27644-47-9

Upstream product

• 14850-23-8 trans-4-Octene 
• 201230-82-2 carbon monoxide 
• 111-66-0 oct-1-ene 
• 1942-45-6 4-Octyne 
• 111-67-1 2-octene 
• 592-99-4 4-octene 
• 14919-01-8 (E)-3-octene 
• 13389-42-9 trans-2-Octene 
• 124-38-9 carbon dioxide 
• 67-56-1 methanol 
• 14850-22-7 oct-3-ene 
• 7642-15-1 (Z)-oct-4-ene 

Relevant academic research and scientific papers

A modular family of phosphine-phosphoramidite ligands and their hydroformylation catalysts: steric tuning impacts upon the coordination geometry of trigonal bipyramidal complexes of type [Rh(H)(CO)2(P^P?)]

Four new phosphine-phosphoramidite bidentate ligands have been synthesised and studied in rhodium-catalysed hydroformylation. Variable temperature NMR studies have been used along with HPIR to investigate the coordination mode of the trigonal bipyramidal complexes formed from [Rh(acac)(CO)2], ligand and syngas. It was found that small changes to the ligand structure have a large effect on the geometry of the active catalytic species. The rhodium catalysts of these new ligands were found to give unusually high iso-selectivity in the hydroformylation of propene and 1-octene.

Phosphonium-based aminophosphines as bifunctional ligands for sequential catalysis of one-pot hydroformylation-acetalization of olefins

A series of ionic phosphonium-based aminophosphines L1-L3 were prepared and fully characterized, in each of which the involved bifunctional moieties of the phosphine fragment and Lewis acidic phosphonium were linked together by stable chemical bonds and bridged by one N-atom. The molecular structure of the L2-ligated Rh-complex (Rh-L2) indicated that such bifunctionalities were well retained without incompatibility problems. Investigations on co-catalysis over L1-L3 showed that L3 exhibited the best sequential catalysis for both hydroformylation and acetalization. The phosphine fragment in L3 was responsible for hydroformylation together with the Rh-complex and the phosphonium acted as the Lewis acidic catalyst in charge of acetalization. The L3-Rh(acac)(CO)2 system also exhibited good generality to hydroformylation-acetalization of a wide range of olefins in different alcohols.

Co-catalysis of a bi-functional ligand containing phosphine and Lewis acidic phosphonium for hydroformylation-acetalization of olefins

A novel ionic bi-functional ligand of L2 containing a phosphine and a Lewis acidic phosphonium with I- as the counter-anion was prepared and fully characterized. The molecular structure indicated that the bi-functionalities in L2 were well retained without the incompatibility problem for quenching of the acidity of the phosphonium cation by the Lewis basic phosphine fragment or the anionic I- when the incorporated phosphine fragment and the Lewis acidic phosphonium were strictly located in the confined cis-positions. The co-catalysis over L2-Rh(acac)(CO)2 in the ways of synergetic catalysis and sequential catalysis was successfully fulfilled for one-pot hydroformylation-acetalization, which proved not to be the result of the simple mixture of the mono-phosphine (L4) and the phosphonium salt (L4′). In L2, the phosphonium not only acted as a Lewis acid organocatalyst to drive the sequential acetalization of aldehydes, but also contributed to the synergetic catalysis for the preceding hydroformylation through stabilizing the Rh-acyl intermediate with the phosphine cooperatively. The L2-Rh(acac)(CO)2 system is also generally applied to hydroformylation-acetalization of a wide range of olefins in different alcohols. Advantageously, as an ionic phosphonium-based ligand, L2 could be recycled for 7 runs with Rh(acac)(CO)2 together in RTIL of [Bmim]BF4 without obvious activity loss or metal leaching.

Molybdenum carbonyl grafted onto silicate intercalated cobalt-aluminum hydrotalcite: A new potential catalyst for the hydroformylation of octene

We present the first example of molybdenum carbonyl grafted on diaminosiloxane-functionalized cobalt-aluminum hydrotalcite (CA-HTSi-DA-Mo) as a promising catalyst for the hydroformylation of olefins. The catalyst showed 80% conversion with selective formation of branched aldehyde. About 70% of the catalytic activity retains even after three cycles.

METHOD FOR HYDROFORMYLATION OF UNSATURATED COMPOUNDS

The invention relates to a method for hydroformylation of unsaturated compounds such as olefins and alkynes using mixtures of synthesis gas (CO/H2), in which either the unsaturated compounds and a catalyst are heated to a reaction temperature of 60 to 200° C. and the synthesis gas is then added, or the unsaturated compounds and the catalyst are brought into contact with pure CO at normal temperature in a preformation step, then are heated to reaction temperature and on reaching the reaction temperature the CO is replaced by the synthesis gas. The pressure is 1 to 200 bar and the CO:H2 ratio in the synthesis gas is in the range from 1:1 to 50:1. The iridium catalyst used comprises a phosphorus-containing ligand in the iridium:ligand ratio in the range from 1:1 to 1:100. With high catalyst activities and low catalyst use, very high turnover frequencies are achieved.

