DOCSLIB.ORG

United States Patent Office

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
United States Patent Office 3,590,077 United States Patent Office Patented June 29, 1971 2 propane-1,3-diol and L(--)-threo-1-p-nitrophenyl-2-N,N- 3,590,077 dimethylamino-propane-1,3-diol and their acid addition SALTS OF CHRYSANTHEMIC ACID WITH 1-p- NITROPHENYL - 2-N,N - DIMETHYL-AMINO salts. The said diastereoisomers are unexpectedly excel PROPANE-1,3-DIOLS lent agents for the resolution of racemic acids since they Georges Muller, Nogent-sur-Marne, Gaston Amiard, form salts of greater stability and better crystallizability Thorigny, Andre Poittevin, Les Lilas, and Vesperto and the bases are less soluble in aqueous media than Torelli, Maisons Alfort, France, assignors to Roussel known resolving agents such as ephedrine or L(--)- UCLAF, Paris, France threo-1-p-nitrophenyl-2-amino-propane-1,3-diol. No Drawing. Continuation-in-part of application Ser. No. The disastereoisomers of the invention are particu 610,219, Jan. 19, 1967. This application July 5, 1968, O larly useful for the resolution of racemic mixtures of Ser. No. 742,485 Claims priority, application France, Jan. 26, 1966, 1,5-dioxo - 7a - lower alkyl-5,6,7,7a-tetrahydroindane-4- 47,305; July 7, 1967, 113,580 acetic acids which have been difficult to separate with The portion of the term of the patent subsequent to known resolution agents due to the very slight solubility Mar. 9, 1987, has been disclaimed differences and poor stability of diastereoisomeric salts Int, C. C07c 91/20 formed therewith, such as with L(--)-threo-1-p-nitro U.S. C. 260-501.7 4 Claims phenyl-2-amino-propane-1,3-diol. Other racemic acids may be resolved with the novel compounds of the inven tion and examples of said acids are polyhydronaph ABSTRACT OF THE DISCLOSURE thalenic acids, tetrahydroindane acids and ox-amino acids. Optical isomers of 1-p-nitrophenyl-2-N,N-dimethyl 20 1,5-dioxo - 7a - methyl - 5,6,7,7a - tetrahydroindane-4- amino-propane-1,3-diol and acid addition salts thereof, acetic acid, which is described in French Pat. No. useful for the separation of racemic compounds and 1,384,854, is useful as an intermediate for the prepara preparation thereof. tion of various steroids, such as B-nor-steroids and estra diol derivatives. To resolve a racemic mixture of the 25 said acid, D(-)-threo-1-p-nitrophenyl-2-N,N-dimethyl amino-propane-1,3-diol can be added to a solution of PRIOR APPLICATION the racemic acid in an ethyl acetate-ethanol-water solvent The present application is a continuation-in-part of to crystallize the dextrorotatory salt of D(-)-threo-1-p- our commonly assigned, copending U.S. patent appli nitrophenyl-2-N,N-dimethylamino-propane-1,3-diol with cation Ser. No. 610,219, filed Jan. 19, 1967 now U.S. 30 dextrorotatory 1,5-dioxo-7a-methyl-5,6,7,7a-tetrahydroin Pat. No. 3,499,929. dane-4-acetic acid, separating the said crystals from the PRIOR ART mother liquor, treating the crystals with first alkaline conditions and then acid conditions to recover (--) 1,5- The importance of the separation of racemic com dioxo-7a-methyl-5,6,7,7a-tetrahydroindane - 4 - acetic acid pounds such as racemic acids, which are formed in the having a melting point of 129° C. and a specific rotation synthesis of natural products of which only one isomer of fox 20=225-1 (0.5% in water), evaporating the is active, is well known. The resolution of racemic acids mother liquor taking up in water the residue, treating is currently effected by combining the acid with an the aqueous solution with alkaline conditions, separating optically active base to form a mixture of two diastereo the crystals formed, acidifying the filtrate, then purifying isomeric salts which can be separately recovered and 40 the reaction mixture, extracting with an organic solvent, purified and then decomposed into the corresponding evaporating the extracts and treating the residue with dextrorotatory or levorotatory acid. Optically active bases L(--)-threo-1-p-nitrophenyl-2-N,N-dimethylamino-pro such as brucine, morphine, quinine, L(--)-threo-1-p- pane-1,3-diol to form the corresponding levorotatory salt nitrophenyl-2-amino-propane-1,3-diol, etc., have been which can be subjected to alkaline and then acid treat used as resolution agents. 