DOCSLIB.ORG

United States Patent Office Patented Oct

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
United States Patent Office Patented Oct 2,956,952 United States Patent Office Patented Oct. 18, 1960 2 reaction conditions, phosphonate polymers having mo 2,956,952 lecular weights in the range of about 1,000 to 3,500 or LUBRICATING OL COMPOSITIONS CONTAINING higher, preferably about 1,200 to 3,000 may be pre POLYMERS OF BIS-(BETA CHLOROETHYL) WIN pared. If desired, the polymerization reaction may be YL PHOSPHONATE carried out in the presence of an inert diluent or solvent William P. FitzGerald, Florham Park, Anthony H. such as, for example, highly refined mineral oils (e.g. Gleason, Westfield, Arnold J. Morway, Clark, and Al white oils), Xylene, cyclohexane, etc. fred H. Matuszak, Westfield, N.J., assignors to Esso Copolymers of bis-(beta chloroethyl) vinyl phos Research and Engineering Company, a corporation of phonate may be prepared employing generally the same reaction conditions as those set forth above for the phos Delaware 0. phonate polymers. The phosphonate monomer may be No Drawing. Filed Aug. 8, 1955, Ser. No. 527,174 copolymerized with the following monomers: ethylene, propylene, isobutylene, styrene, a-methylacrylamide, 7 Claims. (Cl. 252-49.9) acrylamide, a-methylacrylonitrile, acrylonitrile, isobutyl This invention relates to polymeric materials and a-methacrylate, isobutylacrylate, n-butyl a-methylacry more particularly relates to polymers and copolymers 5 late, n-butylacrylate, isopropyl a-methylacrylate, iso of bis-(beta chloroethyl) vinyl phosphonate, especially propylacrylate, n-propyl a-methylacrylate, n-propyl ac copolymers of ethylene and bis-(beta chloroethyl) vinyl rylate, ethyl a-methylacrylate, ethyl acrylate, methyl phosphonate. The invention also relates to methods of a-methylacrylate, methyl acrylate, a-methylacrylic acid, preparing such polymeric materials and to the uses of 20 acrylic acid, vinylidene chloride, vinyl chloride, vinyl such compounds, particularly as lubricant additives. propionate, vinyl acetate, etc. The preferred monomers The polymeric materials of the present invention com which are copolymerized with the phosphonate mono prise as a monomer bis-(beta chloroethyl) vinyl phos mers are alkenes containing about 2 to 8 carbon atoms, phonate which has the following structural formula: such as, for example, ethylene, propylene, butylene, iso 25 butylene, amylene, isoamylenes, hexene, isohexenes, CICH-CH-) heptene, isoheptenes, octene and isooctenes. The pre O=P-CH-CH ferred alkene is ethylene. However, the higher mo CICH-CH-) lecular weight alkenes have the advantage that the co It has been found that this phosphonate may be poly polymerization may be carried out at relatively lower merized by heating the monomer at elevated pressures 30 pressures, frequently at the vapor pressure of the alkene employing a peroxide catalyst. It has also been found at the particular reaction temperature being employed. that this monomer may be copolymerized with other un Generally the preferred copolymers have constituent saturated organic compounds to prepare copolymers by monomers consisting of an alkene (containing about 2 carrying out the polymerization at elevated tempera to 8 carbon atoms, preferably ethylene) and bis-(beta tures and pressures employing peroxide catalysts. It 35 chloroethyl) vinyl phosphonate in the mole ratio of has further been found that either the phosphonate about 10:1 to 100:1, preferably about 20:1 to 60:1. polymer, phosphonate copolymer or mixtures thereof It will be understood, of course, that copolymers hav are very effective extreme pressure or load-carrying agents ing a mole ratio (alkene to phosphonate) of less than for lubricants, particularly mineral and synthetic lubri about 10:1 may be prepared, that is, copolymers hav cating oil compositions. 40 ing properties approaching those of the phosphonate The phosphonate polymers are prepared by heating homopolymers. By employing the aforementioned re bis-(beta chloroethyl) vinyl phosphonate at a tempera action conditions, copolymers having molecular weights ture in the range of about 90° C. to 185 C., prefer generally of about 500 to 5,000, and preferably about ably about 110° C. to 160° C., employing pressures of 600 to 3,000, may be prepared. about 100 to 10,000 p.s. i., preferably about 250 to 2500 45 It will be understood that mixtures of monomers such p.s. i. The polymerization is catalyzed by any of the as ethylene and propylene may be copolymerized with well-known peroxide polymerization catalysts. Specific the phosphonate monomer. If desired, the copolymer examples of such peroxide catalysts include benzoyl per ization reaction may be carried out using an inert diluent oxide, cumene hydroperoxide, tertiary butyl hydroper or solvent such as those previously described for pre oxide, ditertiary butyl peroxide, 2,2-bis-(tertiary butyl) 50 paring the homopolymers. The tendency of the phos peroxybutane, acetyl peroxide, acetyl