DOCSLIB.ORG

(12) United States Patent (10) Patent No.: US 9.221,727 B2 Cheung Et Al

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
(12) United States Patent (10) Patent No.: US 9.221,727 B2 Cheung Et Al US009221727B2 (12) United States Patent (10) Patent No.: US 9.221,727 B2 Cheung et al. (45) Date of Patent: Dec. 29, 2015 (54) SELECTIVE HYDROGENATION CATALYST USPC .......... 585/269,277: 502/162, 164, 262,327, AND METHODS OF MAKING AND USING 502/328,330, 333,339, 439 SAME See application file for complete search history. (56) References Cited (71) Applicant: Chevron Phillips Chemical Company LP, The Woodlands, TX (US) U.S. PATENT DOCUMENTS (72) Inventors: Tin-Tack Peter Cheung, Kingwood, TX 3,463,830 A 8/1969 Dunning et al. (US); Zongxuan Hong, Houston, TX 3,625,755 A 12, 1971 Potrafike (US) (Continued) (73) Assignee: Chevron Phillips Chemical Company FOREIGN PATENT DOCUMENTS LP, The Woodlands, TX (US) CN 1422695 A 6, 2003 (*) Notice: Subject to any disclaimer, the term of this CN 1425,637 A 6, 2003 patent is extended or adjusted under 35 (Continued) U.S.C. 154(b) by 0 days. OTHER PUBLICATIONS (21) Appl. No.: 14/669,541 Boitiaux, J.P. et al., “Hydrogenation of highly unsaturated hydrocar bons over highly dispersed Pd catalyst. Part II: Ligand effect of (22) Filed: Mar. 26, 2015 piperidine.” Applied Catalysis, 1985, vol. 15, pp. 317-326, Elsevier Science Publishers B.V., Amsterdam, XPOO2577931. (65) Prior Publication Data (Continued) US 2015/O197464 A1 Jul. 16, 2015 Primary Examiner — Cam N. Nguyen (74) Attorney, Agent, or Firm — Conley Rose, P.C.; Rodney Related U.S. Application Data B. Carroll; Lynda Jolly (62) Division of application No. 14/134,282, filed on Dec. (57) ABSTRACT 19, 2013, now Pat. No. 9,012,348, which is a division A composition comprising a Supported hydrogenation cata of application No. 12/710,781, filed on Feb. 23, 2010, lyst comprising palladium and an organophosphorous com now Pat. No. 8,633,127. pound, the Supported hydrogenation catalyst being capable of (60) Provisional application No. 61/157,491, filed on Mar. selectively hydrogenating highly unsaturated hydrocarbons 4, 2009. to unsaturated hydrocarbons. A method of making a selective hydrogenation catalyst comprising contacting a Support with (51) Int. C. a palladium-containing compound to form a palladium Sup C07C 5/10 (2006.01) ported composition, contacting the palladium Supported BOI.3L/00 (2006.01) composition with an organophosphorus compound to form a (Continued) catalyst precursor, and reducing the catalyst precursor to form the catalyst. A method of selectively hydrogenating highly (52) U.S. C. unsaturated hydrocarbons to an unsaturated hydrocarbon CPC. C07C5/09 (2013.01); B01J 23/44 (2013.01); enriched composition comprising contacting a Supported B01J 23/66 (2013.01); B01J 27/13 (2013.01); catalyst comprising palladium and an organophosphorous (Continued) compound with a feed comprising highly unsaturated hydro (58) Field of Classification Search carbon under conditions suitable for hydrogenating at least a CPC ............. C07C 5/10; B01J 31/24: B01J 31/26; portion of the highly unsaturated hydrocarbon feed to form B01J 31/28: B01J 23/44; B01J 23/56; B01J the unsaturated hydrocarbon enriched composition. 