DOCSLIB.ORG

Synthesis and Characteristics of Phosphonate- Containing Maleimide Polymers

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Synthesis and Characteristics of Phosphonate- Containing Maleimide Polymers Polymer Journal, Vol.33, No. 9, pp 676—684 (2001) Synthesis and Characteristics of Phosphonate- Containing Maleimide Polymers ∗,∗∗ ∗,† ∗∗ Wei-Jye SHU, Li-Hsiang PERNG, and Wei-Kuo CHIN ∗Department of Chemical Engineering, Ta-Hwa Institute of Technology, Chiung-Lin, 307 Hsinchu, Taiwan, Republic of China ∗∗Department of Chemical Engineering, National Tsing Hua University, 300 Hsinchu, Taiwan, Republic of China (Received March 12, 2001; Accepted May 17, 2001) ABSTRACT: Phosphonate-containing N-phenyl maleimide monomers were synthesized by a two-step reaction. All maleimide polymers were synthesized by free radical polymerization in toluene solution using azobis(isobutyronitrile) (AIBN) as initiator. The structures of the maleimide monomers were identified by 1H, 13C, 31P-NMR, and element analysis. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TG) were used to analyze the thermal properties of the polymers. The degree of polymerization in phosphonate-containing maleimide polymers should be affected by side chains. The introduction of phosphonate into a side chain of maleimide polymer may reduce the glass transition temperature (Tg) and thermal stability, but increase char yield of solid residue as an excellent flame retardant. Tg and thermal stability of the phosphonate-containing maleimide polymers depended on substitution of the phenyl ring in the side chain. Phosphonate-containing maleimide polymers with halogen or sulfur atom may combine the flame retarding mechanism of gas-phase and solid-phase to promote their flame retardancy. KEY WORDS Phosphonate-Containing Maleimide Polymers / Flame Retardant / The combustibility of organic polymers limits their properties, studies of phosphorus-containing flame re- application. Therefore, the development of organic tardant have changed gradually from additive type to polymers with flame retardancy has become an impor- reactive type. tant study topic. Traditional flame retarding polymers N-substituted maleimide monomers, such as N- are prepared from physical blending with flame retard- phenylmaleimide (PM), N-hydroxyphenylmaleimide ing additives.1, 2 Flame retarding additives are always (HPM) and halogen-substituted N-hydroxyphenylm- halogens. Halogen ions catch free radicals released aleimide (XHPM), are usually designed to modify ther- during combustion and interrupt combustion reactions mal stability and fire resistance of organic matrix ma- to get higher flame resistance. Nevertheless, such de- terials.5–8 All these monomers are homopolymerized composition reactions release simultaneously smoke or copolymerized with monomers such as styrene for and toxic substances. The applications of halogen- the purpose of materials-modification. Copolymers, for containing flame retardants are limited due to more and example, of PM with styrene,9–11 methyl methacry- more strict environment laws. In contrast, the devel- late,12–14 acrylonitrile15 or vinyl acetate16 have higher opment of non-halogen flame-retardants, such as the thermal stability and fire resistance. HPM polymer phosphorus-containing flame-retardants with the lower use is limited since the phenol group induces chain smoke density and toxicity will become the mainstream transfer during polymerization to lead lower polymer- in the future. Like halogens, phosphorus-containing ization. The introduction of substituted side groups compositions evolved in gas phase catch free radicals in the HPM monomer17 promote polymerization. released during combustion and interrupt combustion Halogen-substituted XHPM polymers possess thermal reactions. The thermal decomposition of phosphorus- stability from imide ring and flame retardancy from containing polymer, mainly having a flame retarding halides.18–20 Studies on phosphorus-introduced flame ability in condensed phase,3 produces condensation re- retardant systems are few in the literature.21 We de- actions and catalyzes the chain transfer of carbonization signed N-phenylmaleimide polymers with different to form high char yield of solid residue. The char layer substituted phosphonate-containing side groups to prevent heat transfer, brings down the burning temper- study thermal stability and flame retarding properties. ature and inhibits the release of combustible gas to get a fine fireproof effect.3, 4 Due to restrictions in applica- tions for some reasons such as processing or physical †To whom correspondence should be addressed (Tel: +886-3-5923551, Fax: +886-3-5927310, E-mail: [email protected] (Li-Hsiang Perng)). 