45 ment to obtain (-)-1,5-dioxo-7a-methyl-5,6,7,7a-tetra However, tests have shown that the resolution of an hydroindane-4-acetic acid with a melting point of 129° C. acid very often runs into great difficulties of a technical and a specific rotation of oil0=-225-1 (0.5% in nature which cannot be predicted. The base should form water). Of course, the order of addition of the optically easily crystallizable stable salts with one of the diastereo active isomers of the invention may be reversed with isomeric salts being distinctly less soluble than the other 50 the levorotatory salt being recovered first. in order to facilitate the separation of the salts. Also, Another valuable use for the diastereoisomers of the the base to be separated should preferably be slightly invention is the resolution of dl-trans chrysanthemic acid soluble in aqueous media so that it may be recovered into its optically active isomers. This process is charac without great difficulty after decomposition of its salt. terized in the addition of D(-) or L(--) threo-1-p-nitro 55 phenyl-2-N,N-dimethylaminopropane-1,3-diol to a solu OBJECTS OF THE INVENTION tion of dl-trans chrysanthemic acid in an organic solvent It is an object of the invention to provide novel, to form the corresponding crystalline diastereoisomeric optically active isomers of 1-p-nitrophenyl-2-N,N-di salt in a mother liquor, separating the crystalline salt and methylaminopropane-1,3-diol and its acid addition salts. subjecting the latter to acid hydrolysis to get the optical It is another object of the invention to provide a 60 isomer of trans chrysanthemic acid and recovering the novel process for the preparation of the optically active other optical isomer of trans chrysanthemic acid from isomers of 1-p-nitrophenyl-2-N,N-dimethylamino-pro the mother liquor. pane-1,3-diol and its acid addition salts. The organic solvent may be an aliphatic ether such It is a further object of the invention to provide novel as ethyl ether, isopropyl ether, etc.; an aromatic hydro salts of the said optically active diol. 65 carbon such as benzene or toluene; an aliphatic alcohol These and other objects and advantages of the inven Such as methanol; an aliphatic acid ester such as ethyl tion will become obvious from the following detailed acetate. Particularly preferred is isopropyl ether contain description. ing up to 15% of methanol. The acid hydrolysis is preferably effected with a strong mineral acid such as THE INVENTION 70 hydrochloric acid. The novel compounds of the invention consist of The process of the invention for the preparation of the D(-)-threo-1-p-nitrophenyl - 2 - N,N-dimethylamino threo-1-p-nitrophenyl-2-N,N-dimethylamino-propane-1,3- 3,590,077 3 4. diols comprises subjecting a diastereoisomer of threo-1-p- in water). The product was soluble in water and in alco nitrophenyl-2-amino-propane-1,3-diol to reductive alkyla hols and slightly soluble in ethyl acetate. tion with a mixture of formaldehyde and formic acid to This compound is not described in the literature. form the corresponding N,N-dimethylamino compound, Step B-Preparation of dextrorotatory 1,5-dioxo-7a which can be converted into an acid addition salt with an methyl-5,6,7,7a-tetrahydroindane-4-acetic acid: 24 gm. of organic or inorganic acid. the dextrorotatory salt of D(-)-threo-1-p-nitrophenyl-2- In the following examples, there are described several N,N-dimethylamino-propane-1,3-diol with dextrorotatory preferred embodiments to illustrate the invention. How 1,5-dioxo-7a-methyl-5,6,7,7a-tetrahydroindane - 4 - acetic ever, it should be understood that the invention is not acid were introduced into 100 cc. of ice water under an intended to be limited to the specific embodiments. O atmosphere of nitrogen. Then 50 cc. of N-sodium hydrox ide were very slowly and under agitation added to the EXAMPLE I reaction mixture. The reaction mixture was then filtered Preparation of D(-) and L(--)-threo-1-p-nitrophenyl and the filtrate was recovered, washed repeatedly with 2-N,N-dimethylamino-propane-1,3-diols ethyl acetate, then acidified with concentrated hydrochlo A reaction mixture of 50gm. of D(-)-threo-1-p-nitro 5 ric acid. Ammonium sulfate was added until saturation phenyl-2-amino-propane-1,3-diol, 50 cc. of 30% formol Was attained, and finally, the reaction mixture was ex and 50 cc. of 98% formic acid was heated for about 3 tracted several times with methylene chloride. The ex hours in a steam bath after which it was distilled to dry tracts were combined, dried over magnesium sulfate, ness under vacuum. The oily residue obtained was dis treated with animal black and evaporated to dryness under solved in 150 cc. of water and after 40 cc. of 22 Béam 20 WaCLEllin. monium hydroxide were added, the mixture was main The residue was taken up in 20 cc. of toluene and tained for about 15 minutes at a temperature of about allowed to stand for crystallization. The crystals formed 80° C. Then 60 cc. of ammonium hydroxide were again were vacuum filtered, washed with iced toluene and dried added at a high temperature and the entire mixture was to obtain.
