DOCSLIB.ORG

A Novel Reaction of Primary Amines with Trichloroacetonitrile

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
A Novel Reaction of Primary Amines with Trichloroacetonitrile A NOVEL REACTION OF PRIMARY AMINES WITH TRICHLOROACETONITRILE by John Constantin Grivas A thesis submitted to the Faculty of Graduate Studies and Research of McGill University in partial fulfilment of the requirements for the degree of Master of Science McGill University Montreal, Canada April 1957 AC~ The author gratefully acknowledges the guidance given by Dr. A. Taurins who directed this work. TABLE OF CONI'ENI'S GENERAL IID'RODUCTION ••• • • • • • • • • • • • • • • • •••• 1 HISTORICAL INTRODUCTION • • • • • • • • • • • • • • • • • • • • 2 Amidines: Nomenclature and classification • • • • • • • • • 2 Preparations from nitriles and amines • • • • • • 3 The chemistry of trichloroacetonitrile • • • • • • • • • • 20 Reaction of P,Yridine with bromine • • • • • • • • • • • • • 24 Pyridine perbromides as brominating agents • • • • • • • • 27 DISCUSSION • • • • • • • • • • • • • • • • • • • • • • • • • • • 30 Reaction of primary amines with trichloroacetonitrile • • • 30 Aspects or the reaction mechanism • • • • • • • • • • • • • 36 E:trect or N-substituted trichloroacetamidines on the skin • • • • • • • • • • • • • • • • • • • • • • 43 Reaction of pyridine dibromide with aniline • • • • • • • • 44 Correlation between the infrared spectra and the structure of N-substituted trichloroacetamidines • • • • 47 EXPERIMENTAL • • • • • • • • • • • • • • • • • • • • • • • • • • 56 Preparations of: Ethyl trichloroacetate • • • • • • • • • • • • • • • • 56 2,2,2-Trichloroacetamide • • • • • • • • • • • • • • • 56 Trichloroacetonitrile • • • • • • • • • • • • • • • • 57 N-phenyltrichloroacetamidine • • • • • • • • • • • • • 57 N-phenyltrichloroacetamidine hydrochloride • • • • • • 5S N-methyltrichloroacetamine • • • • • • • • • • • • • • 5S N-methyltrichloroacetamidinium picrate • • • • • • • • 59 N-ethyltrichloroacetamidine • • • • • • • • • • • • • 59 N-ethyltrichloroacetamidine bydrochloride • • • • • • 60 N-benz.yltrichloroacetamidine • • • • • • • • • • • • • 61 Methylamine hydrochloride and trichloro- acetonitrile • • • • • • • • • • • • • • • • • • • 62 Ethylamine hydrochloride and trichloro- acetonitrile • • • • • • • • • • • • • • • • • • • 62 Reaction of trichloroacetonitrile and hydrazine • • • 63 Preparation of pyridine dibromide: In acetonitrile • • • • • • • • • • • • • • • • • • • 64 In carbon tetrachloride • • • • • • • • • • • • • • • 65 Reaction of p,yridine dibromide with aniline • • • • • • • • 65 TABLE OF CON'l'Em'S (ii) Preparation of: 2,4,6-Tribromoacetanilide • • • • • • • • • • • • • • 67 2,4,6-Tribromobenzanilide • • • • • • • • • • • • • • 67 2,4,6-Tribromoformanilide • • • • • • • • • • • • • • 67 Infrared absorption spectra • • • • • • • • • • • • • • • • SUMMARY AND CON'l'RIBUTIONS TO Knll.EDGE • • • • • • • • • • • • • BIBLIOGRAPHY • • • • • • • • • • • • • • • • • • • • • • • • • • 74 GENERAL INTRODUCTION The addition of free amines to the nitrile group of trichloro­ acetonitrile CCl.3 C=N is not mentioned in any reviews or textboolœ summarizing the general chemical properties of nitriles. The reason for this is that this reaction bas not been described in any chemical jour­ nal. It has been mentioned only in the German Patent 671,785 (1939), which states that the reaction has been carried out under anhydrous conditions at low temperature. We round that trichloroacetonit!ile reacts with primary and secondary aliphatic, aromatic and heterocyclic amines at mild conditions without any catalysts, even in dilute solutions at room temperature. There are no side-products of reactions, and the products formed are of high purity and uniformity. The objective of the first phase of this research was to stuqy the preparation and characterization