A HYDROGENATION CATALYST DERIVED FROM COMPLEX COMPOUNDS OF PLATINUM GROUP METALS AND A METHOD OF PREPARING SAME

... 1,262,885. Organometallic compounds; Group VIII metal complexes. INSTITUTA KHIMICHESKOI FIZIKI AN SSSR. 15 Jan., 1969, No. 2410/69. Headings C2C and C2J. [Also in Division C5] A noble metal-containing organo-compound is prepared by a process which comprises forming a complex having a "semi-sandwich" structure by reacting, in the absence of aluminium halide, a salt of a metal selected from ruthenium, rhodium, palladium, osmium, iridium and platinum with a ligand selected from aromatic hydrocarbons, alkyl-substituted quinones, aromatic carboxylic acids, aromatic amino acids, peptides containing aromatic amino acids and compounds exhibiting benzenoid-quinonoid tautomerism, and thereafter reducing the complex, for example by ethanol in solution wherein the complex is formed or by the use of a reducing agent selected from hydrogen, sodium borohydride and dihydropyridine compounds. Exemplified ligands are 1,3,5-triphenylbenzene, duroquinone, phenylacetic acid, N-phenylanthranilic acid, phenylalanine ...

RECOVERY OF RHODIUM FROM CARBONYLATION RESIDUES

Novel metallocene-based phosphorus chiral phosphines

ORGANOMETALLIC COMPLEXES AND CHEMICAL PROCESS USING SAME

... 1,217,417. Organometallic complexes. NATIONAL DISTILLERS & CHEMICAL CORP. 5 July, 1968 [14 July, 1967; 17 July, 1967], No. 32314/68. Headings C2C and C2J. [Also in Division C5E] The invention comprises organometallic complexes of the formula where n is zero or an integer from 1 to 4; each R is selected from lower alkyl (C 1 -C 4 ) group, aryl group having from 6 to 16 carbon atoms, hydroxy group, nitro group, halide, dialkyl. amino, diarylamino and alkarylamino groups having 2 to 12 carbon atoms, or alkoxy or aryloxy group having 1 to 6 carbon atoms; M is Ru, Pt, Os, Pd, Ir, or Rh; Y is chloride bromide, nitrate, acetate, thiocyanate or cyanide group; A is -CR1 =N- (where R1 is hydrogen or an alkyl or aryl group having 1 to 10 carbon atoms), and Z is an alkyl group having 1 to 10 carbon atoms, aryl group or alkaryl, an alkoxy or aryloxy group having 1 to 10 carbon atoms, a hydroxy group, or an alkylamino, dialkylamino, arylamino or diarylamino group having 1 to 12 carbon ...

PROCEDURE FOR THE CLEANING AND RUECKGEWINNUNG WITH OF THE CARBONYLIERUNG POLLUTED ONE BY METHYL ACETATE AND/OR DIMETHYLETHER RESULTING, KATALYSATORLOESUNG.

PROCEDURE FOR THE RECUPERATION OF HOMOGENEOUS METAL HYDRIDE CATALYSTS

Process for recovering homogeneous metal hydrate catalysts

LIGANDS FOR USE IN CATALYTIC PROCESSES

PROCESS FOR THE PRODUCTION OF ASYMMETRIC TRANSFORMATION CATALYSTS

The present invention relates to process for the production of chiral ligands comprising providing a starting material of Formula (A): wherein X* is a chiral or achiral directing group; and (i) is an optionally substituted mono- or polycyclic aryl or cycloalkyl group; ortholithiating the substrate; converting the ortho-lithiated substrate to a phosphine group having the formula -PR1 R1", R1 being selected from substituted and unsubstituted, branched- and straight-chain alkyl, substituted and unsubstituted cycloalkyl, substituted and unsubstituted carbocyclic aryl, and substituted and unsubstituted heteroaryl wherein the or each heteroatom is independently selected from sulphur, nitrogen, and oxygen, R1" being different from R1 and being selected from substituted and unsubstituted, branched- and straight- chain alkyl, substituted and unsubstituted cycloalkyl, substituted and unsubstituted carbocyclic aryl, and substituted and unsubstituted heteroaryl wherein the or each heteroatom is independently ...

MICROENCAPSULATED CATALYST, METHODS OF PREPARATION AND METHODS OF USE THEREOF

A microencapsulated catalyst is prepared by dissolving or dispersing a catalyst in a first phase (for example an organic phase), dispersing the first phase in a second, continuous phase (for example an aqueous phase) to form an emulsion, reacting one or more microcapsule wall-forming materials at the interface between the dispersed first phase and the continuous second phase to form a microcapsule polymer shell encapsulating the dispersed first phase core and optionally recovering the microcapsules from the continuous phase. The catalyst is preferably a transition metal catalyst and the encapsulated catalyst may be used for conventional catalysed reactions. The encapsulated catalyst may recovered from the reaction medium and re-cycled.

CATALYST RECOVERY PROCESS

PROCESS FOR REMOVING METALLIC CORROSION PRODUCTS FROM A CONTAMINATED CATALYST SOLUTION PRODUCED ON CARBONYLATION OF METHANOL AND/OR METHYL ACETATE AND/OR DIMETHYL ETHER

Verfahren zur Herstellung organischer Isocyanate

Verfahren zur kontinuierlichen Herstellung von gesättigten, höheren Carbonylverbindungen

Procedure for the production of Malondialdehyd derivatives.

УЛУЧШЕННЫЙ СПОСОБ КАРБОНИЛИРОВАНИЯ

Описывается способ увеличения значения TON системы катализатора монокарбонилирования этиленненасыщенных соединений при использовании монооксида углерода в присутствии сореагента, отличного от воды или ее источника и содержащего подвижный атом водорода. Система катализатора может быть получена в результате объединения: (а) металла из групп (8), (9) или (10) или его подходящего для использования соединения; (b) лиганда, описывающегося общей формулой (I), где группы X3 и X4 независимо представляют собой одновалентные радикалы, содержащие до 30 атомов, или X3 и X4 совместно образуют двухвалентный радикал, содержащий до 40 атомов, а X5 содержит до 400 атомов; Q1 представляет собой атом фосфора, мышьяка или сурьмы; и с) необязательно источника анионов. Способ включает стадию добавления к системе катализатора воды или ее источника. Способ предпочтительно реализуют в присутствии электроположительного металла.

PRODUCTION OF AROMATIC ISOCYANATES

PROCESS OF WASTE TREATMENT Of a REACTION OF CARBONYLATION, IN ORDER TO EXTRACT some FROM NOBLE METAL

A METHOD FOR REMOVING the TAR OF MIXTURES SELECTIVELY COMING From a CATALYTIC REACTION OF CARBONYLATION

AMIDINE-CARBOXYLIC ACID COMPLEX, BRIDGED POLYNUCLEAR COMPLEX DERIVED THEREFROM, PRODUCTION METHODS THEREFOR, AND USE FOR PREPARING SUPPORTED METAL OR METAL OXIDE CLUSTERS

An amidine-carboxylic acid complex in accordance with an aspect of the invention has an amidine ligand and a carboxylic acid ligand that are coordinated to one metal atom or a plurality of metal atoms of the same element. A multiple-complex-containing compound, i.e. a bridged polynuclear complex, in accordance with the aspect of the invention is formally derived from two or more such amidine-carboxylic acid complexes, linked by a polyvalent carboxylic acid ligand. The bridged polynuclear complex may be used in a production method to support metal (oxide) clusters on a porous support by impregnating these with a solution thereof, followed by drying and firing.

RECLAMATION OF METAL CATALYSTS USED IN THE PRODUCTION OF DIARYL CARBONATES

L'invention concerne un procédé de régénération efficace d'espèces de catalyseurs métalliques provenant de flux d'extraits aqueux de synthèse de carbonates de diaryle. Ledit procédé consiste à traiter un flux d'extrait aqueux contenant du métal provenant d'un mélange issu de la production de carbonates de diaryle avec un agent de précipitation qui peut précipiter de manière sélective une ou plusieurs espèces de catalyseurs métalliques de l'extrait. L'utilisation de ces procédés permet de diminuer nettement les problèmes d'ordre financier et écologique liés à la préparation des carbonates de diaryle.

Synthesis of aliphatic 1, 3-diols utilizing reduced ligand concentration and water extraction

This invention is a process for synthesizing aliphatic 1,3-diols in one step by hydroformylation and hydrogenation of oxirane, carbon monoxide, and hydrogen employing a catalyst comprising a cobalt carbonyl compound and a cocatalyst metal compound ligated with a ligand in a ligand to cocatalyst metal atom molar ratio in the range of 0.2:1.0 to 0.6:1.0, optionally in the presence of a promoter, where recovery of product is preferably accomplished via water extraction of a diol rich phase from the bulk reaction mixture. The process modifications can, particularly in combination, be beneficial with respect to product recovery, catalyst recycle, and overall economics of a one-step process for producing aliphatic 1,3-diols.

Process for preparation of ethanol

Ethanol is prepared with high selectivity from methanol, carbon monoxide and hydrogen by using cobalt phosphate as main catalyst in combination with a platinum group element as co-catalyst or without using such co-catalyst, and further with or without a phosphorus compound. Recovery of the catalyst can be carried out easily.

Heteroaromatic diphosphines as chiral ligands

Chiral diphosphines constituted by an aromatic pentatomic biheterocyclic system, suitable to act as chiral ligands, complexes between said diphosophines and transition metals, and their utilization as chiral catalysts in sterocontrolled reactions, such as diastereo- and enantioselective reduction reactions. Process for the preparation of said chiral diphosophines and process for the preparation of said complexes and for their utilization as chiral catalysts in sterocontrolled reactions.

Verfahren zur Herstellung von Aldehylen und Ketonen

VERFAHREN ZUR REINIGUNG UND RUECKGEWINNUNG DER BEI DER CARBONYLIERUNG VON METHYLACETAT UND/ODER DIMETHYLETHER ANFALLENDEN, VERUNREINIGTEN KATALYSATORLOESUNG

YMMETRISCHE UMWANDLUNGEN

PROCESS FOR PREPARATIONS OF ETHANOL

Process for preparation of Ethanol.

Ethanol is prepared with high selectivity from methanol, carbon monoxide and hydrogen by using cobalt phosphate as main catalyst in combination with a platinum group element as co-catalyst or without using such co-catalyst, and further with or without a phosphorus compound. Recovery of the catalyst can be carried out easily.

PROCEDURE FOR THE PRODUCTION OF CATALYSTS FOR ASYMMETRICAL TRANSFORMATIONS

PROCEDURE FOR THE CLEANING AND RECUPERATION OF WITH OF THE CARBONYLIERUNG POLLUTED ONE BY METHYL ACETATE AND/OR DIMETHYLETHER RESULTING, KATALYSATORLOESUNG.

PROCEDURE FOR RECUPERATION OF EDELMETAL.

Synthesis of aliphatic 1,3-diols utilizing reduced ligand concentration and water extraction

REGENERATING NOBEL METAL CARBONYL COMPLEXE CATALYSTS

PROCESS FOR PURIFYING AND RECOVERING CONTAMINATED CATALYST SOLUTION OBTAINED IN THE CARBONYLATION OF METHYL ACETATE AND/OR DIMETHYLETHER

PROCESS FOR PURIFYING AND RECOVERING CONTAMINATED CATALYST SOLUTION OBTAINED IN THE CARBONYLATION OF METHYL ACETATE AND/OR DIMETHYLETHER The disclosure relates to a process for purifying and recovering a contaminated catalyst solution which is obtained in the carbonylation of methyl acetate and/or dimethylether, the catalyst solution containing carbonyl complexes of noble metals of group VIII of the Periodic System of the elements, quaternary heterocyclic aromatic nitrogen compounds or quaternary organophosphorus compounds as organic promoters, and optionally compounds of carbonylyielding common metals as inorganic promoters, undistillable organic contaminants as well as acetic acid, acetic anhydride and ethylidene diacetate. To this end, the disclosure provides for the catalyst solution to be distillatively freed from its volatile constituents and for the remaining solid distillation residue to be freed from the organic contaminants by extraction with aliphatic ethers; and for the remaining ...

PROCESS FOR PURIFYING AND RECOVERING CONTAMINATED CATALYST SOLUTION OBTAINED IN THE CARBONYLATION OF METHYL ACETATE AND/OR DIMETHYLETHER

PROCESS FOR PURIFYING AND RECOVERING CONTAMINATED CATALYST SOLUTION OBTAINED IN THE CARBONYLATION OF METHYL ACETATE AND/OR DIMETHYLETHER

ELECTRONICALLY TUNED LIGANDS

A phosphino- or arsenoamidine of Formula (1) M is Phosphorus or Arsenic (P, As); X, Y, and Z can be independently selected from hydrogen, alkyl, aryl (pendant or fused), halogen, alkoxy (C1-C10), cyano, nitro, amino, alkylamino, dialkylamino, -CO2H, -CO(lower alkoxy), -CO(lower alkyl), -NCOH, -NCO(lower alkyl), NSO2(alkyl), - NSO2(aryl), hydroxy, alkyl, sulfonoxyalkyl, sulfonoxyaryl, or alkoxyalkyl; R1 is hydrogen, C1-C10 alkyl, branched alkyl or cycloalkyl; aryl, substituted aryl, heteroaryl or substituted heteroaryl where the heteroatoms may include atoms of nitrogen, oxygen, or sulfur, may be acyl, aroyl, substituted aroyl, heteroaroyl, or substituted heteroaroyl, or SO2R4 where R4 is chosen from the group alkyl, aryl, heteroaryl, substituted aryl or substituted heteroaryl groups in direct attachment, with the provisos that R2 and R3 can be the same or different and are hydrogen, aryl or heteroaryl as defined above, substituted aryl or heteroaryl as defined (with substituents as defined ...

RECOVERY OF PRECIOUS METALS FROM CATALYST RESIDUE

T 1790 RECOVERY OF PRECIOUS METAL FROM CATALYST RESIDUE The invention relates to a process for recovering a precious metal, particularly palladium, from a non-aqueous effluent comprising the metal and dissolved salt and/or polyether contaminants, wherein the effluent is contacted with a reduction agent, the precious metal is deposited onto a carrier, preferably comprising a combustible carbonaceous material, and the metal loaded carrier is separated from the effluent. VM6/T1790FF ...

СПОСОБ ИЗВЛЕЧЕНИЯ ГОМОГЕННЫХ МЕТАЛЛГИДРИДНЫХ КАТАЛИЗАТОРОВ

... 1. Способ извлечения гомогенного металлгидридного катализатора на основе благородного металла VIII группы из потока реактора в форме, подходящей для его рециркуляции в реактор, включающий стадии (a) извлечения из реактора потока, включающего гомогенный металлгидридный катализатор на основе благородного металла VIII группы; (b) контактирования потока с твердым кислым абсорбентом при условиях процесса, которые дают возможность по меньшей мере части металла стать связанной с абсорбентом; (c) подвержения металла, связанного с абсорбентом, воздействию текучей десорбирующей среды, содержащей водород и растворитель, при условиях процесса, обеспечивающих возможность десорбции металла; и (d) извлечения активного металлгидридного катализатора на основе благородного металла VIII группы. 2. Способ по п.1, где текучая десорбирующая среда представляет собой единую жидкую фазу. 3. Способ по п.2, где единая жидкая фаза представляет собой сверхкритическую фазу. 4. Способ по п.1, где текучая десорбирующая ...

PROCESS OF RECOVERY, USING AN AMINE, RHODIUM OF RESIDUES OF CARBONYLATION

PRODUCTION OF AROMATIC ISOCYANATES

PROCESS OF NOBLE METAL RECOVERY CONTAINED IN RESIDUES OF CARBONYLATION

PROCEDE DE RECUPERATION DE METAUX NOBLES A PARTIR DE RESIDUS D'UNE REACTION CATALYTIQUE DE CARBONYLATION

PROCEDE DE RECUPERATION DE METAUX NOBLES A PARTIR DE RESIDUS D'UNE REACTION CATALYTIQUE DE CARBONYLATION. ON TRAITE LES RESIDUS LOURDS, PRODUITS PAR DES REACTIONS DE CARBONYLATION CATALYSEES PAR DU METAL NOBLE ET CONTENANT DES METAUX NOBLES DU GROUPE VIII, EN PARTICULIER LE RHODIUM, PAR DES REACTIFS DESTINES A PRECIPITER DES SOLIDES COMPORTANT LA QUASI-TOTALITE DU METAL NOBLE CONTENUE DANS LES RESIDUS. DES REACTIFS CONVENABLES COMPRENNENT UN OU DES HYDROXYDES DE METAUX ALCALINS, PEROXYDES DE METAUX ALCALINS, BOROHYDRURES DE METAUX ALCALINS ET AUTRES AGENTS REDUCTEURS, COMME LE FORMALDEHYDE ET DU BISULFITE DE SODIUM ACIDIFIE. LES SOLIDES PEUVENT ETRE RENVOYES DIRECTEMENT, POUR LEUR REUTILISATION DANS LA REACTION DE CARBONYLATION, OU BIEN ON PEUT LES TRAITER ENCORE POUR RECUPERER LE OU LES METAUX NOBLES.

USE OF CERTAIN PLANTS PLATINOIDES STORAGE FOR IMPLEMENTING ORGANIC CHEMISTRY REACTIONS

L'invention concerne l'utilisation de plantes accumulatrices de métaux du groupe du platine (platinoïdes) pour la mise en œuvre de réactions chimiques.

PROCESS FOR RECOVERING HOMOGENEOUS METAL HYDRATE CATALYSTS

The present invention relates to a process for recovery of homogeneous metal hydride catalyst from a reactor stream as catalyst suitable for recycle to a reactor comprising the steps of: removing a stream from a reactor, said stream comprising the homogeneous metal hydride catalyst; contacting the stream with a solid acidic absorbent under process conditions which allow at least some of the metal to become bound to the absorbent; subjecting the metal bound to the absorbent, under process conditions which allow desorption of the metal, to a fluid stripping medium comprising hydrogen and solvent; and recovering the active metal hydride catalyst.

Preparation of optically active phospholanes, their metal complexes and use in asymmetric synthesis

Phospholanes and diphospholanes of the formula I см. иллюстрацию в PDF-документе where: R1 and R2 are, independently of one another, C1 -C6 -alkyl, aryl, alkylaryl, R1 is also hydrogen, A is either R1 or см. иллюстрацию в PDF-документе B is a linker having 1-5 carbon atoms between the two phosphorus atoms, and their use as catalyst in asymmetric synthesis.

Method for recovering and recycling catalyst constituents

Catalytic materials including divalent palladium compounds, divalent cobalt compounds and bromide sources such as tetraalkylammonium and hexaalkylguanidinium bromides are removed from organic carbonylation reaction mixtures comprising said materials in combination with diaryl carbonate and hydroxyaromatic compound. The removal steps include extraction with an aqueous complexing solution for palladium, extraction with an aqueous non-basic and preferably ionic extractant for cobalt, and extraction with water to remove bromide source. These steps may be combined into an integrated process. Further steps of recycle of the palladium by reduction to elemental palladium and conversion to a catalytically active species, and conversion of cobalt to a catalytically active species, may be included in the integrated process.

Recovery of spent acid catalyst from alkylation of hydrocarbons

A method of recovery of acid catalyst from acid soluble oil being formed in a process for alkylation of hydrocarbons and containing valuable amounts of spent acid catalyst which method comprises, treating the acid soluble oil with hydrogen in the presence of a catalyst comprising one or more metals from Group VIII of the Periodic Table supported on an acid resistant carrier; and recycling the hydrotreated acid soluble oil to the alkylation process.

Process for the purification and recovery of the impure catalyst solution obtained in the carbonylation of methyl acetate and/or dimethyl ether

The disclosure relates to a process for purifying and recovering a contaminated catalyst solution which is obtained in the carbonylation of methyl acetate and/or dimethylether, the catalyst solution containing carbonyl complexes of noble metals of group VIII of the Periodic System of the elements, quaternary heterocyclic aromatic nitrogen compounds or quaternary organophosphorus compounds as organic promoters, and optionally compounds of carbonyl-yielding common metals as inorganic promoters, undistillable organic contaminants as well as acetic acid, acetic anhydride and ethylidene diacetate. To this end, the disclosure provides for the catalyst solution to be distillatively freed from its volatile constituents and for the remaining solid distillation residue to be freed from the organic contaminants by extraction with aliphatic ethers; and for the remaining undissolved mixture of noble metal/carbonyl-complex, organic and optionally inorganic promoters to be filtered off and recycled into ...

