- Application of organic amine additive in synthesis of fluorescent dye intermediate through olefin hydroformylation reaction
-
The invention discloses application of an organic amine additive in synthesis of a fluorescent dye intermediate through olefin hydroformylation reaction, and the application comprises the following steps: S1, the structure of the additive involved in the patent takes a nitrogen atom as a center, and three substituent groups linked with the nitrogen atom are alkyl groups or aromatic groups; and S2, in the hydroformylation reaction process, very few additives are introduced into the reaction system. The activity of a rhodium-aryl phosphine catalyst and the chemical selectivity of a product aldehyde can be obviously improved by using proper types and quantity of additives. The organic amine additive has the characteristics that compared with other types of additives reported in the literature, the organic amine additive can better regulate and control the activity of a rhodium-aryl phosphine catalyst and greatly improve the chemical selectivity of the product aldehyde, the organic amine additive provided by the invention can overcome the defects of other types of additives reported in the literature, and the cost of hydroformylation industrial production of various olefins is reduced.
- -
-
Paragraph 0015-0023
(2021/07/31)
-
- Boosting the hydrolytic stability of phosphite ligand in hydroformylation by the construction of superhydrophobic porous framework
-
The development of a catalyst that delivers high activities and selectivities with excellent durability is of great importance. Numerous efficient catalysts suffer from the inherent hydrolysis liabilities, plaguing their practical applications. Herein, we show that this challenge can be tackled by constructing them into superhydrophobic porous frameworks, as exemplified by a water-sensitive phosphite ligand, tris(2-tert-butylphenyl) phosphite. The efficiency and long-term stability of the developed system are remarkably high in the hydroformylation of internal olefins after metalation with Rh species, superior to the corresponding homogeneous analogues. The significantly boosted hydrolytic stability allows for catalytic transformations using water as a green solvent, which not only facilitates the isolation of the products, but also furnishes the aldehydes with higher regioselectivities for the desired linear form in comparison with that operated under benchmark conditions using toluene as a reaction medium. Given these promising results, we anticipate the strategy advanced herein will form the basis for constructive perspectives in the enhancement of the water resistance of catalysts and the development of high performance hydroformylation catalysts.
- Tang, Yongquan,Dong, Ke,Wang, Sai,Sun, Qi,Meng, Xiangju,Xiao, Feng-Shou
-
-
- Synthesis of an Azaphosphatriptycene and Its Rhodium Carbonyl Complex
-
A 10-aza-9-phosphatriptycene is accessible on a gram scale, in three laboratory steps from commercially available precursors. Infrared spectroscopy of a rhodium(I) carbonyl complex bearing this ligand reflects the weak σ-donor/strong π-acceptor character of the phosphine; the solid-state structure reveals moderate steric demand. This ligand supports highly active catalysts for the hydroformylation of cyclic alkenes.
- Cao, Yu,Napoline, Jonathan W.,Bacsa, John,Pollet, Pamela,Soper, Jake D.,Sadighi, Joseph P.
-
p. 1868 - 1871
(2019/05/16)
-
- Hydroformylation of unsaturated esters and 2,3-dihydrofuran under solventless conditions at room temperature catalysed by rhodium: N-pyrrolyl phosphine catalysts
-
Rhodium complexes of the type HRh(CO)L3 (where L is an N-pyrrolyl phosphine, such as P(NC4H4)3, PPh(NC4H4)2, or PPh2(NC4H4)) were applied in the hydroformylation of less reactive unsaturated substrates, namely allyl acetate, butyl acrylate, methyl acrylate, 2,3-dihydrofuran and vinyl acetate. Even at room temperature, these catalysts enabled complete substrate conversion and high chemoselectivity towards the corresponding aldehydes. High conversion of vinyl acetate (88% in 6 h) to the branched aldehyde was obtained with HRh(CO)[P(NC4H4)3]3 at 25 °C. An increase of the turnover frequency, TOF, up to 2000 mol mol-1 h-1 was achieved in this reaction under 20 bar of syngas (H2/CO = 1) at 80 °C. The introduction of chiral phosphines, BINAP or Ph-BPE, to this system resulted in the production of a branched aldehyde with enantioselectivity, ee, up to 44 and 81%, respectively. High activity combined with high enantioselectivity was achieved due to the formation of the mixed rhodium hydrides HRh(CO)[P(NC4H4)3](BINAP) and HRh(CO)[P(NC4H4)3](Ph-BPE), identified by the NMR method.
