DOCSLIB.ORG

Highly Linear-Selective Hydroformylation of 1-Alkenes Using Formaldehyde As a Syngas Substitute

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Highly Linear-Selective Hydroformylation of 1-Alkenes Using Formaldehyde As a Syngas Substitute COMMUNICATIONS DOI: 10.1002/adsc.200900713 Highly Linear-Selective Hydroformylation of 1-Alkenes using Formaldehyde as a Syngas Substitute Gouki Makado,a Tsumoru Morimoto,a,* Yasuko Sugimoto,a Ken Tsutsumi,a Natsuko Kagawa,b and Kiyomi Kakiuchia a Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), Takayama, Ikoma, Nara 630-0192, Japan Fax : (+81)-743-72-6081; e-mail: [email protected] b Department of Medicinal Organic Chemistry, Chiba University Yayoi, Inage, Chiba 263-8522, Japan Received: October 14, 2009; Revised: November 30, 2009; Published online: February 9, 2010 Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.200900713. Abstract: A highly linear-selective hydroformyla- appeared regarding the use of paraformaldehyde in tion of 1-alkenes using formaldehyde without the hydroformylation reactions without the direct use of direct use of syngas is described. One rhodium(I) syngas,[4,5,6] although they have not yet afforded syn- complex catalyzes two processes in the overall hy- thetically useful levels of productivity and regioselec- droformylation of 1-alkenes using formaldehyde as tivity.[7] The method using formaldehyde consists of the syngas substitute to give hydroformylated alde- two cooperative catalytic processes: the catalytic de- hydes with excellent regioselectivities. A high regio- carbonylation of formaldehyde to give a carbonyl selectivity (linear/branched=up to 98/2) and chemi- moiety and hydrogen, and their use in the subsequent cal yield (up to 95%) can be achieved by the simul- hydroformylation of alkenes. Regardless of the com- taneous use of two types of phosphanes as ligands. plexity involved in the overall catalysis, the aforemen- tioned reports have used only a single catalyst for the Keywords: alkenes; formaldehyde; homogeneous two different processes. It is, however, possible that catalysis; hydroformylation; rhodium two discrete catalysts could be used in the decarbony- lation and hydroformylation processes. Herein we wish to report on a highly selective, highly efficient hydroformylation without the direct use of syngas by using two different types of catalysts, which are suita- Hydroformylation involves the addition of carbon ble for each process. monoxide and hydrogen (CO/H2, syngas) to alkenes In order to simultaneously generate two types of in the presence of a transition metal catalyst to give rhodium catalysts in one reaction system, we adopted homologous linear (l) and/or branched (b) alde- a strategy in which two different rhodium species are hydes.[1] Because of its versatility, it represents syn- generated in situ by adding two phosphanes to a thetic routes to various aldehydes that are useful in a single rhodium complex. For the success of the strat- wide range of areas from fine and specialty chemicals egy, it is essential that the decarbonylation process is production to pharmaceuticals synthesis.[2] Since the controlled by one phosphane more strongly than the discovery of the reaction by Roelen in 1938,[3] consid- other and that the hydroformylation process is re- erable efforts have been devoted to the development versed. BINAP was a promising candidate as an effec- of new catalysts including new ligands and the utiliza- tive ligand for a rhodium catalyst in the decarbonyla- tion of novel reaction media, such as the use of an tion process, because it is known that the rhodium aqueous biphase, supercritical carbon dioxide, fluo- complex having BINAP is a more efficient catalyst rous biphase, or ionic liquids, in attempts to improve for the decarbonylation of aldehydes than xantphos.