СИНТЕЗ АЛИФАТИЧЕСКИХ 1,3-ДИОЛОВ С ИСПОЛЬЗОВАНИЕМ ПОНИЖЕННОЙ КОНЦЕНТРАЦИИ ЛИГАНДОВ И ЭКСТРАКЦИИ ВОДОЙ

Изобретение относится к усовершенствованному способу получения алифатических 1,3-диолов, который включает в себя: (а) приведение в контакт при температуре в пределах от 30 до 150°С и давлении в пределах от 3 до 25 МПа оксирана, монооксида углерода и водорода в, по существу, не смешивающемся с водой растворителе в присутствии эффективного количества гомогенного биметаллического катализатора гидроформилирования, содержащего соединение карбонила кобальта, и сокатализатора на основе металла, который выбирают из группы, состоящей из рутения, и который связан с фосфиновым лигандом, необязательно, в присутствии промотора, где молярное отношение лиганда к атому металла сокатализатора находится в пределах от 0,2:1,0 до 0,4:1,0, при условиях реакции, эффективных для получения смеси продуктов реакции, содержащей алифатический 1,3-диол; b) добавление к указанной смеси продуктов реакции водного раствора и экстрагирование в указанный водный раствор большей части алифатического 1,3-диола при температуре ...

СПОСОБ РЕГЕНЕРАЦИИ ОТРАБОТАННОГО КИСЛОТНОГО КАТАЛИЗАТОРА

Изобретение относится к каталитическим процессам алкилирования алифатических углеводородов, в частности к способу регенерации отработанного кислотного катализатора, применяемого для алкилирования углеводородов. Способ регенерации включает обработку реагентом жидкой фазы. В качестве жидкой фазы обработке подвергают масло, образующееся в качестве побочного продукта во время процесса алкилирования. В качестве реагента используют водород. Обработку осуществляют в присутствии катализатора, содержащего по меньшей мере один металл из группы III Периодической системы, нанесенный на устойчивый к воздействию кислоты носитель. Катализатор содержит по меньшей мере один металл из группы, включающей платину, палладий и их смеси. Носитель выбран из группы, включающей двуокись кремния, цеолиты и активированный уголь. Обработку водородом осуществляют при 20-200oC и парциальном давлении водорода 1-150 бар. Усовершенствованный способ позволяет повысить экономичность процесса алкилирования углеводородов на ...

VERFAHREN ZUR RÜCKGEWINNUNG HOMOGENER METALLHYDRIDKATALYSATOREN

ELEKTRONISCH ABGESTIMMTE LIGANDE

Novel chiral phosphane ligands are useful for the production of catalysts for asymmetric reactions for hydrosilylation, amination, alkyl substitution and Grignard coupling

Chiral phosphane ligands (I) are new. Chiral phosphane ligands of formula (I) are new. R<1> = H, alkyl, alkenyl, (hetero)aromatic aryl, O-alkyl, NH-alkyl, N-(alkyl)2 where the alkyl groups are optionally bonded to each other via an oxygen bridge, O-aryl, NH-aryl or N-(alkyl)(aryl); R<2> - R<9> = R<1> or O-CO-alkyl, O-CO-aryl, F, Cl, Br, OH, NO2, Si(alkyl)3, CF3, CN, CO2H, COH, SO3H, CONH2, CONH(alkyl), CON(alkyl)2, SO2(alkyl), SO(alkyl), SO(aryl), SO2(aryl), SO3(aryl), S-alkyl, S-aryl, NH-CO(alkyl), CO2(alkyl), CONH2, CO(alkyl), NHCOH, NHCO2(alkyl), CO(aryl), CO2(aryl), CONH2, CO(alkyl), NHCOH, NHCO2(alkyl), CO(aryl),CO2(aryl), CHCH-CO2(aryl), CH=CH-CO2H, PO(aryl)2, PO(alkyl)2, PO3H or PO(o-alkyl)2 where two or more neighboring groups are optionally bonded to form a condensed ring system; alkyl = 1-12C alkyl; alkenyl = optionally unsaturated 2-4C alkenyl optionally substituted by Cl, F, 1-12C alkyl, -1-12C alkoxy, 5-10C aryl, 5-10C aryloxy, NH2, 1-12C alkylamine, 1-12C dialkylamine; and ...

VERFAHREN ZUR HERSTELLUNG VON AETHANOL

PROCESS FOR THE HYDROFORMYLATION OF OLEFINS

Method for the recovery of group VIII noble metal solid complexes

A method for the recovery of a Group VIII noble metal solid complex is described, which comprises bringing an organic compound-containing solution containing therein a Group VIII noble metal complex having a tertiary organophosphorous compound as a ligand into contact with an oxidizing agent in the presence of a free tertiary organophosphorous compound, an organic polar solvent, water, and a basic substance to preciptate a solid complex of the Group VIII noble metal, and a separating the precipitated Group VIII noble metal solid complex from the solution.

HETEROAROMATIC DIPHOSPINE AS CHIRALE LIGAND

PROCEDURE FOR THE DISTANCE OF METALLIC CORROSION PRODUCTS FROM A WITH OF THE CARBONYLIERUNG OF METHANOL AND/OR METHYL ACETATE AND/OR DIMETHYLETHER RESULTING, POLLUTED ONE KATALYSATORLOESUNG.

RECUPERATION OF METAL CATALYSTS FOR THE PRODUCTION OF DIARYLCARBONATEN

PROCEDURE FOR THE RECUPERATION POLLUTED ONE BY PRECIOUS METALS OF THE GROUP OF VIII OF THE PERIODIC SYSTEM OF THE ELEMENTS FROM WITH OF THE CARBONYLIERUNG OF METHYL ACETATE AND/OR DIMETHYLETHER RESULTING KATALYSATORLOESUNG.

Procedure for the production of organic isocyanates

ELECTRONICALLY CO-ORDINATED LIGANDE

Redox procedure for the production of aldehydes and Ketonen from Olefinen

CHIRALE PHOSPHIN AND/OR ARSINLIGANDEN ON METALLOCENBASIS

ENTERPRISE PARTICLE EMISSION BY USE OF METAL FUEL ADDITIVE OF GROUP OF PLATINUM AND FLOW OXIDATION CATALYST, REDUCED BY DIESEL ENGINES WITH

METALLOCENE-BASED CHIRAL PHOSPHINE OR ARSINE LIGANDS

The present invention relates to metallocene-based phosphine ligands having chirality at phosphorus and at least one other element of chirality (planar chirality and/or chirality at carbon); and to the use of such ligands in asymmetric transformation reactions to generate high enantiomeric excesses of formed compounds. A method for the preparation of ligands according to the invention involving the conversion of the ortho-lithiated substituted metallocene to a phosphine chiral at phosphorus is also disclosed.

PROCESS FOR RECOVERING NOBLE METALS BELONGING TO GROUP VIII OF THE PERIODIC SYSTEM OF THE ELEMENTS FROM A CONTAMINATED CATALYST SOLUTION ORIGINATING FROM THE CARBONYLATION OF METHYL ACETATE AND/OR DIMETHYLETHER

PROCESS FOR RECOVERING NOBLE METALS BELONGING TO GROUP VIII OF THE PERIODIC SYSTEM OF THE ELEMENTS FROM A CONTAMINATED CATALYST SOLUTION ORIGINATING FROM THE CABONYLATION OF METHYL ACETATE AND/OR DIMETHYLETHER The disclosure relates to a process for recovering noble metals belonging to group VIII of the Periodic System of the elements from a contaminated catalyst solution originating from the carbonylation of methyl acetate and/or dimethylether, the catalyst solution containing carbonyl complexes of these noble metals, organic compounds of the nitrogen group and/or salts of alkali metals, alkaline earth metals, chromium, iron, cobalt or nickel as promoters,undistillable organic contaminants as well as acetic acid, acetic anhydride and ethylidene diacetate, wherein the volatile constituents are distillatively removed from the catalyst solution and the remaining distillation residue is water-treated, whereby the noble metal/carbonyl-complex is precipitated together with the organic contaminants ...

PROCESS FOR THE PREPARATION OF ALKYL NONADIENOATE ESTERS

In the process for reacting mixture of 1,3-buta-diene, carbon monoxide and a monoalkanol of the general formula ROH in which R is a straight or branched chain alkyl group of from 1 to about 12 carbon atoms in the presence of, as catalyst, a palladium-ligand complex which comprises (a) a member selected from the group consisting of zerovalent palladium, a palladiumcontaining composition which can provide zerovalent palladium under reaction conditions and palladium (II) salt, (b) a strong ligand consisting of tertiary phosphine having a pKa in water of not greater than about 6, and (c) a weak ligand consisting of tertiary phosphine having a pKa in water of greater than about 6, to provide alkyl nonadienoate ester, optionally containing at least one phenol promoter, and if desired, an alkoxide ion.

CATALYST COMPOSITIONS FOR HYDROFORMYLATION AND METHODS OF USE THEREOF

Disclosed are highly active cationic cobalt phosphine complexes, both mono- and bimetallic, that can catalyze hydroformylation reactions. The disclosed catalysts can be utilized in methods that provide reaction processes that are hundreds of times faster than high pressure HCo(CO)4 or phosphine-modified HCo(CO)3(PR3) catalysts and operate at considerably lower pressures and temperatures. Also disclosed are methods of hydroformylation using the described transition metal complexes. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.

HETEROAROMATIC DIPHOSPHINES AS CHIRAL LIGANDS

Chiral diphosphines constituted by an aromatic pentatomic biheterocyclic sys tem, suitable to act as chiral ligands, complexes betwee n said diphosphines and transition metals, and their utilization as chiral cat alysts instereocontrolled reactions, such as diastereo- and enantioselective reduction reactions. Process for the preparation of said ch iral diphosphines and process for the preparation of sai d complexes and for their utilization as chiral catalysts in stereocontrolled reactions.

HETEROAROMATIC DIPHOSPHINES AS CHIRAL LIGANDS

Chiral diphosphines constituted by an aromatic pentatomic biheterocyclic system, suitable to act as chiral ligands, complexes between said diphosphines and transition metals, and their utilization as chiral catalysts instereocontrolled reactions, such as diastereo- and enantioselective reduction reactions. Process for the preparation of said chiral diphosphines and process for the preparation of said complexes and for their utilization as chiral catalysts in stereocontrolled reactions.

A METHOD FOR REMOVING the TAR OF MIXTURES SELECTIVELY COMING From a CATALYTIC REACTION OF CARBONYLATION

PROCESS FOR PREPARING AN ORGANIC ISOCYANATE

Carbonylation and hydroformylation, hydrogenizing process using halogenous complexes

Hydrogenation, hydroformylation or carbonylation process

PROCEDE DE RECUPERATION, A L'AIDE D'UNE AMINE, DU RHODIUM DE RESIDUS DE CARBONYLATION

PROCEDE DE RECUPERATION, A L'AIDE D'UNE AMINE, DU RHODIUM DE RESIDUS DE CARBONYLATION. LES RESIDUS FORMES PENDANT LA CARBONYLATION D'ESTERS OU D'ETHERS-OXYDES, NOTAMMENT LORS DE LA PRODUCTION D'ANHYDRIDE ACETIQUE OU DE DIACETATE D'ETHYLIDENE, CONTIENNENT DU METAL NOBLE, TYPIQUEMENT DU RHODIUM, AYANT SERVI DE CATALYSEUR ET QU'IL FAUT RECUPERER AVANT DE POUVOIR JETER LES RESIDUS. ON LIBERE LE RHODIUM DES RESIDUS EN TRAITANT CEUX-CI PAR DES AMINES, DE PREFERENCE DES AMINES ALIPHATIQUES PRIMAIRE ETOU L'HYDRAZINE, CE QUI PERMET D'EXTRAIRE LE RHODIUM LORS D'UN CONTACT SUBSEQUENT AVEC UN HYDRACIDE HALOGENE AQUEUX. LE RHODIUM OBTENU PEUT ETRE RECYCLE, DIRECTEMENT OU APRES TRAITEMENT, VERS LA REACTION DE CARBONYLATION.

PROCESS FOR THE PREPARATION OF ASYMMETRICALLY SUBSTITUTED BIARYLDIPHOSPHINES

Provided is a process for the preparation of asymmetrically substituted biaryldiphosphine ligands of the formula (I), wherein R1 is C1-6-alkyl or C3-10-cycloalkyl optionally substituted with one or more halogen atoms, and R2 and R3 are equal and are selected from the group consisting of aryl, C5-10-cycloalkyl and C1-6-alkyl, or R2 is C5-10-cycloalkyl or C1-6-alkyl, and R3 is aryl optionally substituted with one or more substituents selected from the group consisting of halogen atoms, nitro, amino, C1-6-alkyl, C1-6-alkoxy and di-C1-6-alkylamino groups, and each C1-6-alkyl, C5-10-cycloalkyl, C1-6-alkoxy and di-C1-6-alkylamino group in R2 and R3 optionally being substituted with one or more halogen atoms, from 2,2',6,6'-tetrabromobiphenyl by a sequence of brominemetal exchanges and subsequent reactions. © KIPO & WIPO 2007 ...

RECOVERY RHODIUM CARBONYLATION RESIDUES

PROCESS FOR THE PREPARATION OF ASYMMETRICALLY SUBSTITUTED BIARYLDIPHOSPHINES

La présente invention concerne un procédé de préparation de ligands biaryldiphosphine à substitution asymétrique représentés par la formule (I), dans laquelle R1 représente alkyle C1-6 ou cycloalkyle C3-10 éventuellement substitué par un ou plusieurs atomes d'halogène, R2 et R3 sont égaux et sont sélectionnés dans le groupe formé par: aryle, cycloalkyle C5-10 et alkyle C1-6, ou bien R2 représente cycloalkyle C5-10 ou alkyle C1-6, et R3 représente aryle éventuellement remplacé par un ou plusieurs substituants sélectionnés dans le groupe formé par: des atomes d'halogène, nitro, amino, alkyle C1-6, alcoxy C1-6 et des groupes alkylamino di-C1-6, chaque alkyle C1-6, cycloalkyle C5-10, alcoxy C1-6 et groupe alkylamino di-C1-6 présent dans R2 et R3 étant facultativement remplacé par un ou plusieurs atomes d'halogène, à partir du 2,2',6,6'-tétrabromobiphényle par une séquence d'échanges bromine-métal et les réactions qui suivent. Formule (I) ...

PROCESS FOR PRODUCING CYCLIC AMINE

A process for easily producing a cyclic amine in high yield. The process for cyclic amine production comprises aminating, with hydrogen and ammonia, a cyclic ketone in which at least either of the carbon atoms in the α-positions with respect to the carbonyl group is tertiary or quaternary, wherein the amination is conducted in the presence of both a metallic catalyst comprising a platinum-group metal or a compound thereof and an ammonium salt. The metallic catalyst preferably is any of ruthenium, rhodium, palladium, ruthenium-carbon, rhodium-carbon, and palladium-carbon.

Recovery of rhodium from carbonylation residues

Residues are formed in the carbonylation of esters or ethers, particularly in the production of acetic anhydride or ethylidene diacetate. Such residues contain noble metal, typically rhodium used as a catalyst, which must be recovered before the residues can be disposed of. In the process of the invention, the rhodium values are freed from the residues by a series of treatments with amines and other reagents, thereby enabling the rhodium to be extracted by subsequent contact with an aqueous halogen acid.

СПОСОБ РЕГЕНЕРАЦИИ ОТРАБОТАННОГО КИСЛОТНОГО КАТАЛИЗАТОРА

Объектом изобретения является способ регенерации отработанного кислотного катализатора, применяемого для алкилирования углеводородов, включающий обработку реагентом жидкой фазы в присутствии катализатора, содержащего по меньшей мере один металл из групп VIII Периодической системы, нанесенный на устойчивый к воздействию кислоты носитель, с использованием водорода в качестве реагента, причем в качестве жидкой фазы обработке подвергают масло, образующееся в качестве побочного продукта во время процесса алкилирования.

ELEKTRONISCH ABGESTIMMTE LIGANDE

New bidentate organophosphorus ligands with a chiral carbon center, used in complex compounds for use as catalysts in asymmetric reactions or polymerizations, especially asymmetric hydroformylation or hydrogenation

Bidentate organophosphorus ligands in which a diorganophosphino-alkyl group with a chiral carbon center is separated from another diorganophosphine group by 1-6 carbon atoms forming part of a non-aromatic, optionally cyclic, optionally heteroatom-containing system, a metallocene or an aromatic or heteroaromatic ring system, is new. Bidentate organophosphorus ligands of formula (I), in which a diorganophosphino-alkyl group with a chiral carbon center is separated from another diorganophosphine group by 1-6 carbon atoms forming part of a non-aromatic, optionally cyclic, optionally heteroatom-containing system, a metallocene or an aromatic or heteroaromatic ring system, is new. (R<1>Y)(R<2>Y)PXZ-C asterisk HR<3>-PR<4>R<5> (I) R<1>-R<5> = H or a 1-50C carbon-containing group selected from 1-24C alkyl, 3-8C cycloalkyl or cycloalkenyl, 6-14C aryl, phenyl, naphthyl, fluorenyl and 2-13C heteroaryl with 1-4 N, O or S atoms (all optionally mono- or poly-substituted with 1-20C alkyl, 2-20C alkenyl ...

RÜCKGEWINNUNG VON METALLKATALYSATOREN FÜR DIE HERSTELLUNG VON DIARYLCARBONATEN

Process for the production of asymmetric transformation catalysts

METHOD FOR THE RECOVERY OF GROUP VIII NOBLE METAL SOLID COMPLEXES

PROCEDURE FOR THE CLEANING AND RECUPERATION OF WITH OF THE CARBONYLIERUNG POLLUTED ONE BY METHYL ACETATE AND/OR DIMETHYLETHER RESULTING, KATALYSATORLOESUNG.

PROCEDURE FOR THE RECUPERATION OF PRECIOUS METALS.

Transfer Hydrogenation of Cyclopamine Analogs

Provided herein is a process for the transfer-hydrogenation of ketone analogs of members of the jervine type of Veratrum alkaloids, such as cyclopamine. Also provided herein are novel ruthenium transfer-hydrogenation catalysts.

Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

Process

The present invention provides a continuous process for the epoxidation of an olefinic compound with an oxidant, which process comprises reaction of an olefinic compound with an oxidant in the presence of a catalyst in an apparatus that comprises a reactive distillation column, which column comprises (i) a reactive section, which comprises the catalyst (ii) a rectifying section situated above the reactive section and adapted to allow separation of reagents and/or by-products from products (ix) a stripping section situated below the reactive section and adapted to allow separation of product from reagents and/or by-products (x) a vessel situated below the stripping section and adapted to provide a source of heat for the column and in which initial vaporisation of one or more of the reagents can occur, wherein the temperature in the reactive section (i) is a temperature at which the reaction between the olefinic compound and the oxidant takes place and the temperature in the stripping section (iii) is higher than the temperature in the rectifying section (ii).

Method for producing formic acid

An object of the present invention is providing a method for producing formic acid under mild reaction conditions and by a simple procedure. As a means for achieving the object, the method for producing formic acid of the present invention is characterized by a reaction between carbon dioxide and hydrogen in the presence of an ionic liquid. According to the present invention, it is possible to generate formic acid effectively, because the method does not require that carbon dioxide be brought into a supercritical state and because no basic substances are required to be added to the reaction system.

Magnetic catalyst

Disclosed is a magnetic catalyst formed by a single or multiple nano metal shells wrapping a carrier, wherein at least one of the metal shells is iron, cobalt, or nickel. The magnetic catalyst with high catalyst efficiency can be applied in a hydrogen supply device, and the device can be connected to a fuel cell. Because the magnetic catalyst can be recycled by a magnet after generating hydrogen, the practicability of the noble metals such as Ru with high catalyst efficiency is dramatically enhanced.