of N-substituted trichloro­ acetamidines by the interaction of several primary amines, on trichloro­ acetonitrile, and to record the infrared spectra of these synthetic products. There are plans to continue this work by extending the scope of reaction to various secondary and heterocyclic amines. Another angle of research will be the physical-organic stuqy of the kinetics of this reaction, and the kinetics of hydrolysis of the new N-substituted trichloroacetamidine~. The other problem in this research was to stuqy the interaction of pyridine dibromide with aniline in acetonitrile solution. 2. HISTORICAL AMIDINES Nomenclature and Classification Amidines are monoacid bases characterized by the formula (I) N-R' R" R-~-N/ (I) 'R,nt where R, R', Rtt, Rttt are hydrogen, al~l or ar,yl radicals and their substitution products. In general, an amidine is named after the acid or amide which may be obtained from it by hydrolysis, according to the system employed in the Chemical Abstracts; thus (II) is acetamidine. (II) The carbon atoms adjacent to the amidine carbon atom are designated in the same manner as those adjacent to a carbonyl group ( 0<, f1', 0 , d ... etc.); thus (III) is named 6?-phenylpropionamidine. c H - CH -CH -C -NH (III) 6 5 2 2 Il 2 NH The nitrogen atoms of the imino and amino groups are not differ- entiated by this system and are referred to as N and N'. If it is difficult to name the compound as a derivative of an acid, the amidine group is referred to as carboxamidine, e.g. (IV) is named stilbene-4,4'-dicarboxamidine. 3. NH ~N-C" .CH =CH (IV) Amidines may be classified into five general types according to the number and distribution of the substituents on the nitrogen atoms. NH I. Unsubstituted R-C~ '~ II. Monosubstituted or III. Symmetrical disubstituted ;NR' NHRt R-e or R-C.,? 'NHR'' ~NR' ~NH IV. Unsymmetrical disubstituted R-C~ 'NR'R'' v. Trisubstituted The preparation of amidines from nitriles and amines Cornell (1) has prepared unsubstituted amidines in low yields by heating the corresponding nitriles with ammonium chloride in liquid ammonia in sealed tubes; he observed that no reaction occurs when only the nitrile and ammonia were used. Bernthsen (2) by a similar procedure prepared many unsubstituted amidines in ver,y low yields. Pinner (3,4) dèscribed the synthesis of unsubstituted amidines from nitriles via the imidic esters; the nitrile was dissolved or suspended in anhydrous alcohol and treated with an excess of dry hydrogen chloride forming an imidic ester hydrochloride (V), which was then caused to react with ammonia 1 as in the following scheme .hNH R-C.:N + R'OH + HCl~R-C~ .HCl (V) OR' ~NH (V) + ~R-C .HCl + R'OH 'NH 2 AYdrogen bromide may be substituted for hydrogen chloride and alcohols other than ethanol may be used (3). The above method is general and mononitriles as well as dinitriles, aliphatic or aromatic, have been used (5). Thus Lamb and White (6) prep­ ared decanebis-(N-cyclohexylcarbonamidine) (VI) which cr,ystallized from acetone-alcohol mixture in needles, m.p. 122°. (VIa) VI Pinner (.3) and Gautier (7) obtained even formamidine hydro­ chloride (VII) from cyanogen. ..,..,oR H-C=:N + ROH + HCl- H-C 'NH•HCl 00 ~- -e/ NH H C ,----z H + .3~- 'ibo. .HCl + ROH ~NH.HCl ~NH (VII) Functional groups which do not react with the reagents or the products do not alter the course of the reaction and hydrochloric acid seems to be necessary (8,9). 