23/58 21 Claims, 2 Drawing Sheets 10 20 US 9,221,727 B2 Page 2 (51)51) Int. Cl. 6,603,038 B1 8/2003 Hagemevergemey et al. 6,635,600 B1 10/2003 Kimble et al. BOI 2L/00 (2006.01) 6,821.412 B1 1 1/2004 Fujukawa et al. BOI 2L/04 (2006.01) 6,831,035 B2 12/2004 Puckette et al. BOI. 23/00 (2006.01) 6,852,661 B1 2/2005 Ahlers et al. BOI. 23/02 (2006.01) 6,969,694 B2 11/2005 Zhang 7,148,176 B2 12/2006 Beller et al. BOI. 23/240 (2006.01) 7,160,835 B2 1/2007 Tsuji BOI. 23/242 (2006.01) 7,408,089 B2 8/2008 Ryu BOI. 23/44 (2006.01) 7,417,007 B2 * 8/2008 Cheung .................... B01J 23.44 BOI. 23/58 (2006.01) 502,208 C07C5/09 (2006.01) 7,586,010 B2 9, 2009 Liu et al. 7,704,912 B2 4/2010 Reetz et al. BOI. 23/66 (2006.01) 7,737,075 B2 6/2010 Ryu BOI 27/3 (2006.01) 7,737,079 B2 6/2010 Ryu BOI 3/16 (2006.01) 7.919,431 B2 * 4/2011 Johnson ................... BO1J 23.50 BOI 3/18 (2006.01) 8,633,127 B2 1/2014 Ch 1 502,324 w - - eung et al. SE7 3.08: 8,729,326 B2 * 5/2014 Cheung.................... B01J 23.44 502/230 BOI. 37/28 (2006.01) 9.012,348 B2 4/2015 Cheung et al. CIOG 45/40 (2006.01) 2003/0144139 A1 7/2003 Shimizu et al. BOI.3L/02 (2006.01) 2003/O15827O A1 8/2003 Mahajan 2003/0228977 A1 12/2003 Yokozawa et al. C07C ". (2006.01) 2004/0092388 A1 5/2004 Shimizu et al. BOIJ 35/OO (2006.01) 2004/O138056 A1 7, 2004 Zhao et al. BOIJ 35/02 (2006.01) 2004/0192983 A1 9/2004 Bergmeister et al. BOIJ 35/IO (2006.01) 2004/026012.6 A1 12/2004 Augustine et al. (52) U.S. Cl. 2007/0027030 Al 22007 Cheung et al. CPC .......... Bot to 71 (2013.01). Botvi/161, 200706183 Al 72007 Bergmeister, III et al. (2013.01); B01J 31/185 (2013.01); B01.J FOREIGN PATENT DOCUMENTS 31/1845 (2013.01); B01J 31/1865 (2013.01); B01J 31/1875 (2013.01); B01J 31/24 CN 102341,175. A 2, 2012 (2013.01); B01J 3 1/2404 (2013.01); B01.J EP O933129 A1 8, 1999 EP 2403642 A2 1, 2012 370203 (2013.01); B01J 37/28 (2013.01): JP O8066633. A 3, 1996 C07C5/05 (2013.01); C10G 45/40 (2013.01); JP O9000937 A 1, 1997 B01J 35/008 (2013.01); B01.J35/023 (2013.01); JP 2007518676 A 7/2007 B01.J35/1009 (2013.01); B01.J35/1014 WO OO23403 A1 4/2000 (2013.01); B01J 37/024 (2013.01); B01.J WO 2005.000773 A1 1, 2005 223 1/645 (2013.01); B01J 2531/824 (2013.01); WO 2010101736 A2 9, 2010 C07C 2521/04 (2013.01); C07C 2531/26 WO 2010101736 A3 9, 2010 (2013.01); C10G 2300/703 (2013.01) OTHER PUBLICATIONS (56) References Cited Database, WPI. Week 200365, Thompson Scientific, London, GB, 2003-680539, CN1425637A, Jun. 25, 2003, 1 page, XP002577876. U.S. PATENT DOCUMENTS Kwon, Min Serk, et al., “Palladium nanoparticles entrapped in alu 3,635,841 A 1/1972 Keith et al. minum hydroxide: dual catalyst for alkene hydrogenation and aero 3,947.495 A 3, 1976 Murib et al. bic alcohol oxidation.” Organic Letters, 2005, vol. 7, No. 6, pp. 4,120,901 A 10, 1978 Hobbs et al. 1077-1079, American Chemical Society, XP002577877. 