Load more

Recommended publications
  • 2354 Metabolism and Ecology of Purine Alkaloids Ana Luisa Anaya 1
    [Frontiers in Bioscience 11, 2354-2370, September 1, 2006] Metabolism and Ecology of Purine Alkaloids Ana Luisa Anaya 1, Rocio Cruz-Ortega 1 and George R. Waller 2 1Departamento de Ecologia Funcional, Instituto de Ecologia, Universidad Nacional Autonoma de Mexico. Mexico DF 04510, 2Department of Biochemistry and Molecular Biology, Oklahoma State University. Stillwater, OK 74078, USA TABLE OF CONTENTS 1. Abstract 2. Introduction 3. Classification of alkaloids 4. The importance of purine in natural compounds 5. Purine alkaloids 5.1. Distribution of purine alkaloids in plants 5.2. Metabolism of purine alkaloids 6. Biosynthesis of caffeine 6.1. Purine ring methylation 6.2. Cultured cells 7. Catabolism of caffeine 8. Caffeine-free and low caffeine varieties of coffee 8.1. Patents 9. Ecological role of alkaloids 9.1. Herbivory 9.2. Allelopathy 9.2.1. Mechanism of action of caffeine and other purine alkaloids in plants 10. Perspective 11. Acknowledgements 12. References 1. ABSTRACT 2. INTRODUCTION In this review, the biosynthesis, catabolism, Alkaloids are one of the most diverse groups of ecological significance, and modes of action of purine secondary metabolites found in living organisms. They alkaloids particularly, caffeine, theobromine and have many distinct types of structure, metabolic pathways, theophylline in plants are discussed. In the biosynthesis of and ecological and pharmacological activities. Many caffeine, progress has been made in enzymology, the amino alkaloids have been used in medicine for centuries, and acid sequence of the enzymes, and in the genes encoding some are still important drugs. Alkaloids have, therefore, N-methyltransferases. In addition, caffeine-deficient plants been prominent in many scientific fields for years, and have been produced.