benzoyl peroxide, phonate to form homopolymers in the copolymerization lauroyl peroxide, oleyl peroxide, etc., the persulfates such reaction is reduced by employing relatively high pres as the alkali persulfates (e.g. sodium, potassium, etc.), Sures and relatively high concentrations of the other ammonium persulfate, hydrogen peroxide. The pre monomer, e.g., ethylene. The reaction conditions (par ferred catalysts are organic peroxides or hydroperoxides 55 ticularly the pressures and proportions of monomers) in having the formula carrying out the copolymerization reaction may be con ROOR." trolled so as to produce a mixture of an essentially pure phosphonate polymer and a copolymer of the phos where R is an alkyl or acyl radical and R' is a hydrogen phonate and the other monomer, e.g., ethylene. Gen atom, an alkyl radical or an acyl radical. The alkyl 60 erally these mixtures may be promoted by the use of and acyl radicals preferably contain about 4 to 10 carbon relatively low pressures, e.g., 100 to 2,000 p.s. i. Under atoms. Generally from about 0.01 to 2.0% by weight, controlled reaction conditions, a solid phosphonate poly based on the monomers, will be employed. Lesser or mer as well as a liquid or semi-liquid copolymer of greater proportions may be employed if desired. the phosphonate and ethylene may be prepared in a Generally it is desired that the polymerization reac 65 tion temperature be equal to or in excess of the thermal simultaneous reaction. In this case, the phosphonate decomposition temperature of the specific peroxide cata polymer and the phosphonate-ethylene copolymer may lyst being used. This polymerization reaction may be be separately recovered and employed individually as carried out either on a batch or a continuous basis as useful lubricating oil additives. However, if desired, the desired. Generally the reaction will be carried out for 70 polymer-copolymer mixture may also be employed as a a period of time in the range of about 1 to 16 hours, lubricating oil additive. preferably about 2 to 4 hours. By employing the above The bis-(beta chloroethyl) vinyl phosphonate which is 2,956,952 3. 4. employed as a monomer in the present invention may be traction with solvents of the type of phenol, sulfur di prepared by initially reacting chloroethanol and POs in oxide, furfural, dichloroethyl ether, nitrobenzene, croton accordance with the following equation: aldehyde, etc. Hydrogenated oils or white oils may be employed as well as synthetic oils prepared, for exam o–CH-CH.Cl ple, by the polymerization of olefins or by the reaction 6CCH-CHOH -- POs - 2Peo-CH-CH.Cl -- 3H2O of oxides of carbon with hydrogen or by the hydrogena O-CH-CHC tion of coal or its products. In certain instances crack This reaction may be conveniently carried out at a tem ing coal tar fractions and coal tar or shale oil distill perature of about 100 to 500 F. The resultant tri lates may also be used. Also for special applications (chloroethyl) phosphite may then be reacted with a vinyl O various organic esters or animal, vegetable or fish oils halide in accordance with the following chemical equa or their hydrogenated, polymerized or voltolized prod tion: ucts may be employed, either alone or in admixture with mineral oils. / Synthetic lubricating oils having a viscosity of at least P-O-CH-CH2C - CH=CHBr - I5 30 SSU at 100 F. may also be used, such as esters Yo-CH-CH.Cl of monobasic acids (e.g. ester of C. Oxo alcohol with Ca Oxo acid, ester of C13 Oxo alcohol with octanoic o-CH-CH.Cl -- BrCH-CH2Cl acid, etc.), esters of dibasic acids (e.g. di-2-ethyl hexyl o–PCH=CH,O-CECHC sebacate, di-nonyl adipate, etc.), esters of glycols (e.g. 20 C. Oxo acid diester of tetraethylene glycol, etc.), com This reaction may be conveniently carried out at a tem pleX esters (e.g. the complex ester formed by reacting perature in the range of about 100 to 300 F. The one mol of sebacic acid with two moles of tetraethylene bis-(beta chloroethyl) vinyl phosphonate may also be glycol and two moles of 2-ethyl-hexanoic acid, complex prepared by reacting a vinyl halide with an alkali metal ester formed by reacting one mole of tetraethylene salt of a di-(chloroethyl) acid phosphite. Preferred 25 glycol with two moles of sebacic acid and two moles halides are those of bromine and chlorine and preferred of 2-ethyl hexanol, complex ester formed by reacting alkali metals are sodium and potassium. together one mole of azelaic acid, one mole of tetra The polymeric materials of this invention comprising ethylene glycol, one mole of Ca Oxo alcohol, and one bis-(beta chloroethyl) vinyl phosphonate as a mono mole of Ca Oxo acid), esters of phosphoric acid (e.g. the mer are very effective as extreme pressure or load-carry 30 ester formed by contacting three moles of the mono methyl ing agents in lubricants such as greases and lubricating ether of ethylene glycol with one mole of phosphorus oil compositions containing mineral oil and synthetic oxychloride, etc.), halocarbon oils (e.g.
