DOCSLIB.ORG

A Process for Preparing an Acyl Halide Or Sulfonyl Halide

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text

Load more

~™ llll III II II III II III I II II III (19) J European Patent Office Office europeen des brevets (1 1 ) EP0 751 131 A1 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) Int. CI.6: C07D 233/18, C07C 51/60, 02.01.1997 Bulletin 1997/01 C07C 303/02, C07B 41/1 0 (21) Application number: 96108936.4 (22) Date of filing: 04.06.1996 (84) Designated Contracting States: • Hayashi, Hidetoshi DE FR IT NL Ohmuta-shi, Fukuoka-ken, 836 (JP) • Mizuta, Hideki (30) Priority: 20.06.1995 JP 152826/95 Ohmuta-shi, Fukuoka-ken, 837 (JP) (71) Applicant: MITSUI TOATSU CHEMICALS, Inc. (74) Representative: Strehl Schubel-Hopf Groening & Chiyoda-Ku Tokyo 1 00 (JP) Partner Maximilianstrasse 54 (72) Inventors: 80538 Munchen (DE) • Nagata, Teruyuki Ohmuta-shi, Fukuoka-ken, 836 (JP) (54) A process for preparing an acyl halide or sulfonyl halide (57) A preparation process of acyl halide or sulfonyl halide which comprises reacting corresponding carboxylic acid or sulfonic acid with a haloiminium salt represented by the general formula (1): R'-N -R2 X ( 1 ) XCrU/n wherein R1 and R2 are same or different lower alkyl groups, X is a halogen atom, and n is an integer of 2 or 3. CO LO o Q_ LU Printed by Rank Xerox (UK) Business Services 2.13.10/3.4 EP0 751 131 A1 Description 1 . Field of the Invention 5 The present invention relates to a preparation process of acyl halide or sulfonyl halide. 2. Description of the Related Art In recent years, acyl halide has become important in industry as an intermediate for preparing heat resistant resin, 10 medicines and agricultural chemicals. For example, lauroyl chloride is used in industry as an intermediate in the prep- aration of peroxides and surface active agents. Further, terephthaloyl chloride is used for preparing polyesters in indus- try. 5-Amino-2,4,6-triiodoisophthaloyl dihalide which is obtained by halogenating the acid portion of 5-amino-2,4,6-trii- odoisophthalic acid (hereinafter referred to simply as TIPA) is an important compound as a raw material of X-ray con- 15 trast medium. Sulfonyl halide has also become important in industry as an intermediate for preparing medicines and agricultural chemicals. Acyl halide is generally prepared by chlorinating carboxylic acid with a chlorinating agent such as thionyl chloride, phosphorus pentachloride, phosphorus trichloride, phosphoryl chloride and phosgene. However, thionyl chloride, phos- 20 phorus pentachloride, phosphorus trichloride and phosphoryl chloride are expensive, and have problems on the treat- ment of sulfur oxides, phosphate compounds and other byproducts which are formed by the reaction. Thus, production in an industrial scale accompanies various disadvantages and difficulties in view of economy and environmental pro- tection. Further, phosgene has lower reactivity than the above chlorinating agents and requires use of a catalyst. Exem- plary catalysts which can be used include dimethylformamide, quaternary ammonium salt and sulfonium salt. 25 Dimethylformamide and other lower aliphatic amides are generally used as inexpensive catalysts having high activity. However, even though these catalysts are used, an active species which is formed from phosgene and dimethylfor- mamide and the other lower aliphatic amides is labile at high temperatures and leads to a problem of drastically increas- ing the formation velocity of tarry materials at temperatures higher than 100 °C. Further, sulfonyl halide is generally prepared, for example, by chlorinating sulfonic acid with a chlorinating agent 30 such as thionyl chloride and phosphorus pentachloride. For example, methanesulfonyl chloride is prepared from meth- anesulfonic acid and thionyl chloride. However, thionyl chloride, phosphorus pentachloride and other chlorinating agents are expensive, and have problems on the treatment of sulfur oxides, phosphate compounds and other byprod- ucts which are formed by the reaction. Thus, production in an industrial scale accompanies various disadvantages and difficulties in view of economy and environmental protection. Chlorosulfonic acid is frequently used for preparing sulfo- 35 nyl chloride in industry. For example, p-toluenesulfonyl chloride is prepared in industry from toluene and chlorosulfonic acid and benzenesulfonyl chloride is prepared in industry from benzene and chlorosulfonic acid. However, chlorosul- fonic acid causes a violent decomposition reaction with water and forms hydrochloric acid and sulfuric acid. Conse- quently, handling of chlorosulfonic acid accompanies considerable disadvantages and difficulties as a result of severe corrosivity and strong toxicity. 