КАТАЛИТИЧЕСКАЯ СИСТЕМА

Описывается каталитическая система, состоящая из соединения общей формулы I или его соли, объединяемого с металлом VIIIB группы, где А1 и А2, а также А3, А4 и A5 (когда присутствуют), К, D, Е, X1-X4, Q1, Q2, M, L1 имеют значения, указанные в формуле изобретения. Система пригодна для карбонилирования этиленовых ненасыщенных соединений. 10 н. и 35 з.п.ф-лы, 9 табл.

НОВОЕ КАРБОКСИЛАТНОЕ СОЕДИНЕНИЕ, СПОСОБ ЕГО ПОЛУЧЕНИЯ И СОДЕРЖАЩАЯ ЕГО ПАРФЮМЕРНАЯ КОМПОЗИЦИЯ

Изобретение относится к новому карбоксилатному соединению, представленному следующей общей формулой (1), в которой R представляет собой алкильную группу, имеющую от двух до четырех атомов углерода. Изобретение относится к парфюмерной композиции, содержащей карбоксилатное соединение, представленное следующей общей формулой (1), а также к способу получения карбоксилатного соединения, представленного следующей общей формулой (1), который включает взаимодействие 2,2-диметил-3-метилен-бицикло[2,2,1]гептана, представленного следующей формулой (2),с монооксидом углерода и затем со спиртом, имеющим от двух до четырех атомов углерода, в присутствии фторида водорода. Предложенное новое карбоксилатное соединение полезно в качестве смешивающегося парфюмерного сырья и имеет свежий хвойный запах. 3 н. и 2 з.п. ф-лы, 4 пр., 1 табл.

СПОСОБ ПОЛУЧЕНИЯ ЭФИРОВ МЕТАКРИЛОВОЙ КИСЛОТЫ

Изобретение относится к усовершенствованному способу получения эфиров метакриловой кислоты, в частности, метилметакрилата безопасным способом, который включает (а) селективное удаление пропадиена из смеси, включающей пропин и пропадиен, растворенные в полярном органическом растворителе, с образованием концентрированной смеси пропина в растворителе; (b) отпаривание пропина в дистилляционной колонне из потока пара концентрированной смеси растворителя, содержащего пропин, с образованием потока газообразного пропина; (с) конденсацию потока газообразного пропина с образованием конденсированного потока пропина и (d) взаимодействие конденсированного потока пропина с окисью углерода и спиртом в присутствии катализатора карбонилирования; причем отпаривание пропина осуществляют в дистилляционной колонне, имеющей внутренний конденсатор, установленный для конденсации части потока пара для подачи орошения. Способ обеспечивает непрерывную работу процесса, преодолевая недостатки предшествующего уровня ...

СПОСОБ ПОЛУЧЕНИЯ ЭФИРОВ АЛКИНИЛКАРБОНОВЫХ КИСЛОТ

Сущность изобретения: продукт-эфиры алкинилкарбоновых кислот ф-лы RC ≡ CCOOR′ , где R - низший алкил, фенил; R′ - низший алкил. Выход 75,0 - 86,9%. Реагент 1: алкин RC ≡ CH . Реагент 2: оксид углерода. Условия реакции: в присутствии кислорода, одноатомного спирта, катализатора-монохлорида меди и хлорида палладия, при 11 - 26oС и концентрации хлорида палладия -0,0014 - 0,0064 моль/л, монохлорида меди 0,2 - 0,5 моль/л и отношении Рсо/Р02 - 0,67 - 2,1. 1 табл.

КАТАЛИТИЧЕСКАЯ СИСТЕМА

... 1. Каталитическая система, способная катализировать карбонилирование этилен-ненасыщенного соединения, эта система может быть получена посредством объединенияa) металла группы VIB или группы VIIIB, или его соединения,b) бидентатного фосфинового, арсинового или стибинового лиганда иc) кислоты,где указанный лиганд присутствует в молярном избытке, по меньшей мере, 2:1, по сравнению с указанным металлом или указанным металлом в соединении указанного металла, и указанная кислота присутствует в молярном избытке, по меньшей мере, 2:1, по сравнению с указанным лигандом.2. Каталитическая система по п.1, в которой соотношение указанного лиганда к указанному металлу находится в пределах 5:1-750:1.3. Каталитическая система по п.1, в которой соотношение указанного лиганда к указанному металлу находится в пределах 10:1-500:1.4. Каталитическая система по п.1, в которой соотношение указанного лиганда к указанному металлу находится в пределах 20:1-40:1,5. Каталитическая система по п.1, в которой соотношение ...

Способ получения смеси глицеридов 2,5-диеновых алифатических карбоновых кислот

VERFAHREN ZUR HERSTELLUNG VON CYCLODODEKADIEN-MONOCARBONSAEUREESTERN UND REDUKTION ZU DEN CYCLODODEKAN- MONOCARBONSAEUREESTERN

VERFAHREN ZUR HERSTELLUNG VON GERADKETTIGEN FETTSAEUREN ODER IHRER ESTER

VERFAHREN ZUR CARBONYLIERUNG VON ACETYLENISCH UNGESÄTTIGTEN VERBINDUNGEN

VERFAHREN ZUR HERSTELLUNG EINER HOEHEREN FETTSAEURE

Verfahren zur Karbonylierung von Olefin.

Verfahren zur Karbonylierung von Olefin.

VERFAHREN ZUR HERSTELLUNG VON ALKYLESTERN GESAETTIGTER ALIPHATISCHER CARBONSAEUREN

CARBONYLATION OF ETHYLENE OR PROPYLENE

HERSTELLUNGSVERFAHREN VON ALKYLIDENDIESTERN.

VERFAHREN ZUR HERSTELLUNG VON BUTANDICARBONSAEUREESTERN

VERFAHREN ZUR HERSTELLUNG EINES DIESTERS VON DICARBONSAEUREN

FORMATION OF ISOBUTYRIC ACID OR METHYL ISOBUTYRATE

PROCESS FOR THE PREPARATION OF SATURATED LINEAR ESTERS BY CARBONYLATION OF MONOOLEFINIC COMPOUNDS

VERFAHREN ZUM CARBONYLIEREN VON PENTENNITRIL

PROCESS FOR THE PRODUCTION OF PURE ADIPINIC-ACID MONOESTERS

UNSATURATED CARBOXYLATE ESTERS

ESTERS OF ALPHA-ETHYLENICALLY UNSATURATED ALCOHOLS

CARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

Manufacture of carboxylic acid esters

Methyl, ethyl, or propyl esters of carboxylic acids with more than 4 carbon atoms, are prepared by reacting ethylene and/or propylene, carbon mon-oxide and ROH (R = H or CH3) under superatmospheric pressure in the presence of an aqueous (70-80%) HBF4 solution, or methanolic (55-75%) HBF solution. When ethylene is used esters of the C5, C7, C9, C11 carboxylic acids are formed, and when propylene is used C4, C7, C10, C13 carboxylic acid esters are formed, if a mixture of the two is used the acid residue contains an even number of carbon atoms. The process may be continuous with liquified olefines and examples describe the preparation of ethyl esters of a -methyl - a - ethylbutyric and a - methylbutyric acid; isopropyl esters of isobutyric acid, and C7-carboxylic acids; methyl esters of C5, C7, C9- -13 and above C13 carboxylic acids; methyl esters of isobutyric acid, C7-, C10- and C13-carboxylic esters.

A novel catalytic formulation and its preparation technical field

Process for separating cobalt component from hydroesterification reaction mixture

A cobalt component is separated from a hydroesterification reaction mixture obtained by reacting a polyhydric alcohol with an olefin and carbon monoxide in the presence of a cobalt carbonyl complex and a pyridine base, by contacting (a) pyridine or gamma -picoline and (b) water with said reaction mixture containing the cobalt component and the product of a fatty acid ester of the polyhydric alcohol to separate it into two phases consisting of a phase containing the fatty acid ester of polyhydric alcohol and a phase containing a cobalt component. In the process, the weight ratio of pyridine or gamma -picoline to the product ester is 0.5 to 5 and the weight ratio of water to pyridine or gamma -picoline is 0.05 to 10.

CARBONYLATION OF COMPOUNDS

CARBONYLATION OF OLEFINICALLY UNSATURATED HYDROCARBONS

... 1328850 Carbonylation MOBIL OIL CORP 30 Dec 1970 [20 Feb 1970 17 Aug 1970] 61912/70 Heading C2C Carboxylic acids and esters are prepared by the liquid phase carbonylation of olefinically unsaturated hydrocarbons with carbonmonoxide and hydroxylic compounds in the presence of a palladium salt catalyst of formula L m PdX y in which L is an organic phosphine, X is an anion, m an integer of 1-4, and y is 1 or 2, and a tin cocatalyst. The ligand may be triphenyl, tri-ptolyl, tri-p-trifluoromethyl phenyl, tri-p-anisyl and tri-n-butyl phosphines or palladium dichloride-1,2-diphenyl phosphino ethane and the tin cocatalyst may be stannous chloride dihydrate, anhydrous stannous chloride, stannic chloride, stannic chloride pentahydrate, and triphenyl tin chloride. Examples describe the treatment of propylene, 1-butene, 1-pentene, 2- pentene, 1-hexene, 1-octene, cis-2-hexene, and 1-octadecene with various catalysts to yield the corresponding esters.

Production of esters

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 ...

A process for the production of aliphatic and cycloaliphatic monocarboxylic acid alkyl esters

Alkyl esters of aliphatic or cycloaliphatic monocarboxylic acids and minor amounts of the corresponding free acids are prepared by reacting an aliphatic or cycloaliphatic olefinic hydrocarbon containing at least 6 carbon atoms with carbon monoxide under elevated pressure in the presence of a catalyst comprising a mixture of hydroxy and alkoxy fluoroboric acids, the alkoxy groups of which contain 1-3 carbon atoms, the mol ratio of combined water plus alcohol to boron trifluoride in the catalyst mixture being not less than 1 : 1 and not greater than 2 : 1 and treating the resulting reaction product with a C1-3 alkanol to form the alkyl ester and render the catalyst separable. The amount of alcohol used is preferably stoichiometrically equivalent to the amount of olefine which has reacted with the carbon monoxide. The regenerated catalyst which separates may be re-used though make-up water corresponding to that lost in by-product carboxylic acid formation may be required. The carbonylation ...

The preparation of acrylic esters

Acrylic esters are prepared by dissolving acetylene in a solvent and reacting it with carbon monoxide and a C1-12 aliphatic, monohydric alcohol in the presence of a catalyst known to catalyse the reaction at 220-270 DEG , preferably 240-250 DEG C., and 2000-4500, preferably 2500-3500 p.s.i. The reactant alcohol is the preferred solvent. Other suitable solvents include dioxan, tetrahydrofuran and water. The reaction may be carried out batchwise or continuously. The alcohol may be primary, secondary or tertiary and is preferably used in slight excess. Generally 0.5 to 5 per cent by weight based on the alcohol of a catalyst such as a nickel halide is used. In examples: (1) methyl acrylate is prepared by dissolving acetylene in methanol and then reacting with carbon monoxide using a nickel bromide catalyst; by-products are mainly dimethyl ether; (2) 2-methylhexyl acrylate is similarly prepared from 2-methylhexanol.

Improvements in the production of acrylic compounds

Nickel carbonyl, for use as a catalyst in the production of acrylic compounds (see Group IV (b)), may be prepared by treating nickel salt solutions with carbon monoxide at elevated temperature and pressure in the presence of an organic compound which forms with nickel carbonyl a compound in which the carbon monoxide is in a more unstable form than in nickel carbonyl; such organic compounds are those which liberate CO in a solution of nickel carbonyl in ethanolic hydrochloric acid at room temperature; a comprehensive list of such compounds is given (see Group IV (b)). The nickel salts may be of inorganic or organic acids, such as halogen hydracids, sulphuric, nitric, hydrocyanic, carbonic, propionic, butyric and acrylic acids. Solvents such as water, alcohols, acetone and tetrahydrofuran may be used. Preferred conditions are 50-250 DEG C. and 50-200 atmospheres.ALSO:Acrylic compounds are prepared by reacting acetylene, carbon monoxide and a compound with reactive hydrogen in an acid medium ...

PROCESS FOR PREPARING DIESTERS OF DICARBOXYLIC ACIDS

PROCESS FOR PREPARING DIESTERS OF DICARBOXYLIC ACIDS

Methods

A method for preparing a partially fluorinated ester comprising acyl and alkoxy groups wherein the acyl group comprises a branched or linear fluorine containing C3-C8 group with one of the structures (I) or (II), wherein X and Y are independently selected from H, CH3, F, Cl CH2F, CF3 and CH2CF3 (wherein both X and Y cannot be H) comprising reacting an unsaturated halocarbon of formula (III) wherein A and B are independently selected from the group comprising H, CH3, F, Cl, CH2F, CF3 and CH2CF3 (wherein both A and B cannot be H) with carbon monoxide and an alcohol, in the presence of a catalyst. A compound of formula CH3CF(CH3)CO2R, CH3CHFCH2CO2R, CF3CH(CH2F)CO2R, CH3CH2CHFCO2R, CF3CH2CH(CF3)CO2R, CF3CCl(CH3)CO2R or CF3CHClCH2CO2R (where R is CnH2n+1-xFx, n is 1 to 10 and x is 0 to 2n+1). Use of a partially fluorinated ester as a pharmaceutical intermediate, a battery solvent of in the preparation of a polyol ester or a fluoro(meth)acrylate. Partially fluorinated polyol esters and their ...

HYDROLYSIS-RESISTANT ESTER LUBRICATING OILS

... 1454484 Long-chain carboxylic esters CHEMISCHE WERKE HULS AG 8 Feb 1974 [10 Feb 1973] 05796/74 Heading C2C [Also in Division C5] A process for the manufacture of hydrolysisresistant carboxylic acid esters comprises subjecting a (C 13 -C 18 ) linear olefin, the double bond isomers of which are distributed according to a thermodynamic equilibrium, to a hydroformulation reaction and reacting the resulting aldehyde by a Tischtschenko reaction. A rhodium triphenylphosphine catalyst is suitably used in the first stage. The ester product is suitably used as a lubricant.

PROCEDURE FOR THE PRODUCTION OF ISOBUTYRYLFLUORID

HYDRAULIC FORMULATION REACTION IN PRESENCE OF SULFUR OF CONTAINING ADDITIVES

VERFAHREN ZUR HERSTELLUNG VON ISOBUTYRYLFLUORID

PROCEDURE FOR THE PRODUCTION OF FATTY ACID ESTERS.

PROCEDURE FOR CARBONYLIERUNG OF OLEFINISCH INSATIATED CONNECTIONS WITH A PALLADIUM CATALYST.

PROCEDURE FOR THE PRODUCTION OF SATISFIED LINEAR ESTERS THROUGH CARBONYLIERUNG OF MONOOLEFINI CONNECTIONS.

