Module Five: Cyanide & Fumigants
Total Page:16
File Type:pdf, Size:1020Kb
Load more
Recommended publications
-
DNA Alkylation by Leinamycin Can Be Triggered by Cyanide and Phosphines
Bioorganic & Medicinal Chemistry Letters 11 (2001) 1511–1515 DNA Alkylation by Leinamycin Can Be Triggered by Cyanide and Phosphines Hong Zang, Leonid Breydo, Kaushik Mitra, Jeffrey Dannaldson and Kent S. Gates* Departments of Chemistry and Biochemistry, University of Missouri-Columbia, Columbia, MO 65211, USA Received 24 January 2001; accepted 14 March 2001 Abstract—Previous work has shown that alkylation of DNA by the antitumor agent leinamycin (1) is potentiated by reaction of the antibiotic with thiols. Here, it is shown that other soft nucleophiles such as cyanide and phosphines can also trigger DNA alkylation by leinamycin. Overall, the results suggest that reactions of cyanide and phosphines with leinamycin produce the oxathiolanone intermediate (2), which is known to undergo rearrangement to the DNA-alkylating episulfonium ion 4. # 2001 Elsevier Science Ltd. All rights reserved. Leinamycin (1) is a potent antitumor antibiotic that properties of the antibiotic. Here we report that phos- contains a unique 1,2-dithiolan-3-one 1-oxide hetero- phines and cyanide are able to trigger DNA alkylation cycle.1,2 Reaction of thiols with this sulfur heterocycle in by the antitumor antibiotic leinamycin. Results of our leinamycin initiates chemistry that leads to oxidative chemical model reactions and DNA-damage experi- DNA damage and DNA alkylation.3À6 Thiol-triggered ments suggest that reaction of cyanide and phosphines DNA alkylation by leinamycin involves initial conver- with leinamycin affords the critical oxathiolanone inter- sion of the parent antibiotic to the oxathiolanone form mediate (2), which subsequently undergoes rearrangement 2,5,7 followed by rearrangement to the episulfonium ion to the DNA-alkylating episulfonium ion 4. -
Sodium and Specialty Cyanides Production Facility Nicholas A
University of Pennsylvania ScholarlyCommons Department of Chemical & Biomolecular Senior Design Reports (CBE) Engineering 4-20-2018 Sodium and Specialty Cyanides Production Facility Nicholas A. Baylis University of Pennsylvania, [email protected] Parth N. Desai University of Pennsylvania, [email protected] Kyle J. Kuhns University of Pennsylvania, [email protected] Follow this and additional works at: https://repository.upenn.edu/cbe_sdr Part of the Biochemical and Biomolecular Engineering Commons Baylis, Nicholas A.; Desai, Parth N.; and Kuhns, Kyle J., "Sodium and Specialty Cyanides Production Facility" (2018). Senior Design Reports (CBE). 101. https://repository.upenn.edu/cbe_sdr/101 This paper is posted at ScholarlyCommons. https://repository.upenn.edu/cbe_sdr/101 For more information, please contact [email protected]. Sodium and Specialty Cyanides Production Facility Abstract Sodium cyanide and specialty cyanide production are essential operations for various industrial processes, with primary applications in mining and mineral processing. Sodium cyanide, despite the high toxicity inherent in the material and its production process, is expected to grow 5% annually, with a projected global demand of 1.1 million tonnes in 2018. This report details a process design for producing sodium cyanide through the use of two intermediate reactions and successive downstream separations. The first major step is the production of hydrogen cyanide gas from ammonia and methane derived from natural gas, via the industry standard Andrussow reaction over a platinum-rhodium gauze catalyst. Aqueous sodium cyanide is produced via a neutralization reaction of absorbed hydrogen cyanide gas with aqueous sodium hydroxide. Downstream processes include the crystallization of solid sodium cyanide from the aqueous product, with the solid product being removed from slurry and brought to low-moisture content through a series of solid-liquid separations. -
9.7 Summary of Substitution and Elimination Reactions of Alkyl Halides 421