4,204,997 A 5, 1980 Hobbs et al. Song, Choong Eui, et al., “Supported chiral catalysts on inorganic 4.325,834 A 4, 1982 Bartish et al. materials.” Chem. Rev., 2002, vol. 102, pp. 3495-3524. American 4,384,981 A 5, 1983 Dines et al. Chemical Society, XP002297471. 4.404,124 A 9, 1983 Johnson et al. UOP Method 578-02, “Automated Pore Volume and Pore Size Dis 4.418,227 A * 1 1/1983 Pez ........................ B01J 31,121 568,861 tribution of Porous Substances by Mercury Porosimetry.” UOPLLC, 4.484.015 A 11, 1984 Johnson et al. 1984, pp. 1-14. 4,713,363 A 12, 1987 Hucul Westermark, Gunnar, et al., “An infrared study on the chemisorption 4,774,221 A 9, 1988 Medem et al. of tertiary phosphines on coinage and platinum group metal Sur 4,786,623 A 11, 1988 Grenouillet et al. faces.” Colloids and Surfaces A: Physicochemical and Engineering 4,889,949 A 12/1989 Grenouillet et al. Aspects, 1999, vol. 150, pp. 31-43, Elsevier Science, B.V. 5,028,576 A 7, 1991 Drent et al. Westermark, Gunnar, et al., “Chemisorption of tertiary phosphines 5,113,022 A 5/1992 Abatjoglou et al. 5,166,116 A 11/1992 Drent et al. on coinage and platinum group metal powders. An infrared reflec 5,189,003 A 2f1993 Klusener et al. tance absorption spectroscopic, enhanced Raman spectroscopic and 5,482.596 A 1, 1996 Wu surface coverage study.” Colloids and Surfaces A: Physicochemical 5,712.403 A 1/1998 Sato et al. and Engineering Aspects, 1998, vol. 144, pp. 149-166, Elsevier Sci 5,880,301 A 3, 1999 Shibasaki et al. ence B.V. 6,005,123 A 12/1999 Dessau et al. Filing Receipt and provisional patent specification entitled "Selective 6,127.588 A * 10/2000 Kimble .................... B01J 23.44 585,259 hydrogenation catalyst and methods of making and using same.” by 6,140,265 A 10, 2000 Haber et al. Tin-Tack Peter Cheung, et al., filed Mar. 4, 2009 as U.S. Appl. No. 6, 197,716 B1 3/2001 Baumeister et al. 61/157,491. 6, 197,720 B1 3, 2001 Heineke et al. Foreign communication from a related counterpart application— 6,232,262 B1 5, 2001 Sielcken et al. Invitation to Pay Additional Fees, PCT/US2010/025.038, 9 pages, 6,541,417 B2 4/2003 Kasztelan et al. Jun. 14, 2010. US 9,221,727 B2 Page 3 (56) References Cited Foreign communication from a related counterpart application— Australian Examination Report, Application No. 2010221662, Oct. OTHER PUBLICATIONS 8, 2014, 3 pages. Foreign communication from a related counterpart application— Foreign communication from a related application—International Philippines Examination Report, Application No. 1201 1501710, Search Report and Written Opinion, PCT/US2010/025038, Nov. 26, Feb. 5, 2015, 1 page. Foreign communication from a related counterpart application— 2010, 18 pages. Australian Examination Report, Application No. 201320 1876, Oct. Foreign communication from a related counterpart application— 15, 2014, 3 pages.
