- PRODUCING BDO VIA HYDROFORMYLATION OF ALLYL ALCOHOL MADE FROM GLYCERIN
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A method including hydroformylating, with syngas, allyl alcohol in an allyl alcohol feed, to produce a hydroformylation product comprising 4-hydroxybutyraldehyde and 3-hydroxy-2-methylpropionaldehyde; and producing a 1,4-butanediol (BDO) product comprising BDO and 1,3-methylpropanediol via hydrogenation of at least a portion of the hydroformylation product. A method including hydroformylating, with syngas, allyl alcohol in a feed comprising bio-allyl alcohol, to produce a hydroformylation product comprising 4-hydroxybutyraldehyde and 3-hydroxy-2-methylpropionaldehyde; and producing a BDO product comprising BDO and 1,3-methylpropanediol via hydrogenation of at least a portion of the hydroformylation product. A method including hydroformylating, with syngas, bio-allyl alcohol in a feed comprising bio-allyl alcohol, to produce a hydroformylation product comprising 4-hydroxybutyraldehyde and 3-hydroxy-2-methylpropionaldehyde; producing a BDO product comprising BDO and 1,3-methylpropanediol via hydrogenation of at least a portion of the hydroformylation product; and removing a byproduct of the production of the bio-allyl alcohol prior to hydroformylating the bio-allyl alcohol and/or from the BDO-product.
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Paragraph 0050
(2019/09/06)
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- OLEFIN HYDROFORMYLATION METHODS FOR OBTAINING BRANCHED ALDEHYDES
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The present technology relates to methods of hydroformylating allyl alcohol to 4- hydroxybutanal and 2-memyl-3-hydroxypropanal, comprising (i) admixing allyl alcohol with CO and H2 to form a starting material mixture, and (ii) reacting the starting material mixture in the presence of a catalyst under conditions capable of forming a product mixture comprising 4- hydroxybutanal and 2-methyl-3-hydroxypropanal, wherein the catalyst is a transition metal complex comprising a transition metal ion and a diphosphine ligand with a bite angle from, about 70° to about 100°, and wherein the ratio of 4-hydroxybutanal to 2-methyl-3-hydroxypropanal in the product mixture is less than 1.5: 1.
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Paragraph 0061
(2017/05/20)
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- Backbone-Modified Bisdiazaphospholanes for Regioselective Rhodium-Catalyzed Hydroformylation of Alkenes
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A series of tetraaryl bisdiazaphospholane (BDP) ligands were prepared varying the phosphine bridge, backbone, and substituents in the 2- and 5-positions of the diazaphospholane ring. The parent acylhydrazine backbone was transformed to an alkylhydrazine via a borane reduction procedure. These reduced ligands contained an all sp3 hybridized ring mimicking the all sp3 phospholane of (R,R)-Ph-BPE, a highly selective ligand in asymmetric hydroformylation. The reduced bisdiazaphospholane (red-BDP) ligands were shown crystallographically to have an increased C-N-N-C torsion angle - this puckering resembles the structure of (R,R)-Ph-BPE and has a dramatic influence on regioselectivity in rhodium catalyzed hydroformylation. The red-BDPs demonstrated up to a 5-fold increase in selectivity for the branched aldehyde compared to the acylhydrazine parent ligands. This work demonstrates a facile procedure for increased branched selectivity from the highly active and accessible class of BDP ligands in hydroformylation.
- Wildt, Julia,Brezny, Anna C.,Landis, Clark R.
