryl, —O—(C-C)-heteroaryl, —COO-alkyl, —COO-aryl, —C—O-alkyl, —C—O-aryl, NH, halogen and the residues are also capable of forming a larger condensed ring;'}wherein the recited alkyl groups, aryl groups, cycloalkyl, heteroalkyl groups, heteroaryl groups may be substituted as follows:{'sub': 1', '12', '1', '12, '—(C-C)-alkyl, —O—(C-C)-alkyl, halogen;'}{'sup': 1', '2', '3', '4, 'and at least one of the radicals R, R, R, Rdoes not represent phenyl.'}9. Process according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 1', '12', '4', '14', '1', '12', '3', '14, 'wherein R, R, R, Rare each independently selected from: —(C-C)-alkyl, —(C-C)-aryl, cycloalkyl, —(C-C)-heteroalkyl, —(C-C)-heteroaryl, halogen and the residues are also capable of forming a larger condensed ring;'}wherein the recited alkyl groups, aryl ...

PROCESS FOR PD-CATALYZED HYDROXYCARBONYLATION OF DIISOBUTENE: RATIO OF 3,5,5-TRIMETHYLHEXANOIC ACID/H20

Process for Pd-catalyzed hydroxycarbonylation of diisobutene: ratio of 3,5,5-trimethylhexanoic acid/H2O.

PLATINUM COMPLEXES HAVING BINAPHTHYL-BASED DIPHOSPHINE LIGANDS FOR THE SELECTIVE CATALYSIS OF THE HYDROXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

Platinum complexes having binaphthyl-based diphosphine ligands for the selective catalysis of the hydroxycarbonylation of ethylenically unsaturated compounds. 2. Complex according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 6', '20, 'wherein at least two of the R, R, R, Rradicals are a —(C-C)-heteroaryl radical having at least six ring atoms.'}3. Complex according to claim 1 ,{'sup': 1', '3, 'sub': 6', '20, 'wherein the Rand Rradicals are each a —(C-C)-heteroaryl radical having at least six ring atoms.'}4. Complex according to claim 1 ,{'sup': 1', '3, 'wherein the Rand Rradicals are each 2-pyridyl.'}5. Complex according to claim 1 ,{'sup': 2', '4, 'sub': 1', '12, 'wherein Rand Rare —(C-C)-alkyl.'}6. Complex according to claim 1 ,{'sup': 2', '4, 'wherein Rand Rare tert-butyl.'}9. Process according to claim 8 ,wherein the ethylenically unsaturated compound is selected from: ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, or mixtures thereof.10. Process according to claim 8 ,wherein the acid in process step c) is selected from acetic acid, perchloric acid, sulfuric acid, phosphoric acid, methylphosphonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, tert-butanesulfonic acid, p-toluenesulfonic acid, 2-hydroxypropane-2-sulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, dodecylsulfonic acid, camphorsulfonic acid.11. Process according to claim 8 ,wherein the acid in process step c) is acetic acid.12. Process according to claim 8 ,{'sub': 2', '2', '2', '2', '2', '2', '3', '2', '2', '2, 'wherein the substance comprising Pt is selected from: platinum dichloride (PtCl), platinum(II) acetylacetonate [Pt(acac)], platinum(II) acetate [Pt(OAc)], dichloro(1,5-cyclooctadiene)platinum(II) [Pt(cod)Cl], bis(dibenzylideneacetone)platinum [Pt(dba)], bis(acetonitrile) ...

PROPYL-BRIDGED DIPHOSPHINE LIGANDS FOR ALKOXYCARBONYLATION

Propyl-bridged diphosphine compounds, metal complexes of these compounds and the use thereof for alkoxycarbonylation. 2. Compound according to claim 1 ,{'sup': 1', '2, 'where Rand Rare the same radical.'}3. Compound according to claim 1 ,{'sup': 1', 't, 'where Ris Bu.'}4. Compound according to claim 1 ,{'sup': 2', 't, 'where Ris Bu.'}6. Complex comprising Pd and a compound according to .7. Process comprising the process steps of:a) initially charging an ethylenically unsaturated compound;{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'b) adding a compound according to and a compound comprising Pd;'}c) adding an alcohol;d) feeding in CO;e) heating the reaction mixture, with conversion of the ethylenically unsaturated compound to an ester.8. Process according to claim 7 ,wherein the ethylenically unsaturated compound is selected from:ethene, propene, 1-butene, cis-2-butene, trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis-2-pentene, trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene (2,3-dimethyl-2-butene), heptene, 1-octene, 2-octene, di-n-butene, or mixtures thereof.9. Process according to claim 7 ,wherein the compound in process step b), comprising Pd, is selected from:{'sub': 2', '2', '2', '2', '2', '3', '2, 'PdCl, PdBr, Pd(acac), Pd(dba)(dba=dibenzylideneacetone), PdCl(CHCN).'}10. Process according to claim 7 ,wherein the alcohol in process step c) is selected from:methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, tent-butanol, 3-pentanol, cyclohexanol, phenol, or mixtures thereof.11. Process according to claim 7 ,wherein the reaction mixture is heated in process step e) to a temperature in the range from 80° C. to 160° C.12. Process according to claim 7 ,wherein CO is fed in in process step d) such that the reaction proceeds at a CO pressure in the range from 20 bar to 50 bar.13. Process according to claim 7 ,wherein the process comprises the additional process step f):f) ...

PROCESS FOR THE ALKOXYCARBONYLATION OF OLEFINS IN A MEDIUM HAVING A LOW BRØNSTED ACID CONCENTRATION

Process comprising the following process steps: a) introducing an ethylenically unsaturated compound; b) adding a ligand-metal complex comprising Pd and a bidentate phosphine ligand, or adding a bidentate phosphine ligand and a compound which comprises Pd; c) adding an alcohol; d) supplying CO; e) heating the reaction mixture, the ethylenically unsaturated compound being reacted to form an ester, where the reaction mixture is admixed with less than 0.1 mol %, based on the amount of substance of the ethylenically unsaturated compound, of Brønsted acids having an acid strength of pKa ≦3, characterized in that the phosphine ligand is substituted on at least one phosphorus atom by at least one heteroaryl radical.

FERROCENE-BASED COMPOUNDS AND PALLADIUM CATALYSTS BASED THEREON FOR THE ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

The invention relates to a compound of formula (I) 2. Compound according to claim 1 ,{'sup': 1', '3, 'where Rand Rare each independently selected from furyl, thienyl, 2-pyrrolyl, 4-imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, furazanyl, tetrazolyl.'}3. Compound according to claim 1 ,{'sup': 1', '3, 'where Rand Rare each independently selected from furyl and thienyl.'}4. Compound according to claim 1 ,{'sup': 2', '4, 'sub': 1', '12', '3', '12', '6', '20, 'where Rand Rare each independently selected from —(C-C)-alkyl, —(C-C)-cycloalkyl and —(C-C)-aryl.'}5. Compound according to claim 1 ,{'sup': 2', '4, 'sub': 1', '12, 'where Rand Rare each —(C-C)-alkyl.'}6. Compound according to claim 1 ,{'sup': 1', '3, 'where Rand Rmay each independently be substituted by one or more substituents selected from'}{'sub': 1', '12', '3', '12', '1', '12', '1', '12', '6', '20', '3', '12', '6', '20', '6', '20', '1', '12', '6', '20', '1', '12, '—(C-C)-alkyl, —(C-C)-cycloalkyl, —O—(C-C)-alkyl, —O—(C-C)-alkyl-(C-C)-aryl, —O—(C-C)-cycloalkyl, —(C-C)-aryl, —(C-C)-aryl-(C-C)-alkyl, —(C-C)-aryl-O—(C-C)-alkyl.'}7. Compound according to claim 1 ,{'sup': 3', '4, 'sub': 1', '12', '3', '12', '3', '12', '6', '20, 'where Rand R, if they are —(C-C)-alkyl, —(C-C)-cycloalkyl, —(C-C)-heterocycloalkyl or —(C-C)-aryl,'}{'sub': 1', '12', '3', '12', '1', '12', '1', '12', '6', '20', '3', '12', '6', '20', '6', '20', '1', '12', '6', '20', '1', '12, 'may each independently be substituted by one or more substituents selected from —(C-C)-alkyl, —(C-C)-cycloalkyl, —O—(C-C)-alkyl, —O—(C-C)-alkyl-(C-C)-aryl, —O—(C-C)-cycloalkyl, —(C-C)-aryl, —(C-C)-aryl-(C-C)-alkyl, —(C-C)-aryl-O—(C-C)-alkyl.'}10. Complex comprising Pd and a compound according to .12. Process according to claim 11 ,wherein the ethylenically unsaturated compound is selected from ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1- ...

METHOD FOR SYNTHESIZING 2-ALKYL-4-TRIFLUOROMETHYL-3-ALKYLSULFONYLBENZOIC ACIDS

A process for preparing 2-alkyl-4-trifluoromethyl-3-alkylsulfonylbenzoic acids of the formula (I) is described. 2. The process as claimed in claim 1 , wherein Rand Rare each methyl.3. The process as claimed in claim 1 , wherein sodium cyanide claim 1 , potassium cyanide claim 1 , zinc cyanide claim 1 , potassium hexacyanoferrate(II) or acetone cyanohydrin is used as cyanide source.4. The process as claimed in claim 1 , wherein the cyanide source is used in a molar ratio of from 1:1 to 1.5:1 claim 1 , based on the compound of formula (II).5. The process as claimed in claim 1 , wherein nickel(II) chloride or nickel(II) bromide in an amount of from 0.5 to 5 mol percent and the phosphine ligand in an amount of from 0.5 to 10 mol percent based on the compound of formula (II) are used for producing the nickel catalyst.6. The process as claimed in claim 1 , wherein bis(2-diphenylphosphinophenyl) ether (dpephos) claim 1 , bis(diphenylphosphino)ferrocene (dppf) or rac-2 claim 1 ,2′-bis(diphenylphosphino)-1 claim 1 ,1′-binaphthyl (BINAP) is used as phosphine ligand in a molar ratio of from 1.5:1 to 3:1 claim 1 , based on the nickel compound.7. The process as claimed in claim 1 , wherein bis(2-diphenylphosphinophenyl) ether (dpephos) is used as phosphine ligand.8. The process as claimed in claim 1 , wherein from 2 to 10 mol percent of zinc claim 1 , based on the compound of formula (II) claim 1 , are used as reducing agent.9. The process as claimed in claim 1 , wherein NaWOis used in an amount of from 5 to 15 mol percent as oxidation catalyst and hydrogen peroxide is used in an amount of from 3 to 8 molar equivalents claim 1 , in each case based on the compound of formula (Va).12. The compound as claimed in claim 11 , wherein Ris methyl. The invention relates to a process for preparing 2-alkyl-4-trifluoromethyl-3-alkylsulfonylbenzoic acids which are useful as intermediates for the preparation of agrochemically active compounds.Agrochemically active compounds for the ...

PROCESS FOR THE PREPARATION OF ESTERS BY MEANS OF CARBONYLATION OF ETHERS

The invention relates to a process comprising the process steps of: a) initially charging an ether having from 3 to 30 carbon atoms; b) adding a phosphine ligand and a compound comprising Pd, or adding a comprising Pd and a phosphine ligand; c) feeding in CO; d) heating the reaction mixture, with conversion of the ether; wherein the phosphine ligand is a compound of formula (I) where m and n are each independently 0 or 1; R 1 , R 2 , R 3 , R 4 are each independently selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 20 )-heteroaryl; at least one of the R 1 , R 2 , R 3 , R 4 radicals is a —(C 3 -C 20 )-heteroaryl radical; and R 1 , R 2 , R 3 , R 4 , if they are —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl or —(C 3 -C 20 )-heteroaryl, may each independently be substituted by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )-cycloalkyl, —S—(C 1 -C 12 )-alkyl, —S—(C 3 -C 12 )-cycloalkyl, —COO—(C 1 -C 12 )-alkyl, —COO—(C 3 -C 12 )-cycloalkyl, —CONH—(C 1 -C 12 )-alkyl, —CONH—(C 3 -C 12 )-cycloalkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 3 -C 12 )-cycloalkyl, —N—[(C 1 -C 12 )-alkyl] 2 , —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl, —(C 3 -C 20 )heteroaryl-(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl-O—(C 1 -C 12 )-alkyl, —COOH, —SO 3 H, —NH 2 , halogen; and wherein no alcohol is added to the reaction mixture.

METHOXYCARBONYLATION WITH FORMIC ACID AND METHANOL

Process for methoxycarbonylation with formic acid and methanol. 2. Process according to claim 1 ,wherein no CO gas is supplied to the reaction mixture.3. Process according to claim 1 ,wherein HCOOH serves as the only CO source for the reaction.4. Process according to claim 1 ,wherein the compound in process step b) is selected from:{'sub': 2', '2', '3', '3', '2', '2', '3', '2, 'Pd(acac), PdCl, Pd(dba)*CHCl (dba=dibenzylideneacetone), Pd(OAc), Pd(TFA), Pd(CHCN)Cl.'}5. Process according to claim 1 ,wherein the process comprises the additional process step g):g) addition of an acid.6. Process according to claim 5 ,{'sub': 2', '4', '3', '3', '3', '3, 'wherein the acid is selected from: HSO, CHSOH, CFSOH, PTSA.'}7. Process according to claim 1 ,wherein the employed volume of HCOOH based on 2 mmol of olefin is in the range from 0.4 ml to 0.6 ml.8. Process according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 1', '12', '1', '12', '4', '14', '4', '14', '1', '12', '1', '12', '3', '14', '3', '14', '2, 'wherein R, R, Rand Rare each independently selected from: —(C-C)-alkyl, —O—(C-C)-alkyl, —(C-C)-aryl, —O—(C-C)-aryl, cycloalkyl, —(C-C)-heteroalkyl, —O—(C-C)-heteroalkyl, —(C-C)-heteroaryl, —O—(C-C)-heteroaryl, —COO-alkyl, —COO-aryl, —C—O-alkyl, —C—O-aryl, NH, halogen and the residues are also capable of forming a larger condensed ring;'}wherein the recited alkyl groups, aryl groups, cycloalkyl, heteroalkyl groups, heteroaryl groups may be substituted as follows:{'sub': 1', '12', '1', '12, '—(C-C)-alkyl, —O—(C-C)-alkyl, halogen;'}{'sup': 1', '2', '3', '4, 'and at least one of the radicals R, R, R, Rdoes not represent phenyl.'}9. Process according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 1', '12', '4', '14', '1', '12', '3', '14, 'wherein R, R, Rand Rare each independently selected from: —(C-C)-alkyl, —(C-C)-aryl, cycloalkyl, —(C-C)-heteroalkyl, —(C-C)-heteroaryl, halogen and the residues are also capable of forming a larger condensed ring;'}wherein the recited alkyl groups, ...

BENZENE-BASED DIPHOSPHINE LIGANDS FOR ALKOXYCARBONYLATION

The invention relates to compounds of formula (I) 3. Compound according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 3', '20, 'where at least two of the R, R, R, Rradicals are a —(C-C)-heteroaryl radical.'}4. Compound according to claim 1 ,{'sup': 1', '3, 'sub': 3', '20, 'where the Rand Rradicals are each a —(C-C)-heteroaryl radical.'}5. Compound according to claim 1 ,{'sup': 1', '3, 'sub': 3', '20, 'where the Rand Rradicals are each a —(C-C)-heteroaryl radical;'}{'sup': 2', '4, 'sub': 1', '12', '3', '12', '3', '12', '6', '20, 'and Rand Rare each independently selected from —(C-C)-alkyl, —(C-C)-cycloalkyl, —(C-C)-heterocycloalkyl, —(C-C)-aryl.'}6. Compound according to claim 1 ,{'sup': 1', '3, 'sub': 3', '20, 'where the Rand Rradicals are each a —(C-C)-heteroaryl radical;'}{'sup': 2', '4, 'sub': 1', '12, 'and Rand Rare each independently selected from —(C-C)-alkyl.'}7. Compound according to claim 1 ,{'sup': 1', '2', '3', '4, 'where R, R, R, R, if they are a heteroaryl radical, are each independently selected from furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, furazanyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzofuranyl, indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl.'}9. Complex comprising Pd and a compound according to .11. Process according to claim 10 ,wherein the ethylenically unsaturated compound comprises 2 to 30 carbon atoms and optionally one or more functional groups selected from carboxyl, thiocarboxyl, sulpho, sulphinyl, carboxylic anhydride, imide, carboxylic ester, sulphonic ester, carbamoyl, sulphamoyl, cyano, carbonyl, carbonothioyl, hydroxyl, sulphhydryl, amino, ether, thioether, aryl, heteroaryl or silyl groups and/or halogen substituents.12. Process according to claim 10 ,wherein the ethylenically unsaturated compound is selected from ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1- ...