Load more

Recommended publications
  • Synthetic Routes to Bromo-Terminated Phosphonate Films and Alkynyl Pyridine Compounds for Click Coupling
    University of Mary Washington Eagle Scholar Student Research Submissions Spring 5-7-2018 Synthetic Routes to Bromo-Terminated Phosphonate Films and Alkynyl Pyridine Compounds for Click Coupling Poornima Sunder Follow this and additional works at: https://scholar.umw.edu/student_research Part of the Biochemistry Commons Recommended Citation Sunder, Poornima, "Synthetic Routes to Bromo-Terminated Phosphonate Films and Alkynyl Pyridine Compounds for Click Coupling" (2018). Student Research Submissions. 226. https://scholar.umw.edu/student_research/226 This Honors Project is brought to you for free and open access by Eagle Scholar. It has been accepted for inclusion in Student Research Submissions by an authorized administrator of Eagle Scholar. For more information, please contact [email protected]. Synthetic Routes to Bromo-Terminated Phosphonate Films and Alkynyl Pyridine Compounds for Click Coupling Poornima Rachel Sunder Thesis submitted to the faculty of University of Mary Washington in partial fulfillment of the requirements for graduation with Honors in Chemistry (2018) ABSTRACT Click reactions are a highly versatile class of reactions that produce a diverse range of products. Copper-catalyzed azide-alkyne cycloaddition (CuAAC) click reactions require an azide and a terminal alkyne and produce a coupled product that is “clicked” through a triazole ring that can have a variety of substituents. In this work, bromo-terminated phosphonate films on copper oxide surfaces were explored as the platform for click coupling, as the terminal azide needed for the reaction can be generated through an in situ SN2 reaction with a terminal bromo group. The reactions were characterized using model reactions in solution before being conducted on modified copper oxide surfaces.
    [Show full text]
  • H-Phosphonates: Versatile Synthetic Precursors to Biologically Active Phosphorus Compounds*
    Pure Appl. Chem., Vol. 79, No. 12, pp. 2217–2227, 2007. doi:10.1351/pac200779122217 © 2007 IUPAC H-Phosphonates: Versatile synthetic precursors to biologically active phosphorus compounds* Adam Kraszewski1,‡ and Jacek Stawinski1,2,‡ 1Institute of Bioorganic Chemistry, Polish Academy of Sciences, Noskowskiego 12/14, 61-704 Poznan, Poland; 2Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, S-10691 Stockholm, Sweden Abstract: In this review, a short account of H-phosphonate chemistry and its application to the synthesis of biologically important phosphates and their analogs is given. Keywords: H-phosphonates; phosphate analogs; biological activity; nucleic acids; drugs. INTRODUCTION Located at the crossroad of various bioinformation exchange pathways, phosphorus-containing com- pounds play a key role in living organisms as carriers of genetic information and important signalling, regulatory, energy transfer, and structural compounds [1]. Due to this pivotal role, biologically impor- tant phosphorus compounds have become therapeutic targets in various modern medicinal techniques, such as antisense [2] and antigene [3] approaches to modulation gene expression, or a gene silencing technique using short interfering RNA (siRNA) [4]. To maximize the desired biological effect and to minimize cytotoxicity, a biologically active com- pound has to have very precisely adjusted chemical and pharmacokinetic properties. This can be achieved by, e.g., changing pKa values of the ionizeable functions, changing electronegativity of the substituents, their size, hydrophobicity, etc. These features can also influence transport of a drug across cell membranes, its preferential degradation in normal or activation in the neoplastic or virus-infected cells, and can contribute to the overall efficiency of the drug. A prominent example here are antiviral pronucleotides in which the phosphate moiety is masked with alkyl or aryl groups that are removed chemically and enzymatically in cells to produce an active antiviral nucleotide [5].