Method for producing substituted fluorine-containing olefin

This invention relates to a method of reacting fluoroolefin with an organic magnesium compound in the presence of a catalyst comprising nickel or palladium so as to efficiently produce fluoroolefin, such as TFE, in which a fluorine (F) atom or atoms bonded to the sp 2 hybridized carbon atom are substituted with an organic group.

Supported metal catalysts

The present invention relates to supported metal catalysts, wherein the catalysts are modified by at least one amine, a method for the preparation thereof and hydrogenation processes utilising the supported metal catalysts.

Catalysts for ring-closing metathesis

A catalyst composition is provided, which may be used for ring closing metathesis. In the composition, a catalyst is immobilized on a siliceous mesocellular foam support. A suitable catalyst for use in the composition is a Grubbs-type catalyst or a Hoveyda-Grubbs-type catalyst.

Polyhedral oligomeric silsesquioxane (poss) bonded ligands and the use thereof

The present invention relates to POSS-modified ligands and to the use thereof in catalytically effective compositions in hydroformylation.

Chelating Carbene Ligand Precursors and Their Use in the Synthesis of Metathesis Catalysts

Chelating ligand precursors for the preparation of olefin methathesis catalysts are disclosed. The resulting catalysts are air stable monomeric species capable of promoting various methathesis reactions efficiently, which can be recovered from the reaction mixture and reused. Internal olefin compounds, specifically beta-substituted styrenes, are used as ligand precursors. Compared to terminal olefin compounds such as unsubstituted styrenes, the beta-substituted styrenes are easier and less costly to prepare, and more stable since they are less prone to spontaneous polymerization. Methods of preparing chelating-carbene methathesis catalysts without the use of CuCl are disclosed. This eliminates the need for CuCl by replacing it with organic acids, mineral acids, mild oxidants or even water, resulting in high yields of Hoveyda-type methathesis catalysts. The invention provides an efficient method for preparing chelating-carbene metathesis catalysts by reacting a suitable ruthenium complex in high concentrations of the ligand precursors followed by crystallization from an organic solvent.

Method for producing alcohol and/or amine from amide compound

Disclosed herein is a method for producing an alcohol and an amine from an amide under an atmosphere of hydrogen with the use of, as a catalyst, a ruthenium complex that is easily prepared, easy to handle, and relatively cheaply obtained. Specifically, the method is a method for producing an alcohol and/or an amine from an amide compound under an atmosphere of hydrogen with the use of as a catalyst, a ruthenium carbonyl complex represented by the following general formula (1): RuXY(CO)(L) (1) wherein X and Y may be the same or different from each other and each represents an anionic ligand and L represents a tridentate aminodiphosphine ligand containing two phosphino groups and a —NH— group.

Metathesis Catalysts Containing Onium Groups

Disclosed herein is a general method for the preparation of complexes containing a quaternary onium group in an inert ligand. Some of these complexes may be represented by formula 1: Methods for the preparation of complexes of formula 1, the preparation of intermediates and the use of complexes of formula 1 in metathesis reactions and a method for conducting an olefin metathesis reaction are also described.

Electrocatalytic alkenes and alkynes dimerizations and trimerizations

The present disclosure relates generally to carbon to carbon coupling processes, and more specifically, to dimerization or trimerization by electrocatalysis of alkenes and alkynes at room temperature.

Novel metal complex catalysts and uses thereof

The invention relates to novel metal complexes useful as catalysts in redox reactions (such as, hydrogen (H 2 ) production). In particular, the invention provides novel transition metal (e.g., cobalt (Co) or nickel (Ni)) complexes, in which the transition metal is coupled with N,N-Bis(2-pyridinylmethyl)-2,2′-Bipyridine-6-methanamine (DPA-Bpy), 6′-((bis(pyridin-2-ylmethyl)amino)methyl)-N,N-dimethyl-2,2′-bipyridin-6-amine (DPA-ABpy), or a derivative thereof. The invention also relates to a method of producing H 2 from an aqueous solution by using the metal complex as a catalyst. In certain embodiments, the invention provides a metal complex of the formulae as described herein.

Novel ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof

The present invention relates to novel Ruthenium catalysts and related borohydride complexes, and the use of such catalysts, inter alia, for (1) hydrogenation of amides (including polyamides) to alcohols and amines; (2) preparing amides from alcohols with amines (including the preparation of polyamides (e.g., polypeptides) by reacting dialcohols and diamines and/or by polymerization of amino alcohols); (3) hydrogenation of esters to alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di-lactones) or polyesters); (4) hydrogenation of organic carbonates (including polycarbonates) to alcohols and hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (5) dehydrogenative coupling of alcohols to esters; (6) hydrogenation of secondary alcohols to ketones; (7) amidation of esters (i.e., synthesis of amides from esters and amines); (8) acylation of alcohols using esters; (9) coupling of alcohols with water to form carboxylic acids; and (10) dehydrogenation of beta-amino alcohols to form pyrazines. The present invention further relates to the novel uses of certain pyridine Ruthenium catalysts.

Use of supported ionic liquid phase (silp) catalyst systems in the hydroformylation of olefin-containing mixtures to aldehyde mixtures with a high content of aldehydes unbranched in the 2 position

The present invention provides a composition comprising: a) an inert porous support material, b) an ionic liquid, c) a metal selected from group 9 of the Periodic Table of the Elements, d) a phosphorus-containing organic ligand, e) at least one organic amine. The present invention further provides a process for hydroformylating olefin-containing hydrocarbon mixtures to aldehydes with addition of the inventive composition as a catalytically active composition, wherein: a) the water content of the olefin-containing hydrocarbon mixture is adjusted to not more than 20 ppm, b) the content of polyunsaturated compounds in the olefin-containing hydrocarbon mixture is adjusted to not more than 3000 ppm, c) a molar ratio of organic amines according to claims 10 - 13 to phosphorus-containing organic ligands according to claims 8 - 9 of at least 4:1 is established, d) a molar ratio of phosphorus-containing organic ligands according to claims 8 - 9 to rhodium of at least 10:1 is established.

Method for producing urethanes

The invention relates to a method for producing urethanes or ureas or mixtures of urethanes and ureas by oxidative carbonylation of organic amines in the presence of carbon monoxide, oxygen and a catalyst, where the catalyst used is a transition metal complex containing the structural feature: [Mn+(O˜N˜O)2−](n-2)+(L)m(Z−)n-2 and the method is carried out under halogen-free reaction conditions. The invention further relates to transition metal complexes containing said structural feature and also to the use of such transition metal complexes as catalysts in the production of urethanes or ureas or mixtures of urethanes and ureas.

Method For Producing Beta-Fluoroalcohol

A production method of a β-fluoroalcohol includes performing a reaction of an α-fluoroester with hydrogen gas (H 2 ) in the presence of a specific ruthenium complex (i.e. a ruthenium complex of the general formula [2], preferably a ruthenium complex of the general formula [4]). This production method can employ a suitable hydrogen pressure of 1 MPa or less by the use of such a specific ruthenium complex and does not require a high-pressure gas production facility when put in industrial practice. In addition, this production method can remarkably reduce the amount of catalyst used therein (to e.g. a substrate/catalyst ratio of 20,000) in comparison to the substrate/catalyst ratio conventional reduction of α-fluoroalcohol. It is possible by these reduction in hydrogen pressure and catalyst amount to largely reduce the production cost of the β-fluoroalcohol.

New palladium catalyst, method for its preparation and its use

The invention relates to palladium(0) tris{tri-[3,5-bis(trifluoromethyl)-phenyl]-phosphine} complex of formula (I), as well as to its preparation and use. This compound is outstandingly stable, and can be used as catalyst with excellent results.

Method for Producing Unsaturated Compounds

The invention relates to a method for producing compositions containing unsaturated compounds, wherein (A) one or more unsaturated monocarboxylic acids having 10 to 24 C-atoms or esters of said monocarboxylic acids and optionally (B) one or more compounds having at least one C═C double bond (wherein the compounds (B) are different from the compounds (A)) are subjected to a tandem isomerization/metathesis reaction sequence in the presence of a palladium catalyst and a ruthenium catalyst, providing that the palladium catalysts used are compounds that contain at least one structural element Pd—P(R 1 R 2 R 3 ), wherein the radicals R 1 to R 3 , independently of one another, each comprise 2 to 10 C-atoms, which may be aliphatic, alicyclic, aromatic or heterocyclic respectively, providing that at least one of the radicals R 1 to R 3 contains a beta-hydrogen, wherein the palladium catalyst is used as such or is produced in situ, providing that the method is carried out in the absence of substances that have a pKa value of 3 or less.

DECARBOXYLATIVE CONJUGATE ADDITIONS AND APPLICATIONS THEREOF

Synthetic methods are described herein operable to efficiently produce a wide variety of molecular species through conjugate additions via decarboxylative mechanisms. For example, methods of functionalization of peptide residues are described, including selective functionalization of peptide C-terminal residues. In one aspect, a method of peptide functionalization comprises providing a reaction mixture including a Michael acceptor and a peptide and coupling the Michael acceptor with the peptide via a mechanism including decarboxylation of a peptide reside. 1. A method of peptide functionalization comprising:providing a reaction mixture including a Michael acceptor and a peptide; andcoupling the Michael acceptor with the peptide via a mechanism including decarboxylation.2. The method of claim 1 , wherein coupling of the peptide and the Michael acceptor provides a 1 claim 1 ,4-addition adduct.4. The method of claim 1 , wherein the peptide comprises at least three amino acids.5. The method of claim 1 , wherein the peptide comprises at least five amino acids.6. The method of claim 1 , wherein the peptide is a protein.7. The method of claim 1 , wherein decarboxylation occurs subsequent to formation of a carboxyl radical at a peptide residue.8. The method of claim 7 , wherein carboxyl radical formation is initiated by a single electron transfer (SET) process.9. The method of claim 8 , wherein the SET process is oxidative.10. The method of claim 8 , wherein the SET process is reductive.11. The method of claim 7 , wherein an α-amino radical is formed by the decarboxylation at the peptide residue.12. The method of claim 11 , wherein the α-amino radical undergoes conjugate addition with the Michael acceptor.13. The method of claim 8 , wherein the reaction mixture further comprises catalyst for initiating the SET process.14. The method of wherein the catalyst is transition metal catalyst.15. The method of claim 13 , wherein the catalyst is photoredox catalyst.16. The method of ...

Immobilized Ruthenium-Triphos Catalysts for Selective Hydrogenolysis of Amides

A compound represented by the structure of formula (I): 5. The compound of claim 4 , wherein L comprises trimethylenemethane.7. The method of claim 6 , wherein the Ru-containing compound comprises [Ru(COD)(methylallyl)].8. A catalyst composition comprising:(a) an oxidic support; and{'claim-ref': {'@idref': 'CLM-00004', 'claim 4'}, '(b) the compound of immobilized on the support.'}9. The catalyst composition of claim 8 , wherein the oxidic support comprises silica claim 8 , magnesia claim 8 , titania claim 8 , or alumina.10. The catalyst composition of claim 8 , wherein the oxidic support comprises silica.11. The catalyst composition of claim 8 , wherein L comprises trimethylenemethane.13. The process of claim 12 , wherein the oxidic support comprises silica claim 12 , magnesia claim 12 , titania claim 12 , and alumina.14. The process of claim 12 , wherein the oxidic support comprises silica.15. The process of claim 12 , wherein L comprises trimethylenemethane.16. The process of claim 13 , wherein L comprises trimethylenemethane.17. The process of claim 14 , wherein L comprises trimethylenemethane.18. The process of claim 12 , wherein the amide comprises a lactam.19. The process of claim 13 , wherein the amide comprises a lactam.20. The process of claim 17 , wherein the amide comprises a lactam. This is application claims the benefit of Provisional Application No. 62/691,936 filed on Jun. 29, 2018 under 35 U.S.C. § 119(e)(1); the entire content of the provisional application is hereby incorporated by reference.The invention generally relates to the field of organic chemistry. It particularly relates to silyl ether triphos compounds, organometallic complexes containing the silyl ether triphos compounds, catalysts containing the organometallic complexes immobilized on oxidic supports, methods of making, and/or methods of using the compounds, complexes, and catalysts.The hydrogenolysis of amides to amines under mild reaction conditions represents a challenging chemical ...

Rh-C3N4 HETEROGENEOUS CATALYST FOR PREPARING ACETIC ACID BY CARBONYLATION REACTION

This invention relates to a catalyst for use in the preparation of acetic acid through a methanol carbonylation reaction using carbon monoxide, and particularly to a heterogeneous catalyst represented by Rh/C 3 N 4 configured such that a complex of a rhodium compound and 3-benzoylpyridine is immobilized on a carbon nitride support.

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 ...

BIPYRIDYL COMPOUND

There are provided a compound capable of being a novel ligand allowing regioselective borylation to be performed in the aromatic borylation reaction, and a catalyst using the same compound. There is provided a bipyridyl compound represented by a general formula (): (wherein A represents a single bond, a vinylene group or an ethynylene group; 2. The bipyridyl compound according to claim 1 , wherein A is a single bond.3. The bipyridyl compound according to claim 1 , wherein Ris a hydrogen atom claim 1 , a halogen atom claim 1 , an alkyl group having 1 to 10 carbon atoms claim 1 , an alkenyl group having 2 to 10 carbon atoms claim 1 , a cycloalkyl group having 3 to 7 carbon atoms claim 1 , an aryl group having 6 to 10 carbon atoms claim 1 , an aryloxy group having 6 to 10 carbon atoms claim 1 , an alkoxy group having 1 to 10 carbon atoms claim 1 , a Calkylamino group claim 1 , a di(Calkyl)amino group or a Calkoxycarbonyl group.4. The bipyridyl compound according to claim 1 , wherein Ris a hydrogen atom claim 1 , an optionally substituted alkyl group having 1 to 10 carbon atoms claim 1 , an optionally substituted alkenyl group having 2 to 10 carbon atoms claim 1 , an optionally substituted cycloalkyl group having 3 to 7 carbon atoms claim 1 , an optionally substituted aryl group having 6 to 10 carbon atoms claim 1 , an optionally substituted alkoxy group having 1 to 10 carbon atoms or an optionally substituted aryloxy group having 6 to 10 carbon atoms.5. An aromatic borylation catalyst comprising the bipyridyl compound according to as a ligand.6. The catalyst according to claim 5 , wherein the bipyridyl compound is coordinated to iridium. The present invention relates to a bipyridyl compound useful as a ligand of a metal catalyst and a catalyst including the same bipyridyl compound as a ligand.The Suzuki-Miyaura reaction performing a cross coupling between an organic halogen compound and an organic boron compound is an important method for carbon-carbon bond formation ...

PROCESS FOR THE PREPARATION OF CHIRAL 3-AMINO-PIPERIDINS, USEFUL INTERMEDIATES FOR THE PREPARATION OF TOFACITINIB

Object of the present invention is an improved process for the preparation of (3R,4R)-1-benzyl-4-methylpiperidin-3-amine by means of chiral Rhodium catalysts. 2. The process according to the claim 1 , wherein the compound of formula (II) or salt thereof has an enantiomeric excess higher than 67% claim 1 , or of at least 70%.3. The process according to claim 1 , wherein the Rh(I) complex is a neutral complex of the general formula (IVa) or (IVb):{'br': None, 'sub': '2', '[RhLA]\u2003\u2003(IVa) or'}{'br': None, 'sub': '2', '[RhLA]\u2003\u2003(IVb),'}{'sub': 4-12', '2-12, 'wherein L represents a Cdiene or two Calkene molecules, and A is chlorine, bromine, iodine, trifluoromethanesulfone, tetrafluoroboarte or acetylacetonate.'}4. The process according to the claim 3 , wherein L is norbornadiene or 1 claim 3 ,5-cyclooctadiene.5. The process according to claim 3 , wherein A is trifluoromethansulfone.8. The process according to claim 1 , wherein the asymmetrical hydrogenation is carried out at a temperature from 30° C. to 60° C. and the solvent is 2 claim 1 ,2 claim 1 ,2-trifluoroethanol claim 1 , or is carried out at a temperature from 50° C. to 70° C. and the solvent is methanol.9. The process according to claim 1 , wherein the asymmetrical hydrogenation is carried out in 2 claim 1 ,2 claim 1 ,2-trifluoroethanol and the pressure is from 2 to 15 bar claim 1 , or is carried in methanol and the pressure is from 10 to 20 bar.10. The process according to claim 1 , wherein the asymmetrical hydrogenation is carried out in from 5 to 10 volumes of 2 claim 1 ,2 claim 1 ,2-trifluoroethanol or from 10 to 20 volumes of methanol.17. The process according to claim 4 , wherein A is trifluoromethansulfone. This application claims benefit to European Patent Application No. EP17178755.9, filed Jun. 29, 2017, the entire contents of which are incorporated by reference herein as if fully set forth.The object of the present invention is an improved process for the synthesis of a key ...

Processes for the preparation of a diarylthiohydantoin compound

Disclosed are processes and intermediates for the preparation of compound (X), which is currently being investigated for the treatment of prostate cancer.

ALKANE DEHYDROGENATION PROCESS

Disclosed herein are processes for dehydrogenation of an alkane to an alkene using an iridium pincer complex. In the dehydrogenation reactions, hydrogen that is co-formed during the process must be removed for the chemical reaction to proceed and to prevent the excess hydrogen from poisoning the catalyst. In one embodiment the process comprises providing an alkane feedstock comprising at least one alkane and contacting the alkane with an iridium pincer complex in the presence of a hydrogen acceptor selected from the group consisting of ethylene, propene, or mixtures to form an alkene product. The processes disclosed herein can accomplish facile, low-temperature transfer dehydrogenation of alkanes with unprecedented selectivities and TONs at a reasonable rate of conversion. 1. A process for preparing alpha-olefins from an at least one alkane , comprising the steps of:providing an alkane feedstock in a gaseous phase comprising the at least one alkane;contacting the at least one alkane in the gaseous phase with an iridium pincer complex in the presence of a gaseous hydrogen acceptor selected from the group consisting of ethylene, propene, and mixtures thereof; andrecovering an alpha-olefin product.2. The process of claim 1 , wherein the at least one alkane in the gaseous phase is selected from the group consisting of a butane claim 1 , a pentane claim 1 , an octane claim 1 , a nonane claim 1 , a decane claim 1 , a dodecane claim 1 , and mixtures thereof.5. The process of claim 1 , wherein the iridium pincer complex is (PCP)Ir(CH) or (p-OK-PCP)Ir(CH).6. The process of claim 1 , wherein the iridium pincer complex is unsupported.7. The process of claim 1 , wherein the iridium pincer complex is immobilized on a solid support.8. The process of claim 7 , wherein the solid support is selected from the group consisting of a silica claim 7 , a γ-alumina claim 7 , a basic alumina claim 7 , a florisil claim 7 , and a neutral alumina.9. The process of claim 8 , wherein the solid ...

POLYCYCLOOLEFIN MONOMERS AND CATALYST ACTIVATED BY COMPOUND CAPABLE OF GENERATING PHOTOACID AS 3D PRINTING MATERIALS

Embodiments in accordance with the present invention encompass compositions containing a latent catalyst and a compound capable of generating a Bronsted acid with a counterion capable of coordinating and activating the latent catalyst along with one or more monomers which undergo ring open metathesis polymerization (ROMP) when said composition is exposed to a suitable radiation to form a three-dimensional (3D) object. The catalyst system employed therein can be sensitive to oxygen and thus inhibits polymerization in ambient atmospheric conditions. The three-dimensional objects made by this process exhibits improved mechanical properties, particularly, high distortion temperature, impact strength, elongation to break, among others. Accordingly, compositions of this invention are useful as 3D inkjet materials for forming high impact strength objects of various sizes with microscale features lower than 100 microns, among various other uses. 2. The composition according to claim 1 , wherein said composition comprising first and second monomer of formula (I) distinct from each other and one of said first and second monomers having a viscosity below 50 centipoise claim 1 , and wherein said first monomer is completely miscible with said second monomer to form a clear solution.3. The composition according to claim 1 , wherein said composition comprising a monomer of formula (I) wherein m is 1 and each of R claim 1 , R claim 1 , Rand Rare hydrogen.4. The composition according to claim 3 , wherein said composition comprising a compound of formula (IV) where Ris hydrogen.5. The composition according to claim 1 , wherein said composition comprising first and second monomer of formula (I) distinct from each other claim 1 , wherein said first monomer is of formula (I) wherein m is 1 and each of R claim 1 , R claim 1 , Rand Rare hydrogen; and wherein said second monomer is of formula (I) wherein m is 0 claim 1 , Ris decyl and each of R claim 1 , Rand Rare hydrogen.8. The ...

