Abstract:
A process for the minimization of phosphonium ion ligand degradation products formed during reaction of a polyunsaturated olefin or an unconjugated functionalized olefin in the presence of a transition metal-triorganophosphine ligand complex catalyst to form as a product, by-product, or intermediate product a conjugated functionalized olefin having a carbon-carbon double bond conjugated to an α-electron-withdrawing group, such as, an α,β-unsaturated aldehyde, ketone, ester, acid, or nitrile. The minimization process involves conducting the reaction under selected conditions of conversion, temperature, pressure, or a combination thereof; and/or by selecting a triorganophosphine ligand with a specified steric and/or electronic property. Further, a process for reversion of phosphonium ion ligand degradation product(s) back to useful triorganophosphine ligand(s), the reversion involving treating a reaction product fluid containing the degradation product(s) with an inert gas, hydrogen, synthesis gas, or a mixture thereof under conditions sufficient to regenerate the triorganophosphine ligand(s).
Abstract:
A novel bis-chelating composition characterized by formula I: wherein M is a Group VB element; RI and R2 are each independently selected from hydrogen and monovalent hydrocarbyl radicals; or R1 and R2 are bonded together to form a diradical; or one of RI or R2 is hydrogen or a monovalent hydrocarbyl radical, while the other of R1 or R2 is a hydrocarbyl radical bonded to an atom in Ar; wherein Ar is selected from 1,2-arylenes; Q is selected from 1,2-arylenes, 2,2′-bisarylenes and alkyl diradicals; and W is selected from II, III, IV, or V: wherein M is as defined hereinbefore; each R is independently selected from hydrogen and monovalent hydrocarbyl radicals; X is selected from alkyl and aryl diradicals; Ar1 and Ar2 are each independently selected from 1,2-arylenes; Ar3 and Ar4 are each independently selected from monovalent aryl radicals; and n in formula IV is 0 or 1. The composition finds utility as a ligand in catalysts for carbonylation processes.
Abstract translation:特征在于式I的新型双螯合组合物:其中M是VB族元素; R 1和R 2各自独立地选自氢和一价烃基; 或者R 1和R 2结合在一起形成双基; 或R 1或R 2中的一个为氢或一价烃基,而R 1或R 2中的另一个为与Ar中的原子键合的烃基; 其中Ar选自1,2-亚芳基; Q选自1,2-亚芳基,2,2'-双芳烯和烷基双基; W选自II,III,IV或V:其中M如上所定义; 每个R独立地选自氢和一价烃基; X选自烷基和芳基双基; Ar 1和Ar 2各自独立地选自1,2-亚芳基; Ar 3和Ar 4各自独立地选自单价芳基; 式IV中的n为0或1.该组合物用作羰基化反应催化剂中的配体
Abstract:
An extraction process for a non-aqueous hydroformylation product composition to separate an aldehyde product and to recover a hydroformylation catalyst. The process involves mixing a non-aqueous hydroformylation product composition containing a mixture of formyl-substituted fatty acid triglyceride esters derived from hydroformylating a seed oil, a transition metal-organophosphine ligand wherein the organophosphine is ionically-charged, optionally free ionically-charged organophosphine ligand, and a polar organic solubilizing agent with water and an extraction solvent having low water solubility to recover an organic phase containing the mixture of formyl-substituted fatty acid triglycerides and the low solubility extraction solvent and an aqueous phase containing the transition metal-organophosphine ligand, optional free ligand, the organic solubilizing agent, and water. Optionally, the low solubility extraction solvent can be prepared in situ in the hydroformylation step.
Abstract:
An aldehyde composition derived by hydroformylation of a transesterified seed oil and containing a mixture of formyl-substituted fatty acids or fatty acid esters having the following composition by weight: greater than about 10 to less than about 95 percent monoformyl, greater than about 1 to less than about 65 percent diformyl, and greater than about 0.1 to less than about 10 percent triformyl-substituted fatty acids or fatty acid esters, and having a diformyl to triformyl weight ratio of greater than about 5/1; preferably, greater than about 3 to less than about 20 percent saturates; and preferably, greater than about 1 to less than about 20 percent unsaturates.
