- Methyl-modified cage-type phosphorus ligand and preparation method thereof Preparation method and application thereof
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The invention discloses a methyl-modified cage-type phosphorus ligand, a preparation method and application thereof, in particular to a synthesis design, wherein methyl is further introduced on a phenyl ring of triphenylphosphine, and a methyl-modified cage-type phosphorus ligand is synthesized, and when a methyl meta-substituted cage-type phosphorus ligand is used as a hydroformylation reaction catalyst the proportion of n-structural aldehyde and isomeric aldehyde is 2.6. TOF-1 The methyl-substituted cage-type phosphorus ligand is excellent in performance, stable in property and recyclable, has excellent substrate applicability in the hydroformylation catalytic reaction, has a good industrial application prospect, and has very important significance in metal organic catalysis.
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Paragraph 0075-0084; 0087-0088
(2021/09/15)
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- Homogeneous hydroformylation of long chain alkenes catalyzed by water soluble phosphine rhodium complex in CH3OH and efficient catalyst cycling
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The hydroformylation of long chain alkenes catalyzed by a water soluble Rh/TPPTS complex (TPPTS: sodium salt of sulfonated triphenylphosphine) in methanol was investigated. The mixture of rhodium precursor HRh(CO)(TPPTS)3, ligand TPPTS, methanol and a long chain alkene becomes a single phase under reaction conditions, which make the hydroformylation reaction proceed homogeneously. Both the conversion of long chain alkene and the selectivity to aldehydes (including the aldehydes forming methylacetals) could reach up to 97.8% and 97.6%, respectively, with 3323 h?1 of TOF (TOF: turnover frequency is defined as the moles of converted alkene per mole of Rh per hour). After the solvent methanol was removed under the reaction temperature, two phases were formed automatically. The colourless product phase could be efficiently separated from the precipitate rhodium catalyst phase by centrifuge. The catalyst was reused for five times without obvious loss of rhodium and the catalytic activity. The rhodium leaching in product mixture was less than 0.03% of the total rhodium.
- Liu, Yan-li,Zhao, Jian-gui,Zhao, Yuan-jiang,Liu, Hui-Min,Fu, Hai-yan,Zheng, Xue-li,Yuan, Mao-lin,Li, Rui-xiang,Chen, Hua
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p. 7382 - 7387
(2019/03/19)
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- Integration of phosphine ligands and ionic liquids both in structure and properties-a new strategy for separation, recovery, and recycling of homogeneous catalyst
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The major limitation of classic biphasic ionic liquid (IL) catalysis is the heavy use of solvent ILs, which not only violates green chemistry principles but also even worsens catalytic efficiency. So it has always been a challenge finding ways to use ILs more efficiently, economically, and greenly to construct highly effective and long term stable IL catalytic systems. In this work, we synthesized a class of room temperature phosphine-functionalized polyether guanidinium ionic liquids (RTP-PolyGILs) by a convenient ion exchange reaction of polyether guanidinium ionic liquids (PolyGILs) with phosphine-sulfonate ligands based on the concept of the integration of both the phosphine ligand and IL. The resulting RTP-PolyGILs existed as liquids at room temperature and possessed dual functions of both the phosphine ligand and solvent IL; therefore they could both form catalysts by complexing with transition metals and act as catalyst carriers, thus achieving the integration of phosphine ligands with ILs both in structure and properties. Based on the unique properties of these multi-functional integrated RTP-PolyGILs, we constructed a highly effective homogeneous catalysis-biphasic separation (HCBS) system for Rh-catalyzed hydroformylation of higher olefins using only a catalytic amount of RTP-PolyGILs (equivalent to 0.025-0.4 mol% of 1-alkenes). Our HCBS system could be flexibly regulated with regard to catalytic performance (activity and linear selectivity) by changing the structure or type of the sulfonated ligand anion on RTP-PolyGILs. Specifically, it presented a TOF value of 3000-26000 h-1 and a linear selectivity of 68%-98% (corresponding to the l/b ratio of 2.2-37.5) with a total turnover number (TTON) of 11000-45000 and an extremely low Rh leaching of only 0.02-0.4 ppm. Therefore, the HCBS system can effectively combine the advantages of both homogeneous (high activity and good selectivity) and biphasic catalysis (easy catalyst separation). We additionally extended the application of the HCBS system to the hydrogenation of olefins to demonstrate the universality of the RTP-PolyGILs in catalytic reactions.
- Jin, Xin,Feng, Jianying,Song, Hongbing,Yao, Jiajun,Ma, Qingqing,Zhang, Mei,Yu, Cong,Li, Shumei,Yu, Shitao
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p. 3583 - 3596
(2019/07/10)
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- Heterogeneous hydroformylation of long-chain alkenes in IL-in-oil Pickering emulsion
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An efficient heterogeneous catalytic system for hydroformylation of long-chain alkenes is highly desirable for both academy and industry. In this study, an IL-in-oil Pickering emulsion system was employed for heterogeneous hydroformylation of 1-dodecene with Rh-sulfoxantphos as the catalyst and surface modified dendritic mesoporous silica nanospheres (DMSN) as the stabilizer. The IL-in-oil Pickering emulsion system outperformed IL-oil biphase, water-in-oil Pickering emulsion and IL-oil micelle system under similar reaction conditions to afford n/b ratio of 98:2, chemoselectivity of 94% and TOF of 413 h-1, among the highest ever reported for IL-oil biphase hydroformylation of long-chain alkenes. The high efficiency of IL-in-oil Pickering emulsion was primarily attributed to the increased interface area and unique properties of ILs. Studies also revealed that solid stabilizers with large and open pore channels could greatly increase the reaction rate of Pickering emulsion systems by accelerating the diffusion rate. The recyclable IL-in-oil Pickering emulsion is promising not only for hydroformylation of long-chain alkenes but also for catalytic reactions with immiscible liquids.