PROCEDURE FOR THE PRODUCTION OF ESTERS THROUGH CARBONYLIERUNG MONOINSATIATED CONNECTIONS.

CATALYST AND PROCEDURE FOR THE SYNTHESIS OF SATISFIED CARBONIC ACID ESTERS.

PROCEDURE FOR THE PRODUCTION BETA, GAMMAUNGES|TTIGTER CARBONIC ACIDS.

PROCEDURE FOR THE PRODUCTION OF PREDOMINANTLY LINEAR ONE ALIPHATIC CARBONIC ACID ESTERS.

ORGANIC REACTIONS WITH CO-GENERATING MATERIALEN

DIPHOSPHIN

PROCEDURE FOR THE CONTINUOUS ONE CARBONYLIERUNG OF OLEFINEN

BY A UNTIL PHOSPHORINAN DERIVATIVE AND CONNECTION SUITABLE FOR THE PRODUCTION OF A CARBONYLIERUNGS OF CATALYST SYSTEM

Procedure for the simultaneous production of Methyl-2, 5-hexadienoat and methyl acrylate

PROCEDURE FOR THE CARBONYLIEREN OF AETHYLENISCH INSATIATED CONNECTIONS

Carbonylation catalyst system

Process for the preparation of propyne

Derivatives of polyamines with one primary amine group and secondary or tertiary amines groups

Process to prepare a terminal aldehyde

PROCESS FOR THE PREPARATION OF BETA-GAMMA UNSATURATED ESTERS

A process for the carbonylation of allylic butenyl ether (e.g., methyl crotyl ether, 3-methoxybutene-1 and mixtures thereof) or mixture of butadiene and alcohol (e.g., methanol) and production of beta-gamma unsaturated carboxylic acid esters (e.g., methyl-3-pentenoate) utilizing a rhodium-containing catalyst (e.g., dicarbonylacetylacetonate rhodium(I) or the like) promoted with an iodide-containing compound (e.g., HI, AlI3, SnI4, TiI4, CrI3, and CoI2 or the like). Such a process is particularly useful in the production of difunctional monomers and intermediates in the synthesis of adipic acid. The representative reaction showing (a) butadiene in the presence of methanol under catalytic reaction conditions producing the 3-methoxybutene-1 intermediate (a positional isomer of methyl crotyl ether) which is then combined with carbon monoxide to produce methyl pentenoate is illustrative of the overall carbonylation.

PROCESS FOR PREPARING CARBOXYLIC ACID OR ESTER THEREOF

PROCESS FOR CONTINUOUS PRODUCTION OF FULL ESTERS OF POLYOLS

PREPARATION OF 4-SUBSTITUTED BUT-3-ENE-1-CARBOXYLIC ACIDS AND THEIR ESTERS

PROCESS FOR THE CARBONYLATION OF ALLENICALLY UNSATURATED COMPOUNDS

PROCESS FOR PREPARING .beta.,.gamma.-UNSATURATED CARBOXYLIC ACID ESTERS

PREPARATION PROCESS OF CINNAMATE ESTER

PREPARATION PROCESS OF CINNAMATE ESTERS

A cinnamte ester is prepared by reacting carbon monoxide, oxygen, and its corresponding styrene compound and alcohol in the presence of a catalyst which contains, as essential components, (a) a platinum group metal or a compound thereof; (b) a copper or iron compound; and (c) a compound of at least one metal selected from groups 4A, 5A, 7A, 8A(the iron group only), 1B(exclusive of copper) and 2B.

PROCESS FOR THE CARBONYLATION OF ALLENICALLY UNSATURATED COMPOUNDS

K 604 PROCESS FOR THE CARBONYLATION OF ALLENICALLY UNSATURATED COMPOUNDS The process for the carbonylation of an allenically unsaturated compound with CO in the presence of water, an alcohol and/or a carboxylic acid is carried out in the presence of a catalyst formed by combining: a) a Pd(II) compound, b) ? 15 mol of an organic phosphine per gram atom of Pd(II), and c) a protonic acid having a pK > 1.5 and/or a carboxylic acid having a PKa ? 1.5, both measured at 18 .degree.C in aqueous solutions.

PROCESS FOR THE SELECTIVE OXIDATIVE CARBONYLATION OF CONJUGATED DIENES

Process for the selective oxidative carbonylation of conjugated dienes Process for the selective oxidative carbonylation of a conjugated diene, in particular butadiene, with carbon nonoxide and an alcohol in a quantity of at least 2 mol equivalents per mol diene, in the presence of a catalyst system comprising at least the following components: (a) a compound of a metal, selected from one or more platinum group metals, (b) an oxidizing agent in the form of quinone and/or derivatives thereof, and (c) a compound of a metal, selected from manganese or vanadium, which specific catalyst systems can be used as such or in the form of a solution or suspension in a suitable solvent.

CARBOALKOXYLATION OF BUTADIENE TO FORM DIALKYL ADIPATE

TITLE Carboalkoxylation of Butadiene to Form Dialkyl Adipate Production of dialkyl adipate by reaction of butadiene, carbon dioxide, and a lower alkyl alcohol in the presence of a cobalt catalyst and a tertiary nitrogen base cocatalyst to form a liquid mixture containing alkyl 3-pentenoate, adding alkanoic acid to the mixture in an amount sufficient to keep the cobalt catalyst active, and then reacting the mixture to form dialkyl adipate. The acid addition increases the rate of reaction relative to catalyst deactivation rate and reduces the consumption of the tertiary nitrogen base cocatalyst.

PROCESS FOR PREPARING ESTERS BY CARBONYLATION OF MONOOLEFINIC COMPOUNDS

L'invention a trait à un procédé de préparation d'esters par carbonylation de composés monooléfiniques. Selon ce procédé, on fait réagir du monoxyde de carbone et un alcool sur un composé renfermant une liaison oléfinique unique en présence de cobalt, d'une base azotée tertiaire et de ruthénium. Ce procédé convient notamment à la préparation d'esters linéaires.

PROCESS FOR THE CARBONYLATION OF DIOLEFINS

Conjugated diolefins (e.g., 1,3-butadiene) are carbonylated by the palladium-catalyzed addition of carbon monoxide and an alcohol of the formula ROH (e.g., benzyl alcohol) whereby polycarboxylic esters are formed in which the pair of double bonds of the conjugated diolefin has been transformed into a moie?y having the formula: In the process, the olefin, carbon monoxide, and alcohol are reacted in the presence of a palladium(II) salt, a copper(II) salt, and a base, at certain concentrations and at a pressure and temperature sufficient to effect the carbonylation. The resulting unsatusated diester can be hydrolyzed and hydrogenated or vice versa to obtain the corresponding linear diacid (e.g., adipic acid).

PROCESS FOR THE CARBONYLATION OF OLEFINS

A process for the carbonylation of an olefin with carbon monoxide in the presence of water. an alcohol, and/or a carboxylic acid. the reaction being conducted In the presence of an essentially halide-free palladium catalyst and a tri-organophosphine and in the absence of sodium acetate. the tri-organophosphine containing at least one aliphatic carbon atom bound to phosphorus and the molar ratio of the organophosphine to palladium being less than 10:1.

PREPARATION OF ACIDS AND ESTERS

Propylene and ethylene may be carbonylated to form carboxylic acid esters or carboxylic acids in the presence of a catalyst complex containing 1 mole of BF3 and 1 mole of a second complexing component. The carboxylic acid product or acid portion of the ester product has one more carbon atom than the olefin reacted. High yields of these products are obtained. In the case of the formation of the ester, the second complexing component is an alcohol, while in the case of the preparation of carboxylic acid, the second complexing component is water. Methyl isobutyrate and methyl propionate formed by the carbonylation of propylene and ethylene, respectively, in the presence of a BF3 CH3OH catalyst may be dehydrogenated to prepare methyl methacrylate and methyl acrylate, respectively. Similarly, the isobutyric acid and propionic acid formed from propylene and ethylene, respectively, in the presence of BF3 H2O catalyst may be dehydrogenated to prepare methacrylic acid and acrylic acid, respectively ...

PROCESS FOR PREPARING LINEAR FATTY ACIDS

PROCESS FOR THE PRODUCTION OF BUTANEDIOL

APPLICATION FOR LETTERS PATENT FOR A process for the production of butanediol which comprises reacting propylene, oxygen and acid in the presence of a catalyst to produce a carboxylate which is reacted with hydrogen and carbon monoxide to produce diol esters which are deesterified to butanediols.

PRODUCTION OF CARBOXYLIC ACID ESTERS

PROCESS FOR THE CARBONYLATION OF ACETYLENICALLY UNSATURATED COMPOUNDS

PROCESS FOR THE CARBONYLATION OF ACETYLENICALLY UNSATURATED COMPOUNDS Process for the preparation of alpha,beta-olefinically unsaturated compounds by means of carbonylation of acetylenically unsaturated compounds with carbon monoxide in the presence of a hydroxyl-containing compound in the liquid phase, carried out in the presence of a catalytic system that can be formed from: (a) a palladium compound (b) a protonic acid (c) an organic phosphine according to the formula I wherein R1 represents a heterocyclic 5 or 6 atom ring, comprising at least nitrogen as hetero atom, which ring is optionally substituted and/or may form part of a larger condensed ring structure that is optionally substituted, and wherein R2 and R3 each have the aforesaid meaning of R1 or may represent an optionally substituted aryl group, and organic phosphines and compositions comprising said phosphines as well as catalytic systems whereof said phosphines form part.

COMPOUND SUITABLE FOR USE AS A CATALYST OR FOR PRODUCING A CATALYST SYSTEM DERIVED FROM A BIS-PHOSPHORINANE

... .he invention relates to a compound of formula (I) wherein X represents a low alkylen group, an arylene group or an alkarylene group, L1 has formula (II) wherein Y1 represents oxygen, sulphur or N-R17, R11, R12, R13, R14, R15, R16, R17 independently represent hydrogen, alkyl or aryl, L2 has formula (III) wherein Y2 represents oxygen, sulphur or N-R27, R21, R22, R23, R24, R25, R26, R27 independently represent hydrogen, alkyl or aryl wherein L1 and L2 can be identical or different. The inventive compound is suitable for use as a catalyst or for producing a catalyst system.

PROCESS FOR PRODUCING .alpha.-ACETOXYPROPIONALDEHYDE

PALLADIUM CATALYZED CARBONYLATION OF CONJUGATED DIENES AND RECIRCULATION OF THE CATALYST

PROCESS FOR PREPARING ESTERS BY CARBONYLATION OF MONOOLEFINIC COMPOUNDS

PROCESS FOR PREPARING DIESTERS OF DICARBOXYLIC ACIDS

MANUFACTURE OF BUTANEDICARBOXYLIC ACID ESTERS

AN ADAMANTYL CATALYST SYSTEM

... ²²²A catalyst system capable of catalysing the carbonylation of an olefinally ²unsaturated compound is described. The 5 catalyst system is obtainable by ²combining: (a) a metal of Group VIB or Group VIII B or a compound thereof; and ²(b) a bidentate phosphine of general formula (I) Ad) s (CR4R5R6) T Q2-A- (K, ²D) Ar (E, Z) -B-Q1 (Ad) u (CR1R2R3) v. Ad represents an optionally substituted ²adamantyl radical bonded to the phosphorous atom via any one of its tertiary ²carbon atoms. A method of production of the catalyst is also illustrated.² ...

METAL COMPLEXES FOR USE IN THE CARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

The invention concerns metal complexes and their preparation, in particular a metal complex MLnXm, where M is a metal of group 8, 9 or 10 and X is a halide, HCO3-, NO3-, CO32- or carboxylate. n is a number equal to or less than the coordination number of the metal and m is 1 or 2 and is equal to the oxidation state of the metal. The ligand L may be a bidentate phosphine of formula (I), (II), (III) or (IV) as set out herein. The process of production comprises reacting an ammine compound of metal M with a complexing compound, which is preferably a phosphine.

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

The invention relates to a compound of formula (I) (see formula I) where R1, R2, R3, R4 are each independently selected from -(C1-C12)-alkyl, -(C3-C12)-cycloalkyl, -(C3-C12)-heterocycloalkyl, -(C5-C20)-aryl, -(C3-C20)-heteroaryl; at least one of the R1, R2, R3, R4 radicals is a -(C6-C20)-heteroaryl radical having at least six ring atoms; and R1, R2, R3, R4, if they are -(C1-C12)-alkyl, -(C3-C12)-cycloalkyl, -(C3-C12)-heterocycloalkyl, -(C6-C20)-aryl, -(C3-C20)-heteroaryl or -(C6-C20)-heteroaryl, may each independently be substituted by one or more substituents selected from -(C1-C12)-alkyl, -(C3-C12)-cycloalkyl, -(C3-C12)-heterocycloalkyl, -O-(C1-C12)-alkyl, -O-(C1-C12)-alkyl-(C6-C20)-aryl, -O-(C3-C12)-cycloalkyl, -S-(C1-C12)-alkyl, -S-(C3-C12)-cycloalkyl, -COO-(C1-C12)-alkyl, -COO-(C3-C12)-cycloalkyl, -CONH-(C1-C12)-alkyl, -CONH-(C3-C12)-cycloalkyl, -CO-(C1-C12)-alkyl, -CO-(C3-C12)-cycloalkyl, -N-[(C1-C12)-alkyl]2, -(C6-C20)-aryl, -(C6-C20)-aryl-(C1-C12)-alkyl, -(C6-C20)-aryl-O-(C1-C12 ...

CARBONYLATION CATALYST SYSTEM

PRODUCTION OF ALPHA-(3-BENZOYLPHENYL)-PROPIONIC ACID DERIVATIVE

This Invention provides a method of producing highly pure .alpha.-(3-benzoylphenyl)propionic acid derivatives, which are medicines per se or which can easily afford the same, from readily available 3-ethylbenzophenone in a very simplified manner efficiently and economically. The Method comprises dehydrogenating 3-ethylbenzophenone in vapor phase in the presence of an inert gas and carbonylating the formed 3-ethenylbenzophenone in the presence of a carbonylation catalyst comprising a transition metal complex.

PALLADIUM CATALYZED CARBOALKOXYLATION OF BUTADIENE

TITLE Palladium Catalyzed Carboalkoxylation of Butadiene A process for the preparation of linear alkyl pentenoates by reacting butadiene, carbon monoxide and an alkyl alcohol in an organic solvent with a homogeneous catalytic mixture containing five components namely, palladium, chloride, a strong acid, an aryl monodentate phosphine, and a N-heterocyclic base. PI-0487 ...