    [Show full text]
  • The Hydrolysis of Phosphinates and Phosphonates: a Review
    molecules Review The Hydrolysis of Phosphinates and Phosphonates: A Review Nikoletta Harsági and György Keglevich * Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, 1521 Budapest, Hungary; [email protected] * Correspondence: [email protected]; Tel.: +36-1-463-1111 (ext. 5883) Abstract: Phosphinic and phosphonic acids are useful intermediates and biologically active com- pounds which may be prepared from their esters, phosphinates and phosphonates, respectively, by hydrolysis or dealkylation. The hydrolysis may take place both under acidic and basic conditions, but the C-O bond may also be cleaved by trimethylsilyl halides. The hydrolysis of P-esters is a challenging task because, in most cases, the optimized reaction conditions have not yet been explored. Despite the importance of the hydrolysis of P-esters, this field has not yet been fully surveyed. In order to fill this gap, examples of acidic and alkaline hydrolysis, as well as the dealkylation of phosphinates and phosphonates, are summarized in this review. Keywords: hydrolysis; dealkylation; phosphinates; phosphonates; P-acids 1. Introduction Phosphinic and phosphonic acids are of great importance due to their biological activity (Figure1)[ 1]. Most of them are known as antibacterial agents [2,3]. Multidrug- resistant (MDR) and extensively drug-resistant (XDR) pathogens may cause major problems Citation: Harsági, N.; Keglevich, G. in the treatment of bacterial infections. However, Fosfomycin has remained active against The Hydrolysis of Phosphinates and both Gram-positive and Gram-negative MDR and XDR bacteria [2]. Acyclic nucleoside Phosphonates: A Review. Molecules phosphonic derivatives like Cidofovir, Adefovir and Tenofovir play an important role 2021, 26, 2840.
    [Show full text]
  • Discovery of Phosphonic Acid Natural Products by Mining the Genomes of 10,000 Actinomycetes
    Discovery of phosphonic acid natural products by mining the genomes of 10,000 actinomycetes Kou-San Jua, Jiangtao Gaoa, James R. Doroghazia, Kwo-Kwang A. Wanga, Christopher J. Thibodeauxa, Steven Lia, Emily Metzgera, John Fudalaa, Joleen Sua, Jun Kai Zhanga,b, Jaeheon Leea, Joel P. Cionia,b, Bradley S. Evansa, Ryuichi Hirotaa,c, David P. Labedad, Wilfred A. van der Donka,e,1, and William W. Metcalfa,b,1 aCarl R. Woese Institute for Genomic Biology, University of Illinois, Urbana, IL 61801; bDepartment of Microbiology, University of Illinois, Urbana, IL 61801; cDepartment of Molecular Biotechnology, Graduate School of Advanced Sciences of Matter, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8530, Japan; dBacterial Foodborne Pathogens and Mycology Research, US Department of Agriculture, Agricultural Research Service, National Center for Agricultural Utilization Research, Peoria, IL 61604; and eDepartment of Chemistry and Howard Hughes Medical Institute, University of Illinois, Urbana, IL 61081 Edited by Jerrold Meinwald, Cornell University, Ithaca, NY, and approved July 31, 2015 (received for review January 14, 2015) Although natural products have been a particularly rich source of generally adopted. If we hope to revitalize the use of natural human medicines, activity-based screening results in a very high products in the pharmaceutical industry, genome mining must be rate of rediscovery of known molecules. Based on the large number shown to be a high-throughput discovery process complementary of natural product biosynthetic genes in microbial genomes, many or superior to existing methods (13, 14). Here, we demonstrate the have proposed “genome mining” as an alternative approach for feasibility of this approach in a campaign to identify the full ge- discovery efforts; however, this idea has yet to be performed ex- netic repertoire of phosphonic acid natural products encoded by a perimentally on a large scale.