PHOTOCATALYTIC DEGRADATION OF SUGAR

Systems having at least one photonic antenna molecule and at least one catalyst for degrading a sugar to degradation products using light energy are disclosed. Also disclosed are the devices and methods that use the systems for photocatalytically degrading a sugar into degradation products. 1. A system for photocatalytically degrading a sugar , the system comprising:at least one photonic antenna molecule; andat least one catalyst;wherein the photonic antenna molecule is capable of collecting a light energy and transferring the light energy to the catalyst; andwherein the catalyst is capable of degrading the sugar to produce at least one degradation product.2. The system of claim 1 , wherein the photonic antenna molecule is selected from the group consisting of 5-hydroxytryptamine claim 1 , an acridine claim 1 , an Alexa Fluor® dye claim 1 , an ATTO dye claim 1 , a BODIPY® dye claim 1 , Coumarin 6 claim 1 , a CY dye claim 1 , DAPI claim 1 , an ethidium compound claim 1 , a Hoechst dye claim 1 , Oregon Green claim 1 , rhodamine claim 1 , a compound comprising Ru(bpy) claim 1 , a compound comprising (Pt(pop)) claim 1 , a YOYO dye claim 1 , and a SeTau dye.3. The system of claim 1 , wherein the photonic antenna molecule is fluorescein.4. The system of claim 1 , wherein the catalyst is a metal nanoparticle.5. The system of claim 4 , wherein the metal nanoparticle comprises a metal selected from the group consisting of ruthenium claim 4 , palladium claim 4 , gold claim 4 , silver claim 4 , nickel claim 4 , tungsten claim 4 , molybdenum claim 4 , gallium claim 4 , iridium claim 4 , rhodium claim 4 , osmium claim 4 , copper claim 4 , cobalt claim 4 , iron claim 4 , and platinum claim 4 , or a mixture thereof.6. The system of claim 4 , wherein the metal nanoparticle comprises a lanthanide.7. The system of claim 4 , wherein the metal nanoparticle comprises a metal selected from the group consisting of platinum claim 4 , nickel claim 4 , and europium.8. The system of claim 5 , ...

DEHYDROGENATION CATALYST, AND CARBONYL COMPOUND AND HYDROGEN PRODUCTION METHOD USING SAID CATALYST

Objects of the present invention are to provide a novel dehydrogenation reaction catalyst, to provide a method that can produce a ketone, an aldehyde, and a carboxylic acid with high efficiency from an alcohol, and to provide a method for efficiently producing hydrogen from an alcohol, formic acid, or a formate, and they are accomplished by a catalyst containing an organometallic compound of Formula (1). 2. The method according to claim 1 , wherein the oxygen-containing compound is an alcohol.3. The method according to claim 1 , wherein the oxygen-containing compound is formic acid or a formate.4. The method according to claim 1 , wherein L is an aquo ligand.5. The method according to claim 1 , wherein Ar is an optionally substituted cyclopentadienyl group claim 1 , and M is iridium.6. A dehydrogenation catalyst comprising an organometallic compound of Formula (1) claim 1 , wherein it is for use in the method according to .7. A method for producing a carbonyl compound claim 1 , wherein an alcohol is dehydrogenated by use of the dehydrogenation method according to to produce a corresponding carbonyl compound.8. The method according to claim 7 , wherein the carbonyl compound is a ketone or an aldehyde.9. The method according to claim 7 , wherein the alcohol is a primary alcohol claim 7 , the carbonyl compound is a carboxylic acid claim 7 , and a solvent comprising water is used.10. A method for producing hydrogen claim 1 , wherein hydrogen is prepared by dehydrogenation of an alcohol claim 1 , a mixture containing an alcohol and water claim 1 , formic acid claim 1 , or a formate using the dehydrogenation method according to .12. The organometallic compound according to claim 11 , wherein Ar is an optionally substituted cyclopentadienyl group claim 11 , and M is iridium.14. The organometallic compound according to claim 13 , wherein Ar is an optionally substituted cyclopentadienyl group claim 13 , and M is iridium.15. A method for dehydrogenating an oxygen-containing ...

WATER-INSOLUBLE RUTHENIUM CATALYST COMPOSITION FOR USE IN AQUEOUS HYDROGENATION REACTIONS

The invention relates to a method for converting a precatalyst complex to an active catalyst complex, wherein the precatalyst complex and the active catalyst complex comprise a ruthenium atom and an optically active ligand that is insoluble in water, and the active catalyst complex furthermore comprises a monohydride and a water molecule. The method comprises the steps of providing water as an activation solvent system with a pH value equal or below 2, and solving said precatalyst complex, an acid, and hydrogen therein. The invention further relates to a method for manufacturing a catalyst composition, a method for hydrogenating a substrate molecule and a reaction mixture. 1. A method for converting a precatalyst complex to an active catalyst complex ,wherein said precatalyst complex and said active catalyst complex comprise a ruthenium atom and an optically active ligand that is insoluble in water, andwherein said active catalyst complex comprises a monohydride and a water molecule,said method comprising the steps of:a) providing an activation solvent system comprising water, said precatalyst complex,', 'a solubilizer,', 'an acid, and', 'hydrogen,, 'b) adding to, particularly solving in, said activation solvent system'}characterized in thatthe pH value of said activation solvent system is equal or below 2 after addition of said acid.2. The method according to claim 1 , wherein said activation solvent system comprises ≧50% (v/v) claim 1 , ≧75% (v/v) claim 1 , ≧80% (v/v) claim 1 , ≧90% (v/v) claim 1 , ≧99% (v/v) or 100% water.3. The method according to claim 1 , wherein said solubilizer is a surfactant that is capable of forming micelles in water and that is resistant to hydrolysis at pH≦2.4. A method for obtaining a catalyst composition claim 1 , comprising the steps ofa) providing water as a preparation solvent system, andb) adding to, particularly solving in, said preparation solvent system an optically active ligand, wherein said optically active ligand is ...

METHOD FOR REDUCTION OF ORGANIC MOLECULES

A method for the reduction organic molecules comprising a Ruthenium-Triphosphine complex with aromatic ligands at the phosphors which are ortho or meta substituted. 1. A method for the reduction of organic molecules , comprising the step ofa) hydrogenating at least one organic molecule in the presence of a Ruthenium-Triphosphine-complex whereby the triphosphine-complex comprises at least one aryl and/or heteroaryl moeity bound to a phosphine which is substituted in ortho and/or meta position to the phosphine.2. The method according to claim 1 , wherein the Ruthenium-Triphosphine-complex comprises a phosphororganic compound where two or all three phosphors have an aryl and/or heteroaryl moeity which is substituted in ortho and/or meta position to the phosphine bound thereto.4. The method according to claim 1 , wherein step a) is performed under acidic conditions.5. The method according to claim 1 , wherein step a) is performed under acidic conditions whereby the (initial) concentration of acid is ≧0.5 to ≦20 times the concentration of Ruthenium (in mol:mol).6. The method according to claim 5 , wherein step a) is performed under acidic conditions whereby the acid is selected out of the group comprising sulfonic acids claim 5 , especially methanesulfonic acid claim 5 , trifluormethansulfonic acid claim 5 , p-toluolsulfonic acid claim 5 , p-bromobenzosulfonic acid claim 5 , p-nitrobenzosulfonic acid claim 5 , sulfuric acid claim 5 , hydrochloric acid claim 5 , hydrofluoric acid claim 5 , trifluoracetic acid claim 5 , perchloric acid claim 5 , bis(trifluoromethane)sulfonimide or mixtures thereof7. The method according to claim claim 5 , wherein step a) is carried out at an initial hydrogen pressure of ≧1 bar.8. The method according to claim 1 , wherein step a) is carried out in a dipolar protic or aprotic solvent or in CO The present invention relates to a method for reducing organic molecules, especially by using Ruthenium-Triphosphine-complexes.In the prior art, e.g. ...

METHOD FOR PRODUCING HYDROGEN GAS FROM FORMIC ACID

A method for producing A hydrogen gas from formic acid, characterized in that at least one heterogeneous catalyst is used to transform the formic acid into hydrogen gas. The at least one heterogeneous catalyst contains heterogenised ruthenium. According to a first aspect of the invention, the at least one heterogeneous catalyst contains at least one hydrophilic phosphine ligand which is m-TPPTS (meta-trisulfonated triphenylphosphine). The at least one heterogeneous catalyst is preferably obtained by mixing an aqueous solution of RuClwith hydrophilic phosphine, firstly activated by carrying out a homogeneous reaction with formic acid and by adding at least one solid structure. 113-. (canceled)14. A method of producing hydrogen gas from formic acid , the method comprising:using at least one heterogeneous catalyst to transform formic acid to hydrogen gas.15. The method according to claim 14 , further comprising the at least one heterogeneous catalyst containing heterogenised ruthenium.16. The method according to claim 14 , further comprising the at least one heterogeneous catalyst containing at least one hydrophilic phosphine ligand.17. The method according to claim 16 , further comprising using m-TPPTS (meta-trisulfonated triphenylphosphine) as the at least one hydrophilic phosphine ligand.18. The method according to claim 14 , further comprising obtaining the at least one heterogeneous catalyst by mixing an aqueous solution of RuClwith hydrophilic phosphine claim 14 , firstly activated by carrying out a homogeneous reaction with formic acid and by adding at least one solid structure.19. The method according to claim 14 , further comprising the at least one heterogeneous catalyst containing silica modified with phosphine ligands.20. The method according to claim 19 , further comprising preparing linkers from parent bromoalkenes and coupled with PPhnucleophile and the ligand is covalently bonded to the silica surface and the ruthenium phosphine complex is anchored in a ...

METHOD FOR ALKYLATION OF AMINES

The present invention provides a simple, efficient, and industrially advantageous method for the alkylation of amines. The present invention relates to a production method for N-alkylamines whereby an amine is reacted with an alcohol in the presence of a ruthenium complex represented by general formula (1): RuXY(CO)(L) (wherein X and Y can be the same or different and represent a monovalent anionic ligand, and L represents a tridentate aminodiphosphine ligand). 3. The production method according to claim 1 , wherein the N-alkylamine has the following general formula (4):{'br': None, 'sup': 'A', 'R—NH—R\u2003\u2003(4)'}wherein, in the general formula (4),{'sup': 'A', 'Rrepresents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heterocyclic group, an alkenyl group, an alkynyl group, a cycloalkenyl group, an alkyloxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, a hydroxyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an alkenyloxycarbonyl group, an alkynyloxycarbonyl group, a cycloalkenyloxycarbonyl group, a carboxamide group or an alkoxysulfonyl group, which groups may comprise substituent(s); and'}R represents an optionally substituted hydrocarbon group, an optionally substituted aryl group or an optionally substituted heterocyclic group, {'br': None, 'sup': 'A', 'sub': '2', 'R—NH\u2003\u2003(5)'}, 'wherein the amine has the following general formula (5){'sup': 'A', 'wherein, in the general formula (5), Rrepresents the same group as in the definition in the general formula (4), and'} {'br': None, 'R—OH\u2003\u2003(6)'}, 'the alcohol has the following general formula (6)wherein, in the general formula (6), R represents the same group as in the definition in the general formula (4).6. The method according to claim 1 , wherein the alcohol is a primary or secondary alcohol.7. The method according to claim 1 , wherein the alcohol is methanol or ethanol.8. ...

Platinum metallacycles comprising n, p, or as ringatoms and their use as catalysts in 1,2-hydrosilylation reactions of dienes

Described herein are platinum complexes of Formula (I) for hydrosilylation of 1,3-dienes. Methods of using the platinum complexes for selective 1,2-hydrosilylation of 1,3-dienes are also provided.

Synthesis of (S)-6-Hydroxytryptophan and Derivatives Thereof

The present invention relates to novel methods and compounds for synthesizing amanitin derivatives. The invention in particular relates to methods for synthesizing (S)-6-hydroxy-tryptophan derivatives which can be used as building blocks for synthesizing amanitin derivatives or amatoxin drug conjugates. The invention further relates to intermediate compounds of said synthesis pathways for use in amanitin derivative and amatoxin drug conjugate synthesis, and to the use of particular catalysts suited for mediating said synthesis pathways.

METHOD FOR CATALYTIC PREPARATION OF HYDROMORPHONE, HYDROCODONE, AND OTHER OPIATES

Methods are provided for efficient preparation of hydromorphone or hydrocodone by redox isomerization of morphine or codeine allylic alcohols, respectively, using transition metal aminophosphine catalysts formed in situ. 2. The method of claim 1 , wherein Ris H or Calkyl; Ris H claim 1 , Calkyl claim 1 , Calkenyl claim 1 , or Ccycloalkyl; and Ris H claim 1 , or —OH.3. The method of claim 2 , wherein Ris H or CH; Ris CH claim 2 , allyl claim 2 , or cyclopropylmethyl; and Ris H or —OH.4. The method of claim 3 , wherein Ris H or CH; Ris CH; and Ris H or —OH.5. The method of claim 4 , wherein Ris H or CH; Ris CH; and Ris H.6. The method of claim 5 , wherein Ris H; Ris CH; and Ris H.7. The method of claim 5 , wherein Ris CH; Ris CH; and Ris H.8. The method of claim 7 , wherein the compound of formula (II) is codeine base or a hydrate thereof or concentrated poppy straw-codeine (CPS-C).9. The method of claim 1 , wherein X is halo; and R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , R claim 1 , Rand Rare each optionally substituted aryl.10. The method of claim 9 , wherein M is Rh; R claim 9 , R claim 9 , R claim 9 , R claim 9 , R claim 9 , R claim 9 , Rand Rare each phenyl; m is 1; and n is 1.11. The method of claim 1 , wherein the exposing comprises adding 0.05-0.3 mol % of the compound of formula (III) to the compound of formula (II) claim 1 , to transform the compound of formula (II) into the compound of formula (I) or salt or solvate thereof.12. The method of claim 11 , wherein the transformation of compound (II) into the compound of formula (I) is greater than 97% claim 11 , 99% claim 11 , 99.5% claim 11 , or 99.9% by HPLC.13. The method of claim 1 , further comprising dissolving the compound of formula (II) in a solvent selected from the group consisting of methanol claim 1 , ethanol claim 1 , isopropanol claim 1 , n-propanol claim 1 , water claim 1 , methylene chloride/methanol claim 1 , tetrahydrofuran claim 1 , and acetone prior to the exposing step.14 ...

Catalyst for preparing 1,5-pentanediol via hydrogenolysis of tetrahydrofurfuryl alcohol, method and application thereof

The present invention provides a method for preparing 1,5-pentanediol via hydrogenolysis of tetrahydrofurfuryl alcohol. The catalyst used in the method is prepared by supporting a noble metal and a promoter on an organic polymer supporter or an inorganic hybrid material supporter, wherein the supporter is functionalized by a nitrogen-containing ligand. When the catalyst is used in the hydrogenolysis of tetrahydrofurfuryl alcohol to prepare 1,5-pentanediol, a good reaction activity and a high selectivity can be achieved. The promoter and the nitrogen-containing ligand in the supporter are bound to the catalyst through coordination, thereby the loss of the promoter is significantly decreased, and the catalyst has a particularly high stability. The lifetime investigation of the catalyst, which has been reused many times or used continuously for a long term, suggests that the catalyst has no obvious change in performance, thus reducing the overall process production cost.

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

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. 2: The process according to claim 1 , wherein{'sup': '1', 'sub': 1', '6', '6', '14', '1', '4, 'claim-text': {'sub': 6', '14', '6', '14', '1', '4', '1', '4', '1', '4', '1', '4', '1', '4, 'wherein C-C-aryl in the C-C-aryl-C-C-alkyl moiety is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C-C-alkyl, C-C-haloalkyl, C-C-alkoxy and C-C-haloalkoxy'}, 'Ris C-C-alkyl or C-C-aryl-C-C-alkyl,'}{'sup': 2', '3, 'sub': 1', '4, 'Rand Rare the same and are selected from C-C-alkyl,'}{'sup': '4', 'sub': 1', '4', '1', '4', '1', '4', '1', '4, 'Ris C-C-alkyl, C-C-haloalkyl, C-C-alkoxy, C-C-haloalkoxy, phenyl or benzyl,'}n is 0, 1 or 2, and{'sup': '5', 'sub': 1', '6', '1', '6, 'each substituent R, if present, is independently selected from the group consisting of halogen, C-C-alkyl and C-C-haloalkyl.'}3: The process according to claim 1 , wherein{'sup': '1', 'Ris methyl, ethyl or n-propyl,'}{'sup': 2', '3, 'Rand Rare methyl,'}{'sup': '4', 'sub': 1', '4, 'Ris C-C-alkyl,'}n is 0, 1 or 2, and{'sup': '5', 'sub': 1', '6, 'each substituent R, if present, is independently selected from the group consisting of halogen and C-C-alkyl.'}6: The process according to claim 1 , wherein the hydrogenation is conducted using hydrogen gas at a pressure of from 1 to 300 bar.7: The process according to claim 1 , wherein the amount of iridium catalyst used is within the range of from 0.001 mol % to 5 mol % claim 1 , based on the amount of the compound of the formula (II).8: The process according to claim 1 , wherein the hydrogenation is conducted at a temperature within the range of from 20° C. to 130° C.9: The process according to claim 1 , wherein the hydrogenation is conducted in presence of a ...

High Density Cyclic Fuels Derived From Linear Sesquiterpenes

A method to generate cyclic hydrocarbons from farnesene to increase both the density and net heat of combustion of the product fuels. The high density hydrocarbons produced by this method have applications for missile, UAV, jet, and diesel propulsion.

Process for producing alkylalkoxysilanes

A process produces a C- to C-alkyltrialkoxysilane by hydrosilylation, wherein alkoxy represents methoxy, ethoxy or propoxy. Initially, a mixture is charged of at least one hydroalkoxysilane from the group of hydrotrialkoxysilane, hydroalkyldialkoxysilane, and hydrodialkylalkoxysilane, and a Pt catalyst. The mixture is then heated to a temperature of 30° C. to 60° C. Subsequently, with mixing, an omega-unsaturated or mono-unsaturated C- to C-hydrocarbon, at least one carboxylic acid and at least one alcohol as cocatalysts are added to the mixture. The mixture is then reacted and subsequently worked up to obtain the product. 1. A process for producing a C- to C-alkyltrialkoxysilane by hydrosilylation , wherein alkoxy represents methoxy , ethoxy or propoxy , the process comprising: at least one hydroalkoxysilane selected from the group consisting of hdrotrialkoxysilane, hydroalkyldialkoxysilane, and hydrodialkylalkoxysilane, and', 'a Pt catalyst,, 'a) initially charging a mixture of'}b) heating the mixture to a temperature of 30° C. to 60° C.,{'sub': 3', '20, 'c) subsequently, with mixing, adding/metering an omega-unsaturated or mono-unsaturated C- to C-hydrocarbon, at least one carboxylic acid and at least one alcohol as cocatalysts, and'}d) reacting the mixture and subsequently working up the mixture.2. The process according to claim 1 , wherein the at least one hydroalkoxysilane and the at least one alcohol are employed in a molar ratio of 1:0.01 to 1:0.2.3. The process according to claim 1 , wherein the at least one hydroalkoxysilane and the Pt catalyst are employed in a molar ratio of 1:1×10to 1:1×10.4. The process according to claim 1 , wherein the at least one hydroalkoxvsilane and the at least one carboxylic acid are employed in a molar ratio of 1:1×10to 1:10×10.5. The process according to claim 1 , wherein the at least one hydroalkoxysilane and the C- to C-hydrocarbon are employed in a molar ratio of 1:1 to 1:1.2.6. The process according to claim 1 , wherein ...