09_BRCLoudon_pgs4-3.qxd 11/26/08 12:25 PM Page 420 420 CHAPTER 9 • THE CHEMISTRY OF ALKYL HALIDES The occurrence of some inversion also shows that the lifetime of a tertiary carbocation is 8 very small. It takes about 10_ second for a chloride counterion to diffuse away from a carbo- cation and be replaced by solvent. The carbocations that undergo inversion do not last long enough for this process to take place. The competition of backside substitution (which gives inversion) with racemization shows that the lifetime of the carbocation is approximately in 8 this range. In other words, a typical tertiary carbocation exists for about 10_ second before it is consumed by its reaction with solvent. This very small lifetime provides a graphic illustration just how reactive carbocations are. PROBLEMS 9.27 The optically active alkyl halide in Eq. 9.61 reacts at 60 C in anhydrous methanol solvent to give a methyl ether A plus alkenes. The substitution reaction° is reported to occur with 66% racemization and 34% inversion. Give the structure of ether A and state how much of each enantiomer of A is formed. 9.28 In light of the ion-pair hypothesis, how would you expect the stereochemical outcome of an SN1 reaction (percent racemization and inversion) to differ from the result discussed in this section for an alkyl halide that gives a carbocation intermediate which is considerably (a) more stable or (b) less stable than the one involved in Eq. 9.61? E. Summary of the SN1 and E1 Reactions Let’s summarize the important characteristics of the SN1 and E1 reactions. -
Kinetic Modeling of the Thermal Destruction of Nitrogen Mustard
Kinetic Modeling of the Thermal Destruction of Nitrogen Mustard Gas Juan-Carlos Lizardo-Huerta, Baptiste Sirjean, Laurent Verdier, René Fournet, Pierre-Alexandre Glaude To cite this version: Juan-Carlos Lizardo-Huerta, Baptiste Sirjean, Laurent Verdier, René Fournet, Pierre-Alexandre Glaude. Kinetic Modeling of the Thermal Destruction of Nitrogen Mustard Gas. Journal of Physical Chemistry A, American Chemical Society, 2017, 121 (17), pp.3254-3262. 10.1021/acs.jpca.7b01238. hal-01708219 HAL Id: hal-01708219 https://hal.archives-ouvertes.fr/hal-01708219 Submitted on 13 Feb 2018 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Kinetic Modeling of the Thermal Destruction of Nitrogen Mustard Gas Juan-Carlos Lizardo-Huerta†, Baptiste Sirjean†, Laurent Verdier‡, René Fournet†, Pierre-Alexandre Glaude†,* †Laboratoire Réactions et Génie des Procédés, CNRS, Université de Lorraine, 1 rue Grandville BP 20451 54001 Nancy Cedex, France ‡DGA Maîtrise NRBC, Site du Bouchet, 5 rue Lavoisier, BP n°3, 91710 Vert le Petit, France *corresponding author: [email protected] Abstract The destruction of stockpiles or unexploded ammunitions of nitrogen mustard (tris (2- chloroethyl) amine, HN-3) requires the development of safe processes. -
Nerve Agent - Lntellipedia Page 1 Of9 Doc ID : 6637155 (U) Nerve Agent
This document is made available through the declassification efforts and research of John Greenewald, Jr., creator of: The Black Vault The Black Vault is the largest online Freedom of Information Act (FOIA) document clearinghouse in the world. The research efforts here are responsible for the declassification of MILLIONS of pages released by the U.S. Government & Military. Discover the Truth at: http://www.theblackvault.com Nerve Agent - lntellipedia Page 1 of9 Doc ID : 6637155 (U) Nerve Agent UNCLASSIFIED From lntellipedia Nerve Agents (also known as nerve gases, though these chemicals are liquid at room temperature) are a class of phosphorus-containing organic chemicals (organophosphates) that disrupt the mechanism by which nerves transfer messages to organs. The disruption is caused by blocking acetylcholinesterase, an enzyme that normally relaxes the activity of acetylcholine, a neurotransmitter. ...