Large P−P Distance Diphosphines and Their Monophosphine Analogues as Ligands in the Palladium-Catalyzed Telomerization of 1,3-Butadiene and Methanol
摘要:
The potential of diphosphines based on a dibenzodioxocin or benzofurobenzofuran backbone possessing large P P distances was studied for the selective telomerization of 1,3-butadiene with methanol under commercially relevant process conditions to obtain 1-methoxyocta-2,7-diene (1-MOD). They were found to act as monophosphines. New bulky monophosphine analogues of the same backbone and ferrocene were also evaluated. Several ligands showed improved selectivity and yield compared to the benchmark ligand PPh3 and monoxantphos. Especially 1,6-bis(diphenylphosphino)-5a,10b-dihydro-5a,10b-dimethyl-3,8-dimethylbenzofuro[3,2-b]benzofuran (3) and, 2,10-di-tert-buty1-4-diphenylphosphino-6,12-methano-12H-dibenzo[2,1-d: 1 ',2"-g][1,3]dioxocin (7), a diphosphine and a monophosphine, respectively, stand out as excellent ligands in terms of yield, selectivity, and stability.
The present invention relates to a process for preparing a catalyst comprising ruthenium nanoparticles supported on a solid support, obtainable by: (a) reacting a ruthenium (0) complex selected from the group consisting of [Ru(diene)(triene)], [Ru(R6)(diene)], and Ru3(CO)12, with a phosphine ligand of formula (I) in the presence of hydrogen; and (b) reacting the ruthenium nanoparticles obtained in Step (a) with a porous solid support, and to the obtained supported phosphine-ruthenium nanoparticles. It is also related to a process for hydrogenating an aromatic compound into the corresponding cyclic saturated or partially unsaturated compound by reaction with hydrogen and in the presence of an effective amount of the obtained supported ruthenium nanoparticles.
[EN] A COMPOUND COMPRISING RUTHENIUM NANOPARTICLES SUPPORTED ON A POROUS SOLID SUPPORT FOR THE HYDROGENATION OF AROMATIC COMPOUNDS.<br/>[FR] COMPOSÉ COMPRENANT DES NANOPARTICULES DE RUTHÉNIUM SUPPORTÉES SUR UN SUPPORT SOLIDE POREUX POUR L'HYDROGÉNATION DES COMPOSÉS AROMATIQUES
申请人:FUNDACIÓ INST CATAL D INVESTIGACIÓ QUÍMICA ICIQ
公开号:WO2014056889A1
公开(公告)日:2014-04-17
The present invention relates to a process for preparing a catalyst comprising ruthenium nanoparticles supported on a solid support, obtainable by: (a) reacting a ruthenium (0) complex selected from the group consisting of [Ru(diene)(triene)], [Ru(R6)(diene)], and Ru3(CO)12, with a phosphine ligand of formula (I) in the presence of hydrogen; and(b) reacting the ruthenium nanoparticles obtained in Step(a) with a porous solid support, and to the obtained supported phosphine-ruthenium nanoparticles. It is also related to a process for hydrogenating an aromatic compound into the corresponding cyclic saturated or partially unsaturated compound by reaction with hydrogen and in the presence of an effective amount of the obtained supported ruthenium nanoparticles.
Large P−P Distance Diphosphines and Their Monophosphine Analogues as Ligands in the Palladium-Catalyzed Telomerization of 1,3-Butadiene and Methanol
作者:Mathieu J.-L. Tschan、Josep-Maria López-Valbuena、Zoraida Freixa、Hélène Launay、Henk Hagen、Jordi Benet-Buchholz、Piet W. N. M. van Leeuwen
DOI:10.1021/om100980m
日期:2011.2.28
The potential of diphosphines based on a dibenzodioxocin or benzofurobenzofuran backbone possessing large P P distances was studied for the selective telomerization of 1,3-butadiene with methanol under commercially relevant process conditions to obtain 1-methoxyocta-2,7-diene (1-MOD). They were found to act as monophosphines. New bulky monophosphine analogues of the same backbone and ferrocene were also evaluated. Several ligands showed improved selectivity and yield compared to the benchmark ligand PPh3 and monoxantphos. Especially 1,6-bis(diphenylphosphino)-5a,10b-dihydro-5a,10b-dimethyl-3,8-dimethylbenzofuro[3,2-b]benzofuran (3) and, 2,10-di-tert-buty1-4-diphenylphosphino-6,12-methano-12H-dibenzo[2,1-d: 1 ',2"-g][1,3]dioxocin (7), a diphosphine and a monophosphine, respectively, stand out as excellent ligands in terms of yield, selectivity, and stability.