- Tao, Lin,Zhong, Mingmei,Chen, Jian,Jayakumar, Sanjeevi,Liu, Lina,Li, He,Yang, Qihua
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p. 188 - 196
(2018/01/12)
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- Nonaqueous Biphasic Hydroformylation of Long Chain Alkenes Catalyzed by Water Soluble Phosphine Rhodium Catalyst with Polyethylene Glycol Instead of Water
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Abstract: The application of polyethylene glycol (donated as PEG), as an environmentally benign solvent instead of water, in rhodium catalyzed hydroformylation of long chain alkenes by using water soluble phosphine BISBIS or TPPTS (TPPTS: sodium salt of sulfonated triphenylphosphine, BISBIS: sodium salt of sulfonated 2,2′-bis(diphenylphosphinomethyl)-1,1′-biphenyl) is herein reported. The conversion of long chain alkenes in PEG-200 could reach above 95.0% after a short reaction time (15?min). In addition, an efficient phase separation and recycling of PEG-200 and catalyst were achieved. The leaching of rhodium into product phase detected by ICP-AES was less than 0.06?wt% of the initial amount. Graphical Abstract: [Figure not available: see fulltext.].
- Zhao, Yuanjiang,Liu, Yanli,Wei, Jianzhang,Fu, Haiyan,Zheng, Xueli,Yuan, Maolin,Li, Ruixiang,Chen, Hua
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p. 438 - 442
(2017/12/04)
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- Iron Catalyzed Hydroformylation of Alkenes under Mild Conditions: Evidence of an Fe(II) Catalyzed Process
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Earth abundant, first row transition metals offer a cheap and sustainable alternative to the rare and precious metals. However, utilization of first row metals in catalysis requires harsh reaction conditions, suffers from limited activity, and fails to tolerate functional groups. Reported here is a highly efficient iron catalyzed hydroformylation of alkenes under mild conditions. This protocol operates at 10-30 bar syngas pressure below 100 °C, utilizes readily available ligands, and applies to an array of olefins. Thus, the iron precursor [HFe(CO)4]-[Ph3PNPPh3]+ (1) in the presence of triphenyl phosphine catalyzes the hydroformylation of 1-hexene (S2), 1-octene (S1), 1-decene (S3), 1-dodecene (S4), 1-octadecene (S5), trimethoxy(vinyl)silane (S6), trimethyl(vinyl)silane (S7), cardanol (S8), 2,3-dihydrofuran (S9), allyl malonic acid (S10), styrene (S11), 4-methylstyrene (S12), 4-iBu-styrene (S13), 4-tBu-styrene (S14), 4-methoxy styrene (S15), 4-acetoxy styrene (S16), 4-bromo styrene (S17), 4-chloro styrene (S18), 4-vinylbenzonitrile (S19), 4-vinylbenzoic acid (S20), and allyl benzene (S21) to corresponding aldehydes in good to excellent yields. Both electron donating and electron withdrawing substituents could be tolerated and excellent conversions were obtained for S11-S20. Remarkably, the addition of 1 mol % acetic acid promotes the reaction to completion within 16-24 h. Detailed mechanistic investigations revealed in situ formation of an iron-dihydride complex [H2Fe(CO)2(PPh3)2] (A) as an active catalytic species. This finding was further supported by cyclic voltammetry investigations and intermediacy of an Fe(0)-Fe(II) species was established. Combined experimental and computational investigations support the existence of an iron-dihydride as the catalyst resting state, which then follows a Fe(II) based catalytic cycle to produce aldehyde.
- Pandey, Swechchha,Raj, K. Vipin,Shinde, Dinesh R.,Vanka, Kumar,Kashyap, Varchaswal,Kurungot, Sreekumar,Vinod,Chikkali, Samir H.
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supporting information
p. 4430 - 4439
(2018/04/05)
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- Multiphasic aqueous hydroformylation of 1-alkenes with micelle-like polymer particles as phase transfer agents
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Micelle-like polymer particles have been applied in aqueous multiphasic hydroformylation reactions of long chain alkenes. These colloids act as phase transfer agents for the nonpolar substrates and as carriers for the catalyst bearing sulfonated ligands by electrostatic attraction. The catalyst performance and the phase separation were optimized with special focus on the conversion, selectivity and catalyst recovery, as those are key points in multiphasic systems to achieve a feasible industrial process. The effect on the catalyst performance of the number of sulfonate groups and electron withdrawing trifluoromethyl groups in the ligand has been studied. The approach was successfully demonstrated for 1-alkenes from 1-hexene to 1-dodecene. For 1-octene, a TOF of more than 3000 h?1 could be achieved at a substrate to catalyst ratio of 80?000, while keeping the rhodium and phosphorous leaching below 1 ppm. In repetitive batch experiments the catalyst was recycled four times, yielding an accumulated TON of more than 100?000 for 1-octene.
