5393-69-1Relevant academic research and scientific papers
Linear-selective hydroformylation of vinyl ether using Rh (acac)(2,2′-bis{(di[1H-indol-1-yl]phosphanyl)oxy}-1,1′-binaphthalene) – Possible way to synthesize 1,3-propanediol
Wan, Kefeng,Zhao, Jiangui,Qin, Song,Zheng, Xueli,Fu, Haiyan,Li, Ruixiang,Chen, Hua,Yang, Jijun,Yang, Chunji
, (2020/07/24)
Three bidentate phosphoramidite ligands were synthesized, characterized, and employed in Rh-catalyzed hydroformylation of vinyl ethers. The complex Rh(acac)(2,2′-bis{(di[1H-indol-1-yl]phosphanyl)oxy}-1,1′-binaphthalene} (acac = acetylacetone) (Rh-L4) was also synthesized and characterized. Rh-L4 showed good regioselectivity for the hydroformylation of vinyl ethers under mild reaction conditions: 2 MPa of syngas, 1:1 (H2/CO) substrate/catalyst molar ratio 1000:1, and 60 °C. The linear selectivity was up to 98%, and in most cases was about 80%, with no hydrogenation product formation observed, which could be a potential way to synthesize 1,3-propanediol. A mechanism study including density functional theory computational analysis showed that both Rh–H and CO insertion steps in the hydroformylation of vinyl ether were linear-preferred in our catalyst system.
Tetradentate phosphine ligand and preparation method thereof, hydroformylation catalyst and reaction method, and preparation method of 1, 3-propylene glycol
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Paragraph 0070-0071; 0076-0077; 0081-0092, (2020/08/25)
The invention provides a tetradentate phosphine ligand, a preparation method of the tetradentate phosphine ligand, a hydroformylation catalyst, a reaction method of the hydroformylation catalyst and apreparation method of 1, 3-propylene glycol, and belongs to the technical field of compound materials. The general formula of the tetradentate phosphine ligand is shown in the specification, whereinR1 is hydrogen or halogen, R2 is a nitrogen-containing heterocyclic ring or a complex of the tetradentate phosphine ligand and a rhodium complex, can be used for carrying out a hydroformylation catalytic reaction, and can be used for preparing 1, 3-propylene glycol.
Process for synthesis of acrylic acid precursors via hydroformylation of vinyl ether
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, (2008/06/13)
A process is disclosed for the preparation of acrylic acid precursors by a hydroformylation process which comprises reacting a vinyl ether with carbon monoxide and hydrogen in the presence of a catalyst comprising a rhodium carbonyl compound and a phosphine ligand at a mild temperature and pressure until there is substantial formation of the intermediate 2- and 3-ethoxypropanals, followed by oxidation of said aldehydes and pyrolysis to said acrylic acid.
FACTORS AFFECTING REGIOSLECTIVITY IN THE RHODIUM-CATALYSED HYDROFORMYLATION OF VINYL ETHERS
Lazzaroni, Raffaelo,Bertozzi, Sergio,Pocai, Paolo,Troiani, Francesco,Salvadori, Piero
, p. 371 - 376 (2007/10/02)
The rhodium catalysed hydroformylation of vinyl ethers ROCH=CH2, where R is an alkyl, a benzyl or a phenyl group, has been investigated over the 20-100 deg C temperature range in the presence of Rh4(CO)12 or 2/PPh3 (1/6) as catalytic precursors.A mixture of 2-alkoxy-(or phenoxy)propanal (the α-isomer) and 3-alkoxy-(or phenoxy)propanal (the β-isomer) is obatined in good yield.The isomeric composition of the aldehydes depends on the structure of the substrate, on the catalytic precursor employed, and on the reaction temperature.The α-isomer predomines in all the cases, its predominance being greater (i) at low temperatures, (ii)in the presence of Rh4(CO)12 as catalyst precursor, and (iii) when a phenyl group is present in the β or γ position with respect to the double bond in the substrate.Electronic factors arising from the presence in the substrate of the oxygen atom and a phenyl group are more impotrant than the steric hindrance of tghe R group in detrmining the regioselectivity of the reaction.