[8] the efficiency and selectivity (regio- and enantioselec- In addition, we also have recently reported that the tivity) of the reaction. A recent innovation in this use of BINAP ligand facilitates a rhodium(I)-cata- chemistry involves the development of a protocol lyzed CO gas-free carbonylation reaction using para- using formaldehyde (HCHO) as a syngas substitute. formaldehydeACHTUNGRE as the CO substitute.[5e] Towards a re- This promises to be an experimentally convenient al- gioselective hydroformylation process, we selected ternative to the transformation. Some reports have xantphos, which is a representative ligand for the ex- Adv. Synth. Catal. 2010, 352, 299 – 304 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 299 COMMUNICATIONS Gouki Makado et al. tremely highly linear-selective hydroformylation cata- Next, we investigated the effect of BINAP or xant- lyzed by a rhodium complex.[9] phos on the efficiency and selectivity of hydroformy- We initially carried out the rhodium-catalyzed hy- lation using syngas. Using BINAP and/or xantphos as droformylation reaction of 1-decene (1) with formalin ligand(s), the turnover frequency (TOF) in the early under the catalytic conditions consisting of [RhCl- stage (1 h) of the hydroformylation of 1-decene (1) ACHTUNGRE (cod)]2, BINAP, and xantphos: 1 (1 mmol), formalin with atmospheric syngas was examined: 1-decene ACHTUNGRE (0.37 mL of 37 wt% aqueous solution, 5 mmol equiva- (1 mmol), [RhCl(cod)]2 (0.005 mmol), and phos- ACHTUNGRE lents to formaldehyde), [RhCl(cod)]2 (0.01 mmol), phane(s) (0.02 mmol) in toluene (6 mL) under atmos- BINAP (0.02 mmol), xantphos (0.02 mmol) in toluene pheric syngas (CO/H2 =1/1) at 90 8C for 1 h. When (6 mL) at 90 8C for 20 h. The reaction proceeded with only BINAP was used as a ligand, linear (2-l) and an extremely high regioselectivity to give the linear branched (2-b) aldehydes were formed in a ratio of 2- aldehyde 2-l and the branched aldehyde 2-b in 80% l/2-b= 65/35 (TOF= 3.05 hÀ1). When only xantphos yield in a ratio of 2-l/2-b=97/3, along with 18% of was used, the reaction proceeded much more smooth- isomers of 1-decene (Table 1, entry 1).[10] In contrast, ly (TOF= 19.9 hÀ1) to give these aldehydes with a the use of BINAP or xantphos resulted in a low selec- high linear-selectivity of 2-l/2-b =93/7. Furthermore, tivity or a low efficiency (entries 2 and 3). These re- the use of a combination of BINAP (0.01 mmol) and sults indicate that, when a combination of BINAP xantphos (0.01 mmol) resulted in a slight decrease in and xantphos was used, each phosphane functions the reaction rate (TOF=10.9 hÀ1), although the uniquely and specifically (BINAP in the decarbonyla- linear-selectivity (2-l/2-b=94/6) remained the same. tion and xantphos in the hydroformylation), to ach- These findings suggest that, for the simultaneous use ieve the highly linear-selective hydroformylation, as of BINAP and xantphos, the rhodium species associ- we expected. ated with the xantphos ligand controls the regioselec- tivity and the efficiency of the overall reaction. Furthermore, 31P NMR experiments (Figure 1) im- plied that two rhodium species participate in the reac- Table 1. Effective use of a combination phosphanes in ACHTUNGRE Rh(I)-catalyzed hydroformylation of 1-decene 1 using for- tion of entry 1 in Table 1. A mixture of [RhCl(cod)]2, malin.