- Bibouche, Bachir,Peral, Daniel,Stehl, Dmitrij,S?derholm, Viktor,Schom?cker, Reinhard,Von Klitzing, Regine,Vogt, Dieter
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p. 23332 - 23338
(2018/07/10)
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- Based on [...] functionalized polyether alkyl guanidine salt ion liquid of the two-phase hydroformylation of olefins method
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The present invention relates to a method for biphasic hydroformaylation of olefins based on a phosphine-functionalized polyether alkyl guanidine salt ionic liquid. A biphasic catalytic system is used in the method, wherein the catalytic system consists of the phosphine-functionalized polyether alkyl guanidine salt ionic liquid, a rhodium catalyst, a reaction substrate - olefins and a reaction product - aldehydes; liquid/liquid biphasic hydroformylation of olefins is performed at a certain reaction temperature and syngas pressure; the phosphine-functionalized polyether alkyl guanidine salt ionic liquid acts both as a phosphine ligand and as a rhodium catalyst carrier; there is no need to add any other ionic liquid to the system; separation and recycling of the rhodium catalyst are realized by liquid/liquid biphasic separation after the reaction; the rhodium catalyst is capable of being recycled for multiple times with no obvious decrease in catalytic activity or selectivity; the TOF value of the system reaches 240-2700h-1; and the highest catalytic cycle cumulative TON value reaches 47138.
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Paragraph 0045; 0046; 0047; 0062
(2018/09/26)
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- Supported rhodium liquid metal catalysts for the hydroformylation of olefins
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The hydroformylation of olefins in supported room temperature liquid metals was developed, and the supported Rh liquid metal catalysts (Rh SLMCs) showed unprecedented activity and high selectivity for the hydroformylation of olefins to aldehydes. The turnover frequency is up to 7000?h?1, much higher than that of homogeneous RhCl3?+?3PPh3 catalyst. Moreover, the Rh SLMCs can be recovered conveniently without obvious deactivation, and the total turnover number is up to 250?000. The active Rh(I) catalyst formed in situ can be reduced back to Rh(0) by the free electrons in liquid metal when H2/CO gas is emitted, and thus Rh is not leaked into the organic solvent. Long-chain olefins, cycloolefins and styrenes were applied, and the corresponding aldehydes were obtained in good to excellent yields.
- Sun, Hao,Guo, Wanwan,Liu, Junmei,Feng, Zhipeng,Li, Ruyue,Zhou, Xuyang,Huang, Jun
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- Efficient water-soluble catalytic system RhI-CAP for biphasic hydroformylation of olefins
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Rhodium-catalysed hydroformylation of styrene and aliphatic olefins under biphasic conditions in the presence of watersoluble 1,4,7-triaza-9-phosphatricyclo[5.3.2.14,9]tridecane (CAP) chemoselectively affords aldehydes. Multiple catalyst reuse without loss in performance is demonstrated.
- Eliseev, Oleg L.,Bondarenko, Tatyana N.,Britvin, Sergey N.,Khodorchenko, Polina P.,Lapidus, Albert L.
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p. 264 - 266
(2018/06/01)
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- Water-soluble phosphane-substituted cyclodextrin as an effective bifunctional additive in hydroformylation of higher olefins
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In cyclodextrin (CD)-mediated aqueous biphasic catalysis, favoring contacts between the CD ("host"), the organic substrate ("guest") and the water-soluble catalyst is crucial for the reaction to proceed efficiently at the aqueous/organic interface. Grafting the catalyst onto the CD backbone thus appears as an attractive approach to favor the molecular recognition of the substrate and its subsequent catalytic conversion into products. In this context, a new water-soluble β-CD-based phosphane was synthesized and characterized by NMR, tensiometric and ITC measurements. The β-CD-based phosphane consisted of a 3,3′-disulfonatodiphenyl phosphane connected to the primary face of β-CD by a dimethyleneamino spacer. Intra- and intermolecular inclusion processes of one of the two sulfophenyl groups into the β-CD cavity were identified in water. However, the association constant (Ka) related to the β-CD/sulfophenyl group couple was low. Accordingly, the inclusion process was easily displaced upon coordination to rhodium complexes. The efficacy of the resulting Rh-complex coordinated by β-CD-based phosphanes was assessed in Rh-catalyzed hydroformylation of higher olefins. The catalytic system proved to be far more successful and efficient than a system consisting of supramolecularly interacting phosphanes and CDs. The catalytic activity was up to 30-fold higher while the chemo- and regioselectivities remain rather unchanged.
