DOCSLIB.ORG

United States Patent Office Patented Aug

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
United States Patent Office Patented Aug 3,598,829 United States Patent Office Patented Aug. 10, 1971 2 3,598,829 The term lower alkyl is intended to include those hav CERTAIN SOXAZOLYLPYRONES AND ing 1 to 4 carbon atoms. The term halo is intended to SOTHAZOLYLPYRONES include chlorine, bromine, iodine and fluorine. Victor John Bauer, Montvale, and Sidney Robert Safir, e In general, the compounds are crystalline solids, soluble River Edge, N.J., assignors to American Cyanamid in Water. Company, Stamford, Conn. No Drawing. Continuation-in-part of application Ser. No. The compounds of the present invention may be pre 662,281, Aug. 22, 1967, which is a continuation-in-part pared by either of several general reaction sequences. of application Ser. No. 535,714, Mar. 21, 1966. This Thus, a 1-(4-pyridyl)-1,3-alkyldione or a 1-(4-pyridyl)- application Nov. 10, 1969, Ser. No. 875,524 1,3-alkyldione salt is reacted with a hydroxylamine salt int. C. C07d 31/48 O Such as the hydrochloride, in a polar solvent, such as U.S. C. 260-294.8D 9 Claims Water or alcohol, at a temperature of 25 to 100° C. for a time of one minute to twenty-four hours with or with out the addition of a base, such as sodium carbonate, to ABSTRACT OF THE DESCLOSURE provide either a 4-isoxazolylpyridine or a 1-(4-pyridyl)- 5 1,3-alkyldione oxime. When an oxime is formed, it is con This application describes the preparation of isoxazolyl Verted to a 4-isoxazolylpyridine by treatment with a de pyridines and isothiazolylpyridines as new compounds and hydrating agent, such as acetyl chloride or concentrated also their use in preparing the corresponding quaternary Sulfuric acid, at a temperature of 0 to 100° C. for a time isoxazolylpyridinium salts and quaternary isothiazolyl of one minute to twenty-four hours. Alternatively, an pyridinium salts. The quaternary isoxazolylpyridinium acetylene is allowed to react with a pyridine nitrile oxide, salts and quaternary isothiazolylpyridinium salts are use formed in situ from an isonicotinohydroxamyl chloride ful for their hypoglycemic activity. and triethylamine, to provide a 4-isoxazolylpyridine. For the Synthesis of isothiazolylpyridinium salts, and isoxa This application is a continuation-in-part of our appli Zolylpyridine is hydrogenated to provide an amino-pyr cation Ser. No. 662,281, filed Aug. 22, 1967, now U.S. 25 idyl-butenone, which is fused with phosphorus penta Pat. 3,511,848, which in turn is a continuation-in-part of Sulfide to provide an isothiazolylpyridine. our application Ser. No. 535,714, filed Mar. 21, 1966, These reactions are illustrated as follows: now abandoned. Method A PRIOR ART 30 Applicants are aware of British Pat. 875,887, directed R-éCH-5-( N or to pyridinium salts. However, the subject matter of the present application is not disclosed therein. R SUMMARY OF THE INVENTION QNa 9 NEOH.HCl 35 R-C-cCEIC- Y Nr. -, ( -- or This invention relates to new organic compounds. More SN- R1 particularly, it relates to isoxazolylpyridines and isothi R1 azolylpyridines, intermediates for preparation of quater NOH. O. NOH nary isoxazolylpyridinium salts and quaternary isothi azolylpyridinium salts. 40 The new compounds of the present invention may be illustrated by the following formula: R Nott S. R -41s. N. R-(-CH,-( N - 4 O Nz1 CD 45 ==/ N-1 R R1 R1 wherein R is selected from the group consisting of hydro gen, lower alkyl, and trihalo (lower) alkyl, R is selected RCCH2C-Not Y , R-4 ty Y from the group consisting of hydrogen and lower alkyl, No-1 k, Z is a trivalent radical selected from the group con 50 R1 sisting of Method B NOE h, $, N% -(-C) r-r-wlers =N -N - O Null and I Ri N R -S N^ so Resor;RC 4 YN and the dotted line represents one double bond, the posi 60 YN2 tion of which is dependent upon the definition of Z. When R1 R1 Z is Method C N / R -.) NH O NSo-1 N- (DN - R-(-CH- YN/ N R1 -- R NH O the double bond is adjacent to R and when Z has the 70 R-(-CH-)- N - N Y- S. other meanings, the double bond is adjacent to the pyr Ns 1 1 idinium ring. R1 R 3,598,829 4 Oral hypoglycemic activity is also observed in other species. For example, 1-methyl-4-(3-methyl-5-isoxazolyl)- pyridinium chloride, when administered to normal cock erels and guinea pigs causes a reduction in blood sugar levels. In addition, 1 - methyl-4-(3-methyl-5-isoxazolyl)- pyridinium chloride displays pronounced hypoglycemic activity in mice rendered experimentally hyperglycemic by an intravenous injection of alloxan. These results are recorded in Table II. O TABLE II.-ORAL HYPO GLYCEMIC ACTIVITY 1 OF1-METH YL-5-ISOXAZOLYL)PYRIDINIUM CELORIDE IN COCKER ELS, GUINEA PIGS AND ALLOXANIZED MICE wherein R and R1 are as hereinbefore defined. Time Percent The 4 - isoxazolylpyridines and 4-isothiazolylpyridines Dose, after reduction 2 are quaternized to 4-isoxazolylpyridinium salts and 4 Immolf dosing, in blood isothiazolylpyridinium salts by reaction with a lower alkyl, 5 Species and treatment kg. hrs. glucose lower alkenyl, cycloalkyl (lower) alkyl, or lower alkoxy Cockerels, drug (10)------------------ 1.99 2 343-47 Guinea pigs, saline (10), drug (6) ----- 5 6 13-2 (lower) alkyl halide at a temperature of 0 to 150 C. 354-6 with or without a solvent, such as alcohol, for a time Alloxanized mice, saline (28), drug (27). 0. 4 1-2 of one minute to twenty-four hours in an open vessel or 347-5 a sealed bomb. 20 i Cockerels and guinea pigs were fasted 24 hours before dosing. Food was withheld from all animals after dosings. Among the compounds of the present invention, are, 2 Values are means == SE. of number of animals indicated in parentheses for example, 4-(3-methyl - 5 - isoxazolyl)pyridine, 4-(3- and are expressed as percent reduction from predose levels or from Saline control in the case of cockerels (blood glucose of 10 saliane control cockerels ethyl - 5 - isoxazolyl)pyridine, 4 - (3 - cyclopropyl-5- was 143als 5 mg. percent). isoxazolyl)pyridine, 4 - (3 - trifluoromethyl-5-isoxazolyl) 3 Significantly different from control. pyridine, 4 - (5 - trifluoromethyl - 3 - isoxazolyl)pyridine, 25 These results show that the compounds prepared from 4 - (5 - isoxazolyl)pyridine, 4 - (5 - methyl-3-isoxazolyl) the intermediates of the present invention are useful in pyridine, 3 - methyl - 4 - (3 - methyl - 5 - isoxazolyl)pyr the lowering of blood glucose in normal and hypergly idine, 4 - (5 - methyl - 3 - isothiazolyl)pyridine and 4-(3- cemic warm-blooded animals. methyl-5-isothiazolyl)pyridine. The compounds prepared from the intermediates of this The compounds directly prepared from the intermedi 30 invention can be used in compositions such as tablets; the ates of the present invention show hypoglycemic activity principal active ingredient is mixed with conventional based on the following data which shows a reduction in tableting ingredients such as corn starch, lactose, sucrose, blood sugar levels in mice, guinea pigs and cockerels. Sorbitol, talc, Stearic acid, magnesium stearate, dicalcium When the compounds are administered orally to normal phosphate, gums, and fractionally similar materials as mice, a reduction of blood sugar levels is observed. Mice pharmaceutical diluents or carriers. The tablets or pills used in these studies are MF-1 (Manor Farms, 18-25 of the novel compositions can be laminated or otherwise grams). The compounds are administered by gavage as compounded to provide a dosage form affording the ad saline solutions. Control animals receive an equivalent vantage of prolonged or delayed action or predetermined volume of vehicle. Food is withheld from animals after Successive action of the enclosed medication. For ex dosing. Blood glucose is determined 2 to 6 hours after 40 ample, the tablet or pill can comprise an inner dosage and dosing by the method of Hoffman J. Biol. Chem., 120, an Outer dosage component, the latter being in the form 51 (1937) as adapted to the Technicon AutoAnalyzer® of an envelope over the former. The two components can and is expressed as percent change from saline controls. be separated by an enteric layer which serves to resist Blood samples are obtained from the tail veins of mice. disintegration in the stomach and permits the inner com The testing data is summarized in Table I. 45 ponent to pass intact into the duodenum or to be delayed TABLE I.