ORGANOMETALLIC COMPLEX CATALYST

An organometallic complex catalyst that makes it possible to obtain a higher yield of a desired product than conventional catalysts in a cross-coupling reaction. The organometallic complex catalyst has a structure represented by formula (1) and is for use in a cross-coupling reaction. In formula (1), M is the coordination center and represents a metal atom such as Pd or an ion thereof. R1, R2, and R3 may be the same or different and are a substituent such as a hydrogen atom. R4, R5, R6, and R7 may be the same or different and are a substituent such as a hydrogen atom. X represents a halogen atom. R8 represents a substituent that has a π bond and 3-20 carbon atoms. With regard to the electron-donating properties of R1-R7 with respect to the coordination center M of the ligand containing R1-R7 that is indicated in formula (2), R1-R7 are arranged in combination such that the TEP value obtained from infrared spectroscopy shifts toward the low frequency side compared to the TEP value of the ligand of formula (2-1). 3. The ligand according to claim 1 , wherein the organometallic complex catalyst represented by the formula (1) is used in a C—N cross-coupling reaction. This application is a divisional of U.S. application Ser. No. 16/466,413, filed on Jun. 4, 2019, which is a 371 of International Application No. PCT/JP2017/043890, filed on Dec. 6, 2017, which is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2016-237942, filed on Dec. 7, 2016 and Japanese Patent Application No. 2016-237941, filed on Dec. 7, 2016, the entire contents of which are incorporated herein by reference.The present invention relates to an organometallic complex catalyst for use in a cross-coupling reaction. More specifically, the present invention relates to an organometallic complex catalyst for use in a cross-coupling reaction which has a ligand having a nitrogen-containing heterocyclic carbene structure.Aromatic amines are widely used in medicines, ...

CATALYST SYSTEM CONTAINING A METATHESIS CATALYST AND AT LEAST ONE PHENOLIC COMPOUND AND A PROCESS FOR METATHESIS OF NITRILE-BUTADIENE RUBBER (NBR) USING THE CATALYST SYSTEM

The present invention relates to a catalyst system containing a metathesis catalyst containing at least one N-heterocyclic carbene ligand and at least one phenolic compound and to a process for performing the metathesis on nitrile rubbers for reducing their molecular weight using a metathesis catalyst containing at least one N-heterocyclic carbene ligand (NHC ligand) and at least one phenolic compound. 2. The catalyst system of claim 1 , wherein the metathesis catalyst is selected from the group consisting of:dichloro(fluorenylidene)(1,3-dimesityldihydroimidazolylidene)(triphenylphosphino)ruthenium,1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxyphenylmethylene)ruthenium,[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)bis(3-bromopyridine)ruthenium(II), and,1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)(2-isopropoxy-5-nitrobenzylidene)ruthenium(II)chloride.3. The catalyst system of wherein the phenolic compound of general formula (Z1) is selected from the group consisting of:2,2′-methylene-bis(4-methyl-6-tert-butylphenol),2,6-di-tert-butyl-4-methylphenol, and,2,2′-methylenebis(4-methyl-6-nonylphenol).4. The catalyst system of claim 1 , wherein the molar ratio of metathesis catalyst to phenolic compound of general formula (Z1) or (Z2)=1:(0.01-1000).5. A process of performing a metathesis of nitrile rubber claim 1 , the process comprising the use of the catalyst system of .6. A process of reducing the molecular weight of nitrile rubbers claim 1 , in which nitrile rubber is subjected to a metathesis reaction in the presence of a complex catalyst system of .7. The process of claim 6 , wherein the amount of metathesis catalyst is 1 to 1000 ppm of noble metal claim 6 , based on the employed nitrile rubber.8. The process of claim 6 , wherein the amount of phenolic compound of general formula (Z1) or (Z2) is 0.0001 phr to 5 phr claim 6 , based on the nitrile rubber to be degraded.9. The process of claim 6 , ...

PROCESS FOR PREPARING ALDEHYDES AND SEPARATION OF THE CATALYST SYSTEM BY MEMBRANE SEPARATION

The present invention provides a process for preparing aldehydes from C2 to C20 olefins using a subsequent membrane separation to separate the homogeneously dissolved catalyst system, wherein prior to the membrane separation a gas exchange that increases the partial pressure fraction of carbon monoxide or hydrogen is carried out in order to boost catalyst retention by the membrane. 1. A process for preparing aldehydes , said process comprising at least{'sub': '2', 'a hydroformylation through the reaction of C2 to C20 olefins with syngas in the presence of a homogeneously dissolved catalyst system that comprises at least Co or Rh, in at least one reaction zone, yielding a liquid reaction output containing the product, wherein the partial pressure fraction of CO or Hin the hydroformylation constitutes not more than 75% of the total gas pressure, the total gas pressure being the sum of the pressures occurring from all the gaseous substances present, and'}a membrane separation for separating the homogeneously dissolved catalyst system, wherein,{'sub': 2', '2, 'before the membrane separation, a gas exchange with CO or His carried out, as a result of which the partial pressure fraction of CO or Hconstitutes more than 80% of the total gas pressure.'}2. The process according to claim 1 , wherein the hydroformylation is carried out at a pressure of from 10 to 350 bar.3. The process according to claim 1 , wherein the hydroformylation is carried out at a temperature of from 80 to 250° C.4. The process according to claim 1 , wherein the homogeneously dissolved catalyst system comprises at least Rh and a phosphorus-containing ligand.5. The process according to claim 1 , wherein the phosphorus-containing ligand is a phosphine claim 1 , a monophosphite claim 1 , a bisphosphite or mixtures thereof.6. The process according to claim 1 , wherein the total gas pressure after the gas exchange is from 1 to 70 bar.7. The process according to claim 1 , wherein the membrane separation is ...

PHOSPHORAMIDITE DERIVATIVES IN THE HYDROFORMYLATION OF OLEFIN-CONTAINING MIXTURES

The invention relates to: a) phosphoramidites of formula (I); b) transition-metal-containing compounds of the formula Me(acac)(CO)L, wherein L is selected from formula (I); c) catalytically active compositions in hydroformylation that have the compounds mentioned under a) and b); d) a method for the hydroformylation of unsaturated compounds by using the catalytically active composition mentioned under c); and e) a multi-phase reaction mixture, containing unsaturated compounds, a gas mixture, which comprises carbon monoxide and hydrogen, aldehydes, and the catalytically active composition described under c). 2. Phosphoramidites according to claim 1 , where Q is selected from substituted or unsubstituted 1 claim 1 ,1′-biphenyl claim 1 , 1 claim 1 ,1′-binaphthyl and ortho-phenyl radicals.3. Phosphoramidites according to claim 2 , where Q is selected from substituted or unsubstituted 1 claim 2 ,1′-biphenyl radicals.4. Phosphoramidites according to claim 3 , where Ris selected from C-C-alkyl claim 3 , substituted or unsubstituted cycloalkyl and aryl radicals;{'sup': 2', '1', '2', '1', '2, 'sub': 1', '5, 'Ris selected from C-C-alkyl, substituted or unsubstituted cycloalkyl and aryl radicals, but Rand Rare not i-propyl radicals, or Rand Rtogether with N form a heterocyclic structure via alkylene groups.'}5. Phosphoramidites according to claim 4 , where Ris selected from C-C-alkyl claim 4 , C-C-cycloalkyl and phenyl radicals; Ris selected from C-C-alkyl claim 4 , C-C-cycloalkyl and phenyl radicals claim 4 , but Rand Rare not i-propyl radicals claim 4 , or Rand Rtogether with N form a heterocyclic structure via alkylene groups.8. Transition metal compounds according to claim 7 , where Q is selected from substituted or unsubstituted 1 claim 7 ,1′-biphenyl claim 7 , 1 claim 7 ,1′-binaphthyl and ortho-phenyl radicals.9. Transition metal compounds according to claim 8 , where Q is selected from substituted or unsubstituted 1 claim 8 ,1′-biphenyl radicals.10. Transition metal ...

Dehydrogenation of neat formic acid

A formic acid decomposition catalyst system includes metal-ligand complexes having formula 1: wherein M is a transition metal; R 1 , R 2 are independently C 1-6 alkyl groups; o is 1, 2, 3, or 4; R 3 are independently hydrogen, C 1-6 alkyl groups, OR 14 , NO 2 , or halogen; R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , are independently hydrogen or C 1-6 alkyl groups; R 14 is a C 1-6 alkyl group; and X − is a negatively charge counter ion.

Methods for producing butanol

Methods and compositions for producing 1-butanol are described herein. In some examples, the methods can comprise, contacting a reactant comprising ethanol with a catalyst system, thereby producing a product comprising 1-butanol. The catalyst system can comprise, for example, an iridium catalyst and a nickel, copper, and/or zinc catalyst. The nickel, copper, and zinc catalysts can comprise nickel, copper, and/or zinc and a sterically bulky ligand.

HETEROGENEOUS CATALYSTS FOR NMR/MRI ENHANCEMENT VIA SIGNAL AMPLIFICATION BY REVERSIBLE EXCHANGE (SABRE)

Heterogeneous iridium catalysts for nuclear spin polarization enhancement in solution via signal amplification by reversible exchange are provided. Also provided are methods for preparing heterogeneous iridium catalysts, and methods of using heterogeneous iridium catalysts for nuclear spin polarization enhancement in solution via signal amplification by reversible exchange. 4. The catalyst of claim 1 , wherein the solid support is selected from a nanoparticle claim 1 , a titanium dioxide nanoparticle claim 1 , silica claim 1 , a polymer microbead claim 1 , and a polystyrene microbead.5. The catalyst of claim 1 , wherein L is a bond.6. The catalyst of claim 1 , wherein L is a linker claim 1 , wherein the linker is derived from an amino acid or 4-dimethylamino-pyridine.7. The catalyst of claim 1 , wherein Ris mesityl.8. The catalyst of claim 1 , wherein Ris mesityl.9. The catalyst of claim 1 , wherein Rand Rare each hydrogen.10. The catalyst of claim 1 , wherein Ris chloro.11. The catalyst of claim 1 , wherein Ris an unsubstituted or substituted pyridinyl.15. The catalyst of claim 14 , wherein the solid support is a TiOnanoparticle. This application claims priority to U.S. Provisional Application No. 62/025,743, filed Jul. 17, 2014, which is herein incorporated by reference in its entirety.This invention was made with government support under Award No. W81XWH-12-1-0159/BC112431 awarded by the Department of Defense; Grant No. 3R00CA134749-03 awarded by the National Institutes of Health; Grant No. 1R21EB018014-01A1 awarded by the National Institutes of Health; Grant No. CHE-1416268 awarded by the National Science Foundation; and Grant No. CHE-1416432 awarded by the National Science Foundation. The Government has certain rights in the invention.The present disclosure relates to heterogeneous catalysts, and more particularly, to preparation and use of heterogeneous iridium catalysts for nuclear spin polarization enhancement in solution via signal amplification by ...

Catalyst complex with carbene ligand

Catalytic complexes including a metal atom having anionic ligands, at least one nucleophilic carbene ligand, and an alkylidene, vinylidene, or allenylidene ligand. The complexes are highly stable to air, moisture and thermal degradation. The complexes are designed to efficiently carry out a variety of olefin metathesis reactions.

Chelating Carbene Ligand Precursors and Their Use in the Synthesis of Metathesis Catalysts

Chelating ligand precursors for the preparation of olefin methathesis catalysts are disclosed. The resulting catalysts are air stable monomeric species capable of promoting various methathesis reactions efficiently, which can be recovered from the reaction mixture and reused. Internal olefin compounds, specifically beta-substituted styrenes, are used as ligand precursors. Compared to terminal olefin compounds such as unsubstituted styrenes, the beta-substituted styrenes are easier and less costly to prepare, and more stable since they are less prone to spontaneous polymerization. Methods of preparing chelating-carbene methathesis catalysts without the use of CuCl are disclosed. This eliminates the need for CuCl by replacing it with organic acids, mineral acids, mild oxidants or even water, resulting in high yields of Hoveyda-type methathesis catalysts. The invention provides an efficient method for preparing chelating-carbene metathesis catalysts by reacting a suitable ruthenium complex in high concentrations of the ligand precursors followed by crystallization from an organic solvent. 2. The chelating carbene complex of claim 1 , wherein the chelating carbene complex is prepared by a method comprising contacting a metathesis-active metal carbene complex of the formula XXLLM=CRRwith a beta-substituted styrene ligand precursor claim 1 , wherein{'sup': 1', '2', '1, 'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'X, X, L, and M are as defined in ;'}{'sup': 2', '1', '2', '1', '2, 'Lis any neutral electron donor, and wherein any of two or three of X, X, L, and Lmay form a multidentate ligand; and'}{'sup': 1', '2', '1', '2, 'Rand Rare each, independently, selected from hydrogen or a substituent selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, alkylcarboxylate, arylcarboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkylsulfinyl, or trialkylsilyl, wherein each of the substituents is substituted or ...

Complexes

The present invention provides a complex of formula (1), 2. The complex of claim 1 , wherein M is palladium.3. The complex of claim 1 , wherein Rand Rare tert-butyl.4. The complex of claim 1 , wherein Rand Rare cyclohexyl.5. The complex of claim 4 , wherein Rand Rare phenyl.6. The complex of claim 1 , wherein Rand Rare linked to form a 4- to 7-membered ring.7. The complex of claim 1 , wherein Ris phenyl claim 1 , 2-dimethylaminophenyl claim 1 , 3-dimethylaminophenyl claim 1 , or 4-dimethylaminophenyl.8. The complex of claim 1 , wherein Ris furanyl claim 1 , thiophenyl claim 1 , pyrrolyl claim 1 , pyridinyl claim 1 , or quinolinyl.9. The complex of claim 1 , wherein X is Cl.10. The complex of claim 1 , wherein each Ris independently methyl claim 1 , phenyl claim 1 , or substituted phenyl.12. A method for performing a carbon-carbon coupling reaction or a carbon-nitrogen coupling reaction in the presence of a catalyst claim 1 , the method comprising using a catalyst that is a complex of .13. A method for performing a carbon-carbon coupling reaction or a carbon-nitrogen coupling reaction in the presence of a catalyst claim 2 , the method comprising using a catalyst that is a complex of . This application is a divisional of U.S. patent application Ser. No. 13/806,575, filed Mar. 11, 2013, which is the National Stage of International Patent Application No. PCT/GB2011/051171, filed Jun. 22, 2011, which claims priority from U.S. Provisional Patent Application No. 61/357,744, filed Jun. 23, 2010, the disclosures of each of which are incorporated herein by reference in their entireties for any and all purposes.The present invention relates to transition metal complexes and, in particular, to π-allyl complexes, such as π-allylpalladium and π-allylnickel complexes. The invention also relates to the use of the transition metal complexes in coupling reactions.In many transitions metal mediated reactions, the active catalyst is formed in situ by the additional of a transition ...

Cross-Coupling Reaction Catalysts, and Methods of Making and Using Same

The present invention provides novel transition-metal precatalysts that are useful in preparing active coupling catalysts. In certain embodiments, the precatalysts of the invention are air-stable and moisture-stable. The present invention further provides methods of making and using the precatalysts of the invention. 2. The precatalyst of claim 1 , wherein each occurrence of M is independently selected from the group consisting of Pd claim 1 , Ni claim 1 , and Pt.3. The precatalyst of claim 1 , wherein at least one applies:(a) the two occurrences of M in (I) are identical;(b) the two ligands comprising 5-membered rings are identical;(c) each occurrence of Z is independently selected from the group consisting of CH and CR.46-. (canceled)7. The precatalyst of claim 1 , wherein each occurrence of X is independently selected from the group consisting of triflate claim 1 , pentafluoroethanesulfonate claim 1 , heptafluoropropanesulfonate claim 1 , and nonafluorobutanesulfonate.8. (canceled)11. The precatalyst of claim 9 , wherein M is selected from the group consisting of Pd claim 9 , Ni claim 9 , and Pt.12. (canceled)13. The precatalyst of claim 9 , wherein each occurrence of Z is independently selected from the group consisting of CH and CR.14. The precatalyst of claim 9 , wherein X is selected from the group consisting of triflate claim 9 , pentafluoroethanesulfonate claim 9 , heptafluoropropanesulfonate claim 9 , and nonafluorobutanesulfonate.15. (canceled)16. The precatalyst of claim 9 ,wherein L is selected from the group consisting of 1,3-bis(2,6-diisopropyl phenyl)-1,3-dihydro-2H-imidazol-2-ylidene and 1,3-bis(2,6-bis-(diphenylmethyl)-4-methoxyphenyl)imidazol-2-ylidene, orwherein L is a bidentate phosphine ligand.17. (canceled)18. The precatalyst of claim 16 , wherein L is a bidentate phosphine ligand selected from the group consisting of AmPhos (di-t-butylphosphino-4-dimethylaminobenzene) claim 16 , DavePhos (2-dicyclohexylphosphino-2′-(N claim 16 ,N- ...

INTEGRATED CAPTURE AND CONVERSION OF CO2 TO METHANOL OR METHANOL AND GLYCOL

A process for producing methanol includes combining a hydrogenation catalyst, hydrogen, and COwith a condensed phase solution comprising an amine under conditions effective to form methanol and water. A process for coproduction of methanol and a glycol includes combining an epoxide, a hydrogenation catalyst, hydrogen, and COwith a condensed phase solution comprising an amine under conditions effective to form methanol and a glycol. 1. A process , comprising:{'sub': 2', '2, 'producing methanol and a glycol by combining an epoxide, a hydrogenation catalyst, hydrogen, and COwith a condensed phase comprising an amine under conditions effective to provide a reaction between the epoxide, hydrogen, and COto form methanol and the glycol, wherein at least 10 mol % of the epoxide is consumed in the reaction.'}2. The process of claim 1 , wherein the condensed phase is a condensed phase solution further comprising the CO.3. The process of claim 2 , further comprising preparing the condensed phase solution by contacting a gas stream comprising COwith an amine-containing solvent or solution prior to combining the epoxide claim 2 , the hydrogenation catalyst claim 2 , and the hydrogen with the condensed phase solution.4. The process of claim 3 , wherein contacting the gas stream with the amine-containing solvent or solution is performed:(i) at a temperature T′ within a range of from 20° C. to 60° C.; or(ii) at an initial pressure P′ within a range of from 0.1 MPa to 5 MPa; or(iii) both (i) and (ii).5. The process of claim 1 , wherein the conditions effective to form methanol and the glycol comprise:{'sub': 'MG', '(i) a temperature Twithin a range of from 50° C. to 170° C.; or'}{'sub': 'MG', '(ii) an initial pressure Pwithin a range of from 3 MPa to 10 MPa; or'}{'sub': 'MG', '(iii) a time twithin a range of from 3 seconds to 36 hours; or'}(iv) any combination of (i), (ii), and (iii).6. The process of claim 1 , further comprising:{'sub': '2', '(i) combining the epoxide, the CO, and ...

MONONUCLEAR RUTHENIUM COMPLEX AND ORGANIC SYNTHESIS REACTION USING SAME

Provided is a mononuclear ruthenium complex that comprises a ruthenium-silicon bond that is represented by formula (1) and that exhibits excellent catalyst activity in each of a hydrosilylation reaction, a hydrogenation reaction, and reduction of a carbonyl compound. 2. The mononuclear ruthenium complex of wherein L is at least one two-electron ligand selected from the group consisting of molecular hydrogen claim 1 , amine claim 1 , imine claim 1 , nitrogen-containing heterocycle claim 1 , arsine claim 1 , alcohol claim 1 , thiol claim 1 , ether claim 1 , sulfide claim 1 , nitrile claim 1 , isonitrile claim 1 , aldehyde claim 1 , ketone claim 1 , C-Calkene claim 1 , C-Calkyne claim 1 , and triorganohydrosilane.3. The mononuclear ruthenium complex of or wherein n and m each are 2 claim 1 , and L is at least one ligand selected from sulfide claim 1 , thiol claim 1 , and triorganohydrosilane claim 1 , with the proviso that two L's may bond together.4. The mononuclear ruthenium complex of wherein Rto Rare each independently an alkyl claim 3 , aryl or aralkyl group which may be substituted with X which is as defined above claim 3 ,{'sup': 7', '8', '9', '10', '11', '12', '7', '12, "L's are triorganohydrosilanes represented by H—SiRRRand H—SiRRRwherein Rto Rare each independently an alkyl, aryl or aralkyl group which may be substituted with X which is as defined above,"}{'sup': 1', '3', '4', '6', '7', '9', '10', '12', '4', '6', '7', '9, 'at least one pair of any one of Rto Rand any one of Rto Ror any one of Rto R, or at least one pair of any one of Rto Rand any one of Rto Ror any one of Rto Rmay bond together to form a crosslinking substituent, or'}{'sup': 1', '3', '4', '6', '7', '9', '10', '12', '4', '6', '7', '9, 'at least one pair of any one of Rto Rand any one of Rto Ror any one of Rto Rmay bond together to form a crosslinking substituent, and at least one pair of any one of Rto Rand any one of Rto Ror any one of Rto Rmay bond together to form a crosslinking ...