SYNTHESIS OF BUILDING BLOCKS AND FEEDSTOCKS FOR MANUFACTURING RENEWABLE POLYMERS

Disclosed are methods or processes of synthesizing building blocks and feedstocks for producing a broader range of polymers, including renewable polymers, from renewable resources such as CO. In a process of manufacturing a renewable feedstock for polymer production, a COderived lactone is prepared and processed to form the renewable feedstock. The process may include alkoxycarbonylation of the COderived lactone to form a diester and hydrogenation of the diester. 1. A process of manufacturing a renewable feedstock for polymer production , the process comprising:{'sub': '2', 'preparing a COderived lactone; and'}{'sub': '2', 'processing the COderived lactone to form the renewable feedstock.'}2. The process of claim 1 , wherein processing the COderived lactone comprises hydrogenating the COderived lactone to form a hydrogenated COderived lactone.3. The process of claim 2 , wherein the hydrogenated COderived lactone is processed to form 2-ethylideneheptanoic acid using one or both of a homogeneous hydrogenation system and a heterogeneous hydrogenation system.5. The process of claim 2 , wherein the hydrogenated COderived lactone is processed using a Rh/phosphine biphasic hydrogenation system.6. The process of claim 2 , wherein the hydrogenated COderived lactone is processed by using a thiol click reaction to produce a regioselective polymer.8. The process of claim 2 , wherein the hydrogenated COderived lactone is processed using an alkene metathesis.12. A process of manufacturing a renewable feedstock for polymer production claim 2 , the process comprising:{'sub': '2', 'preparing a COderived lactone; and'}{'sub': '2', 'alkoxycarbonylating the COderived lactone to form a diester.'}13. The process of claim 12 , further comprising hydrogenating the diester to form the renewable feedstock.15. The process of claim 12 , wherein alkoxycarbonylating the COderived lactone includes a palladium compound catalyst.16. The process of claim 15 , wherein the palladium compound catalyst ...

PROCESS FOR PD-CATALYZED HYDROXYCARBONYLATION OF DIISOBUTENE: SULFURIC ACID/LIGAND RATIO

Process for Pd-catalyzed hydroxycarbonylation of diisobutene:sulfuric acid/ligand ratio. 2. Process according to claim 1 ,wherein the compound in process step b) is selected from:{'sub': 2', '2', '2', '2', '2', '3', '2, 'PdCl, PdBr, Pd(acac), Pd(dba)(dba=dibenzylideneacetone), PdCl(CHCN).'}3. Process according to claim 1 ,wherein the sulfuric acid is added in an amount which is in the range from 3.5 mol to 5 mol of sulfuric acid per mole of ligand L1.4. Process according to claim 1 ,wherein the reaction mixture is heated to a temperature in the range from 80° C. to 160° C. in process step g).5. Process according to claim 1 ,wherein the CO is fed in in process step f) such that the reaction proceeds under a CO pressure in the range from 10 bar to 40 bar. The invention relates to a process for Pd-catalyzed hydroxycarbonylation of diisobutene:sulfuric acid/ligand ratio.Carboxylic acids including propionic acid, adipic acid and fatty acids are used in the preparation of polymers, pharmaceuticals, solvents and food additives. The routes leading to carboxylic acids generally include the oxidation of hydrocarbons, alcohols or aldehydes, the oxidative cleavage of olefins by ozonolysis, the hydrolysis of triglycerides, nitriles, esters or amides, the carboxylation of Grignard or organolithium reagents, and the halogenation and subsequent hydrolysis of methyl ketones in the haloform reaction.The hydrocarboxylation of olefins is a highly promising and environmentally-friendly method for obtaining carboxylic acids. Acetic acid is produced by carbonylation of methanol, which is carried out with iodide. In the Koch reaction, the addition of water and carbon monoxide to alkenes is catalyzed by strong bases. This method is effective with alkenes that form secondary and tertiary carbocations, e.g. isobutylene to pivalic acid. The hydrocarboxylation occurring with the simultaneous addition of CO and HO to alkenes/alkynes provides a direct and convenient method for synthesizing ...

FERROCENE-BASED COMPOUNDS AND PALLADIUM CATALYSTS BASED THEREON FOR THE ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

The invention relates to a compound of formula (I) 2. Compound according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 6', '20, 'where at least two of the R, R, R, Rradicals are a —(C-C)-heteroaryl radical having at least six ring atoms.'}3. Compound according to claim 1 ,{'sup': 1', '3, 'sub': 6', '20, 'where the Rand Rradicals are each a —(C-C)-heteroaryl radical having at least six ring atoms.'}4. Compound according to claim 1 ,{'sup': 1', '3, 'sub': 6', '20, 'where the Rand Rradicals are each a —(C-C)-heteroaryl radical having at least six ring atoms;'}{'sup': '2', 'sub': 6', '20', '1', '12', '3', '12', '3', '12', '6', '20, 'Ris —(C-C)-heteroaryl having at least six ring atoms or is selected from —(C-C)-alkyl, —(C-C)-cycloalkyl, —(C-C)-heterocycloalkyl, —(C-C)-aryl;'}{'sup': '4', 'sub': 1', '12', '3', '12', '3', '12', '6', '20, 'and Ris selected from —(C-C)-alkyl, —(C-C)-cycloalkyl, —(C-C)-heterocycloalkyl, —(C-C)-aryl.'}5. Compound according to claim 1 ,{'sup': 1', '3, 'sub': 6', '20, 'where the Rand Rradicals are each a —(C-C)-heteroaryl radical having at least six ring atoms;'}{'sup': 2', '4, 'sub': 1', '12', '3', '12', '3', '12', '6', '20, 'and Rand Rare selected from —(C-C)-alkyl, —(C-C)-cycloalkyl, —(C-C)-heterocycloalkyl, —(C-C)-aryl.'}6. Compound according to claim 1 ,{'sup': 1', '3, 'sub': 6', '20, 'where the Rand Rradicals are each a —(C-C)-heteroaryl radical having at least six ring atoms;'}{'sup': 2', '4, 'sub': 1', '12, 'and Rand Rare —(C-C)-alkyl.'}7. Compound according to claim 1 ,{'sup': 1', '2', '3', '4, 'where R, R, R, R, if they are a heteroaryl radical, are each independently selected from pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzofuranyl, indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl.'}10. Complex comprising Pd and a compound according to .12. Process according to claim 11 ,wherein the ethylenically unsaturated compound is selected from ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1- ...

METHOD FOR PREPARING DI- OR TRICARBOXYLIC ESTERS BY ALKOXYCARBONYLATION OF DIENES HAVING CONJUGATED DOUBLE BONDS

The invention relates to a method comprising the method steps of: 2. Method according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 1', '12', '6', '20', '3', '20, 'where R, R, R, Rare selected from —(C-C)-alkyl, —(C-C)-aryl, —(C-C)-heteroaryl.'}3. Method according to claim 1 ,{'sup': 5', '6, 'sub': 1', '12, 'where R, Rare selected from —H, —(C-C)-alkyl.'}4. Method according to claim 1 ,{'sup': 1', '2', '3', '4', '5', '6, 'sub': 6', '20', '1', '12, 'where R, R, R, Rare each —(C-C)-aryl and R, Rare each selected from —H, —(C-C)-alkyl.'}5. Method according to claim 1 ,wherein the diene comprises 4 to 30 carbon atoms.7. Method according to claim 1 ,wherein the catalyst precursor is selected from palladium dichloride, palladium dibromide, palladium diiodide, palladium(II) acetylacetonate, palladium(II) acetate, bis(dibenzylideneacetone)palladium.8. Method according to claim 1 ,wherein the catalyst precursor is selected from palladium dichloride, palladium dibromide, palladium diiodide.9. Method according to claim 1 ,wherein the alcohol in method step c) comprises 1 to 12 carbon atoms.10. Method according to claim 1 ,wherein the alcohol in method step c) is selected from methanol, ethanol, 1-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, cyclohexanol, 2-ethylhexanol, isononanol, 2-propylheptanol, benzyl alcohol, 1-phenylethanol or 2-phenylethanol.11. Method according to claim 1 ,wherein the alcohol in method step c) is selected from methanol, ethanol, isopropanol, n-butanol or 2-phenylethanol. The present invention relates to a novel method for preparing di- or tricarboxylic esters by alkoxycarbonylation of dienes having conjugated double bonds.Dienes having conjugated double bonds (1,3-dienes), particularly 1,3-butadiene and isoprene, have diverse application in the chemical industry and serve for example as base material for preparing synthetic rubber. A further promising application is the ...

PROCESS FOR PD-CATALYZED HYDROXYCARBONYLATION OF DIISOBUTENE: LIGAND/PD RATIO

Process for Pd-catalyzed hydroxycarbonylation of diisobutene: ligand/Pd ratio. 2. Process according to claim 1 ,wherein the compound in process step b) is selected from:{'sub': 2', '2', '2', '2', '2', '3', '2, 'PdCl, PdBr, Pd(acac), Pd(dba)(dba=dibenzylideneacetone), PdCl(CHCN).'}3. Process according to claim 1 ,wherein the ligand L1 is added in an amount in the range from 1.25 mol to 1.75 mol of ligand per mole of Pd.4. Process according to claim 1 ,wherein the reaction mixture is heated to a temperature in the range from 80° C. to 160° C. in process step f).5. Process according to claim 1 ,wherein the CO is fed in in process step e) such that the reaction proceeds under a CO pressure in the range from 10 bar to 40 bar.6. Process according to claim 1 ,wherein the process comprises the additional process step g):g) addition of sulfuric acid. The invention relates to a process for Pd-catalyzed hydroxycarbonylation of diisobutene: ligand/Pd ratio.Carboxylic acids including propionic acid, adipic acid and fatty acids are used in the preparation of polymers, pharmaceuticals, solvents and food additives. The routes leading to carboxylic acids generally include the oxidation of hydrocarbons, alcohols or aldehydes, the oxidative cleavage of olefins by ozonolysis, the hydrolysis of triglycerides, nitriles, esters or amides, the carboxylation of Grignard or organolithium reagents, and the halogenation and subsequent hydrolysis of methyl ketones in the haloform reaction.The hydrocarboxylation of olefins is a highly promising and environmentally-friendly method for obtaining carboxylic acids. Acetic acid is produced by carbonylation of methanol, which is carried out with iodide. In the Koch reaction, the addition of water and carbon monoxide to alkenes is catalyzed by strong bases. This method is effective with alkenes that form secondary and tertiary carbocations, e.g. isobutylene to pivalic acid. The hydrocarboxylation occurring with the simultaneous addition of CO and HO to ...

PROCESS FOR DOUBLE CARBONYLATION OF ALLYL ALCOHOLS TO CORRESPONDING DIESTERS

The invention relates to a process for doubly carbonylating allyl alcohols to the corresponding diesters, wherein a linear or branched allyl alcohol is reacted with a linear or branched alkanol (alcohol) with supply of CO and in the presence of a catalytic system composed of a palladium complex and at least one organic phosphorus ligand and in the presence of a hydrogen halide selected from HCl, HBr and HI. 1. Process for doubly carbonylating allyl alcohols to diesters ,characterized in that a linear or branched allyl alcohol is reacted with a linear or branched alkanol with supply of CO and in the presence of a catalytic system composed of a palladium complex and at least one organic phosphorus ligand and in the presence of a hydrogen halide selected from HCl, HBr and HI.3. Process according to claim 1 ,{'sub': 1', '20', '1', '20', '7', '11, 'characterized in that the alkanols are compounds of the general formula ROH where R is a C- to C-alkyl, a C- to C-cycloalkyl or a C- to C-aralkyl group.'}4. Process according to claim 1 ,characterized in that the reaction is conducted in the liquid phase at a temperature of 70 to 250° C.5. Process according to claim 1 ,characterized in that reaction is conducted under a pressure of 2 to 100 bar.6. Process according to claim 1 ,characterized in that the palladium complex is formed in situ proceeding from a pre-complex, using, as palladium source, palladium-containing salts and complexes as precursor.7. Process according to claim 6 ,characterized in that the palladium complex is selected from the group comprising Pd acetate, Pd acetylacetonate, Pd halides, Pd-halogen-1,5-cyclooctadienes, Pd nitrates, Pd oxide and diammonium hexachloropalladate.8. Process according to claim 1 ,characterized in that the phosphine ligands have a mono- or bidentate structure, preferably selected from the group comprisingL1—(9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine),L2—10,10′-(oxybis(2,1-phenylene))bis(10H-phenoxaphosphinine),L3—2,2 ...

Method for Fluoroalkylation of Enamines

The invention discloses a method for fluoroalkylation of enamines with a fluoro alkyl halide in the presence of a base.

PLATINUM COMPLEXES HAVING BINAPHTHYLDIPHOSPHINE LIGANDS FOR THE CATALYSIS OF THE HYDROXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

Platinum complexes having binaphthyldiphosphine ligands for the catalysis of the hydroxycarbonylation of ethylenically unsaturated compounds. 2. Complex according to claim 1 , wherein at least two of the R claim 1 , R claim 1 , R claim 1 , Rradicals are a -(C-C)-heteroaryl radical having at least six ring atoms.3. Complex according to Claim 1 , wherein the Rand Rradicals are each a -(C6-C20)-heteroaryl radical having at least six ring atoms.4. Complex according to Claim 1 , wherein the Rand Rradicals are each 2-pyridyl.5. Complex according to Claim 1 , wherein Rand Rare -(C-C12)-alkyl.6. Complex according to Claim 1 , wherein Rand Rare tent-butyl.9. Process according to claim 8 , wherein the ethylenically unsaturated compound is selected from: ethene claim 8 , propene claim 8 , 1-butene claim 8 , cis- and/or trans-2-butene claim 8 , isobutene claim 8 , 1 claim 8 ,3-butadiene claim 8 , 1-pentene claim 8 , cis- and/or trans-2-pentene claim 8 , 2-methyl-1-butene claim 8 , 3-methyl-1-butene claim 8 , 2-methyl-2-butene claim 8 , hexene claim 8 , tetramethylethylene claim 8 , heptene claim 8 , 1-octene claim 8 , 2-octene claim 8 , di-n-butene claim 8 , or mixtures thereof.10. Process according to claim 8 , wherein the acid in process step c) is selected from: acetic acid claim 8 , perchloric acid claim 8 , sulfuric acid claim 8 , phosphoric acid claim 8 , methylphosphonic acid claim 8 , methanesulfonic acid claim 8 , trifluoromethanesulfonic acid claim 8 , tert-butanesulfonic acid claim 8 , p-toluenesulfonic acid (PTSA) claim 8 , 2-hydroxypropane-2-sulfonic acid claim 8 , 2 claim 8 ,4 claim 8 ,6-trimethylbenzenesulfonic acid claim 8 , dodecylsulfonic acid claim 8 , camphorsulfonic acid.11. Process according to any of to claim 8 , wherein the acid in process step c) is acetic acid.12. Process according to any of to claim 8 , wherein the substance comprising Pt is selected from: platinum dichloride (PtC1) claim 8 , platinum(II) acetylacetonate [Pt(acac)] claim 8 , platinum( ...

PROCESS FOR THE DIRECT CONVERSION OF DIISOBUTENE TO A CARBOXYLIC ACID

Process for the direct conversion of diisobutene to a carboxylic acid. 2. Process according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 6', '20, 'wherein at least two of the R, R, R, Rradicals are a —(C-C)-heteroaryl radical having at least six ring atoms.'}3. Process according to claim 1 ,{'sup': 1', '3, 'sub': 6', '20, 'wherein the Rand Rradicals are each a —(C-C)-heteroaryl radical having at least ring atoms.'}4. Process according to claim 1 ,{'sup': 1', '3, 'sub': 6', '20, 'wherein the Rand Rradicals are each a —(C-C)-heteroaryl radical having at least six ring atoms;'}{'sup': '2', 'sub': 6', '20', '1', '12', '3', '12', '3', '12', '6', '20, 'Ris —(C-C)-heteroaryl having at least six ring atoms or is selected from —(C-C)-alkyl, —(C-C)-cycloalkyl, —(C-C)-heterocycloalkyl, —(C-C)-aryl;'}{'sup': '4', 'sub': 1', '12', '3', '12', '3', '12', '6', '20, 'and Ris selected from —(C-C)-alkyl, —(C-C)-cycloalkyl, —(C-C)-heterocycloalkyl, —(C-C)-aryl.'}5. Process according to claim 1 ,{'sup': 1', '3, 'sub': 6', '20, 'wherein the Rand Rradicals are each a —(C-C)-heteroaryl radical having at least six ring atoms;'}{'sup': 2', '4, 'sub': 1', '12', '3', '12', '3', '12', '6', '20, 'and Rand Rare selected from —(C-C)-alkyl, —(C-C)-cycloalkyl, —(C-C)-heterocycloalkyl, —(C-C)-aryl.'}6. Process according to claim 1 ,{'sup': 1', '3, 'sub': 6', '20, 'wherein the Rand Rradicals are each a —(C-C)-heteroaryl radical having at least six ring atoms;'}{'sup': 2', '4, 'sub': 1', '12, 'and Rand Rare —(C-C)-alkyl.'}7. Process according to claim 1 ,{'sup': 1', '2', '3', '4, 'wherein R, R, R, R, if they are a heteroaryl radical, are each independently selected from pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzofuranyl, indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl.'}9. Process according to claim 1 ,wherein the substance in process step b) is selected from:{'sub': 2', '2', '2', '2', '2', '3', '2, 'PdCl, PdBr, Pd(acac), Pd(dba)(dba=dibenzylideneacetone), PdCl(CHCN).'}10. Process ...

SELECTIVE REDUCTION OF ALDEHYDES AND KETONES

The present invention relates to a selective reduction of specific aldehydes and ketones to their corresponding alcohols.