--DECREASE IN BLOOD GLUCOSE IN NORMAL, MICE, AFTER, ORAL ADMINIS TRATION OF SOXAZOLYLEPYRIDINIUM SALTS Percent decrease in blood glucose, dose, Hours Eng./kg. after Compound dosing 25 250 500 1-methyl-4-(3-methyl-5-isoxazolyl)pyridinium chloride 36-5 08 695 1-methyl-4-(3-ethyl-5-isoxazolyl)pyridinium chloride 243 4-7 637 1-allyl-4-(3-methyl-5-isoxazolyl)pyridinium chloride -9 98 39-14 1-methyl-4-(5-isoxazolyl)pyridinium chloride----- 2 24.4 6 10.6 24.2 48 25.2 34-3 07 2. 1,3-dimethyl-4-(3-methyl-5-isoxazolyl)pyridinium chloride.------------- 2 122 277 304 k 1410 36-13 768 All 2-3 763 1-(2-methoxyethyl)-4-(3-methyl-5-isoxazolyl)pyridinium chloride------ 8-7 263 30-7 t as 7 5-6 31.13 9 97 221 -methyl-4-(5-trifluoromethyl-3-isoxazolyl)pyridinium chloride-------- 7 E72 68 116 344 29 1-methyl-4-(5-methyl-3-isoxazolyl)pyridinium chloride----------------- 2 El5 30-9 144 0-4 578 53-li 1-cyclopropylmethyl-4-(3-methyl-5-isoxazolyl)pyridinium bromide...-- -80 10-8 10-5 -2011 E09 11-6 i-ethyl-4-(3-methyl-5-isoxazolyl)pyridinium iodide--------------------- 2 0-2 146 3-4 4 ---------- 165 20-7 1-ethyl-4-(3-ethyl-5-isoxazolyl)-pyridinium iodide...-------------------- 22:-4 5-5 24 t 307 320 385 1-propyl-4-(3-methyl-5-isoxazolyl)-pyridinium bromide---------------- 2 -52 163 223 4 54 35 75 1-methyl-4-(3-methyl-5-isoxazolyl)-pyridinium iodide------------------ 5 13-3 is 359 40-9 1-methyl-4-(5-methyl-3-isoxazolyl)-pyridinium iodide--- 3 562-12 93-1 ---------- Values are means standard errors of 4 to 8 mice per dose and are expressed as percent decrease from predose walues.
Load more

Recommended publications
  • The System Pyridine-Hydrogen Chloride As an Acid Medium by Hyman Mitchner a Thesis.Submitted in Partial Fulfilment of the Requir
    THE SYSTEM PYRIDINE-HYDROGEN CHLORIDE AS AN ACID MEDIUM BY HYMAN MITCHNER A THESIS.SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE in the Department of CHEMISTRY We accept this thesis as conforming to the standard required from candidates for the degree of MASTER OF SCIENCE Members of the Department of Chemistry THE UNIVERSITY OF BRITISH COLUMBIA APRIL, 1953 ABSTRACT Pyridine salts were investigated as acids in the pyridine system. The mono and the dihydrochloride salts were found to be the best dissolving reagents for the a metals and the sulphides used. Pyridine hydrochloride was most effective in the molten state, whereas pyridine dihydrochloride was found to be quite reactive at room temperature when dissolved in a chloroform solution. Side reactions were investigated and were found to occur only with Mg, Al, and Zn with molten pyridinium chloride. The complex salts, (C5HeN.H)8[MnClB3c5HBN and (C5HBN.H)HgCl4 were isolated and investigated. 1 I AKNOWLEDG-EMENT Sincere appreciation is expressed to Dr. K. Starke for his'encouragement and help in making this work possible. TABLE OF CONTENTS PAGE INTRODUCTION 1. Water as an unique solvent 1 2. Historical approach to reactions in nonaqueous systems a. Confusion and misconcepts in the acid- has e theory.............................. 1 b. Bronsted theory of acids and bases.. «,...© 4- 3. Disadvantages of water as a solvent........... 5 4. Alms of investigation ...... 5 EXPERIMENTAL 1. Purity of reagents 7 2. Preparation of pyridinium salts a. Pyridinium nitrate 7 b. Pyridinium trlchloroacetate 7 Co Pyridinium thiocyanate 8 d. Pyridinium oxalate 8 e.