0 ==C-OC H 0 =C-OC H O=C-OC H 2 5 1 _.,.,_ 1 25 1 2 5 CH -C-NH c~.c= N c~- c=NH 2 1 1 OC H NH 2 5 2 There are limitations as to the type of the unsubstituted amidines which can be prepared by Pinnerts method. Acyl or benzoil cyanides cannot be used, as they give their esters with the evolution of hydrogen cyanide (.3). HCl c H -c -C=N + ROH C6H5-C-OR + HC=N 6 5 Il - M 0 0 Ortho-substituted aromatic nitriles were unreactive with alcohols and hydrogen chloride, whereas their isomers formed imidic esters, converted to amidines; thus p-toluenenitrile (VIII) and 0-naphthlenenitrile (IX) were ......... found reactive, while 0-toluenenitrile (X), ~ -naphthalenenitrile (XI), 2-amino-4 methylbenzonitrile (XII) and 2-nitro-4 methylbenzonitrile (XII) 6. gave negative results. VIII IX : x XI : XII . XIII Steric hindrance plays an important role in these reactions, but the exact limitations are unknown; an example is the formation of o-alkoxybenzamidines (XVI) from o-alkoxybenzonitriles (XIV), (10) XIV xv XV + NH OR 3 C=NH O 1 • HCl ~ XVI The mechanism of this reaction is not known yet; nevertheless, Knorr (16) suggested that the following process involving an ammonium ion may be possible. .. .. ~ ,.NH NH NH '-Il Il R-C-ORt ~R-ë-OR :~ ~RC::.NH + ROH .,. R-J1 l +S @ffi3 :~ Monosubstituted amidines may be prepared from the salts of the al~l and aryl primary amines and nitriles under the influence of heat (11,12), but it has the disadvantage that disubstituted amidines are also formed as by-products. Thus, N-phenyl-phenylacetamidine (XVIII) was obtained by heating aniline hydrochloride with ben~l nitrile (XVII) at 220-240° in sealed tube for one day (13,14). Starting with nitriles, via imidic esters, monosubstituted amidines may be produced by replacing the ammonia with primary amines (3,15). 8. Hill and Rabinowitz (17) prepa.red some amidines of the "Halo­ caine" type using the same method, (a) by replacing the methyl groups of Holocaine (XIX), which is regarded as an efficient local anaesthetic !or opthalmic purposes, with alkyl or aralkyl groups, and (b) by replacing one phenetidine group by the amino (XX) or dialkylamino groups (XXI) XIX xx XXI An example is the preparation of the Holocaine itself by treating two molecular equivalents of p-phenetidine (XXII) in dry ether with a sus- pension of the imidic ester hydrochloride in the same solvent; the mixture was allowed to stand for 21 days at room temperature and occasionally
Load more

Recommended publications
  • Synthesis of 1,2,4 Oxadiazol-5-Imine, 1,2,4-Triazol-3-Imine and Derivatives: a Substituted Cyanamide-Based Strategy for Heterocycle Synthesis
    Synthesis of 1,2,4 oxadiazol-5-imine, 1,2,4-triazol-3-imine and derivatives: A Substituted Cyanamide-based Strategy for Heterocycle Synthesis Shreesha V. Bhat A thesis submitted in partial fulfilment of the requirements of the University of Lincoln for the degree of Doctor of Philosophy June 2017 Statement of Originality “I, Shreesha V. Bhat, hereby declare that this submission is my own work and to the best of my knowledge it contains no materials previously published or written by another person, or substantial proportions of material which have been published or accepted for the award of any other degree or diploma at University of Lincoln or any other educational institution, except where references have been made in the thesis. Any contribution made to the research by others, with whom I have worked at the University of Lincoln or elsewhere, is explicitly acknowledged in the thesis. I also declare that the intellectual content of this thesis is the product of my own work, except to the extent that assistance from others in the project's design and conception or in style, presentation and linguistic expression is acknowledged.” (Shreesha V. Bhat) ii | P a g e Abstract Considering the importance of nitrogen-rich heterocycles in drug discovery, a novel strategy towards heterocycle synthesis was envisioned using cyanamide chemistry. Synthesis which involve mild conditions, avoids multi-step sequence and non-toxic reagents are desirable for generation of large combinatorial libraries of drug molecules. We envisaged that the NCN linkage of the cyanamide as well as the concomitant use of the nucleo-and electrophilic centres of the cyanamide could provide a novel synthetic route towards nitrogen heterocycles.