    [Show full text]
  • Resolution of Racemic 5-Phenyl-2-Pentanol
    Patentamt JEuropaischesEuropean Patent Office 11) Publication number: 0 078 145 Office europeen des brevets A1 © EUROPEAN PATENT APPLICATION © Int. ci * C 07 B 19/00 C 07 C 33/20, C 07 D 491/22 C 07 C 69/80 //C07D215/22, C07D221/12, (C07D491/22, 313/00, 221/00, 221/00, 209/00, 209/00) @ Priority: 22.10.81 US 313560 © Applicant: PFIZER INC. 235 East 42nd Street New York, N.Y.10017(US) © Date of publication of application: 04.05.83 Bulletin 83/18 © Inventor: Moore, Bernard Shields 39 Savi Avenue © Designated Contracting States: Waterford Connecticut(US) AT BE CH DE FR GB IT U LU NL SE © Representative: Graham, Philip Colin Christison et al, Pfizer Limited Ramsgate Road Sandwich, Kent CT13 9NJIGB) © Resolution of racemic 5-phenyl-2-pentanol. Racemic 5-phenyl-2-pentanol is resolved via its hemiph- thalate ester, followed by diastereomer salt formation with (+)-brucine, separation of the brucine salt of (S)-5-phenyl-2- pentylhemi-phthalate and recovery of the (S)-alcohol there- from. The (S)-5-phenyl-2-pentanol is a valuable intermediate for organic synthesis. The separated (+)-brucine salt of (S)-5-phenyl-2-pentylhemiphthalate is a novel and useful intermediate. This invention relates to a process for resolution of racemic 5-phenyl-2-pentanol to (S)-5-phenyl-2- pentanol, a valuable intermediate in the synthesis of analgesic agents. More specifically, the process comprises esterifying racemic 5-phenyl-2-pentanol to form the hemiphthalate ester, followed by treating said ester with (+)-brucine, separating (S)-5-phenyl- 2-pentylhemiphthalate(+)-brucine salt, decomposing said salt to regenerate (S)-5-phenyl-2-pentylhemiphthalate, and hydrolyzing said ester to (S)-5-phenyl-2-pentanol.
    [Show full text]
  • Concentration and Frequency Dependent Dielectric Permittivity and Dielectric Loss Study of Brucine - Chloroform Solution Using Time Domain Reflectometry (TDR)
    International Journal of Science and Research (IJSR) ISSN: 2319-7064 ResearchGate Impact Factor (2018): 0.28 | SJIF (2019): 7.583 Concentration and Frequency Dependent Dielectric Permittivity and Dielectric Loss Study of Brucine - Chloroform Solution using Time Domain Reflectometry (TDR) A. R. Lathi Associate Professor, A.E.S. College, Hingoli, Maharashtra, India Abstract: Dielectric permittivity (ε’) and dielectric loss (ε’’) of Brucine-Chloroform solution over a frequency range of 10 MHz to 30 GHz have been measured using Time Domain Reflectometry (TDR). Observations are taken for different molar concentrations of Brucine-Chloroform (0M to 0.3M) at 298°K. Step pulse without sample R1(t) and with sample Rx(t) were recorded in time window of 5nS and digitized in 2000 points. The effect of concentration and frequency on dielectric permittivity and dielectric loss has been presented in this paper. Keywords: Dielectric permittivity; Dielectric Loss; Brucine; TDR 1. Introduction 2.2 Experimental Setup Brucine is a natural alkaloid which comes under Indole The time domain Reflectometry is used to describe a Group II [1]. Brucine was discovered in 1819 by Pelletier technique of observing time dependence reflection response and Caventoy in the bark of Strychnos nux-vomica tree. The of sample under study. H.Fellmer - Feldegg [7] developed structure of Brucine related to Strychnine [2]. Brucine TDR for measurement of dielectric loss and dielectric having anti-tumor effect [3]. It is also used in Chinese permittivity at very high frequency range. The schematic medicine as analgesic agent[4]. Brucine has antiprolifrative block diagram of the experimental setup of TDR [8,9] is effects in different cancer cell lines [5].
    [Show full text]
  • The Anti-Tumor Effects of Alkaloids from the Seeds of Strychnos Nux-Vomica
    Journal of Ethnopharmacology 106 (2006) 179–186 The anti-tumor effects of alkaloids from the seeds of Strychnos nux-vomica on HepG2 cells and its possible mechanism Xu-Kun Deng a,1,WuYinb,1, Wei-Dong Li a, Fang-Zhou Yin a, Xiao-Yu Lu a, Xiao-Chun Zhang a, Zi-Chun Hua b, Bao-Chang Cai a,∗ a College of Pharmacy, Nanjing University of Chinese Medicine, Nanjing 210029, China b State Key Lab of Pharmaceutic Biotechnology, Nanjing University, Nanjing 210093, China Received 6 April 2005; received in revised form 12 December 2005; accepted 15 December 2005 Available online 26 January 2006 Abstract To screen the anti-tumor effects of the four alkaloids: brucine, strychnine, brucine N-oxide and isostrychnine from the seed of Strychnos nux- vomica, MTT assay was used to examine the growth inhibitory effects of these alkaloids on human hepatoma cell line (HepG2). Brucine, strychnine and isostrychnine revealed significant inhibitory effects against HepG2 cell proliferation, whereas brucine N-oxide didn’t have such an effect. In addition, brucine caused HepG2 cell shrinkage, membrane blebbing, apoptotic body formation, all of which are typical characteristics of apoptotic programmed cell death. The results of flow cytometric analysis demonstrated that brucine caused dose-dependent apoptosis of HepG2 cells through cell cycle arrest at G0/G1 phase, thus preventing cells entering S or G2/M phase. Immunoblot results revealed that brucine significantly decreased the protein expression level of cyclooxygenase-2, whereas increased the expression caspase-3 as well as the caspase-3-like protease activity in HepG2 cells, suggesting the involvement of cyclooxygenase-2 and caspase-3 in the pro-apoptotic effects exerted by brucine.