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p. 3142 - 3151
(2017/09/05)
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- Synthesis and characterization of hydrotalcite and hydrotalcite compounds and their application as a base catalyst for aldol condensation reaction
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Previous Studies on MgO doped by alkali cations have shown that solid catalyst are efficient for the aldolization, because of having preferably a high concentration of surface basic hydroxyl groups. Indeed the Mg-Al hydrotalcites actuvated by calcinations at temperatures not exceeding 1073K are mixed oxides of Mg(Al)O type. They show the structure of MgO with smaller crystallographic parameters, then in periclase (MgO). The decrease of the size of the unit cell with increasing Al content can be accounted for by the smaller ionic size of Al3+(0.050 nm), then Mg2+ (0.060 nm). These mixed oxides contain both basic sites identified to O2- and OH- in amounts depending upon the calcinations temperature, i.e., is of the dehydroxylation degree of the hydrotalcite and Lewis acid sites provided by Al3+ and Mg2. The existence of acid-base pairs justifies the catalytic properties of hydrotalcites for the Aldolisation. The synthesized Hydrotalcites were then characterized using XRD and TGA/DTA techniques, which confirmed that the synthesized materials are hydrotalcite like compounds. There after the synthesized Hydrotalcites were successfully applied for the typical Aldol Condensation reaction of propionaldehyde and formaldehyde to get desired product methacrolein. We tested catalytic activity of synthesized hyrotalcites and from the results it was clear that, the Mg - Al hydrotalcite catalyzed Aldol reaction propionaldehyde coversion of 57.78% and with selectivity 51.23% to methacrolein. Ni- Al hydrotalcite showed a propionaldehyde conversion of 53.46% with 35.46% selectivity. Co - Al XRD pattern of the formed material confirms that the material is not hydrotalcite like. This material also did not show any catalytic activity for the above said Aldol condensation reaction.
- Bhat, Baber Masood
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p. 1751 - 1760
(2013/06/27)
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- NOVEL HYDROFORMYLATION PROCESS
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The present invention relates to a process for producing 4-hydroxybutyraldchyde, characterized in that allyl alcohol dissolved in polar solvents is reacted with CO and H2 in the presence of a catalytic system which is formed from a rhodium complex and a cyclobutane ligand which contains at least two trans-coordinated 1,3-dialkylphenyl- phosphinomethyl groups, with the exclusion of catalysts which contain an aliphatic, araliphatic or cycloaliphatic phosphine as ligand. In which R1 is alkyl, preferably methyl, ethyl or propyl R2 is H or an alkoxy group, R3 and R4 independently of one another, are H, CH2OR1, CH2O-aralkyl, CH2OH, CH2-[P(3,5-R1,R1-4-R2-phenyl)2] or CH2O-(CH2-CH2-O)m-H where m is a number from 1 to 1000.
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Page/Page column 5
(2013/02/28)
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- LIGANDS AND CATALYST SYSTEMS FOR HYDROFORMYLATION PROCESSES
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The present invention relates to ligands and catalyst systems for the hydroformylation of short and long chain olefins, preferably for the hydroformylation of ally alcohol producing 4-hydroxybutyraldehyde. The ligands disclosed herein are all-trans phosphinomethyl-cyclobutane ligands, such as, for example, all-trans- 1,2,3, 4-tetra[bis-(3, 5-xylyl)phosphinomethyl]-cyclobutane. The catalyst systems comprise these all-trans phosphinomethyl-cyclobutane ligands in combination with an organometallic rhodium complex such as, e.g., (acctylacetonato)-dicarbonyl-rhodium (I). The ligands and catalyst systems of the present invention may be employed in the hydroformylation of olefins, in particular in the hydroformylation of allylalcohol, and provide improved selectivity and high reaction yields. wherein R1 is alkyl, preferably methyl, ethyl or propyl, R2 is H or an alkoxy group, R3 and R4, independently of one another, CH2OR1, CH2O-aralkyl, CH2OH,CH2-[P(3,5-R1,R1-4-R2-phenyl)2] or CH2O-(CH2-CH2-O)m-H (with m being an integer between 1 and 1.000).
