27649-40-7Relevant academic research and scientific papers
A new biogenerated Rh-based catalyst for aqueous biphasic hydroformylation
Paganelli, Stefano,Piccolo, Oreste,Baldi, Franco,Gallo, Michele,Tassini, Riccardo,Rancan, Marzio,Armelao, Lidia
, p. 32 - 36 (2015)
A new bio-generated rhodium based system embedded in a peculiar polysaccharide matrix (Rh-EPS), was obtained and purified from cultures of bacterial cells of Klebsiella oxytoca DSM 29614. The product was analyzed with different techniques to obtain information on its structure-property correlation. In order to determine its catalytic activity and selectivity in the aqueous biphasic hydroformylation some olefins were chosen as model substrates, obtaining fine-good results.
Chemo- And regioselective hydroformylation of alkenes with CO2/H2over a bifunctional catalyst
Hua, Kaimin,Liu, Xiaofang,Wei, Baiyin,Shao, Zilong,Deng, Yuchao,Zhong, Liangshu,Wang, Hui,Sun, Yuhan
supporting information, p. 8040 - 8046 (2021/11/01)
As is well known, CO2 is an attractive renewable C1 resource and H2 is a cheap and clean reductant. Combining CO2 and H2 to prepare building blocks for high-value-added products is an attractive yet challenging topic in green chemistry. A general and selective rhodium-catalyzed hydroformylation of alkenes using CO2/H2 as a syngas surrogate is described here. With this protocol, the desired aldehydes can be obtained in up to 97% yield with 93/7 regioselectivity under mild reaction conditions (25 bar and 80 °C). The key to success is the use of a bifunctional Rh/PTA catalyst (PTA: 1,3,5-triaza-7-phosphaadamantane), which facilitates both CO2 hydrogenation and hydroformylation. Notably, monodentate PTA exhibited better activity and regioselectivity than common bidentate ligands, which might be ascribed to its built-in basic site and tris-chelated mode. Mechanistic studies indicate that the transformation proceeds through cascade steps, involving free HCOOH production through CO2 hydrogenation, fast release of CO, and rhodium-catalyzed conventional hydroformylation. Moreover, the unconventional hydroformylation pathway, in which HCOOAc acts as a direct C1 source, has also been proved to be feasible with superior regioselectivity to that of the CO pathway.
Rh-catalyzed highly regioselective hydroformylation to linear aldehydes by employing porous organic polymer as a ligand
Wang, Zhaozhan,Yang, Yong
, p. 29263 - 29267 (2020/10/06)
In this work, we developed a new structural porous organic polymer containing biphosphoramidite unit, which can be used as a solid bidentate phosphorous ligand for rhodium-catalyzed solvent-free higher olefins hydroformylation. The resultant catalyst demonstrated unprecedently high regioselectivity to linear aldehydes and could be readily recovered for successive reuses with good stability in both catalytic activity and regioselectivity. This journal is
Phosphonium-based aminophosphines as bifunctional ligands for sequential catalysis of one-pot hydroformylation-acetalization of olefins
Wang, Peng,Liu, Huan,Li, Yong-Qi,Zhao, Xiao-Li,Lu, Yong,Liu, Ye
, p. 3854 - 3861 (2016/06/14)
A series of ionic phosphonium-based aminophosphines L1-L3 were prepared and fully characterized, in each of which the involved bifunctional moieties of the phosphine fragment and Lewis acidic phosphonium were linked together by stable chemical bonds and bridged by one N-atom. The molecular structure of the L2-ligated Rh-complex (Rh-L2) indicated that such bifunctionalities were well retained without incompatibility problems. Investigations on co-catalysis over L1-L3 showed that L3 exhibited the best sequential catalysis for both hydroformylation and acetalization. The phosphine fragment in L3 was responsible for hydroformylation together with the Rh-complex and the phosphonium acted as the Lewis acidic catalyst in charge of acetalization. The L3-Rh(acac)(CO)2 system also exhibited good generality to hydroformylation-acetalization of a wide range of olefins in different alcohols.
New tetraphosphite ligands for regioselective linear hydroformylation of terminal and internal olefins
Zhang, Zongpeng,Chen, Caiyou,Wang, Qian,Han, Zhengyu,Dong, Xiu-Qin,Zhang, Xumu
, p. 14559 - 14562 (2016/02/19)
We successfully developed new tetraphosphite ligands L1-L5 and applied them to the rhodium-catalyzed hydroformylation of terminal and internal olefins. High catalytic reactivities and excellent regioselectivities for linear aldehydes were obtained in the rhodium-catalyzed hydroformylation of simple olefins (l/b ratio up to 90, 98.9% linear selectivity, 99.2% conversion) using the tetraphosphite ligand L2. And the tetraphosphite ligand L2 also displayed moderate to good linear regioselectivities for challenging substrates styrene and internal olefin 2-octene.