    [Show full text]
  • EPA's Hazardous Waste Listing
    Hazardous Waste Listings A User-Friendly Reference Document September 2012 Table of Contents Introduction ..................................................................................................................................... 3 Overview of the Hazardous Waste Identification Process .............................................................. 5 Lists of Hazardous Wastes .............................................................................................................. 5 Summary Chart ............................................................................................................................... 8 General Hazardous Waste Listing Resources ................................................................................. 9 § 261.11 Criteria for listing hazardous waste. .............................................................................. 11 Subpart D-List of Hazardous Wastes ............................................................................................ 12 § 261.31 Hazardous wastes from non-specific sources. ............................................................... 13 Spent solvent wastes (F001 – F005) ......................................................................................... 13 Wastes from electroplating and other metal finishing operations (F006 - F012, and F019) ... 18 Dioxin bearing wastes (F020 - F023, and F026 – F028) .......................................................... 22 Wastes from production of certain chlorinated aliphatic hydrocarbons (F024
    [Show full text]
  • 24Amino Acids, Peptides, and Proteins
    WADEMC24_1153-1199hr.qxp 16-12-2008 14:15 Page 1153 CHAPTER COOϪ a -h eli AMINO ACIDS, x ϩ PEPTIDES, AND NH3 PROTEINS Proteins are the most abundant organic molecules 24-1 in animals, playing important roles in all aspects of cell structure and function. Proteins are biopolymers of Introduction 24A-amino acids, so named because the amino group is bonded to the a carbon atom, next to the carbonyl group. The physical and chemical properties of a protein are determined by its constituent amino acids. The individual amino acid subunits are joined by amide linkages called peptide bonds. Figure 24-1 shows the general structure of an a-amino acid and a protein. α carbon atom O H2N CH C OH α-amino group R side chain an α-amino acid O O O O O H2N CH C OH H2N CH C OH H2N CH C OH H2N CH C OH H2N CH C OH CH3 CH2OH H CH2SH CH(CH3)2 alanine serine glycine cysteine valine several individual amino acids peptide bonds O O O O O NH CH C NH CH C NH CH C NH CH C NH CH C CH3 CH2OH H CH2SH CH(CH3)2 a short section of a protein a FIGURE 24-1 Structure of a general protein and its constituent amino acids. The amino acids are joined by amide linkages called peptide bonds. 1153 WADEMC24_1153-1199hr.qxp 16-12-2008 14:15 Page 1154 1154 CHAPTER 24 Amino Acids, Peptides, and Proteins TABLE 24-1 Examples of Protein Functions Class of Protein Example Function of Example structural proteins collagen, keratin strengthen tendons, skin, hair, nails enzymes DNA polymerase replicates and repairs DNA transport proteins hemoglobin transports O2 to the cells contractile proteins actin, myosin cause contraction of muscles protective proteins antibodies complex with foreign proteins hormones insulin regulates glucose metabolism toxins snake venoms incapacitate prey Proteins have an amazing range of structural and catalytic properties as a result of their varying amino acid composition.