PROCESS FOR PREPARING OLEFINS

... 4-Isobutylstyrene and other olefinic compounds corresponding to the formula C(R3)(R4)=C(R2)A are prepared by reacting an organic compound having the formula AX with a vinyl or substituted vinyl compound having the formula C(R3)(R4)=C(R2)H in the presence of a catalyst comprising (a) palladium or a palladium salt and (b) a ligand corresponding to formula (I) in which formulae A is aryl, substituted aryl, heteroaryl, substituted heteroaryl, benzyl, substituted benzyl, vinyl, or substituted vinyl; R2, R3, and R4 are independently selected from hydrogen, alkyl, cycloalkyl, alkyl-substituted cycloalkyl, aryl, substitued aryl, alkoxy, alkylthio, heteroaryl, substituted heteroaryl, alkanoyl, aroyl, substituted aroyl, heteroarylcarbonyl, substituted heteroarycarbonyl, trifluoromethyl, and halo; X is chloro, bromo, iodo, or diazonium; Ar is phenyl, substituted phenyl, naphthyl, or substituted naphthyl; R' and R" are independently selected from hydrogen, alkyl, aryl, or substituted aryl; and n is ...

Verfahren zur Durchführung einer Kondensationsreaktion mit Acetylen.

Verfahren zur Herstellung eines Dicarbonsäureestergemisches.

Verfahren zur Herstellung von Methylakrylat

Verfahren zur Herstellung von Methacrylsäure und deren Ester

Procédé de fabrication d'un acétal de B-formyl-propionate

NORBORNANE-2-SPIRO-alpha-CYCLOALKANONE-alpha'-SPIRO-2''-NORBORNANE-5,5'',6,6''-TETRACARBOXYLIC DIANHYDRIDE, NORBORNANE-2-SPIRO-alpha-CYCLOALKANONE-alpha'-SPIRO-2''-NORBORNANE-5,5'',6,6''-TETRACARBOXYLIC ACID AND ESTER THEREOF, METHOD FOR PRODUCING NORBORNANE-2-SPIRO-alpha-CYCLOALKANONE-alpha'-SPIRO-2''-NORBORNANE-5,5'',6,6''-TETRACARBOXYLIC DIANHYDRIDE, POLYIMIDE OBTAINED BY USING THE SAME, AND METHOD FOR PRODUCING POLYIMIDE

A norbornane-2-spiro-α-cycloalkanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride represented by the following general formula (1): [in the formula (1), n represents an integer of 0 to 12, and R 1 s, R 2 , R 3 each independently represents a hydrogen atom or the like].

NOVEL CARBOXYLATE COMPOUND AND METHOD OF PRODUCING THE SAME AND PERFUME COMPOSITION THEREOF

There are provided a novel carboxylate compound useful as a blending perfume raw material and having a brisk pine-like odor and a method of producing the same and a perfume composition containing such a carboxylate compound. This invention relates to a novel carboxylate compound and a method of producing the same and a perfume composition thereof, and more particularly to a novel carboxylate compound useful as a blending perfume raw material and a method of producing the same and a perfume composition containing the carboxylate compound.It is known that compounds useful as a perfume are present among esters. For example, Non-patent Literature 1 discloses that geranyl acetate having a rose-like odor, methyl jasmonate having a jasmine-like sweet odor, FRUITATE having a fruity odor, methyl benzoate having a strong, dry fruity odor and so on are useful as a blending perfume material.NPL 1: Mototaka Nakajima, “Basic Knowledge of Perfume and Flavor Blending” 1995, page 215, 235, 244-246, published by Sangyo-Tosho Co., Ltd.It is an object of the invention to provide a novel carboxylate compound useful as a blending perfume raw material and having a brisk pine-like odor and a method of producing the same and a perfume composition containing such a carboxylate compound.The inventors have synthesized various compounds and made studies on their odors and found out that novel carboxylate compounds represented by the following general formula (1):(wherein R is an alkyl group having two to four carbon atoms) have a brisk pine-like odor.That is, the invention relates to a novel carboxylate compound and a method of producing such a carboxylate compound and a perfume composition containing such a carboxylate compound and is constituted as follows: [1] A carboxylate compound represented by the following general formula (1):wherein R is an alkyl group having two to four carbon atoms.[2] A perfume composition containing a carboxylate compound represented by the following general ...

PLANT BASED MONOMERS AND POLYMERS

The preparation of cyclohexadienes from one or more plant oils is disclosed. The cyclohexadiene can be used to form polymers or derivatized to form other monomers that can be used to form polymeric materials. 1. A process for preparing cyclohexadiene , the process comprising:contacting an oil derived from a plant with a metathesis catalyst to produce 1,4-cyclohexadiene and residual plant oil;separating the 1,4-cyclohexadiene from the residual plant oil; andisomerizing the 1,4-cyclohexadiene to 1,3-cyclohexadiene.2. The process of claim 1 , further comprising derivatizing the 1 claim 1 ,3-cyclohexadiene to a PTA mimic.3. A process of forming a polymer comprising polymerizing one or more monomers made from .4. The polymer of .5. A process of forming a polymer comprising polymerizing one or more monomers made from .6. The polymer of .7. A process for preparing polymerizable monomer from plant oil claim 5 , the process comprising:contacting an oil derived from a plant with a metathesis catalyst to produce 1,4-cyclohexadiene and residual plant oil;separating the 1,4-cyclohexadiene from the residual plant oil; andderivatizing the 1,4-cyclohexadiene to a PTA mimic.8. The process of further comprising:isomerizing the 1,4-cyclohexadiene to 1,3-cyclohexadiene; andderivatizing the 1,3-cyclohexadiene to a PTA mimic.9. A process of forming a polymer comprising polymerizing one or more monomers made from .10. A process of forming a polymer comprising polymerizing one or more monomers made from .11. The polymer of .12. The polymer of .13. A process of preparing 1 claim 10 ,3-cyclohexadiene claim 10 , the process comprising:contacting the 1,4-cyclohexadiene with a solid base catalyst to form 1,3-cyclohexadiene.14. The process of further comprising converting the 1 claim 13 ,3-cyclohexadiene to a saturated or unsaturated bicyclic monomer or a monocyclic monomer.15. A process of forming a polymer comprising polymerizing one or more monomers made from .16. The polymer of . This ...

NOVEL CARBOXYLIC ACID ESTER COMPOUND AND METHOD FOR PRODUCING SAME, AND FRAGRANCE COMPOSITION

The present invention provides a novel carboxylic acid ester compound useful as a fragrance component or a material for a compound fragrance and a method for producing the same, and provides a fragrance composition including the carboxylic acid ester compound. The present invention also provides an acyl fluorides of a 2,4-dimethyl-bicyclo[2.2.2]octane compound and the esters thereof, useful as the raw materials (inclusive of the intermediates of organic synthesis), for example, for the medicines, agricultural chemicals, fragrances, functional resins, optical functional materials and electronic functional materials. The carboxylic acid ester compound of the present invention is a compound represented by the general formula (1). 3. A fragrance composition comprising the carboxylic acid ester compound of .5. The carboxylic acid ester compound of claim 2 , wherein claim 2 , in formula (1a) claim 2 , R is a methyl group.6. The carboxylic acid ester compound of claim 2 , wherein claim 2 , in formula (1a) claim 2 , R is an ethyl group.7. The carboxylic acid ester compound of claim 2 , wherein claim 2 , in formula (1 a) claim 2 , R is an n-propyl group.8. The carboxylic acid ester compound of claim 2 , wherein claim 2 , in formula (1a) claim 2 , R is an iso-propyl group.9. The carboxylic acid ester compound of claim 2 , wherein claim 2 , in formula (1a) claim 2 , R is an n-butyl group.10. The carboxylic acid ester compound of claim 2 , wherein claim 2 , in formula (1a) claim 2 , R is an iso-butyl group.11. The carboxylic acid ester compound of claim 2 , wherein claim 2 , in formula (1a) claim 2 , R is a tert-butyl group.12. The fragrance composition of claim 3 , wherein the content of the carboxylic acid ester compound is from 0.01 to 90% by mass claim 3 , based on a total mass of the fragrance composition.13. The fragrance composition of claim 3 , wherein the content of the carboxylic acid ester compound is from 0.1 to 50% by mass claim 3 , based on a total mass of the ...

Synthesis and Characterization of Open Metal Clusters

The present invention is directed to the synthesis of novel stable open metal clusters by selective oxidation of bound ligands. The synthesis comprises, for example, using an amine based oxidant for decarbonylation of specific carbonyl ligands. The synthesis can also comprise further removal of a bound amine group by an acid. The resulting metal cluster contains a coordinatively unsaturated site comprising a carbonyl vacancy. The resulting metal cluster can be used as a catalyst in a variety of chemical transformations. 1. A method for preparing an open metal carbonyl cluster comprising chemically reacting a closed metal carbonyl cluster and an opening agent , with the opening agent reacting with a bound carbonyl group so as to unbind it from the cluster and leave behind a CO-labile ligand on the cluster.2. The method of claim 1 , wherein the opening agent is an oxidant.3. The method of claim 2 , wherein the oxidant is trimethylamine oxide.4. The method of claim 1 , wherein the CO-labile ligand is a nitrogen-containing compound coordinating through nitrogen or an oxygen-containing compound coordinating through oxygen.5. The method of claim 1 , wherein the CO-labile ligand is an ether claim 1 , amine claim 1 , dioxygen or nitrogen.6. The method of claim 1 , wherein the open metal carbonyl cluster obtained comprises CO-labile ligands or vacant CO sites.7. The method of claim 1 , wherein the closed metal carbonyl cluster is an Ircarbonyl cluster.8. The method of claim 1 , wherein the closed metal carbonyl cluster is bound with three sterically protective ligands.9. The method of claim 8 , wherein the ligands are calixarene phosphine ligands.10. The method of claim 1 , wherein the closed metal carbonyl cluster is an Ircarbonyl cluster bound with three calixarene phosphine ligands claim 1 , and the opening agent is trimethylamine oxide.11. The method of claim 6 , wherein the open metal carbonyl cluster prepared comprises CO-labile ligands in vacated CO sites.12. The ...

METHODS FOR COPRODUCTION OF TEREPHTHALIC ACID AND STYRENE FROM ETHYLENE OXIDE

The present invention provides methods for the production of terephthalic acid and derivatives thereof using ethylene oxide, carbon monoxide and furan as feedstocks. The process is characterized by high yields and high carbon efficiency. The process can utilize 100% biobased feedstocks (EO via ethanol, CO via biomass gasification, and furan via known processes from cellulosic feedstocks). In one aspect, processes of the invention coproduce biobased terephthalic acid and biobased styrene. 1. A process for production of a chemical product comprising terephthalic acid or tereohthalate by utilizing furan , ethylene oxide , and carbon monoxide as the feedstocks , the process comprising the steps of:reacting the ethylene oxide and carbon monoxide to form beta propiolactone; andderiving the chemical product from the beta propiolactone wherein the chemical product comprises at least one of terephthalic acid, a mono or diester of terephthalic aid, and a mono or bis metal salt of terephthalic acid.2. The process of wherein the carbon efficiency of the process is greater than 80%.3. The process of claim 2 , comprising the step of:converting the beta propiolactone to an unsaturated compound selected from the group consisting of: acrylic acid, an ester of acrylic acid an acrylate salt and a mixture of any two or more of these and deriving the chemical product from the unsaturated compound.4. The process of claim 3 , comprising the step of reacting the unsaturated compound with the furan to provide a seven carbon compound containing a cyclohexene ring and deriving the chemical product from the seven carbon compound.5. The process of claim 4 , further comprising the step of dehydrating the seven carbon compound to provide a compound containing a mono-substituted benzene ring and disproportionating the compound containing the mono-substituted benzene ring to produce at least a portion of the chemical product.6. The process of claim 5 , wherein the disproportionation of the mono- ...

Method for preparing polyoxymethylene dimethyl ether carbonyl compound and methyl methoxyacetate

A method for preparing a polyoxymethylene dimethyl ether carbonyl compound and/or methyl methoxyacetate as intermediates for producing ethylene glycol, which comprises passing a raw material: polyoxymethylene dimethyl ether or methylal together with carbon monoxide and hydrogen gas through a reactor carrying an acidic molecular sieve catalyst, and performing a reaction to prepare a corresponding product under an appropriate condition where no other solvent is added, in which the process of the reaction is a gas-liquid-solid three-phase reaction, the raw material of polyoxymethylene dimethyl ether or methylal has a high conversion rate, each product has a high selectivity, the catalyst has a long service life, additional solvents are not required to be used, and reaction conditions are relatively mild.

PROCESS FOR THE CARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS, NOVEL CARBONYLATION LIGANDS AND CATALYST SYSTEMS INCORPORATING SUCH LIGANDS

A novel bidentate ligand of general formula (I) 2. A process for the carbonylation of ethylenically unsaturated compounds comprising reacting said compound with carbon monoxide in the presence of a source of hydroxyl groups , optionally , a source of anions and of a catalyst system , the catalyst system obtainable by combining:(a) a metal of Group 8, 9 or 10 of the Periodic Table or a compound thereof; and{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, '(b) the bidentate ligand of formula (I) according to'}3. The bidentate ligand according to claim 1 , wherein the group Xis selected from a cyclic structure which is unsaturated claim 1 , saturated or part unsaturated.4. The bidentate ligand according to claim 3 , wherein the group Xis selected from a cyclic structure which is unsaturated.5. The bidentate ligand according to claim 4 , wherein the groups Xis aromatic.6. The bidentate ligand according to claim 1 , wherein the group Xis selected from an aromatic nitrogen heterocycle having 3-14 ring atoms.7. The bidentate ligand according to claim 1 , wherein the group Xis selected from an aziridine claim 1 , azirine claim 1 , azetidine claim 1 , azete claim 1 , pyrrolidone claim 1 , pyrrole claim 1 , pyridine claim 1 , piperidine claim 1 , azepane claim 1 , azepine claim 1 , azocane claim 1 , azocine imidazolidine claim 1 , pyrazolidine claim 1 , imidazole claim 1 , benzimidazole claim 1 , imidazoline claim 1 , pyrazole claim 1 , indazole claim 1 , pyrazoline claim 1 , pyrazine claim 1 , pyrimidine claim 1 , pyridazine claim 1 , piperazine claim 1 , hexahydro-pyrimidine claim 1 , hexahydro-pyridazine claim 1 , indole claim 1 , isoindole claim 1 , quinoline claim 1 , isoquinoline claim 1 , quinazoline claim 1 , benzopyrazine claim 1 , acridine or benzoquinoline radical.8. The bidentate ligand according to claim 1 , wherein the group Xis an alkyl amine claim 1 , aryl amine claim 1 , dialkylamine claim 1 , or trialkyl amine radical.9. The bidentate ligand according to ...