    [Show full text]
  • Part One Amino Acids As Building Blocks
    Part One Amino Acids as Building Blocks Amino Acids, Peptides and Proteins in Organic Chemistry. Vol.3 – Building Blocks, Catalysis and Coupling Chemistry. Edited by Andrew B. Hughes Copyright Ó 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 978-3-527-32102-5 j3 1 Amino Acid Biosynthesis Emily J. Parker and Andrew J. Pratt 1.1 Introduction The ribosomal synthesis of proteins utilizes a family of 20 a-amino acids that are universally coded by the translation machinery; in addition, two further a-amino acids, selenocysteine and pyrrolysine, are now believed to be incorporated into proteins via ribosomal synthesis in some organisms. More than 300 other amino acid residues have been identified in proteins, but most are of restricted distribution and produced via post-translational modification of the ubiquitous protein amino acids [1]. The ribosomally encoded a-amino acids described here ultimately derive from a-keto acids by a process corresponding to reductive amination. The most important biosynthetic distinction relates to whether appropriate carbon skeletons are pre-existing in basic metabolism or whether they have to be synthesized de novo and this division underpins the structure of this chapter. There are a small number of a-keto acids ubiquitously found in core metabolism, notably pyruvate (and a related 3-phosphoglycerate derivative from glycolysis), together with two components of the tricarboxylic acid cycle (TCA), oxaloacetate and a-ketoglutarate (a-KG). These building blocks ultimately provide the carbon skeletons for unbranched a-amino acids of three, four, and five carbons, respectively. a-Amino acids with shorter (glycine) or longer (lysine and pyrrolysine) straight chains are made by alternative pathways depending on the available raw materials.
    [Show full text]
  • Hydrolysis of Haloacetonitriles: Linear Free Energy Relationship, Kinetics and Products
    Wat. Res. Vol. 33, No. 8, pp. 1938±1948, 1999 # 1999 Elsevier Science Ltd. All rights reserved Printed in Great Britain PII: S0043-1354(98)00361-3 0043-1354/99/$ - see front matter HYDROLYSIS OF HALOACETONITRILES: LINEAR FREE ENERGY RELATIONSHIP, KINETICS AND PRODUCTS VICTOR GLEZER*, BATSHEVA HARRIS, NELLY TAL, BERTA IOSEFZON and OVADIA LEV{*M Division of Environmental Sciences, Fredy and Nadine Herrmann School of Applied Science, The Hebrew University of Jerusalem, 91904, Jerusalem, Israel (First received September 1997; accepted in revised form August 1998) AbstractÐThe hydrolysis rates of mono-, di- and trihaloacetonitriles were studied in aqueous buer sol- utions at dierent pH. The stability of haloacetonitriles decreases and the hydrolysis rate increases with increasing pH and number of halogen atoms in the molecule: The monochloroacetonitriles are the most stable and are also less aected by pH-changes, while the trihaloacetonitriles are the least stable and most sensitive to pH changes. The stability of haloacetonitriles also increases by substitution of chlorine atoms with bromine atoms. The hydrolysis rates in dierent buer solutions follow ®rst order kinetics with a minimum hydrolysis rate at intermediate pH. Thus, haloacetonitriles have to be preserved in weakly acid solutions between sampling and analysis. The corresponding haloacetamides are formed during hydrolysis and in basic solutions they can hydrolyze further to give haloacetic acids. Linear free energy relationship can be used for prediction of degradation of haloacetonitriles
    [Show full text]
  • Recent Advances in Cyanamide Chemistry: Synthesis and Applications
    molecules Review Recent Advances in Cyanamide Chemistry: Synthesis and Applications M. R. Ranga Prabhath, Luke Williams, Shreesha V. Bhat and Pallavi Sharma * School of Chemistry, Joseph Banks Laboratories, University of Lincoln, Lincoln LN6 7DL, UK; [email protected] (M.R.R.P.); [email protected] (L.W.); [email protected] (S.V.B.) * Correspondence: [email protected]; Tel.: +44-015-2288-6885 Academic Editor: Margaret A. Brimble Received: 9 March 2017; Accepted: 7 April 2017; Published: 12 April 2017 Abstract: The application of alkyl and aryl substituted cyanamides in synthetic chemistry has diversified multi-fold in recent years. In this review, we discuss recent advances (since 2012) in the chemistry of cyanamides and detail their application in cycloaddition chemistry, aminocyanation reactions, as well as electrophilic cyanide-transfer agents and their unique radical and coordination chemistry. Keywords: cyanamide; synthesis; aminocyanation; cycloaddition; electrophilic