Metallorganocatalysis For Asymmetric Transformations

A ligand having the structure or its enantiomer; (I) wherein: each one of R a , R b , R c and R d is selected from alkyl, cycloalkyl, and aryl; the bridge group is selected from CH 2 NH; *CH(CH 3 )NH(C*,R); and the organocatalyst is an organic molecule catalyst covalently bound to the bridge group. Also, a catalyst having the structure or its enantiomer: (II) wherein: each one of R a , R b , R c and R d is selected from alkyl, cycloalkyl, and aryl; the bridge group is selected from CH 2 NH; *CH(CH 3 )NH(C*,R); and *CH(CH 3 )NH(C*,S); the organocatalyst is an organic molecule catalyst covalently bound to the bridge group; and M is selected from the group consisting of Rh, Pd, Cu, Ru, Ir, Ag, Au, Zn, Ni, Co, and Fe.

P-CHIROGENIC ORGANOPHOSPHORUS COMPOUNDS

Novel P-chirogenic organophosphorus compounds of general formula (I), a process for the synthesis of the compounds of formula (I), and intermediate products of general formulae (II), (III) and (IV), as shown below, are involved in the synthesis of compounds (I). 2. The process according to claim 1 , wherein the electrophile is selected from the group consisting of boronate reagents claim 1 , aldehydes claim 1 , ketones claim 1 , acyl chlorides claim 1 , halosilanes claim 1 , haloalkanes claim 1 , and Michael acceptors such as α claim 1 ,β-insaturated ester claim 1 , α claim 1 ,β-insaturated ketones claim 1 , and α claim 1 ,β-insaturated phosphine derivatives.3. The process according to claim 1 , wherein the oxidative reagent is selected from the group consisting of transition metal salts and transition metal complexes claim 1 , wherein the metal is selected from the group comprising iron claim 1 , copper.4. The process according to claim 1 , wherein compound (VII) is chiral. The present invention relates to novel P-chirogenic organophosphorus compounds of general formula (I). The present invention also provides a process for the synthesis of said compounds of formula (I). The present invention also relates to intermediate products of general formulae (II), (III) and (IV), as shown below, which are involved in the synthesis of compounds (I).Compounds of general formula (I) may useful as agrochemical and therapeutic substances, or as reagents or intermediates for fine chemistry.Further, the invention relates to metal complexes comprising compounds (I) as ligands. The novel compounds and complexes of the present invention are useful in asymmetric catalysis by transition metal complexes or organocatalysis, especially for asymmetric hydrogenation or allylation.During the past decades, asymmetric organocatalysis and organometallic catalysis made a breakthrough and became methodologies of choice for the synthesis of chiral substances on laboratory as well as on industrial ...

COMPLEX CATALYSTS BASED ON AMINO-PHOSPHINE LIGANDS FOR HYDROGENATION AND DEHYDROGENATION PROCESSES

The present application discloses novel PWNN and PWNWP metal catalysts for organic chemical syntheses including hydrogenation (reduction) of unsaturated compounds or dehydrogenation of substrates. The range of hydrogenation substrate compounds includes esters, lactones, enals, enones, enolates, oils and fats, resulting in alcohols, enols, diols, and triols as reaction products. The catalysts of current application can be used to catalyze a hydrogenation reaction under solvent free conditions. The present catalysts also allow the hydrogenation to proceed without added base, and it can be used in place of the conventional reduction methods employing hydrides of the main-group elements. Furthermore, the catalysts of the present application can catalyze a dehydrogenation reaction under homogenous and/or acceptorless conditions. As such, the catalysts provided herein can be useful in substantially reducing cost and improving the environmental profile of manufacturing processes for a variety of chemicals. 2. The compound of claim 1 , wherein when R′ is PR claim 1 , R is H claim 1 , or when Rand R′ do not form part of a heteroaryl Ris H.3. The compound of claim 1 , wherein R′ taken together with Rand the atoms to which they are attached forms a substituted or unsubstituted heteroaryl claim 1 , such as pyridyl claim 1 , furanyl claim 1 , imidazolyl claim 1 , pyrazolyl or oxazolyl.54. The compound of any one of - claims 1 , wherein n is 1 claims 1 , or m is 1 or both n and m are 1.76. The compound of any one of - coordinated to a transition metal.8. The compound of claim 7 , wherein the transition metal is a group 7 (manganese group) metal claim 7 , a group 8 (iron group) metal claim 7 , group 9 (cobalt group) metal claim 7 , or group 10 (nickel group) metal.9. The compound of claim 7 , wherein the transition metal is Ru or Os.11. The metal complex of claim 10 , which comprises the PWNN ligand wherein R′ taken together with Rand the atoms to which they are attached forms a ...

PHENANTHROLINE BASED PINCER COMPLEXES USEFUL AS CATALYSTS FOR THE PREPARATION OF METHANOL FROM CARBONDIOXIDE

The present invention relates to a novel phenonthroline based pincer complexes and process for preparation thereof. The present invention also provides a one pot process for the conversion of carbon dioxide to methanol in the presence of a molecularly defined pincer-type single-site Ru-catalyst and secondary amine. Further the present invention provides the use of phenonthroline based pincer complexes for the esterification of alcohols and hydrogenation of esters under mild conditions. 3. The phenanthroline based pincer complexes of formula (I) as claimed in claim 1 , wherein the said catalyst is used for hydrogenation of lactones to diols and esters to alcohols4. The phenanthroline based pincer complexes of formula (I) as claimed in claim 1 , wherein the said catalyst is used for dehydrogenation of diols to lactones claim 1 , alcohol to esters and secondary alcohols to ketones.6. The process as claimed in claim 8 , wherein solvent used in step (a) is selected from hexane claim 8 , heptane claim 8 , tetrahydrofuran (THF) claim 8 , diethyl ether claim 8 , toluene claim 8 , and etheylbenzene.8. The process as claimed in claim 1 , wherein catalyst of formula 1 used in step (i) is selected from HCl(CO)Ru(Phen-(Bu)PNN) (3); H(CO)Ru-(Phen-(Bu)PNN) (4); H(CO)Ru(η1BH4)(Phen-(tBu)PNN) (5a); HCl(CO)Ru(BPy-PNN); [H(CO)Ru(BPy-PNN)]; and H(CO) Ru(Py-PNN)].9. The process as claimed in claim 7 , wherein said steps (ii) and (vi) are absent when [H(CO)Ru(BPy-PNN)] catalyst is used. The present invention relates to phenonthroline based pincer complex of formula (I) and process for preparation thereof. Particularly the present invention relates to use of phenonthroline based pincer complex of formula (I) as catalyst for the esterification of alcohols and hydrogenation of esters including lactones under mild conditions. More particularly the present invention relates to a one pot process for the conversion of carbon dioxide to methanol in the presence of a pincer based catalyst and a ...

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- ...

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.

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 , ...

Catalysts for (e)-selective olefin metathesis

This invention relates generally to olefin metathesis catalyst compounds, to the preparation of such compounds, and the use of such catalysts in the metathesis of olefins and olefin compounds, more particularly, in the use of such catalysts in (E)-selective olefin metathesis reactions. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemicals chemistry.

METHOD FOR IN-SITU FORMATION OF METATHESIS CATALYSTS

Synthetic methods for the in-situ formation of olefin metathesis catalysts are disclosed, as well as the use of such catalysts in metathesis reactions of olefins and olefin compounds. In one aspect, a method is provided for synthesizing an organometallic compound of the formula 2. The compound of claim 1 , wherein M is Ru or Os.3. The compound of claim 1 , wherein L claim 1 , L claim 1 , and Lare independently selected from phosphine claim 1 , sulfonated phosphine claim 1 , phosphite claim 1 , phosphinite claim 1 , phosphonite claim 1 , arsine claim 1 , stibine claim 1 , ether claim 1 , amine claim 1 , amide claim 1 , imine claim 1 , sulfoxide claim 1 , carboxyl claim 1 , nitrosyl claim 1 , pyridine claim 1 , substituted pyridine claim 1 , imidazole claim 1 , substituted imidazole claim 1 , pyrazine claim 1 , thioether claim 1 , and thiocarbonyl.4. The compound of claim 3 , wherein the phosphine is of the formula PRRR claim 3 , wherein R claim 3 , R claim 3 , and Rare each independently selected from aryl claim 3 , substituted aryl claim 3 , alkyl claim 3 , substituted alkyl claim 3 , cycloalkyl claim 3 , substituted cycloalkyl claim 3 , heterocycles claim 3 , and substituted heterocycles.5. The compound of claim 1 , wherein Xand Xare independently selected from hydrogen claim 1 , halide claim 1 , C-Calkyl claim 1 , C-Caryl claim 1 , C-Calkoxy claim 1 , C-Caryloxy claim 1 , C-Calkoxycarbonyl claim 1 , C-Caryloxycarbonyl claim 1 , C-Cacyl claim 1 , C-Cacyloxy claim 1 , C-Calkylsulfonato claim 1 , C-Carylsulfonato claim 1 , C-Calkylsulfanyl claim 1 , C-Carylsulfanyl claim 1 , C-Calkylsulfinyl claim 1 , or C-Carylsulfinyl claim 1 , any of which claim 1 , with the exception of hydrogen and halide claim 1 , are optionally further substituted with one or more groups selected from halide claim 1 , C-Calkyl claim 1 , C-Calkoxy claim 1 , and C-Caryl.9. A method of performing an olefin metathesis reaction claim 1 , comprising contacting the compound of with an olefin.10. The ...

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 ...

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- ...

LIGHT UPCONVERSION MICROCAPSULES

A composition, method, and article of manufacture are disclosed. The composition is a microcapsule that includes a transparent shell encapsulating a mixture comprising light upconversion molecules. The method is a method of forming a microcapsule, which includes obtaining light upconversion molecules, forming an emulsion of the light upconversion molecules and a shell formation solution, and encapsulating the light upconversion molecules in a transparent shell. The article of manufacture comprises the microcapsule. 1. A microcapsule , comprising:a transparent shell encapsulating a mixture, the mixture comprising light upconversion molecules.2. The microcapsule of claim 1 , wherein the light upconversion molecules comprise a molecular sensitizer and a molecular annihilator.3. The microcapsule of claim 1 , wherein the mixture further comprises a non-polar solvent.4. The microcapsule of claim 1 , wherein the transparent shell is a urea-formaldehyde shell.5. The microcapsule of claim 1 , wherein the light upconversion molecules comprise a molecular sensitizer selected from the group consisting of a transition metal complex of a porphyrin and a transition metal complex of a phthalocyanine.6. The microcapsule of claim 1 , wherein the light upconversion molecules comprise a molecular annihilator selected from the group consisting of a furanyldiketopyrrolopyrrole and a perylene.7. A method of forming a microcapsule claim 1 , comprising:obtaining light upconversion molecules;forming an emulsion that includes the light upconversion molecules and a shell formation solution; andencapsulating the light upconversion molecules in a transparent shell.8. The method of claim 7 , wherein the light upconversion molecules comprise a molecular sensitizer and a molecular annihilator.9. The method of claim 8 , further comprising:forming a reaction system that includes the microcapsule, a photocatalyst, and a substrate; andexposing the reaction system to light having sufficient energy to ...

SURFACE-MODIFIED LIGHT UPCONVERSION SILICA PARTICLES

A composition, method, and article of manufacture are disclosed. The composition includes a silica particle with light upconversion molecules bound to its surface. The method includes obtaining silica particles and light upconversion molecules having sidechains with reactive functional groups. The method further includes binding the light upconversion molecules to surfaces of the silica particles. The article of manufacture includes the composition. 1. A composition , comprising:a silica particle; andlight upconversion molecules bound to a surface of the silica particle.2. The composition of claim 1 , wherein the light upconversion molecules comprise molecular sensitizers.3. The composition of claim 1 , wherein the light upconversion molecules comprise molecular annihilators.4. The composition of claim 1 , wherein the light upconversion molecules comprise molecular annihilators and molecular sensitizers.5. The composition of claim 1 , wherein the surface of the silica particle includes a first face and a second face.6. The composition of claim 5 , wherein the light upconversion molecules comprise molecular sensitizers bound to the first face of the silica particle.7. The composition of claim 6 , wherein the light upconversion molecules comprise molecular annihilators bound to the second face of the silica particle.8. A method of forming surface-modified particles claim 6 , comprising:obtaining silica particles;obtaining light upconversion molecules having sidechains with reactive functional groups; andbinding the light upconversion molecules to surfaces of the silica particles.9. The method of claim 8 , wherein the reactive functional groups are silyl groups.10. The method of claim 8 , further comprising forming a reaction environment claim 8 , the reaction environment comprising:the surface-modified particles;a photocatalyst; anda substrate.11. The method of claim 8 , wherein the silica particles are Janus particles.12. The method of claim 8 , wherein the light ...

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.

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.

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.

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.

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 ...

HYDROCARBON POLYMERS HAVING TWO AZLACTONE END GROUPS

Fis formula (IIa) and Fis formula (IIb): 2. Hydrocarbon polymer according to claim 1 , characterized in that:{'sup': 14', '15, 'sub': 1', '4, 'the Rand Rradicals represent a C-Calkyl radical or else form, with the carbon atom to which they are connected, a cyclohexyl radical;'}g and d represent 0 or 1;{'sup': 1', '2', '3', '4', '5', '6', '7', '8, 'R, R, R, R, R, R, Rand Rrepresent a hydrogen atom or an alkyl radical comprising from 1 to 14 carbon atoms;'}x and y are within a range extending from 0 to 2, the sum x+y being within a range extending from 0 to 2;{'sup': 9', '10', '11', '12, 'R, R, Rand Rrepresent a hydrogen atom or a radical, the hydrocarbon part of which comprises from 1 to 14 carbon atoms;'}{'sup': '13', 'sub': '2', 'Rrepresents the divalent —CH— radical;'}z is an integer equal to 1 or 2; andthe number-average molecular weight Mn is within a range extending from 3000 to 50 000 g/mol.8. An adhesive comprising the hydrocarbon polymer as defined in claim 1 , as a mixture in stoichiometric amounts with an amino compound comprising at least two amine groups.9. Process for assembling two substrates by adhesive bonding claim 1 , comprising:{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'coating, on at least one of the two substrates to be assembled, with a liquid adhesive composition obtained by mixing an amino compound comprising at least two amine groups with the hydrocarbon polymer as defined in ; then'}actually bringing the two substrates into contact. A subject matter of the present invention is hydrocarbon polymers comprising two azlactone (also known as oxazolone) end groups, their preparation and their use as adhesive.Polyurethanes are widely used in the field of adhesives, due to the versatility of their properties, rendered possible by their very high number of structural forms.Polyurethanes are conventionally synthesized by reaction between a diol and a diisocyanate. Diisocyanates are toxic compounds as such and are generally obtained from ...

CATALYST COMPOSITIONS AND THEIR USE FOR HYDROGENATION OF NITRILE RUBBER

This invention relates to novel catalyst compositions based on Ruthenium- or Osmium-based complex catalysts of the Grubbs-Hoveyda, Grela or Zhan type and specific co-catalysts comprising at least one vinyl group, pref. ethyl vinyl ether, and to a process for selectively hydrogenating nitrile rubbers in the presence of such catalyst compositions, preferably with a preceding metathesis step using the same complex catalyst as in the hydrogenation step. 2. The catalyst composition according to wherein the co-catalyst has the general formula (1){'br': None, 'sub': '2', 'CH═CRR′\u2003\u2003(1)'}in which R and R′ are identical or different and shall meanhydrogen or{'sup': 1', '1', '2', '2', '2', '3', '4, 'sub': 2', '2', 'n', 'm', '2', 'n', 'm', '2', '2', 'p', '2, 'claim-text': wherein', {'sup': '2', 'X is identical or different and means oxygen (O) or NR'}, {'sup': '2', 'Rare identical or different and represent H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl,'}, {'sup': '3', 'sub': 1', '8', '2', 'n', '2, 'Rare identical or different and represent C-Calkyl or —(CH)—O—CH═CH,'}, {'sup': '4', 'sub': 2', 'p', '2, 'Rrepresents (CH)—O—CH═CH,'}, 'n is in the range of from 1 to 5,', 'm is in the range of from 1 to 10,', 'p is in the range of from 0 to 5, or', {'sup': 1', '1', '2', '2, 'sub': 2', 'q, 'where in the alternative, if R and R′ both represent a group OR, both Rmay be linked to each other and together represent a divalent group —(C(R))— with q being 2, 3 or 4 and Rbeing identical or different and having the above defined meanings, or'}], 'ORwherein Rshall mean alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, C(═O)(R), —C(═O)N(R), —[(CH)—X]R, —[(CH)—X]—CH═CH, or —(CH)—C(R)R'}{'sup': 5', '5', '5, 'sub': '2', 'SR, SOR, SOR'}{'sup': '5', 'wherein Rrepresents alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl, or'}{'sup': 6', '7', '6', '7, 'N(RR), P(RR)'}{'sup': 6', '7', '2, 'wherein Rand Rare identical or different and shall mean alkyl, cycloalkyl, ...

Chiral synthesis of fused bicyclic raf inhibitors

The present disclosure generally relates to improved synthesis of fused bicyclic Raf inhibitor enantiomers of formula (I), (Ia), (Ib), (II), (IIa), or (IIb), or a pharmaceutically acceptable salt, tautomer, or stereoisomer thereof, with high enantiomeric excess (% ee). The disclosure also relates to method of using the compound of formula (I), (Ia), (Ib), (II), (IIa), or (IIb), or a pharmaceutically acceptable salt, tautomer, or stereoisomer thereof, for treating diseases such as cancer, including colorectal cancer.

METHOD OF PRODUCING DIALDEHYDE COMPOUND

A method of producing 1,5-pentanedial having an alkyl group at the 3-position, including a step of hydroformylating an aldehyde compound represented by the following general formula (1): 2. The production method according to claim 1 , wherein the hydroformylating step is performed in the presence of a Groups 8 to 10 metal compound and a ligand.3. The production method according to claim 2 , wherein the Groups 8 to 10 metal compound is a rhodium compound. The present invention relates to a method of producing a dialdehyde compound. Specifically, the present invention relates to a method of producing 1,5-pentanedial having an alkyl group at the 3-position.Various compounds have been known as 1,5-pentanedial having an alkyl group at the 3-position. For example, 3-methylglutaraldehyde (3-methyl-1,5-pentanedial, which is hereinafter abbreviated as MGL) is a compound that is useful as a curing agent for a photosensitive material, a leather tanning agent, and a synthetic intermediate (see, for example, PTLs 1 to 3). The known production methods of MGL include a method of hydrolyzing pyranyl ether obtained through Diels-Alder reaction of crotonaldehyde and methyl vinyl ether (see NPLs 1 and 2).The aforementioned ordinary method has room for improvement since the Diels-Alder reaction of crotonaldehyde and methyl vinyl ether has low reactivity and requires severe conditions including a high temperature and a high pressure, the productivity thereof is insufficient due to the prolonged reaction time, and the yield of MGL is low. Accordingly, an object of the present invention is to provide a method of producing 1,5-pentanedial having an alkyl group at the 3-position, such as MGL, under mild conditions with a good yield.The present invention relates to the following items [1] to [4].[1] A method of producing a dialdehyde compound represented by the following general formula (2) (which is hereinafter referred to as a dialdehyde compound (2)):wherein Rrepresents an alkyl group ...