METHODS

A method for preparing a partially fluorinated ester comprising acyl and alkoxy groups wherein the acyl group comprises a branched or linear fluorine containing C-Cgroup with one of the structures: (Formulae (I), (II)) wherein X and Y are independently selected from: —H, —CH, —F, —Cl, —CHF, —CF—OCF, —OCHCF, OCHCFCHFand —CHCF(wherein both X and Y cannot be H) comprising reacting an unsaturated halocarbon: (Formula (III)) wherein A and B are independently selected from the group comprising —H, —CH, —F, —Cl, —CHF, —CF, —OCF, —OCHCF, OCHCFCHFand —CHCF(wherein both A and B cannot be H) with carbon monoxide and an alcohol, in the presence of a catalyst methods. 2. A method according to claim 1 , where the acyl group has 3 to 7 carbon atoms.3. A method according to claim 1 , wherein the acyl group comprises CF—CHFCO; preferably one of the group comprising CFCHCH(F)CO claim 1 , CFCH(CHF)CO and CFCF(CH)CO or wherein the acyl group comprises CF—CHFCO claim 1 , more preferably CFCHCH(CF)CO.4. (canceled)5. A method according to claim 1 , comprising reacting 2 claim 1 ,3 claim 1 ,3 claim 1 ,3-Tetrafluoropropene (1234yf) with carbon monoxide and an alcohol of formula ROH to form CFCF(CH)COR and/or CFCHFCHCOR; or reacting 2-chloro-3 claim 1 ,3 claim 1 ,3-trifluoropropene (1233xf) with carbon monoxide and an alcohol to form CFCCl(CH)COR and/or CFCHClCHCOR.6. A method according to claim 1 , comprising reacting 1 claim 1 ,3 claim 1 ,3 claim 1 ,3-Tetrafluoropropene (1234ze) with carbon monoxide and an alcohol of formula ROH to form CFCH(CHF)COR and/or CFCHCHFCO.7. A method according to claim 1 , comprising reacting 1 claim 1 ,1 claim 1 ,1 claim 1 ,4 claim 1 ,4 claim 1 ,4-hexafluoro-2-butene (1336mzz) with carbon monoxide and an alcohol of formula ROH to form CFCHCH(CF)COR.8. A method according to claim 1 , wherein the alkoxy group is derived from a branched or linear monohydric alcohol with the formula HOCHF claim 1 , wherein n is from 1 to 10 and x has a value from 0 to 2n+1.9. ( ...

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 , ...

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- ...

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

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

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.

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

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

PROCESS FOR THE ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS WITH MONOPHOSPHINE LIGANDS

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

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 ...

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

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

CARBOXYLIC ACID ESTER COMPOUND, PRODUCTION METHOD THEREOF, AND FRAGRANCE COMPOSITION

The present invention has an object of providing a carboxylate compound that is useful as a raw material for fragrance compositions and has a fruity aroma, a method for producing the same, and a fragrance composition containing the carboxylate compound. 2. The carboxylate compound according to claim 1 , wherein R is an ethyl group claim 1 , a n-propyl group claim 1 , or an isopropyl group. The present invention relates to a novel carboxylate compound, a production method thereof, and a fragrance composition containing the carboxylate compound, and in particular, the present invention relates to a carboxylate compound that is useful as a raw material for fragrance compositions, a production method thereof, and a fragrance composition containing the carboxylate compound.Some esters are known to be compounds that are useful as fragrances. For example, geranyl acetate having a rose-like aroma, methyl jasmonate having a jasmine-like sweet aroma, Fruitate (ethyl tri cyclo[5.2.1.0]decane-2-carboxylate) having a fruity scent, and methyl benzoate with an intense dry fruity scent are useful as ingredients for fragrance compositions. Furthermore, Patent Document 1 describes that a carboxylate compound that is a derivative of camphene has a refreshing pine-like aroma.Patent Document 1: WO 2012/063433A problem to be addressed by the present invention is to provide a novel carboxylate compound having a fruity aroma, a method for producing the same, and a fragrance composition containing the carboxylate compound.The present inventors synthesized various compounds and studied the aromas thereof, and they discovered that certain carboxylate compounds have a fruity aroma, thereby arriving at the present invention.The present invention provides the following aspects <1> to <4>.<1> A carboxylate compound represented by Formula (1).where, R is an alkyl group having from 2 to 6 carbons.<2> The carboxylate compound according to <1>, wherein R is an ethyl group, a n-propyl group, or an ...

METHOD FOR PRODUCING METHACRYLIC ACID ESTER

Production of methacrylic acid ester comprising a step of having acetone undergo a dehydration reaction in the presence of a dehydration reaction catalyst to obtain a reaction mixture; a step of separating a mixture containing propyne and propadiene as main components from the obtained reaction mixture; a step of separating the separated mixture containing propyne and propadiene as main components into a liquid, gas, or gas-liquid mixture containing propyne as a main component, and a liquid, gas, or gas-liquid mixture containing propadiene as a main component; and a step of bringing the obtained liquid, gas, or gas-liquid mixture containing propyne as a main component into contact with carbon monoxide and an alcohol having 1 to 3 carbon atoms in the presence of a catalyst containing at least one selected from the group consisting of Group 8 metal elements, Group 9 metal elements, and Group 10 metal elements. 1. A method for producing a methacrylic acid ester , which comprises the following steps:a dehydration reaction step: a step of having acetone undergo a dehydration reaction in the presence of a dehydration reaction catalyst to obtain a reaction mixture containing propyne, propadiene, and water;a propyne/propadiene separation step: a step of separating a mixture containing propyne and propadiene as main components from the reaction mixture obtained in the dehydration reaction step;a propyne purification step: a step of separating the mixture containing propyne and propadiene as main components separated in the propyne/propadiene separation step into a liquid, gas, or gas-liquid mixture containing propyne as a main component, and a liquid, gas, or gas-liquid mixture containing propadiene as a main component; anda carbonylation reaction step: a step of bringing the liquid, gas, or gas-liquid mixture containing propyne as a main component obtained in the propyne purification step into contact with carbon monoxide and an alcohol having 1 to 3 carbon atoms in the ...

Process for the preparation of alkanoic acid esters in a carbonylation process using palladium bidentate biphosphate ligands

The invention relates to a carbonylation process for the preparation of an alkanoic acid ester comprising reacting: (a) an alkene; (b) a source of Pd; (c) a bidentate phosphine ligand of formula I; R 1 R 2 P—R 3 —R—R 4 —PR 5 R 6   (I) wherein P represents a phosphorus atom; R1, R2, R 5 and R 6 can independently represent the same or different optionally substituted organic groups containing a tertiary carbon atom through which the group is linked to the phosphorus atom; R 3 and R 4 independently represent optionally substituted lower alkylene groups and R represents an optionally substituted aromatic group; (d) a source of anions derived from an acid with a pKa<3; (e) carbon monoxide; and (f) an alkanol; characterized in that the process is performed in the presence of between 0.1 and 3 wt water. The process advantageously has a high conversion rate and is suitable for the production of dimethyl adipate, adipate and hexamethylene diamine and products derived thereof such as nylon 6,6 from renewable sources such as plant waste, sewage waste etceteras instead of using fossil sources.

GAS PHASE PRODUCTION OF ALKYL ALKANOATES

An alkane-containing stream is reacted to produce an alkene, which is carbonylated to produce an alkyl alkanoate, e.g., methyl propanoate, by a gas phase process comprising the step of contacting under carbonylation conditions the alkene, e.g., ethylene, carbon monoxide, an alkanol, e.g., methanol, and a solid sulfide-based metal catalyst. 1. A process comprising: (a) providing a gas feed stream comprising >1 mol % of an alkane; (b) at least partially converting the alkane to produce a gaseous first intermediate stream comprising water , unreacted alkane , and >1 mol % of an alkene; (c) removing the majority of the water from the gaseous first intermediate stream to produce a gaseous second intermediate stream comprising at least one alkene; and (d) contacting under gas phase carbonylation conditions the gaseous second intermediate stream , carbon monoxide gas , an alkanol gas and a solid sulfide-based metal catalyst to produce an alkyl alkanoate.2. The process of comprising: (a) providing a gas feed stream comprising >1 mol % of an alkane; (b) at least partially converting the alkane to produce a gaseous first intermediate stream comprising water claim 1 , other hydrocarbons claim 1 , H claim 1 , CO claim 1 , CO claim 1 , unreacted alkane claim 1 , and >1 mol % of an alkene; (c) removing the majority of the water from the gaseous first intermediate stream to produce a gaseous second intermediate stream comprising at least one alkene claim 1 , other hydrocarbons claim 1 , H claim 1 , CO claim 1 , COand unreacted alkane; and (d) contacting under gas phase carbonylation conditions the gaseous second intermediate stream claim 1 , carbon monoxide gas claim 1 , an alkanol gas and a solid sulfide-based metal catalyst to produce an alkyl alkanoate.3. The process of wherein the alkene is of the formula CHin which n is from 2 to 12 claim 1 , and the alkanol comprises from 1 to 30 carbon atoms.4. The process of wherein the alkane is methane and the alkene is ethylene.5. The ...

CONTINUOUS PROCESS FOR THE CARBONYLATION OF ETHYLENE

A continuous process for the production of an alkyl ester product is described. The process includes the steps of carbonylating ethylene with carbon monoxide in the presence of C1-6 alkanol co-reactant to form the alkyl ester product. The carbonylation takes place in the presence of a catalyst system that includes (a) a bidentate ligand, (b) a catalytic metal selected from a group 8, 9 or 10 metal or a compound thereof, and (c) a sulphonic acid capable of forming an acid alkyl ester with the C1-6 alkanol. The process includes the step of separating the alkyl ester product from a carbonylated crude product stream by treatment effective to vaporizing the alkyl ester product in a single stage flash distillation column and providing a purified alkyl ester product stream separated from the bidentate ligand and catalytic metal. 1. A continuous process for the production of an alkyl ester product comprising the steps of carbonylating ethylene with carbon monoxide in the presence of C1-6 alkanol co-reactant to form the said alkyl ester product , wherein the carbonylation takes place in the presence of a catalyst system comprising;a. a bidentate ligand,b. a catalytic metal selected from a group 8, 9 or 10 metal or a compound thereof, andc. a sulphonic acid capable of forming an acid alkyl ester with the C1-6 alkanol, the process including the step of separating the formed alkyl ester product from a carbonylated crude product stream by treatment that vaporizes the alkyl ester product in a single stage flash distillation column and provide a purified alkyl ester product stream separated from the said bidentate ligand and catalytic metal, wherein the said distillation column includes further separation means effective to provide further separation of the product.2. The process of claim 1 , wherein the further separation means is packing in or associated with the upper part of the flash distillation column and/or is provided by trays.3. The process of claim 2 , wherein the ...

DOUBLE ALKOXYCARBONYLATION OF DIENES

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

Double alkoxycarbonylation of dienes as one-pot synthesis

Process for the double alkoxycarbonylation of dienes as one-pot synthesis.

Process For The Sustainable Production Of Acrylic Acid

A process for the production of organic acids having at least three carbon atoms comprises the steps of forming an amount of carbon monoxide and reacting the amount of carbon monoxide with an amount of an unsaturated hydrocarbon. The reaction is preferably carried out in the presence of a supported palladium catalyst, a strong acid, and a phosphine. In some embodiments, the unsaturated hydrocarbon is one of acetylene and methylacetylene, and the organic acid is one of acrylic acid and methyl acrylic acid. The reacting step is preferably performed with carbon monoxide produced from carbon dioxide. 1. A process for the production of an organic acid having at least three carbon atoms , the process comprising the steps of:forming an amount of carbon monoxide; andreacting said amount of carbon monoxide with an amount of an unsaturated hydrocarbon in the presence of:(a) a catalyst comprising multiatom palladium clusters supported on one or more of (i) a metal oxide, (ii) activated carbon, (iii) graphite, (iv) graphene, (v) carbon nanotubes, (vi) fullerenes, (vii) carbon monoliths, (viii) templated carbon, and (ix) diamond;(b) a strong acid; and(c) a phosphine.2. The process of claim 1 , wherein the phosphine is diphenyl-2-pyridylphosphine and the strong acid is trifluoromethane sulfonic acid.3. The process of claim 1 , further comprising initially converting an amount of carbon dioxide obtained from a natural source or from an artificial chemical source to produce said amount of carbon monoxide claim 1 , thereby reducing said amount of carbon dioxide present in nature or diverting said amount of carbon dioxide from being discharged into the environment by said artificial chemical source.4. The process of claim 1 , wherein said unsaturated hydrocarbon is one of acetylene and methylacetylene.5. The process of claim 1 , wherein said organic acid is one of acrylic acid and methyl acrylic acid.6. The process of claim 5 , wherein the reaction temperature is between 50° C. and ...

Compound, Manufacturing Method Therefor, and Method for Manufacturing Optically Active alpha-Aminophosphonate Derivative

A method for producing a compound represented by General Formula (1), the method including: 5. The method according to claim 4 , wherein the reacting is performed using a catalyst containing an asymmetric ligand.6. The method according to claim 5 , wherein the catalyst containing an asymmetric ligand is a copper-optically active phosphine complex. The present invention relates to a method for efficiently synthesizing an optically active α-aminophosphonic acid derivative which is useful as a starting material of a candidate substance of a drug. Specifically, the present invention relates to a novel compound, a method for efficiently synthesizing the novel compound, a method for synthesizing the optically active α-aminophosphonic acid derivative using the novel compound, and a novel optically active α-aminophosphonic acid derivative.Optically active α-aminophosphonic acid derivatives are useful for the synthesis of candidate compounds of pharmaceutical drugs such as antibacterial agents, anti-HIV drugs, and enzyme inhibitors (see, for example, NPLs 1 to 5).Generally employed methods for producing optically active α-aminophosphonic acid derivatives are, for example, methods using chiral auxiliary groups for increasing stereoselectivity (see, for example, NPLs 6 to 9).These techniques, however, use expensive chiral auxiliary groups in a large amount (an equimolar amount or more) and the chiral auxiliary groups cannot be recovered after use, having a problem that they are not economical.Other proposed production methods include a method using, as a catalyst, Cinchona Alkaloid such as quinine, adding diphenyl phosphate to a specific ketimine to obtain an adduct, and synthesizing an optically active α-aminophosphonic acid derivative from the adduct (see, for example, NPL 10).This technique, however, has a problem that stereoselectivity is low unless at least one of two substituents binding to carbon of the C═N bond of the ketimine is an aromatic hydrocarbon group, which ...