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Page/Page column 6-7
(2013/02/28)
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- Self- and cross-aldol condensation of propanal catalyzed by anion-exchange resins in aqueous media
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Carbon-carbon bond formation using strong and weak anion-exchange resins as green catalysts for self- and cross-aldol condensation of propanal in aqueous media was investigated. The reaction pathway followed the route of aldol condensation to a β-hydroxy aldehyde and dehydration to an α,β-unsaturated aldehyde. The resulting products were further converted to hemi-acetal, and/or acetal moieties, which were confirmed by FT-IR and NMR. In self-condensation using strong anion-exchange resin, 97% conversion of propanal was achieved with 95% selectivity to 2-methyl-2-pentenal within 1 h using 0.4 g/mL resin at 35 °C. The conversion and selectivity using weak anion exchanger was lower. During cross-aldol condensation of propanal with formaldehyde, 3-hydroxy-2-methyl-2-hydroxymethylpropanal was obtained as the main product through first and second cross-condensation followed by hydration reaction in acidic aqueous conditions. The strong anion-exchange resin provided maximal propanal conversion of 80.4% to the product with 72.4% selectivity after 7 h reaction at 35 °C and resin concentration of 1.2 g/mL. Using weak anion-exchange resin, the optimal conversion of propanal was 89.9% after 24 h at 0.8 g/mL resin and 35 °C, and the main product was 3-hydroxy-2- methylpropanal by first cross-aldol condensation along with relatively minor amounts of methacrolein and 3-hydroxy-2-methyl-2-hydroxymethylpropanal.
- Pyo, Sang-Hyun,Hedstroem, Martin,Hatti-Kaul, Rajni,Lundmark, Stefan,Rehnberg, Nicola
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experimental part
p. 631 - 637
(2011/12/02)
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- Regioselective hydroformylation of allylic alcohols
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A highly regioselective hydroformylation of allylic alcohols is reported toward the synthesis of β-hydroxy-acid and aldehyde products. The selectivity is achieved through the use of a ligand that reversibly binds to alcohols in situ, allowing for a directed hydroformylation to occur. The application to trisubstituted olefins was also demonstrated, which yields a single diastereomer product consistent with a stereospecific addition of CO and hydrogen.
- Lightburn, Thomas E.,De Paolis, Omar A.,Cheng, Ka H.,Tan, Kian L.
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supporting information; experimental part
p. 2686 - 2689
(2011/06/28)
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- Hydroformylation process
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A catalyst, useful for the hydroformylation of allyl alcohol, is described. The catalyst comprises a rhodium complex and a 6-bis(3,5-dialkylphenyl)phosphino-N-pivaloyl-2-aminopyridine or a 3-bis(3,5-dialkylphenyl)phosphino-2H-isoquinolin-1-one. The invention also includes a process for the production of 4-hydroxybutyraldehyde comprising reacting allyl alcohol with a mixture of carbon monoxide and hydrogen in the presence of a solvent and the catalyst. The process gives a high ratio of the linear product 4-hydroxybutyraldehyde to the branched co-product 3-hydroxy-2-methylpropionaldehyde.
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Page/Page column 7-8
(2010/09/09)
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- Assembly of tunable supramolecular organometallic catalysts with cyclodextrins
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Methylated-β-CDs were used to activate a catalyst by ligand solution trapping, to form second-sphere coordination by ligand complexation, and to increase the regioselectivity of biphasic and homogeneous hydroformylation reactions. Different methylation degrees of the β-CD allow assembly of hydrophobic or hydrophilic catalysts that can be employed in homogeneous or biphasic hydroformylation reactions.
- Leclercq, Loic,Schmitzer, Andreea R.
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experimental part
p. 3442 - 3449
(2010/09/17)
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- Hydroformylation process
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A process for the production of 4-hydroxybutyraldehyde is described. The process comprises reacting allyl alcohol with a mixture of carbon monoxide and hydrogen in the presence of a solvent and a catalyst system comprising a rhodium complex and a substituted or unsubstituted 4,5-bis(di-n-alkylphosphino)xanthene. The process gives high yield of 4-hydroxybutyraldehyde compared to 3-hydroxy-2-methylpropionaldehyde.
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Page/Page column 5
(2009/11/30)
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- Hydroformylation process
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A process for the production of 4-hydroxybutyraldehyde is described. The process comprises reacting allyl alcohol with a mixture of carbon monoxide and hydrogen in the presence of a solvent and a catalyst system comprising a rhodium complex and a trans-1,2-bis(bis(3,5-di-n-alkylphenyl)phosphinomethyl)-cyclobutane. The process gives high yield of 4-hydroxybutyraldehyde compared to 3-hydroxy-2-methylpropionaldehyde.