[a] (R)-BINAP, and xantphos (1:2:2) in toluene-d8 at room temperature showed two signals at d=49.5 ppm (d, JP,Rh = 195 Hz) and 2.3 ppm (d, JP,Rh =91 Hz), [11] which correspond to [RhCl((R)-BINAP)]2 and RhCl(cod)ACHTUNGRE (xantphos),ACHTUNGRE [12] respectively. When 100 equivalents of formalin were added to the mixture, these signals vanished, and two new signals appeared at d=45.6 ppm (dd, JP, P =45 Hz, JP,Rh = 160 Hz) and 20.9 ppm (d, JP,Rh =127 Hz), which are assigned to [11b] RhCl(CO)((R)-BINAP) and RhH(CO)2 (xantphos),ACHTUNGRE [9] respectively. These two rhodium species, ACHTUNGRE RhCl(CO)((R)-BINAP) and RhH(CO)2(xantphos), would be directly involved in the linear-selective hy- droformylation catalysis using formaldehyde in the presence of both BINAP and xantphos. From the above results, an acceptable reaction pathway is as follows. Thus, the present reaction in- cludes two catalytic processes: the decarbonylation of Entry BINAP xantphos Conv.[b] Yield (2-l/2-b)[b] formaldehyde leading to the formation of a carbonyl moiety and H and subsequent hydroformylation 1 2 mol% 2 mol% 98% 80% (97/3) 2 2 4 mol% – 85% 85% (64/36) using the resulting carbonyl moiety and H2 3 – 4 mol% 77% 8% (88/12) (Scheme 1). Each process proceeds in a general manner. Oxidative addition of the aldehydic CÀH [a] Conditions: 1 (1 mmol), formalin (37%; 0.37 mL, bond in formaldehyde to Rh, followed by decarbony- ACHTUNGRE 5 mmol), [RhCl(cod)]2 (0.01 mmol), ligand (0.04 mmol), lative hydride migration and subsequent reductive 8 toluene (6 mL), 90 ,20h. elimination, yields an Rh-CO species and H . On the [b] Yields are the sum of 2-l and 2-b. Values in parentheses 2 are the ratios of 2-l/2-b. Conversions, yields, and ratios other hand, addition of in situ generated Rh-H species were determined by GC. cod= 1,5-cyclooctadiene; to 1-alkene and subsequent insertion of the carbonyl BINAP=2,2’-bis(diphenylphosphino)-1,1’-binaphthyl; formed earlier, followed by hydrogenolysis by H2, xantphos=9,9-dimethyl-4,5-bis(diphenylphosphino)xan- afford the aldehyde with the regeneration of the Rh- thene. H species. These are taken up by two different rhodi- 300 asc.wiley-vch.de 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Synth. Catal. 2010, 352, 299 – 304 Highly Linear-Selective Hydroformylation of 1-Alkenes using Formaldehyde 31 ACHTUNGRE Figure 1. P NMR spectra of (a) a mixture of [RhCl(cod)]2,(R)-BINAP, and xantphos (1:2:2) in toluene-d8 solution and (b) the reaction of the mixture with formalin.
Load more

Recommended publications
  • 2. Catalysis Involving CO
    2. Catalysis Involving CO (Source: Collman / Hegedus + Chiusoli / Maitlis + original papers mentioned below) !1 General Reactivity of CO-Complexes 1 is the resonance representing the pure "-donation of CO to the metal. 3 is contributing the most when the # back donation from the metal to CO is weak. The carbon is more electrophilic here. 2 is the extreme structure that evidences the # back donation of the metal to the #* of CO. !2 – Synthesis Gas and Water Gas Shift Reaction CO / H2 as feedstock. – Hydrocarbonylation (or Hydroformylation) of Olefins / Oxo Reaction Synthesis of aldehydes and alcohols from alkenes with cobalt and rhodium catalysts. – Carbonylation of Alcohols: Monsanto’s Acetic Acid Process Preparation of acetic acid from methanol and CO. !3 Synthesis Gas (Syn Gas, CO / H2) as Feedstock Steam over coal: C + H2O → CO + H2 0 0 (!ΔH 298 K = 131 kJ/mol; !ΔG1073 K= –12 kJ/mol) Steam reforming of methane: CH4 + H2O → CO + 3 H2 0 0 (!ΔH 298 K = 206 kJ/mol; !ΔG1073 K= –24 kJ/mol) Coupled with partial oxidation to give an endothermic overall reaction: H 0 2 C + H2O + O2 → CO + CO2 + H2 (Δ 298 K = –285 kJ/mol) 1 H 0 CH4 + 2 O2 → CO + 2 H2 (Δ 298 K = –36 kJ/mol) !4 Water-Gas-Shift Reaction (WGSR) Allows adjust the CO : H2 ratio by converting CO to H2: !!⇀ CO + H2O ↽!! CO2 + H2 Drawback: CO2 as byproduct. Catalysts: Heterogeneous Cr2O3 (T = 350°C) Cu-Zn-oxide (T = 200 – 300°C) Fe3O4 Homogeneous Carbonyl complexes: [FeH(CO)4]–, [RhI2(CO)2]–, [RuCl(bipy)2(CO)]+ !5 Homogeneously Catalyzed WGSR Principle: O CO OH– – CO2 M M CO M C M H – OH – + H O – ! M H 2 M + OH + H2 !6 Catalytic WGSR ! !7 Hydroformylation or Oxo Synthesis Synthesis of aldehydes and alcohols from alkenes.