Bulky phosphinines: From a molecular design to an application in homogeneous catalysis

The design and preparation of an asymmetrically substituted and bulky phosphinine was achieved by introducing sterically demanding substituents into specific positions of a rigid phosphorus-heterocyclic framework. Compound 5 shows, at the same time, axial chirality and a sufficiently high energy barrier for internal rotation to prevent enantiomerization. Both enantiomers of 5 were isolated by means of chiral analytical HPLC, and their absolute configurations could be assigned by combining experimental data and DFT calculations. Despite its substitution pattern, 5 can still coordinate to transition-metal centers through the lone pair of electrons on the phosphorus atom. Rapid C-H activation on the adjacent aryl substituent at the 2-position of the phosphorus heterocycle was achieved by using [{CpIrCl2}2] (Cp=1,2,3,4,5- pentamethylcyclopentadienyl) as a metal precursor. A racemic mixture of 5 was applied as a π-accepting low-coordinate phosphorus ligand in the Rh-catalyzed hydroformylation of trans-2-octene, which showed a clear preference for the formation of 2-methyloctanal. Bulky phosphinines: An asymmetrically substituted, bulky, and atropisomeric phosphinine has been prepared and characterized (see figure). Rapid C-H activation on the 2-aryl substituent of the phosphorus heterocycle was achieved with [{CpIrCl2}2] (Cp=1,2,3,4,5-pentamethylcyclopentadienyl) as a metal precursor. A racemic mixture of the phosphinine acted as a π-accepting low-coordinate phosphorus ligand in the Rh-catalyzed hydroformylation of 2-octene. Copyright

CATALYST AND METHOD HAVING SELECTIVITY TO ISOBUTYRALDEHYDE VIA CATALYST INDUCTION

Industrially relevant product selectivities and reaction rates are obtained from rhodium catalyzed hydroformylation of propylene via the use of a novel induction period in which the supramolecular ligand assembly, the rhodium precatalyst and an initial substrate are allowed to form a hydroformylation catalyst that is more selective toward branched aldehydes. Upon heating this incubated mixture and addition of propylene, iso-butyraldehyde is obtained in higher concentrations and rates that are otherwise unattainable.

CATALYSTS AND PROCESSES FOR PREPARING ALDEHYDES

Use of a unique supramolecular assembly of a pyridylphosphine ligand and a metal centered porphyrin complex is shown to give unprecedented selectivities to branched aldehydes via rhodium catalyzed hydroformylation of unsubstituted linear alpha-olefins such as propylene and 1-octene. Increasing the syngas pressure is shown to have a beneficial effect on branched aldehyde selectivity as is increasing the ratio of carbon monoxide to hydrogen used in the hydroformylation reaction.

Highly active hydroformylation catalysts: Synthesis, characterisation and catalytic performance

The phoszone ligand [(Ph2P)(bis-3,5-CF3-Ph)]NN= CH(penta-fluoro-Ph) transformed in liquid CO2 at room temperature in presence of [Rh(cod)2]OTf into [Rh(cod)(η2-P,P′- Ph2POPPh2)]OTf. Replacing the O-atom in Ph 2POPPh2 by a PrN-group leads to the ligand PrN(PPh 2)2 acting similarly as a bidentate ligand in [Rh(cod)(η2-P,P′-PrN(PPh2)2)]OTf. Hydroformylation of 1-octene with in situ catalysts formed by the ligands with [Rh(cod)2]OTf showed hydroformylation activities at 50 % conversion of 16,000 h-1 (PrN(PPh2)2/[Rh(cod) 2]OTf) and 24,000 h-1 (phoszone/[Rh(cod)2]OTf), respectively.

A bulky phosphite modified rhodium catalyst for efficient hydroformylation of disubstituted alkenes and macromonomers in supercritical carbon dioxide

The hydroformylation of disubstituted alkenes and related macromonomers in supercritical CO2 is demonstrated. Higher turnover frequencies were observed for the 1,2-disubstituted alkenes than for the 1,1-disubstituted alkenes. The turnover frequency for poly(styrene) macromonomer hydroformylation compares well with that observed for cyclohexene. The turnover frequency observed for poly(methyl methacrylate) macromonomer hydroformylation is considerably lower than that observed for methyl methacrylate. Unprecedented turnover frequencies are observed in comparison with previous studies where CO2 has been applied as a solvent. This is achieved using rhodium modified with a readily available bulky phosphite ligand without the need of ligand modification to improve solubility in supercritical CO2.