TRIESTERS OF CYCLOHEXANETRIPROPIONIC ACID

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

METHOD FOR PREPARING ORGANIC CARBOXYLIC ESTER BY USING COMBINED CATALYST OF ARYL BIDENTATE PHOSPHINE LIGAND

Disclosed is a method for preparing an organic carboxylic ester by using a combined catalyst of an aryl bidentate phosphine ligand. The method includes subjecting a terminal olefin, carbon monoxide, and an alcohol to a hydroesterification reaction in the presence of a combined catalyst of a palladium compound, an aryl bidentate phosphine ligand, and an acidic additive, to generate an organic carboxylic ester having one more carbon atom than the terminal olefin. 1. A method for preparing an organic carboxylic ester , comprising the step of:subjecting a terminal olefin, carbon monoxide, and an alcohol to a hydroesterification reaction in an organic solvent in the presence of a combined catalyst to generate an organic carboxylic ester having one more carbon atom than the terminal olefin,wherein the combined catalyst comprises a palladium compound, an aryl bidentate phosphine ligand, and an acidic additive.2. The method as claimed in claim 1 , wherein:a molar ratio of the aryl bidentate phosphine ligand to the palladium compound ranges from 0.1:1 to 100:1; anda molar ratio of the acidic additive to the palladium compound ranges from 0.1:1 to 100:1.3. The method as claimed in claim 2 , wherein:the molar ratio of the aryl bidentate phosphine ligand to the palladium compound ranges from 2:1 to 10:1; andthe molar ratio of the acidic additive to the palladium compound ranges from 2:1 to 20:1.5. The method as claimed in claim 4 , wherein claim 4 , in the substituted Caryl and substituted Cheteroaryl claim 4 , a substituent is selected from the group consisting of —Calkyl claim 4 , —Ccycloalkyl claim 4 , —Cheterocycloalkyl claim 4 , —Caryl claim 4 , —Cheteroaryl claim 4 , —O—Calkyl claim 4 , —O—Calkyl-Caryl claim 4 , —O—Ccycloalkyl claim 4 , —S—Calkyl claim 4 , —S—Ccycloalkyl claim 4 , —COO—Calkyl claim 4 , —COO—Ccycloalkyl claim 4 , —CONH—Calkyl claim 4 , —CONH—Ccycloalkyl claim 4 , —CO—Calkyl claim 4 , —CO—Ccycloalkyl claim 4 , —N—(Calkyl) claim 4 , —Caryl claim 4 , —Caryl- ...

PHOSPHORAMIDITE DERIVATIVES IN THE HYDROFORMYLATION OF UNSATURATED COMPOUNDS

The invention relates to the following subject matters: a) phosphoramidites of the formula (I); b) transition metal-containing compounds of the formula Me(acac)(CO)L, wherein L is selected from the formula (I); c) catalytically active compositions in the hydroformylation, which contain the compounds listed in a) and b); d) method for hydroformylation of unsaturated compounds using the catalytically active composition listed under c); and e) multi-phase reaction mixture containing unsaturated compounds, gas mixture comprising carbon monoxide, hydrogen, aldehydes, and the catalytically active compositions described in 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 not the same as Rand they are independently selected from C-C-alkyl claim 3 , aryl claim 3 , carboxamide and tosyl radicals.7. Transition metal compounds according to claim 6 , where Q is selected from substituted or unsubstituted 1 claim 6 ,1′-biphenyl claim 6 , 1 claim 6 ,1′-binaphthyl and ortho-phenyl radicals.8. Transition metal compounds according to claim 7 , where Q is selected from substituted or unsubstituted 1 claim 7 ,1′-biphenyl radicals.9. Transition metal compounds according to claim 8 , where Ris not the same as Rand they are independently selected from C-C-alkyl claim 8 , aryl claim 8 , carboxamide and tosyl radicals.11. Transition metal compounds of the formula Me(acac)(CO)L with Me=transition metal according to claim 10 , where Me is selected from rhodium claim 10 , iridium claim 10 , ruthenium claim 10 , cobalt.12. Transition metal compounds according to claim 11 , where the transition metal is rhodium.13. Catalytically active compositions in the hydroformylation comprising ...

PROCESS FOR DOUBLE CARBONYLATION OF ALLYL ALCOHOLS TO CORRESPONDING DIESTERS

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

YLIDE-FUNCTIONALISED PHOSPHANES FOR USE IN METAL COMPLEXES AND HOMOGENEOUS CATALYSIS

The invention relates to ylide-functionalized phosphane ligands, the production of same and use in transition metal compounds, as well as the use of same as catalysts in organic reactions. 1. (canceled)2. The method of claim 8 , wherein in the phosphane ligands{'sub': 1-10', '1-6', '4-10', '6-14', '2-10', '6-14, '(i) the alkyl groups are selected from linear, branched-chain or cyclic Calkyl groups, preferably from Calkyl groups or C-cycloalkyl groups, the aryl groups are selected from Caryl groups, the alkenyl groups are selected from mono- or polyunsaturated linear, branched-chain or cyclic Calkenyl groups, and the heteroaryl groups are selected from Cheteroaryl groups; and/or'}{'sup': 11', '12', '3', '11', '11', '11', '11', '11, 'sub': 1-6', '6-10', '2', '2', '1-6, '(ii) the functional groups are selected from alkyl (—R), especially Calkyl groups, Caryl (—R), halogen (—Hal), hydroxy (—OH), cyano (—CN), alkoxy (—OR), amino (—NR, —NHR, —NH), mercapto (—SH, —SR), wherein R, independently of further Rresidues, is selected from Calkyl residues.'}4. The method of claim 8 , wherein in the phosphane ligands R claim 8 , Rand Rare independently selected from the group consisting of methyl claim 8 , ethyl claim 8 , butyl claim 8 , cyclohexyl claim 8 , phenyl claim 8 , and combinations thereof.5. The method of claim 8 , wherein in the phosphane ligands claim 8 , R claim 8 , Rand Rare the same and are selected from the group consisting of methyl claim 8 , ethyl claim 8 , butyl claim 8 , cyclohexyl claim 8 , phenyl claim 8 , and combinations thereof claim 8 , especially cyclohexyl and phenyl.6. The method of claim 8 , wherein in the phosphane ligands claim 8 , X is selected from the group consisting of methyl claim 8 , ethyl claim 8 , cyclohexyl claim 8 , phenyl claim 8 , p-tolyl claim 8 , trimethylsilyl claim 8 , p-tolylsulfonyl claim 8 , or combinations thereof.7. The method of claim 8 , wherein in the phosphane ligands claim 8 , Rand Rare independently selected from the ...

PROCESS FOR THE MANUFACTURE OF ALPHA, ALPHA-BRANCHED CARBOXYLIC ACID VINYL ESTERS

The invention relates to a process for the manufacture of α,α-branched carboxylic acids vinyl esters comprising the following steps: 1. A process for the manufacture of α ,α-branched carboxylic acid vinyl esters comprising the following steps:isomerising and converting an olefin feed with CO and water under Koch reaction conditions to make an acid with a ratio of Non Blocking isomers (NB) versus Blocking isomers (B) of NB/B above 1.5, wherein a blocking isomer has a tertiary carbon atom in alpha position of the carboxylic acid and in the beta position of the carboxylic acid, wherein a non-blocking isomer has primary carbon atoms in the beta position of the carboxylic acidconverting the resulting acid into a vinyl ester.2. The process of wherein the olefin feed is a propylene oligomer.3. The process of wherein the olefin feed has an isomer ratio of (BR1+BR2)/BR3=Ya above 20 claim 1 , with BR1=weight of olefin with one branching alkyl group claim 1 , BR2=weight of olefin with two branching alkyl groups and BR3=weight of olefin with three or more branching alkyl groups.4. The process of wherein the starting olefin feed has an isomer ratio of (BR1+BR2)/BR3=Yb below 20 claim 1 , with BR1=weight of olefin with one branching alkyl group claim 1 , BR2=weight of olefin with two branching alkyl groups and BR3=weight of olefin with three or more branching alkyl groups.5. The process of wherein the oligomer is mainly a trimer or mainly a tetramer of propylene.6. The process of claim 1 , wherein the isomerisation is carried out under Koch conditions and wherein the water content of the catalyst in the Koch reaction is below 12% wt and a residence time of more than 30 minutes is used.7. The process of wherein the resulting acid is reacted with acetylene in presence of a zinc catalyst.8. The process of wherein the oligomer is mainly a trimer of propylene and wherein the resulting acids are reacted with acetylene in presence of a zinc salt to produce vinyl ester of branched ...

Stable long-term method for producing c5-aldehydes

The invention relates to a process for preparing aldehydes having five carbon atoms, in which an input mixture containing 10% by weight to 50% by weight of linear butenes and less than 5% by weight of 1-butene is hydroformylated with synthesis gas in the presence of a catalyst system comprising rhodium and at least one bisphosphite ligand, wherein the hydroformylation is effected in a reactor from which, over an operating period, a cycle gas containing at least a portion of the products and unconverted reactants from the hydroformylation is continuously drawn off and partly condensed, and uncondensed components of the cycle gas are recycled into the reactor, and wherein, after the operating period has expired, the hydroformylation is stopped, the reactor is freed of reaction residues and the hydroformylation is restarted. It is based on the problem of making such a process more economically viable. The problem is solved by using a bisphosphite of the formula (1) and/or (2) as ligand, extending the operating period to more than 8000 h, and not separating solid reaction residues out of the reactor during the course of the operating period.

Method for manufacturing olefin derivative

There is provided a method for manufacturing an olefin derivative which is capable of improving the yield and manufacturing efficiency. The method for manufacturing an olefin derivative according to the present invention comprises a first step of reacting an olefin with an alcohol and carbon monoxide in the presence of a palladium catalyst and an oxidizing agent in a reactor to thereby synthesize a carboxylic acid or a carboxylate ester, a second step of discharging at least part of a gas in the reactor out of the reactor, and separating carbon monoxide from the gas discharged during the first step; and a third step of supplying the carbon monoxide separated from the gas in the second step to the reactor during the first step.

PROCESS FOR PREPARING ESTERS FROM FORMATES AND OLEFINICALLY UNSATURATED COMPOUNDS

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

Gas Phase Production of Alkyl Alkanoate

Alkyl alkanoates, e.g., methyl propionate, are made by a gas phase process comprising the step of contacting under carbonylation conditions an alkene (e.g., ethylene), carbon monoxide, an alkanol (e.g., methanol), and a solid sulfide-based metal catalyst (e.g., iron sulfide). The alkyl alkanoate can be converted in a second step to an alkyl ester of an aliphatic carboxylic acid, e.g., methyl methacrylate, through condensation with an aldehyde, e.g., formaldehyde. 1. A process comprising the step of contacting under carbonylation conditions an alkene gas , carbon monoxide gas , an alkanol gas and a solid sulfide-based metal catalyst to produce an alkyl alkanoate.2. A two-step process comprising:A. Contacting under carbonylation conditions an alkene gas, carbon monoxide gas, an alkanol gas, and a solid, sulfide-based metal catalyst to produce an alkyl alkanoate; andB. Contacting under condensation conditions the alkyl alkanoate of Step A with an aldehyde to produce an alkyl ester of an aliphatic carboxylic acid.3. The process of in which the solid claim 1 , sulfide-based metal catalyst comprises a Group VIII metal.4. The process of in which the solid claim 3 , sulfide-based metal catalyst comprises at least one of iron claim 3 , cobalt claim 3 , rhodium and nickel.5. The process of in which the alkene gas is of the formula CHin which n is from 2 to 12.6. The process of in which the carbonylation conditions are halogen-free.7. The process of in which the alkene gas is ethylene gas.8. The process of in which the alkanol comprises 1-30 carbon atoms.9. The process of in which the alkanol is methanol.10. The process of in which the carbonylation conditions include a temperature from 200° C. to 400° C. and a pressure from 0.1 MPa to 10 MPa.11. The process of conducted in a trickle-bed reactor.12. The process of in which the condensation conditions include a temperature from 200° C. to 400° C. and a pressure from 0.1 MPa to 10 MPa.13. A process comprising the step of ...

BUTYL-BRIDGED DIPHOSPHINE LIGANDS FOR ALKOXYCARBONYLATION

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

Process for the preparation of acrylate esters from alkyl lactates

Catalytic hydroesterification of alkyl lactates give alkyl 2-(propionyloxy)propanoates, starting from alkyl lactate, carbon monoxide, ethylene gas, and a palladium catalyst. Pyrolysis of alkyl 2-(propionyloxy)propanoates gives acrylate esters.

Mixture of different asymmetrical bisophosphites and use thereof as a catalyst mixture in hydroformylation

The invention relates to a mixture of unsymmetric bisphosphites, to a process for preparation thereof, to the reaction thereof with metals to give mixtures comprising complexes of the bisphosphites and the metal, and to the use thereof as a catalytically active composition in hydroformylation reactions, and also to the hydroformylation reaction itself.

Mixtures of constitutionally isomeric bisphosphites

The invention relates to mixtures of constitutional isomer bisphosphites of formulae (1a) and (2a), to a method for the production thereof, to the reaction thereof with metals to form mixtures containing complex compounds of the constitutional isomer bisphosphites of formulae (1a) and (2a) and the metal, and to the use thereof as a catalytically active composition in hydroformylation reactions. Said hydroformylactically active compositions comprises, in addition to the complex compounds of metal and the constitutional isomer bisphosphites of formulae (1a) and (2a), non-bound bisphosphites of the constitutional isomer bisphosphites of formulae (1a) and (2a) and at least one additional component.

HYDROCARBONYLATION OR METHOXYCARBONYLATION OF 1,3-DIENE DERIVATIVES WITH PALLADIUM COMPLEX

The present invention concerns a process of carbonylation of poly-unsaturated diene with high selectivity for the preparation of a β,γ-unsaturated carboxylic acid or ester in the presence of water or alcohol and catalyzed by [PdClP] complex wherein Pis two mono or one bidendate phosphine ligand. 3. A process according to claim 1 , wherein said Ris a hydrogen or a Calkyl group.4. A process according to claim 1 , wherein said compound (I) is 4 claim 1 ,8 claim 1 ,12-trimethyltrideca-3 claim 1 ,7 claim 1 ,11-trienoic acid or ester claim 1 , in the form of a mixture of isomers of conformation E and Z wherein the (3E)/(3Z) ratio is comprised between about 1 and 2.5.5. A process according to claim 1 , wherein Prepresents two monodentate monophosphines of formula P(R)Ar wherein Rrepresents claim 1 , simultaneously or independently claim 1 , a CCcyclic or branched alkyl group or an Ar group and Ar represents a Cto Cheteroaromatic or aromatic group optionally substituted by one to five halogen atoms claim 1 , Chalo- or perhalo-hydrocarbon groups claim 1 , Calkoxy groups or Calkyl groups.6. A process according to claim 5 , wherein P(R)Ar represents triphenylphosphine claim 5 , tri-ortho-tolylphosphine claim 5 , tri-meta-tolylphosphine claim 5 , tri-para-tolylphosphine claim 5 , ((4-Trifluoromethyl)phenyl)di-tert-butylphosphine claim 5 , tri-2-furylphosphine.7. A process according to claim 1 , wherein Prepresents a bidentate biphosphine having a natural bite-angle comprised between 95° to 130°.8. A process according to claim 7 , wherein said bidentate biphosphine represents a compound of formula (Ar)PQP(Ar)wherein Ar has the same meaning as defined above and Q is oxybis(2 claim 7 ,1-phenylene) or 9 claim 7 ,9-dimethyl-9H-xanthene-4 claim 7 ,5-diyl.9. A process according to claim 7 , wherein said bis(di-Ar-phosphine) is 1 claim 7 ,1′-[(oxydi-2 claim 7 ,1-phenylene)]bis[1 claim 7 ,1-diphenylphosphine claim 7 , 4 claim 7 ,5-Bis(diphenylphosphino)-9 claim 7 ,9-dimethylxanthene.10. ...