40 2-Chloro-1 ,3-dimethylimidazolinium chloride has been known as a halogenating agent of a primary hydroxyl group in Japanese Laid Open Patent Hei 4-308538. However, the example of utilizing the compounds for preparation of acyl halide or sulfonyl halide has not yet been known. SUMMARY OF THE INVENTION 45 The present invention has been carried out in order to overcome the problems on the conventional preparation process of acyl halide or sulfonyl halide. The first object of the invention is to provide an excellent preparation process in economy. The second object of the invention is to provide an excellent process in view of environmental protection. As a result of an intensive investigation in order to achieve these objects, the present inventors have completed the so invention having the following constitution. That is, the aspect of the invention is, 1) a preparation process of corresponding acyl halide or sulfonyl halide comprising reacting carboxylic acid or sul- fonic acid with a haloiminium salt represented by the general formula (1): 55 2 EP0 751 131 A1 wherein R1 and R2 are same or different lower alkyl groups, X is a halogen atom, and n is an integer of 2 or 3, and 2) a preparation process of corresponding acyl halide or sulfonyl halide comprising blowing phosgene into carbox- ylic acid or sulfonic acid in the presence of a cyclic urea compound represented by the general formula (2): wherein R1 and R2 are same or different lower alkyl groups, and n is an integer of 2 or 3, forming a haloiminium salt represented by the general formula (1): wherein R1 and R2 and n are the same as above, and X is a halogen atom, and reacting said carboxylic acid or said sulfonic acid with the haloiminium salt. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS The haloiminium salt which can be used in the invention is represented by the general formula (1). Exemplary lower alkyl groups represented by R1 and R2 in the general formula (1) include lower alkyl groups having 1 - 4 carbon atoms such as a methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl group. Exemplary halogen atoms represented by X include a fluorine, chlorine, bromine and iodine atom. The chlorine atom is preferred in particular. Preferred examples of the haloiminium salt represented by the gen- eral formula (1) include 2-chloro-1,3-dimethylimidazolinium chloride (hereinafter referred to simply as DMC), 2-chloro- 1 ,3-diisopropylimidazolinium chloride, and 2-chloro-1,3-dimethyl-3,4,5,6-tetrahydropyrimidinium chloride. The haloiminium salt can be obtained with ease by reacting a cyclic urea compound which is known as a readily available solvent and is represented by the formula (2): wherein R1 and R2 and n are the same as above, with a known halogenating agent such as oxalyl halide, phosphorus trihalide. phosphorus pentahalide, phosphorus oxyhalide, phosgene and trichloromethyl chloroformate. Phosgene is now in mass production in a polyurethane industry, inexpensive, and free from generation of industrial wastes such as EP0 751 131 A1 phosphorus compounds, and thus is most preferred. The reaction is carried out by dissolving either the compound of the general formula (2) or the halogenating agent in a suitable solvent such as carbon tetrachloride, adding the other reagent by portions to the solution obtained, and reacting for several to dozens of hours at room temperature to 70°C. The haloiminium salt of the general formula (1) 5 thus obtained can be used after isolation. However, the reaction mixture can also be used as intact for the reaction of the invention without isolating the haloiminium salt. In the first place, the method for reacting the haloiminium salt with carboxylic acids will be illustrated. The amount of the haloiminium salt is stoichiometric or more, preferably 1 .0 - 2.0 times by equivalent, more prefer- ably 1.1 - 1 .3 times by equivalent for the carboxylic acid. 10 After finishing the reaction, the haloiminium salt returns to the compound represented by the formula (2), and the compound can be converted again into the haloiminium salt by reacting with the halogenating agent. The invention includes embodiments for reacting formed iminium chloride with carboxylic acid while preparing imi- nium chloride wherein X is chlorine atom in the general formula (1). That is, the desired acid chloride can be obtained by charging phosgene into a solution containing the carboxylic acid raw material and the cyclic urea compound of the 15 general formula (2). In the reaction, the cyclic urea of the general formula (2) reacts at first with phosgene to form imi- nium chloride wherein X is chlorine atom in the general formula (1), and successively carboxylic acid is halogenated by iminium chloride to form the desired carbonyl chloride. In this step, iminium chloride wherein X is chlorine atom in the general formula (1) returns to original cyclic urea of the general formula (2). Consequently, the amount of cyclic urea of the general formula (2) for use in the reaction is preferably 0.01 equiv- 20 alent or more, more preferably 0.05 - 0.1 equivalent for an equivalent of carboxylic acid. Use of cyclic urea in still more amount does not increase reaction velocity. The amount of phosgene used in the reaction is 1 .0 - 2.0 equivalents, preferably 1.1 - 1 .3 equivalents for an equiv- alent of carboxylic acid.
Recommended publications
  • Organic Chemistry