- Leblond,Potier,Menuel,Bricout,Machut-Binkowski,Landy,Tilloy,Monflier,Hapiot
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p. 3823 - 3830
(2017/09/07)
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- A kind of [...] functionalized polyether quaternary phosphonium ionic liquid and its olefin hydroformylation reaction in the application of the (by machine translation)
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The invention relates to a functionalized polyether quaternary phosphonium salt [...] ionic liquid, and a functionalized polyether quaternary phosphonium salt based on [...] ionic liquid two-phase hydroformylation of olefins of the method, the method uses a two-phase catalytic system, the catalytic system is composed of [...] functionalized polyether quaternary phosphonium ion liquid, rhodium catalyst and reaction substrate olefin and reaction aldehyde composition, in a certain reaction temperature and the synthesis gas is conducted under a pressure liquid/liquid two-phase hydroformylation reaction, [...] functionalized polyether quaternary phosphonium ionic liquid is phosphine, at the same time also acts as the rhodium catalyst carrier, system do not need in in addition introducing other ionic liquid, after the reaction through a simple liquid/liquid two-phase separation [...] separation and recycle of the catalyst, the catalytic system has higher catalytic activity, rhodium catalyst can be circulated many times, catalytic activity and selectivity without significant decrease. (by machine translation)
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Paragraph 0052-0054; 0067-0069
(2017/11/16)
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- Highly efficient heterogeneous hydroformylation over rh-metalated porous organic polymers: Synergistic effect of high ligand concentration and flexible framework
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A series of diphosphine ligand constructed porous polymers with stable and flexible frameworks have been successfully synthesized under the solvothermal conditions from polymerizing the corresponding vinyl-functionalized diphosphine monomers. These insoluble porous polymers can be swollen by a wide range of organic solvents, showing similar behavior to those of soluble analogues. Rather than just as immobilizing homogeneous catalysts, these porous polymers supported with Rh species demonstrate even better catalytic performance in the hydroformylations than the analogue homogeneous catalysts. The sample extraordinary performance could be attributed to the combination of high ligand concentration and flexible framework of the porous polymers. Meanwhile, they can be easily separated and recycled from the reaction systems without losing any activity and selectivity. This excellent catalytic performance and easy recycling heterogeneous catalyst property make them be very attractive. These diphosphine ligand constructed porous polymers may provide new platforms for the hydroformylation of olefins in the future.
- Sun, Qi,Dai, Zhifeng,Liu, Xiaolong,Sheng, Na,Deng, Feng,Meng, Xiangju,Xiao, Feng-Shou
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supporting information
p. 5204 - 5209
(2015/05/05)
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- From alkenes to alcohols by cobalt-catalyzed hydroformylation-reduction
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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.
- Achonduh, George,Yang, Qian,Alper, Howard
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supporting information
p. 1241 - 1246
(2015/03/05)
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- Enantioselective Hydroformylation of 1-Alkenes with Commercial Ph-BPE Ligand
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A rhodium complex, in conjunction with commercially available Ph-BPE ligand, catalyzes the branch-selective asymmetric hydroformylation of 1-alkenes and rapidly generates α-chiral aldehydes. A wide range of terminal olefins including 1-dodecene were examined, and all delivered high enantioselectivity (up to 98:2 er) as well as good branch:linear ratios (up to 15:1). (Chemical Equation Presented).
- Yu, Zhiyong,Eno, Meredith S.,Annis, Alexandra H.,Morken, James P.
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supporting information
p. 3264 - 3267
(2015/07/15)
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- Crucial role of additives in iridium-catalyzed hydroformylation
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Abstract This paper presents the new highly selective iridium-catalyzed hydroformylation of 1-octene with an Ir(cod)(acac)/PPh3/salt catalyst system. The addition of inorganic salts such as LiCl suppresses the hydrogenation of 1-octene and increases the yield of desired hydroformylation products. Even low amounts of LiCl (LiCl/Ir = 2/1) significantly increase the chemoselectivity of aldehydes up to 94% with a 1-octene conversion of 90% within 7 h. This catalyst is applicable to other alkenes such as 1-pentene or 1-dodecene. The high selectivities and the remarkable activity of the optimized iridium catalyst are promising in terms of successfully implementing on an industrial scale in the future.
- Behr, Arno,K?mper, Alexander,Nickel, Martin,Franke, Robert
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p. 243 - 248
(2015/09/01)
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- Synergetic effect of randomly methylated β-cyclodextrin and a supramolecular hydrogel in Rh-catalyzed hydroformylation of higher olefins
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A significant improvement in Rh-catalyzed hydroformylation of very hydrophobic alkenes was achieved using a biphasic catalytic system consisting of a substrate-containing organic phase and a catalyst-containing hydrogel phase [consisting of poly(ethylene glycol) 20000 (PEG20000) and α-cyclodextrin (α-CD)]. The catalytic performance of the Pickering emulsion that resulted from the formation of α-CD/PEG20000 crystallites at the oil droplet surface proved to be greatly dependent upon the presence of additives. We showed that controlled uploads of randomly methylated β-cyclodextrin (RAME-β-CD) within the supramolecular hydrogel could positively affect both the catalytic activity and chemoselectivity of the hydroformylation reaction. Conversely, no Pickering emulsion could be observed using excess RAME-β-CD, resulting in the subsequent degradation of the catalytic performance. Optical microscopy and optical fluorescence microscopy supported the catalytic results and allowed us to explain the role of RAME-β-CD. Indeed, controlled uploads of RAME-β-CD prevented the saturation of the oil droplet surface. RAME-β-CD acted as a fluidifier of the Pickering emulsion and accelerated the dynamics of exchange between the substrate-containing organic phase and the catalyst-containing hydrogel phase. Morever, RAME-β-CD acted as a receptor that participated in the conversion of the alkene by supramolecular means.