Load more

Recommended publications
  • Phosphorus-Containing Amino Acids with a P–C Bond in the Side Chain Or a P–O, P–Sorp–N Bond: Cite This: RSC Adv., 2020, 10, 6678 from Synthesis to Applications
    RSC Advances View Article Online REVIEW View Journal | View Issue Phosphorus-containing amino acids with a P–C bond in the side chain or a P–O, P–SorP–N bond: Cite this: RSC Adv., 2020, 10, 6678 from synthesis to applications a b b Mathieu Arribat, Florine Cavelier * and Emmanuelle Remond´ * Since the discovery of (L)-phosphinothricin in the year 1970, the development of a-amino acids bearing a phosphorus group has been of renewed interest due to their diverse applications, including their use in [18F]-fluorolabeling, as fluorescent probes, as protecting groups and in the reversible immobilization of amino acids or peptide derivatives on carbon nanomaterials. Considerable progress has also been achieved in the field of antiviral agents, through the development of phosphoramidate prodrugs, which increase significantly the intracellular delivery of nucleoside monophosphate and monophosphonate analogues. This review aims to summarize the strategies reported in the literature for the synthesis of P(III), P(IV) and P(V) phosphorus-containing amino acids with P–C, P–O, P–SorP–N bonds in the side Received 2nd December 2019 Creative Commons Attribution-NonCommercial 3.0 Unported Licence. chains and their related applications, including their use in natural products, ligands for asymmetric Accepted 22nd January 2020 catalysis, peptidomimetics, therapeutic agents, chemical reagents, markers and nanomaterials. The DOI: 10.1039/c9ra10917j discussion is organized according to the position of the phosphorus atom linkage to the amino acid side rsc.li/rsc-advances chain, either in an a-, b-, g-ord-position or to a hydroxyl, thiol or amino group. 1. Introduction phosphinothricin has engendered the development of numerous drugs for neurodegenerative disease treatment.
    [Show full text]
  • Some Transition Metal Complexes of Trivalent Phosphorus Esters
    AN ABSTRACT OF THE THESIS OF HARRY VAUGHN STUDER for the MASTER OF SCIENCE (Name) (Degree) inCHEMISTRY (Inorganic) presented on ///( (Major) / (Date') Title: SOME TRANSITION METAL COMPLEXES OF TRIVALENT PHOSPHORUS ESTERS Redacted for Privacy Abstract approved: Dr. In T. Yoke r The ligands in the series EtnP(OEt)3_11, n = 0 - 3,all form pseudotetrahedral high-spin bis -complexes with cobalt (II) chloride. Magnetic, spectrophotometric, conductivity, and molecular weight data show that the phosphorus ester ligands (but not the phosphine) also form five-coordinate low-spin tris-complexes; these can be isolated with the phosphonite and phosphinite ligands, while the existence of the tris -phosphite is marginal.At cobalt (II) to phosphorus ester mole ratios of 1:2, a mixture of species is present in all cases.All are non-conducting in nitrobenzene. The ester complexes are much more susceptible to autoxidation than is the phosphine complex. Some Transition Metal Complexes of Trivalent Phosphorus Esters by Harry Vaughn Studer A THESIS submitted to Oregon State University in partial fulfillment of the requirements for the degree of Master of Science June 1972 APPROVED: Redacted for Privacy Profes of Chemi str y / in crge of major Redacted for Privacy Head of Department of Chemistry Redacted for Privacy Dean of Graduate School Date thesis is presented Typed by Donna Olson f arry Vatighn Studer ACKNOWLEDGEMENTS The author wishes to thank his research advisor, Dr. John T. Yoke, for his expert direction of this research, for his patience, and for the opportunity of learning through association with him. Acknowledgement is made to the donors of the Petroleum Re- search Fund, administered by the American Chemical Society, for the support of this work.
    [Show full text]
  • Metal Complexes As Catalysts for the Synthesis of Heterocycles
    METAL COMPLEXES AS CATALYSTS FOR THE SYNTHESIS OF HETEROCYCLES Steven Lal Department of Chemistry, Imperial College London A thesis submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy, Imperial College London May 2013 1 Declaration I certify that all the work in this thesis is solely my own, except where explicitly stated and appropriately referenced. No part of the thesis has been submitted previously for a degree at this, or any other, university. 2 Copyright Notice Imperial College of Science, Technology and Medicine Department Of Chemistry Metal Complexes as Catalysts for the Synthesis of Heterocycles © 2013 Steven Lal [email protected] The copyright of this thesis rests with the author and is made available under a Creative Commons Attribution Non-Commercial No Derivatives License. Researchers are free to copy, distribute or transmit the thesis on the condition that they attribute it, that they do not use it for commercial purposes and that they do not alter, transform or build upon it. For any reuse or redistribution, researchers must make clear to others the license terms of this work. Steven Lal Department of Chemistry Imperial College London Exhibition Road London SW7 2AZ UK www.imperial.ac.uk 3 Contents Abstract ...................................................................................................................................... 8 Acknowledgements .................................................................................................................