    [Show full text]
  • Nomination Background: 1-Butyl-3-Methylimidazolium Chloride
    Ionic Liquids 1-Butyl-3-methylimidazolium Chloride (CAS No. 79917-90-1) 1-Butyl-1-methylpyrrolidinium Chloride (CAS No. 479500-35-1) N-Butylpyridinium Chloride (CAS No. 1124-64-7) Review of Toxicological Literature May 2004 Ionic Liquids 1-Butyl-3-methylimidazolium Chloride (CAS No. 79917-90-1) 1-Butyl-1-methylpyrrolidinium Chloride (CAS No. 479500-35-1) N-Butylpyridinium Chloride (CAS No. 1124-64-7) Review of Toxicological Literature Prepared for National Toxicology Program (NTP) National Institute of Environmental Health Sciences (NIEHS) National Institutes of Health U.S Department of Health and Human Services Contract No. N01-ES-35515 Project Officer: Scott A. Masten, Ph.D. NTP/NIEHS Research Triangle Park, North Carolina Prepared by Integrated Laboratory Systems, Inc. Research Triangle Park, North Carolina May 2004 Toxicological Summary for Ionic Liquids 05/2004 Abstract Ionic liquids are salts of organic cations with melting points generally below 100 °C and are being widely investigated as replacements for volatile organic solvents in industrial and laboratory processes because they are thought to be "environmentally benign." Although some efforts have begun to study their potential for ecotoxicity, limited vertebrate or genetic toxicity testing has been done. Three ionic liquids, 1-butyl-3-methylimidazolium chloride ([bmim]Cl), 1-butyl-1-methylpyrrolidinium chloride ([bmpy]Cl), and N-butylpyridinium chloride ([NBuPy]Cl), were nominated to the National Toxicology Program (NTP) for toxicological testing based on their widespread interest as possible alternatives to organic solvents. These chlorides are representative of the three most common cation classes of ionic liquids being investigated: imidazolium, pyridinium, and pyrrolidinium. The chlorides, soluble in water and polar organic liquids, are generally prepared from approximately equimolar amounts of the appropriately substituted heterocyclic compound and butyl chloride, often under both heat and pressure.
    [Show full text]
  • Pyridinium Chlorides Equipped with Long Chains As Amphiphiles for Potential Nonviral Gene Delivery§
    Issue in Honor of Prof. Alexandru T. Balaban ARKIVOC 2005 (x) 272-284 Pyridinium chlorides equipped with long chains as amphiphiles for potential nonviral gene delivery§ Mariana Viorica Bogatian,a* Valentin Cimpeanu,a Călin Deleanu,a,d Andreea Cristina Corbu,a,d Gheorghe Bogatian,b and Teodor Silviu Balabanc* a Costin D. Nenitzescu Institute of Organic Chemistry, Romanian Academy, Splaiul Independentei, 202B, 71141, P.O. Box 108, Bucharest 35, Romania b Vigra Marketing & Services s.r.l., Str. Graţioasǎ 6, Bucharest, Romania c Forschungszentrum Karlsruhe, Institut für Nanotechnologie, Postfach 3640, D-76021 Karlsruhe, Germany d National NMR Laboratory, P. O. Box 35 – 98 Bucharest, Romania E-mail: [email protected] or [email protected] Dedicated to Prof. Dr. Alexandru T. Balaban on the occasion of his 75th birthday (received 29 Jun 05; accepted 20 Aug 05; published on the web 23 Aug 05) Abstract Pyridinium chlorides with long alkyl substituents were prepared, sometimes in quantitative yields, using a macroporous, strongly basic, anion exchange resin of the styrene-divinylbenzene type. This procedure opens the way to convert readily available and highly pure pyrylium salts with tailored amphiphilicity inducing substituents, into pyridinium perchlorates, and then by this optimized anion exchange procedure into the corresponding chlorides. Previous transfection studies using long chain pyridinium perchlorates have proven acute cell toxicity whereas the corresponding chlorides were benign and had good to high transfection efficiencies, superior to commercial nonviral vectors. All new compounds were fully characterized and can now be made available in large quantities. Keywords: Pyridinium chloride, amphiphile, nonviral, gene delivary Introduction Recent in depth studies of cationic amphiphiles have demonstrated practical utility for the latter for delivery of DNA and RNA into cells.