- Potier, Jonathan,Menuel, Stephane,Monflier, Eric,Hapiot, Frederic
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p. 2342 - 2346
(2014/07/21)
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- METHOD FOR HYDROFORMYLATION OF UNSATURATED COMPOUNDS
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The invention relates to a method for hydroformylation of unsaturated compounds such as olefins and alkynes using mixtures of synthesis gas (CO/H2), in which either the unsaturated compounds and a catalyst are heated to a reaction temperature of 60 to 200° C. and the synthesis gas is then added, or the unsaturated compounds and the catalyst are brought into contact with pure CO at normal temperature in a preformation step, then are heated to reaction temperature and on reaching the reaction temperature the CO is replaced by the synthesis gas. The pressure is 1 to 200 bar and the CO:H2 ratio in the synthesis gas is in the range from 1:1 to 50:1. The iridium catalyst used comprises a phosphorus-containing ligand in the iridium:ligand ratio in the range from 1:1 to 1:100. With high catalyst activities and low catalyst use, very high turnover frequencies are achieved.
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Paragraph 0091
(2014/02/16)
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- Pickering emulsions based on supramolecular hydrogels: Application to higher olefins' hydroformylation
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Supramolecular hydrogels elaborated from a mixture of native α-cyclodextrin and poly(ethylene glycol)s in water proved to be effective media for higher olefins Rh-catalyzed hydroformylation due to the formation of Pickering emulsions.
- Potier, Jonathan,Menuel, Stephane,Chambrier, Marie-Heleine,Burylo, Laurence,Blach, Jean-Francois,Woisel, Patrice,Monflier, Eric,Hapiot, Frederic
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p. 1618 - 1621
(2013/07/26)
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- Selective hydroformylation-acetalization of various olefins using simple and efficient Rh-phosphinite complex catalyst
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A simple and efficient Rh-phosphinite complex catalyst was studied for the selective hydroformylation of various olefins. The influence of various reaction parameters including the effect of temperature, pressure, catalyst loading, time, and solvents was studied. The protocol was also applied for the synthesis of various acetals via tandem hydroformylation-acetalization of olefins in alcohols as solvents. High activity and selectivity for acetal formation was achieved in the absence of co-catalysts with admirable substrate to catalyst mole ratio (TON 2500). The developed protocol works for a wide range of olefins to synthesize corresponding aldehydes and acetals under optimized reaction conditions.
- Khan, Shoeb R.,Bhanage, Bhalchandra M.
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p. 5998 - 6001
(2013/10/22)
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- Selective hydroformylation of olefins over the rhodium supported large porous metal-organic framework MIL-101
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Highly porous and crystalline metal-organic framework MIL-101 has been synthesized and used for the preparation of rhodium supported catalyst. Acetylacetonato(1,5-cyclooctadiene)rhodium(I) has been used as catalyst precursor. The material has been characterized by XRD, XPS, SAXS, FTIR, SEM, TEM, AAS, and nitrogen adsorption. The catalytic properties of Rh@MIL-101 have been investigated in the hydroformylation of olefins with different structure and chain length to the corresponding aldehydes. High conversion and selectivity to n-aldehydes have been achieved in the hydroformylation of n-alk-1-enes. The obtained results show that the rhodium species are highly dispersed and preferentially located at internal and less accessible sites at the supertetrahedral units.
- Van Vu, Toan,Kosslick, Hendrik,Schulz, Axel,Harloff, Joerg,Paetzold, Eckhard,Schneider, Mathias,Radnik, Joerg,Steinfeldt, Norbert,Fulda, Gerhard,Kragl, Udo
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p. 410 - 417
(2013/10/22)
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- Supramolecular encapsulated rhodium catalysts for branched selective hydroformylation of alkenes at high temperature
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This study reveals that, in contrast to expectations, supramolecular encapsulated rhodium catalysts can be used at industrially relevant temperatures (75-80 °C), providing highly active catalysts. The unprecedented regioselectivity for the branched aldehydes can be retained if high carbon monoxide (CO) concentrations are used.
- Besset, Tatiana,Norman, David W.,Reek, Joost N. H.
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supporting information
p. 348 - 352
(2013/05/22)
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- Thermoregulated phase-transfer rhodium nanoparticle catalyst for hydroaminomethylation of olefins
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Rh nanoparticles used as catalysts for hydroaminomethylation reaction is reported for the first time. An efficient and recyclable Rh nanoparticle catalyst stabilized by thermoregulated ligand Ph2P(CH 2CH2O)nCH3 (n = 16) was studied for the hydroaminomethylation of olefins in the aqueous/1-butanol biphasic system through thermoregulated phase-transfer catalysis, which allows not only for a homogeneous catalytic reaction, but also for an easy biphasic separation. Under the optimized conditions, the conversion of 1-octene and the product amine selectivity were as high as 99% and 97%, respectively. After reaction, the Rh nanoparticle catalyst can be separated from products by simple phase separation and recycled directly for the next run.