    [Show full text]
  • Addition of A-Lithioalkane Phosphonates to Nitriles, Synthesis of ；3-Keto Phosphonate and Enamine Phosphonates
    Communications to the Editor Bull. Korean Chem. Soc., Vol. 10, No. 6, 1989 613 Addition of a-Lithioalkane Phosphonates to Nitriles, Synthesis of ；3-Keto Phosphonate and Enamine Phosphonates Kilsung Lee and Dong Young Oh * Department of Chemistry, Korea Advanced Institute of Science and Technology, Seoul 130-650 Received August 28, 1989 ^-Keto phosphonates bearing a a -hydrogen are in­ 0 0 N" 0 NH teresting for the conversion under Wittig-Horner condition (EtO)J다% .1，叶如닌T (EtO)5PCH--CPh 二二 (EtO)?PCH-CPh into the corresponding ff,/3-unsaturated ketones.1 fi-Keto £ S 2. PhCN £ c phosphonates fully substituted at the a-carbon do not find 4 5 such frequent use as synthetic intermediates, but because the geometry and spatial demands of phosphorus group are comparable to those of quaternary carbon, the isosteric re­ placement of carbon with phosphorus has been studied in biologically active molecules.2 In marked contrast to a number of investigations that in­ corporate phosphonate reagents or focus on the biological ac­ tivities of phosphonates, r이atively little work has appeared describing general new synthesis of this functionality (par­ ticularly in case of fully substituted /9-keto phosphonate).3 Recently developed reaction of dialkyl phosphoro chloridites with a -hydroxy carbonyl compounds in the presence of a a-hydrogen dimerized products were obtained as side pro­ Lewis acid is a good candidate for fully substituted g-ket。 ducts, as previously reported by G. Sumrell.5*2 In the case of phosphonates.4 However, its process is limited due primary an phenyl or thiophenyl substituent on the carbon to the to the availability of starting material.
    [Show full text]
  • Cyclophostin, (±)-Cyclipostin P, Their Phosphonate Analogs and New
    University of Missouri, St. Louis IRL @ UMSL Dissertations UMSL Graduate Works 8-2-2011 Synthesis of (±)-Cyclophostin, (±)-Cyclipostin P, Their hoP sphonate Analogs and New Chemistry of Vinyl Phosphonates Raj Kumar Malla University of Missouri-St. Louis, [email protected] Follow this and additional works at: https://irl.umsl.edu/dissertation Part of the Chemistry Commons Recommended Citation Malla, Raj Kumar, "Synthesis of (±)-Cyclophostin, (±)-Cyclipostin P, Their hospP honate Analogs and New Chemistry of Vinyl Phosphonates" (2011). Dissertations. 416. https://irl.umsl.edu/dissertation/416 This Dissertation is brought to you for free and open access by the UMSL Graduate Works at IRL @ UMSL. It has been accepted for inclusion in Dissertations by an authorized administrator of IRL @ UMSL. For more information, please contact [email protected]. Synthesis of (±)-Cyclophostin, (±)-Cyclipostin P, Their Phosphonate Analogs and New Chemistry of Vinyl Phosphonates by Raj Kumar Malla A Dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy (Chemistry) University of Missouri-St. Louis August, 2011 Committee Prof. Christopher D. Spilling (Chair and Advisor) Prof. Alexei V. Demchenko Prof. Cynthia M. Dupureur Prof. Eike B. Bauer Abstract Synthesis of (±)-Cyclophostin, (±)-Cyclipostin P, Their Phosphonate Analogs and New Chemistry of Vinyl Phosphonates Raj Kumar Malla Doctor of Philosophy University of Missouri-St. Louis Prof. Christopher D. Spilling, Advisor This work is divided into 2 parts: a) total synthesis of (±)-cyclophostin, (±)-cyclipostin P and their monocyclic analogs b) development of a metathesis based methodology for transformation of vinyl phosphonates. Cyclophostin (1) and cyclipostins (2) are bioactive natural bicyclic organophosphates.