    [Show full text]
  • Chemical Capabilities Listing Laboratory, R&D, Industrial and Manufacturing Applications
    Page 1 of 3 Chemical Capabilities Listing Laboratory, R&D, Industrial and Manufacturing Applications Acacia, Gum Arabic Barium Oxide Chromium Trioxide Acetaldehyde Bentonite, White Citric Acid, Anhydrous Acetamide Benzaldehyde Citric Acid, Monohydrate Acetanilide Benzoic Acid Cobalt Oxide Acetic Acid Benzoyl Chloride Cobaltous Acetate Acetic Anhydride Benzyl Alcohol Cobaltous Carbonate Acetone Bismuth Chloride Cobaltous Chloride Acetonitrile Bismuth Nitrate Cobaltous Nitrate Acetyl Chloride Bismuth Trioxide Cobaltous Sulfate Aluminium Ammonium Sulfate Boric Acid Cottonseed Oil Aluminon Boric Anhydride Cupferron Aluminum Chloride, Anhydrous Brucine Sulfate Cupric Acetate Aluminum Chloride, Hexahydrate n-Butyl Acetate Cupric Bromide Aluminum Fluoride n-Butyl Alcohol Cupric Carbonate, Basic Aluminum Hydroxide tert-Butyl Alcohol Cupric Chloride Aluminum Nitrate Butyric Acid Cupric Nitrate Aluminum Oxide Cadmium Acetate Cupric Oxide Aluminum Potassium Sulfate Cadmium Carbonate Cupric Sulfate, Anhydrous Aluminum Sulfate Cadmium Chloride, Anhydrous Cupric Sulfate, Pentahydrate 1-Amino-2-Naphthol-4-Sulfonic Acid Cadmium Chloride, Hemipentahydrate Cuprous Chloride Ammonium Acetate Cadmium Iodide Cuprous Oxide, Red Ammonium Bicarbonate Cadmium Nitrate Cyclohexane Ammonium Bifluoride Cadmium Oxide Cyclohexanol Ammonium Bisulfate Cadmium Sulfate, Anhydrous Cyclohexanone Ammonium Bromide Cadmium Sulfate, Hydrate Devarda's Alloy Ammonium Carbonate Calcium Acetate Dextrose, Anhydrous Ammonium Chloride Calcium Carbide Diacetone Alcohol Ammonium Citrate
    [Show full text]
  • Simultaneous HPTLC Determination of Strychnine and Brucine in Strychnos Nux-Vomica Seed
    Original Article Simultaneous HPTLC determination of strychnine and brucine in strychnos nux-vomica seed Abid Kamal, Kamal Y. T., Sayeed Ahmad, F. J. Ahmad, Kishwar Saleem1 Bioactive Natural ABSTRACT Products Laboratory, Objective: A simple, sensitive, and specific thin layer chromatography (TLC) densitometry method has Department of been developed for the simultaneous quantification of strychnine and brucine in the seeds of Strychnos nux- Pharmacognosy, Faculty of Pharmacy, Jamia vomica. Materials and Methods: The method involved simultaneous estimation of strychnine and brucine Hamdard, Hamdard after resolving it by high performance TLC (HPTLC) on silica gel plate with chloroform–methanol–formic acid Nagar, 1Department of (8.5:1.5:0.4 v/v/v) as the mobile phase. Results: The method was validated as per the ICH guidelines for Chemistry, Jamia Millia precision (interday, intraday, intersystem), robustness, accuracy, limit of detection, and limit of quantitation. Islamia, Jamia Nagar, The relationship between the concentration of standard solutions and the peak response was linear within the New Delhi, India concentration range of 50–1000 ng/spot for strychnine and 100–1000 ng/spot for brucine. The method precision was found to be 0.58–2.47 (% relative standard deviation [RSD]) and 0.36–2.22 (% RSD) for strychnine and Address for correspondence: brucine, respectively. Accuracy of the method was checked by recovery studies conducted at three different Dr. Sayeed Ahmad, E- mail: sahmad_jh@yahoo. concentration levels and the average percentage recovery was found to be 100.75% for strychnine and 100.52% co.in for brucine, respectively. Conclusions: The HPTLC method for the simultaneous quantification of strychnine and brucine was found to be simple, precise, specific, sensitive, and accurate and can be used for routine analysis and quality control of raw material of S.