    Organic Chemistry

    Wisebridge Learning Systems Organic Chemistry Reaction Mechanisms Pocket-Book WLS www.wisebridgelearning.com © 2006 J S Wetzel LEARNING STRATEGIES CONTENTS ● The key to building intuition is to develop the habit ALKANES of asking how each particular mechanism reflects Thermal Cracking - Pyrolysis . 1 general principles. Look for the concepts behind Combustion . 1 the chemistry to make organic chemistry more co- Free Radical Halogenation. 2 herent and rewarding. ALKENES Electrophilic Addition of HX to Alkenes . 3 ● Acid Catalyzed Hydration of Alkenes . 4 Exothermic reactions tend to follow pathways Electrophilic Addition of Halogens to Alkenes . 5 where like charges can separate or where un- Halohydrin Formation . 6 like charges can come together. When reading Free Radical Addition of HX to Alkenes . 7 organic chemistry mechanisms, keep the elec- Catalytic Hydrogenation of Alkenes. 8 tronegativities of the elements and their valence Oxidation of Alkenes to Vicinal Diols. 9 electron configurations always in your mind. Try Oxidative Cleavage of Alkenes . 10 to nterpret electron movement in terms of energy Ozonolysis of Alkenes . 10 Allylic Halogenation . 11 to make the reactions easier to understand and Oxymercuration-Demercuration . 13 remember. Hydroboration of Alkenes . 14 ALKYNES ● For MCAT preparation, pay special attention to Electrophilic Addition of HX to Alkynes . 15 Hydration of Alkynes. 15 reactions where the product hinges on regio- Free Radical Addition of HX to Alkynes . 16 and stereo-selectivity and reactions involving Electrophilic Halogenation of Alkynes. 16 resonant intermediates, which are special favor- Hydroboration of Alkynes . 17 ites of the test-writers. Catalytic Hydrogenation of Alkynes. 17 Reduction of Alkynes with Alkali Metal/Ammonia . 18 Formation and Use of Acetylide Anion Nucleophiles .
  • Methanesulfonyl Chloride

    Methanesulfonyl Chloride

    A Publication of Reliable Methods for the Preparation of Organic Compounds Working with Hazardous Chemicals The procedures in Organic Syntheses are intended for use only by persons with proper training in experimental organic chemistry. All hazardous materials should be handled using the standard procedures for work with chemicals described in references such as "Prudent Practices in the Laboratory" (The National Academies Press, Washington, D.C., 2011; the full text can be accessed free of charge at http://www.nap.edu/catalog.php?record_id=12654). All chemical waste should be disposed of in accordance with local regulations. For general guidelines for the management of chemical waste, see Chapter 8 of Prudent Practices. In some articles in Organic Syntheses, chemical-specific hazards are highlighted in red “Caution Notes” within a procedure. It is important to recognize that the absence of a caution note does not imply that no significant hazards are associated with the chemicals involved in that procedure. Prior to performing a reaction, a thorough risk assessment should be carried out that includes a review of the potential hazards associated with each chemical and experimental operation on the scale that is planned for the procedure. Guidelines for carrying out a risk assessment and for analyzing the hazards associated with chemicals can be found in Chapter 4 of Prudent Practices. The procedures described in Organic Syntheses are provided as published and are conducted at one's own risk. Organic Syntheses, Inc., its Editors, and its Board of Directors do not warrant or guarantee the safety of individuals using these procedures and hereby disclaim any liability for any injuries or damages claimed to have resulted from or related in any way to the procedures herein.
  • Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides

    Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides

    Proceedings of the Iowa Academy of Science Volume 61 Annual Issue Article 26 1954 Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides B. R. Bluestein Coe College Albert Hybl Coe College Yoshimi Al Nishioka Coe College Let us know how access to this document benefits ouy Copyright ©1954 Iowa Academy of Science, Inc. Follow this and additional works at: https://scholarworks.uni.edu/pias Recommended Citation Bluestein, B. R.; Hybl, Albert; and Nishioka, Yoshimi Al (1954) "Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides," Proceedings of the Iowa Academy of Science, 61(1), 225-232. Available at: https://scholarworks.uni.edu/pias/vol61/iss1/26 This Research is brought to you for free and open access by the Iowa Academy of Science at UNI ScholarWorks. It has been accepted for inclusion in Proceedings of the Iowa Academy of Science by an authorized editor of UNI ScholarWorks. For more information, please contact [email protected]. Bluestein et al.: Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlor Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides By B. R. BLUESTEIN, ALBERT HYBL* AND YosHIMI AL NISHIOKA INTRODUCTION The reaction kinetics of the alcoholysis of substituted benzoyl chlorides was studied. The mechanism of the alcoholysis reaction, which is most generally accepted ( 1), shows that the overall re­ action should be second-order and that the reaction should be first-order with respect to the acid chloride and first-order with respect to the alcohol. This rate study was carried out using a large excess of alcohol as the solvent, thus obtaining pseudo-first order rate constants, first-order with respect to the acid chloride only.
  • Solvent-Free and Safe Process for the Quantitative Production of Phosgene from Triphosgene by Deactivated Imino-Based Catalysts

    Solvent-Free and Safe Process for the Quantitative Production of Phosgene from Triphosgene by Deactivated Imino-Based Catalysts

    Organic Process Research & Development 2010, 14, 1501–1505 Solvent-Free and Safe Process for the Quantitative Production of Phosgene from Triphosgene by Deactivated Imino-Based Catalysts Heiner Eckert* and Johann Auerweck Department of Chemistry, Technische UniVersitaet Muenchen, Lichtenbergstr. 4, Garching 85747, Germany Abstract: Scheme 1. Decomposition of triphosgene (1a) into carbon tetrachloride, carbon dioxide, and 1 equiv of phosgene (3) Phosgene is quantitatively formed from solid triphosgene in a solvent-free and safe process without any reaction heat, catalyzed by planar N-heterocycles with deactivated imino functions. The rate of phosgene generation is adjustable to the rate of phosgene consumption in the subsequent phosgenation reaction by thermal control, catalyst concentration, and in some cases, specific proper- ties of selected metal phthalocyanines. A thermal runaway reaction of this process is impossible. phosgene in most reactions, yet several phosgenation reactions are advantageously carried out with phosgene, that is, when excessive triphosgene is difficult to remove during the reaction Introduction workup because of its high boiling point of over 200 °C. Its Phosgene (3) is a highly useful and versatile chemical in excess can be destroyed by hydrolysis, when phosgenation performing syntheses.1a Although consisting of only four atoms, products are not sensitive to moisture as are carbonates, four important transformations can be carried out with it in carbamates, ureas, diarylketones, alkylhalides, cyanides, and organic
  • Efficient Esterification of Oxidized L-Glutathione and Other Small Peptides