    [Show full text]
  • Advanced Studies on the Synthesis of Organophosphorus Compounds
    ALMA MATER STUDIORUM UNIVERSITÀ DI BOLOGNA DOTTORATO DI RICERCA IN SCIENZE CHIMICHE (XIX° ciclo) Area 03 Scienze Chimiche-CHIM/06 Chimica Organica Dipartimento di Chimica Organica “A. Mangini” Coordinatore: Chiar.mo Prof. Vincenzo Balzani Advanced Studies on the Synthesis of Organophosphorus Compounds Dissertazione Finale Presentata da: Relatore: Dott. ssa Marzia Mazzacurati Prof. Graziano Baccolini Co-relatore: Dott.ssa Carla Boga INDEX Index: Keywords…………………………………………………………….………….VII Chapter 1…………………………………………………………………………..3 GENERAL INTRODUCTION ON PHOSPHORUS CHEMISTRY 1.1 Organophosphorus Chemistry………………………………………………….4 1.1.1 Phosphines………………………………………………………………..5 1.1.2 Phosphonates……………………………………………………………..6 1.1.3 Phosphites………………………………………………………………...7 1.2 Uses of Organophosphorus Compounds………………………………………..7 1.2.1 Agricultural Application………………………………………………….8 1.2.2 Catalysis……………………………………………………………..…....9 1.2.3 Organophosphorus Conpounds in Medicine…………………………….11 1.2.4 Phosphorus in Biological Compounds…………………………………..12 1.3 References……………………………………………………………………..15 Chapter 2…………………………………………………………………………17 THE HYPERCOORDINATE STATES OF PHOSPHORUS 2.1 The 5-Coordinate State of Phosphorus……………………………………….17 2.2 Pentacoordinated structures and their non rigid character…………………….18 2.3 Permutational isomerization…………………………………………………..19 2.3.1 Berry pseudorotation……………………………………………………20 2.3.2 Turnstile rotation………………………………………………………..21 2.4 The 6-Coordinate State of Phosphorus……………………………………….22 2.5 References…………………………………………………………………......24 I Chapter
    [Show full text]
  • Organophosphorus Chemistry (Kanda, 2019)
    Baran lab Group Meeting Yuzuru Kanda Organophosphorus Chemistry 09/20/19 bonding and non-bonding MOs of PH3 bonding and non-bonding MOs of PH5 # of R P(III) ← → P(V) O P P R R R R R R phosphine phosphine oxide D3h C3v C2v O O JACS. 1972, 3047. P P P P R NH R OH R OH R NH Chem. Rev. 1994, 1339. R 2 R R R 2 D C phosphineamine phosphinite phosphinate phosphinamide 3h 4v O O O R P R P R P R P R P R P NH2 NH2 OH OH NH2 NH2 H2N HO HO HO HO H2N phosphinediamine phosphonamidite phosphonite phosphonate phosphonamidate phosphonamide O O O O H N P P P P P P P P 2 NH HO HO HO HO HO HO H2N H N 2 NH2 NH2 OH OH NH2 NH2 NH2 2 H2N HO HO HO HO H2N H2N phosphinetriamine phosphorodiamidite phosphoramidite phosphite phosphate phosphoramidate phosphorodiamidate phosphoramide more N O more O Useful Resources more N P P P Corbridge, D. E. C. Phosphorus: Chemistry, Biochemistry and H OH H H H H H H H Technology, 6th ed.; CRC Press Majoral, J. P. New Aspects In Phosphorus Chemistry III.; Springer phosphinous phosphane phosphane Murphy, P. J. Organophosphorus Reagents.; Oxford acid oxide Hartley, F. R. The chemistry of organophosphorus compounds, O O volume 1-3.; Wiley P P P Cadogan. J. I. G. Organophosphorus Reagents in Organic H OH H OH H OH HO HO H Synthesis.; Academic Pr phosphonate phosphonus acid phosphinate Not Going to Cover ↔ (phosphite) Related GMs Metal complexes, FLP, OPV Highlights in Peptide and Protein NH S R • oxidation state +5, +4, +3, +2, +1, 0, -1, -2, -3 Synthesis (Malins, 2016) R P-Stereogenic Compounds P P R P • traditionally both +3 and -3 are written as (III) R • 13/25th most abundant element on the earth (Rosen, 2014) R • but extremely rare outside of our solar system Ligands in Transition Metal phosphine imide phosphine sulfide phosphorane Catalysis (Farmer, 2016) Baran lab Group Meeting Yuzuru Kanda Organophosphorus Chemistry 09/20/19 Me P Me Me Low-Coordinate Low Oxidation State P tBu tBu P P phosphaalkyne R N P PivCl 2 P Me Cl TMS OTMS NaOH R = tBu Nb N tBu PTMS3 P O H O P NR2 then Na/Hg tBu N -2 Nb tBu R2N Me Nb N tBu 5x10 mbar, 160 ºC NR2 95% R2N Me N O 1.