    [Show full text]
  • Reactions of Alkenes and Alkynes with Formaldehyde Catalyzed by Rhodium Systems Containing Phosphine Ligands
    J. Mex. Chem. Soc. 2017, 61(2), 120-127 Article © 2017, Sociedad Química de México ISSN 1870-249X Reactions of alkenes and alkynes with formaldehyde catalyzed by rhodium systems containing phosphine ligands Merlín Rosales,1* Beatriz González,1 Jessely Molina,1 Homero Pérez,1 María Modroño-Alonso2 and Pablo J. Baricelli2 1 Universidad del Zulia (L.U.Z.), Facultad Experimental de Ciencias. Departamento de Química, Laboratorio de Química Inorgánica (LQI). Maracaibo (Venezuela). 2 Universidad de Carabobo, Facultad de Ingeniería, Centro de Investigaciones Químicas, Valencia (Venezuela). * Corresponding author: Tel +584143602104 FAX +582614127701 Ciudad Universitaria. Módulo 2. Maracaibo. Venezuela e-mail adress: merlin2002 @cantv.net; [email protected] (M. Rosales) Received October 18th, 2016; Accepted March 8th, 2017. Abstract. The reaction of alkenes (allyl alcohol, styrene and C6 Resumen. La reacción de alquenos (alcohol alílico, estireno y alquenos alkenes) with formaldehyde was efficiently performed by using Rh C6) con formaldehido se realizó eficientemente usando precatalizado- precatalysts formed in situ by the addition of triphenylphosphine res de Rh formados in situ por adición de trifenilfosfina (PPh3), (PPh3), 1,2-bis(diphenylphosphino)ethane (dppe) or 1,1,1-tris(diphen- 1,2-bis(difenilfosfino)etano (dffe) o 1,1,1-tris(difenilfosfinometil) etano ylphosphinomethyl)ethane (triphos) to the complex Rh(acac)(CO)2 at (trifos) al complejo Rh(acac)(CO)2 a 130ºC en 1,4-dioxano, produ- 130ºC in 1,4-dioxane, yielding their corresponding aldehydes; the best ciendo los correspondientes aldehídos. El mejor sistema catalítico fue 2 catalytic system was Rh(acac)(CO)2/2dppe, which generates the cat- Rh(acac)(CO)2/2dffe, el cual genera el complejo catiónico [Rh(k -P,P- 2 + + ionic complex [Rh(k -P,P-dppe)2] .
    [Show full text]
  • Hydroformylation of Formaldehyde with Rhodium Catalyst
    Patentamt O JEuropâischesEuropean Patent Office © Publication number: 002 908 Office européen des brevets Bl @ EUROPEAN PATENT SPECIFICATION (46) Date of publication of patent spécification: 12.05.82 © Int. Cl.3: C 07 C 47/19, 8 01 J 31/°2' C 07 C 45/50 © Application number: 78300820.4 @ Date of filing: 1 4.1 2.78 © Hydroformylation of formaldehyde with rhodium cataiyst. © Priority: 16.12.77 US 861474 @ Proprietor: MONSANTO COMPANY Patent Department 800 North Lindbergh Boulevard © Date of publication of application: St. Louis, Missouri 631 66 (US) 11.07.79 Bulletin 79/14 @ Inventor: Spencer, Alwyn © Publication of the grant of the patent: Johnson Matthey Research Centre Blount's Court 1 2.05.82 Bulletin 82/1 9 Jonning Common Reading R64-9NH (GB) @ Designated Contracting States: © Representative: Lunt, John Cooper etal, BECHDEFRGBLUNLSE Monsanto House 1 0-1 8 Victoria Street London, SW1H ONQ(GB) "© References cited: DE- A- 3 940 432 DE - A - 2 741 589 GB - A - 1 335 531 US - A - 3 940 432 Chemical Abstracts vol. 87, no. 19. 1977, Columbus, Ohio, USA T. MIZOROKI "Syntheses of oxygen-containing C2-compounds using carbon monoxide" page 541, column 1, abstract no. 151 634g Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art.