Method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on basis of phosphine-functionalized polyether imidazolium salt ionic liquid
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Paragraph 0051; 0079; 0080; 0081, (2017/11/17)
The invention relates to a method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on the basis of a phosphine-functionalized polyether imidazolium salt ionic liquid. According to the method, a two-phase catalytic system is adopted, the catalytic system comprises a phosphine-functionalized polyether imidazolium salt ionic liquid, a polyether imidazolium salt ionic liquid, a rhodium catalyst, a reaction substrate olefin and a reaction product aldehyde, a liquid/liquid two-phase hydroformylation reaction is performed at certain reaction temperature and under certain synthesis gas pressure, the rhodium catalyst is separated and cycled through simple two-phase separation after the reaction ends, the rhodium catalyst can be recycled multiple times, and the catalytic activity and the selectivity are not remarkably reduced. The TOF value of the system reaches 400-3,300 h and the catalytic cycle accumulated TON value reaches 33,975.
A modular family of phosphine-phosphoramidite ligands and their hydroformylation catalysts: steric tuning impacts upon the coordination geometry of trigonal bipyramidal complexes of type [Rh(H)(CO)2(P^P?)]
How, Rebecca C.,Hembre, Robert,Ponasik, James A.,Tolleson, Ginette S.,Clarke, Matthew L.
, p. 118 - 124 (2015/12/31)
Four new phosphine-phosphoramidite bidentate ligands have been synthesised and studied in rhodium-catalysed hydroformylation. Variable temperature NMR studies have been used along with HPIR to investigate the coordination mode of the trigonal bipyramidal complexes formed from [Rh(acac)(CO)2], ligand and syngas. It was found that small changes to the ligand structure have a large effect on the geometry of the active catalytic species. The rhodium catalysts of these new ligands were found to give unusually high iso-selectivity in the hydroformylation of propene and 1-octene.
Molybdenum carbonyl grafted onto silicate intercalated cobalt-aluminum hydrotalcite: A new potential catalyst for the hydroformylation of octene
Sakthivel, Ayyamperumal,Mahato, Nihar Ranjan,Baskaran, Thangaraj,Christopher, Jayaraj
, p. 55 - 61 (2015/04/27)
We present the first example of molybdenum carbonyl grafted on diaminosiloxane-functionalized cobalt-aluminum hydrotalcite (CA-HTSi-DA-Mo) as a promising catalyst for the hydroformylation of olefins. The catalyst showed 80% conversion with selective formation of branched aldehyde. About 70% of the catalytic activity retains even after three cycles.
From alkenes to alcohols by cobalt-catalyzed hydroformylation-reduction
Achonduh, George,Yang, Qian,Alper, Howard
supporting information, p. 1241 - 1246 (2015/03/05)
The cobalt-catalyzed hydroformylation of alkenes in the presence of a range of novel cyclic phosphine ligands was investigated. The effect of various parameters such as solvents, additives, cobalt/phosphine ratio, CO/H2 (1:2), and nature of the alkenes was examined. The results revealed that both terminal and internal alkenes are hydroformylated in high yields to give mainly linear products at moderate temperature and syn gas pressure. The linearity ranges from 43 to 85%, with Lim-10 giving the highest proportion of linear product.
Method for Producing Isononanoic Acid Esters, Starting from 2-Ethyl Hexanol
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Paragraph 0077-0080; 0083, (2015/06/17)
A Process for preparing carboxylic esters of a mixture of structurally branched C9 monocarboxylic acids proceeding from 2-ethylhexanol is characterized in that (a) 2-ethylhexanol is dehydrated to an octene mixture in the presence of a catalyst; (b) the octene mixture obtained in step a) is reacted in the presence of a transition metal compound of group VIII of the periodic table of the elements with carbon monoxide and hydrogen to give a mixture of isomeric isononanals; (c) the mixture of isomeric isononanals obtained in step b) is oxidized to a mixture of structurally branched C9 monocarboxylic acids; and (d) the mixture of structurally branched C9 monocarboxylic acids obtained in step c) is reacted with alcohols to give carboxylic esters.