    [Show full text]
  • Acscatal.0C01923.Pdf
    This is a repository copy of Phosphoranyl Radical Fragmentation Reactions Driven by Photoredox Catalysis. White Rose Research Online URL for this paper: https://eprints.whiterose.ac.uk/163811/ Version: Published Version Article: Rossi-Ashton, James A., Clarke, Aimee K., Unsworth, William P. orcid.org/0000-0002- 9169-5156 et al. (1 more author) (2020) Phosphoranyl Radical Fragmentation Reactions Driven by Photoredox Catalysis. ACS Catalysis. pp. 7250-7261. ISSN 2155-5435 https://doi.org/10.1021/acscatal.0c01923 Reuse This article is distributed under the terms of the Creative Commons Attribution (CC BY) licence. This licence allows you to distribute, remix, tweak, and build upon the work, even commercially, as long as you credit the authors for the original work. More information and the full terms of the licence here: https://creativecommons.org/licenses/ Takedown If you consider content in White Rose Research Online to be in breach of UK law, please notify us by emailing [email protected] including the URL of the record and the reason for the withdrawal request. [email protected] https://eprints.whiterose.ac.uk/ This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. pubs.acs.org/acscatalysis Perspective Phosphoranyl Radical Fragmentation Reactions Driven by Photoredox Catalysis James A. Rossi-Ashton,* Aimee K. Clarke, William P. Unsworth, and Richard J. K. Taylor Cite This: ACS Catal. 2020, 10, 7250−7261 Read Online ACCESS Metrics & More Article Recommendations ABSTRACT: Photocatalytic generation of phosphoranyl radicals is fast emerging as an essential method for the generation of diverse and valuable radicals, typically via deoxygenation or desulfurization processes.
    [Show full text]
  • Measuring the Electronic Effect of Some Phosphines and Phosphites
    Measuring the electronic effect of some phosphines and phosphites By Sanaa Moftah Ali Abushhewa A dissertation submitted to the University of Manchester for the degree of Master of Science by research in the Faculty of Engineering and Physical Sciences. School of Chemistry 2010 Contents page Abstract 6 Declaration 7 Acknowledgement 8 1. Introduction 9 1.1 History of Phosphorus 9 1.2 Phosphorus (III) compounds 10 1.3 Preparation and Properties of Phosphines 11 1.4 Preparation and Properties of Phosphites 12 1.5 Bonding of phosphorus (III) ligands 14 1.6 Measurement of Electronic and Steric Effects 15 1.7 Steric parameter 17 1.8 Electronic parameter 17 1.9 Effects of electronegative substituents 21 1.10 Phosphines and Phosphites ligand effects 21 2. Experimental section 24 General conditions 25 2.1- Preparation of phosphites 25 2.1.1- Synthesis of 2, 2’- Biphenyl Chlorophosphite 25 2.1.2- Synthesis of 1H,1H,2H,2H-perfluorodecyldiphenyl phosphinite 25 2 2.1.3- Synthesis of 3-fluorophenyldiphenyl phosphinite 26 2.1.4- Synthesis of 2-fluorophenyldiphenyl phosphinite 26 2.1.5- Synthesis of 2, 2-biphenyltrifluoroethyl phosphinite 27 2.1.6- Synthesis of 2, 2'-biphenylhexafluoroisopropyl phosphinite 27 2.1.7-Synthesis of 2, 2'-biphenylpropyl phosphite 28 2.2-Preparation of P(III) Selenides 28 2.2.1- Synthesis of triphenylphosphine selenide 28 2.2.2- Synthesis of triphenylphosphite selenide 29 2.2.3- Synthesis of tris(2,4,6-trimethylphenyl)phosphite selenide 29 2.2.4- Synthesis of diphenyl(o-tolyl) phosphine selenide 30 2.2.5- Synthesis of 2, 2’-biphenyl