    [Show full text]
  • Hydroformylation of 1-Hexene Over Rh/Nano-Oxide Catalysts
    Catalysts 2013, 3, 324-337; doi:10.3390/catal3010324 OPEN ACCESS catalysts ISSN 2073-4344 www.mdpi.com/journal/catalysts Article Hydroformylation of 1-Hexene over Rh/Nano-Oxide Catalysts Maija-Liisa Kontkanen 1, Matti Tuikka 1,2, Niko M. Kinnunen 1, Sari Suvanto 1 and Matti Haukka 1,2,* 1 Department of Chemistry, University of Eastern Finland, P.O. Box 111, FI-80101 Joensuu, Finland; E-Mails: [email protected] (M.-L.K.); [email protected] (M.T.); [email protected] (N.M.K.); [email protected] (S.S.) 2 Department of Chemistry, University of Jyväskylä, P.O. Box 35, University of Jyväskylä, Finland * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +358-40-805-4666; Fax: +358-4-260-2501. Received: 26 January 2013; in revised form: 25 February 2013 / Accepted: 6 March 2013 / Published: 21 March 2013 Abstract: The effect of nanostructured supports on the activity of Rh catalysts was studied by comparing the catalytic performance of nano- and bulk-oxide supported Rh/ZnO, Rh/SiO2 and Rh/TiO2 systems in 1-hexene hydroformylation. The highest activity with 100% total conversion and 96% yield of aldehydes was obtained with the Rh/nano-ZnO catalyst. The Rh/nano-ZnO catalyst was found to be more stable and active than the corresponding rhodium catalyst supported on bulk ZnO. The favorable morphology of Rh/nano-ZnO particles led to an increased metal content and an increased number of weak acid sites compared to the bulk ZnO supported catalysts. Both these factors favored the improved catalytic performance.
    [Show full text]
  • Hydroformylation of C3 and C8 Olefins in Hydrocarbon Gas-Expanded Solvents
    HYDROFORMYLATION OF C3 AND C8 OLEFINS IN HYDROCARBON GAS-EXPANDED SOLVENTS By Dupeng Liu Submitted to the graduate degree program in Chemical & Petroleum Engineering and the Graduate Faculty of the University of Kansas in partial fulfillment of the requirements for the degree of Doctor of Philosophy. Chairperson: Bala Subramaniam Raghunath V. Chaudhari Jon Tunge Aaron Scurto Kevin Leonard Date Defended: April 30th, 2018 The dissertation committee for Dupeng Liu certifies that this is the approved version of the following dissertation: HYDROFORMYLATION OF C3 AND C8 OLEFINS IN HYDROCARBON GAS-EXPANDED SOLVENTS Chairperson: Bala Subramaniam Date Approved: May 8th, 2018 ii Abstract Hydroformylation involves the addition of syngas to the double bond of an alkene yielding aldehydes used to produce basic building blocks for myriad consumer goods. Resource-efficient technologies that conserve feedstock and energy continue to be of interest to industry. It has been shown previously by our group that the use of CO2-expanded liquids significantly enhances the Rh-catalyzed 1-octene hydroformylation rate and selectivity. This dissertation extends this concept by employing light alkanes such as propane and n-butane as compressed solvents in propylene and 1-octene hydroformylation, respectively. Phase behavior measurements demonstrate that at identical H2 or CO fugacities in the vapor phase, the H2 and CO solubilities in either propane- or propylene-expanded solvents (PXLs) are greater than those in the corresponding neat solvents by as high as 76% at 70 °C and 1.5 MPa. The H2/CO ratio in PXLs is enhanced by simply increasing the propane partial pressure. In contrast, the H2/CO in the neat solvent at a given temperature is constant at all syngas partial pressures.