NOVEL IMINES WITH TUNABLE NUCLEOPHILICITY AND STERIC PROPERTIES THROUGH METAL COORDINATION: APPLICATIONS AS LIGANDS AND METALLOORGANOCATALYSTS

The invention describes phospho-amino pincer-type ligands, metal complexes thereof, and catalytic methods comprising such metal complexes for conversion of carbon dioxide to methanol, conversion of aldehydes into alcohols, conversion of aldehydes in the presence of a trifluoromethylation agent into trifluorinated secondary alcohols, cycloaddition of carbon dioxide to an epoxide to provide cyclic carbonates or preparation of an amide from the combination of an alcohol and an amine. 2. The composition of claim 1 , wherein R claim 1 , R claim 1 , R claim 1 , and Rare each a alkyl claim 1 , each Z is CH and Ris a hydrogen atom.3. The composition of claim 2 , wherein R claim 2 , R claim 2 , R claim 2 , and Rare each a Calkyl.4. The composition of claim 2 , wherein Ris a methyl group or a hydrogen.5. The composition of claim 1 , wherein X is a hydride.6. The composition of claim 1 , wherein X is a halide.7. The composition of claim 1 , wherein the base is an organic base.8. The composition of claim 7 , wherein the organic base is an amine or an alkoxide.9. The composition of claim 8 , wherein the amine is an alkylamine comprising NRRR claim 8 , wherein R claim 8 , R claim 8 , and Rare each independently a hydrogen atom claim 8 , alkyl claim 8 , aryl claim 8 , aralkyl claim 8 , or a substituted version of any one of these groups claim 8 , wherein one or more of R claim 8 , R claim 8 , and Rcan form a ring or an aromatic amine.10. The composition of claim 9 , wherein the aromatic amine is pyridine. This International Application claims priority to U.S. Provisional Patent Application Ser. No. 62/049,022, filed Sep. 11, 2014, entitled “Novel Imines with tunable nucleophilicity and steric properties through metal coordination: Applications as ligands and Metalloorganocatalysts”, the contents of which are incorporated herein in their entirety for all purposes.The present invention relates generally to the field of chemistry and catalysis. More particularly, it relates to ...

STABLE POLYCYCLOOLEFIN POLYMER AND INORGANIC NANOPARTICLE COMPOSITIONS AS OPTICAL MATERIALS

Embodiments in accordance with the present invention encompass compositions encompassing a latent organo-ruthenium catalyst, an organo-ruthenium compound and a pyridine compound along with one or more monomers which undergo ring open metathesis polymerization (ROMP) when said composition is heated to a temperature from 80° C. to 150° C. or higher to form a substantially transparent film. Alternatively the compositions of this invention also undergo polymerization when subjected to suitable radiation. The monomers employed therein have a range of refractive index from 1.4 to 1.6 and thus these compositions can be tailored to form transparent films of varied refractive indices. The compositions of this invention further comprises inorganic nanoparticles which form transparent films and further increases the refractive indices of the compositions. Accordingly, compositions of this invention are useful in various opto-electronic applications, including as coatings, encapsulants, fillers, leveling agents, among others. 2. The composition according to claim 1 , wherein said composition comprises first and second monomer of formula (I) distinct from each other and one of said first and second monomers having a refractive index of at least 1.5 and viscosity below 100 centipoise claim 1 , and wherein said first monomer is completely miscible with said second monomer to form a clear solution.3. The composition according to claim 1 , wherein said composition forms a substantially transparent film when heated to a temperature from 80° C. to 150° C.4. The composition according to claim 3 , wherein said film has a transmission of equal to or higher than 90 percent of the visible light.5. The composition according to claim 3 , wherein said film has a transmission of equal to or higher than 95 percent of the visible light.7. The composition according to claim 1 , wherein in the organo-ruthenium compound of formula (II):X is chlorine;{'sub': 7', '8, 'Rand Rare the same or different ...

PALLADIUM CATALYSTS WITH IMPROVED PERFORMANCE IN BIOLOGICAL ENVIRONMENTS

Provided herein are palladium (Pd) catalysts with improved performance in biological environments. In particular, formulations, methods of preparations, and storage conditions are provided that provide improved performance of Pd catalysts under protein-rich conditions. 1. A Pd catalyst composition comprising phosphine-coordinated palladium ions , wherein phosphine ligand is present at 6-12 fold excess over palladium in the composition.2. The Pd catalyst composition of claim 1 , wherein the phosphine ligand is a strong π-acceptor aryl phosphine.3. (canceled)4. The Pd catalyst composition of claim 3 , wherein the phosphine ligand is selected from the group consisting of DANPHOS claim 3 , o-DANPHOS claim 3 , p-DANPHOS claim 3 , DAN2PHOS claim 3 , o-DAN2PHOS p-DAN2PHOS claim 3 , and DANPHOS/DAN2PHOS derivatives with alternative solubilizing groups.5. The Pd catalyst composition of claim 4 , wherein the phosphine ligand is o-DANPHOS.6. The Pd catalyst composition of claim 1 , wherein the palladium is provided as a Palladium(II) salt selected from the group consisting of: Palladium acetate (Pd(OAc)) claim 1 , Palladium trifluoroacetate (Pd(TFA)) claim 1 , Palladium nitrate (Pd(NO)) claim 1 , Palladium chloride (PdCl) claim 1 , Palladium bromide (PdBr) claim 1 , Sodium tetrachloropalladate (NaPdCl) claim 1 , Potassium tetrachloropalladate (KPdCl) claim 1 , Lithium tetrachloropalladate (LiPdCl) claim 1 , Sodium tetrabromopalladate (NaPdBr) claim 1 , Potassium tetrabromopalladate (KPdBr) claim 1 , Pd(dibenzylideneacetone) claim 1 , Pd(dibenzylideneacetone) claim 1 , and Buchwald precatalysts.7. The Pd catalyst composition of claim 1 , wherein the phosphine-coordinated palladium ions are in aqueous solution.8. The Pd catalyst composition of claim 1 , wherein the phosphine-coordinated palladium ions are lyophilized.910.-. (canceled)11. A method for the preparation of a Pd catalyst claim 1 , comprising combining a palladium(II) salt with a phosphine ligand in buffered or un- ...

TRANSFER HYDROGENATION OF CYCLOPAMINE ANALOGS

Provided herein is a process for the transfer-hydrogenation of ketone analogs of members of the jervine type of alkaloids, such as cyclopamine. Also provided herein are novel ruthenium transfer-hydrogenation catalysts. 3. The process of wherein the ring carbon atom that is directly attached to the hydroxyl group on the compound of formula (II-AA) has an (S) stereochemical configuration and Ris hydrogen in the β-position.4. The process of claim 1 , wherein the ruthenium transfer-hydrogenation catalyst comprises an amino alcohol ligand.5. The process of claim 4 , wherein the amino alcohol ligand is achiral.7. The process of claim 6 , wherein Rand Rare both —CHand Ris —CHCH.8. The process of claim 1 , wherein the ruthenium transfer-hydrogenation catalyst comprises an optionally substituted benzene ligand.9. The process according to claim 8 , wherein the optionally substituted benzene ligand is selected from benzene claim 8 , mesitylene claim 8 , p-cymene claim 8 , and hexamethylbenzene.10. The process according to claim 9 , wherein the ruthenium transfer-hydrogenation catalyst is generated from (hexamethylbenzene)ruthenium chloride dimer and an achiral amino alcohol.14. The process according to claim 13 , wherein Xis chloro.17. The process of claim 16 , wherein Rand Rare each methyl claim 16 , Ris ethyl claim 16 , each of R claim 16 , R claim 16 , R claim 16 , R claim 16 , R claim 16 , and Ris methyl claim 16 , and Xis Cl.18. The process of claim 1 , wherein the hydrogen donor is an organic alcohol.19. The process of claim 18 , wherein the reducing is carried out in an ether solvent.20. The process of claim 19 , wherein the reducing is carried out at a temperature of about 10° C. to about 40° C.21. The process of claim 19 , wherein the reducing is carried out in the presence of base. This application is a continuation of U.S. patent application Ser. No. 13/232,851, filed Sep. 14, 2011, now allowed, which claims the benefit of U.S. Provisional Patent Application No. 61/ ...

BIS(PHOSPHINE)-CARBODICARBENE CATALYST COMPLEXES AND METHODS OF USING THE SAME

An organometallic complex of a tridentate bis(phosphine)-carbodicarbene ligand and a transition metal, is described. In some embodiments the ligand has the structure of Formula (I): The complexes are useful in methods of making an allylic amine carried out by reacting a 1,3-diene with a substituted amine in the presence of such an organometallic complex to produce by intermolecular hydroamination the allylic amine. 1. An organometallic complex , comprising:(a) a tridentate bis(phosphine)-carbodicarbene ligand, and(b) a transition metal.4. The complex of claim 1 , wherein said transition metal is selected from the group consisting of ruthenium claim 1 , nickel claim 1 , palladium claim 1 , platinum claim 1 , rhodium claim 1 , iridium claim 1 , cobalt claim 1 , iron claim 1 , silver claim 1 , gold claim 1 , and molybdenum.5. The complex of claim 2 , wherein R claim 2 , R claim 2 , R claim 2 , and Rare each independently selected alkyl or aryl.6. The complex of claim 2 , wherein at least one R′ is S-L- claim 2 , where S is a solid support and L is a linking group.7. The complex of claim 2 , wherein each R′ is independently hydrogen claim 2 , halo claim 2 , loweralkyl claim 2 , loweralkoxy claim 2 , or hydroxyl.8. A reaction mixture comprising an organometallic complex of claim 1 , a solvent claim 1 , a 1-3 claim 1 , diene substrate claim 1 , and a substituted amine substrate.11. A method of making an allylic amine claim 1 , comprising:{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'reacting a 1,3-diene with a substituted amine in the presence of an organometallic complex of in a catalytic amount to produce by intermolecular hydroamination said allylic amine.'}14. A tridentate bis(phosphine)-carbodicarbene pincer ligand. This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/979,749, filed Apr. 15, 2014, the disclosure of which is incorporated by reference herein in its entirety.The present invention concerns carbodicarbene ligands, ...

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( ...

METHODS FOR RECOVERING AND REUSING SELECTIVE HOMOGENEOUS HYDROGENATION CATALYST

The present invention pertains to a method for recovering a selective homogeneous hydrogenation catalyst and a method for reusing the recovered selective homogeneous hydrogenation catalyst. The method for recovering a selective homogeneous hydrogenation catalyst comprises: a step for synthesizing cyclododecene by selectively hydrogenating a first reaction solution containing cyclododecatriene, triphenylphosphine, formaldehyde, and ruthenium chloride, wherein a selective homogeneous hydrogenation catalyst is prepared during the selective hydrogenation reaction from the triphenylphosphine, formaldehyde, and ruthenium chloride to synthesize the cyclododecene; and a step for distilling and separating unreacted cyclododecatriene and cyclododecadiene, as well as the product cyclododecene, from a second reaction solution in which the cyclododecene synthesis has been completed, and recovering the selective homogeneous hydrogenation catalyst. 1. A method for recovering a selective homogeneous hydrogenation catalyst , comprising:a step of synthesizing cyclododecene by selectively hydrogenating a first reaction solution containing cyclododecatriene, triphenylphosphine, formaldehyde, and ruthenium chloride, the cyclododecene being synthesized by preparation of a selective homogeneous hydrogenation catalyst from the triphenylphosphine, the formaldehyde, and the ruthenium chloride during the selective hydrogenation; anda step of distilling and separating unreacted cyclododecatriene and cyclododecadiene, and the cyclododecene that is a product from a second reaction solution in which the cyclododecene synthesis is completed, and recovering the selective homogeneous hydrogenation catalyst.2. The method of claim 1 , wherein the distillation and separation is performed at a temperature of 100 to 200° C. and a pressure of 0.5 bar or less.3. The method of claim 1 , wherein the recovering of the selective homogeneous hydrogenation catalyst is performed at a temperature of 10 to 30° C. ...

TRANSITION METAL COMPLEX CONTAINING SULFONAMIDE OR AMIDE GROUP FOR OLEFIN METATHESIS REACTION AND APPLICATION THEREOF

Disclosed is a novel transition metal complex containing N-heterocyclic carbene and a sulfonamide group, or N-heterocyclic carbene and an amide group, and application thereof, the transition metal complex having a wider range of general purposes in olefin metathesis and being able to be variably controlled in reactivity. 1. A transition metal complex , represented by the following Chemical Formula A:{'br': None, '(L1)M(A)(L2)n(L3)m \u2003\u2003[Chemical Formula A]'}wherein,M is a transition metal,L1 means a phosphine ligand or N-heterocyclic carbene ligand containing a substituted or unsubstituted alkyl of 1 to 30 carbon atoms or a substituted or unsubstituted aryl of 6 to 30 carbon atoms,L2 and L3, which are the same or different, are each a monovalent ligand selected from among a hydrogen atom, a deuterium atom, a halogen, a cyano, a substituted or unsubstituted alkyl of 1 to 30 carbon atoms, a substituted or unsubstituted aryl of 6 to 50 carbon atoms, a substituted or unsubstituted arylalkyl of 7 to 50 carbon atoms, a substituted or unsubstituted alkenyl of 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl of 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl of 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy of 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy of 6 to 30 carbon atoms, a substituted or unsubstituted arylthioxy of 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy of 1 to 30 carbon atoms, a substituted or unsubstituted heteroaryl of 2 to 50 carbon atoms bearing O, N, or S as a heteroatom, a substituted or unsubstituted carboxylate anion of 1 to 30 carbon atoms, and a nitrate (NO3-); ora neutral ligand selected from among a phosphine containing a substituted or unsubstituted alkyl of 1 to 30 carbon atoms or a substituted or unsubstituted aryl of 6 to 50 carbon atoms, carbon monoxide, an amine containing a substituted or ...

MONOCARBONYL RUTHENIUM AND OSMIUM CATALYSTS

The invention relates to monocarbonyl complexes of ruthenium and osmium with bi- and tridentate nitrogen and phosphine ligands. The invention relates to methods for preparing these complexes and the use of these complexes, isolated or prepared in situ, as catalysts for reduction reactions of ketones and aldehydes both via transfer hydrogenation or hydrogenation with hydrogen. 3. The complex of claim 1 , of formula (VII):{'br': None, '[MX(CO)(NN)(PP)]W \u2003\u2003(VII)'}{'sub': 2', '2', '2', '2', '2, 'provided that when X is Cl or H, (NN) is not ethylenediamine or 2-(aminomethyl)pyridine and the diphosphine (PP) is not PhP(CHCHCH)PPh.'}4. The complex of claim 1 , of formula (VIII):{'br': None, 'MXY(CO)(HCNN)(P) \u2003\u2003(VIII).'}5. The complex of claim 1 , of formula (IX):{'br': None, 'MX(CO)(CNN)(P) \u2003\u2003(IX).'}7. The complex of claim 1 , of formula (XI):{'br': None, 'MX(CO)(CP)(HCP) \u2003\u2003(XI)'}{'sup': 23', '21', '22, 'sub': '3', 'provided that when X is Cl and Ris —CH, R-Rare not phenyl.'}8. The complex of claim 1 , of formula (XII):{'br': None, 'MXY(CO)(PP)(P) \u2003\u2003(XII).'}9. The complex of claim 1 , of formula (XIII):{'br': None, 'MXY(CO)(HCN)(PP) \u2003\u2003(XIII).'}10. The complex of claim 1 , of formula (XIV):{'br': None, 'MXY(CO)(PNN) \u2003\u2003(XIV).'}11. The complex of claim 1 , wherein X and Y are the same and are Cl claim 1 , H claim 1 , a C1-C20 alkoxide claim 1 , or a C1-C20 carboxylate.18. A process for preparing a complex of formula (XII) of claim 8 , comprising reacting a compound of formula MXY(CO)(PPh) claim 8 , or formula MXY(CO)(PPh)(dmf) claim 8 , wherein (dmf) is dimethylformamide claim 8 , with a phosphine (P) that is:{'sup': 16', '17', '18', '16', '18, 'a phosphine of formula PRRR, wherein R-Rare each, independently, H, a C1-C20 aliphatic group, or a C5-C20 aromatic group; or'}an optically active phosphine that is (S)-neomenthyldiphenylphosphine or (R)-(+)-2-(diphenylphosphino)-2′-methoxy-1,1′-binaphthyl;or a ...

HIGHLY EFFICIENT PROCESS FOR THE PREPARATION OF SITAGLIPTIN VIA RHODIUM CATALYZED ASYMMETRIC HYDROGENATION

The present invention provides highly efficient process for the preparation of enantiomerically enriched Sitagliptin of Formula (Ia). More particularly, a direct rhodium catalyzed asymmetric hydrogenation in the presence of bis-phosphine chiral ligand has been developed to yield enantiopure Sitagliptin product with the highest enantiomeric excess of 85-99.9%. 14-. (canceled)6. The process of claim 5 , wherein the rhodium catalyst is [Rh(COD)OTf].7. The process of claim 6 , wherein the additive is selected from the group consisting of salicylic acid claim 6 , acetic acid claim 6 , ammonium chloride claim 6 , phosphoric acid claim 6 , ammonium salicylate claim 6 , tetramethyl ammonium iodide claim 6 , tetraethyl ammonium iodide claim 6 , tetra butyl ammonium bromide claim 6 , butyl phosphoric acid claim 6 , dibutyl phosphate claim 6 , and tributyl phosphate.8. The process of claim 6 , wherein the solvent is selected from the group consisting of methanol claim 6 , dichloromethane claim 6 , tetrahydrofuran claim 6 , trifluoroethanol claim 6 , toluene claim 6 , 1 claim 6 ,4-dioxane claim 6 , and ethyl acetate. This application is a national-stage application under 35 U.S.C. § 371 of International Application No. PCT/IN2019/050896, filed Dec. 9, 2019, which International Application claims benefit of priority to Indian Application No. 201811046767, filed Dec. 11, 2018.The present disclosure provides highly efficient process for the preparation of enantiomerically enriched Sitagliptin. More particularly, a direct rhodium catalyzed asymmetric hydrogenation in the presence of bis-phosphine chiral ligand has been developed to yield enantiopure Sitagliptin product with the highest enantiomeric excess of 85-99.9%.Beta amino acids and its derivatives have lot of medicinal significance. Beta amino acids are also present in peptides and different heterocycles. In beta amino acids, the amino group is linked to the beta carbon. Different free forms and derivatives of beta amino acid ...

PHOSPHINE SUBSTITUTED FERROCENYL COMPLEX

A functionalized magnetic nanoparticle including an organometallic sandwich compound and a magnetic metal oxide. The functionalized magnetic nanoparticle may be reacted with a metal precursor to fol in a catalyst for various C—C bond forming reactions. The catalyst may be recovered with ease by attracting the catalyst with a magnet. 2. (canceled)3. The complex of claim 1 , wherein Ris an optionally substituted alkyl.4. The complex of claim 1 , wherein Ris an optionally substituted aryl.5. The complex of claim 1 , wherein X is NH.620-. (canceled) This application claims the priority of the filing date of the U.S. Provisional Patent Application No. 62/406,449 filed Oct. 11, 2016, the disclosure of which is hereby incorporated herein by reference in its entirety.This project was funded by the National Plan for Science, Technology and Innovation (MAARIFAH)-King Abdulaziz City for Science and Technology through the Science and Technology Unit at King Fahd University of Petroleum and Minerals (KFUPM), the Kingdom of Saudi Arabia, award number 15-NAN4650-04.Aspects of this technology are described in an article “Magnetic nanoparticle-supported ferrocenylphosphine: a reusable catalyst for hydroformylation of alkene and Mizoroki-Heck olefination” by M. Nasiruzzaman Shaikh, Md. Abdul Aziz, Aasif Helal, Mohamed Bououdina, Zain H. Yamania, and Tae-Jeong Kim, in RSC Advances, 2016, pages 41687-41695, which is incorporated herein by reference in its entirety.The present disclosure relates to a functionalized magnetic nanoparticle including an organometallic sandwich compound and a functional group which can bind to a nanoparticle. The disclosure also relates to a magnetic catalyst which catalyzes C—C bond forming reactions such as hydroformylation and the Mizoroki-Heck coupling reaction.Carbon-carbon bond formation reactions mediated by various transition metals have emerged as increasingly important methodologies for the preparation of numerous organic building blocks for drugs, ...