PROCESS FOR THE ALKOXYCARBONYLATION OF ETHERS

The invention relates to a process comprising the following process steps: a) introducing an ether having 3 to 30 carbon atoms; b) adding a phosphine ligand and a compound which comprises Pd, or adding a complex comprising Pd and a phosphine ligand; c) adding an alcohol; d) supplying CO; e) heating the reaction mixture, the ether being reacted for form an ester; where the phosphine ligand is a compound of formula (I) where m and n are each independently 0 or 1; R 1 , R 2 , R 3 , R 4 are each independently selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 20 )-heteroaryl; at least one of the R 1 , R 2 , R 3 , R 4 radicals is a —(C 3 -C 20 )-heteroaryl radical; and R 1 , R 2 , R 3 , R 4 , if they are —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl or —(C 3 -C 20 )-heteroaryl, may each independently be substituted by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )-cycloalkyl, —S—(C 1 -C 12 )-alkyl, —S—(C 3 -C 12 )-cycloalkyl, —COO—(C 1 -C 12 )-alkyl, —COO—(C 3 -C 12 )-cycloalkyl, —CONH—(C 1 -C 12 )-alkyl, —CONH—(C 3 -C 12 )-cycloalkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 3 -C 12 )-cycloalkyl, —N—[(C 1 -C 12 )-alkyl] 2 , —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl, —(C 3 -C 20 )-heteroaryl-(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl-O—(C 1 -C 12 )-alkyl, —COOH, —OH, —SO 3 H, —NH 2 , halogen.

PHOSPHINE LIGAND AND PALLADIUM CATALYSTS BASED THEREON FOR THE ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

The invention relates to a compound of formula (1) 2. Complex comprising Pd and a compound according to .4. Process according to claim 3 , wherein the ethylenically unsaturated compound is selected from ethene claim 3 , propene claim 3 , 1-butene claim 3 , cis- and/or trans-2-butene claim 3 , isobutene claim 3 , 1 claim 3 ,3-butadiene claim 3 , 1-pentene claim 3 , cis- and/or trans-2-pentene claim 3 , 2-methyl-1-butene claim 3 , 3-methyl-1-butene claim 3 , 2-methyl-2-butene claim 3 , hexene claim 3 , tetramethylethylene claim 3 , heptene claim 3 , 1-octene claim 3 , 2-octene claim 3 , di-n-butene claim 3 , or mixtures thereof.5. Process according to claim 3 , wherein the ethylenically unsaturated compound comprises 8 to 22 carbon atoms.6. Process according to claim 3 , wherein the compound comprising Pd in process step b) is selected from palladium dichloride claim 3 , palladium(II) acetylacetonate claim 3 , palladium(II) acetate claim 3 , dichloro(1 claim 3 ,5-cyclooctadiene)palladium(II) claim 3 , bis(dibenzylideneacetone)palladium claim 3 , bis(acetonitrile)dichloropalladium(II) claim 3 , palladium(cinnamyl) dichloride.7. Process according to claim 3 , wherein the alcohol in process step c) is selected from methanol claim 3 , ethanol claim 3 , 1-propanol claim 3 , 1-butanol claim 3 , 1-pentanol claim 3 , 1-hexanol claim 3 , 2-propanol claim 3 , tert-butanol claim 3 , 3-pentanol claim 3 , cyclohexanol claim 3 , phenol claim 3 , or mixtures thereof. The present invention relates to an improved phosphine ligand and to the use thereof in alkoxycarbonylation.The alkoxycarbonylation of ethylenically unsaturated compounds is a process of increasing significance. An alkoxycarbonylation is understood to mean the reaction of ethylenically unsaturated compounds such as olefins with carbon monoxide and alcohols in the presence of a metal or a metal complex and a ligand to give the corresponding esters:Among the alkoxycarbonylation reactions, ethene methoxycarbonylation to ...

PROCESS FOR THE ALKOXYCARBONYLATION OF ALCOHOLS

The invention relates to a process comprising the following process steps: a) introducing a first alcohol, the first alcohol having 2 to 30 carbon atoms; b) adding a phosphine ligand and a compound which comprises Pd, or adding a complex comprising Pd and a phosphine ligand; c) adding a second alcohol; d) supplying CO; e) heating the reaction mixture, the first alcohol reacting with CO and the second alcohol to form an ester; where the phosphine ligand is a compound of formula (I) where m and n are each independently 0 or 1; R 1 , R 2 , R 3 , R 4 are each independently selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 20 )-heteroaryl; at least one of the R 1 , R 2 , R 3 , R 4 radicals is a —(C 3 -C 20 )-heteroaryl radical; and R 1 , R 2 , R 3 , R 4 , if they are —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl or —(C 3 -C 20 )-heteroaryl, may each independently be substituted by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )-alkyl, —S—(C 1 -C 12 )-alkyl, —S—(C 3 -C 12 )-cycloalkyl, —COO—(C 1 -C 12 )-alkyl, —COO—(C 3 -C 12 )-cycloalkyl, —CONH—(C 1 -C 12 )-alkyl, —CONH—(C 3 -C 12 )-cycloalkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 3 -C 12 )-cycloalkyl, —N—[(C 1 -C 12 )-alkyl] 2 , —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl, —(C 3 -C 20 )-heteroaryl-(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl-O—(C 1 -C 12 )-alkyl, —COON, —OH, —SO 3 H, —NH 2 , halogen.

MONOPHOSPHINE COMPOUNDS AND PALLADIUM CATALYSTS BASED THEREON FOR THE ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

The invention relates to compounds of formula (I) 2. Compound according to claim 1 ,{'sup': '1', 'sub': 1', '12, 'where Ris —(C-C)-alkyl.'}3. Compound according to claim 1 ,{'sup': '2', 'sub': 6', '20', '3', '20, 'where Ris selected from —(C-C)-aryl and —(C-C)-heteroaryl.'}4. Compound according to claim 1 ,{'sup': '2', 'where Ris selected from phenyl, pyrimidyl and imidazolyl.'}5. Compound according to claim 1 ,{'sup': '3', 'where Ris selected from heteroaryl groups having five or six ring atoms.'}6. Compound according to claim 1 ,{'sup': '3', 'where Ris selected from pyrimidyl and imidazolyl.'}7. Compound according to claim 1 ,{'sup': 1', '2', '3, 'sub': 1', '12, 'where R, Rand Rmay each independently be substituted by one or more substituents selected from —(C-C)-alkyl.'}9. Complex comprising Pd and a compound according to .11. Process according to claim 10 , wherein the ethylenically unsaturated compound is selected from ethene claim 10 , propene claim 10 , 1-butene claim 10 , cis- and/or trans-2-butene claim 10 , isobutene claim 10 , 1 claim 10 ,3-butadiene claim 10 , 1-pentene claim 10 , cis- and/or trans-2-pentene claim 10 , 2-methyl-1-butene claim 10 , 3-methyl-1-butene claim 10 , 2-methyl-2-butene claim 10 , hexene claim 10 , tetramethylethylene claim 10 , heptene claim 10 , 1-octene claim 10 , 2-octene claim 10 , di-n-butene claim 10 , and mixtures thereof.12. Process according to claim 10 ,wherein the compound comprising Pd in process step b) is selected from palladium dichloride, palladium(II) acetylacetonate, palladium(II) acetate, dichloro(1,5-cycloocta-diene)palladium(II), bis(dibenzylideneacetone)palladium, bis(acetonitrile)dichloro-palladium(II), palladium(cinnamyl) dichloride.13. Process according to claim 10 ,wherein the alcohol in process step c) is selected from methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, tert-butanol, 3-pentanol, cyclohexanol, phenol, and mixtures thereof.14. Process according to claim 10 , ...

1, 1' -BIS(PHOSPHINO)FERROCENE LIGANDS FOR ALKOXYCARBONYLATION

Compound of formula (I) 2. Compound according to claim 1 ,{'sup': 2', '4, 'sub': 1', '12, 'where R, Rare each independently selected from —(C-C)-alkyl, cyclohexyl and phenyl.'}3. Compound according to claim 1 ,{'sup': 1', '3, 'where the R, Rare each a heteroaryl radical having five to ten ring atoms.'}4. Compound according to claim 1 ,{'sup': 1', '3, 'where R, Rare each independently selected from furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, furazanyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzofuranyl, indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl.'}5. Compound according to claim 1 ,{'sup': 1', '3, 'where Rand Rare each pyridyl.'}6. Compound according to claim 1 ,{'sup': 1', '3', '2', '4, 'where Rand Rare each identical radicals and Rand Rare each identical radicals.'}8. Complex comprising Pd and a compound according to .9. Process comprising the following process steps:a) initially charging an ethylenically unsaturated compound;{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'b) adding a compound according to and a compound comprising Pd;'}c) adding an alcohol;d) feeding in CO;e) heating the reaction mixture, with conversion of the ethylenically unsaturated compound to an ester.10. Process according to claim 9 ,wherein the ethylenically unsaturated compound comprises 2 to 30 carbon atoms and optionally one or more functional groups selected from carboxyl, thiocarboxyl, sulpho, sulphinyl, carboxylic anhydride, imide, carboxylic ester, sulphonic ester, carbamoyl, sulphamoyl, cyano, carbonyl, carbonothioyl, hydroxyl, sulphhydryl, amino, ether, thioether, aryl, heteroaryl or silyl groups and/or halogen substituents.11. Process according to claim 9 ,wherein the ethylenically unsaturated compound is selected from ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, ...

SELECTIVE REDUCTION OF ESTERS TO ALCOHOLS

The present invention relates to a selective reduction of esters to their corresponding alcohols. 2. Process according to claim 1 , wherein the process is carried out in the presence of at least one base.3. Process according to claim 1 , wherein the process is carried out in the presence of at least one base of formula (VIII){'br': None, 'sup': '1', 'sub': 1', '5, 'M(OC—Calkyl)\u2003\u2003(VIII),'}{'sup': '1', 'wherein Mis an alkali metal, is used.'}4. Process according to claim 1 , wherein the process is carried out in the presence of at least one base of formula (VIII′) claim 1 ,{'br': None, 'sup': '1', 'sub': 3', '5, 'M(OC—Calkyl)\u2003\u2003(VIII′)'}wherein{'sup': '1', 'Mis Li, Na or K.'}5. Process according to claim 1 , wherein the process is carried out in the presence of at least one base selected form the group consisting of KOtBu claim 1 , NaOtBu and LiOtBu.8. Process according to claim 1 , whereinthe catalyst of formula (III) is used in an amount of 0.001-0.5 mol-% (based on the number of moles of the compounds of formula (I)).9. Process according to claim 1 , wherein the reduction is a transfer hydrogenation.10. Process according to claim 1 , wherein the process is carried out with Hgas.11. Process according to claim 10 , wherein the process is carried out at a pressure of 10-50 bar.12. Process according to claim 1 , wherein the process is carried out at a temperature of 30-150° C. The present invention relates to a selective reduction of esters to their corresponding alcohols.Reduction of an ester into the corresponding alcohol is a fundamental and very important reaction in organic chemistry, and is used in a large number of chemical processes. The obtained alcohols are used as such or are important intermediates in further chemical processes.To reduce such esters, usually harsh reaction conditions have to be applied.Furthermore, the reduction of esters usually requests the use of highly reactive reducing agents such as LiAIHor NaBH, which are not easy ...

MARKOVNIKOV-SELECTIVE PALLADIUM CATALYST FOR CARBONYLATION OF ALKYNES WITH HETEROARENES

Markovnikov-selective palladium catalyst for carbonylation of alkynes with heteroarenes. 2. Use of a compound according to claim 1 ,for catalysing a carbonylation reaction.3. A process comprising the following process steps:a) initially charging an alkyne,{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'b) adding a compound according to and a substance including Pd,'}c) feeding in N-methylpyrrole and CO,d) heating the reaction mixture, with conversion of the alkyne to the product. The invention relates to Markovnikov-selective palladium catalyst for carbonylation of alkynes with heteroarenes.The development of ligands plays a key role and provides significant innovations in homogenous catalysis and organic synthesis. Illustrative examples include polymerizations, organometallic coupling reactions, carbonylations, hydrogenations and metathesis. Although a plethora of nitrogen- and phosphorous-based ligands have been developed over the last decades, their rational design to afford highly active catalyst systems, which can easily be prepared and modified, continues to be an important topic in this area.Among the privileged ligand classes known, especially bi- and multidentate derivatives create highly stable and selective organometallic complexes.The problem addressed by the invention was that of providing a compound which is to have good properties as ligands in palladium catalyst for carbonylation of alkynes and reaches a good result regarding the yield of the carbonylation reaction.The problem is solved by a compound according to claim ,Compound having the structure (1):Additionally claimed is the use of the compound as ligand in a ligand-metal complex for catalysis of a carbonylation reaction.Use of a compound described above in a ligand-metal complex for catalysis of a carbonylation reaction.The process in which the compound is used as ligand in a ligand-metal complex for conversion of an olefin to an aldehyde is likewise claimed.A process comprising the ...

PD-CATALYZED DECOMPOSITION OF FORMIC ACID

Process for Pd-catalyzed decomposition of formic acid 2. Process according to claim 1 ,wherein the compound in process step b) is selected from:{'sub': 2', '2', '3', '3', '2', '2', '3', '2, 'Pd(acac), PdCl, Pd(dba)*CHCl (dba=dibenzylideneacetone), Pd(OAc), Pd(TFA), Pd(CHCN)Cl.'}3. Process according to claim 1 ,{'sub': '2', 'wherein the compound in process step b) is Pd(OAc).'}4. Process according to claim 1 ,wherein the process comprises additional process step f):f) addition of an acid.5. Process according to claim 4 ,{'sub': 2', '4', '3', '3', '3', '3, 'wherein the acid in process step f) is selected from: HSO, CHSOH, CFSOH, PTSA.'}6. Process according to claim 4 ,wherein the acid in process step f) is PTSA.7. Process according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 1', '12', '1', '12', '4', '14', '4', '14', '1', '12', '1', '12', '3', '14', '3', '14', '2, 'wherein R, R, R, Rare each independently selected from: —(C-C)-alkyl, —O—(C-C)-alkyl, —(C-C)-aryl, —O—(C-C)-aryl, cycloalkyl, —(C-C)-heteroalkyl, —O—(C-C)-heteroalkyl, —(C-C)-heteroaryl, —O—(C-C)-heteroaryl, —COO-alkyl, —COO-aryl, —C—O-alkyl, —C—O-aryl, NH, halogen and the residues are also capable of forming a larger condensed ring;'}wherein the recited alkyl groups, aryl groups, cycloalkyl, heteroalkyl groups, heteroaryl groups may be substituted as follows:{'sub': 1', '12', '1', '12, '—(C-C)-alkyl, —O—(C-C)-alkyl, halogen;'}{'sup': 1', '2', '3', '4, 'and at least one of the radicals R, R, R, Rdoes not represent phenyl.'}8. Process according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 1', '12', '4', '14', '1', '12', '3', '14, 'wherein R, R, R, Rare each independently selected from: —(C-C)-alkyl, —(C-C)-aryl, cycloalkyl, —(C-C)-heteroalkyl, —(C-C)-heteroaryl, halogen and the residues are also capable of forming a larger condensed ring;'}wherein the recited alkyl groups, aryl groups, cycloalkyl, heteroalkyl groups, heteroaryl groups may be substituted as follows:{'sub': 1', '12', '1', '12, '—(C-C)-alkyl, ...

RU-CATALYSED DOMINO HYDROFORMYLATION / HYDROGENATION / ESTERIFICATION USING IMIDAZOLE LIGANDS

Ru-catalysed domino hydroformylation/hydrogenation/esterification using imidazole ligands.

1, 1' -BIS(PHOSPHINO)FERROCENE LIGANDS FOR ALKOXYCARBONYLATION

Diastereomer mixture comprising diastereomers of the formulae (I.1) and (I.2) where R 2 , R 4 are each independently selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl; the R 1 , R 3 radicals are each a —(C 3 -C 20 )-heteroaryl radical; R 1 , R 3 may each independently be substituted by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )-cycloalkyl, —S—(C 1 -C 12 )-alkyl, —S—(C 3 -C 12 )-cycloalkyl, —COO—(C 1 -C 12 )-alkyl, —COO—(C 3 -C 12 )-cycloalkyl, —CONH—(C 1 -C 12 )-alkyl, —CONH—(C 3 -C 12 )-cycloalkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 3 -C 12 )-cycloalkyl, —N—[(C 1 -C 12 )-alkyl] 2 , —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl, —(C 3 -C 20 )-heteroaryl-(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl-O—(C 1 -C 12 )-alkyl, —COOH, —OH, —SO 3 H, —NH 2 , halogen; and R 2 , R 4 , if they are —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl or —(C 6 -C 20 )-aryl, may each independently be substituted by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )-cycloalkyl, —S—(C 1 -C 12 )-alkyl, —S—(C 3 -C 12 )-cycloalkyl, —COO—(C 1 -C 12 )-alkyl, —COO—(C 3 -C 12 )-cycloalkyl, —CONH—(C 1 -C 12 )-alkyl, —CONH—(C 3 -C 12 )-cycloalkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 3 -C 12 )-cycloalkyl, —N—[(C 1 -C 12 )-alkyl] 2 , —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl, —(C 3 -C 20 )-heteroaryl-(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl-O—(C 1 -C 12 )-alkyl, —COOH, —OH, —SO 3 H, —NH 2 , halogen. The invention further relates to Pd complex mixtures ...