CATALYST SYSTEM

The present invention provides a catalyst system capable of catalysing the carbonylation of an ethylenically unsaturated compound, which system is obtainable by combining: 137-. (canceled)38. A process for the carbonylation of an ethylenically unsaturated compound comprising an ethylenically unsaturated compound with carbon monoxide and a hydroxyl group containing compound in the presence of a catalyst system , which system is obtained by combining:a) a metal of Group VIB or Group VIIIB or a compound thereof,b) a bidentate phosphine, arsine, or stibine ligand, andc) an acid,wherein said ligand is present in at least a 2:1 molar excess compared to said metal or said metal in said metal compound, and said acid is present in at least a 2:1 molar excess compared to said ligand.39. A process as claimed in wherein the ratio of said ligand to said metal is in the range 5:1 to 750:1.40. A process as claimed in wherein the ratio of said ligand to said metal is in the range 10:1 to 500:1.41. A process as claimed in wherein the ratio of said ligand to said metal is in the range 20:1 to 40:1.42. A process as claimed in wherein the ratio of said acid to said ligand is in the range 20:1 to 40:1.43. A process as claimed in wherein the molar ratio of said acid to said metal is in the range 10:1 to 75000:1.44. A process as claimed in wherein the molar ratio of said acid to said metal is in the range 100:1 to 25000:1.45. A process as claimed in wherein the molar ratio of said acid to said metal is in the range 200:1 to 400:1.46. A process as claimed in wherein said ligand is a bidentate phosphine ligand.48. A process as claimed in wherein Rto Reach independently represent lower alkyl claim 47 , aryl claim 47 , or Het.49. A process as claimed in wherein said ligand is represented as:{'br': None, 'sub': S', 'T', 'u', 'v, 'sup': 7', '8', '9', '2', '1', '1', '2', '3, '(Ad)(CRRR)Q-A-(K,D)Ar(E,Z)—B-Q(Ad)(CRRR),'}{'sup': 3', '13', '14', '15, 'sub': w', 'x, 'wherein K, D, E and Z may ...

METHOD FOR PRODUCING ESTER COMPOUND AND PALLADIUM CATALYST USED IN THE METHOD

A method for producing an ester compound includes reacting a compound having at least one cyclic structure of a norbornene ring and a norbornadiene ring with an alcohol and carbon monoxide by using a palladium catalyst and an oxidizing agent, to thereby introduce ester groups to carbon atoms forming a double bond in the cyclic structure and obtaining the ester compound, wherein the palladium catalyst includes a palladium acetate having a nitrite ligand in an amount of 10% by mole or more in terms of metal, and the palladium acetate having a nitrite ligand is represented by the general formula (1): Pd(CHCOO)(NO). 1. A method for producing an ester compound , comprising reacting a compound having at least one cyclic structure of a norbornene ring and a norbornadiene ring with an alcohol and carbon monoxide by using a palladium catalyst and an oxidizing agent , to thereby introduce ester groups to carbon atoms forming a double bond in the cyclic structure and obtain the ester compound , wherein {'br': None, 'sub': 3', '3', '5', '2, 'Pd(CHCOO)(NO)\u2003\u2003(1).'}, 'the palladium catalyst comprises a palladium acetate having a nitrite ligand in an amount of 10% by mole or more in terms of metal, and the palladium acetate having a nitrite ligand is represented by the following general formula (1)2. The method for producing an ester compound according to claim 1 , whereinthe palladium catalyst comprises the palladium acetate having a nitrite ligand in an amount of 30% by mole or more in terms of metal.3. A palladium catalyst used with an oxidizing agent in a method for producing an ester compound claim 1 , the method comprising reacting a compound having at least one cyclic structure of a norbornene ring and a norbornadiene ring with an alcohol and carbon monoxide claim 1 , to thereby introduce ester groups to carbon atoms forming a double bond in the cyclic structure and obtain the ester compound claim 1 , wherein {'br': None, 'sub': 3', '3', '5', '2, 'Pd(CHCOO)(NO)\ ...

Palladium Catalyst System Comprising Zwitterion And/Or Acid-Functionalyzed Ionic Liquid

The present invention concerns a catalyst system in particular a catalyst system comprising Palladium (Pd), a zwitterion and/or an acid-functionalized ionic liquid, and one or more phosphine ligands, wherein the Pd catalyst can be provided by a complex precursor, such as Pd(CH 3 COO) 2 , PdCl 2 , Pd(CH 3 COCHCOCH 3 ), Pd(CF 3 COO) 2 , Pd(PPh 3 ) 4 or Pd 2 (dibenzylideneacetone) 3 . Such catalyst systems can be used for e.g. alkoxycarbonylation reactions, carboxylation reactions, and/or in a co-polymerization reaction, e.g. in the production of methyl propionate and/or propanoic acid, optionally in processes forming methyl methacrylate and/or methacrylic acid. Catalyst systems according to the invention are suitable for reactions forming separable product and catalyst phases and supported ionic liquid phase SILP applications.

METHODS OF MAKING 1,19-NONADECANEDIESTER AND DERIVATIVES THEREOF

Linear α, ω-nonadecanediester derivatives and methods of making the derivatives are described. The methods include reacting a linear α, ω-nonadecanediester or a linear α, ω-nonadecanedicarboxylic acid with a reactant optionally in the presence of at least one of a solvent and a catalyst to form the α, ω-nonadecanediester derivative. Methods of making linear α, ω-nonadecanediester or diester derivatives are also described. 1. A method of making a linear α , ω-nonadecanediester derivative comprising:reacting a linear α, ω-nonadecanediester or a linear α, ω-nonadecanedicarboxylic acid with a reactant optionally in the presence of at least one of a solvent and a catalyst to form the α, ω-nonadecanediester derivative; wherein the reactant is a poly alkoxy alcohol, and the α, ω-nonadecanediester derivative is an α, ω-nonadecane di-poly alkoxy alcohol; or wherein the reactant is a caprolactone polyol and the α, ω-nonadecanediester derivative is an α, ω-nonadecane di-poly oxepan-2-one; or wherein the reactant is benzimidizole, and wherein the α, ω-nonadecanediester derivative is an α, ω-nonadecane di-benzimidizole; or wherein the reactant is an amine selected from piperazine, 1,4-diamino cyclohexane, isophorone diamine, and dicyclohexyl methane diamine, and wherein the α, ω-nonadecanediester derivative is an α, ω-nonadecane alt-(amine) wherein the alt-(amine) is derived from piperazine, 1,4-diamino cyclohexane, isophorone diamine, or dicyclohexyl methane diamine.25-. (canceled)6. The method of wherein the reactant is the poly alkoxy alcohol claim 1 , and the α claim 1 , ω-nonadecanediester derivative is the α claim 1 , ω-nonadecane di-poly alkoxy alcohol; and wherein the α claim 1 , ω-nonadecanediester or the α claim 1 , ω-nonadecanedicarboxylic acid is reacted in the presence of the catalyst.7. The method of wherein the poly alkoxy alcohol comprises a poly(ethylene glycol) having a MW in a range of about 200 to about 2000.8. The method of wherein the catalyst comprises an ...

PROCESS FOR PREPARING CARBOXYLIC ACIDS OR SALTS THEREOF FROM HYDROCARBONS

The invention relates to a process for preparing carboxylic acids or salts thereof by hydrolysis or saponification of an ester, which is obtained by alkoxycarbonylation of a C2 to C20 hydrocarbon having at least one multiple bond, preferably having at least one olefinic double bond, in which the homogeneous catalyst system used is separated from the product mixture by means of membrane separation. In a development of the present invention, the ester thus formed is converted into another ester by transesterification and then hydrolyzed or saponified. 1. ProccssThe process for preparing a carboxylic acid or salt thereof , with the process comprising the following steps:a) preparing an ester by reacting (carbonylating) a C2 to C20 hydrocarbon having at least one multiple bond, preferably having at least one olefinic double bond, with carbon monoxide and with an alcohol A in the presence of a homogeneous catalyst system in a reaction zone to obtain a product mixture;b) carrying out a membrane separation to separate the homogeneous catalyst system from the product mixture, whereby the homogeneous catalyst system and unreacted hydrocarbon and/or unreacted alcohol A, preferably unreacted alcohol A, are enriched in the retentate and the ester formed in step a) is enriched in the permeate, wherein the membrane material used is a membrane material capable of OSN (organic solvent nanofiltration) that includes at least one separation-active layer;c) separating the ester formed in step a) from the permeate in at least one separation step selected from thermal separation, for example distillation, extraction, crystallization and membrane separation;d) hydrolyzing or saponifying the ester prepared in step a) in the presence of an acidic catalyst or a saponifying agent to obtain a reaction mixture that comprises at least the carboxylic acid or salt thereof, the eliminated alcohol A, water and unreacted ester;e) separating the carboxylic acid or salt thereof formed in step d) in at ...

PROCESS FOR PREPARING AN ESTER BY ALKOXYCARBONYLATION

The invention relates to a process for preparing an ester by alkoxycarbonylation of a C2 to C20 hydrocarbon having at least one multiple bond, preferably having at least one olefinic double bond, in which the homogeneous catalyst system used is separated from the product mixture by means of membrane separation and recycled into the reaction zone. In a development of the present invention, the ester thus formed is converted into another ester by transesterification. 1. A process for preparing an ester by carbonylation of a C2 to C16 hydrocarbon , with the process comprising the following steps:a) reacting (carbonylating) a C2 to C16 hydrocarbon having at least one olefinic double bond with carbon monoxide and with an alcohol that is a mono- or polyol (two or more OH groups) having 1 to 50 carbon atoms or is a mixture of two or more mono- and/or polyols and which, when it is a monool, is used in a molar ratio to the C2 to C16 hydrocarbon (alcohol:C2 to C16 hydrocarbon) of 2 to 20 or which, when it is a polyol, is used in a molar ratio to the hydrocarbon used (hydrocarbon:polyol) of 2 to 20, in the presence of a homogeneous catalyst system comprising at least one metal of groups 8 to 10 of the periodic table of the elements or a compound thereof, a phosphorus-containing ligand and an acid, in a reaction zone to obtain a liquid product mixture that comprises at least the ester formed by the reaction, the homogeneous catalyst system, low boilers, high boilers and unreacted alcohols;b) carrying out a membrane separation to separate the homogeneous catalyst system from the liquid product mixture, whereby the homogeneous catalyst system and additionally unreacted hydrocarbon and/or unreacted alcohol, preferably unreacted alcohol, are enriched in the retentate and the ester formed in step a) is enriched in the permeate, wherein the membrane material used is an OSN (organic solvent nanofiltration) membrane material that is acid-stable, i.e. stable in the presence of the acid ...

Process for the carbonylation of ethylenically unsaturated compouds

A process for the carbonylation of ethylenically unsaturated compounds is described. The process comprises reacting an ethylenically unsaturated compound with carbon monoxide in the presence of a source of hydroxyl groups and a catalyst system. The catalyst system is obtained by combining: (a) metal of Group VIII or a compound thereof: and (b) a bidentate phosphine of general formula (I) The carbonylation reaction is carried out at a temperature of between -30°C to 49°C and under a CO partial pressure of less than 30 x105 N.m-2.

A catalyst system

The present invention provides a catalyst system capable of catalysing the carbonylation of an ethylenically unsaturated compound, which system is obtainable by combining: a) a metal of Group VIB or Group VIIIB or a compound thereof, b) a bidentate phosphine, arsine or stibine ligand, and c) an acid, wherein said ligand is present in at least a 2:1 molar excess compared to said metal or said metal in said metal compound, and that said acid is present in at least a 2:1 molar excess compared to said ligand, a process for the carbonylation of an ethylenically unsaturated compound, a reaction medium, and use of the system.

Improved catalyst system

A continuous carbonylation process for high turnover carbonylation, and a carbonylation reaction medium and product stream thereof . The process comprises carbonylating an ethylenically unsaturated compound with carbon monoxide in the presence of a source of hydroxyl groups and a catalyst system. The catalyst system comprising: (a) a bidentate phosphine, arsine or stibine ligand; and (b) a catalytic metal selected from a group VIB or group VIIIB metal or a compound thereof . The catalytically active concentration of said catalytic metal, measured as the ACCF (product Kg . hr-1. Dm-3 ) , is maintained at less than 0.5.

A process for the carbonylation of an ethylenically unsaturated compound and a catalyst system

A process for the carbonylation of an ethylenically unsaturated compound comprising the step of reacting said compound with carbon monoxide in the presence of a co- 5 reactant having a mobile hydrogen atom and a catalyst system is described. The catalyst system is obtainable by combining: (a) a metal of Group 8, 9 or 10 or a suitable compound thereof; (b) a ligand of general formula (I): and c) optionally, a source of anions. The invention is characterised in that the catalyst system includes an enhancer compound comprising an aromatic ring or ring system substituted by at least one hydroxyl group wherein the hydroxyl group pKa at 25°C is greater than 3.0 and less than 9.1, the said enhancer compound excluding 3- quinolinol. Catalyst systems for use with the enhancer compound are described as are a method of increasing the efficacy of a catalyst system for the carbonylation of ethylenically unsaturated compounds and a method of increasing the rate of carbonylation of an ethylenically unsaturated compound comprising the step of adding such a compound to the reaction.

Process for the carbonylation of ethylene

A process for the liquid-phase carbonylation of ethylene in the presence of a catalyst system comprising a Group VIII metal or compound thereof, a phosphine ligand and a source of anions, and in the presence of a source of hydroxyl groups, is carried out in conditions in which the molar ratio of ethylene to carbon monoxide in the gaseous phase of the reactor is greater than 1:1 and preferably greater than 5:1. The higher ratios of ethylene to carbon monoxide are beneficial in increasing the turnover number of the catalyst system.

Process for the carbonylation of ethylene and catalyst system for use therein

A catalyst system capable of catalysing the carbonylation of ethylene and a process which uses such a system wherein the catalyst system is obtainable by combining a metal of Group VIII, e.g. palladium, or a compound thereof and a bidentate phosphine, e.g. bis (di-t-butyl phosphino) - o - xylene.