    [Show full text]
  • United States Patent Office Patented Dec
    3,549,689 United States Patent Office Patented Dec. 22, 1970 2 of 35 to 127, i.e. chloro, bromo or iodo, and R3 is lower 3,549,689 alkyl, e.g., having from 1 to 6 carbon atoms, such as PHENOXY-ALKANOC ACDS methyl, ethyl, propyl, butyl, amyl or hexyl, preferably Albert J. Frey, Essex Fells, Rudolf G. Griot, Florham methyl or ethyl. Park, and Hans Ott, Convent Station, N.J., assignors to Sandoz-Wander, Inc., Hanover, N.J., a corporation (1) alkali metal base of Delaware No Drawing. Filed May 23, 1967, Ser. No. 640,465 (2) R at C. CO7 c 103/22 OH X-C-COOR3 U.S. C. 260-471 39 Claims ke O ---> -N-(-(e) Step a ABSTRACT OF THE DISCLOSURE H. O The compounds are or - (o - benzamidophenoxy)-lower II alkanoic acids, e.g., 2 - 4-chloro-2-(p-chlorobenzamido)- phenoxy)-isobutyric acid. They are useful as anti-inflam matories. They are prepared by benzoylating an o-amino phenol to form the corresponding o-benzamidophenol, which is then condensed with a suitable c-halo-lower alkanoic acid alkyl ester to form the corresponding ox (o-benzamidophenoxy)-lower alkanoic acid alkyl ester, 20 which is then hydrolyzed to its acid. This invention relates to phenoxy-alkanoic acids and more particularly to c. - (o - benzamidophenoxy) - lower 2 5 alkanoic acids and processes for their preparation. The invention also relates to intermediates in the preparation of said ox - (o-benzamidophenoxy) - lower alkanoic acids, and to processes for the preparation of said intermediates. The or - (o - benzamidophenoxy) - lower alkanoic acids 30 According to reaction scheme A, in Step (a) the de of this invention have the formula: sired compound III is formed from a suitable compound II.
    [Show full text]
  • Alcohol and Tobacco Tax and Trade Bureau, Treasury § 21.102
    Alcohol and Tobacco Tax and Trade Bureau, Treasury § 21.102 § 21.99 Brucine alkaloid. (d) Dryness at 20 °C. Miscible without ° ´ (a) Identification test. Add a few drops turbidity with 19 volumes of 60 Be1. of concentrated nitric acid to about 10 gasoline. (e) Freezing point (first needle). Above mg of brucine alkaloid. A vivid red ° color is produced. Dilute the red solu- 20 C. (f) Place five drops tion with a few drops of water and add Identification test. of a solution containing approximately a few drops of freshly made dilute 0.1 percent tertiary butyl alcohol in stannous chloride solution. A reddish ethyl alcohol in a test tube. Add 2 ml purple (violet) color is produced. (b) Melting point. 178 °±1 °C. Dry the of Denige’s reagent (dissolve 5 grams of alkaloid in an oven for one hour at 100 red mercuric oxide in 20 ml of con- °C., increase the temperature to 110° centrated sulfuric acid; add this solu- and dry to a constant weight before tion to 80 ml of distilled water, and fil- taking melting point. ter when cool). Heat the mixture just to the boiling point and remove from NOTE. Brucine alkaloid tetrahydrate melts the flame. A yellow precipitate forms at 105 °C. while the anhydrous form melts at within a few seconds. ° 178 C. (g) Nonvolatile matter. Less than 0.005 (c) Strychnine test. Brucine alkaloid percent by weight. shall be free of strychnine when tested (h) Odor. Characteristic odor. by the method listed under Brucine (i) Residual odor after evaporation. Sulfate, N.F.