    [Show full text]
  • Pyridine N-Heterocyclic Carbene Precursors Johnathon T. Hutt
    Hutt and Aron Efficient, Single-Step Access to Imidazo[1,5-a]pyridine N-Heterocyclic Carbene Precursors Johnathon T. Hutt and Zachary D. Aron Department of Chemistry, Indiana University, 800 E. Kirkwood Ave. Bloomington, IN 47405-7102 [email protected] Supporting Information Table of Contents I. General Methods SI2 II. Materials SI3 III. General Experimental Procedures SI3 IV. Experimental Procedures SI5 V. 1H and 13C NMR Data of the Products SI31 SI 1 Hutt and Aron Methods: Proton and carbon nuclear magnetic resonance (NMR) spectra were recorded on Varian i400 (1H NMR at 400MHz and 13C at 100MHz) and Varian i500 (1H NMR at 300MHz and 13C at 75MHz) 1 spectrometers using solvent resonance as the internal standard ( H NMR: CDCl3 at 7.24 ppm, CD3OD at 3.31 ppm, CD3CN at 1.94ppm, and D2O at 4.79ppm; 13C NMR: CDCl3 at 77.16 ppm, 1 CD3OD at 49.00 ppm, and CD3CN at 1.32ppm). H NMR data are reported as follows: chemical shift, multiplicity (s = singlet, bs = broad singlet, d = apparent doublet, t = apparent triplet, q = apparent quartet, quint = apparent quintet, and m = multiplet), coupling constants (Hz), and integration. For carbon spectra of compounds containing Boron, q is used to denote any observed 1:1:1:1 quartets. Infrared spectra (IR) were obtained on an Avatar 360-FT IR E.S.P. and recorded in wavenumbers (cm-1). UV-Vis spectra were obtained using a Varian Cary 5000 spectrometer using a 1 cm path length quartz cell. High-resolution mass spectra were obtained using LCT KC366 with electron impact ionization.
    [Show full text]
  • Resin Selection Guide for Corrosion Resistance — Derakane™ Epoxy Vinyl Ester Resins Chemical Resistance for FRP Applications 2 Contents Foreword
    resin selection guide for corrosion resistance — derakane™ epoxy vinyl ester resins chemical resistance for FRP applications 2 contents foreword .................................................................................................................................... 4 brief product description ....................................................................................................... 5 how to use the chemical resistance table .......................................................................... 6 special cases ........................................................................................................................... 9 mixtures of alternating environments ................................................................................ 10 derakane™ epoxy vinyl ester resins – special resistance inquiry form ........................ 11 chemical name/cas numbers ............................................................................................ 12 chemical resistance table: maximum service temperatures for derakane™, derakane™ momentum™, and derakane™ signia™ resins ............................................................................................. 14 derakane™ chemical resistance guide foreword Derakane™, Derakane™ Momentum™, and Derakane™ Because many of the variables that affect the Signia™ epoxy vinyl ester resins (from this point forward performance of a laminate are beyond Ashland’s referred to as Derakane™ resins) are designed and control, no warranty concerning the use of
    [Show full text]
  • United 'States Patent O?