    [Show full text]
  • (12) Patent Application Publication (10) Pub. No.: US 2003/0032845 A1 Han Et Al
    US 20030032845A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2003/0032845 A1 Han et al. (43) Pub. Date: Feb. 13, 2003 (54) HYDROFORMYLATION OF ETHYLENE Related U.S. Application Data OXIDE (63) Continuation-in-part of application No. 09/924,822, (76) Inventors: Yuan-Zhang Han, West Chester, PA filed on Aug. 8, 2001, now abandoned. (US); Krishnan Viswanathan, Houston, TX (US) Publication Classification Correspondence Address: (51) Int. Cl. ................................................ C07C 29/15 LYONDELL CHEMICAL COMPANY (52) U.S. Cl. ............................................ 568/862; 568/867 3801 WEST CHESTER PIKE NEWTOWN SQUARE, PA 19073 (US) (57) ABSTRACT (21) Appl. No.: 10/038,975 1,3-propanediol is formed from ethylene oxide containing formaldehyde and acetaldehyde impurities by hydroformy (22) Filed: Jan. 4, 2002 lation and hydrogenation. Patent Application Publication Feb. 13, 2003 US 2003/0032845 A1 N y so US 2003/0032845 A1 Feb. 13, 2003 HYDROFORMYLATION OF ETHYLENE OXDE wise, the procedures described in recently filed applications Ser. No. 09/882,346, 09/882,347 and 09/882,641 filed Jun. RELATED APPLICATION 15, 2001 can be employed and are incorporated herein by 0001. This application is a continuation-in-part of appli reference. cation Ser. No. 09/924,822 filed Aug. 8, 2001. 0010 Generally speaking, ethylene oxide which has been employed as feed in prior procedures is a commercial grade BACKGROUND OF THE INVENTION of ethylene oxide from which a predominance of the impu rities coproducted during ethylene oxide formation have 0002) 1. Field of the Invention been removed. Generally, the aldehyde Specifications for 0003. This invention relates to the catalytic hydroformy such commercial ethylene oxide are a maximum of 30-50 lation of ethylene oxide and especially to a process wherein ppm by weight of aldehyde expressed as acetaldehyde.
    [Show full text]
  • And Regioselective Hydroformylation of Alkenes with CO2/H2 Over a Bifunctional Catalyst
    Chemo- and Regioselective Hydroformylation of Alkenes with CO2/H2 over a Bifunctional Catalyst Kai HUA Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210 (P. R. China). Fang Liu Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210 (P. R. China). Yin Wei Low-Carbon Conversion Science and Engineering Long Shao Shanghai Advanced Research Institute, Chinese Academy of Sciences Chao Deng ShanghaiTech University Ming Zhang Shanghai Advanced Research Institute, Chinese Academy of Sciences Lin Xia Shanghai Advanced Research Institute, Chinese Academy of Sciences Liangshu Zhong Shanghai Advanced Research Institute https://orcid.org/0000-0002-4167-8630 Hui Wang ( [email protected] ) Shanghai Advanced Research Institute, Chinese Academy of Sciences Yuhan Sun Shanghai Advanced Research Institute, Chinese Academy of Sciences Article Keywords: CO2, H2, chemo- and regioselective hydroformylation of alkenes, bifunctional catalyst Posted Date: October 7th, 2020 DOI: https://doi.org/10.21203/rs.3.rs-85641/v1 License: This work is licensed under a Creative Commons Attribution 4.0 International License. Read Full License Version of Record: A version of this preprint was published at Green Chemistry on January 1st, 2021. See the published version at https://doi.org/10.1039/D0GC03913F. Chemo- and Regioselective Hydroformylation of Alkenes with CO2/H2 over a Bifunctional Catalyst Kaimin Hua1,2, Xiaofang Liu1,* Baiyin Wei1,3, Zilong Shao1, Yuchao Deng1,3, Jianming Zhang1, Lin Xia1, Liangshu Zhong1,3, Hui Wang1,* Yuhan Sun1,3,4* Abstract: Combining CO2 and H2 to prepare building blocks for high-value-added products is an attractive yet challenging approach. A general and selective rhodium- catalyzed hydroformylation of alkenes using CO2/H2 as a syngas surrogate is described here.
    [Show full text]
  • Preparation and Characterization of Rh/Mgsnts Catalyst for Hydroformylation of Vinyl Acetate: the Rh0 Was Obtained by Calcination
    Article Preparation and Characterization of Rh/MgSNTs Catalyst for Hydroformylation of Vinyl Acetate: The Rh0 was Obtained by Calcination Penghe Su 1, Ya Chen 1, Xiaotong Liu 1, Hongyuan Chuai 1, Hongchi Liu 1, Baolin Zhu 1,2, Shoumin Zhang 1,2 and Weiping Huang 1,2,3,* 1 College of Chemistry, Nankai University, Tianjin 300071, China; [email protected] (P.S.); [email protected] (Y.C.); [email protected] (X.L.); [email protected] (H.C.); [email protected] (H.L.); [email protected] (B.Z.); [email protected] (S.Z.) 2 The Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, China 3 Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300071, China * Correspondence: [email protected]; Tel.: +86-138-2009-6974 Received: 01 February 2019; Accepted: 18 February 2019; Published: 26 February 2019 Abstract: A simple and practical Rh-catalyzed hydroformylation of vinyl acetate has been synthesized via impregnation-calcination method using silicate nanotubes (MgSNTs) as the supporter. The Rh0 (zero valent state of rhodium) was obtained by calcination. The influence of calcination temperature on catalytic performance of the catalysts was investigated in detail. The catalysts were characterized in detail by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectrometer (XPS), atomic emission spectrometer (ICP), and Brunauer–Emmett–Teller (BET) surface-area analyzers. The Rh/MgSNTs(a2) catalyst shows excellent catalytic activity, selectivity and superior cyclicity. The catalyst could be easily recovered by phase separation and was used up to four times. Keywords: silicate nanotubes; Rh; hydroformylation; vinyl acetate 1.