676 Phosphonate-Containing Maleimide C–OH); 168.4 (2–C=O). EA(%): C, 63.1; H, 3.8; N, EXPERIMENTAL 7.1 (calc.: C, 63.5; H, 3.7; N, 7.4). N-(2,6-Dibromo-4-hydroxyphenyl)maleimide Materials (DBHPMI).24 With the same type of flask as 4-Aminophenol, 3-aminophenol, 4-amino-2,6-dib- above, 10 g (0.0288 mol) 4-amino-2,6-dibromophenol romophenol, maleic anhydride, and cuprous (I) chlo- were added gradually to a solution of maleic anhydride ride were obtained from Lancaster. Acetic anhydri- (3.5 g) in 50 mL THF and the mixture was stirred 5 h de and triethylamine (TEA) were obtained from TE- in a water bath to obtain a clear amic acid solution. DIA. Diethyl chlorophosphonate (DECP), diphen- The mixture including stoichiometric amounts of ylphosphoryl chloride (DPPC), and diethyl chloroth- acetic anhydride, 0.5 g cobalt acetate and 1.5 g TEA, iophosphonate (DECTP) were obtained from Aldrich was added dropwise to this solution of amic acid Chemicals. Cobalt acetate was obtained from Showa. already raised temperature to 80◦C. After stirring 5 h, All reagents were used as received. Tetrahydrofu- the mixture was distilled to remove THF and obtain ran (THF) was distilled after dehydration with sodium. the precipitate. The precipitate was washed several N,N-Dimethylformamide (DMF) was dried over CaH2. times with de-ionic water to reach a neutral state and Other solvents were purified by conventional methods. recrystallized several times with ethyl acetate/n-hexane to obtain the bromine-containing N-phenyl maleimide Synthesis monomer dried under reduced pressure. , N-Hydroxyphenylmaleimide.22 23 In a three-neck Yield 60% as fine golden yellow needles, mp 202– flask equipped with a teflon-stirrer and a thermometer 203◦C. 1H NMR (d- chloroform), δ (ppm): 6.84 (2 H, and purged with nitrogen gas at a constant flow rate, s, –CO–CH=CH–CO–); 6.65 (2 H, s, 2–H,6–H); 10 g (0.0917 mol) of 3-(or 4)-aminophenol were added 3.64 (1 H, 4–OH). 13C NMR (d-chloroform), δ (ppm): gradually into the solution of maleic anhydride (11 g) 115.5 (3–C,5–C); 122.6 (1–C–N–); 128.5 (2–C,6– in 50 mL of DMF and the mixture was stirred 2 h in C); 134.5 (–CO–CH=CH–CO–); 157.1 (4–C–OH); a water bath to obtain a clear amic acid solution. A 170.4 (2–C=O). EA (%): C, 34.0; H, 1.5; N, 4.2 (calc.: mixture of 5.5 g phosphorus pentaoxide, 2.5 g sulfuric C, 34.6; H, 1.4; N, 4.0). acid and 50 mL DMF was then added dropwise to the Phosphonate-containing Monomers.25 The flask as ◦ amic acid solution, already raised temperature to 80 C, above with ice bath was charged with 100 mL THF over a period of 1 h. After stirring for 6 h, the mix- and added to a mixture of 0.016 mol N-hydroxy- ture was cooled and poured into 500 mL ice water to phenylmaleimide, 3 mL TEA and 0.012 g Cu2Cl2.A obtain the precipitate by filtering. The precipitate was solution of 0.0192 mol chlorophosphonate (such as di- washed several times with de-ionic water and recrys- ethyl chlorophosphonate, DECP 3.3 g) in 50 mL THF tallized several times with isopropanol to obtain the N- was added gradually to the mixture during 2 h. The re- phenylmaleimide monomer dried under reduced pres- action was kept at room temperature for 12 h. The mix- sure. ture was filtered to remove the precipitate of amine hy- (i) N-(3-Hydroxyphenyl)maleimide (3HPMI). drochloride and distilled to remove THF to obtain the ◦ 1 Yield 64% as straw yellow powder, mp 137–138 C. H precipitate. The precipitate was dissolved in 100 mL NMR(DMSO), δ(ppm): 6.73(2 H, m, 2 –H, and 4 – ethyl acetate and extracted by 1% NaOH solution to H or 6 –H); 6.88 (1 H, dd, J = 8.2 and 2.4 Hz, 4 – obtain the organic layer. The organic layer was iso- H or 6 –H); 7.13 (2 H, s, –CO–CH=CH–CO–); 7.24 lated and dried with anhydrous magnesium sulfate. The (1 H, dd, J = 8.2 and 8.2 Hz, 5 –H); 4.05 (1 H, s, 3 – organic layer was recrystallized with n-hexane to ob- OH). 13C NMR (DMSO), δ (ppm): 113.8 (2 –C); 114.7 tain the phosphonate-containing N-phenyl maleimide (4 –C); 117.2 (6 –C); 129.5 (5 –C); 132.4 (1 –C–N–); monomer dried under reduced pressure. 134.6 (–CO–CH=CH–CO–); 157.6 (3 –C–OH); 169.9 (i) Diethyl (3-(N-maleimido) phenyl) phosphonate (2–C=O). EA(%): C, 63.0; H, 3.9; N, 7.0 (calc.: C, (3MIP). Yield 78% as a dark brown liquid, 1H NMR 63.5; H, 3.7; N, 7.4). (d-chloroform), δ (ppm): 7.38 (1 H,d, 2–H); 7.14 (ii) N-(4-Hydroxyphenyl)maleimide (4HPMI). (1 H,d, 6–H); 7.29 (2 H, d, 4–H,5–H); 6.83 (2 H, s, – ◦ Yield 71% as orange needles, mp 185–186 C. 1H NMR CO–CH=CH–CO–); 3.87 (2 H, q, O–CH –CH ); 1.65 2 3 (d-chloroform), δ (ppm): 7.38 (2 H,d, 2 –H,6–H); (3 H, t, O–CH –CH ). 13C NMR (d-chloroform), δ 2 3 7.19 (2 H, d, 3 –H,5–H); 6.83 (2 H, s, –CO–CH=CH– (ppm): 151.5 (3–C–O–P), 130.5 (5–C); 132.4 (1– 13 CO–); 3.70 (1 H, 4 –OH).
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]
  • 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.
    [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]