    Efficient Esterification of Oxidized L-Glutathione and Other Small Peptides

    Molecules 2015, 20, 10487-10495; doi:10.3390/molecules200610487 OPEN ACCESS molecules ISSN 1420-3049 www.mdpi.com/journal/molecules Communication Efficient Esterification of Oxidized L-Glutathione and Other Small Peptides Emily R. Vogel, William Jackson and Douglas S. Masterson * Department of Chemistry and Biochemistry, the University of Southern Mississippi, 118 College Drive #5043, Hattiesburg, MS 39406, USA; E-Mails: [email protected] (E.R.V.); [email protected] (W.J.) * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +1-601-266-4714. Academic Editor: Derek J. McPhee Received: 17 May 2015 / Accepted: 4 June 2015 / Published: 8 June 2015 Abstract: Oxidized L-glutathione was esterified to the tetra methyl ester using thionyl chloride in methanol solvent. Other alcohols were tested and the reaction progress was monitored via ESI-MS. This procedure proved to be compatible with other small peptides not containing serine and cysteine residues. In contrast to previously reported methods this procedure provided convenient access to esterified peptides requiring no purification, extended reaction times, or complicated reaction setups. Keywords: esterification; peptide esterification; amino acids; carboxylic acids; esters 1. Introduction The design and synthesis of novel glutathione analogues are studied extensively for their pharmacological properties in the treatment of a wide range of diseases [1–3]. Reduced glutathione (GSH), -L-glutamyl-L-cysteinyl-glycine, is prone to reactivity at the sulfhydryl, terminal amino group, and both carbonyls. Thus, the synthesis of GSH analogues are a synthetic challenge to chemists, and the clever manipulation of protecting groups are needed to prevent unwanted reactions.
  • 덴드리틱 벤질 클로라이드의 효율적인 합성 Facile Synthesis of Dendritic Benzyl Chlorides from Their Alcohols W

    덴드리틱 벤질 클로라이드의 효율적인 합성 Facile Synthesis of Dendritic Benzyl Chlorides from Their Alcohols W

    Polymer(Korea), Vol. 31, No. 5, pp 417-421, 2007 덴드리틱 벤질 클로라이드의 효율적인 합성 이재욱F,7ㆍ한승철Fㆍ김희주ㆍ김정환ㆍ이언엽ㆍ김병기ㆍ성새름ㆍ강화신ㆍ김지현FFㆍ허도성FFF 동아대학교 화학과, F동아대학교 의생명과학과, FF동국대학교 생명화학공학과, FFF인제대학교 의생명화학과 (2007년 5월 9일 접수, 2007년 6월 29일 채택) Facile Synthesis of Dendritic Benzyl Chlorides from Their Alcohols with Methanesulfonyl Chloride/Et3N Jae Wook Lee*,7, Seung Choul Han*, Hee Joo Kim, Jung Hwan Kim, Un Yup Lee, Byoung-Ki Kim, Sae Reum Sung, Hwa-Shin Kang, Ji Hyeon Kim**, and Do-Sung Huh*** Department of Chemistry, Dong-A University, Hadan-2-dong, Busan 604-714, Korea *Department of Medical Bioscience, Dong-A University, Hadan-2-dong, Busan 604-714, Korea **Department of Chemical & Biochemical Engineering, Dongguk University, Seoul 100-715, Korea ***Department of Biomedicinal Chemistry, Inje University, Gim Hai 621-749, Korea (Received May 9, 2007; Accepted June 29, 2007) 초록： 덴드리틱 벤질 알코올을 트리에틸아민과 메탄술포닐클로라이드와 반응시켜서, 덴드리틱 벤질 클로라이드 의 효율적인 합성이 이루어졌다. 이 반응은 히드록시기의 메실화 반응과 염소화 반응의 2단계 반응으로 이루어지 는데, 중간체의 분리없이 한 반응 용기내에서 반응이 진행되는 경제적인 방법이다. Abstract： A successful rapid synthesis of dendritic benzyl chlorides from dendritic benzyl alcohols using methanesulfonyl chloride/Et3N as activating agents was described. In this method, each dendritic benzyl chloride can be prepared in one pot: no isolation of intermediate mesylated dendrons is required. The key steps in the syntheses of dendritic benzyl chlorides were the mesylation of the hydroxymethyl group followed by the chlorination by in-situ generated triethylammonium chloride. Keywords： benzylic alcohol, chlorination. Introduction vation and coupling steps in high yield. In addition, the coupling step must be very efficient to enable complete Dendrimers represent a novel type of polymeric material reaction.
  • United States Patent (19) 11) 4,128,586 Ratcliffe 45) Dec