Process for the Decarboxylation, Isomerization, Hydrogenation, Dehydrogenation and Cyclization Aromatization of Fatty Acids Yielding Products with Significant Aromatic Content

Disclosed herein are processes for the decarboxylation, isomerization, hydrogenation, dehydrogenation, and cyclization/aromatization of fatty acids involving contacting a starting material which is an unsaturated fatty acid, unsaturated fatty acid derivative, or an unsaturated triglyceride, in the presence of a catalyst at a temperature at which decarboxylation, isomerization, hydrogenation, dehydrogenation, and cyclization/aromatization occurs and recovering the unsaturated organic compound product; wherein the catalyst is chloro-1,5-cyclooctadiene iridium (I) dimer. The product may contain at least about 8% by volume aromatic content and less than about 25% by volume aromatic content, and wherein the product contains less than about 1% by volume of naphthalenes.

CATALYSTS FOR ELECTROLESS METALLIZATION CONTAINING FIVE-MEMBERED HETEROCYCLIC NITROGEN COMPOUNDS

Catalysts include five-membered nitrogen containing heterocyclic compounds as ligands for metal ions which have catalytic activity. The catalysts are used to electrolessly plate metal on metal clad and un-clad substrates. 16-. (canceled)8: The catalyst of claim 7 , wherein the one or more compounds are chosen from hydantoin claim 7 , 1-methylhydantoin claim 7 , 1 claim 7 ,3-dimethylhydantoin claim 7 , 5 claim 7 ,5-dimethylhydantoin claim 7 , allantoin claim 7 , 1 claim 7 ,3-dihydroxymethyl-5 claim 7 ,5-dimethylhydantoin and succinimide.9: The catalyst of claim 7 , wherein a molar ratio of the one or more compounds to metal ions is from 1:1 to 4:1.10: The catalyst of claim 7 , wherein the one or more compounds are in amounts of 25 ppm to 1000 ppm. The present invention is directed to catalysts for electroless metallization containing five-membered heterocyclic nitrogen compounds. More specifically, the present invention is directed to catalysts for electroless metallization containing five-membered heterocyclic nitrogen compounds which are stable during storage and electroless metallization.Conventional printed circuit boards (PCBs) consist of laminated non-conductive dielectric substrates that rely on drilled and plated through holes (PTHs) to form a connection between the opposite sides and/or inner layers of a board. Electroless plating is a well-known process for preparing metallic coatings on surfaces. Electroless plating of a dielectric surface requires the prior deposition of a catalyst. The most commonly used method to catalyze or activate laminated non-conductive dielectric substrate regions, prior to electroless plating, is to treat the board with an aqueous tin-palladium colloid in an acidic chloride medium. The colloid consists of a metallic palladium core surrounded by a stabilizing layer of tin(II) ions. A shell of [SnCl] complexes act as surface stabilizing groups to avoid agglomeration of colloids in suspension.In the activation process, the palladium ...

Process for the separation and purification of a mixed diol stream

Disclosed is a process for the purification of a mixed diol stream. The mixed diol stream comprising two-, three-, and four-carbon diols is separated into component diols by extraction with a hydrophobic solvent mixture. The diols recovered in the extractant may be removed from the extractant stream by back extraction with water or by distillation with an azeotrope-forming agent present, preferably an azeotroping agent already present in the extractant mixture.

PROCESS FOR RUTHENIUM-CATALYZED TRANSVINYLATION OF CARBOXYLIC ACIDS

The invention relates to a process for transvinylation of a carboxylic acid feedstock with a vinyl ester feedstock to obtain a vinyl ester product and the corresponding acid of the vinyl ester feedstock in the presence of one or more ruthenium catalysts, wherein a) the vinyl ester feedstock, the carboxylic acid feedstock and a ruthenium catalyst are fed to the reactor, and b) the transvinylation reaction is carried out, characterized in that a carbonyl-free Ru(III) carboxylate is used as the ruthenium catalyst and in that no carbon monoxide is supplied, c) the reaction is carried out at a temperature of 110 to 170° C., d) upon completion of the transvinylation reaction, the vinyl ester feedstock and the corresponding acid are separated from the reaction mixture by distillation, e) the vinyl ester product is separated by distillation from the bottom product of the distillation, and f) the remaining reaction mixture is recycled into the reactor. 1. A process for transvinylation of a reactant carboxylic acid with a reactant vinyl ester to afford a product vinyl ester and the corresponding acid of the reactant vinyl ester in the presence of one or more ruthenium catalysts , whereina) the reactant vinyl ester, the reactant carboxylic acid and a ruthenium catalyst are supplied to the reactor, andb) the transvinylation reaction is performed,whereinthe ruthenium catalyst employed is a carbonyl-free Ru(III) carboxylate and no carbon monoxide is supplied,c) the reaction is performed at a temperature of 110° C. to 170° C.,d) after completion of the transvinylation reaction the reactant vinyl ester and the corresponding acid are distillatively removed from the reaction mixture, ande) the product vinyl ester is distillatively removed from the bottoms product of the distillation, andf) the remaining reaction mixture is recycled into the reactor.2. The process as claimed in claim 1 , wherein the residence time in the reaction zone is 0.25 to 5 hours.3. The process as claimed in ...

Method of Manufacturing Nitrone Compound

A method of manufacturing nitrone compounds is provided. The method includes: providing a nitro compound; and performing a photoreaction of the nitro compound, a catalyst and an additive under visible light to obtain the nitrone compound. 1. A method of manufacturing nitrone compound , comprising:providing a nitro compound; andperforming a photoreaction of the nitro compound, a catalyst and an additive under visible light to obtain the nitrone compound.2. The method of claim 1 , wherein the catalyst is Ru(bpy)Cl.6HO claim 1 , Ru(bpy)Cl claim 1 , Ru(bpy)(BF) claim 1 , Ru(bpy)(PF) claim 1 , Ir[dF(CF)ppy](dtbbpy)(PF) or Ir(ppy)(dtbbpy)(PF).3. The method of claim 1 , wherein a wavelength of the visible light is within the range of 350 to 700 nm.4. The method of claim 3 , wherein a wavelength of the visible light is within the range of 450 to 460 nm.5. The method of claim 1 , wherein the nitro compound is a second order or third order nitro compound.6. The method of claim 1 , wherein the additive is diisopropylethylamine (DIPEA) claim 1 , diisopropylisobutylamine (DIPIBA) or a derivative of 1 claim 1 ,4-Dihydropyridine (DHP).7. The method of claim 6 , wherein when the additive is diisopropylisobutylamine (DIPIBA) claim 6 , an aldehyde compound is further added in the photoreaction.8. The method of claim 6 , wherein the derivative of 1 claim 6 ,4-Dihydropyridine (DHP) is Hantzsch ester.9. The method of claim 1 , wherein the catalyst is performed a photoredox catalyst reaction in the photoreaction. This application claims priority from Taiwan Patent Application No. 104125714, filed on Aug. 6, 2015, in the Taiwan Intellectual Property Office, the content of which are hereby incorporated by reference in their entirety for all purposes.1. Field of the InventionThe present invention relates to a manufacturing method, in particular with respect to a manufacturing method of manufacturing nitrone compound.2. Description of the Related ArtNitrone compound is a key intermediate for ...

Curable silicone compositions

The present invention relates to silicone compositions which can be crosslinked thermally by hydrosilylation, a process for producing them, platinum catalysts used for this purpose and the use of the crosslinkable compositions.

RUTHENIUM-PHENOL CATALYSTS FOR TRANSFER HYDROGENATION REACTIONS

The present invention is directed towards a catalyst which is obtainable by contacting in situ a ruthenium precursor and a phenol derivative. Furthermore, the present invention is directed towards the use of said catalyst in transfer hydrogenation reactions. In particular, the present invention is directed to a method for preparing menthone starting from isopulegol. 115-. (canceled)17. The ruthenium catalyst of claim 16 , wherein the phenol derivative is of formula (Ic) claim 16 , and{'sup': 1', '2', '3', '4, 'sub': 1', '10', '3', '10, 'R, R, R, Rindependently are hydrogen, linear C-C-alkyl, or branched C-C-alkyl, or'}{'sup': 3', '4, 'R, Rtogether with the carbon atoms to which they are bound form an anellated aromatic ring;'}{'sup': 6', '7', '8', '9, 'sub': 1', '10', '3', '10, 'R, R, R, Rindependently are hydrogen, linear C-C-alkyl, or branched C-C-alkyl, or'}{'sup': 6', '7, 'R, Rtogether with the carbon atoms to which they are bound form an anellated aromatic ring;'}{'sup': '10', 'Ris hydrogen or hydroxy, and'}X is a chemical bond or alkylene.18. The ruthenium catalyst of claim 16 , wherein the ruthenium precursor which has labile ligands is represented by the formula (II){'br': None, 'sub': m', 'n, '[RuL]\u2003\u2003(II)'}whereinRu is in the oxidation state (+II), (+III) or (+IV);each L independently is hydride, halide, alkyl, aliphatic olefins optionally substituted by 1, 2 or 3 substituents which are independently selected from the group consisting of halogen, alkyl, substituted alkyl, cycloalkyl, aryl, and OH, cyclic olefins optionally substituted by 1, 2 or 3 substituents which are independently selected from the group consisting of halogen, alkyl, substituted alkyl, cycloalkyl, aryl, and OH, —CO, 1,3-dialkyldionate, alkanoate, or aryl optionally substituted by 1, 2, 3, 4 or 5 substituents, in particular 1, 2, 3 substituents which are independently selected from the group consisting of halogen, alkyl, substituted alkyl, alkoxy and OH;m is an integer in a ...

REACTIONS OF OLEFIN DERIVATIVES IN THE PRESENCE OF METHATHESIS CATALYSTS

The invention provides a method for synthesizing musk macrocycles comprising contacting an easily accessible diene starting materials bearing a Z-olefin moiety and performing a ring closing metathesis reaction in the presence of a Group 8 olefin metathesis catalyst. 112.-. (canceled)14. The olefin metathesis catalyst according to claim 13 , wherein:M is Ru;n is 0;m is 0;{'sup': 'a', 'sub': 1', '10', '1', '10', '3', '10', '3', '10', '5', '24', '5', '24, 'Ris unsubstituted C-Calkyl, substituted C-Calkyl, unsubstituted C-Ccycloalkyl, substituted C-Ccycloalkyl, unsubstituted C-Caryl or substituted C-Caryl;'}{'sup': b', 'a', 'b, 'sub': 1', '10', '1', '10', '3', '10', '3', '10', '5', '24', '5', '24, 'Ris unsubstituted C-Calkyl, substituted C-Calkyl, unsubstituted C-Ccycloalkyl, substituted C-Ccycloalkyl, unsubstituted C-Caryl or substituted C-Caryl; or Rand Rare linked together to form a five or a six-heterocyclic membered ring with the sulfoxide group;'}{'sup': 1', '2, 'Xand Xare independently halogen;'}{'sup': '1', 'Ris hydrogen;'}{'sup': 2', '1', '2, 'sub': 1', '6, 'Ris unsubstituted phenyl, substituted phenyl, C-Calkyl or substituted 1-propenyl; or Rand Rare linked together to form an optionally substituted indenylidene;'}{'sup': 5', '5, 'Xand Yare independently N;'}{'sup': 11', '12', '13', '14, 'sub': s', 't, 'Q is a two-atom linkage having the structure —[CRR]—[CRR]—;'}{'sup': 11', '12', '13', '14, 'R, R, R, and Rare independently hydrogen;'}“s” and “t” are independently 1;{'sup': '3', 'sub': 3', '10', '3', '10', '5', '24', '5', '24', '1', '20', '1', '2M', '1', '20', '1', '20', '5', '24', '5', '24', '5', '24', '5', '24', '6', '24', '6', '24', '6', '24', '6', '24, 'Ris unsubstituted C-Ccycloalkyl, substituted C-Ccycloalkyl, unsubstituted C-Caryl, or C-Caryl substituted with up to three substituents selected from: unsubstituted C-Calkyl, substituted C-Calkyl, unsubstituted C-Cheteroalkyl, substituted C-Cheteroalkyl, unsubstituted C-Caryl, substituted C-Caryl, ...

PHARMACEUTICAL PROCESS AND INTERMEDIATES

The present disclosure concerns the large-scale manufacture of pharmaceutical compounds, and novel intermediates for use in the manufacture. International Patent Application WO2011154737 discloses morpholine pyrimidines useful for treating cancer, processes for their preparation and pharmaceutical compositions thereof. In particular, WO2011154737 discloses, as experimental Example 2.02 on page 60, the compound 4-{4-[(3R)-3-methylmorpholin-4-yl]-6-[1-((R)—S-methylsulfonimidoyl)cyclopropyl]pyrimidin-2-yl}-1H-pyrrolo[2,3-b]pyridine (hereafter referred to as the compound of Formula (I)). The structure of the compound of Formula (I) is shown below. A synthetic route to the compound of Formula (I) is described at pages 51 to 57, 66 and 67 of WO2011154737, and is summarised below in Scheme 1. 9. The process according to claim 8 , wherein the compound of Formula (XIII) is prepared by reacting a compound of Formula (VIII) with OH—Rwherein Ris a phthalimide or tetrachlorophthalimide group.17. The compound according to any or claim 8 , wherein LGis chlorine and LG claim 8 , if present claim 8 , is chlorine.18. Use of a compound of any one of to claim 8 , or a salt thereof claim 8 , as a pharmaceutical intermediate.21. A process for preparing a compound of Formula (I) as claimed in claim 20 , wherein step (i) further comprises the addition of diethanolamine after reaction with a boron reagent in the presence of a palladium catalyst.24. The process for preparing a compound of Formula (I) as claimed in any of to claim 20 , further comprising the steps:(a) cyclopropanating a compound of Formula (IX) followed by hydrolysis to form a compound of Formula (VIII);(b) reacting a compound of Formula (VIII) with an acylating agent to form a compound of Formula (VII);(c) reacting a compound of Formula (VII) with urea or thiourea to form a compound of Formula (VI);(d) reacting a compound of Formula (VI) with a suitable reagent to form a compound of Formula (V);(e) reacting a compound of ...

6,6'-([1,1'-BIPHENYL]-2,3'-DIYLBIS(OXY))DIDIBENZO[D,F][1,3,2]DIOXAPHOSPHEPINES

6,6′-([1,1′-Biphenyl]-2,3′,-diylbis)oxy))didibenzo[d,f][1,3,2]dioxaphosphepines and the use thereof in hydroformylation. 2. Compound according to claim 1 , where R claim 1 , R claim 1 , R claim 1 , Rare selected from: —H claim 1 , —(C-C) alkyl.3. Compound according to claim 1 , where at least one of the radicals R claim 1 , R claim 1 , R claim 1 , Ris —H.4. Compound according to claim 1 , where R claim 1 , R claim 1 , R claim 1 , Rare —H.5. Compound according to claim 1 , where R claim 1 , R claim 1 , R claim 1 , Rare selected from: —H claim 1 , —O—(C-C) alkyl.6. Compound according to claim 1 , where at least one of the radicals R claim 1 , R claim 1 , R claim 1 , Ris —H.7. Compound according to claim 1 , where R claim 1 , R claim 1 , R claim 1 , Rare —H.9. Use of a compound according to in a ligand-metal complex for catalysis of a hydroformylation reaction.10. Process comprising the process steps of:a) initially charging an olefin,{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'b) adding a compound according to and a substance containing a metal selected from: Rh, Ru, Co, Ir,'}{'sub': '2', 'c) feeding in Hand CO,'}d) heating the reaction mixture from steps a) to c), with conversion of the olefin to an aldehyde. The invention relates to 6,6′-([1,1′-biphenyl]-2,3′-diylbis(oxy))didibenzo[d,f][1,3,2]dioxaphosphepines and to the use thereof in hydroformylation.Phosphorus-containing compounds play a crucial role as ligands in a multitude of reactions, e.g. in hydrogenation, in hydrocyanation and also in hydroformylation.The reactions between olefin compounds, carbon monoxide and hydrogen in the presence of a catalyst to give the aldehydes with one carbon atom more are known as hydroformylation or the oxo process. Catalysts used in these reactions are frequently compounds of the transition metals of group VIII of the periodic table of the elements. Known ligands are, for example, compounds from the phosphine, phosphite and phosphonite classes, each containing trivalent ...

NEW DIPHOSPHITES BASED ON CIS-BUTENE-1,4-DIOL

New diphosphites based on cis-butene-1,4-diol. 2. Compound according to claim 1 ,{'sup': ['1', '4', '5', '8'], 'sub': ['1', '12'], '#text': 'where R, R, R, Rare selected from: —H, —(C-C) alkyl.'}3. Compound according to claim 1 ,{'sup': ['1', '4', '5', '8', 'l'], '#text': 'where the radicals R, R, R, Rare not all simultaneously —Bu.'}4. Compound according to claim 1 ,{'sup': ['1', '4', '5', '8', 'l'], '#text': 'where the radicals R, R, R, Rare not —Bu.'}5. Compound according to claim 1 ,{'sup': ['1', '4', '5', '8'], '#text': 'where at least one of the radicals R, R, R, Ris —H.'}6. Compound according to claim 1 ,{'sup': ['2', '3', '6', '7'], 'sub': ['1', '12'], '#text': 'where R, R, R, Rare selected from: —H, —O—(C-C) alkyl.'}7. Compound according to claim 1 ,{'sup': ['2', '3', '6', '7'], '#text': 'where at least one of the radicals R, R, R, Ris —H.'}8. Compound according to claim 1 ,where the compound has the structure (I).10. Compound according to claim 1 ,where the compound has the structure (II).12. Use of a compound according to in a ligand-metal complex for catalysis of a hydroformylation reaction.13. Process comprising the process steps of:a) initially charging an olefin,{'claim-ref': {'@idref': 'CLM-00001', '#text': 'claim 1'}, '#text': 'b) adding a compound according to and a substance containing a metal selected from: Rh, Ru, Co, Ir,'}{'sub': '2', '#text': 'c) feeding in Hand CO,'}d) heating the reaction mixture from steps a) to c), with conversion of the olefin to an aldehyde. The invention relates to new diphosphites based on cis-butene-1,4-diol.Phosphorus-containing compounds play a crucial role as ligands in a multitude of reactions, e.g. in hydrogenation, in hydrocyanation and also in hydroformylation.The reactions between olefin compounds, carbon monoxide and hydrogen in the presence of a catalyst to give the aldehydes with one carbon atom more are known as hydroformylation or the oxo process. Catalysts used in these reactions are frequently compounds ...

METAL CATALYST, METHOD OF C-N COUPLING USING THE SAME AND APPLICATIONS OF THE SAME

The present disclosure relates to a metal catalyst for C—H bond activation and/or C—N coupling reaction, and a method using the same and application thereof. Specifically, a metal catalyst represented by the following formula: 4. The metal catalyst according to claim 1 , wherein W claim 1 , X claim 1 , and Y are the same.5. The metal catalyst according to claim 1 , wherein M is Ni claim 1 , Pd claim 1 , Fe claim 1 , Co claim 1 , Cr claim 1 , Mn claim 1 , Cu claim 1 , or Pt.6. A method for C—H bond activation and/or C—N coupling reaction comprising using the metal catalyst according to .7. The method according to claim 6 , wherein the C—N coupling reaction forms C—N bonds between a spcarbon and a primary or secondary amine to form substituted or an alkylated amine.8. The method according to claim 7 , wherein the primary or secondary amine is an aliphatic or aromatic amine.9. The method according to claim 7 , wherein spcarbon is an aliphatic and aromatic hydrocarbon.10. The method according to claim 6 , wherein the C—H bond activation and/or C—N coupling reaction is performed under ambient and mild conditions.11. The method according to claim 6 , wherein the C—H bond activation and/or C—N coupling reaction is performed without the presence of an oxidant or a base.12. The method according to claim 6 , wherein the C—N coupling reaction forms C—N bonds between aliphatic amines claim 6 , to form a cyclic amine.13. The method according to claim 6 , wherein the C—N coupling reaction forms C—N bonds between primary amines claim 6 , to obtain an oligomeric compound.14. The method according to claim 6 , wherein the C—H bond activation and/or C—N coupling reaction is performed in presence of an oxidant or a base.15. The method according to claim 14 , the C—H bond activation and/or C—N coupling reaction is performed in presence of an oxidant that is selected from a group consisting of oxygen claim 14 , hydrogen peroxide claim 14 , t-butylhydroperoxide claim 14 , peracetic acid ...