Copper-catalysed Process for the Production of Substituted or Unsubstituted Trifluormethylated Aryl and Heteroaryl Compounds

The present invention relates to a process for the production of trifluoromethylated unsubstituted or substituted aryl or heteroaryl compounds which comprises reacting an unsubstituted or substituted aryl or heteroaryl halide with a trifluoroacetate of formula (I) or (II), 2. Process according to wherein the trifluoroacetate of formula (I) is methyl trifluoroacetate or ethyl trifluoroacetate.3. Process according to wherein the trifluoroacetate of formula (II) is sodium trifluoroacetate.4. Process according to wherein the copper salt is a salt from the group copper iodide claim 1 , copper bromide claim 1 , copper chloride claim 1 , copper acetate claim 1 , copper(II) fluoride claim 1 , copper tetrafluoride claim 1 , copper sulphate and copper trifluoromethylsulfonate.6. Process according to wherein the ligand is ethylene diamine claim 4 , 2-dimethylaminopyridine or 1 claim 4 ,10-phenathroline.7. Process according to wherein the anorganic halogenide salt is a salt from the group caesium fluoride claim 1 , rubidium fluoride claim 1 , lithium fluoride claim 1 , sodium fluoride claim 1 , potassium fluoride and the trifluoroacetacid is caesium trifluoroacetate.8. Process according to wherein the reaction is carried out in N claim 1 ,N-dimethylformamide (DMF) claim 1 , N claim 1 ,N-dimethylacetamide or N-methylpyrlidone as solvent.9. Process according to wherein the reaction is carried out in the temperature range from 80-250° C. with or without solvent.10. Process according to wherein the unsubstituted or substituted aryl compound is an substituted or unsubstituted aryl iodide or aryl bromide and the substituted or unsubstituted heteroaryl compound is substituted or unsubstituted heteroaryl iodide or heteroaryl bromide. The present invention relates to copper-catalysed process for the production of substituted or unsubstituted trifluormethylated aryl or heteroaryl compounds with trifluoroacetates as CF-source.The presence of fluorine in organic molecules can dramatically ...

PROCESS FOR HOMOGENEOUSLY CATALYZED, HIGHLY SELECTIVE DIRECT AMINATION OF PRIMARY ALCOHOLS WITH AMMONIA TO PRIMARY AMINES WITH A HIGH VOLUME RATIO OF LIQUID PHASE TO GAS PHASE AND/OR HIGH PRESSURES

The present invention relates to a process for preparing primary amines comprising the process steps 1. A process for preparing a primary amine , the process comprisingA)contacting (i) a solution of a primary alcohol in a fluid, nongaseous phase with (ii) free ammonia or an ammonia-releasing compound and (iii) a homogeneous catalyst, to form a primary amine, and optionallyB) isolating the primary aminewherein a volume ratio of a volume of a liquid phase to a volume of a gas phase in the contacting is greater than 0.05 and/orthe contacting is performed at a pressure greater than 10 bar.2. The process of claim 1 , wherein in the contactingthe ammonia is present in a molar ratio based on hydroxyl groups in the primary alcohol of at least 5:1.3. The process of claim 1 , whereinthe primary alcohol comprises a carboxyl or ester group.4. The process of claim 1 , whereinthe primary alcohol comprises an aliphatic alkyl radical comprising at least three carbon atoms covalently bound to one another and no quaternary carbon atom.5. The process of claim 1 , whereinthe primary alcohol comprises no heteroatoms.6. The process of claim 4 , whereinthe aliphatic alkyl radical is a linear or branched alkyl radical comprising at least 4 carbon atoms.7. The process of claim 1 , whereinthe primary alcohol is selected from the group consisting of 1-butanol, 2-methyl-1-propanol, 1-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 1-hexanol, 4-methyl-1-pentanol, 3-methyl-1-pentanol, 2-methyl-1-pentanol, 2-ethyl-1-butanol, tripropylene glycol, an anhydrohexitol, and tripropylene glycol.8. The process of claim 1 , whereina concentration of the primary alcohol in (i) is from 0.1 to 10000 mmol/l.9. The process of claim 1 , whereinthe catalyst is selected from the group consisting of:an alkali metal alkoxide, an aluminum alkoxide, a lanthanide alkoxide,an inorganic compound comprising a noble metal,and a coordination compound comprising one or more noble metals selected from the group consisting ...

PROCESS FOR THE DIRECT AMINATION OF ALCOHOLS USING AMMONIA TO FORM PRIMARY AMINES BY MEANS OF A XANTPHOS CATALYST SYSTEM

The present invention relates to a chemocatalytic liquid-phase process for the direct one-stage amination of alcohols to primary amines by means of ammonia in high yields using a catalyst system containing at least one transition metal compound and a xantphos ligand. 2. The process according to claim 1 ,wherein{'sup': 1', '2', '3', '4, 'sub': 3', '2, 'R=R=R=R=phenyl, and A=—C(CH)—.'}3. The process according to claim 1 ,whereinthe xantphos ligand is carbonylchlorohydrido[9,9-dimethyl-4,5-bis(diphenylphosphino)xantheno]ruthenium(II)].4. The process according to claim 1 ,whereinthe alcohol is an aliphatic, linear ω-hydroxycarboxylic acid having a carbon chain comprising at least 8 carbon atoms.5. The process according to claim 1 ,whereinthe alcohol has a concentration of from 0.1 to 1000 mmol/l, based on the fluid phase.6. The process according to claim 1 ,wherein the contacting comprises contacting with liquid or supercritical ammonia, with a solution of ammonium salts in a solvent, or both.7. The process according to claim 1 ,wherein in the contacting,the ammonia has a molar ratio to hydroxyl groups in the alcohol of at least 5:1.8. The process according to claim 1 ,wherein the contacting is carried out at a pressure of from 1 to 1000 bar.9. The process according to claim 1 ,wherein the contacting is carried out in a temperature range of from 80 to 220° C.10. The process according to claim 1 ,whereina volume ratio of a liquid phase to a gas phase in the contacting is greater than or equal to 0.05.11. The process according to claim 1 ,wherein the process is carried out in an absence of hydrogen.12. The process according to claim 1 , wherein the alcohol has a concentration of from 0.1 to 100 mmol/l based on the fluid phase.13. The process according to claim 1 , wherein the alcohol has a concentration of from 0.1 to 10 mmol/l based on the fluid phase.14. The process according to claim 1 , wherein in the contacting claim 1 , the ammonia has a molar ratio to hydroxyl ...

PHOTOSENSITIZERS AND USE THEREOF FOR GENERATING HYDROGEN FROM WATER

The invention relates to novel complexes and to the use thereof as photosensitizers for generating hydrogen from water. 2. The compound of in claim 1 , wherein X is oxygen or sulfur.4. The compound of claim 1 , wherein:{'sup': 1', '30, 'Rto Reach, independently, represent hydrogen, halogen, straight-chain or branched alkyl having 1-20 carbon atoms or phenyl; or'}{'sup': 1', '30, 'Rto Rare joined to one another in pairs by a single or double bond to form aromatic or aliphatic rings.'}5. (canceled)6. A catalyst system claim 1 , comprising at least one compound of .7. The catalyst system as claimed in claim 6 , further comprising at least one water reduction catalyst and at least one electron donor.8. A process for preparing hydrogen by reduction of water claim 6 , the process comprising reducing water in the presence of the catalyst system of to form hydrogen.9. Hydrogen obtained by the process of .11. The compound of claim 2 , wherein:{'sup': 1', '30, 'Rto Reach, independently, represent hydrogen, halogen, straight-chain or branched alkyl having 1-20 carbon atoms or phenyl; or'}{'sup': 1', '30, 'Rto Rare joined to one another in pairs by a single or double bond to form aromatic or aliphatic rings.'} The present invention relates to novel complexes and their use as photosensitizers for producing hydrogen from water.Alternative energy generation, for example wind power or solar energy, are playing an increasingly important role in the worldwide supply of energy. The associated fluctuation in the quantity of energy provided requires the use of energy stores for bridging energy minimum phases (night, lack of wind, etc.). Hydrogen is in this context considered to be a promising energy store.In addition, hydrogen is a valuable starting material for the preparation of a wide variety of important basic chemicals, e.g. ammonia and methanol, and specialty chemicals which can be prepared by hydrogenation. A future hurdle for the chemical utilization of hydrogen is that the ...

METHOD FOR HYDROFORMYLATION OF UNSATURATED COMPOUNDS

The invention relates to a method for hydroformylation of unsaturated compounds such as olefins and alkynes using mixtures of synthesis gas (CO/H), in which either the unsaturated compounds and a catalyst are heated to a reaction temperature of 60 to 200° C. and the synthesis gas is then added, or the unsaturated compounds and the catalyst are brought into contact with pure CO at normal temperature in a preformation step, then are heated to reaction temperature and on reaching the reaction temperature the CO is replaced by the synthesis gas. The pressure is 1 to 200 bar and the CO:Hratio in the synthesis gas is in the range from 1:1 to 50:1. The iridium catalyst used comprises a phosphorus-containing ligand in the iridium:ligand ratio in the range from 1:1 to 1:100. With high catalyst activities and low catalyst use, very high turnover frequencies are achieved. 1. A method for hydroformylating an unsaturated compound with a synthesis gas mixture comprising carbon monoxide and hydrogen , the method comprising:(a1) heating the unsaturated compound and a catalyst to a reaction temperature of 60 to 200° C. and(a2) adding the synthesis gasor(b1) contacting the unsaturated compound and the catalyst with pure carbon monoxide at normal temperature in a preformation step,(b2) heating the mixture to a reaction temperature of 60 to 200° C. and(b3) on reaching the reaction temperature, replacing the carbon monoxide with the synthesis gas mixture,{'sub': '2', 'where a reaction pressure is in a range from 0.1 to 20.0 MPa, a CO:Hmolar ratio in the synthesis gas mixture is in a range from 1:1 to 50:1 and the unsaturated compound is reacted in the presence of a polar solvent and of the catalyst, wherein the catalyst is an iridium catalyst comprising a ligand comprising phosphorus, wherein an iridium:ligand molar ratio is in a range from 1:1 to 1:100.'}2. The method of claim 1 , wherein the CO:Hmolar ratio in the synthesis gas mixture is in a range from 1:1 to 10:1.3. The method of ...

PROCESS FOR THE PREPARATION OF DEUTERATED COMPOUNDS CONTAINING N-ALKYL GROUPS

The present invention relates to a process for deuteration of amines in the alpha and/or beta position of the N-atom by using a deuterium source and a Ruthenium(II) based catalyst. 1. A process for preparing a deuterated compound (II) containing at least one structural element of the formula N—C—C , which is not part of an aromatic ring system , and wherein the amount of deuterium at the carbon atom in the alpha position and/or the carbon atom in the beta position of the structural element is at least 1% , comprising reacting a compound (1) comprising a residue which contains at least one structural element N—C—C , wherein at least one H atom is at each carbon atom of the structural element and the N—C—C element is not part of an aromatic ring system , with a deuterium source in the presence of a catalyst of formula (2) 1-UH-tetra-Z-cyclopentadienyl-(tetra-Z-2 ,4-cyclopentadien-1-U)-μ-hydro-tetra-L-diruthenium(II) (2) , wherein{'sub': '5', 'UH is OH, NHR, or SH;'}{'sub': '5', 'U is O, NRor S;'}{'sub': 5', '1', '6', '2, 'Ris (C-C)alkyl, phenyl or —CH-phenyl;'}{'sub': 1', '6', '1', '6, 'Z is, independently of each other, (C-C)alkyl or phenyl, wherein each phenyl is optionally substituted by (C-C)alkyl or phenyl, wherein phenyl is optionally substituted 1 or more times by halogen, and'}L is CO, CN or COD.2. The process according to claim 1 , wherein the structural element in a compound (I) is N—C(H)—C(H)wherein m is 1 or 2 and n is 1 claim 1 , 2 or 3.3. The process according to claim 1 , wherein the structural element in a compound (I) is N—CH—CH.4. The process according to claim 1 , wherein the residue containing the structural element in compound (I) is —N(C)alkylene claim 1 , —NH(C-C)alkyl claim 1 , —N((C-C)alkyl)((C-C)alkyl) claim 1 , —(C-C)alkylene-N((C-C)alkyl) claim 1 , —(C-C)alkylene-N((C-C)alkyl)((C-C)alkyl)) or (C-C)heterocycloalkyl.5. The process according to claim 1 , wherein compound (I) is a compound of formula (I){'br': None, 'sub': 1', '1', '2', '3', '4 ...

Method for Preparation of Fluoro Alkylated Compounds by Homogeneous NI Catalysis

The invention discloses a method for the preparation of fluoro alkylated compounds by homogeneous Ni catalyzed fluoro alkylation with fluoro alkyl halides in the presence of a base. 2. The method according to claim 1 , wherein{'sub': '3', 'LIG is compound of formula (DPEPhos) or PhP.'}3. The method according to claim 1 , wherein{'sub': 2', '3', '3', '4, 'BAS is selected from the group consisting of CsCO, KPO, NaH and NaOtBu.'}5. The method according to claim 1 , wherein by 1, 2 or 3 in case of COMPSUBST-I being a monocyclic compound with 5 endocyclic atoms,', 'by 1, 2, 3, 4 or 5 in case of COMPSUBST-I being a monocyclic compound with 6 endocyclic atoms,', 'by 1, 2, 3 or 4 in case of COMPSUBST-I being a bicyclic compound wherein a 5-membered and a 6-membered ring are ortho-fused,', 'by 1, 2, 3, 4 or 5 in case of COMPSUBST-I being a bicyclic compound wherein two 6-membered rings are ortho-fused,, 'COMPSUBST-I is unsubstituted or substituted'}{'sub': 1-4', '3', '2', 'm', '2, 'identical or different substituents independently from each other selected from the group consisting of Calkyl, CM alkoxy, OH, C(H)═O, N(R10)R11, CN, F, Cl, Br, CF, (CH)—C(O)Y1, and S(O)R50;'}{'sub': '1-4', 'said Calkyl substituent of COMPSUBST-I is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the group consisting of halogen;'}{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'with R10, R11, m, Y1, R50 and halogen as defined in .'}7. The method according to claim 1 , wherein{'sub': 1-20', '2', 'n3', '2, 'FAHALIDE is selected from the group consisting of perfluoro Calkyl-X1, Br—(CF)—Br, and FHC—X1;'}with n3 being an integer of 2 to 10.8. The method according to claim 1 , whereinn3 is 2, 3, 4, 5, 6.9. The method according to claim 1 , wherein{'sub': 21', '10', '21', '10', '17', '8', '17', '8', '13', '6', '13', '6', '9', '4', '9', '4', '7', '3', '7', '3', '3', '3', '2', '4', '2', '2, 'FAHALIDE is selected from the group consisting of FC—I, FC—Br, FC—I, ...

Method for Preparation of Fluoro Alkylated 1,4-Dioxene by Homogeneous NI Catallysis

The invention discloses a method for the preparation of fluoro alkylated 1,4-dioxene by homogeneous Ni catalyzed fluoro alkylation with fluoro alkyl halides of -dioxane in the presence of a base. 2. The method according to claim 1 , wherein NISALT is NiCland LIG is compound of formula (dppb).3. The method according to claim 1 , wherein BAS is selected from the group consisting of CsCO claim 1 , NaCO claim 1 , KPO claim 1 , NaH and NaOtBu.4. The method according to claim 1 , wherein FAHALIDE is selected from the group consisting of perfluoro Calkyl-X1 claim 1 , Br—(CF)—Br claim 1 , and FHC—X1;with n3 being an integer of 2 to 10.5. The method according to claim 1 , wherein n3 is 2 claim 1 , 3 claim 1 , 4 claim 1 , 5 claim 1 , 6.6. The method according to claim 1 , wherein FAHALIDE is selected from the group consisting of FC—I claim 1 , FC—Br claim 1 , FC—I claim 1 , FC—Br claim 1 , FC—I claim 1 , FC—Br claim 1 , FC—I claim 1 , FC—Br claim 1 , FC—I claim 1 , FC—Br claim 1 , FC—I claim 1 , FC—Br claim 1 , Br—(CF)—Br claim 1 , FHC—I claim 1 , and FHC—Br.7. The method according to claim 1 , wherein FAHALIDE is selected from the group consisting of FC—I claim 1 , FC—I claim 1 , FC—I claim 1 , FC—I claim 1 , FC—I claim 1 , and FC—I.8. The method according to claim 7 , wherein the reaction is done neat or in a solvent SOL.9. The method according to claim 8 , wherein SOL is selected from the group consisting of alkanes claim 8 , chlorinated alkanes claim 8 , ketones claim 8 , ethers claim 8 , esters claim 8 , aliphatic nitrils claim 8 , aliphatic amides claim 8 , sulfoxides claim 8 , CFand mixtures thereof The invention discloses a method for the preparation of fluoro alkylated 1,4-dioxene by homogeneous Ni catalyzed fluoro alkylation with fluoro alkyl halides of 1,4-dioxane in the presence of a base.I. Hanna in Tetrahedron Letters, 1999, 40, 2521-2524 discloses that furans are important functional groups that can be found in many natural products and have frequently been ...

IN-SITU GENERATION OF RUTHENIUM CATALYSTS FOR OLEFIN METATHESIS

The present invention relates to a process for preparing olefins by means of metathesis, which comprises the following steps 2. The process according to claim 1 , wherein the anionic ligands X are identical and are each chlorine and Lis selected from the group consisting of nitrogen bases claim 1 , phosphanes claim 1 , phosphinites claim 1 , phosphonites claim 1 , phosphites and arsanes.3. The process according to claim 2 , wherein Lis selected from the group consisting of benzene claim 2 , toluene claim 2 , xylene claim 2 , cymene claim 2 , trimethylbenzene claim 2 , tetramethylbenzene claim 2 , hexamethylbenzene claim 2 , tetrahydronaphthalene and naphthalene claim 2 , and Lis selected from the group consisting of N-heterocyclic carbenes and phosphanes.4. The process according to claim 3 , wherein Lis selected from the group consisting of P(phenyl) claim 3 , P(cyclohexyl)and N-heterocyclic carbenes of the formula VI claim 3 , VII claim 3 , VIII claim 3 , IX claim 3 , X and XI.6. The process according to claim 5 , wherein the ruthenium compound is a compound of the general formula RuXLL(II) claim 5 , wherein the anionic ligands X are identical and are each chlorine and Lis selected from the group consisting of N-heterocyclic carbenes and phosphanes.7. The process according to claim 6 , wherein Lis selected from the group consisting of benzene claim 6 , toluene claim 6 , xylene claim 6 , cymene claim 6 , trimethylbenzene claim 6 , tetramethylbenzene claim 6 , hexamethylbenzene claim 6 , tetrahydronaphthalene and naphthalene claim 6 , and Lis selected from the group consisting of P(cyclohexyl)and the N-heterocyclic carbenes of the formulae VI claim 6 , VII claim 6 , VIII claim 6 , IX claim 6 , X and XI.8. The process according to claim 7 , wherein the ruthenium compound is selected from the group consisting of compounds of the formulae A claim 7 , B and C.9. The process according to claim 5 , wherein the ruthenium compound is a compound of the general formula RuXL( ...

