PROCESS FOR PREPARING AROMATIC OLEFINS USING PALLADACYCLE CATALYSIS

The invention relates to a process for preparing monofunctional, bifunctional or polyfunctional aromatic olefins of the formula (I) ( I ) where R1a to R5a are, independently of one another, hydrogen, C1-C8-alkyl, alkoxy-(C1-C8), acyloxy-(C1-C8), O-phenyl, phenyl, fluorine, chlorine, bromine, iodine, OH, NO2, OSO2CF3, CN, COOH, CHO, SO3H, SO2R, SOR, NH2, NH-alkyl- (C1-C8), N-alkyl2-(C1-C8), CHal3, NHCO-alkyl-(C1-C4), N-alkyl-(C1-C4)-CO-alkyl-(C1-C4), COO-alkyl-(C1-C8), CONH2, CO-alkyl-(C1-C8), NHCOH, NCOO-alkyl-(C1-C4), CO-phenyl, COO-phenyl, CHCH-CO2-alkyl-(C1-C8), CHCHCO2H, PO-phenyl2, PO-alkyl2-(C1-C4), where one of the radicals R1a to R5a can also be R6a is hydrogen, alkyl (C1-C8), phenyl, O-alkyl-(C1-C8), fluorine, R7a and R8a are, independently of one another, hydrogen, CN, CO2H, CO2-alkyl-(C1-C8), CONH2, CONH-alkyl-(C1-C4), CON(alkyl)2-(C1-C4)-fluorine, CO2-phenyl, alkyl, (C1-C8)-phenyl, PO(phenyl), Po(alkyl-(C1-C4))2, CO-phenyl, CO-alkyl-(C1-C4), O-alkyl-(C1-C4), NH-alkyl ...

NOVEL PALLADACYCLES AND A PROCESS FOR THEIR PREPARATION

The invention relates to palladacycles of the formula (I) ( I ) where: R1, R2, R3, R4, R5, R6 are, independently of one another, hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, fluorine, NH2, NH-alkyl(C1-C4), N(alkyl)2-(C1-C4), CO2-(C1-C4)-alkyl, OCO-alkyl-(C1-C4), or phenyl, R7, R8 are (C1-C8)-alkyl, (C3-C12)-cycloalkyl, substituted or unsubstituted aryl or where R1 and R2, R2 and R3, R3 and R4, R5 and R6 together form an aliphatic or aromatic ring, and Y is an anion of an inorganic or organic acid.

PRODUCTION OF BIPHENYLS USING PALLADACYCLE AS CATALYST

PURPOSE: To obtain the subject biphenyl useful as a fine chemical for liquid crystals and so on in high purity by a simple method comprising allowing an arylsulfonate to react with an arylboron derivative in the presence of a specific palladium compound as a catalyst. CONSTITUTION: This method for producing the biphenyl of formula I (R1a-R10a are each H, a 1-12C alkyl, an alkenyl, an alkynyl, an alkoxy, an acyloxy, O- phenyl or the like) (preferably a 4-alkyl-2'-cyanobiphenyl) comprises allowing an aromatic halide or arylsulfonate of formula II to react with an arylboron derivative of formula III [X is Br, Cl, OSO2CF3 or the like; Y is B(OH)2, a B(O-alkyl)2 or the like] in the presence of a palladium compound of formula IV (R1-R6 are each H, a 1-4C alkyl, a 5-8C cycloalkyl, a 1-4C alkoxy or the like) {preferably trans-di-μ-acetate-bis[di-o-triphosphino)benzyl]dipalladium} as a catalyst. COPYRIGHT: (C)1996,JPO ...

NEW PALLADACYCLE AND ITS PRODUCTION

PURPOSE: To obtain a new palladacycle useful as a catalyst for synthesizing a substituted styrene, producing stilbene and cinnamic acid from an aryl halide, and the like by reacting a specific phosphine with a palladium compound in an organic solvent. CONSTITUTION: The palladacycle {for example, trans-di-μ-bromo- bis[0-(ditolylphosphino)benzyl]dipalladium (II)} represented by formula I [R1 to R6 are each H, a 1-4C alkyl, a 1-4C alkoxy, F, NH2, phenyl or the like; R7 and R8 are each a 1-3C alkyl, a 3-12C cycloalkyl or a (substituted) aryl; R1 and R2, R2 and R3, R3 and R4, or R5 and R6 together form an alicyclic group or an aromatic ring group; Y is an inorganic or organic anion], and useful as a catalyst for synthesizing a substituted styrene, producing stilbene and cinnamic acid from an aryl halide, and the like. The compound of the formula I is obtained by reacting a phosphine of formula II with a palladium salt, a palladium complex or an alkali metal palladate. COPYRIGHT: (C)1996,JPO ...

PRODUCTION METHOD OF MALONIC ACID OR A SALT THEREOF.

L'acide malonique ou un de ses sels est produit en rendement élevé par oxydation catalytique de 3- hydroxypropionaldéhyde ou d'acide 3-hydroxypropionique en phase aqueuse avec de l'oxygène ou un gaz contenant de l'oxygène. La réaction se fait en présence d'au moins 10 % en poids de métal noble du groupe du platine par rapport au composant en C3 utilisé. On préfère les catalyseurs de support de Pd et de Pt.