Abstract:
A process for the minimization of phosphonium ion ligand degradation products formed during reaction of a polyunsaturated olefin or an unconjugated functionalized olefin in the presence of a transition metal-triorganophosphine ligand complex catalyst to form as a product, by-product, or intermediate product a conjugated functionalized olefin having a carbon-carbon double bond conjugated to an α-electron-withdrawing group, such as, an α,β-unsaturated aldehyde, ketone, ester, acid, or nitrile. The minimization process involves conducting the reaction under selected conditions of conversion, temperature, pressure, or a combination thereof; and/or by selecting a triorganophosphine ligand with a specified steric and/or electronic property. Further, a process for reversion of phosphonium ion ligand degradation product(s) back to useful triorganophosphine ligand(s), the reversion involving treating a reaction product fluid containing the degradation product(s) with an inert gas, hydrogen, synthesis gas, or a mixture thereof under conditions sufficient to regenerate the triorganophosphine ligand(s).
Abstract:
A novel organophosphorus composition and synthesis thereof, the composition being characterized by one phosphite moiety, one phosoxophite moiety, and a plurality of sterically bulky substituents. The novel composition finds utility as a ligand in Group VIII transition metal phosoxophite complex catalysts and complex catalyst precursors that are used in carbonylation processes, preferably, hydroformylation processes. Additionally, there is disclosed a novel method of preparing a phosphoromonochloridite composition that finds utility as a precursor to the novel phosoxophite composition.
Abstract:
Novel ligands for use in MRI contrast agents and which have the formula ##STR1## wherein R.sub.1 -R.sub.14, M", l, m, and n are defined herein.
Abstract:
A process for making an amino acid by the steps of: (a) contacting a compound of formula I with a hydroformylation catalyst and synthesis gas to produce a mixture of aldehyde compounds comprising the formulas IIa, IIb and IIc; (b) reacting the mixture of aldehyde compounds from step (a) to produce a mixture of derivative compounds; (c) contacting the mixture of derivative compounds from step (b) with an enantioselective hydrolase enzyme in the presence of water to produce an L-amino acid having the formula IV; (d) isolating the amino acid having the formula IV in substantially pure form, wherein in formulas I, IIa, IIb, IIc, IIIa, IIIb, IIIc and IV, R is H, alkyl or aryl and R1 and R2 are the same or different alkyl groups and wherein R1 and R2 may be fused.
Abstract:
The invention relates to an improved process for the preparation of an advanced synthetic intermediate of ACE inhibitors. In one aspect, the present invention is based on a novel process for the preparation of an aldehyde of formula (I), wherein (N)PrG is a protected amino group, R is an alkyl or aralkyl group and X1-4 are each independently H or a non-reacting substituent, which comprises hydroformylation of an α-olefin of formula (II), by reaction with syngas (CO/H2) in the presence of, as catalyst, a group VII transition metal complex of a phosphorus-containing ligand. Aldehyde (I), the product of linear hydroformylation, is formed in preference to aldehyde (III). In another aspect of the invention, α-olefin (II) is a novel composition. The process to convert (II) to (I) enables an efficient manufacturing route to MDL 28,726 and analogues.
Abstract:
A non-aqueous hydroformylation process with liquid catalyst recycle involving a hydroformylation step and one or more stages of phase separation to recover a high molecular weight aldehyde product with efficient recovery of rhodium catalyst. The process includes a hydroformylation step to prepare a non-aqueous hydroformylation reaction product composition comprising one or more aldehyde products, one or more conjugated polyolefins, a rhodium-organophosphorus ligand complex, free organophosphorus ligand, and an organic solubilizing agent for said complex and said free ligand, and thereafter one or more stages of phase separation using added water under a carbon monoxide gas, hydrogen gas, or a mixture thereof. The process requires a specific range of total pressure for the hydroformylation, a specific range of total pressure for at least one of the separation stages, and a minimum sum of the total pressure of the hydroformylation step and the total pressure of the separation stage containing said gas.