cyanation; radical reaction; coordination chemistry 1. Introduction Cyanamide enjoys a rich chemical history, which can be traced to its unique and chemically promiscuous nitrogen-carbon-nitrogen (NCN) connectivity. The chemistry of the nitrile-substituted amino-group of the ‘cyanamide-moiety’ is dominated by an unusual duality of a nucleophilic sp3-amino nitrogen and an electrophilic nitrile unit. The reported use of unsubstituted cyanamide (NH2CN) and metal cyanamides (MNCN, where M = metal) date back as far as the late 19th century, where the likes of calcium cyanamide (CaNCN) was used as a fertilizer, and later as source of ammonia and nitric acid, which fueled the industrial production of metal cyanamides. In contrast, the reported use of the corresponding substituted organic cyanamides (RNHCN or RR’NCN) gathered pace only in more recent years.
    [Show full text]
  • Lithium Promoted Mesoporous Manganese Oxide Catalyzed Oxidation of Allyl Ethers
    ARTICLE https://doi.org/10.1038/s41467-019-08619-x OPEN Lithium promoted mesoporous manganese oxide catalyzed oxidation of allyl ethers Biswanath Dutta1, Ryan Clarke 1, Sumathy Raman2, Timothy D. Shaffer2, Laura Achola1, Partha Nandi2 & Steven L. Suib1,3 Herein we report the first example of the catalytic aerobic partial oxidation of allyl ether to its acrylate ester derivative. Many partial oxidations often need an expensive oxidant such as 1234567890():,; peroxides or other species to drive such reactions. In addition, selective generation of esters using porous catalysts has been elusive. This reaction is catalyzed by a Li ion promoted mesoporous manganese oxide (meso-Mn2O3) under mild conditions with no precious metals, a reusable heterogeneous catalyst, and easy isolation. This process is very attractive for the oxidation of allyl ethers. We report on the catalytic activity, selectivity, and scope of the reaction. In the best cases presented, almost complete conversion of allyl ether with near complete chemo-selectivity towards acrylate ester derivatives is observed. Based on results from controlled experiments, we propose a possible reaction mechanism for the case in which N-hydroxyphthalimide (NHPI) is used in combination with trichloroacetonitrile (CCl3CN). 1 Department of Chemistry, University of Connecticut, U-3060, 55 North Eagleville Road, Storrs, CT 06269, USA. 2 Corporate Strategic Research, ExxonMobil, 1545 US 22 East, Annandale, NJ 08801, USA. 3 Institute of Materials Science, University of Connecticut, U-3060, 55 North
    [Show full text]
  • Cation Clock Reactions for the Determination of Relative Reaction Kinetics in Glycosylation Reactions
    Wayne State University Wayne State University Dissertations 1-1-2018 Cation Clock Reactions For The etD ermination Of Relative Reaction Kinetics In Glycosylation Reactions Philip Adero Wayne State University, Follow this and additional works at: https://digitalcommons.wayne.edu/oa_dissertations Part of the Organic Chemistry Commons Recommended Citation Adero, Philip, "Cation Clock Reactions For The eD termination Of Relative Reaction Kinetics In Glycosylation Reactions" (2018). Wayne State University Dissertations. 2086. https://digitalcommons.wayne.edu/oa_dissertations/2086 This Open Access Dissertation is brought to you for free and open access by DigitalCommons@WayneState. It has been accepted for inclusion in Wayne State University Dissertations by an authorized administrator of DigitalCommons@WayneState. CATION CLOCK REACTIONS FOR THE DETERMINATION OF RELATIVE REACTION KINETICS IN GLYCOSYLATION REACTIONS by PHILIP OUMA ADERO DISSERTATION Submitted to the Graduate School of Wayne State University, Detroit, Michigan in the partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY 2018 MAJOR: CHEMISTRY (Organic) Approved By: __________________________________________ Advisor Date __________________________________________ __________________________________________ __________________________________________ __________________________________________ DEDICATION This dissertation is dedicated to God for his providence and mercy, and to my family for the unconditional love and support ii ACKNOWLEDGMENTS I would like to express my profound gratitude to my graduate adviser, Professor David Crich for his guidance and encouragement throughout my research work in his laboratory at Wayne State University. I thank him for the confidence he had in me, for his constant unwavering support for my academic excellence and for inspiration and mentorship throughout my Ph.D studies. I wish to thank my committee members comprising; Prof. Jennifer Stockdill, Prof.