    2,859,217 United ‘States Patent O? ice ‘ Patented Nov. 4, 1958 1. 2 Ordinarily, if a particular halide ion is desired in the 2,859,217 ?nal bis-quaternary ammonium compound, the prepara ACETYLCHOLINE ESTERASE INHIBITORS tion of the compound is carried ‘outwith the speci?c halide Quentin F. Super, Indianapolis, Ind., assignor to Eli Lilly initially present in the bis-(phenacyl-halide) reactant. and Company, Indianapolis, Ind., a corporation , of However, if for some reason ‘this method of preparation Indiana . is not desirable, itis possible to ‘interchange the halide ions in the ?nal bisjquaternary ammonium compound by No Drawing. Application September 28, 1956 , methods well knownrzto. the ‘art. For example,~a ‘bis Serial No. 612,575 quaternary ammonium bromidelcan be reacted with vsilver 5 Claims. (Cl. 260-296) 10 chloride to yieldthe ‘less‘soluble silver bromide and the bis-quaternary vammonium chloride. Other methods such My invention relates to certain ‘novel bis-quaternary as theuse of ion :exchange ~resins and simple lmetathetic ammonium compounds. processes can be employed. Thecompounds provided by my .inventionycan'be rep The method of halide ‘interchange can be used also to resented by the following formula: prepare the bis-(phenacylihalide) starting material. For in which X is an oxygen or a sulphur atom; Hal is a example, 4,4’-oxy-‘bis-'(phenacyl-chloride) and excess so halogen atom having an atomic numbergreater than 16, dium iodide reacted together in acetone solution give, for example, chlorine, bromine‘or iodine; and Aml and 4,4'-oxy-bis-_(phenacyl-iodide) . Amz represent tertiary amines, such as tri-lower alkyl 20 The compounds provided by this invention .are useful amines, as for example, triethylamine, trimethylamine, pharmaceuticalagents.
    [Show full text]
  • Synthesis of N-Arylpyridinium Salts Bearing a Nitrone Spin Trap As Potential Mitochondria-Targeted Antioxidants
    View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Enlighten: Publications Robertson, L. and Hartley, R.C. (2009) Synthesis of N-arylpyridinium salts bearing a nitrone spin trap as potential mitochondria-targeted antioxidants. Tetrahedron, 65 (27). pp. 5284-5292. ISSN 0040-4020 http://eprints.gla.ac.uk/32200 Deposited on: 25 January 2011 Enlighten – Research publications by members of the University of Glasgow http://eprints.gla.ac.uk SYNTHESIS OF N-ARYLPYRIDINIUM SALTS BEARING A NITRONE SPIN TRAP AS POTENTIAL MITOCHONDRIA-TARGETED ANTIOXIDANTS Linsey Robertson, Richard C. Hartley*, Centre for the Chemical Research of Ageing, WestCHEM Department of Chemistry, University of Glasgow, Glasgow, G12 8QQ, UK NH N 2 N Cl Cl O N O MeOH 2 + O N tBu N tBu OR NO2 OR R = lipophilic chain 1 Synthesis of N-Arylpyridinium Salts Bearing a Nitrone Spin Trap as Potential Mitochondria- targeted Antioxidants Linsey Robertson and Richard C. Hartley. Centre for the Chemical Research of Ageing, WestCHEM Department of Chemistry, University of Glasgow, Glasgow, G12 8QQ, UK Abstract – The generation of excess reactive oxygen species (ROS) in mitochondria is responsible for much of the oxidative stress associated with ageing (aging), and mitochondrial dysfunction is part of the pathology of neurodegeneration and type 2 diabetes. Lipophilic pyridinium ions are known to accumulate in mitochondria and this paper describes a general route for the preparation of nitrone-containing N-arylpyridinium salts having a range of lipophilicities, as potential therapeutic antioxidants. The compatibility of nitrones with the Zincke reaction is the key to their synthesis.