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Page/Page column 5-6
(2008/06/13)
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- Hydroformylation process
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A process for the production of 4-hydroxybutyraldehyde is described. The process comprises reacting allyl alcohol with a mixture of carbon monoxide and hydrogen in the presence of a solvent and a catalyst system comprising a rhodium complex and a 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis[bis(3,5-di-n-alkylphenyl)phosphino]butane. The process gives high yield of 4-hydroxybutyraldehyde compared to 3-hydroxy-2-methylpropionaldehyde.
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Page/Page column 5-6
(2008/06/13)
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- PROCESS FOR THE HYDROFORMYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS
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The present invention provides a process for the hydroformylation of ethylenically unsaturated compounds, which process comprises reacting said ethylenically unsaturated compound with carbon monoxide and hydrogen, in the presence of a catalyst system and a solvent, the catalyst system obtainable by combining: a) a metal of Group VIII or a compound thereof; and b) a bidentate phosphine, the process characterised in that a chlorine moiety is present in at least one of the said Group VIII metal compound or said solvent.
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- Hydroformylation
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The present invention relates to a process for hydroformylating in the presence of a catalyst comprising at least one complex of a metal of transition group VIII with mono-phosphorus compounds which are capable of dimerizing via noncovalent bonds as ligands, to such catalysts and to their use.
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- Hydrogen bonding as a construction element for bidentate donor ligands in homogeneous catalysis: Regioselective hydroformylation of terminal alkenes
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A new concept for the construction of bidentate ligands for homogeneous metal complex catalysis is described. The concept relies on the self-assembly of monodentate ligands through hydrogen bonding. As a prototype of such systems, 6-diphenylphosphanyl-2-pyridone (6-DPPon) was shown to form a chelate in the coordination sphere of a transition metal center through unusual pyridone/hydroxypyridine hydrogen bonding (X-ray). This hydrogen bonding stays intact in a catalytic reaction as proven upon highly regioselective hydroformylation of terminal alkenes. Regioselectivities and reactivities observed rank the 6-DPPon/rhodium system among the most active and regioselective catalysts for n-selective hydroformylation of terminal alkenes. Copyright
- Breit, Bernhard,Seiche, Wolfgang
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p. 6608 - 6609
(2007/10/03)
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- Hydroformylation of allyl alcohol
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A process for the hydroformylation of allyl alcohol is disclosed, which comprises reacting allyl alcohol with carbon monoxide and hydrogen in the presence of a rhodium compound and a diphosphine compound represented by formula (I) or (II) STR1 wherein R1 represents an alkyl group or a substituted or unsubstituted aryl group; and R2 and R3 each represents an alkyl group or a hydrogen atom.
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- Rhodium-Catalyzed Hydroformylation of Allyl Alcohol. A Potential Route to 1,4-Butanediol
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A detailed study of the rhodium-catalyzed hydroformylation of allyl alcohol to 4-hydroxybutanal (1) and 3-hydroxy-2-methylpropanal (2) was carried out, using RhH(CO)(PPh3)3 and its polymer-bound analogues.The reaction is complicated by isomerization of allyl alcohol to propanal, hydrogenation to propanol, and the production of higher boiling products.The product distribution and normal/branched selectivity were studied as a function of the P/Rh ratio, pressure, temperature, H2/CO ratio, and phosphine ligand.Ligands employed included triphenylphosphine, tributylphosphine, triphenyl phosphite, tris(p-chlorophenyl) phosphite, 1,2-bis(diphenylphosphino)ethane, (Ph2PCH2CH2)2PPh (triphos), and 1,1'-bis(diphenylphosphino)ferrocene.The highest n/b selectivities at high conversions were achieved with 1,1'-bis(diphenylphosphino)ferrocene where yields of 1 in excess of 80percent could be routinely achieved at 60 deg C and 800 psi, H2/CO = 1:1.The variation in selectivity with respect to reaction variables was compared to the behavior of olefins in hydroformylations.
- Pittman, Charles U.,Honnick, William D.
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p. 2132 - 2139
(2007/10/02)
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