79710-86-4Relevant articles and documents
Application of organic amine additive in synthesis of fluorescent dye intermediate through olefin hydroformylation reaction
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Paragraph 0015-0023, (2021/07/31)
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.
Hydroformylation of unsaturated esters and 2,3-dihydrofuran under solventless conditions at room temperature catalysed by rhodium: N-pyrrolyl phosphine catalysts
Alsalahi,Trzeciak
, p. 16990 - 16999 (2019/11/14)
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.
Backbone-Modified Bisdiazaphospholanes for Regioselective Rhodium-Catalyzed Hydroformylation of Alkenes
Wildt, Julia,Brezny, Anna C.,Landis, Clark R.
, p. 3142 - 3151 (2017/09/05)
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.