    [Show full text]
  • Resource-Efficient Catalytic Technologies for Shale Gas Upgrading
    Resource-Efficient Catalytic Technologies for Shale Gas Upgrading Bala Subramaniam, Christopher J. Lyon and Darryl Fahey Center for Environmentally Beneficial Catalysis Department of Chemical and Petroleum Engineering University of Kansas, Lawrence, KS Shale Gas Monetization Workshop Montgomery, TX March 27, 2014 Outline • The global chemical industry • Emerging feedstocks for making chemicals • The need for resource-efficient technologies • Examples with LCA analyses • Concluding remarks The Center for Environmentally Beneficial Catalysis Growth of Global Chemical Industry [Global Chemical Outlook, UN Environment Programme, 2012] The Center for Environmentally Beneficial Catalysis Petrochemicals Chemical intermediates (building blocks) Consumer goods • <10% of crude oil used to make chemicals • Chemicals more profitable than fuels The Center for Environmentally Beneficial Catalysis Natural Gas and Biomass as Alternate Feedstocks Chemical intermediates Biomass (building blocks) and Shale Gas Consumer goods - US natural gas production up ~28% since 2006, thanks to increased shale gas production [EIA, 2013] - Biomass abundant for making chemical intermediates The Center for Environmentally Beneficial Catalysis Natural Gas Typical Shale Gas Production by Source Composition [Energy Information Administration, 0383-2013] The Center for Environmentally Beneficial Catalysis Proposed Expansion of U.S. Ethylene Production Capacity, 2013-2020 Company Location Proposed capacity, MMTY Chevron Phillips Baytown, TX 1.5 Exxon Mobil Baytown, TX 1.5 Sasol
    [Show full text]
  • Forty-Five Years of Progress for the LP Oxosm Process
    https://doi.org/10.1595/205651317X695875 Johnson Matthey Technol. Rev., 2017, 61, (3), 246–256 JOHNSON MATTHEY TECHNOLOGY REVIEW www.technology.matthey.com Industrial Low Pressure Hydroformylation: Forty-Five Years of Progress for the LP OxoSM Process A long standing collaboration between Johnson Matthey and Dow continues to sustain the high standing of their oxo technology through innovative solutions to address the changing needs of the global oxo alcohol market By Richard Tudor Introduction Retired, Reading, UK The LP OxoSM Process is the rhodium-catalysed Atul Shah* hydroformylation process in wide use today in a variety Johnson Matthey, 10 Eastbourne Terrace, London, W2 of industrial applications. These applications have been 6LG, UK developed, co-marketed and licensed as a cooperation between affiliates of The Dow Chemical Company *Email: [email protected] (‘Dow’) and Johnson Matthey or their predecessors, for over 45 years. The LP OxoSM Process first made an impact in the 1970s when its technical elegancy, environmental Since the mid-1970s when the ‘Low Pressure Oxo’ footprint and economics attracted huge attention by process (LP OxoSM Process) was first commercialised, the world’s producers of normal butyraldehyde for it has maintained its global position as the foremost conversion to the plasticiser alcohol 2-ethylhexanol oxo process, offering particular appeal to independent (2EH). producers of commodity plasticisers facing increasing regulatory pressure. The story of this important The Early Dominance of Cobalt Catalysis industrial process is told from its early beginnings when laboratory discoveries by independent groups of Hydroformylation is the reaction of an unsaturated researchers in USA and UK revealed the remarkable olefinic compound with hydrogen and carbon ability of organophosphine containing rhodium monoxide to yield an aldehyde.