PROCESS FOR PRODUCING METHANOL

A process for catalyzed reaction of CO and Hinto methanol includes the step of reacting the CO and Hwith a catalyst comprising a transition metal and at least one Lewis basic ligand together with at least one nucleophilic promoter so as to produce the methanol as a product. 1. A process for catalyzed reaction of CO and Hinto methanol , the process comprising:{'sub': '2', 'reacting the CO and Hwith a catalyst comprising a transition metal and at least one Lewis basic ligand together with at least one nucleophilic promoter so as to produce the methanol as a product.'}2. The process according to claim 1 , wherein the catalyst is a metal organic complex with at least one ligand comprising N claim 1 , P claim 1 , O claim 1 , or S.3. The process according to claim 2 , wherein the ligand is a pincer type complex.4. The process according to claim 1 , wherein the transition metal is a central ion claim 1 , and wherein the central ion comprises Mn claim 1 , Fe or Mo.6. The process according to claim 1 , wherein the process takes place in presence of a base.7. The process according to claim 6 , wherein the base is a hydroxide and/or an alkoxide of at least one of lithium claim 6 , sodium claim 6 , potassium or calcium.8. The process according to claim 1 , wherein the at least one nucleophilic promoter comprises nitrogen.9. The process according to claim 1 , wherein the at least one nucleophilic promoter comprises at least one N—H-Group.11. The process according to claim 6 , wherein a ratio r1 between at least one nucleophilic promoter and the base is between 1:1 and 3:1 and/or a ratio r2 between the base and the catalyst is between 25:1 and 100:1.12. The process according to claim 1 , wherein the process is run at a temperature below 200° C.13. The process according to claim 1 , wherein the process takes place in a non-polar solvent.14. The process according to claim 1 , wherein all compounds are introduced with a partial pressure between 0.1 and 40 bar.15. The process ...

CHIRAL METAL COMPLEX COMPOUNDS

The invention comprises novel chiral metal complex compounds of the formula 2. The chiral metal complex compound ofwherein{'sup': '3', 'Ris CO or hydrogen; and'}{'sup': '4', 'sub': '3', 'Ris CO or H—BH.'}3. The chiral metal complex compound of claim 1 , wherein M is selected from the manganese group of the periodic system.4. The chiral metal complex compound of claim 1 , wherein M is selected from manganese and iron.18. A method of catalyzing an asymmetric reaction claim 1 , said method comprising catalyzing said reaction with a chiral metal complex compounds of .19. The method of claim 18 , wherein the asymmetric reaction is an asymmetric reduction.20. The method of claim 19 , wherein the reduction is an asymmetric reduction of a C═X double bond.21. The method of claim 20 , wherein the C═X double bond is a bond of a ketone claim 20 , ketoester claim 20 , imine or oxime.22. The chiral metal complex compound of claim 1 , wherein the metal is selected from the group consisting of manganese claim 1 , rhenium claim 1 , iron claim 1 , ruthenium and osmium.23. The chiral metal complex compound of claim 1 , wherein Rand Rare each methyl claim 1 , or Rand Rare each methyl.24. The chiral metal complex compound of claim 5 , wherein Rand Rare each independently C-alkyl.25. The chiral metal complex compound of claim 10 , wherein X is bromine.26. The chiral iron complex intermediate of claim 17 , wherein X is bromine. The invention relates to novel chiral metal complex compounds of the formulawherein M, PR, Rand Rare as defined below and its stereoisomers in the form as a neutral complex or a complex cation with a suitable counter ion.The invention also relates to processes for the preparation of the chiral metal complexes and to their use in asymmetric reactions, particularly in asymmetric reductions of C═X double bonds, namely of ketones (C═O), α- or β-ketoesters (α: —(C═O)—(C═O)—OR) or β: —(C═O)—CR—(C═O)—OR), imines (—C═N—R) or oximes (—C═N—OH).Research in the field of ...

DOUBLE ALKOXYCARBONYLATION OF DIENES

Process for the double alkoxycarbonylation of dienes. 2. Process according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 1', '12, 'wherein at least two of radicals R, R, R, Rare (C-C)-alkyl.'}3. Process according to claim 1 ,{'sup': 1', '2', '3', '4', 't, 'wherein at least two of radicals R, R, R, Rare Bu.'}4. Process according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 1', '12, 'wherein at least three of radicals R, R, R, Rare (C-C)-alkyl.'}5. Process according to claim 1 ,{'sup': 1', '2', '3', '4', 't, 'wherein at least three of radicals R, R, R, Rare Bu.'}6. Process according to claim 1 ,{'sub': 3', '20, 'wherein the (C-C)-heteroaryl radical is 2-pyridyl.'}8. Process according to claim 1 ,wherein the Pd-containing compound in process step c) is selected from: palladium(II) trifluoroacetate, palladium dichloride, palladium(II) acetylacetonate, palladium(II) acetate, dichloro(1,5-cyclooctadiene)palladium(II), bis(dibenzylideneacetone)palladium, bis(acetonitrile)dichloropalladium(II), palladium(cinnamyl)dichloride, palladium iodide, palladium diiodide.9. Process according to claim 1 ,wherein the alcohol in process step d) is selected from: methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, tert-butanol, 3-pentanol.10. Process according to claim 1 ,wherein the alcohol in process step d) is methanol.11. Process according to claim 1 ,wherein the solvent in process step e) is selected from: toluene, xylene, anisole, chlorobenzene, THF, methylfuran, propylene carbonate, cyclohexane, alkane, ester, ether.12. Process according to claim 1 ,wherein the solvent in process step e) is toluene.13. Process according to claim 1 ,wherein the proportion by volume of the solvent, based on the sum of the volumes of the alcohol and solvent, is in the range from 60% by volume to 99.9% by volume.14. Process according to claim 1 ,wherein the diene in process step a) is selected from: 1,3-butadiene, 1,2-butadiene, vinylcyclohexene.15. Process according to claim 1 ...

Method for converting carbon dioxide and bicarbonates into formic acid derivatives using a cobalt complex as a catalytic system

The invention relates to a method for converting carbon dioxide or bicarbonates into formic acid derivatives, i.e. formate salts, formate esters, and formamides, using molecular hydrogen and a catalytic system comprising a cobalt complex of cobalt salt and at least one tripodal, tetradentate ligand. The catalyst complex can be used as a homogeneous catalyst. The invention further relates to the cobalt complexes per se.

PLATINUM COMPLEXES HAVING FERROCENE DIPHOSPHINE LIGANDS FOR CATALYSIS OF THE HYDROXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

Platinum complexes having ferrocene-diphosphine ligands for catalysis of the hydroxycarbonylation of ethylenically unsaturated compounds. 2. Complex according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 6', '20, 'wherein at least two of the R, R, R, Rradicals are a —(C-C)-heteroaryl radical having at least six ring atoms.'}3. Complex according to claim 1 ,{'sup': 1', '3, 'sub': 6', '20, 'wherein the Rand Rradicals are each a —(C-C)-heteroaryl radical having at least six ring atoms.'}4. Complex according to claim 1 ,{'sup': 1', '3, 'wherein the Rand Rradicals are each 2-pyridyl.'}5. Complex according to claim 1 ,{'sup': 2', '4, 'sub': 1', '12, 'wherein Rand Rare —(C-C)-alkyl.'}6. Complex according to claim 1 ,{'sup': 2', '4, 'wherein Rand Rare tert-butyl.'}9. Process according to claim 8 ,wherein the ethylenically unsaturated compound is selected from: ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, or mixtures thereof.10. Process according to claim 8 ,wherein the acid in process step c) is selected from: acetic acid, perchloric acid, sulfuric acid, phosphoric acid, methylphosphonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, tert-butanesulfonic acid, p-toluenesulfonic acid, 2-hydroxypropane-2-sulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, dodecylsulfonic acid, camphorsulfonic acid.11. Process according to claim 8 ,wherein the acid in process step c) is acetic acid.12. Process according to claim 8 ,{'sub': 2', '2', '2', '2', '2', '2', '3', '2', '2', '2, 'wherein the substance comprising Pt is selected from: platinum dichloride (PtCl), platinum(II) acetylacetonate [Pt(acac)], platinum(II) acetate [Pt(OAc)], dichloro(1,5-cyclooctadiene)platinum(II) [Pt(cod)Cl], bis(dibenzylideneacetone)platinum [Pt(dba)], bis(acetonitrile)dichloroplatinum(II) [Pt(CHCN ...

METHOD FOR PREPARING DELTA-LACTONES

The present invention relates to methods of forming delta-lactone compounds by reaction of a diene with carbon dioxide in the presence of Pd and a phosphine ligand. 2. The method of claim 1 , wherein the phosphine ligand is of the formula (PI):{'br': None, 'sub': 5', '6', '7, 'PRRR\u2003\u2003(PI),'} [{'sub': '5', 'Ris substituted aryl, unsubstituted aryl, substituted linear alkyl, unsubstituted linear alkyl, substituted cyclic alkyl, unsubstituted cyclic alkyl, substituted cyclic heteroalkyl, unsubstituted cyclic heteroalkyl, unsubstituted adamantyl or substituted adamantyl;'}, {'sub': '6', 'Ris substituted aryl, unsubstituted aryl, substituted linear alkyl, unsubstituted linear alkyl, substituted cyclic alkyl, unsubstituted cyclic alkyl, substituted cyclic heteroalkyl, unsubstituted cyclic heteroalkyl, unsubstituted adamantyl or substituted adamantyl; and,'}, {'sub': '7', 'Ris substituted aryl, unsubstituted aryl, substituted linear alkyl, unsubstituted linear alkyl, substituted cyclic alkyl, unsubstituted cyclic alkyl, substituted cyclic heteroalkyl, unsubstituted cyclic heteroalkyl, unsubstituted adamantyl or substituted adamantyl.'}], 'wherein3. The method of claim 2 , wherein substituted aryl or unsubstituted aryl refers to aromatic hydrocarbons with a conjugated cyclic molecular ring structure of 3 claim 2 , 4 claim 2 , 5 claim 2 , 6 claim 2 , 7 claim 2 , 8 claim 2 , 9 claim 2 , 10 claim 2 , 11 or 12 carbon atoms; optionally claim 2 , aryl refers to monocyclic claim 2 , bicyclic or polycyclic rings.4. The method of claim 2 , wherein substituted linear alkyl or unsubstituted linear alkyl refers to straight-chain or branched-chain hydrocarbons having 1 claim 2 , 2 claim 2 , 3 claim 2 , 4 claim 2 , 5 claim 2 , 6 claim 2 , 7 claim 2 , 8 claim 2 , 9 claim 2 , 10 claim 2 , 11 claim 2 , 12 claim 2 , 13 claim 2 , 14 claim 2 , 15 claim 2 , 16 claim 2 , 17 claim 2 , 18 claim 2 , 19 or 20 carbon atoms linked exclusively by single bonds.5. The method of claim 2 , wherein ...

TRIESTERS OF CYCLOHEXANETRIPROPIONIC ACID

The invention relates to triesters of cyclohexanetripropionic acid, preparation thereof and use thereof as plasticizers for polymers. 1. A triester of cyclohexanetripropionic acid having three ester groups and three alcohol moieties , wherein the three alcohol moieties of the three ester groups each comprise 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 or 12 carbon atoms.2. The triester of cyclohexanetripropionic acid according to claim 1 , wherein it is a triester of cyclohexane-1 claim 1 ,2 claim 1 ,4-tripropionic acid or a triester of cyclohexane-1 claim 1 ,3 claim 1 ,5-tripropionic acid.3. The triester of cyclohexanetripropionic acid according to claim 1 , wherein the alcohol moieties claim 1 , besides the oxygen of the ester function claim 1 , do not comprise any other heteroatoms claim 1 , and contain no multiple bonds.4. The triester of cyclohexanetripropionic acid according to claim 1 , wherein all alcohol moieties present in one molecule have identical empirical formulae and at the same time identical or different structural formulae.5. The mixture of at least two triesters of cyclohexanetripropionic acid according to .6. The mixture according to claim 5 , wherein the at least two triesters of cyclohexanetripropionic acid differ in their empirical formulae and/or in their structural formulae.7. The triester of cyclohexanetripropionic acid according to claim 1 , wherein it is selected from the group consisting of:{'sup': n', 'n', 'iso', 'n', 'iso', 'n', 'iso', 'n', 'iso', 'n', 'iso', 'n', 'iso, 'tri(butyl) cyclohexane-1,2,4-tripropionate, tri(methylpropyl) cyclohexane-1,2,4-tripropionate, tri(pentyl) cyclohexane-1,2,4-tripropionate, tri(pentyl) cyclohexane-1,2,4-tripropionate, tri(2-methylbutyl) cyclohexane-1,2,4-tripropionate, tri(3-methylbutyl) cyclohexane-1,2,4-tripropionate, tri(hexyl) cyclohexane-1,2,4-tripropionate, tri(hexyl) cyclohexane-1,2,4-tripropionate, tri(heptyl) cyclohexane-1,2,4-tripropionate, tri(heptyl) cyclohexane-1,2,4-tripropionate, tri(octyl ...

NITROGEN CONTAINING BIOPOLYMER-BASED CATALYSTS, A PROCESS FOR THEIR PREPARATION AND USES THEREOF

The present invention relates to a novel process for the preparation of a nitrogen containing biopolymer-based catalyst and to the novel nitrogen containing biopolymer-based catalysts obtainable by this process. In particular, the invention relates to a novel nitrogen containing biopolymer-based catalyst comprising metal particles and at least one nitrogen containing carbon layer. The invention also relates to the use of a nitrogen containing biopolymer-based catalyst in a hydrogenation process, preferably in a process for hydrogenation of nitroarenes, nitriles or imines; in a reductive dehalogenation process of C—X bonds, wherein X is Cl, Br or I, preferably in a process for dehalogenation of organohalides or in a process for deuterium labelling of arenes via dehalogenation of organohalides; or in an oxidation process. Further, the invention relates to a metal complex with the nitrogen containing biopolymer, wherein the metal is a transition metal selected from the group consisting of manganese, ruthenium, cobalt, rhodium, nickel, palladium and platinum, and wherein the nitrogen containing biopolymer is selected from chitosan, chitin and a polyamino acid. 128-. (canceled)30. The method of claim 29 , wherein the transition metal is cobalt.31. The method of claim 29 , wherein the alcohol is ethanol.32. The method of claim 29 , wherein the metal precursor is a metal salt selected from the group consisting of acetate claim 29 , bromide claim 29 , chloride claim 29 , iodide claim 29 , hydrochloride claim 29 , hydrobromide claim 29 , hydroiodide claim 29 , hydroxide claim 29 , nitrate claim 29 , nitrosylnitrate and oxalate salts; or a metal chelate.33. The method of claim 32 , wherein the metal precursor is acetylacetonate chelate.34. The method of claim 29 , wherein the metal complex is dried under vacuum at 60° C.35. The method of claim 29 , wherein the metal complex with the nitrogen containing biopolymer is pyrolysed at temperatures ranging from 600° C. to 800° C.36. ...

Method For Preparation of Alkylated or Fluoro, Chloro and Fluorochloro Alkylated Compounds By Heterogeneous Catalysis

The invention discloses a method for preparation of alkylated or fluoro, chloro and fluorochloro alkylated compounds by a heterogeneous Pt/C-catalyzed alkylation or fluoro, chloro and fluorochloro alkylation with alkyl halides or with fluoro, chloro and fluorochloro alkyl halides in the presence of CsC0or CsHC0. 116-. (canceled)19. The method according to claim 17 , whereinm, n and q are identical or different and independently from each other 0, 1, 2, 3 or 4.21. The method according to claim 17 , whereinX is Br or I.22. The method according to claim 17 , whereinX is I.23. The method according to claim 17 , wherein{'sub': 2', '2, 'compound FCLALKYLHADLIDE is a perfluoroalkyl halide, FHC—Cl or FHC—Br.'}24. The method according to claim 17 , whereinX is Cl, Br or I, and{'sub': '1-20', 'R3 is perfluoro Calkyl; or'}{'sub': 2', '2, 'FCLALKYLHADLIDE is FHC—Cl or FHC—Br.'}25. The method according to claim 17 , wherein{'sub': 21', '10', '17', '8', '13', '6', '9', '4', '3', '3', '3', '2', '2, 'FCLALKYLHALIDE is selected from the group consisting of FC—I, FC—I, FC—I, FC—I, FC—I, FC—Br, FC—Cl, FHC—Cl and FHC—Br.'}26. The method according to claim 17 , whereinthe reaction is done in the presence of a compound COMPSALT;wherein COMPSALT is selected from the group consisting of NaI, KI, CsI and N(R30)(R31)(R32)R33I; and{'sub': '1-10', 'R30, R31, R32 and R33 are identical or different and independently from each other selected from the group consisting of H and Calkyl.'}27. The method according to claim 26 , wherein{'sub': '2-6', 'R30, R31, R32 and R33 are identical or different and independently from each other selected from the group consisting of H and Calkyl.'}28. The method according to claim 26 , wherein{'sub': '4', 'COMPSALT is selected from the group consisting of NaI and (n-Bu)NI.'}29. The method according to claim 17 , whereinthe amount of Pt in CAT is from 0.1 to 20%, the % are % by weight and are based on the combined weight of Pt and C in CAT.30. The method according ...