- Li, Kaoxue,Wang, Yanhua,Xu, Yicheng,Li, Wenjiang,Niu, Mingming,Jiang, Jingyang,Jin, Zilin
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- From olefins to alcohols: Efficient and regioselective ruthenium-catalyzed domino hydroformylation/reduction sequence
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Exploring the alternatives: Ruthenium imidazoyl phosphine complexes catalyze the domino hydroformylation/reduction of alkenes to alcohols in good yields and with good selectivities (see scheme). Linear aliphatic alcohols are synthesized under reaction conditions typically used in industrial hydroformylations. Copyright
- Fleischer, Ivana,Dyballa, Katrin Marie,Jennerjahn, Reiko,Jackstell, Ralf,Franke, Robert,Spannenberg, Anke,Beller, Matthias
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supporting information
p. 2949 - 2953
(2013/04/10)
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- Rhodium nanoparticles as catalysts in the hydroformylation of 1-dodecene and their recycling in thermomorphic solvent systems
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Rhodium nanoparticles of about 3 nm in size were provided in stabilizing polar solvents. These nanoparticles were used in hydroformylation reactions of higher alkenes; 1-dodecene was used as a model substance. With a metal/substrate ratio of 1:1000, a 97% yield of aldehydes was achieved and an n/iso ratio of 72:28 was obtained. The addition of the ligand biphephos decelerated the reaction, but high n/iso ratios of up to 96:4 were achieved. For the first time, an effective catalyst recycling of these long-term stable nanoparticles in a thermomorphic multicomponent solvent (TMS) system was performed. The catalyst phase was recycled for three runs without any evident loss in activity. TEM images proved that after the recycling runs rhodium nanoparticles were still the active catalyst.
- Behr, Arno,Brunsch, Yvonne,Lux, Adrian
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experimental part
p. 2680 - 2683
(2012/07/17)
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- Super long-term highly active and selective hydroformylation in a room temperature-solidifiable guanidinium ionic liquid with a polyether tag
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Here we report a novel room temperature-solidifiable guanidinium methanesulfonate with a polyether tag and its use in Rh-catalysed biphasic hydroformylation of higher olefins. This novel ionic liquid can efficiently immobilize the Rh-TPPTS catalyst and render super long-term high activity and chemoselectivity, and no significant loss of activity, selectivity or Rh was observed after thirty-five cycles.
- Jin, Xin,Yang, Daoxing,Xu, Xinfu,Yang, Zhiqiang
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supporting information
p. 9017 - 9019,3
(2020/08/31)
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- A general and efficient iridium-catalyzed hydroformylation of olefins
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Breaking with conventional wisdom: Hydroformylation catalysts are generally based on rhodium; earlier, cobalt was used. Iridium, which is less expensive than rhodium, was considered too unreactive. However, iridium/phosphine complexes have now been shown to form active catalysts for the hydroformylation of olefins under mild conditions (see scheme; R1, R2=H, alkyl, aryl; R3=H, alkyl). Competing hydrogenation side reactions can be suppressed. Copyright
- Piras, Irene,Jennerjahn, Reiko,Jackstell, Ralf,Spannenberg, Anke,Franke, Robert,Beller, Matthias
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experimental part
p. 280 - 284
(2011/02/28)
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- Efficient platinum(II) catalyzed hydroformylation reaction in water: Unusual product distribution in micellar media
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The hydroformylation of a variety of terminal and internal alkenes is efficiently performed by cationic platinum triflate complexes of the type [P2Pt(H2O)2](OTf)2 under mild conditions in an aqueous micellar medium. The use of surfactants is essential to ensure dissolution of the catalyst and substrate in water with catalysts being positioned on the anionic surface of the micelles. Aldehydes are obtained with linear to branched ratios up to >99:1. With styrene derivatives also the corresponding benzaldehydes are formed. The catalyst can be separated by extraction of the organic products with hexane and recycled for at least four times with only a modest loss of activity and no effect on selectivity.
- Gottardo, Marina,Scarso, Alessandro,Paganelli, Stefano,Strukul, Giorgio
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experimental part
p. 2251 - 2262
(2010/12/25)
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- Aldehydes substituted in alpha position by alkyl residues as odoriferous and aroma substances
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The present invention primarily relates to the use of an aldehyde, substituted in alpha position by an alkyl residue, of the formula having (I) a total of 13 C atoms, wherein R means an unbranched alkyl residue having 6, 7, 8 or 9 C atomsandR′ means an unbranched alkyl residue having 2, 3, 4 or 5 C atoms, or (II) a total of 15 C atoms, wherein R means an unbranched alkyl residue having 8, 9, 10 or 11 C atomsandR′ means an unbranched alkyl residue having 2, 3, 4 or 5 C atoms,or a blend comprising or consisting of two, three or more such aldehydes of type (I) and/or (II),as an odoriferous or aroma substance.
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Page/Page column 10-11
(2010/11/29)
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- Hydroformylation of olefins catalyzed by rhodium complexes with phosphinitecalix[4]arenes
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Hydroformylation of alkenes with various carbon chain lengths and arylalkenes in the presence of the catalytic system consisting of Rh(acac)(CO)2 and phosphinitecalix[4]arenes was studied. The influence of the P/Rh and substrate/catalyst ratios, temperature, and pressure on the process and the product composition was examined.