    [Show full text]
  • Wittig and Wittig-Horner Reactions Under Phase Transfer Catalysis
    CEJC 4(2003)491{542 Review article Wittigand Wittig-Horner reactions underphase transfer catalysis conditions AureliaPascariu, Gheorghe Ilia ¤,AlinaBora, Smaranda Iliescu, AdrianaPopa, Gheorghe Dehelean and Liliana Pacureanu Institute ofChemistry, Romanian A cademy, 24M. Viteazul Bv., R300223Timisoara, Romania Received 2April 2003;accepted 11August 2003 Abstract: Wittig andWittig-Horner reactions arefavorite tools in preparative organic chemistry.Theseole­ nation methodsenjoy widespread andrecognition becauseof their simplicity,convenience, ande¯ ciency.Phase transfer catalysis (PTC) is avery important methodin synthetic organicchemistry havingmany advantages over conventional, homogenous reaction procedures. Inthis paper, weattempt to summarizethe aspects concerningWittig andWittig-Horner reactions that take place under phasetransfer catalysis conditions. c Central EuropeanScience Journals. All rights reserved. ® Keywords: Wittig reactions, Wittig-Horner reactions, phasetr ansfercatalysis 1Introduction Thanks to numerous theoretical and practical implications,the modern chemistry of phosphorus draws increasing attention. Many scientists havededicated their work inves- tigating someof the unexplained aspects of organophosphorus compounds. They have synthesized new compounds and haveused them inthe new ¯eldof ¯ne organic synthesis or in order to clarifysome of the reaction mechanisms. Although vast literature concerning phase transfer catalysisis available, information concerning the Wittig and Wittig-Horner reactions are treated separately,not
    [Show full text]
  • Pyridine and Phosphonate Containing Ligands for Stable Lanthanide Complexation
    Pyridine and phosphonate containing ligands for stable lanthanide complexation. An experimental and theoretical study to assess the solution structure M. Mato-Iglesias, E. Balogh, C. Platas-Iglesias, É. Tóth, A. de Blas, T.R. Blas To cite this version: M. Mato-Iglesias, E. Balogh, C. Platas-Iglesias, É. Tóth, A. de Blas, et al.. Pyridine and phosphonate containing ligands for stable lanthanide complexation. An experimental and theoretical study to assess the solution structure. Dalton Transactions, Royal Society of Chemistry, 2006, 45, pp.5404- 5415. 10.1039/b611544f. hal-00512396 HAL Id: hal-00512396 https://hal.archives-ouvertes.fr/hal-00512396 Submitted on 30 Jun 2021 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. Distributed under a Creative Commons Attribution| 4.0 International License Pyridine and phosphonate containing ligands for stable lanthanide complexation. An experimental and theoretical study to assess the solution structure† Marta Mato-Iglesias,a Edina Balogh,b Carlos Platas-Iglesias,*a Eva´ Toth,´ b,c Andres´ de Blas*a and Teresa Rodr´ıguez Blasa We report an experimental and theoretical study of the stability and solution structure of lanthanide complexes with two novel ligands 2 3 containing pyridine units and phosphonate pendant arms on either ethane-1,2-diamine (L ) or cyclohexane-1,2-diamine (L ) backbones.
    [Show full text]
  • Synthesis and Mechanisms of Phosphoramidates
    Review Openingmolecules Up the Toolbox: Synthesis and Mechanisms of Phosphoramidates Emeka J.Review Itumoh 1,2,3, Shailja Data 1,3 and Erin M. Leitao 1,3,* 1 SchoolOpening of Chemical Sciences, up the The Toolbox:University of Auckland, Synthesis 23 Symonds and Street, Mechanisms Auckland 1010, Newof Zealand; Phosphoramidates [email protected] (E.J.I.); [email protected] (S.D.) 2 Department of Industrial Chemistry, Ebonyi State University, Abakaliki 480001, Ebonyi State, Nigeria 3 The MacDiarmidEmeka J. Itumoh Institute1,2,3 for, Shailja Advanced Data 1,3 Materialsand Erin and M. LeitaoNanotechnology,1,3,* Wellington 6140, New Zealand * Correspondence:1 School of Chemicalerin.leitao@ Sciences,auckland.ac.nz; The University Tel.: of Auckland, +64-9923-5567 23 Symonds Street, Auckland 1010, New Zealand; [email protected] (E.J.I.); [email protected] (S.D.) Academic Editor: Frederik Wurm 2 Department of Industrial Chemistry, Ebonyi State University, Abakaliki 480001, Ebonyi State, Nigeria 3 Received: 3 TheJuly MacDiarmid 2020; Accepted: Institute 11 for Augu Advancedst 2020; Materials Published: and Nanotechnology, 12 August 2020 Wellington 6140, New Zealand * Correspondence: [email protected]; Tel.: +64-9923-5567 Abstract:Academic This review Editor: Frederik covers Wurm the main synthetic routes to and the corresponding mechanisms of phosphoramidateReceived: 3 July formation. 2020; Accepted: The 11 August synthetic 2020; Published: routes 13can August be 2020separated into six categories: salt elimination,Abstract: oxidativeThis review cross-coupling, covers the main azide, synthetic reduction, routes to andhydrophosphinylation, the corresponding and phosphoramidate-aldehyde-dienophilemechanisms of phosphoramidate formation. (PAD). The Examples synthetic routesof some can be separatedimportant into compounds six synthesizedcategories: through salt elimination,these routes oxidative are provided.