Production of esters

A process for the manufacture of an alkyl ester of an aliphatic carboxylic acid comprises the steps of supplying a first feed stream comprising carbon monoxide and an alkene of formula CnH2n to a reactor; supplying a second feed stream comprising an alkyl alcohol, having a formula R-OH where R is an optionally substituted alkyl group, to the reactor; and reacting together said first and second feed streams in the reactor in the presence of a carbonylation catalyst, which catalyses the carbonylation reaction between carbon monoxide and the alkene, to form a product comprising an alkyl alkanoate having the formula CnH2n+1COOR, such that the ratio of alkyl alcohol to alkyl alkanoate present in the reactor is greater than the ratio of alkyl alcohol to alkyl alkanoate present in an azeotropic mixture of the alkyl alcohol and alkyl alkanoate. The process is particularly useful for the manufacture of methyl propionate by the methoxycarbonylation of ethylene.

Process for the carbonylation of a conjugated diene

A process for the carbonylation of a conjugated diene, comprising reacting the conjugated diene with carbon monoxide and a co-reactant having a mobile hydrogen atom in the presence of a catalyst system including: (a) a source of palladium; and (b) a bidentate diphosphine ligand of formula (II): R1R2 > p1R3m-R-R4n-p2 < R5R6 wherein p1 and p2 represent phosphorus atoms; R1, R2, R5, and R6 independently represent the same or different optionally substituted organic radical containing a tertiary carbon atom through which each radical is linked to the phosphorus atom; R3 and R4 independently represent the same or different optionally substituted methylene groups; R represents an organic group comprising the bivalent bridging group C1-C2 through which R is connected to R3 and R4; m and n independently represent a natural number in the range of from 0 to 4, wherein the rotation about the bond between the carbon atoms C1 and C2 of the bridging group is restricted a temperature in the range of from 0 °C to 250 °C, and wherein the dihedral angle between the plane occupied by the three atom sequence composed of C1, C2 and the atom directly bonded to C1 in the direction of p1, and the plane occupied by the three atom sequence C1, C2 and the atom directly bonded to C2 in the direction of p2, is in the range of from 0 to 120°; and (c) a source of an anion.

Process for the preparation of a dicarboxylic acid

A process for the preparation of a dicarboxylic acid, comprising the steps of (a) contacting a conjugated diene with carbon monoxide and water in the presence of a catalyst system including a source of palladium, a source of an anion and a bidentate phosphine ligand, to obtain a mixture containing an ethylenically unsaturated acid and one or more reversible adduct of the conjugated diene and the ethylenically unsaturated acid; and (b) removing unreacted conjugated diene, and the reversible adducts of the conjugated diene from the reaction mixture; and (c) reacting the mixture obtained in step (b) containing the ethylenically unsaturated acid further with carbon monoxide and water to obtain the dicarboxylic acid.

Carbonylation of conjugated dienes

A process for the carbonylation of a conjugated diene is described. The process comprises the steps of reacting a conjugated diene with carbon monoxide and a co-reactant having an active hydrogen in the presence of a solvent system and a catalyst system. The solvent system comprises a an aromatic carboxylic acid or, under some conditions, any carboxylic acid. The catalyst system is obtainable by combining: a. a metal of Group 8, 9 or 10 or a compound thereof: and b. a bidentate ligand of general formula (I) X1(X2)- Q2 - A - R- B - Q1 - X3(X4) (I) A and B each independently represent lower alkylene linking groups; R represents a cyclic hydrocarbyl structure to which Q1 and Q2 are linked, via the said linking group, on available adjacent cyclic atoms of the cyclic hydrocarbyl structure; the groups X1, X2, X3 and X4 independently represent univalent radicals of up to 30 atoms having at least one tertiary carbon atom or X1 and X2 and/or X3 and X4 together form a bivalent radical of up to 40 atoms having at least two tertiary carbon atoms wherein each said univalent or bivalent radical is joined via said at least one or two tertiary carbon atoms respectively to the appropriate atom Q1 or Q2; Q1 and Q2 each independently represent phosphorus, arsenic or 120 antimony; and, optionally, a source of anions. When the ratio of bidentate ligand : group 8, 9 or 10 metal is greater than 10:1 (mol:mol), the reaction proceeds with any carboxylic acid.

tROCESS FOR MAKING 5-CYANOVALERIC ACID, ADIPIC ACID OR DIMETHYL ADIDPATE

Disclosed in a process for making (1) a compound of the formula NC-CH2-CH2-CH2-CH2-CO2R', wherein R' is H or C1 to C12 alkyl, or (2) adipic acid or (3) dimethyl adipate, using as the substrate, 3-pentenenitrile, (2) 3-pentenoic acid or methyl 3-pentenoate, respectively, by contacting the substrate with carbon monoxide and a nucleophile in the presence of a Group VIII metal, a selected ligand, and an acid promoter. The nucleophile, which (a) an alcohol or water, or (b) water or (c) methanol, respectively, in the presence of a Group VIII metal, preferably palladium, a selected phosphine ligand, and an acid promoter.

Method for the carbonylation of pentenoic acid and derivatives thereof

The invention relates to a method for the carbonylation of n-pentenoic acid or derivatives thereof of formula (I), wherein R1 represents CN or COOR?2 and R2¿ represents hydrogen, alkyl or aryl. According to said method, a compound of formula (I) is reacted with carbon monoxide and a compound (II) containing a hydroxyl group in the presence of a catalyst system. The method is characterised in that the catalyst system is obtained by reacting a) a source of a metallic ion of a metal (III) of the 8th subgroup of the periodic table with b) a bidentate phosphine ligand of formula (IV), wherein R?3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14¿ independently of one another represent an inorganic group, which contains a respective carbon atom, by means of which the respective group is linked to the relevant tertiary carbon atom given in formula (IV), L1, L2represent independently of one another a lower alkylene group and X represents an arylene group.

A process for preparing esters of carboxylic acids

Esters or carboxylic acids are prepared from olefins containing at least two carbon atoms by reacting the olefin with carbon monoxide in the presence of: (i) a first complex of a selected Lewis acid with the ester or carboxylic acid, whichever is the reaction product recovered; (ii) a second complex of the Lewis acid with an alcohol, if an ester is being prepared, or with water, if a carboxylic acid is being prepared; and (iii) a metal carbonyl compound containing a Group IB transition metal in the first oxidation state; and by recovering the reaction product(s). The preferred olefin is propylene, the preferred ester to be prepared is methylisobutyrate, the preferred metal is copper and the preferred Lewis acid is boron trifluoride.

二膦的制备方法

一种制备通式为(R 3 -C) 2 P-L 1 -X-L 2 -P-(C-R 3 ) 2 的化合物的方法，其中每个R独立地为任选取代的侧有机基团，通过它该基团与叔碳原子C连接；L 1 、L 2 独立地为连接基团，选自将各自的磷原子与基团X连接的任选取代的低级亚烷基链，X为包括任选取代的芳基部分的桥连基，该芳基部分通过可得到的相邻碳原子与磷原子连接，该方法包括：i)将式H-L 1 -X-L 2 -H所示的化合物与有机金属化合物一起反应，生成式M-L 1 -X-L 2 -M所示的中间体化合物，其中M为碱金属原子，ii)将所述中间体化合物与式(R 3 -C) 2 P-A所示的化合物反应，其中A为卤原子，形成所述通式为(R 3 -C) 2 P-L 1 -X-L 2 -P-(C-R 3 ) 2 的化合物。M优选为锂、钾或钠，中间体化合物可以分离或不分离。反应(i)可在诸如四甲基乙二胺的络合剂存在下有利地进行。

脂环式醇的制造方法

本发明的目的在于廉价且高收率地制造作为调合香料原料等有用的通式(III)所示的脂环式醇，在HF的存在下利用一氧化碳将通式(I)所示的不饱和烃(优选通过二烯化合物的部分还原而得到的物质)羰基化得到通式(II)所示的环己烷羰基化合物，然后还原该环己烷羰基化合物从而得到通式(III)所示的脂环式醇。(式中，R 1 表示碳原子数1～4的烷基。R 2 表示碳原子数1～4的烷基。R 3 表示OH基、氟、OR 4 基的任一种。R 4 表示碳原子数1～4的烷基。)

Efficient and selective chemical recycling of carbon dioxide to methanol, dimethyl ether and derived products

An efficient and environmentally beneficial method of recycling and producing methanol from varied sources of carbon dioxide including flue gases of fossil fuel burning powerplants, industrial exhaust gases or the atmosphere itself. Converting carbon dioxide by chemical or electrochemical reduction secondary treatment to produce essentially methanol, dimethyl ether and derived products.

Processo para a carbonilacao do etileno

METHOD FOR CARBONYLATING AETHYLENE

METHOD FOR CARBONYLATING AETHYLENE

METHOD FOR PRODUCING METHACRYLATE ESTERS

Process for the carbonylation of ethylene

A process for the liquid-phase carbonylation of ethylene, according to the equation C2H4+CO+ROH->C2H5CO2R, in the presence of a catalyst system comprising a Group VIII metal or compound thereof, a phosphine ligand and a source of anions, and in the presence of water or a source of organic hydroxyl groups, is carried out in conditions in which the molar ratio of ethylene to carbon monoxide in the gaseous phase of the reactor is greater than 1:1. The higher ratios of ethylene to carbon monoxide are beneficial in increasing the turnover number of the catalyst system.

Process for the continuous carbonylation of olefins

The invention relates to a process for the continuous carbonylation of olefins whereby an olefin is reacted with carbon monoxide and a nucleophilic compound in the presence of a catalyst system based on: (a) a source of a Group VIII metal cations, (b) a source of an aliphatic diphosphine, and (c) a carboxylic acid which is the hydrocarboxylation product of the olefin, whereby during the process the carboxylic acid is either added continuously or intermittently or is prepared in-situ by continuous or intermittent addition of water.

Proses karbonilasi etilena

BISPHOSPHITE MIXING AND ITS USE AS A CATALYZING MIXTURE IN HYDROFORMILATION

Mezcla de bisfosfitos, un procedimiento para su preparación, así como su reacción con metales en compuestos complejos que contienen mezclas de los bisfosfitos isoméricos constitucionales y el metal, así como a su uso como composición catalíticamente activa en reacciones de hidroformilación, como también la reacción de hidroformilación propiamente dicha. Reivindicación 1: Mezcla que comprende los compuestos (1) y (2), en donde R¹ está seleccionado de -Me, -tBu, -OMe; R² está seleccionado de -Me, -tBu, -OMe; R³ está seleccionado de -Me, -tBu, -OMe; R⁴ está seleccionado de -Me, -tBu, -OMe; siempre que, para el caso de que R¹ sea R³, R² no sea igual a R⁴, para el caso de que R² sea R⁴, R¹ no sea igual a R³, y P puede generar otros enlaces. Reivindicación 16: Procedimiento para la hidroformilación de compuestos insaturados y sus mezclas usando: de una composición de acuerdo con una de las reivindicaciones 12 ó 13 y de una mezcla gaseosa que comprende monóxido de carbono e hidrógeno. Mixture of bisphosphites, a process for their preparation, as well as their reaction with metals in complex compounds containing mixtures of constitutional isomeric bisphosphites and metal, as well as their use as a catalytically active composition in hydroformylation reactions, as well as the reaction of hydroformylation itself. Claim 1: Mixture comprising the compounds (1) and (2), wherein R¹ is selected from -Me, -tBu, -OMe; R² is selected from -Me, -tBu, -OMe; R³ is selected from -Me, -tBu, -OMe; R⁴ is selected from -Me, -tBu, -OMe; provided that, in case R que is R³, R² is not equal to R⁴, in case R² is R⁴, R¹ is not equal to R³, and P can generate other links. Claim 16: Process for the hydroformylation of unsaturated compounds and mixtures thereof using: of a composition according to one of claims 12 or 13 and of a gas mixture comprising carbon monoxide and hydrogen.

Carboxylation process for preparing linear fatty acids or esters

CARBOXYLATION PROCESS FOR PREPARING LINEAR FATTY ACIDS OR ESTERS (D#74,032-1-F) ABSTRACT OF THE DISCLOSURE This invention concerns a process for preparing linear ratty (carboxylic) acids and esters from the reaction of olefins, alcohols (or water) and carbon monoxide. The process is catalyzed by catalytic amounts of dispersions of ligand-stabilized, palladium (II) halide complexes, in quaternary ammonium, phosphonium or arsonium salts of trihalostannate(II) or trihalogermanate(II). These empirically selected palladium catalysts can be re-cycled with fresh olefin feed several times before sub-stantial loss of catalytic activity is encountered. I

A catalyst system

A CATALYST SUITABLE FOR CARBONYLATING ETHYLENICALLY UNSATURATED COMPOUNDS COMPRISING A GROUP VIIIB METAL OR COMPOUND THEREOF AND A METALLOCENE.

PROCEDURE FOR THE CARBONILZATION OF ETHYLENE AND CATALYTIC SYSTEM FOR USE THEREOF.

UN SISTEMA CATALIZADOR CAPAZ DE CATALIZAR LA CARBONILACION DE ETILENO Y UN PROCESO EN EL QUE SE UTILIZA DICHO SISTEMA EN DONDE EL SISTEMA CATALIZADOR SE PUEDE OBTENER COMBINANDO UN METAL DEL GRUPO VIII, P. EJ. PALADIO, O UN COMPUESTO DEL MISMO, Y UNA FOSFINA BIDENTADA, P. EJ. BIS (DI - T - BUTIL FOSFINO) O XILENO. A CATALYST SYSTEM CAPABLE OF CATALYZING ETHYLENE CARBONILATION AND A PROCESS IN WHICH SUCH A SYSTEM IS USED WHERE THE CATALYST SYSTEM CAN BE OBTAINED BY COMBINING A METAL FROM GROUP VIII, P. EJ. PALADIUM, OR A COMPOUND OF THE SAME, AND A BIDENTED PHOSPHINE, P. EJ. BIS (DI - T - BUTIL FOSFINO) OR XYLENE.

Process for carbonylation of ethylene and catalyst system for use therein

METHOD FOR CARBONYLATING AETHYLENIC UNSATURATED COMPOUNDS

부타디엔의 히드록시카르보닐화 방법

본 발명은 부타디엔을 일산화탄소 및 물과 반응시켜 히드록시카르보닐화하여 펜테노산을 제조하는 데에 관한 것이다. 더욱 정확하게는, 본 발명은 용매 매질에 이리듐-기재 촉매 및 요오드-함유 또는 브롬-함유 촉진제의 존재하에 25℃로 측정된 일산화탄소의 분압하에 30℃ 이상에서 부타디엔을 일산화탄소 및 물과 반응시켜 히드록시카르보닐화하는 방법에 있어서, 요오드 또는 브롬/이리듐 몰랄비가 20/1이하이고 반응 혼합물에서 물의 중량 농도가 8% 이하인 것을 특징으로 하는 방법으로 구성된다.