PRODUCTION OF AROMATIC OLEFIN USING PALLADACYCLE CATALYST

PURPOSE: To obtain the subject high-purity compound in a high yield, by reacting a halogenated aromatic compound with an olefin in the presence of a palladacycle catalyst. CONSTITUTION: A compound of formula I (R1a to R5a are each H, a 1-8C alkyl, phenyl, OH, NO2, OSO2CF3, COOH or the like; X is I, Br, CL, OSO2CF3 or the like) is reacted with a compound of formula II (R6a is H, a 1-8C alkyl, phenyl or the like; R7a and R8a are each H, CN, CO2H, CO2-phenyl or the like) in the presence of a compound of formula III (R1 to R6 are each H, a 1-4C alkyl, a 1-4C alkoxy or the like; R7 and R9 are each a 1-8C alkyl, an aryl or the like; Y is an anion) in a solvent (e.g. DMF) at 20-200°C, preferably in the presence of a base (e.g. an alkylamine) to give a compound of formula IV. trans-Di-μ-acetato-bis[O-(di-O-tolylphosphino)benzyl]palladium (II) may be cited as the compound of formula III. COPYRIGHT: (C)1996,JPO ...

PROCESS FOR THE PRODUCTION OF MALONIC ACID OR A SALT THEREOF

Method of preparation of biphenyls using palladacyclen as catalyst

PROCESS FOR THE PRODUCTION OF MALONIC ACID OR A SALT THEREOF

L'acide malonique ou un de ses sels est produit en rendement élevé par oxydation catalytique de 3-hydroxypropionaldéhyde ou d'acide 3-hydroxypropionique en phase aqueuse avec de l'oxygène ou un gaz contenant de l'oxygène. La réaction se fait en présence d'au moins 10% en poids de métal noble du groupe du platine par rapport au composant en C3 utilisé. On préfère les catalyseurs de support de Pd et de Pt.

Process for preparing aromatic olefins using palladacycle catalysis

The invention relates to a process for preparing monofunctional, bifunctional or polyfunctional aromatic olefins of the formula (I) (see formula I) where R1a to R5a are, independently of one another, hydrogen, C1-C8-alkyl, alkoxy-(C1-C8), acyloxy-(C1-C8), O-phenyl, phenyl, fluorine, chlorine, bromine, iodine, OH, NO2, OSO2CF3, CN, COOH, CHO, SO3H, SO2R, SOR, NH2, NH-alkyl-(C1-C8), N-alkyl2-(C1-C8), CHal3, NHCO-alkyl-(C1-C4), N-alkyl-(C1-C4)-CO-alkyl-(C1-C4), COO-alkyl-(C1-C8), CONH2, CO-alkyl-(C1-C8), NHCOH, NCOO-alkyl-(C1-C4), CO-phenyl, COO-phenyl, CHCH-CO2-alkyl-(C1-C8), CHCHCO2H, PO-phenyl2, PO-alkyl2-(C1-C4), where one of the radicals R1a to R5a can also be (see formula V) R6a is hydrogen, alkyl (C1-C8), phenyl, O-alkyl-(C1-C8), fluorine, R7a and R8a are, independently of one another, hydrogen, CN, CO2H, CO2-alkyl-(C1-C8), CONH2, CONH-alkyl-(C1-C4), CON(alkyl)2-(C1-C4)-fluorine, CO2-phenyl, alkyl, (C1-C8)-phenyl, PO(phenyl), PO(alkyl-(C1-C4))2, CO-phenyl, CO-alkyl-(C1-C4), O-alkyl-(C1-C4), NH-alkyl-(C1-C4), PO3H, SO3H, SO3-alkyl (C1-C4), SO2-alkyl-(C1-C4), O-phenyl, by reaction of haloaromatics of the formula (II) (see formula II) with olefins of the formula (III) (see formula III) where R1a to R8a are as defined above, where one of the radicals R1a to R5a can also be X and X is iodine, bromine, chlorine, OSO2CF3, OSO2-phenyl, OSO2CH3, wherein a palladium compound of the formula (IV) (see formula IV) where R1, R2, R3, R4, R5, R6 are, independently of one another, hydrogen, (C1-C4)-alkyl, (C5-C8)-cycloalkyl, (C1-C4)-alkoxy, fluorine, NH2, NH-alkyl(C1-C4), N(alkyl)2-(C1-C4), CO2alkyl-(C1-C4), OCO-alkyl-(C1-C4) or phenyl, or R1 and R2, R2 and R3, R3 and R4, R5 and R6 together form an aliphatic or aromatic ring, and R7, R8 are (C1-C8)-alkyl, (C3-C12)-cycloalkyl, substituted or unsubstituted aryl and Y is an anion of an inorganic or organic acid, is used as catalyst.

Novel palladacycles and a process for their preparation

The invention relates to palladacycles of the formula (I) (see formula I) where: R1, R2, R3, R4, R5, R6 are, independently of one another, hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, fluorine, NH2, NH-alkyl (C1-C4), N(alkyl)2-(C1-C4), CO2-(C1-C4)-alkyl, OCO-alkyl-(C1-C4), or phenyl, R7, R8 are (C1-C8)-alkyl, (C3-C12)-cycloalkyl, substituted or unsubstituted aryl or where R1 and R2, R2 and R3, R3 and R4, R5 and R6 together form an aliphatic or aromatic ring, and Y is an anion of an inorganic or organic acid.

Palladacycles and a process for their preparation

A palladacycle of the formula (I) ##STR1## where: R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are, independently of one another, hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, fluorine, NH 2 , NH-alkyl(C 1 -C 4 ), N(alkyl) 2 -(C 1 -C 4 ), CO 2 -(C 1 -C 4 )alkyl, OCO-alkyl-(C 1 -C 4 ), or phenyl, R 7 and R 8 are, independently of one another, (C 1 -C 8 )-alkyl, (C 3 -C 12 )-cyloalkyl, substituted or unsubstituted aryl or where R 1 , and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 together form an aliphatic or aromatic ring, and Y is an anion of an inorganic or organic acid.