    [Show full text]
  • Mild Reductive Functionalization of Amides Into N‐Sulfonylformamidines
    http://www.diva-portal.org This is the published version of a paper published in ChemistryOpen. Citation for the original published paper (version of record): Trillo, P., Slagbrand, T., Tinnis, F., Adolfsson, H. (2017) Mild Reductive Functionalization of Amides into N-Sulfonylformamidines. ChemistryOpen, 6(4): 484-487 https://doi.org/10.1002/open.201700087 Access to the published version may require subscription. N.B. When citing this work, cite the original published paper. Permanent link to this version: http://urn.kb.se/resolve?urn=urn:nbn:se:umu:diva-138585 DOI:10.1002/open.201700087 Mild Reductive Functionalization of Amides into N- Sulfonylformamidines Paz Trillo,[a] Tove Slagbrand,[a] Fredrik Tinnis,*[a] and Hans Adolfsson*[a, b] The development of aprotocolfor the reductivefunctionaliza- tion of amides into N-sulfonylformamidines is reported. The one-pot procedure is based on amild catalytic reduction of tertiaryamides into the corresponding enamines by the use of Mo(CO)6 (molybdenum hexacarbonyl) and TMDS (1,1,3,3-tetra- methyldisiloxane). The formed enamines were allowed to react with sulfonyl azidestogive the target compounds in moderate to good yields. The amidine functional group is frequently found in biological- ly activecompounds possessing anti-inflammatory,antibacteri- al, antiviral, antibiotic, and anestheticproperties.[1] They are also employed as intermediates and precursors in organic syn- thesis of importantheterocyclic compounds such as imida- zoles, quinazolines,isoquinolines, and pyrimidines.[2] Further- more, amidines are employed as ligandsinmetal complexes and as protecting groups for primary amines.[3] Scheme1.Preparation of amidines through a–c) electrophilic amide activa- The stability of amides makes this functional group valuable tion and d) reductive functionalization of amides.
    [Show full text]
  • Chemicals Found in Pool Water Can Be Derived from a Number of Sources
    CHAPTER 4 CChemicalhemical hhazardsazards hemicals found in pool water can be derived from a number of sources: the source Cwater, deliberate additions such as disinfectants and the pool users themselves (see Figure 4.1). This chapter describes the routes of exposure to swimming pool chemi- cals, the chemicals typically found in pool water and their possible health effects. While there is clearly a need to ensure proper consideration of health and safety issues for operators and pool users in relation to the use and storage of swimming pool chemicals, this aspect is not covered in this volume. Chemicals in pool, hot tub and spa water Source water-derived: Bather-derived: Management-derived: disinfection by-products; urine; disinfectants; precursors sweat; pH correction chemicals; dirt; coagulants lotions (sunscreen, cosmetics, soap residues, etc.) Disinfection by-products: e.g. trihalomethanes; haloacetic acids; chlorate; nitrogen trichloride Figure 4.1. Possible pool water contaminants in swimming pools and similar environments 4.1 Exposure There are three main routes of exposure to chemicals in swimming pools and similar environments: • direct ingestion of water; • inhalation of volatile or aerosolized solutes; and • dermal contact and absorption through the skin. 60 GUIDELINES FOR SAFE RECREATIONAL WATER ENVIRONMENTS llayoutayout SSafeafe WWater.inddater.indd 8822 224.2.20064.2.2006 99:57:05:57:05 4.1.1 Ingestion The amount of water ingested by swimmers and pool users will depend upon a range of factors, including experience, age, skill and type of activity. The duration of ex- posure will vary signifi cantly in different circumstances, but for adults, extended ex- posure would be expected to be associated with greater skill (e.g.