IMPROVED ENANTIOSELECTIVE HYDROGENATION OF 4-SUBSTITUTED 1,2-DIHYDROQUINOLINES IN PRESENCE OF A CHIRAL IRIDIUM CATALYST AND AN ADDITIVE

The invention relates to a process for preparing optically active 4-substituted 1,2,3,4-tetrahydroquinolines comprising enantioselective hydrogenation of the corresponding 4-substituted 1,2-dihydroquinolines in presence of a chiral iridium (P,N)-ligand catalyst and an additive. 2. The process according to claim 1 , wherein the additive is selected from the group consisting of hexafluorophosphoric acid claim 1 , acetic acid claim 1 , trifluoromethylsulfonic acid claim 1 , water claim 1 , pentafluorophenol claim 1 , 3 claim 1 ,5-bis(trifluoromethyl)phenol claim 1 , tetrafluoroboric acid claim 1 , tetrafluoroboric acid diethylether complex claim 1 , nafion claim 1 , amberlyst claim 1 , 1 claim 1 ,1 claim 1 ,1 claim 1 ,3 claim 1 ,3 claim 1 ,3-hexafluoro-2-(trifluoromethyl)propan-2-ol claim 1 , triphenylborane claim 1 , tris[3 claim 1 ,5-bis(trifluoromethyl)phenyl]borane claim 1 , tris(2 claim 1 ,3 claim 1 ,4 claim 1 ,5 claim 1 ,6-pentafluorophenyl)borane claim 1 , borane tetra-hydrofurane complex claim 1 , boric acid claim 1 , aluminum (III) trifluoromethanesulfonate claim 1 , zinc (II) trifluoro-methanesulfonate claim 1 , scandium (III) trifluoromethanesulfonate claim 1 , aluminum (III) fluoride claim 1 , titanium (IV) isopropoxide claim 1 , trimethyl aluminum claim 1 , boron trifluoride claim 1 , complexes of boron trifluoride claim 1 , and mixtures thereof.3. The process according to claim 1 , wherein the additive is selected from the group consisting of hexafluorophosphoric acid claim 1 , pentafluorophenol claim 1 , 3 claim 1 ,5-bis(trifluoromethyl)phenol claim 1 , triphenylborane claim 1 , tris[3 claim 1 ,5-bis(trifluoromethyl)phenyl]borane claim 1 , tris(2 claim 1 ,3 claim 1 ,4 claim 1 ,5 claim 1 ,6-pentafluoro-phenyl)borane claim 1 , aluminum (III) trifluoromethanesulfonate claim 1 , scandium (III) trifluoromethane-sulfonate claim 1 , aluminum (III) fluoride claim 1 , titanium (IV) isopropoxide claim 1 , trimethyl aluminum claim 1 , boron trifluoride claim 1 , ...

Method for Preparation of Alkylated or Fluoro, Chloro and Fluorochloro Alkylated Compounds by Heterogeneous Cobalt Catalysis

The invention discloses a method for preparation of alkylated, fluoro alkylated, chloro alkylated and fluorochloro alkylated compounds by a heterogeneous Co-catalysed alkylation or fluoro, chloro and fluorochloro alkylation with alkyl halides, fluoro alkyl halides, chloro alkyl halides or fluorochloro alkyl halides respectively. 2. The method according to claim 1 , whereinwhen RINGA is a heterocyclic ring, then RINGA has 1, 2 or 3 identical or different endocyclic heteroatoms independently from each other selected from the group consisting of N and S.3. The method according to claim 1 , wherein RINGA is an aromatic ring.6. The method according to claim 1 , wherein m claim 1 , n claim 1 , p and q are identical or different and independently from each other 0 claim 1 , 1 claim 1 , 2 claim 1 , 3 or 4.7. The method according to claim 1 , wherein{'sub': 2-6', '1-6', '1-6', '1-6, 'Y1, Y2 and R13 are identical or different and independently from each other selected from the group consisting of H, OH, C(R14)(R15)R16, Calkyl, O—Calkyl, phenyl, benzyl, O-phenyl, O—Calkylen-O—Calkyl and N(R19)R20.'}10. The method according to claim 1 , wherein R3 is Calkyl claim 1 , wherein all hydrogen atoms are independently substituted by Cl or F.11. The method according to claim 1 , wherein R3 is Calkyl claim 1 , wherein all hydrogen atoms are substituted by F.12. The method according to claim 1 , wherein ALKHAL is selected from the group consisting of FC—I claim 1 , FC—I claim 1 , FC—I claim 1 , FC—I claim 1 , FC—I claim 1 , FC—Br claim 1 , FC—Br claim 1 , FC—Br claim 1 , FC—Br claim 1 , FC—Br claim 1 , FC—Cl claim 1 , FHC—Cl claim 1 , and FHC—Br.13. The method according to claim 1 , wherein Co-L1/C is prepared by reacting Co(OAc).4HO with 1 claim 1 ,10-phenantroline and thereby forming a complex Co (phen)(OAc)which is then absorbed on carbon black and kept at 800° C. for 2 h under argon to provide Co-L1/C. The invention discloses a method for preparation of alkylated, fluoro alkylated, ...

METHOD FOR OBTAINING HYDROGEN BY CATALYTIC DECOMPOSITION OF FORMIC ACID

The invention relates to a method for producing hydrogen by selective dehydration of formic acid using a catalytic system consisting of a transition metal complex of transition metal salt and at least one tripodal, tetradentate ligand, wherein the transition metal is selected from the group comprising Ir, Pd, Pt, Ru, Rh, Co and Fe. The transition metal complex can be used either as a homogeneous catalyst or a heterogenised metal complex, which has been applied to a carrier.

Combination of a Compound Having the Ability to Rearrange a Lysosomal Enzyme and Ambroxol and/or a Derivative of Ambroxol

The present invention is related to a combination comprising a first constituent and a second constituent, wherein the first constituent is a compound having the ability to rearrange a lysosomal protein, wherein the lysosomal protein has a reduced activity, and wherein the second constituent is Ambroxol and/or a derivative of Ambroxol. 1. A method for the treatment of a subject suffering from a disease , wherein the method comprises administering a first constituent and a second constituent to the subject , wherein the first constituent is a compound having the ability to rearrange a lysosomal protein , wherein the lysosomal protein has a reduced activity and is selected from the group consisting of alpha-galactosidase A and alpha-glucosidase , andwherein the second constituent is Ambroxol and/or a derivative of Ambroxol.2. The method of to claim 1 , wherein the disease is a disease having reduced activity of alpha-galactosidase A or alpha-glucosidase.3. The method of claim 1 , wherein the compound having the ability to rearrange a lysosomal protein is a chaperon.46.-. (canceled)7. The method of claim 3 , wherein the chaperon is a pharmacological chaperon and wherein the pharmacological chaperon is a sugar and/or an imino sugar or a pharmaceutically acceptable salt claim 3 , solvate or derivative of the sugar and/or the imino sugar.8. (canceled)9. The method of claim 7 , wherein the sugar is galactose.10. The method of claim 7 , wherein the imino sugar is selected from the group comprising 1-deoxygalactonojirimycin (DGJ) claim 7 , alpha-galacto-homonojirimycin claim 7 , alpha-allo-homonojirimycin claim 7 , beta-1-C-butyl-deoxygalactonojirimycin claim 7 , beta-1-C-butyl-deoxynojirimycin claim 7 , N-nonyl-deoxynojirimycin (NN-DNJ) claim 7 , N-octyl-2 claim 7 ,5-anhydro-2 claim 7 ,5-imino-D-glucitol claim 7 , N-octyl-isofagomine claim 7 , N-octyl-beta-valienamine (NOV) claim 7 , Isofagomine (IFG) claim 7 , calystegine A3 claim 7 , calystegine B1 claim 7 , calystegine ...

PROCESS FOR PREPARING ESTERS FROM FORMATES AND OLEFINICALLY UNSATURATED COMPOUNDS

The invention provides a process for preparing esters from formates and olefinically unsaturated compounds with catalysts based on palladium compounds. In addition, the invention discloses a polyphasic reaction mixture and nonyl methyl ester mixtures prepared by the process according to the invention. 1. A method of producing esters by carbonylation , characterized in that it is carried outi) using at least one palladium-containing compound,ii) at least one olefinically unsaturated compound,iii) at least one phosphorus-containing ligand,iv) at least one formate,v) at least one alcohol,vi) at least one acid,vii) in a temperature range of 80° C. to 120° C.,viii) at a reaction pressure of 0.1 to 0.6 MPa.2. A method according to claim 1 , characterized in that the phosphorus-containing ligand comprises trivalent phosphorus.3. A method according to claim 2 , characterized in that the phosphorus-containing ligand comprises a bidentate structure.5. A method according to claim 1 , characterized in that the formate is selected from methyl formate claim 1 , ethyl formate claim 1 , benzyl formate claim 1 , phenyl formate.6. A method according to claim 5 , characterized in that the at least one alcohol corresponds to the particular formate used.7. A method according to claim 1 , characterized in that the acid is selected from the group of sulphonic acids.8. A method according to claim 7 , characterized in that the sulphonic acids are selected from methanesulphonic acid claim 7 , p-toluenesulphonic acid.9. A method according to claim 1 , characterized in that olefin-containing mixtures are used as olefinically unsaturated compounds.10. A method according to claim 9 , characterized in that the carbonylation is effected with isomerization to the n-terminal ester.11. A method according to claim 1 , characterized in that the olefinically unsaturated compounds comprise nitrogen and/or oxygen.12. A method according to claim 1 , characterized in that the palladium-containing compound ...

PROCESS FOR PHOTOCATALYTIC ACCEPTOR-FREE DEHYDROGENATION OF ALKANES AND ALCOHOLS

A process for photocatalytic acceptor-free dehydrogenation of alkanes and alcohols, in which an alkane or an alcohol is irradiated in the presence of a rhodium complex containing organic phosphorus(III) compounds as ligands as a catalyst, and in the presence of at least one Lewis base is provided. 1. A process for dehydrogenation of an alkane or an alcohol , comprising:irradiating the alkane or alcohol in a reaction mixture comprising a rhodium complex and a Lewis base to remove hydrogen from the alkane or alcohol;whereina hydrogen acceptor is not present, andthe rhodium complex comprises a ligand of an organic phosphorus(III) compound.2. The process according to claim 1 ,wherein the Lewis base is an organic amine.3. The process according to claim 1 ,wherein the Lewis base is a heterocyclic amine.4. The process according to claim 1 ,wherein the Lewis base is at least one selected from the group consisting of a bipyridine, bathocuproin and phenanthroline.5. The process according to claim 4 ,wherein the Lewis base is a bipyridine and is 2,2-bipyridine and/or 4,4-bipyridine.6. The process according to claim 1 ,wherein the Lewis base used is bathocuproin or phenanthroline.7. The process according to claim 1 ,{'sub': '2', 'wherein the reaction is conducted in the presence of CO.'}8. The process according to claim 1 ,wherein the irradiation is conducted with light of wavelength 320 nm to 500 nm.9. The process according to claim 1 ,wherein a temperature of the dehydrogenation is from 45° C. to 120° C.10. The process according to claim 1 , {'br': None, 'sup': '1', 'sub': '2', 'Rh(L)(CO)X\u2003\u2003(I)'}, 'wherein the rhodium complex is of formula (I)wherein{'sup': '1', 'sub': 1', '5', '3, 'Lis P(C-Calkyl), and'}X is chloride, bromide or acetate.11. The process according to claim 10 , wherein{'sup': '1', 'sub': 3', '3, 'Lis PMeor PtBu.'}12. The process according to claim 10 , wherein X is chloride.13. The process according to claim 1 , wherein the rhodium complex is of ...

PLATINUM COMPLEXES HAVING BENZYL-BASED DIPHOSPHINE LIGANDS FOR THE CATALYSIS OF THE ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

Platinum complexes having benzyl-based diphosphine ligands for the catalysis of the alkoxycarbonylation of ethylenically unsaturated compounds. 2. Complex according to claim 1 ,{'sup': 1', '2', '3', '4, 'sub': 5', '20, 'wherein at least two of the R, R, R, Rradicals are a -(C-C)-heteroaryl radical having at least six ring atoms.'}3. Complex according to claim 1 ,{'sup': 1', '3, 'sub': 6', '20, 'wherein the Rand Rradicals are each a -(C-C)-heteroaryl radical having at least six ring atoms.'}4. Complex according to claim 1 ,{'sup': 1', '3, 'wherein the Rand Rradicals are each 2-pyridyl.'}5. Complex according to claim 1 ,{'sup': 2', '4, 'sub': 1', '12, 'wherein Rand Rare -(C-C)-alkyl.'}6. Complex according to claim 1 ,{'sup': 2', '4, 'wherein Rand Rare Cert-butyl.'}9. Process according to claim 8 ,wherein the ethylenically unsaturated compound is selected from: ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, or mixtures thereof.10. Process according to claim 8 ,wherein the alcohol in process step c) is selected from: methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, tert-butanol, 3-pentanol, cyclohexanol, phenol.11. Process according to any of to claim 8 ,wherein the alcohol in process step c) is methanol.12. Process according to claim 8 ,{'sub': 2', '2', '2', '2', '2', '2', '3', '2', '2', '2, 'wherein the substance comprising Pt is selected from: platinum dichloride (PtCl), platinum(II) acetylacetonate [Pt(acac)], platinum(II) acetate [Pt(OAc)], dichloro(1,5-cyclooctadiene)platinum(II) [Pt(cod)Cl], bis(dibenzylideneacetone)platinum [Pt(dba)], bis(acetonitrile)dichloroplatinum(II) [Pt(CHCN)Cl], (cinnamyl)platinum dichloride [Pt(cinnamyl)Cl].'}13. Process according to claim 8 ,{'sub': 2', '2', '2, 'wherein the substance comprising Pt is selected ...

METAL-CATALYZED ALKOXYCARBONYLATION OF A LACTONE

The metal-catalyzed alkoxycarbonylation of a lactone is a method of alkoxycarbonylating a δ-lactone, specifically 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one. The method includes combining the δ-lactone with an alcohol in an organic solvent in the presence of a catalyst system that includes palladium or a salt thereof to form a reaction mixture, which is heated to 110-130° C. at a pressure of 20-50 bar for between 3-5 hours under flow of carbon monoxide gas. The product of the reaction is a substituted 2-octendioate diester. The alcohol may be methyl alcohol, n-butyl alcohol, 2-ethylhexanol, isobutyl alcohol, isopropyl alcohol, benzyl alcohol, or phenol. The solvent may be toluene, acetonitrile, or tetrahydrofuran. The method may include adding an acid to the reaction mixture, which may be dilute (about 5 mol %) sulfuric or p-toluenesulfonic acid. The catalyst system may also include a phosphine ligand. 1. A method for metal-catalyzed alkoxycarbonylation of a δ-lactone , the δ-lactone being 3-ethylidene-6-vinyletetrahydro-2H-pyran-2-one , the method comprising the steps of:adding an alcohol and a catalyst system including palladium or a salt thereof to a solution of the δ-lactone in an organic solvent to form a reaction mixture;placing the reaction mixture under pressure of carbon monoxide (CO) gas;heating the reaction mixture to a temperature of at least 110° C.; andrecovering a 2-octendioate diester product.2. The method for metal-catalyzed alkoxycarbonylation according to claim 1 , wherein the catalyst system further comprises a phosphine ligand.3. The method for metal-catalyzed alkoxycarbonylation according to claim 2 , wherein the phosphine ligand is selected from the group of phosphine ligands having the formulas shown in L1 claim 2 , L2 claim 2 , L3 claim 2 , L4 claim 2 , L5 claim 2 , L6 claim 2 , L7 claim 2 , L8 claim 2 , L9 claim 2 , L10 claim 2 , L11 claim 2 , L12 claim 2 , L13 claim 2 , L14 claim 2 , L15 claim 2 , L16 claim 2 , L17 claim 2 , L18 claim 2 ...

PROCESS FOR PREPARING POLYMERS BY MEANS OF RING-OPENING POLYMERIZATION

The present invention relates to a process for preparing polymers by means of ring-opening metathetic polymerization, consisting of the following steps: 4. Process according to claim 1 , wherein the molar ratio of ruthenium compound to cycloalkene is in the range from 1:200 to 1:1 000 000.5. Process according to claim 1 , wherein a=1 claim 1 , b=1 for the ruthenium compound of formula RuXXLL(I) claim 1 , and so a compound of the general formula RuXXLL(VIII) is used.6. Process according to claim 5 , wherein Xand Xare the same and are each chlorine claim 5 , and wherein Lis selected from the group consisting of benzene claim 5 , toluene claim 5 , xylene claim 5 , p-cymene claim 5 , trimethylbenzene claim 5 , tetramethylbenzene claim 5 , hexamethylbenzene claim 5 , tetrahydronaphthalene and naphthalene.10. Process according to claim 9 , wherein the molar ratio of ruthenium compound to cycloalkene is in the range from 1:200 to 1:1 000 000.11. Process according to claim 10 , wherein a=1 claim 10 , b=1 for the ruthenium compound of formula RuXXLL(I) claim 10 , and so a compound of the general formula RuXXLL(VIII) is used.12. Process according to claim 11 , wherein Xand Xare the same and are each chlorine claim 11 , and wherein Lis selected from the group consisting of benzene claim 11 , toluene claim 11 , xylene claim 11 , p-cymene claim 11 , trimethylbenzene claim 11 , tetramethylbenzene claim 11 , hexamethylbenzene claim 11 , tetrahydronaphthalene and naphthalene.15. Process according to claim 1 , wherein the following steps are also included after step d.:e. adding a hydrogenation catalyst,f. converting at a temperature within a range from 0° C. to 250° C. and at a hydrogen pressure within a range from 1 bar to 100 bar.16. Process according to claim 15 , wherein the molar ratio of hydrogenation catalyst to cycloalkene used is in the range from 1:100 to 1:1 000 000.19. Process according to claim 15 , wherein the molar ratio of ruthenium compound to cycloalkene is in the ...