    United States Patent (19) 11) 4,128,586 Ratcliffe 45) Dec

    United States Patent (19) 11) 4,128,586 Ratcliffe 45) Dec. 5, 1978 (54) CATALYTICREDUCTION OF AROMATIC 2,792,422 5/1957 Harris et al...................... 260/609 D SULFONYL HALDES WITH HYDROGEN 2,820,780 1/1958 Gutcho et al. ....................... 260/12 SULFDE TO YELD AROMATIC THOLS 2,986,581 5/1961 Levy et al. ........................... 260/608 3,994,980 1 1/1976 Kubicek .......................... 260/609 D. (75) Inventor: Charles T. Ratcliffe, Morristown, N.J. FOREIGN PATENT DOCUMENTS (73) Assignee: Allied Chemical Corporation, Morris 461101 4/1975 U.S.S.R.............................. 260/609 D Township, Morris County, N.J. Primary Examiner-Lewis Gotts Appl. No.: 881,952 Assistant Examiner-Molly C. Eakin 21 Attorney, Agent, or Firm-Horst M. Kasper 22) Filed: Feb. 27, 1978 (57) ABSTRACT 51 Int. Cl’............................................ CO7C 149/28 52) U.S. C. ................. 260/609 D; 260/302 S; A process for reducing aromatic sulfonyl halides with 260/302 F, 260/308 R; 260/608; 544/315; hydrogen sulfide. Hydrogen sulfide is contacted with 544/408; 548/337; 548/346; 546/290; 546/179; sulfonyl halides preferably in the presence of a solvent 54.6/139 and of a catalyst. The reaction forms thiols and pro 58) Field of Search ............. 260/609 D, 608, 294.8 R ceeds in the range of between about 50' and 300' C. There is little formation of disulfide and no cleavage of 56) References Cited the thiol group. U.S. PATENT DOCUMENTS 2,402,641 6/1946 Lazler et al. ......................... 260/609 20 Claims, No Drawings 4,128,586 1.
  • Chip Incompatibility Filters

    Chip Incompatibility Filters

    ChIP Incompatibility Filters Filter Name Type Description includes carboxylic acid halides and >1 acyl halide and related SMARTS derivatives like chloroformates, carbamoyl- , imidoyl halides, etc. >1 aldehyde SMARTS R no heteroatom no isocyanate, ketene, etc. >1 alkyl bromide / iodide SMARTS no acyl halide or related or vinyl halide >1 amine aromatic primary SMARTS aromatic carbon bound to N, N not charged >1 amines (aromatic/aliphatic, primary no amide, enamine, etc., no heteroatom SMARTS or secondary) bound to N, N not charged no amide, enamine, etc, no heteroatom >1 amines nucleophilic (aliphatic SMARTS bound to N, no aromatic carbon bound to primary or secondary) N, N not charged >1 aryl bromide / iodide SMARTS any aryl bromide / iodide >1 aryl halide SMARTS any aryl halide any boronic acid derivative, aromatic or >1 boronic acid derivative SMARTS aliphatic >1 carbonyl acid SMARTS any carboxylic or carbamic acid, etc. >1 carboxylic acid anhydrides SMARTS carbon must be bound to carbonyl no heteroatom bound to carbonyl or >1 carboxylic acid ester SMARTS oxygen, no acid, no anydride, etc >1 isocyanate / isothiocyanate SMARTS no restrictions to nitrogen substituents R no heteroatom, no isocyanate, ketene, >1 ketone or aldehyde SMARTS etc. >1 NH any SMARTS R can be anything >1 thioamide and related (any) SMARTS any substitution >1 thiol and related (nucleophic) SMARTS any SH or negative S >2 NH any SMARTS R can be anything acidic compounds I combination sulfonyl acids and carboxylic acids anhydrides, bicarbonates, thio and imino acyl anhydrides and derivatives SMARTS derivatives, etc. includes carboxylic acid halides and acyl halide and related SMARTS derivatives like chloroformates, carbamoyl- , imidoyl halides, etc.
  • "Fluorine Compounds, Organic," In: Ullmann's Encyclopedia Of