    [Show full text]
  • Perdeuterated Pyridinium Molten Salt (Ionic Liquid) for Direct Dissolution and NMR Analysis of Plant Cell Walls
    COMMUNICATION www.rsc.org/greenchem | Green Chemistry Perdeuterated pyridinium molten salt (ionic liquid) for direct dissolution and NMR analysis of plant cell walls Nan Jiang, Yunqiao Pu, Reichel Samuel and Arthur J. Ragauskas* Received 8th July 2009, Accepted 1st September 2009 First published as an Advance Article on the web 14th September 2009 DOI: 10.1039/b913609f A bi-solvent system consisting of perdeuterated pyridinium and co-workers’ initial reports that ionic liquids can dissolve 8 molten salt and DMSO-d6 (dimethyl sulfoxide-d6)has biomass, such as cellulose and wood sawdust, the application of been developed for direct dissolution and nuclear magnetic these solvents to various biomass research efforts has grown sub- resonance (NMR) analysis of plant cell walls, which will stantially. In particular, imidazolium chloride ionic liquids, such shed a new light on efficient detailed structure of the plant as [bmim]Cl and [Amim]Cl, and imidazolium phosphonate have cell walls and benefit lignin engineering for biofuel and been successfully used as green solvents for functionalization 9,10 biomaterial research. or pretreatment of biomass. Our group has recently demon- strated that imidazolium type ionic liquids [mmim][OSO3Me], Increasing societal demand for sustainable development has led [bmim][OSO3Me], and [hmim]OTf are especially well suited to to considerable efforts in the search for renewable energy and dissolve lignin for NMR analysis.11 materials, especially as concerns related to energy security and Despite wide applications of imidazolium ionic liquids (see climate change continue to grow.1 Substantial efforts are being Fig. 1) as the solvents for biomass dissolution and function- made to establish processes that transform differing sources of alization, the tedious multi-step synthesis of perdeuterated biomass into liquid fuels and chemicals as viable alternatives to imidazolium ionic liquids12 has limited their application in nonrenewable petroleum resources.2 To address this challenge, biomass NMR characterization.
    [Show full text]
  • CPC”) to Section 205.605 (B) of the National List
    United States Department of Agriculture Agricultural Marketing Service | National Organic Program Document Cover Sheet https://www.ams.usda.gov/rules-regulations/organic/national-list/petitioned Document Type: ☒ National List Petition or Petition Update A petition is a request to amend the USDA National Organic Program’s National List of Allowed and Prohibited Substances (National List). Any person may submit a petition to have a substance evaluated by the National Organic Standards Board (7 CFR 205.607(a)). Guidelines for submitting a petition are available in the NOP Handbook as NOP 3011, National List Petition Guidelines. Petitions are posted for the public on the NOP website for Petitioned Substances. ☐ Technical Report A technical report is developed in response to a petition to amend the National List. Reports are also developed to assist in the review of substances that are already on the National List. Technical reports are completed by third-party contractors and are available to the public on the NOP website for Petitioned Substances. Contractor names and dates completed are available in the report. December 4, 2019 National Organic Program USDA/AMS/NOP, Standards Division Attention: National List Manager Room 2642-So., Ag Stop 0268 1400 Independence Ave. SW Washington, DC 20250-0268 Re: Petition to add Cetylpyridinium Chloride (“CPC”) to section 205.605 (b) of the National List Safe Foods Corporation is enclosing a petition to add CPC as a processing aid for application onto poultry or poultry parts at slaughter or processing plants. The petition follows the format described in the “Guidelines on Procedures for Submitting National List Petitions” (72 Fed Reg 2167; January 18, 2007), as clarified by the proposed “Update of the Petition and Technical Review Process” (August 27, 2013).
    [Show full text]
  • Research Article Special Issue
    Journal of Fundamental and Applied Sciences Research Article ISSN 1112-9867 Special Issue Available online at http://www.jfas.info THE OXIDATION OF ALCOHOLS WITH PICOLINATE METAL COMPLEX AS CATALYST K. K. Uthumporn*, T. C. Darunee Department of Chemistry, Faculty of Science, Maejo University Chiang Mai, Thailand Published online: 18 April 2018 ABSTRACT The oxidation of alcoholic functionalities is still important both an academic and industrial point of view. The study focused on the development of a catalytic system based on picolinate metal complex to improve the oxidation under mild condition with TBHP. Under these conditions, secondary alcohols were converted smoothly to the corresponding carbonyl compound in high yield with good selectivity. The oxidation of 1-phenyl ethanol was explored to acetophenone with 85.19 % yield in 5 hours. Additionally, the study focused on the oxidation of 2-phenyl alcohol afforded the corresponding aldehyde yield without carboxylic acid. Keywords: picolinate; oxidation; alcohol I. INTRODUCTION The oxidation of abundant raw materials such as hydrocarbons which are derived from petroleum, to produce fine chemicals in the class of carbonyl compounds is still important both an academic and industrial point of view. The transformations generally involve the use of a metal catalyst. Clean oxidants such as O2 and hydroperoxide are widely used for economic and environmental reasons. Over recent years (1), the study of chromium-catalyzed oxidations with hydroperoxide has been explored. The oxidation of alcohols to carbonyl products with pyridinium chlorochromate (Collin’s reagent) is selective and mild although the reaction utilizes chromyl chloride which is very hazardous and toxic. Author Correspondence, e-mail: [email protected] doi: http://dx.doi.org/10.4314/jfas.v10i3s.74 Journal of Fundamental and Applied Sciences is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.