- Karakhanov,Kardasheva,Runova,Terenina,Shadrova
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p. 340 - 344
(2008/09/17)
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- Strategies for the generation of molecularly imprinted polymeric nitroxide catalysts
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(Chemical Equation Presented) Two strategies for preparing catalytically active molecularly imprinted nitroxide-containing polymers are outlined. Both strategies rely upon the thermal rearrangement chemistry of tertiary amine N-oxides. To this end, several polymers were prepared and the polymeric nitroxides were revealed by oxidation with m-CPBA. All of the resulting polymeric catalysts proved to be competent mediators of the oxidation of alcohols.
- Anderson, Christopher D.,Shea, Kenneth J.,Rychnovsky, Scott D.
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p. 4879 - 4882
(2007/10/03)
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- Method for preparing aldehydes by hydroformylation
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A catalyst composition comprising a) more than 70% by weight of a polyethylene glycol of the formula H—(OCH2—CH2)n—OH, where n is an integer of 3 to 16 and the number average molecular weight is less than 650 b) rhodium in elemental form or bound form and c) 2 to 25% by weight of water soluble sulfonated triarylphosphine ligand having 1 to 2 phophorus atoms and not more than 25% by weight of water based on the total amount of the catalyst and its use for the hydroformylation of olefins to aldehydes is described.
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- New methods of hydroformylation of olefins and isomerisation of allyl alcohols using the CoBr2/Zn/CO/t-BuOH reagent system
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The reaction of CoBr2/Zn/CO/t-BuOH gives cobalt carbonyl species that is useful for the hydroformylation of olefins to obtain corresponding aldehydes. The cobalt carbonyl species formed is also useful in isomerisation of allyl alcohols to the corresponding ketones.
- Rajesh,Periasamy
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p. 989 - 993
(2007/10/03)
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- A new, efficient, and in some cases highly regioselective water-soluble polymer rhodium catalyst for olefin hydroformylation
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A water-soluble complex Rh/PPA(Na+)/DPPEA 1 was obtained from poly(4- pentenoic acid) (PPA) and bis[2-(diphenylphosphino)ethyllamine (DPPEA). Complex 1 is a highly active catalyst for the hydroformylation of olefins. Some selectively for linear aldehydes was observed in the hydroformylation of aliphatic olefins, while high ratios of branched aldehydes resulted in the case of vinyl ethers. Complex 1 is also the first polymeric water-soluble metal complex which can catalyze the conversion of vinylarenes to 2- arylpropanals in a highly chemoselective and regioselective manner.
- Ajjou, Abdelaziz Nait,Alper, Howard
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p. 1466 - 1468
(2007/10/03)
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- Two-phase hydroformylation of higher molecular olefins by ethoxylated tris(p-hydroxyphenyl)-phosphine as complex ligand for the rhodiumcarbonyl catalyst
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Water-soluble rhodiumcarbonyl complexes with new nonionic complex ligands prepared by ethoxylation of tris(p-hydroxyphenyl)phosphine were successfully used in the two-phase hydroformylation of higher-molecular olefins. Their efficiency depends likely on a temperature controlled circulation of the catalyst complex between the organic and the water phase: At the temperature of the hydroformylation (100-130°C) the ethoxylated tri-(p-hydroxyphenyl)phosphine becomes water-insoluble (appearance of a miscibility gap) and is now available for the catalysis in the organic phase. After cooling to room temperature the catalyst system is dissolved again in the water phase and can be recovered by a simple phase separation. Johann Ambrosius Barth 1996.
- Jin, Zilin,Yan, Yuanyoung,Zuo, Huanpie,Fell, Bernhard
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p. 124 - 128
(2007/10/02)
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- Hydroformylation of terminal olefins in water-organic media in the presence of a rhodium complex based on functionalized polyethylene oxide
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A study has been made of the hydroformylation of 1-dodecene, allylbenzene, o-allylphenol, phenol allyl ether and allylbenzofuran in water-organic media in the presence of a catalyst obtained from rhodium(I) acetylacetonatodicarbonyl and polyethylene oxide functionalized by phosphine groups. It was established that all the substrates investigated readily enter into the reaction, and the selectivity with respect to aldehydes amounts to 70-90%. Copyright
- Karakhanov,Kardasheva,Neimerovets,Runova
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p. 322 - 326
(2007/10/03)
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- Novel amphiphilic diphosphines: Synthesis, rhodium complexes, use in hydroformylation and rhodium recycling
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For the rhodium-catalysed hydroformylation of higher alkenes the novel amphiphilic diphosphines 2,2′-bis[phenyl(3-pyridyl)phosphinomethyl]-1,1′-biphenyl (L1), 2,2′-bis(diphenylphosphinomethyl)-3,3′-bipyridine (L2), 2,2′-bis[phenyl(3-pyridyl)phosphinomethyl]-3,3′-bipyridine (L3) and 2,2′-bis{[4-(diethylaminomethyl)-phenyl]phenylphosphinomethyl}-1,1′- biphenyl (L4) have been synthesised. With oct-1-ene (80°C, 20 bar CO-H2, toluene), high normal:branded ratios (up to 51:1) were found with 6-8% of isomerised octenes. The diphosphines L1-L3 gave rhodium catalysts up to twice as active as those derived from 2,2′-bis(diphenylphosphinomethyl)-1,1′-biphenyl (bisbi). The rate of hydroformylation using L1-L4 was first order and approximately first order respectively in the rhodium and oct-1-ene concentration; the order in CO pressure was negative and that in H2 pressure slightly negative. For L1 the influence of the L:Rh ratio, temperature and substrate were investigated. Phosphorus-31 and 1H NMR studies showed that the diphosphines (L-L) form [RhH(CO)(PPh3)(L-L)] and [RhH(CO)2(L-L)] complexes, analogously to bisbi. The formation of P-N chelates was not observed. The pH-dependent distribution characteristics of the free diphosphines have been determined; L3 and L4 were quantitatively extracted from an Et2O solution into a H2SO4 solution of pH 2. When L4 was used, rhodium and the excess of L4 were extracted into an acidic aqueous phase at pH 5, allowing separation of the aldehydes, and re-extracted into fresh toluene after neutralisation of the aqueous phase by NaHCO3. Inductively coupled plasma atomic emission spectroscopy established a rhodium recovery up to 92%. Pressurising the recovered rhodium and excess of phosphine to 20 bar CO-H2 at 80°C resulted in regeneration of the original catalytically active species. A retention of catalytic activity of 72% was achieved. Diphosphines L1-L3 proved inappropriate for rhodium-recycling experiments. Extraction into an acidic aqueous phase was effective, but neutralisation of the acidic phase resulted in the formation of rhodium species which cannot be extracted from the aqueous layer.