    "Fluorine Compounds, Organic," In: Ullmann's Encyclopedia Of

    Article No : a11_349 Fluorine Compounds, Organic GU¨ NTER SIEGEMUND, Hoechst Aktiengesellschaft, Frankfurt, Federal Republic of Germany WERNER SCHWERTFEGER, Hoechst Aktiengesellschaft, Frankfurt, Federal Republic of Germany ANDREW FEIRING, E. I. DuPont de Nemours & Co., Wilmington, Delaware, United States BRUCE SMART, E. I. DuPont de Nemours & Co., Wilmington, Delaware, United States FRED BEHR, Minnesota Mining and Manufacturing Company, St. Paul, Minnesota, United States HERWARD VOGEL, Minnesota Mining and Manufacturing Company, St. Paul, Minnesota, United States BLAINE MCKUSICK, E. I. DuPont de Nemours & Co., Wilmington, Delaware, United States 1. Introduction....................... 444 8. Fluorinated Carboxylic Acids and 2. Production Processes ................ 445 Fluorinated Alkanesulfonic Acids ...... 470 2.1. Substitution of Hydrogen............. 445 8.1. Fluorinated Carboxylic Acids ......... 470 2.2. Halogen – Fluorine Exchange ......... 446 8.1.1. Fluorinated Acetic Acids .............. 470 2.3. Synthesis from Fluorinated Synthons ... 447 8.1.2. Long-Chain Perfluorocarboxylic Acids .... 470 2.4. Addition of Hydrogen Fluoride to 8.1.3. Fluorinated Dicarboxylic Acids ......... 472 Unsaturated Bonds ................. 447 8.1.4. Tetrafluoroethylene – Perfluorovinyl Ether 2.5. Miscellaneous Methods .............. 447 Copolymers with Carboxylic Acid Groups . 472 2.6. Purification and Analysis ............. 447 8.2. Fluorinated Alkanesulfonic Acids ...... 472 3. Fluorinated Alkanes................. 448 8.2.1. Perfluoroalkanesulfonic Acids
  • 9-2909-00045/02001 Effective Date: 10/16/2014 Expiration Date: 10/15/2019

    9-2909-00045/02001 Effective Date: 10/16/2014 Expiration Date: 10/15/2019

    Facility DEC ID: 9290900045 PERMIT Under the Environmental Conservation Law (ECL) IDENTIFICATION INFORMATION Permit Type: Air State Facility Permit ID: 9-2909-00045/02001 Effective Date: 10/16/2014 Expiration Date: 10/15/2019 Permit Issued To:TWIN LAKE CHEMICAL INC 520 MILL ST PO BOX 411 LOCKPORT, NY 14094-0411 Contact: JAMES D HODAN TWIN LAKE CHEMICAL INC PO BOX 411 LOCKPORT, NY 14095 (716) 433-3824 Facility: TWIN LAKE CHEMICAL INC 520 MILL ST LOCKPORT, NY 14094 Contact: WILLIAM CASWELL TWIN LAKE CHEMICAL INC 520 MILL ST LOCKPORT, NY 14094-1712 (716) 433-3824 Description: This Air State Facility permit incorporates monitoring conditions for Twin Lake Chemical located in Lockport New York. The facility is a manufacturer of various organic acid chlorides used as intermediaries in the production of other compounds and encompasses two main production buildings and 8 reactors. The primary products produced are trimellitic trichloride, trimellitic Anhydride Monoacid chloride,isophthaloyl chloride, orthophthaloyl chloride, terephthaloyl chloride, and phosphorous pentachloride (2-200 gallon nickel reactors). Phosgene and thionyl chloride are used as chlorinating agents. The phosgene is purchased in 1 ton containers from Vandemark Chemical located next to the facility. Raw materials are added to the batch reactors along with a chlorinating agent and a catalyst. Prior to opening the reactor for chemical addition, the reactor is put under vacuum to remove gases. During the reaction process, the reactor is under slight pressure. Reactor temperatures are monitored. After the reaction is completed, the material is transferred to a distillation unit to refine and separate the product. Air strippers remove chlorinated hydrocarbons from wastewater prior to discharge to Lockport WWTP.
  • Particularly Hazardous Substances