Method of recovering and reactivating catalyst containing cobalt used at time of reaction among olefin and both carbon monoxide and alkanol

催化剂体系

一种适用于羰基化烯属不饱和化合物的催化剂，该催化剂含有第VIIIB族金属或其化合物以及金属茂。

Improved catalyst system

고잔환율의 카르보닐화 (high turnover carbonylation)를 위한 연속적인 카르보닐화 공정, 및 카르보닐화 반응 매질 및 이의 생성물 스트림이 개시된다. 상기 공정은 히드록시기 소스 및 촉매 시스템 존재 하에서 에틸렌성 불포화 화합물을 일산화탄소로 카르보닐화하는 단계를 포함한다. 상기 촉매 시스템은: (a) 이좌배위 포스핀 (bidentate phosphine), 아르신 (arsine) 또는 스티빈 (stibine) 리간드; 및 (b) VIB 족 금속 또는 VIIIB 족 금속 또는 이들의 화합물로부터 선택된 촉매 금속을 포함한다. ACCF (생성물 kg.hr -1 .dm -3 )로 측정된 상기 촉매 금속의 촉매 활성 농도는 0.5 미만으로 유지된다. Continuous carbonylation processes for high turnover carbonylation and carbonylation reaction media and their product streams are disclosed. The process comprises carbonylating an ethylenically unsaturated compound to carbon monoxide in the presence of a hydroxy group source and a catalyst system. The catalyst system comprises: (a) bidentate phosphine, arsine or stibine ligand; And (b) a catalytic metal selected from Group VIB or VIIIB metals or compounds thereof. The catalytically active concentration of the catalytic metal measured by ACCF (product kg.hr -1. Dm -3 ) is maintained below 0.5.

Novel alicyclic-type diol compound, and method for producing same

본 발명의 지환식 디올 화합물은, 하기 식(1)로 표시된다. The alicyclic diol compound of this invention is represented by following formula (1).

펜텐니트릴의 카보닐화 방법

촉매 시스템의 존재하에 펜텐니트릴이 일산화탄소 및 물이나 알콜과 반응하는 펜텐니트릴의 카보닐화에 의한 5-시아노발레르산 또는 이의 에스테르의 제조방법. 촉매 시스템은: (a) 8족 금속 또는 이의 화합물 및 (b) 이좌배위 포스핀, 아르신 및/또는 스티빈 리간드(여기에서, 이좌배위 리간드는 M 1 및 M 2 가 독립적으로 P, As 또는 Sb이고, R이 2가 유기 브리징 그룹이며, 상기 브리징 그룹이 2개의 인 원자를 직접 연결하는 3 내지 5개 원자의 체인을 포함하며, 상기 체인이 탄소 원자와 임의의 질소, 산소 또는 황 원자 혹은 실라노 또는 디알킬실리콘 그룹으로 이루어져 있으며, 상기 알킬 그룹이 독립적으로 탄소 원자 1 내지 4개를 포함하며, R 1 -R 4 가 동일하거나 상이한 임의 치환된 3급 알킬 그룹을 나타내는 화학식 I: R 1 R 2 -M 1 -R-M 2 -R 3 R 4 를 가진다), (c) 수용액중 18℃에서 측정된 3 미만의 pKa를 가지는 산으로 이루어져 있다. 5-시아노발레르산 또는 에스테르의 제조방법이: (i) 제 1 항 내지 제 11 항 중 어느 한 항에 따라 펜텐니트릴을 5-시아노발레르산 또는 에스테르로 카보닐화시키고; (ii) 단계 (i)에서 수득된 5-시아노발레르산 또는 에스테르를 6-아미노카프로산 또는 에스테르로 환원시킨 다음; (iii) 6-아미노카프로산 또는 에스테르를 ε-카프로락탐으로 사이클화시키는 단계를 포함하는 ε-카프로락탐의 제조방법에 사용될 수 있다.

Process for the preparation of tertiary carboxylic acids

Verfahren zur katalytischen Durchführung von Mehrphasenreaktionen in einem Rohrreaktor, bei denen zumindest drei Edukte in drei unterschiedlichen Phasen vorliegen, wobei das Verfahren dadurch gekennzeichnet ist, dass das Verfahren in zumindest einem Rohrreaktor durchgeführt wird, wobei der Katalysator in einer kontinuierlichen Phase enthalten ist, zumindest ein Edukt in dieser kontinuierlichen Phase enthalten ist und zumindest zwei Edukte in der kontinuierlichen Phase dispergiert enthalten sind und der Belastungsfaktor B des Rohrreaktors gleich oder größer 0,2 ist. Insbesondere ist die Mehrphasenreaktion eine Hydrocarboxylierung zumindest eines Olefins zu einer Carbonsäure. A process for the catalytic performance of multiphase reactions in a tubular reactor in which at least three starting materials are present in three different phases, the process being characterized in that the process is carried out in at least one tubular reactor, wherein the catalyst is contained in a continuous phase, at least one Educt is contained in this continuous phase and at least two starting materials are contained dispersed in the continuous phase and the loading factor B of the tubular reactor is equal to or greater than 0.2. In particular, the multiphase reaction is a hydrocarboxylation of at least one olefin to a carboxylic acid.

Catalyst system

FIELD: chemistry. SUBSTANCE: present invention relates to a new catalyst system, a new carbonylation reaction medium and to a method of carbonylation of ethylene-unsaturated compounds using the new catalyst system. The catalyst system, which is capable of catalysing carbonylation of an ethylene-unsaturated compound, can be obtained by combining: a) group VIIIB metal, or its compound, b) bidentate phosphinic or arsinic ligand and c) acid, where the said ligand is present in molar excess of at least 2:1, compared to the said metal or said metal in its compound, and the said acid is present in molar excess ranging from 5:1 to 95:1, compared to the said ligand. In another version the catalyst system, which is capable of catalysing carbonylation of an ethylene-unsaturated compound, can be obtained by combining: a) group VIIIB metal, or its compound, b) bidentate phosphic or arsinic ligand and c) acid, where molar ratio of the said ligand to the said metal or said metal in its compound lies in the range greater than 5:1 to 750:1, and the said acid is present in molar excess of at least 2:1, compared to the said ligand. EFFECT: invention also relates to a method of carbonylation of an ethylene-unsaturated compound, a reaction medium, use of catalyst a system and a complex, which is capable of catalysing carbonylation of an ethylene-unsaturated compound. 39 cl, 35 ex, 9 tbl, 3 dwg РОССИЙСКАЯ ФЕДЕРАЦИЯ (19) RU (11) 2 372 989 (13) C2 (51) МПК B01J B01J B01J C07C 31/24 (2006.01) 23/44 (2006.01) 23/74 (2006.01) 51/14 (2006.01) ФЕДЕРАЛЬНАЯ СЛУЖБА ПО ИНТЕЛЛЕКТУАЛЬНОЙ СОБСТВЕННОСТИ, ПАТЕНТАМ И ТОВАРНЫМ ЗНАКАМ (12) ОПИСАНИЕ ИЗОБРЕТЕНИЯ К ПАТЕНТУ (21), (22) Заявка: 2006133287/04, 17.02.2005 (24) Дата начала отсчета срока действия патента: 17.02.2005 (72) Автор(ы): ИСТХЭМ Грэхам (GB), ТИНДЭЙЛ Нил (GB) (43) Дата публикации заявки: 27.03.2008 2 3 7 2 9 8 9 (45) Опубликовано: 20.11.2009 Бюл. № 32 (56) Список документов, цитированных в отчете о поиске: US 2002/045748 A1, 18.04.2002. WO ...

Sistema catalitico,processo para a preparacao de fosfinas e processo para carbonilacao de um composto acetilenicamente ou olefinicamente insaturado

二羧酸的制备方法

一种制备二羧酸的方法，包括如下步骤：(a)在包含钯源、阴离子源和双齿膦配体的催化剂体系存在下使共轭二烯与一氧化碳和水接触，从而得到包含烯属不饱和酸和所述共轭二烯与烯属不饱和酸的一种或多种可逆加合物的混合物；和(b)从反应混合物中脱除未反应的共轭二烯和共轭二烯的可逆加合物；和(c)使步骤(b)中得到的包含烯属不饱和酸的混合物与一氧化碳和水进一步反应从而得到二羧酸。

Mixture of constitutional isomer bisphosphites

본 발명은 하기 화학식 1a 및 2a의 구조 이성질체 비스포스파이트의 혼합물, 그의 제조 방법, 화학식 1a 및 2a의 구조 이성질체 비스포스파이트 및 금속의 착물 화합물을 함유하는 혼합물을 형성하기 위한 금속과의 그의 반응, 및 히드로포르밀화 반응에서 촉매적으로 활성인 조성물로서의 그의 용도에 관한 것이다. 상기 히드로포르밀화 활성 조성물은 금속 및 화학식 1a 및 2a의 구조 이성질체 비스포스파이트의 착물 화합물 외에도, 화학식 1a 및 2a의 구조 이성질체 비스포스파이트의 비결합 비스포스파이트 및 하나 이상의 추가의 성분을 포함한다. <화학식 1a> <화학식 2a> The invention relates to a mixture of the structural isomeric bisphosphites of the general formula (1a) and (2a), a process for its preparation, its reaction with a metal to form a mixture containing the structural isomer bisphosphites of the general formula (Ia) And their use as a catalytically active composition in a hydroformylation reaction. The hydroformylation active composition comprises unconjugated bisphosphite of the structural isomer bisphosphite of formula (Ia) and (2a) and one or more additional components in addition to the complex compounds of the structural isomer bisphosphite of the formula (Ia) and (IIa). <Formula 1a> &Lt; EMI ID =

Method of obtaining alicyclic alcohol

FIELD: chemistry. SUBSTANCE: invention relates to an improved method of obtaining alicyclic alcohol of structural formula (III) The method includes obtaining a cyclohexanecarbonyl compound, represented by general formula (II) carbonylation of unsaturated hydrocarbon, represented by general formula (I) with the application of carbon monoxide in the presence of HF with further obtaining alicyclic alcohol, represented by general formula (III), and reduction of the said cyclohexanecarbonyl compound, represented by general formula (II). In structural formulas (I)-(III) R 1 represents an alkyl group, containing 1-4 carbon atoms, R 2 represents an alkyl group, containing 1-4 carbon atoms, R 3 represents an OH group, fluorine or an OR 4 group, and R 4 represents an alkyl group, containing 1-4 carbon atoms. EFFECT: method makes it possible to obtain the product with low expenditures, high output and high purity of the cis-form. 11 cl, 2 ex РОССИЙСКАЯ ФЕДЕРАЦИЯ (19) RU (11) (13) 2 530 880 C2 (51) МПК C07C 29/147 (2006.01) C07C 31/135 (2006.01) C07C 67/38 (2006.01) C07C 69/75 (2006.01) ФЕДЕРАЛЬНАЯ СЛУЖБА ПО ИНТЕЛЛЕКТУАЛЬНОЙ СОБСТВЕННОСТИ (12) ОПИСАНИЕ (21)(22) Заявка: ИЗОБРЕТЕНИЯ К ПАТЕНТУ 2012103332/04, 30.06.2010 (24) Дата начала отсчета срока действия патента: 30.06.2010 Приоритет(ы): (30) Конвенционный приоритет: (43) Дата публикации заявки: 10.08.2013 Бюл. № 22 (73) Патентообладатель(и): МИЦУБИСИ ГЭС КЕМИКАЛ КОМПАНИ, ИНК. (JP) R U 01.07.2009 JP 2009-157125 (72) Автор(ы): КИТАМУРА Мицухару (JP), КОТАТИ Синдзи (JP), НАГАСАВА Синия (JP), АТАКА Йосихару (JP) (45) Опубликовано: 20.10.2014 Бюл. № 29 C 2 C 2 A, 31.10.1995. GB1545562 A, 10.05.1979. WO1994013766 A2, 23.06.1994. SU1397424 A1, 23.05.1988. G.W. BUCHANAN ET AL., “13C nuclear magnetic resonance studies. XII. Conformational effects on 13C shieldings in alicyclic oxygenated compounds”, Canadian Journal of Chemistry, 1969, 47(17), pp. 31133118 (85) Дата начала рассмотрения заявки PCT на национальной фазе: 01.02.2012 2 5 3 ...

Catalyst system for carbonylation

내용 없음. No content.

Process for the carbonylation of ethylene

A PROCESS FOR THE LIQUID-PHASE CARBONYLATION OF ETHYLENE IN THE PRESENCE OF A CATALYST SYSTEM COMPRISING A GROUP VIII METAL OR COMPOUND THEREOF, A PHOSPHINE LIGAND AND A SOURCE OF ANIONS, AND IN THE PRESENCE OF A SOURCE OF HYDROXYL GROUPS, IS CARRIED OUT IN CONDITIONS IN WHICH THE MOLAR RATIO OF ETHYLENE TO CARBON MONOXIDE IN THE GASEOUS PHASE OF THE REACTOR IS GREATER THAN 1: 1 AND PREFERABLY GREATER THAN 5:1. THE HIGHER RATIOS OF ETHYLENE TO CARBON MONOXIDE ARE BENEFICIAL IN INCREASING THE TURNOVER NUMBER OF THE CATALYST SYSTEM.

Ethylene carbonylation process and catalyst system for use therein

Carbonylation of Acetylene Unsaturated Compounds

(a) 백금원; (b) 화학식 1의 두자리 리간드; 및 (c) 음이온원에 기본한 촉매 시스템의 존재하에 아세틸렌계 불포화 화합물을 일산화탄소 및 공-반응물을 반응시키는 카보닐화 방법. (a) a platinum source; (b) bidentate ligands of Formula 1; And (c) a carbonylation process in which an acetylenically unsaturated compound is reacted with carbon monoxide and a co-reactant in the presence of a catalyst system based on an anion source. 화학식 1 Formula 1 R 1 R 2 M 1 -R-M 2 R 3 R 4 R 1 R 2 M 1 -RM 2 R 3 R 4 상기 식에서, Where M 1 및 M 2 는 독립적으로 인, 비소 또는 안티몬이고, M 1 and M 2 are independently phosphorus, arsenic or antimony, R은 브리지에 1 내지 5개의 원자를 함유하는 이가 치환 또는 비치환 브리징 그룹을 나타내며, R represents a divalent substituted or unsubstituted bridging group containing 1 to 5 atoms in the bridge, R 1 과 R 2 는 함께 두개의 자유 원자가가 M 1 에 연결되는 치환 또는 비치환 이가 그룹이며, R 1 and R 2 together are a substituted or unsubstituted divalent group in which two free valences are linked to M 1 , R 3 와 R 4 는 함께 두개의 자유 원자가가 M 2 에 연결되는 치환 또는 비치환 이가 그룹이거나 각각 독립적으로 치환 또는 비치환 하이드로카빌 그룹이다. R 3 and R 4 together are a substituted or unsubstituted divalent group in which two free valences are linked to M 2 , or each independently a substituted or unsubstituted hydrocarbyl group.

A catalyst system

A catalyst system

A catalyst system comprising a 1,2-bis-(phosphinoalkyl) ferrocene ligand

A catalyst suitable for carbonylating ethylenically unsaturated compounds comprising a Group VIIIB metal or compound thereof and a metallocene.