- Alsalahi,Trzeciak
-
p. 16990 - 16999
(2019/11/14)
-
- Backbone-Modified Bisdiazaphospholanes for Regioselective Rhodium-Catalyzed Hydroformylation of Alkenes
-
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.
-
p. 3142 - 3151
(2017/09/05)
-
- Hydroformylation of dihydrofurans catalyzed by rhodium complex encapsulated hexagonal mesoporous silica
-
HRh(CO)(PPh3)3 encapsulated hexagonal mesoporous silica (HMS) is found to be an efficient heterogeneous catalyst for the selective hydroformylation of 2,3-dihydrofuran (2,3DHF) and 2,5-dihydrofuran (2,5DHF). The Rh-complex encapsulated in situ in the organic phase of template inside the pores of HMS was found to act as nano phase reactors. Conversion of 2,3-DHF and 2,5-DHF and selectivity of the corresponding aldehydes were thoroughly investigated by studying the reaction parameters: catalyst amount, substrate concentration, partial as well as total pressure of CO and H2, and temperature. The selectivity for the formation of tetrahydrofuran-2-carbaldehyde (THF-2-carbaldehyde) from the hydroformylation of 2,3-DHF was found to be more than the selectivity of the formation of tetrahydrofuran-3-carbaldehyde (THF-3-carbaldehyde) from 2,5-DHF. The reaction paths are suggested and discussed for the selective formation of the corresponding aldehydes. The catalyst was elegantly separated and effectively recycled for six times.
- Khokhar, Munir D.,Shukla, Ram S.,Jasra, Raksh V.
-
-
- Highly selective bisphosphine ligands for asymmetric hydroformylation of heterocyclic olefins
-
The bisphosphine ligand 1c is highly efficient and selective for the asymmetric hydroformylation (AHF) of dihydrofuran and pyrrolines. The AHF of 2,3-dihydrofuran yielded the 2-carbaldehyde in up to 93% ee. The remarkable highest regioselectivity of 2,5-dihydrofuran was obtained to date up to 499 β-isomer/α-isomer with ligand 1c. Furthermore, the highest 96% and 92% ee values were accomplished using the same catalytic system in the AHF of N-Boc pyrroline 11 and 14.
- Zheng, Xin,Xu, Kun,Zhang, Xumu
-
p. 1149 - 1152
(2015/02/19)
-
- Asymmetric Hydroformylation of Heterocyclic Olefins Mediated by Supramolecularly Regulated Rhodium-Bisphosphite Complexes
-
Rhodium complexes derived from conformationally transformable α,ω-bisphosphite ligands combined with a suitable alkali metal BArF salt as a regulation agent (RA) provide high regio- and enantioselectivities in the asymmetric hydroformylation (AHF) of three heterocyclic olefins. The outcome of the AHF could be exquisitely regulated by choosing the appropriate RA with an increase in the ee, the reversal of the regioselectivity, or the complete suppression of one byproduct.
- Rovira, Laura,Vaquero, Mónica,Vidal-Ferran, Anton
-
supporting information
p. 10397 - 10403
(2015/11/03)
-
- Effect of solvent nature on the catalytic hydroformylation of 2,3-dihydrofuran
-
The effect of the solvent nature on the process of hydroformylation of 2,3-dihydrofuran in the presence of the phosphine-containing, complex Rh catalyst HRh(CO)(PPh3)3 has been studied. The influence of solvent polarity and basicity on the conversion of 2,3-dihydrofuran has been revealed, and the composition of tetrahydrofuran aldehydes and the selectivity of their formation have been determined.