    [Show full text]
  • Functional Metal Phosphonates
    FUNCTIONAL METAL PHOSPHONATES A Dissertation by HOUSTON PHILLIPP PERRY 1 1 Submitted to the Office of Graduate Studies of Texas A&M University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY 1 December 2011 Major Subject: Chemistry 2 2 2 Functional Metal Phosphonates Copyright 2011 Houston Phillipp Perry FUNCTIONAL METAL PHOSPHONATES A Dissertation by HOUSTON PHILLIPP PERRY Submitted to the Office of Graduate Studies of Texas A&M University in partial fulfillment of the requirements for the degree of 3 3 DOCTOR OF PHILOSOPHY Approved by: Chair of Committee, Abraham Clearfield Committee Members, Timothy Hughbanks Hongcai Zhou 3 Jaime Grunlan Head of Department, David Russell December 2011 Major Subject: Chemistry iii ABSTRACT Functional Metal Phosphonates. (December 2011) Houston Phillipp Perry, B.S., Texas A&M University Chair of Advisory Committee: Dr. Abraham Clearfield The primary goal of the work described in this dissertation was the incorporation of functionality into metal phosphonates. This was done in one of several ways. The first involved using phosphonate ligands that had covalently attached organic functional groups. In some cases, these ligands undergo reactions during the solvothermal syntheses which can impart new chemical reactivity. Another method used to introduce functionality was to iii iii partially or completely substitute metal atoms within phosphonate clusters to create materials which may have interesting magnetic properties. By controlling the way these clusters pack in the solids, their magnetic properties may be able to be augmented. The final method used to impart functionality to metal phosphonates was the incorporation of N- donor and bulky aryl groups into the phosphonate ligands.
    [Show full text]
  • 6004X0489.Pdf
    Pure & Appl. Chem., Vol. 60, No. 4, pp. 489493, 1988. Printed in Great Britain. @ 1988 IUPAC Kinetics and mechanism of the hydrolysis of functional groups in the side-chain of macrocyclic Cu2+-com piexes Daniel Tschudin and Thomas A. Kaden Institute of Inorganic Chemistry, Spitalstr.51, CH 4056 Basel, Switzerland Abstract- A series of functionalized tetraazamacrocycles 2-8 carrying in their pendant side-chain a group which can be hydrolyzed, have been synthesised and their Cu(I1) complexes prepared. The structure analysis of the Cu(I1) complex with 5 shows a pentacoordinate Cu(I1) surrounded by the four nitrogens of the macrocycle and the carbonyl oxygen of the ester group in a distorted square pyramidal geometry. Whereas the Cu(I1) complexes with the amide derivatives 7 and 8 do not react, the nitrile, the esters of the carbonic acids and of the phosphonate are hydrolyzed in alkaline solution. The kinetics of these reactions were measured and the rate constants determined. The pH-profiles log k/pH are linear with pH for the esters 3-5, whereas those of the nitrile 2 and the phosphonate ester 6 exhibit a plateau at high pH. This allows to state that the hydrolysis of these last two compounds proceeds through an internal OH- attack. For the mechanism of the carbonic acid ester hydrolysis several possibilities are discussed, but no definitive choice is yet possible. INTRODUCTION In several esterases and peptidases metal ions play an important role at the active site (ref.1). In general they are essential for activity and it is thought that the metal ion acts as a Lewis-acid and polarizes the bonds of the reactive group so that a nucleophilic attack is facilitated and thus hydrolysis takes place.
    [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]