    [Show full text]
  • Chemistry of Phosphorylated Formaldehyde Derivatives. Part I
    Molecules 2014, 19, 12949-13009; doi:10.3390/molecules190912949 OPEN ACCESS molecules ISSN 1420-3049 www.mdpi.com/journal/molecules Review Chemistry of Phosphorylated Formaldehyde Derivatives. Part I Vasily P. Morgalyuk Laboratory of Organophosphorus Compounds, Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str., 28, Moscow 119991, Russia; E-Mail: [email protected]; Tel.: +7-499-135-92-50; Fax: +7-495-135-65-49 Received: 8 July 2014; in revised form: 8 August 2014 / Accepted: 15 August 2014 / Published: 25 August 2014 Abstract: The underinvestigated derivatives of unstable phosphorylated formaldehyde acetals and some of the structurally related compounds, such as thioacetals, aminonitriles, aminomethylphosphinoyl compounds, are considered. Separately considered are halogen aminals of phosphorylated formaldehyde, acetals of phosphorylated formaldehyde of H-phosphinate-type and a phosphorylated gem-diol of formaldehyde. Synthetic methods, chemical properties and examples of practical applications are given. Keywords: phosphorylated acetals; -thioacetals; -aminonitriles; -aminomethylphosphinoyl compounds; -chloro(or bromo)aminals; -gem-dioles; -ketene acetale; H-phosphinate 1. Introduction Among organophosphorus compounds, α-phosphorylated carbonyl compounds stand out by the capacity of cleavage of phosphorus–carbon bond under mild conditions when reacted with nucleophiles [1–5]. The cleavage of phosphorus–carbon bond may proceed spontaneously as well. At the same time, α-oxoalkylphosphinoyl compounds also retain properties inherent in carbonyl compounds, for example, they undergo cross aldol condensation. The least stable compounds among them are phosphorylated formaldehyde derivatives, dialkyl formylphosphonates (1) [6–11] and N,N,N',N'-tetraalkyl formylphosphondiamides (2) [12] (Figure 1), whose existence was even disputed in the first half of the 1970s [13,14].
    [Show full text]
  • Synthesis, Purification, and Characterization of Tetraphosphine Ligands Deniz Cevik
    Synthesis, purification, and characterization of tetraphosphine ligands Deniz Cevik To cite this version: Deniz Cevik. Synthesis, purification, and characterization of tetraphosphine ligands. Other. Univer- sité Paris-Saclay, 2017. English. NNT : 2017SACLX026. tel-01631221 HAL Id: tel-01631221 https://pastel.archives-ouvertes.fr/tel-01631221 Submitted on 8 Nov 2017 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. NNT : 2017SACLX026 THESE DE DOCTORAT DE L’UNIVERSITE PARIS-SACLAY PREPAREE A ÉCOLE POLYTECHNIQUE ECOLE DOCTORALE N° 517 2MIB | Sciences chimiques : Molécules, matériaux, instrumentation et biosystèmes Spécialité de doctorat : Chimie Par Mme. Deniz Çevik Synthesis, Purification, and Characterization of Tetraphosphine Ligands Thèse présentée et soutenue à Palaiseau, le 17. Juillet 2017 : Composition du Jury : Mme. Hii, King Kuok (Mimi) Professeur Imperial College London Rapporteure M. Manoury, Eric DR - CNRS au LCC (Toulouse) Rapporteur M. Voituriez, Arnaud DR - CNRS á l’ICSN Président M. van Leeuwen, Piet Chaire d’Attractivité au LPCNO, INSA-Toulouse
    [Show full text]
  • 20. Phosphorus Chemistry