- Wol'F,Vartanyan,Lapidus
-
p. 194 - 196
(2013/07/27)
-
- Highly efficient rhodium catalysts for the asymmetric hydroformylation of vinyl and allyl ethers using C1-symmetrical diphosphite ligands
-
Here, we describe the successful application of novel glucofuranose-derived 1,3-diphosphites in the rhodium-catalysed asymmetric hydroformylation of vinyl acetate, 2,5-dihydrofuran and 2,3-dihydrofuran. In the hydroformylation of vinyl acetate, total regioselectivity and high ee (up to 73%) were obtained. When 2,3- and 2,5-dihydrofuran were the substrates, total chemo- and regioselectivities were achieved together with ees up to 88%. These results correspond to the highest ee values reported to date in the asymmetric hydroformylation of these substrates. The HP-NMR studies of the [RhH(CO) 2(L)] species (L=15 and 17) demonstrated that both ligands coordinate to the Rh centre in an eq-eq fashion. The complex [RhH(CO)2(15)] was detected as a single isomer with characteristic features of eq-eq coordination. However, the broadening of the corresponding signals indicated that this species is rapidly interchanging in solution. In contrast, complex [RhH(CO) 2(17)] was detected as a mixture of two conformational isomers at low temperature due to the greater flexibility of the monocyclic backbone of this ligand.
- Gual, Aitor,Godard, Cyril,Castillon, Sergio,Claver, Carmen
-
experimental part
p. 463 - 477
(2010/06/13)
-
- Phosphabarrelenes as ligands in rhodium-catalyzed hydroformylation of internal alkenes essentially free of alkene isomerization
-
Despite significant research efforts in the past, one of the remaining problems to be solved in industrially important hydroformylation is the chemoselective low-pressure hydroformylation of internal alkenes. We report here on a new class of phosphabarrelene/rhodium catalysts 2 that display very high activity towards hydroformylation of internal alkenes with an unusually low tendency towards alkene isomerization. Preparation of new phosphabarrelene ligands, studies of their coordination properties, as well as results obtained in the rhodium-catalyzed hydroformylation of cyclic and acyclic internal alkenes are reported.
- Fuchs, Evelyn,Keller, Manfred,Breit, Bernhard
-
p. 6930 - 6939
(2007/10/03)
-
- Phosphabarrelene-rhodium complexes as highly active catalysts for isomerization free hydroformylation of internal alkenes
-
A new class of phosphabarrelene-rhodium catalysts is described which allows for the first time hydroformylation of internal alkenes with very high activity and which proceeds essentially free of alkene isomerization.
- Breit, Bernhard,Fuchs, Evelyn
-
p. 694 - 695
(2007/10/03)
-
- Study of the hydroformylation of 2,5-dihydrofuran catalyzed by rhodium diphosphine complexes
-
Rhodium diphosphine systems, including chiral ones, were used as catalyst precursors for the hydroformylation of 2,5-dihydrofuran. The effect of the reaction conditions and the bite angle on the activity and selectivity of the reaction were studied. The s
- Del Rio,Van Leeuwen,Claver
-
p. 560 - 565
(2007/10/03)
-
- Low-pressure Selective Hydroformylation of 2,3- and 2,5-Dihydrofuran with a Rhodium Catalyst. Unexpected Influence of the Auxiliary Ligand Tris(o-t-butylphenyl) Phosphite
-
Hydroformylation of 2,3- and 2,5-dihydrofuran has been achieved in excellent yields and good selectivities under mild conditions using 2(cod)2> and suitable auxiliary ligands (cod = cyclo-octa-1,5-diene).
- Polo, A.,Real, J.,Claver, C.,Castillon, S.,Bayon, J. C.
-
p. 600 - 601
(2007/10/02)
-
- LIQUID-PHASE HYDROFORMYLATION OF 2,3- AND 2,5-DIHYDROFURANS
-
The synthesis of 3-formyl derivatives of the tetrahydrofuran series was carried out by hydroformylation of 2,3-dihydrofuran and 2,5-dimethoxy-2,5-dihydrofuran in the presence of HRh(CO)(PPh3)3.The influence of the temperature, pressure, catalyst concentration, and the nature of the solvent on the conversion of dihydrofuran, the composition of aldehydes obtained and the selectivity of their formation was investigated.
- Vol'f, E. Yu.,Solov'eva, T. Yu.,Vartanyan, M. M.,Brezhnev, L. Yu.,Lapidus, A. L.
-
p. 2356 - 2358
(2007/10/02)
-