USE OF MALEIMIDE DERIVATIVES FOR PREVENTING AND TREATING LEUKEMIA

The present invention is related to a compound of formula (I): a pharmaceutically acceptable salt thereof, a hydrate thereof, a solvate thereof, a metabolite thereof or a prodrug thereof; for use in a method for the treatment and/or prevention of leukemia, wherein X is selected from the group consisting of N—R, O and S; Ris selected from the group consisting of alkyl, cycloalkyl, aryl, arylalkyl and hydrogen; Ris selected from the group consisting of indolyl, substituted indolyl, azaindolyl and substituted azaindolyl; and Ris selected from the group consisting of aryl, substituted aryl, unsubstituted heteroaryl, heterocyclyl and substituted heterocyclyl. 2. The compound of claim 1 , wherein{'sup': '2', 'Rcomprises one, two, three, four, five or six substituents, whereby each and any of the substituents is individually and independently selected from the group comprising halogen, alkyl, alkenyl, alkynyl, acyl, formyl, cycloalkyl, aryl, haloalkyl, polyfluoroalkyl, alkylthio, arylthio, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkylarylamino, alkylimido, hydroxy, alkoxy, aryloxy, carboxyl, alkoxycarbonyl, aryloxycarbonyl, cyano, amino, amido, acylamino, nitro, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkylsulfinamido, arylsulfinamido, alkylsulfonamido and arylsulfonamido.'}3. The compound of any one of to claim 1 , wherein{'sup': '3', 'Rcomprises one, two, three, four, five, six or seven substituents, whereby each and any of the substituents is individually and independently selected from the group comprising hydrogen, alkyl, alkenyl, alkynyl, aryl, acyl, formyl, halogen, haloalkyl, alkylthio, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkylarylamino, hydroxy, alkoxy, aryloxy, carboxyl, alkoxycarbonyl, aryloxycarbonyl, cyano, amino, amido, acylamino, nitro, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkylsulfinamido, arylsulfinamido, alkylsulfonamido and arylsulfonamido.'}4. The compound of any one of to ...

USE OF THERMALLY-TREATED SUPPORTED COBALT CATALYSTS COMPRISING A POLYCYCLIC AROMATIC STRUCTURE CONSISTING OF NITROGEN LIGANDS FOR HYROGENATING AROMATIC NITRO COMPOUNDS

The invention relates to the use of thermally-treated supported cobalt catalysts for hydrogenating aromatic nitro compounds, the cobalt catalysts having been prepared by in situ immobilization of a cobalt-amine complex on an inorganic porous support and subsequent pyrolysis, and, in the cobalt-amine complex used, cobalt being present bonded to an aromatic or heterocyclic nitrogen ligand L, the nitrogen ligand being selected so as to form a polyaromatic structure with the cobalt atom. 1. A process for hydrogenating aromatic nitro compounds which comprises using a thermally-treated supported cobalt as a catalyst for the hydrogenating , wherein the cobalt catalyst has been prepared by in situ immobilization of a cobalt-amine complex on an inorganic porous support and subsequent pyrolysis , and , in the cobalt-amine complex used , cobalt being present bonded to an aromatic or heterocyclic nitrogen ligand L , the nitrogen ligand being selected so as to form a polyaromatic structure with the cobalt atom.3. The process as claimed in claim 1 , wherein the nitrogen ligand L is selected from the group comprising the phenanthrolines L1: 1 claim 1 ,10-phenanthroline and derivatives thereof claim 1 , L1b: 2 claim 1 ,9-dimethyl-4 claim 1 ,7-diphenyl-1 claim 1 ,10-phenanthroline claim 1 , L1c: 4 claim 1 ,7-dimethoxy-1 claim 1 ,10-phenanthroline claim 1 , L1d: 2 claim 1 ,9-dimethyl-1 claim 1 ,10-phenanthroline claim 1 , L2: terpyridine claim 1 , L3: 2 claim 1 ,6-bis(benzimidazolyl)pyridine claim 1 , L4: 1 claim 1 ,1′-bipyridine and L5: pyridine.4. The process as claimed in claim 1 , wherein the inorganic support is composed of carbon (C) claim 1 , AlOor TiO.5. The process as claimed in claim 1 , wherein the catalyst is a cobalt-amine complex supported on carbon with the formula Co-L/C claim 1 , wherein L is selected from L1 to L5 as claimed in claim 1 , the nitrogen ligand preferably being 1 claim 1 ,10-phenanthroline (L1) and its derivatives 2 claim 1 ,9-dimethyl-4 claim 1 ,7- ...

USE OF MALEIMIDE DERIVATIVES FOR PREVENTING AND TREATING CANCER

The present invention is related to a compound of formula (I) a pharmaceutically acceptable salt thereof, a hydrate thereof, a solvate thereof, a metabolite thereof or a prodrug thereof; for use in a method for the treatment and/or prevention of cancer, wherein X is selected from the group consisting of N—R, O and S; R1 is selected from the group consisting of alkyl, cycloalkyl, aryl, arylalkyl and hydrogen; Ris selected from the group consisting of indolyl, substituted indolyl, azaindolyl and substituted azaindolyl; and Ris selected from the group consisting of aryl, substituted aryl, unsubstituted heteroaryl, heterocyclyl and substituted heterocyclyl. 6. The compound of any one of to , wherein X is O.9. The compound of claim 8 , wherein each and any of the substituents is individually and independently selected from the group consisting of fluoro claim 8 , chloro claim 8 , methyl claim 8 , trifluoromethyl claim 8 , vinyl claim 8 , acetyl claim 8 , acetamido claim 8 , methoxy claim 8 , formyl claim 8 , ethoxycarbonyl and ydimethylamidocarbonyl.11. The compound of claim 8 , wherein Ris substituted phenyl and each and any of the substituents is individually any independently selected from the group consisting of alkyl claim 8 , substituted alkyl claim 8 , alkoxy claim 8 , substituted alkoxy claim 8 , alkynly and halogen.15. The compound of any of to claim 8 , preferably any one of to claim 8 , more preferably any one of to claim 8 , wherein each and any of indolyl claim 8 , substituted indolyl claim 8 , azaindolyl and substituted azaindolyl of Ris individually and independently either unprotected or protected at N claim 8 , preferably at N of the 5-membered ring.27. The compound of claim 26 , wherein each and any of the substituents is individually and independently selected from the group consisting of fluoro claim 26 , chloro claim 26 , methyl claim 26 , trifluoromethyl claim 26 , vinyl claim 26 , acetyl claim 26 , acetamido claim 26 , methoxy claim 26 , formyl ...

METHOD FOR PREPARATION OF FLUORO, CHLORO AND FLUOROCHLORO ALKYLATED COMPOUNDS BY HOMOGENEOUS CATALYSIS

The invention discloses a method for preparation of fluoro, chloro and fluorochloro alkylated compounds by homogeneous Pd catalyzed fluoro, chloro and fluorochloro alkylation with fluoro, chloro and fluorochloroalkyl halides in the presence of di(1-adamantyl)-n-butylphosphine and in the presence of 2,2,6,6-tetramethylpiperidine 1-oxyl. 1. A method for the preparation of a fluoro , chloro or fluorochloro alkylated compound by a reaction of a compound COMPSUBST with a compound FCLALKYLHALIDE by homogeneous catalysis using a catalyst CAT{'sub': '2', 'in the presence of BuPAdand'}in the presence of TEMPO andin the presence of a compound BAS,{'sub': 2', '3', '3', '3, 'BAS is selected from the group consisting of CsCO, CsHCO, NEt, and mixtures thereof;'} {'br': None, 'R3-X\u2003\u2003(III)'}, 'FCLALKYLHALIDE is a compound of formula (III);'}X is Cl, Br or I;{'sub': 1-20', '1-20, 'R3 is Calkyl or a Calkyl, wherein in the alkyl chain at least one of the hydrogens is substituted by F or Cl;'}{'sub': 2', '2, 'CAT is selected from the group consisting of Pd(OAc), Pd(TFA), and mixtures thereof;'} [{'sub': 1-10', '3-8', '1-4', '2', '3', '2', 'm', '2, 'the ethene and the cyclohexene being unsubstituted or substituted by 1, 2 or 3 substituents selected from the group consisting of Calkyl, Ccycloalkyl. Calkoxy, N(R10)R11, CN, NO, NO, F, Cl, Br, I, CF, (CH)-C(O)Y1, S(O)R50, CH═C(H)R28, C≡C-R24, benzyl, phenyl, naphthyl and morpholine;'}, {'sub': 1-10', '3-8', '1-4', '2', '3', '2', 'm', '2, 'the ethine being unsubstituted or substituted by 1 substituent selected from the group consisting of Calkyl, Ccycloalkyl, Calkoxy, N(R10)R11, CN, NO, NO, F, Cl, Br, I, CF, (CH)-C(O)Y1, S(O)R50, CH═C(H)R28, C≡C-R24 , benzyl, phenyl and naphthyl;'}], 'COMPSUBST is selected from the group consisting of a compound COMPSUBST-I, ethene, cyclohexene, ethine, and polystyrene;'}COMPSUBST-1 contains a ring RINGA; when RINGA is a heterocyclic ring, then RINGA has 1, 2 or 3 identical or different endocyclic ...

Use of Maleimide Derivatives for Preventing and Treating Cancer

The present invention is related to a compound of formula (I): 1102-. (canceled)104. The method of claim 103 , wherein the compound is 3-(4-acetylphenyl)-4-(2-methyl-1H-indol-3-yl)-1H-pyrrole-2 claim 103 ,5-dione.105. The method of claim 103 , further comprising administering a second therapeutic agent claim 103 , wherein the second therapeutic agent is a chemotherapeutic agent.106vinca. The method of claim 105 , wherein the chemotherapeutic agent is selected from the group consisting of cytarabine claim 105 , etoposide claim 105 , mitoxantron claim 105 , cyclophosphamide claim 105 , retinoic acid claim 105 , daunorubicin claim 105 , doxorubicin claim 105 , idarubicin claim 105 , azacytidine claim 105 , decitabine claim 105 , a tyrosine-kinase inhibitor claim 105 , a antineoplastic antibody claim 105 , alkaloids and steroids.107. The method of claim 106 , wherein the chemotherapeutic agent is a tyrosine kinase inhibitor claim 106 , wherein the tyrosine kinase inhibitor is selected from the group consisting of sorafenib claim 106 , dasatinib claim 106 , nilotinib claim 106 , nelarabine and fludarabine claim 106 , or wherein the chemotherapeutic agent is alemtuzumab.108. The method of claim 103 , wherein the compound has an antiproliferative effect on cells of the cancer. The present invention relates to a chemical compound of formula (I), its use in the treatment of a disease, a pharmaceutical composition comprising the compound, and a method for the treatment of a disease.Cancer is the second leading cause of death in many countries, exceeded only by heart disease. Despite recent advances in cancer diagnosis and treatment, surgery and radiotherapy may be curative if a cancer is found early, but current drug therapies for metastatic disease are mostly palliative and seldom offer a long-term cure. Even with new chemotherapies entering the market, the need continues for new drugs effective in monotherapy or in combination with existing agents as first line therapy, and ...

NITROGEN CONTAINING BIOPOLYMER-BASED CATALYSTS, A PROCESS FOR THEIR PREPARATION AND USES THEREOF

The present invention relates to a novel process for the preparation of a nitrogen containing biopolymer-based catalyst and to the novel nitrogen containing biopolymer-based catalysts obtainable by this process. In particular, the invention relates to a novel nitrogen containing biopolymer-based catalyst comprising metal particles and at least one nitrogen containing carbon layer. The invention also relates to the use of a nitrogen containing biopolymer-based catalyst in a hydrogenation process, preferably in a process for hydrogenation of nitroarenes, nitriles or imines; in a reductive dehalogenation process of C—X bonds, wherein X is Cl, Br or I, preferably in a process for dehalogenation of organohalides or in a process for deuterium labelling of arenes via dehalogenation of organohalides; or in an oxidation process. Further, the invention relates to a metal complex with the nitrogen containing biopolymer, wherein the metal is a transition metal selected from the group consisting of manganese, ruthenium, cobalt, rhodium, nickel, palladium and platinum, and wherein the nitrogen containing biopolymer is selected from chitosan, chitin and a polyamino acid. 1. A process for the preparation of a nitrogen containing biopolymer-based catalyst comprising the steps of:(a) mixing a metal precursor in the presence of a solvent with a nitrogen containing biopolymer to obtain a metal complex with the nitrogen containing biopolymer;(b) if appropriate drying the metal complex with the nitrogen containing biopolymer; and(c) pyrolysing the metal complex with the nitrogen containing biopolymer at temperatures ranging from 500° C. to 900° C. in an inert gas atmosphere to obtain a nitrogen containing biopolymer-based catalyst.2. The process of claim 1 , wherein the metal precursor contains a transition metal.3. The process of claim 1 , wherein the metal precursor contains a transition metal selected from the group consisting of manganese claim 1 , iron claim 1 , ruthenium claim 1 , ...

Carbene-diene complexes of nickel, palladium and platinum

Verwendung von Carben-Dien-Komplexen von Nickel, Palladium und Platin der allgemeinen Formel I, worin bedeutet M Nickel, Palladium oder Platin, L ein monodentater Carbenligand der Formel II oder III A und C unabhängig voneinander Sauerstoff, Schwefel, eine CH 2 -Gruppe, eine C(R 15 ) a (R 16 ) b -Gruppe, eine N(R 17 ) c -Gruppe oder eine Si(R 18 ) d (R 19 ) e -Gruppe, wobei a, b, c, d, e unabhängig voneinander 0 oder 1 und für den Fall, daß a, b, c, d, e mindestens eines der beteiligten Reste 0 ist, A, B und C auch Teile eines Ringsystems sein können, B Sauerstoff, Schwefel, eine N(R 17 ) c -Gruppe oder eine Si(R 18 ) d (R 19 ) e -Gruppe, wobei c, d und e wie vorstehend definiert sind, x und z 0 oder 1, y = 1 und x + y + z = 1 bis 3, R 1 bis R 19 Wasserstoff, einen Alkyl-, einen Aryl-, einen Alkenylrest, O-Alkyl, O-C(O)-Alkyl, O-(Aryl), O-C(O)-Aryl, F, Cl, OH, NO 2 , Si(Alkyl) 3 , CF 3 , CN, CO 2 H, C(O)H, SO 3 H, NH 2 , NH(Alkyl),... Use of carbene-diene complexes of nickel, palladium and platinum of the general formula I, where is meant M nickel, palladium or platinum, L is a monodentate carbene ligand of formula II or III A and C are independently oxygen, sulfur, CH 2 , C (R 15 ) a (R 16 ) b , N (R 17 ) c or Si (R 18 ) d (R 19 ) e - group, where a, b, c, d, e are independently 0 or 1 and in the event that a, b, c, d, e at least one of the radicals 0, A, B and C are also parts of a ring system, B is oxygen, sulfur, an N (R 17 ) c group or a Si (R 18 ) d (R 19 ) e group, where c, d and e are as defined above, x and z are 0 or 1, y = 1 and x + y + z = 1 to 3, R 1 to R 19 are hydrogen, an alkyl, an aryl, an alkenyl, O-alkyl, OC (O) -alkyl, O- (aryl), OC (O) -aryl, F, Cl, OH, NO 2 , Si (alkyl) 3 , CF 3 , CN, CO 2 H, C (O) H, SO 3 H, NH 2 , NH (alkyl), ...

New nickel, palladium and platinum complexes, used in homogeneous catalysis of organic reactions, have ligand with electron-depleted olefinic bond and monodentate carbene ligand of 1,3-di-substituted imidazol(in)-ylidene type

New transition metal complexes (I) of nickel, palladium and platinum have a ligand with electron-depleted olefinic double bond(s) and a monodentate carbene ligand comprising a 1,3-di-substituted imidazol(in)-ylidene compound with (cyclo)alkyl) and/or (hetero)aryl substituents. New transition metal complexes (I) of nickel, palladium and platinum are of the formula: M = Ni, Pd or Pt; L1 = a ligand with electron-depleted olefinic double bond(s); L2 = a monodentate carbene ligand of 1,3-di-substituted imidazol(in)-ylidene type. The full definitions are given in the DEFINITIONS (Full Definitions) Field. Independent claims are also included for the following: (1) bridged transition metal complexes of formula (Ia) or (Ib), where the bridging group L1 is selected so that it has another co-ordination position for a Ni, Pt or Ni atom: (2) preparation of (I).