    [Show full text]
  • This Dissertation Has Been 64—3179 Microfilmed Exactly As Received
    BASE-CATALYZED HYDROLYSIS OF PYRIDINIUM SALTS Item Type text; Dissertation-Reproduction (electronic) Authors Moss, Ernest Kent, 1938- Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 29/09/2021 13:55:45 Link to Item http://hdl.handle.net/10150/284499 This dissertation has been 64—3179 microfilmed exactly as received MOSS, Ernest Kent, 1938- BASE-CATALYZED HYDROLYSIS OF PYRIDINIUM SALTS. University of Arizona, Ph.D., 1963 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan BASE-CATALYZED HYDROLYSIS OF PYRIDINIUM SALTS by Ernest K. Moss A Dissertation Submitted to the Faculty of the DEPARTMENT OF CHEMISTRY In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College THE UNIVERSITY OF ARIZONA 19 6 3 " THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE I hereby recommend that this dissertation prepared under my direction by ~rn::-' !""t K . TToss be accepted as fulfilling the dissertation requirement of the degree of ___n_ o~c _t_o_r__ o__ f __ n _.n_; ,_· __l _o_2_- o_~_h_.,,_r ____________________________ After inspection of the dissertation, the following members of the Final Examination Committee concur in its approval and recommend its acceptance :* *This approval and acceptance is contingent on the candidate's adequate performance and defense of this dissertation at the final oral examination. The inclusion of this sheet bound into the library copy of the -dissertation is evidenceof satisfactory performance at the final examination.
    [Show full text]
  • United States Patent (19) 11 4,206,215 Bailey 45 Jun
    United States Patent (19) 11 4,206,215 Bailey 45 Jun. 3, 1980 54 ANTIMICROBIAL (56) References Cited BIS-4-(SUBSTITUTED-AMINO)-1- U.S. PATENT DOCUMENTS PYRIDINIUMALKANES 3,055,902 9/1962 Walker ............................ 260/296 D 75 Inventor: Denis M. Bailey, East Greenbush, 3,786,058 1/1974 Edwards ....................... 260/294.8 R N.Y. 73 Assignee: Sterling Drug Inc., New York, N.Y. OTHER PUBLICATIONS Walker et al., J. Org. Chem., vol. 26, pp. 2740-2747, 21 Appl. No.: 876,031 (1961). 22 Filed: Feb. 8, 1978 Austin, J. Pharm. Pharmacol., vol. 11, pp. 80-93, (1959). Primary Examiner-John D. Randolph Related U.S. Application Data Attorney, Agent, or Firm-Paul E. Dupont; B. Woodrow 63 Continuation-in-part of Ser. No. 721,315, Sep. 7, 1976, Wyatt abandoned, which is a continuation-in-part of Ser. No. 661,101, Feb. 25, 1976, abandoned. 57 ABSTRACT 30 Foreign Application Priority Data Bis-4-(R-amino)-1-pyridiniumalkanes are prepared by Feb. 11, 1977 (GB United Kingdom ................. 5784/77 reacting a 4-(R-amino)pyridine with an appropriate 51 Int. Cl. ..................... C07D 213/02; A61R 31/44 disubstituted alkane. The compounds are useful as anti 52 U.S. C. .................................... 424/263; 546/261; microbial agents. Certain species are also useful as den 546/264; 252/106 tal plaque-preventive agents. 58 Field of Search ................... 260/296 D; 252/106; 424/263; 546/261,264 45 Claims, No Drawings 4,206,215 1. 2 groups are linked through an alkylene group ANTIMICROBIAL bonded to the nitrogen atoms of the pyridine rings.
    [Show full text]