- Buhling, Armin,Elgersma, Jaap W.,Nkrumah, Steve,Kamer, Paul C. J.,Van Leeuwen, Piet W. N. M.
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p. 2143 - 2154
(2007/10/03)
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- A further breakthrough in biphasic, rhodium-catalyzed hydroformylation: The use of per(2,6-di-O-methyl)-β-cyclodextrin as inverse phase transfer catalyst
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Solvent free biphasic hydroformylation of various water-insoluble terminal olefins can be achieved in high yields and selectivities by using a water-soluble rhodium/triphenylphosphine trisulfonate catalyst and per(2,6-di-o-methyl)-β-cyclodextrin as inverse phase transfer catalyst. The catalytic activities were up to ten times higher than those observed without per(2,6-di-o-methyl)-β-cyclodextrin.
- Monflier, Eric,Tilloy, Sebastien,Fremy, Georges,Castanet, Yves,Mortreux, Andre
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p. 9481 - 9484
(2007/10/02)
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- Effects of changes in the ligands on the skeleton and the catalytic activity of some new rhodium complexes with pyrazolato moieties
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Whereas the reaction of 2 (where pz is either a pyrazolato or 3,5-dimethylpyrazolato group) with 3-(diphenylphosphino)benzoic acid and (2-formylphenyl)diphenylphosphine gives the dinuclearic complexes 2 (1 and 2) and 2 (5 and 6) respectively, 2-(diphenylphosphino)benzoic acid gives the monorhodium compounds (3 and 4).The structures of (6) have been determined by X-ray diffraction analyses.Both, the monorhodium and the dirhodium complexes catalyse the hydroformylation of acyclic and cyclic olefins at 120 deg C and at CO and H2 pressures of 28 atm.At 70-90 deg C the dinuclear complexes with 3-(diphenylphosphino)benzoic acid moieties are substantially more active than the monorhodium compounds.Key words: Rhodium; Phosphine; Hydroformylation; X-ray diffraction
- Schumann, Herbert,Hemling, Holger,Ravindar, Vadde,Badrieh, Yacoub,Blum, Jochanan
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p. 213 - 220
(2007/10/02)
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- COMPARATIVE STUDY OF TRIPHENYLAMINE, TRIPHENYLPHOSPHINE, TRIPHENYLARSINE, TRIPHENYLANTIMONY AND TRIPHENYLBISMUTH AS LIGANDS IN THE RHODIUM-CATALYZED HYDROFORMYLATION OF 1-DODECENE
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Triphenylamine, triphenylphosphine, triphenylarsine, triphenylantimony and triphenylbismuth were evaluated on the basis of olefin to aldehyde converion, and also on the basis of the normal/iso (n/i) product ratio, as ligands in the rhodium-catalyzed hydroformylation of 1-dodecene.Two series of reactions were conducted which differed only in total reaction time (120 minutes vs 135 minutes) and in the ligand/rhodium ratio (60:1 vs 300:1).Both reactions series employed 35 grams of 1-dodecene, a 176 ppm rhodium charge, 100 psig of 1:1 H2/CO, and a reaction temperature of 90 deg C.In the 60:1 vs 330:1 reaction series, triphenylamine gave olefin conversion and n/i ratios of 2.0 percent, 2.0 vs 5.8 percent, 1.8; triphenylphosphine gave 95 percent, 4.4 vs 86.9 percent, 8.7; triphenylarsine gave 58 percent, 3.1 vs 85.8 percent, 3.5; triphenylantimony gave13.0 percent, 6.1 vs 3.5 percent, 9.1 respectively.Triphenylbismuth failed to promote hydroformylation in both reaction series.These data demonstrate that regiospecificity, as measured by the n/i product ratio, varies inversly to increased ligand basicity.
- Carlock, John T.
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p. 185 - 188
(2007/10/02)
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