    [Show full text]
  • SAFETY DATA SHEET Emergency Phone Number
    SAFETY DATA SHEET Product Name: SDA-40-2 (190 U.S. PROOF) Page 1 of 9 MSDS NO: 3953 Effective Date: February 15, 2018 Section 1– identification of substance and of supplier PRODUCT NAME: SDA-40-2 (190 U.S. PROOF) SYNONYMS: Denatured alcohol, Specially denatured alcohol, Ethanol denatured with tertiary butanol and brucine sulphate CHEMICAL FAMILY: Alcohols, alkaloids RECOMMENDED USE: As a solvent in the manufacture of: hair and scalp preparations, bay rum, lotions and creams, deodorants, toilet waters and colognes, shampoos, soaps and bath preparations, external pharmaceuticals, disinfectants, insecticides, fungi- cides and other biocides, cleaning solutions, theater sprays, incense and room deodorants. RESTRICTIONS ON USE: Refer to the alcohol control authority in country in which the product is to be used– Canada Revenue Agen- cy (Excise) in Canada, US Tax and Trade Bureau in US etc. SUPPLIER: Commercial Alcohols, a Trade name of GreenField Global Inc. 6985 Financial Drive, Mississauga, Ontario, Canada L5N 0G3 Web page: http://www.greenfield.com/ Non-Emergency Information Phone Number: (905) 790-7500 Emergency Phone Number: Canutec (613) 996-6666 Section 2– HAZARDS IDENTIFICATION GHS label elements, including precautionary statements: Signal Word: DANGER! Hazard statement(s) H225 Highly flammable liquid and vapor. H315 + H320 Causes skin and eye irritation H335 May cause respiratory irritation. Precautionary statement(s) P501 Dispose of contents and container to an approved waste disposal plant. P240 Ground/bond container and receiving equipment. P337 + P313 If eye irritation persists: Get medical attention. THE INFORMATION AND RECOMMENDATIONS CONTAINED HEREIN ARE BASED UPON DATA BELIEVED TO BE CORRECT. HOWEVER, NO GUARANTEE OR WARRANTY OF ANY KIND, EXPRESSED OR IMPLIED, IS MADE WITH RESPECT TO INFORMATION AND RECOMMEN- DATIONS CONTAINED HEREIN.
    [Show full text]
  • Agenda Item 2 Development of Recommendations for Amendments to the Technical : Instructions for Incorporation in the 2005/2006 Edition
    DGP/19-WP/40 24/09/03 Addendum No. 1 17/10/03 English only DANGEROUS GOODS PANEL (DGP) NINETEENTH MEETING Montreal, 27 October to 7 November 2003 Agenda Item 2 Development of recommendations for amendments to the Technical : Instructions for incorporation in the 2005/2006 edition PACKING INSTRUCTIONS (Presented by the Secretary) ADDENDUM NO. 1 Attached is a List of Substances showing new Packing Instruction numbers as referred to in Annex 2 of WP/40. — — — — — — — — (86 pages) DGP.19.WP.040.Add.1.en.wpd List of Substances showing new Packing Instruction numbers Packing UN Name and description group Class PI No. PI No. PP No. No. 3.1.2 2.2 2.1.1.3 Ltd Qty 1088 ACETAL 3 II 303 Y303 1089 ACETALDEHYDE 3 I F 1090 ACETONE 3 II 303 Y303 1091 ACETONE OILS 3 II 303 Y303 1092 ACROLEIN, STABILIZED 6.1 I S 1093 ACRYLONITRILE, STABILIZED 3 I 306 1098 ALLYL ALCOHOL 6.1 I S 1099 ALLYL BROMIDE 3 I 306 1100 ALLYL CHLORIDE 3 I 306 1104 AMYL ACETATES 3 III 303 Y303 1105 PENTANOLS 3 II 303 Y303 1105 PENTANOLS 3 III 303 Y303 1106 AMYLAMINE 3 II 303 Y303 1106 AMYLAMINE 3 III 303 Y303 1107 AMYL CHLORIDE 3 II 303 Y303 1108 1-PENTENE (n-AMYLENE) 3 I 303 1109 AMYL FORMATES 3 III 303 Y303 1110 n-AMYL METHYL KETONE 3 III 303 Y303 1111 AMYL MERCAPTAN 3 II 304 Y303 5 1112 AMYL NITRATE 3 III 303 Y303 1113 AMYL NITRITE 3 II 303 Y303 1114 BENZENE 3 II 303 Y303 1120 BUTANOLS 3 II 303 Y303 1120 BUTANOLS 3 III 303 Y303 1123 BUTYL ACETATES 3 II 303 Y303 1123 BUTYL ACETATES 3 III 303 Y303 1125 n-BUTYLAMINE 3 II 303 Y303 1126 1-BROMOBUTANE 3 II 303 Y303 1127 CHLOROBUTANES
    [Show full text]