    [Show full text]
  • United States Patent Office Patented Jan
    3,017,356 United States Patent Office Patented Jan. 16, 1962 1. 2 rated aliphatic radical, a cycloaliphatic radical, an aryl 3,017,356 radical, an aralkyl radical, an alkaryl radical, an alkoxy WillianPROCESS B. Hughes, OF andINHIBITING Verner L. Stronberg,CORROSION Webster alkyl radical, an aryloxyalkyl radical, and the like; and Groves, Mo., assignor's to Petroite Corporation, Wii A is an alkylene group; for example, ethylene and propyl mington, Del, a corporation of Delaware ene radicals, such as No Drawing. Original application Mar. 3, 1958, Ser. No. 718,391 Divided and this application Nov. 23, 1959, Ser. No. 854,553 -CH2CH2CH 15 Claims. (C. 252-8.55) CH-CH2 O B This application is a division of Serial No. 718,391, CHs filed March 3, 1958. This invention relates to esters of cyclic amidines of -CH-CH-CH,- the formula gh, CHis O 15 -bH-bH In general, the amidine esters are prepared by reacts o-o-c- ing a hydroxyaliphatic cyclic amidine ()-ROH with less where (A) and (B) are cyclic amidine-containing radicals, than a stoichiometric amount of a polycarboxylic acid to for example, imidazoline and tetrahydropyrimidine radi form a half ester cals (hereafter referred to as “amidine esters'). More 20 particularly, this invention relates to esters wherein. A contains one type of cyclic amidine ring and B contains (a)-R-O C-Z-COH the same or another type not selected in A. This inven which is subsequently reacted with an amidine forming tion also relates to a process of preparing these com polyamine to form the amidine ester pounds which comprises reacting a hydroxy-containing 25 O cyclic amidine with less than a stoichiometric amount of a polycarboxylic acid to form a partial ester and then re Q-R-O-)-2- acting this partial ester with a polyamine capable of form More specifically, the corrosion inhibiting aspect of this ing a second amidine ring of the same or different type.
    [Show full text]
  • PS-Triphenylphosphine
    Technical Note PS-Triphenylphosphine Resin-bound Phosphine PS-Triphenylphosphine is a resin-bound Specifications equivalent of triphenylphosphine. The Chemical Name: Diphenylphosphino-polystyrene capacity of the resin is determined by the Resin Type: 1% Cross-linked poly(styrene-co- quantitation of benzyl bromide uptake in divinylbenzene) DMF (GC, internal standard method). P Loading: Typical loading 2.2 mmol/g, minimum loading 1.8 mmol/g (based on uptake of benzyl bromide) PS-Triphenylphosphine can be used in Bead Size: 75–150 microns, 100–200 mesh Mitsunobu reactions to prepare aryl (95% within) ethers in good-to-excellent yields and in Application: Chlorination of acids and alcohols, high purities (Scheme 1).1 Wittig and Mitsunobu reactions, scavenging of alkyl halides Typical Chlorination Conditions: 0.5 equivalent of acid or alcohol in CCl4, 3 h, reflux Typical Mitsunobu Reaction Conditions: 1.0 1. MP-Carbonate (2.5 eq) equivalent of alcohol, 1.5 equivalent of phenol, X 2. Filter Alphatic or Aryl-OH X 2.2 equivalent of resin, and 1.6 equivalent of di- + PS-PPh3 + DBAD 3. TFA:DCM:H2O (50:48:2) HO 16 hr, RT, THF 4. LLE (extract into MTBE) Aryl or Aliphatic O tert-butyl azodicarboxylate (DBAD) at room tem- 2.2eq 1.6eq 5. Concentrate 1.5eq perature for 16 h Typical Wittig Reaction Conditions: 2.0 equiv- Scheme 1. Mitsunobu reaction using PS-Triphenylphosphine alent of ylide resin, 8.0 equivalent of sodium bis (dimethylsilyl)amide/tetrahydrofuran Mitsunobu general procedure: Add a solution of the phenol to the PS- (NaHMDS/THF), resin washed with THF, followed by 1.0 equivalent of carbonyl compound in THF at Triphenylphosphine resin and allow the suspension to stand for 5 min.