    Particularly Hazardous Substances

    Particularly Hazardous Substances In its Laboratory Standard, OSHA requires the establishment of additional protections for persons working with "Particularly Hazardous Substances" (PHS). OSHA defines these materials as "select" carcinogens, reproductive toxins and acutely toxic materials. Should you wish to add: explosive, violently reactive, pyrophoric and water-reactve materials to this category, the information is included. Carbon nanotubes have also been added due to their suspected carcinogenic properties. This table is designed to assist the laboratory in the identification of PHS, although it is not definitively conclusive or entirely comprehensive. *Notes on the proper use of this table appear on page 12. 1 6 5 2 3 4 Substance CAS National Toxicity National Program Carcinogen Toxin Acute Regulated OSHA Carcinogen Group IARC Carcinogen Toxin Reproductive Violently Reactive/ Explosive/Peroxide Forming/Pyrophoric A-a-C(2-Amino-9H-pyrido[2,3,b]indole) 2648-68-5 2B Acetal 105-57-7 yes Acetaldehyde 75-07-0 NTP AT 2B Acrolein (2-Propenal) 107-02-8 AT Acetamide 126850-14-4 2B 2-Acetylaminofluorene 53-96-3 NTP ORC Acrylamide 79-06-6 NTP 2B Acrylyl Chloride 814-68-6 AT Acrylonitrile 107-13-1 NTP ORC 2B Adriamycin 23214-92-8 NTP 2A Aflatoxins 1402-68-2 NTP 1 Allylamine 107-11-9 AT Alkylaluminums varies AT Allyl Chloride 107-05-1 AT ortho-Aminoazotoluene 97-56-3 NTP 2B para-aminoazobenzene 60-09-3 2B 4-Aminobiphenyl 92-67-1 NTP ORC 1 1-Amino-2-Methylanthraquinone 82-28-0 NTP (2-Amino-6-methyldipyrido[1,2-a:3’,2’-d]imidazole) 67730-11-4 2B
  • Fragment-Based Discovery of a New Class of Inhibitors Targeting Mycobacterial Trna Modification

    Fragment-Based Discovery of a New Class of Inhibitors Targeting Mycobacterial Trna Modification

    Supplementary Data Fragment-based discovery of a new class of inhibitors targeting mycobacterial tRNA modification Sherine E. Thomas*1, Andrew J. Whitehouse*2, Karen Brown3,4, Juan M. Belardinelli5, Ramanuj Lahiri6, M. Daben J. Libardo7, Pooja Gupta1, Sony Malhotra8, Helena I. M. Boshoff7, Mary Jackson5, Chris Abell 2, Anthony G. Coyne2, Tom L. Blundell §1, R. Andres Floto3,4, Vitor Mendes §1 1 Department of Biochemistry, University of Cambridge, 80 Tennis Court Road, Cambridge CB2 1GA, UK. 2 Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK. 3 MRC Laboratory of Molecular Biology, Francis Crick Avenue, Cambridge, CB2 0QH, U.K. 4 Cambridge Centre for Lung Infection, Royal Papworth Hospital, Cambridge, CB23 3RE, U.K. 5 Mycobacteria Research Laboratories, Department of Microbiology, Immunology and Pathology, Colorado State University, Fort Collins, Colorado, USA. 6 National Hansen’s Disease Program, Healthcare Systems Bureau, HRSA, DHHS, USA 7 Tuberculosis Research Section, Laboratory of Clinical Immunology and Microbiology, National Institute of Allergy and Infectious Disease, National Institutes of Health, 9000 Rockville Pike, Bethesda, Maryland 20892, USA. 8 Birkbeck College, University of London, Malet Street, WC1E7HX, UK * Contributed equally § To whom correspondence should be addressed Results Conservation of catalytic residues in mycobacterial TrmD A multiple sequence alignment of 5 mycobacterial TrmD enzyme sequences with 10 TrmD ortholog amino acid sequences (Figure S1) shows conservation of important catalytic residues and residues involved in tRNA recognition and methyl transfer reactions. The catalytic residues Asp169 and Arg154 are highly conserved across TrmD orthologs. Key residues such as Asp50, Gly59, His46 involved in tRNA G36 and G37 base recognition, interactions with bases at positions 38, 32 and anticodon branch of wild type tRNA respectively, are also broadly conserved.