    Professor David L. Van Vranken Chemistry 201: Organic Reaction Mechanisms I Topic 20: Phosphorus Chemistry References: Literature cited Phosphorus Functional Groups ■ Here’s how to name phosphorus functional groups: R R R OR R OR O O R P P P R P P(III) R R OR O R phosphine phosphinite phosphonite phosphite (ester) O O O O R R R OR R OR O O P P P R P R P(V) R R OR O R phosphine oxide phosphinate phosphonate phosphate (ester) ■ Few of these functional groups are common. O O O H P N P HO OH O CH HO F 3 glyphosate sarin Phosphorus Functional Groups ■ pKas reveal the difference in basicity between trialkylphosphines and triarylphosphines Et Ph .. + + N N Ph2N Et Et Ph Ph resonance H H reduces l.p. basicity pKa 11 ~ -5 .. Bu Ph Ph P + + 2 P P not so much Bu Bu Ph Ph H H resonance pKa 9 3 ■ Trialkylphosphines are way more nucleophilic than triarylphosphines Bu Ph Bu P: Ph P: Bu Ph way more nucleophilic Howard ST, et al. Can. J. Chem. 1997, 75, 60. Allman, T.; Goel, R. G. Can. J. Chem. 1982, 60, 716.. POCl3 is a Very Reactive Electrophile ■ Old conditions for elimination of OH groups. Contrast the outcomes. SOCl Cl 2 pyridine OH POCl3 pyridine (solvent) ■ Phosphates don’t substitute very quickly, but Cl3P=O is special ■ Vilsmeier-Haack Reaction - amides attack Cl3P=O + NMe O Cl NMe 2 2 E.A.S. MeO + MeO H2O MeO H OMe OMe workup OMe POCl3 + DMF Mechanism for formation of the Vilsmeier reagent: : .
    [Show full text]
  • (12) United States Patent (10) Patent No.: US 9,365,793 B2 Boffa (45) Date of Patent: *Jun
    US0093.65793B2 (12) United States Patent (10) Patent No.: US 9,365,793 B2 Boffa (45) Date of Patent: *Jun. 14, 2016 (54) METHODS AND COMPOSITIONS FOR (56) References Cited REDUCING WEAR IN INTERNAL COMBUSTON ENGINESLUBRICATED U.S. PATENT DOCUMENTS WITH A LOW PHOSPHOROUS CONTENT 3,997.454 A 12/1976 Adams BORATE-CONTAINING LUBRICATING OL 3,997.457 A 12/1976 Takahashi et al. 4,089,790 A 5, 1978 Adams 4,163,729 A 8, 1979 Adams (71) Applicant: Alexander B. Boffa, Richmond, CA 4,431,552 A 2f1984 Salentine (US) 4472.288 A 9/1984 Frost, Jr. 4.495,075 A 1/1985 Buckley (72) Inventor: Alexander B. Boffa, Richmond, CA 4,534,873. A 8, 1985 Clark 4,717,490 A 1/1988 Salentine (US) 4,975,096 A 12/1990 Buckley, III 5,635,459 A 6/1997 Stoffa et al. (73) Assignee: Chevron Oronite Company LLC, San 5,962,377 A 10/1999 Baumgartet al. Raman, CA (US) 6,306,802 B1 10/2001 Shaub 6,534.450 B1 3/2003 Harrison et al. (*) Notice: Subject to any disclaimer, the term of this 6,569,818 B2 5/2003 Nakazato et al. 6,632,781 B2 10/2003 Harrison et al. patent is extended or adjusted under 35 6,696,393 B1 2, 2004 Boffa U.S.C. 154(b) by 0 days. 6,730,638 B2 5/2004 Farng et al. 6,737,387 B2 5, 2004 Harrison et al. This patent is Subject to a terminal dis 6,777,378 B2 8/2004 Abraham et al.
    [Show full text]
  • Versatile Phosphorus Ligands : Synthesis, Coordination Chemistry and Catalysis
    Versatile phosphorus ligands : synthesis, coordination chemistry and catalysis Citation for published version (APA): Vlugt, van der, J. I. (2003). Versatile phosphorus ligands : synthesis, coordination chemistry and catalysis. Technische Universiteit Eindhoven. https://doi.org/10.6100/IR570885 DOI: 10.6100/IR570885 Document status and date: Published: 01/01/2003 Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication: • A submitted manuscript is the version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal.
    [Show full text]