    [Show full text]
  • Poly(Vinylammonium Formate) and Process for Making Amidine
    Europaisches Patentamt (19) European Patent Office Office europeenpeen des brevets EP0617 054B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) intci.e: C08F 8/12, C08F 8/44 of the grant of the patent: 04.12.1996 Bulletin 1996/49 (21) Application number: 94104538.7 (22) Date of filing: 22.03.1994 (54) Poly(vinylammonium formate) and process for making amidine-containing polymers Poly(Vinylammoniumformiat) und Verfahren zur Herstellung von Amidinegruppen enthaltender Polymeren Poly(formiate vinylique d'ammonium) et procede de preparation de polymeres contenant de groupes amidine (84) Designated Contracting States: (72) Inventor: Ford, Michael Edward BE DE FR GB NL Coopersburg, PA 18036 (US) (30) Priority: 25.03.1993 US 36757 (74) Representative: Kador & Partner Corneliusstrasse 15 (43) Date of publication of application: 80469 Miinchen (DE) 28.09.1994 Bulletin 1994/39 (56) References cited: (73) Proprietor: AIR PRODUCTS AND CHEMICALS, EP-A- 0 374 646 EP-A- 0 528 409 INC. DE-A-3 715 824 US-A- 4 393 174 Allentown, PA 18195-1501 (US) US-A- 4 943 676 DO ^> o Is- CO Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice the Patent Office of the Notice of shall be filed in o to European opposition to European patent granted. opposition a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. a. 99(1) European Patent Convention). LU Printed by Jouve, 75001 PARIS (FR) EP 0 617 054 B1 Description FIELD OF THE INVENTION 5 This invention relates to poly(vinylammonium formate) and to a process for its manufacture.
    [Show full text]
  • Cationic Palladium(II)-Catalyzed Stereoselective Glycosylation with Glycosyl Trichloroacetimidates
    Cationic Palladium(II)-Catalyzed Stereoselective Glycosylation with Glycosyl Trichloroacetimidates Jaemoon Yang, Colleen Cooper-Vanosdell, Enoch A. Mensah, and Hien M. Nguyen* Department of Chemistry and Biochemistry, Montana State UniVersity, Bozeman, Montana 59717 [email protected] ReceiVed NoVember 20, 2007 The development of a new method for stereoselective glycosylation with glycosyl trichloroacetimidate donors employing cationic palladium(II), Pd(CH3CN)4(BF4)2, is described. This process employs Pd(CH3CN)4(BF4)2 as an efficient activator, providing access to a variety of disaccharides and glyco- peptides. This reaction is highly stereoselective and proceeds under mild conditions with low catalyst loading. Interestingly, this palladium catalysis directs â-glucosylations in the absence of classical neighboring group participation. Introduction anhydrous and low temperature (up to -78 °C) conditions, especially if glycosyl donors and acceptors are incorporated with Since the first paper on Schmidt’s glycosylation method was acid-labile protecting groups. Additionally, high catalyst loading published in 1980,1 trichloroacetimidates have been among the is often required since these Lewis acids are oxophilic. This most widely used glycosyl donors. Their popularity comes from has resulted in the continued development of activating reagents their relative ease of synthesis by base-catalyzed addition of and conditions for the activation of trichloroacetimidates. It trichloroacetonitrile to the anomeric hydroxy group.2 The begins with the use of stoichiometric amounts of AgOTf as a glycosyl trichloroacetimidates are often formed in high yield promoter to provide glycosides with excellent yields.8 Two other with excellent anomeric selectivity. The glycosyl trichloroace- improvements utilizing LiClO and LiOTf as promoters have timidates are generally activated with strong and moisture- 4 been described.
    [Show full text]