    [Show full text]
  • Organometallic Chemistry and Applications
    Chemistry 462 Fall 2017 MYD Organometallic Chemistry and Applications Note: Organometallic Compounds and Complexes Contain a M-C Bond. Organometallic chemistry timeline 1760 Louis Claude Cadet de Gassicourt investigates inks based on cobalt salts and isolates Cacodyl from cobalt mineral containing arsenic 1827 William Christopher Zeise produces Zeise's salt; the first platinum / olefin complex 1848 Edward Frankland discovers diethylzinc 1863 Charles Friedel and James Crafts prepare organochlorosilanes 1890 Ludwig Mond discovers nickel carbonyl 1899 Introduction of Grignard reaction 1899 John Ulric Nef discovers alkylation using sodium acetylides. 1900 Paul Sabatier works on hydrogenation of organic compounds with metal catalysts. Hydrogenation of fats kicks off advances in food industry; see margarine! 1909 Paul Ehrlich introduces Salvarsan for the treatment of syphilis, an early arsenic based organometallic compound 1912 Nobel Prize Victor Grignard and Paul Sabatier 1930 Henry Gilman works on lithium cuprates, see Gilman reagent 1951 Walter Hieber was awarded the Alfred Stock prize for his work with metal carbonyl chemistry—(but not the Nobel Prize). 1951 Ferrocene is discovered 1963 Nobel prize for Karl Ziegler and Giulio Natta on Ziegler-Natta catalyst: Polymerization of olefins 1965 Discovery of cyclobutadieneiron tricarbonyl 1968 Heck reaction 1973 Nobel prize Geoffrey Wilkinson and Ernst Otto Fischer on sandwich compounds 1981 Nobel prize Roald Hoffmann and Kenichi Fukui for expression of the Woodward-Hoffman Rules 2001 Nobel prize W. S. Knowles, R. Noyori and Karl Barry Sharpless for asymmetric hydrogenation 2005 Nobel prize Yves Chauvin, Robert Grubbs, and Richard Schrock on metal-catalyzed alkene metathesis 2010 Nobel prize Richard F. Heck, Ei-ichi Negishi, Akira Suzuki for palladium catalyzed cross coupling reactions The following slides are meant merely as examples of the catalytic processes we will explore later this semester.
    [Show full text]
  • 1 IG. Palladium I I. Basic Principles
    P. Wipf 1/30/2007 I. Basic Principles IG. Palladium I - Heck Reactions - Stille, Suzuki, Negishi, Sonogashira etc Cross Couplings - π-Allyl Palladium Chemistry - Heteroatom Couplings - Applications in Natural Product Synthesis 1 P. Wipf 1/30/2007 The Heck Reaction Herbert C. Brown Award for Creative Research in Synthetic Methods (sponsored in part by Sigma-Aldrich since 1998). Richard F. Heck (retired) – University of Delaware (USA) Professor Heck, of “Heck Reaction/Coupling” fame, has had a long and distinguished career in chemistry. Beginning with Co- mediated hydroformylation, Heck was one of the first to apply transition metal catalysis to C-C bond formation. His studies of the mechanisms of transition metal catalyzed reactions led to Pd-mediated couplings that have had a profound impact in many areas of chemistry and materials science. 2 P. Wipf 1/30/2007 Reviews: Shibasaki, M.; Vogl, E. M.; Ohshima, T. "Asymmetric Heck reaction." Advanced Synthesis & Catalysis 2004, 346, 1533-1552. Dounay, A. B.; Overman, L. E. "The asymmetric intramolecular Heck reaction in natural product total synthesis." Chem. Rev. 2003, 103, 2945-2963. Beletskaya, I. P.; Cheprakov, A. V. "The Heck reaction as a sharpening stone of palladium catalysis." Chem. Rev. 2000, 100, 3009-3066. The Complex. Among Pd(0) and Pd(II) complexes commonly used are Pd(PPh3)4, Pd2(dba)2, and Pd2(dba)2CHCl3. Pd(PPh3)4 should be stored cold and under inert gas; the dibenzylideneacetone complexes are more stable catalyst precursors. Both phosphine structure and phosphine/Pd ratio effect catalyst structure and reactivity (the lower the phosphine/Pd ratio, the more reactive the catalyst).
    [Show full text]