Process for preparing polymers by means of ring-opening polymerization

The present invention relates to a process for preparing polymers by means of ring-opening metathetic polymerization, consisting of the following steps: a) providing a reaction mixture consisting of a cycloalkene or a cycloalkene mixture, b) adding a ruthenium compound of the general formula RuX 1 X 2 L 1 a L 2 b (I) where a=0 or 1, b=1 or 2, such that a+b=2; X 1 , X 2 =independently selected anionic ligands; L 1 =uncharged π-binding ligand; L 2 =N-heterocyclic carbene of the formula IIa, IIb or IIc; c) adding a chain transfer agent in a molar ratio in the range from 1:5 to 1:1000 based on the cycloalkene or the sum total of the cycloalkenes in the cycloalkene mixture, d) converting at a temperature within a range from 0° C. to 250° C.

Process for the production of aromatic olefins under the catalysis of palladacycles

Novel nickel-,palladium-and platinum-carbene complexes,their preparation and use in catalytic reactions

The invention relates to novel monocarbene complexes of nickel, palladium or platinum with electron-deficient olefin ligands, to their preparation and to their use in the homogeneous catalysis of organic reactions. In particular, the invention discloses transition metal complexes of the formula (I), (Ia) and (Ib): L1-M-L2 (I) L2-M-L1-M-L2 (Ia) (see formula Ib)

Chiral manganese-triazanonane complexes and process for their preparation

Chiral manganese-triazanonane complexes and process for their preparation

Chiral manganese-triazanonane complexes of formula ÄMnu(L)v(OR)w( mu O)x( mu OAc)yÜX2 (I) are new. u, v = 1 or 2; w, x, y = 0-3; z = 1-3 with the proviso that a) when u = 1, then v = 1, w = 1, 2 or 3 and z = 1, 2 or 3; b) when u = 2, then (i) v = 2, w = 0 or 1, x = 1, y = 2 and z = 1 or 2; (ii) v =2, w = 0 or 1, x = 1, y = 2 and z = 2 or 3; or (iii) v = 2, w = 0 or 1, x = 3, y = 0 and z = 1 or 2; R = 1-12C alkyl; X = PF6<->, F<->, Cl<->, Br<->, I<->, (C6H5)B<-> or ClO4<->; L = a chiral triazanonane ligand of formula (II); R1-R12 = H, R, 3-12C cycloalkyl, 1-12C (sic) alkenyl, OR, 1-12C acyloxy, Ar, heteroaryl, CH2Ar, COOH, COOR, COOAr, CN, halo, trihalomethyl, NH2, NHR, N(R)2, NHAr, NAr2, N-alkylaryl, SR, SOR, SO2R or P(R)2; R = independently 1-12C alkyl; Ar = aryl; R13-R15 = H, R, CH2Ar, Ar or heteroaryl.

METHOD FOR HYDROFORMILATION OF UNSATURATED COMPOUNDS

La presente se refiere a un método para la hidroformilación de compuestos insaturados tales como olefinas y alquinos con mezclas de gas de síntesis (CO/H2), en donde o bien los compuestos insaturados y un catalizador son calentados a una temperatura de reacción de 60 a 200ºC y luego se agrega el gas de síntesis, o los compuestos insaturados y el catalizador se ponen en contacto en un paso de preformado con CO puro a temperatura normal, luego se calientan a temperatura de reacción y al alcanzar la temperatura de reacción el CO es reemplazado por el gas de síntesis. La presión es de 1 a 200 bar, la relación CO:H2 en el gas de síntesis se encuentra en el rango de de 1:1 a 50:1. El catalizador de iridio utilizado comprende un ligando que contiene fósforo con la relación iridio:ligando en el rango de 1:1, a 1:100. Con altas actividades de catalizador y reducida cantidad de catalizador se obtienen frecuencias de conversión muy altas. This refers to a method for the hydroformylation of unsaturated compounds such as olefins and alkynes with mixtures of synthesis gas (CO / H2), wherein either the unsaturated compounds and a catalyst are heated at a reaction temperature of 60 to 200 ° C and then the synthesis gas is added, or the unsaturated compounds and the catalyst are contacted in a preformed step with pure CO at normal temperature, then heated to reaction temperature and upon reaching the reaction temperature the CO is replaced by synthesis gas. The pressure is 1 to 200 bar, the CO: H2 ratio in the synthesis gas is in the range of 1: 1 to 50: 1. The iridium catalyst used comprises a phosphorus-containing ligand with the ratio iridium: ligand in the range of 1: 1, to 1: 100. With high catalyst activities and reduced amount of catalyst very high conversion frequencies are obtained.

Production of higher alpha-olefins, useful for copolymer production, includes telomerizing a conjugated diene with a nucleophile in the presence of a palladium carbene complex catalyst

Production of alpha -olefins with 8-16 carbon atoms by telomerizing a conjugated diene with a nucleophile in the presence of a palladium catalyst, hydrogenating the telomer and cleaving the product, comprises using a carbene complex catalyst as the palladium catalyst. An Independent claim is also included for polyolefins produced by copolymerizing olefins with alpha -olefins produced as above.

Base-catalyzed synthesis of 1-aryl-4-(aryl ethyl)piperazines from aromatic olefins and 1-aryl piperazines

The invention relates to a method for producing a 1-aryl-4-(aryl ethyl)piperazine of formula (I) by reacting a 1-aryl piperazine of formula (II) with an aromatic olefin of formula (III) Ar'CR1=CHR2 in an inert solvent and in the presence of at least one basic catalyst, whereby in formulas (I) to (III); Ar and Ar', independent of one another, represent an aryl radical selected from the group of the condensed and non-condensed C¿6?-C22-aromatic compounds and of the condensed or non-condensed C5-C22-heteroatoms which contain at least one nitrogen, oxygen or sulfur atom in the ring; R1 and R2, independent of one another, represent a hydrogen atom, a C1-C8-alkyl radical or an aryl radical Ar.

New carbene-diene transition metal complex, useful as catalyst in organic reactions, e.g. olefination, contains monodentate imidazoline-type carbene ligand

Carbene-diene complexes (I) of nickel, palladium or platinum are new. Carbene-diene complexes of formula (I) are new. M = nickel, palladium or platinum; L = monodentate carbene ligand of formulae (II) or (III) A, B, C = oxygen, sulfur, CH2, C(R<15>)a(R<16>)b, N(R<17>)c, or Si(R<18>)d(R<19>)e; a'' = lone pair of electrons; a-e = 0 or 1 and when at least one is 0, A, B and C may be part of a ring system; x, y, z = 0-1, or a sum of 1-3; R<1>-R<19> = hydrogen, alkyl, aryl, alkenyl, alkoxy, alkylycarbonyloxy, aryloxy, arylcarbonyloxy, fluoro, chloro, hydroxy, nitro, trialkylsilyl, trifluoromethyl, cyano, carboxy, formyl, sulfonic acid, amino (optionally substituted by 1 or 2 alkyl), dialkylphosphinyl, alkyl- or aryl-sulfinyl or -sulfonyl, alkyloxy- or aryloxy-sulfonyl, alkyl-, aryl or alkenyl-thio, alkylcarbonylamino, alkoxycaronyloxy, carbonylamino, alkylcarbonyl, formylamino, alkoxycarbonylamino, arylcarbonyl, aryloxycarbonyl, 2-(alkoxycarbonyl or carboxy)-vinyl, diarylphosphinyl, diaryl- or dialkyl-phosphinyl oxide, phosphonic acid (or its dialkyl ester), or groups of a condensed ring system; all alkyl and alkenyl have 1-10C, optionally branched and/or substituted with chloro, fluoro, alkyl, alkoxy, phenyl, phenoxy, hydroxy, amino or trifluoromethyl; and aryl is 5-10 membered (hetero)aromatic groups, optionally substituted by chloro, fluoro, alkyl, alkoxy, phenyl or phenoxy. An Independent claim is also included for a method for preparing (I).

Method for the production of polymers by means of ring-opening polymerisation

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Polymeren mittels ringöffnender, metathetischer Polymerisation bestehend aus den folgenden Schritten: a) Bereitstellung einer Reaktionsmischung bestehend aus einem Cycloalken oder einem Cycloalkengemisch, b) Zugabe einer Ruthenium-Verbindung der allgemeinen Formel RuX 1 X 2 L 1 a L 2 b (I), wobei a = 0 oder 1, b = 1 oder 2, so dass gilt a + b = 2; X 1 , X 2 - unabhängig voneinander ausgewählte anionische Liganden; L 1 = neutraler À-bindender Ligand; L 2 = N-heterocyclisches Carben der Formel IIa, IIb oder IIc; c) Zugabe eines Reglers in einem Mol-Verhältnis im Bereich von 1:5 bis 1:1.000 bezogen auf das Cycloalken oder die Summe der Cycloalkene im Cycloalkengemisch, d) Umsetzung bei einer Temperatur in einem Bereich von 0°C bis 250°C. The present invention relates to a process for the preparation of polymers by means of ring-opening, metathetic polymerization consisting of the following steps: a) providing a reaction mixture consisting of a cycloalkene or a cycloalkene mixture, b) adding a ruthenium compound of the general formula RuX 1 X 2 L 1 a L 2 b (I), where a = 0 or 1, b = 1 or 2, so that a + b = 2; X 1, X 2 - independently selected anionic ligands; L 1 = neutral À-binding ligand; L 2 = N-heterocyclic carbene of formula IIa, IIb or IIc; c) addition of a regulator in a molar ratio in the range of 1: 5 to 1: 1000 based on the cycloalkene or the sum of the cycloalkenes in the cycloalkene mixture, d) reaction at a temperature in a range from 0 ° C to 250 ° C.

Neue nickel-, palladium- und platin-carbenkomplexe, ihre herstellung und verwendung in katalytischen reaktionen

Metal complexes containing heterocyclic carbene as catalysts for C-C couplings

Catalyst for reactions that form carbon to carbon bridging bonds, contains a complex of formula (I) : ÄLaMbXcÜn<+)<A)n (I); where A = monovalent anion or polyvalent anion chemical equivalent; L = 5-7-membered monocarbene ring containing at least one N atom next to a carbene C atom, or a dicarbene in which two of these monocarbene rings are connected via a bridging bond, with the exception of compounds containing an imidazole or pyrazole system as a carbene ring; M = Pd, Rh, Ni, Ru or Co; X = mono- or polyvalent, optionally charged ligand; a = 1-5 x b; b = 1-3; c = 0-4 x b; and n = 0-6, with the provision that (c + n) is greater than 0. Also claimed are (i) the use of these catalysts for the above reactions, and (ii) the preparation of compounds containing carbon to carbon bridging bonds via the above reactions.

Substituierte isophosphindoline und ihre verwendung

A PROCEDURE FOR THE TELOMERIZATION OF ACICLIC OLEFINS.

Un procedimiento para la telomerización de olefinas acíclicas que tienen como mínimo dos dobles enlaces conjugados (I) o mezclas que contengan tales olefinas, con nucleófilos (II) usando como catalizador un complejo de carbeno - paladio. A process for the telomerization of acyclic olefins having at least two conjugated double bonds (I) or mixtures containing such olefins, with nucleophiles (II) using as a catalyst a carbine-palladium complex.

Preparation of 1,2-diols, used e.g. as a solvent or intermediate for polymers, agrochemicals, cosmetics and pharmaceuticals, by hydroxylation of an olefin in the presence of oxygen and an osmium, ruthenium or manganese compound

Preparation of mono-, bi and/or polyfunctional 1,2-diols (I), by transition metal-catalyzed asymmetric dihydroxylation of olefins, involves reacting an olefin (II) with molecular oxygen in the presence of an osmium, ruthenium or manganese compound in water (or a water-containing solvent) at pH 7.5-13. Preparation of mono-, bi and/or polyfunctional 1,2-diols of formula (I), by transition metal-catalyzed asymmetric dihydroxylation of olefins, involves reacting an olefin (II) with molecular oxygen in the presence of an osmium, ruthenium or manganese compound in water (or a water-containing solvent) at pH 7.5-13. R1 - R4 = H, A, CN, COOH, COOA, COOAr, COA, COAr, OA, OAr, OCOAr, OCOA, OCOOA, N(A)2, NHA, N(Ar)-2, NO, NO2, NOH, Ar, halo, Si(A)3, CHO, SO3H, SO3A, SO2A, SOA, CF3, NHCOA, CONH2, CONHA, NHCHO, NHCOOA, CHCHCOO, CHCHCOOH, P(O)(Ar)2, P(O)(A)2, PO3H2 or P(O)(OA)2; A = linear, branched and/or cyclic hydrocarbyl (optionally substituted by 1-6 Q); Ar = 5-7 membered, optionally fused aromatic ring containing 4-14C and 0-3 heteroatoms (e.g. N, O or S), optionally substituted by 1-6 Q; Q = A, OA, OCOA, OAr, Ar, halo, OH, NO2, NO, Si(A)3, CN, COOH, CHO, SO3H, NH2, NHA, N(A)2, P(O)(A)2, SO2A, SOA, CF3, NHCOA, COOA, CONH2, COA, NHCHO, NHCOOA, COAr, COOAr, P(O)(Ar)2, PO3H2, P(O)(OA)2 or SO3A.

Method for the dihydroxylation of olefins using transition metal catalysts

This invention relates to process for dihydroxylation of olefins using transition metal catalysts to obtain monofunctional, bifunctional, and/or polyfunctional 1,2-diols of the formula (I) R 1 R 2 C(OH)—C(OH)R 3 R 4   (I) where R 1 to R 4 are defined herein, by reacting an olefin of the formula (II) R 1 R 2 C═CR 3 R 4   (II) where R 1 to R 4 are defined as for formula (I), with molecular oxygen in the presence of an osmium, ruthenium, or manganese compound in water or a water-containing solvent mixture at a pH of from 7.5 to 13.

Chiral manganese triazononane complexes

The chiral manganese-triazonone complex of the general formula (I) is disclosed: Mn.sub.u (L).sub.V (OR).sub.W (μ-O).sub.X (μOAc).sub.y !X.sub.z(I) The complex is useful industrially to prepare chiral compounds.

Method for producing 1-olefins using palladium carbene compounds

Method for producing higher linear fatty acids or esters

The present invention relates to a method of producing linear fatty acids comprising 7 to 28 carbon atoms or esters thereof using a combined biotechnological and chemical method. In particular, the present invention relates to a method of producing dodecanoic acid (i.e. lauric acid), via higher alkanones, preferably 6-undecanone.

Palladacycles and a process for their preparation

Process for the preparation of biphenyls with palladacycles as catalysts

Use of maleimide derivatives for preventing and treating cancer

The present invention is related to a compound of formula (I) a pharmaceutically acceptable salt thereof, a hydrate thereof, a solvate thereof, a metabolite thereof or a prodrug thereof; for use in a method for the treatment and/or prevention of cancer, wherein X is selected from the group consisting of N—R 1 , O and S; R1 is selected from the group consisting of alkyl, cycloalkyl, aryl, arylalkyl and hydrogen; R 2 is selected from the group consisting of indolyl, substituted indolyl, azaindolyl and substituted azaindolyl; and R 3 is selected from the group consisting of aryl, substituted aryl, unsubstituted heteroaryl, heterocyclyl and substituted heterocyclyl.

A process for the homogeneous-catalyzed, highly selective direct amination of primary alcohols with ammonia to primary amines at high volume ratio of liquid to gas phase and / or high pressures

Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von primären Aminen umfassend die Verfahrensschritte A) Bereitstellung einer Lösung eines primären Alkohols in einer fluiden, nicht gasförmigen Phase, B) in Kontakt Bringen der Phase mit freiem Ammoniak und/oder mindestens einer Ammoniak freisetzenden Verbindung und einem homogenen Katalysator und gegebenenfalls C) Isolierung des in Verfahrensschritt B) gebildeten primären Amins, dadurch gekennzeichnet, dass das Volumenverhältnis des Volumens der Flüssigphase zu dem Volumen der Gasphase im Verfahrensschritt B größer 0,05 ist und/oder dass Verfahrensschritt B bei Drücken größer als 10 bar durchgeführt wird. The present invention relates to a process for the preparation of primary amines comprising the process steps A) providing a solution of a primary alcohol in a fluid, non-gaseous phase, B) bringing the phase into contact with free ammonia and / or at least one ammonia-releasing compound and a homogeneous catalyst and optionally C) isolation of the primary amine formed in process step B), characterized in that the volume ratio of the volume of the liquid phase to the volume of the gas phase in process step B is greater than 0.05 and / or that process step B at pressures greater than 10 bar is carried out.

Process for the direct amination of alcohols by means of ammonia to primary amines using a xantphos catalyst system

The present invention relates to a chemocatalytic liquid-phase process for the direct single-stage amination of alcohols to primary amines using ammonia in high yields by means of a catalyst system containing at least one transition metal compound and a xantphos ligand.

cis-4- (2,2,3,3-tetrafluoropropoxy) -cinnamonitrile and trans-4- (2,2,3,3-tetrafluoropropoxy) -cinnamonitrile and a process for their preparation

Process for producing (4-halogeno-2,6-dialkylphenyl)malononitriles

The invention relates to a process for producing (4-halogeno-2,6-dialkylphenyl)malononitriles of formula (I) by reaction of bromoaromatics of formula (II) with malononitrile in the presence of a base, a palladium compound and a phosphine ligand, wherein in a first process step initially only malononitrile and the base are reacted with one another and subsequently in a second process step any water of reaction formed is distilled off together with a portion of the solvent and diluent before in the third process step the bromoaromatic of formula (II), the palladium catalyst and the phosphine ligand are added. The invention further relates to novel (4-halogeno-2,6-dialkylphenyl)malononitriles of formula (I) and to a novel palladium complex of formula (III) and to the use thereof as catalyst.

Method of preparation of biphenyls using palladacyclen as catalyst