--------- --- -·---- - --- -·-- --- --- Contents • 1 Overview • 2 Biological Effects • 2.1 Mechanism of Action • 2.2 Antidotes • 3 Classes • 3.1 G-Series • 3.2 V-Series • 3.3 Novichok Agents • 3.4 Insecticides • 4 History • 4.1 The Discovery ofNerve Agents • 4.2 The Nazi Mass Production ofTabun • 4.3 Nerve Agents in Nazi Germany • 4.4 The Secret Gets Out • 4.5 Since World War II • 4.6 Ocean Disposal of Chemical Weapons • 5 Popular Culture • 6 References and External Links --------------- ----·-- - Overview As chemical weapons, they are classified as weapons of mass destruction by the United Nations according to UN Resolution 687, and their production and stockpiling was outlawed by the Chemical Weapons Convention of 1993; the Chemical Weapons Convention officially took effect on April 291997. Poisoning by a nerve agent leads to contraction of pupils, profuse salivation, convulsions, involuntary urination and defecation, and eventual death by asphyxiation as control is lost over respiratory muscles. -
Sodium Cyanide: Properties, Toxicity, Uses and Environmental Impacts
CHAPTER 39 SODIUM CYANIDE: PROPERTIES, TOXICITY, USES AND ENVIRONMENTAL IMPACTS Kerry Ketcheson and Merv Fingas Emergencies Science Division, Environment Canada, Environmental Technology Centre, River Road, Ottawa, Ontario 39.1 PROPERTIES Sodium cyanide (CAS No. 143-33-9) was first produced in 1834 by F. and E. Rogers, who heated Prussian blue (highly colored mixed oxidation state FeII / III derivatives) and sodium carbonate together (King, 1994). The mixture was cooled and sodium cyanide was extracted with alcohol. The compound had no intended purpose until J. S. MacArthur and the Forrest brothers patented a process for extracting gold and silver from ores in 1887 (Kirk-Othmer, 1979a). By 1899, half the cyanide manufactured in Europe was produced by the Beilby process. From 1900 to 1961, another process, called the Castner process, was used to make sodium cyanide. The Castner process is shown below: ϩ ϩ → ϩ 2Na 2C 2NH322NaCN 3H (39.1) Today, a process based on the neutralization of sodium hydroxide (aqueous) and hydrogen cyanide (gas) is the preferred method, as shown below (Kirk-Othmer, 1993): ϩ → ϩ HCN NaOH NaCN H2 O (39.2) A few chemical reactions that occur with sodium cyanide should be mentioned. In moist air, carbon dioxide (CO2) slowly decomposes sodium cyanide to hydrogen cyanide according to this reaction: ϩ ϩ → ϩ 2NaCN CO22HO Na 23 CO 2HCN (39.3) The carbonate salt produced becomes a brownish color due to the formation of polymeri- zation products of HCN (Ullmann’s, 1987). At elevated temperatures, oxygen reacts with sodium cyanide to yield nitrogen, carbonate, and carbon dioxide according to the two-step reaction (Ullmann’s, 1987): 39.1 39.2 CHAPTER THIRTY-NINE 2NaCN ϩ O → 2NaOCN 2 (39.4) ϩ → ϩ ϩ 2NaOCN 3/2O22322Na CO CO N When sodium cyanide is either stored for a long time or heated, there is a slow hydrolysis of the CϵN bond as per the equation (Ullmann’s, 1987): ϩ → ϩ NaCN 2H23 O HCOONa NH (39.5) Some basic physical properties of sodium cyanide are shown in Table 39.1. -
Fumigation for Rabbit Control
Fumigation for rabbit control Introduction: Fumigation is a valuable tool in successful rabbit management programs. It is an effective follow-up technique to poison baiting and warren ripping, and is a particularly useful control method in areas where other techniques cannot be used (eg poison baiting). Fumigation works by replacing the air in warrens with Figure 1: Phostoxin tablets and dry paper are pushed deep lethal gasses, which are in-turn inhaled by rabbits, into the warren entrance. Image: Invasive Animals CRC causing them to suffocate and die. There are two types of fumigation: Fumigants Chloropicrin: Chloropicrin is a colourless, toxic liquid • pressure fumigation - where the fumigant is generated that is currently used in Australia as an insecticide, soil outside the warren and forced into the warren under and warren fumigant, and rodenticide. Chloropicrin pressure, usually from a pump is classified as a dangerous poison (Schedule 7) as • diffusion (or static) fumigation – where tablets are placed it has a high potential to cause harm, even at low in active burrows (Figure 1) and the fumigant generated exposures. Chloropicrin has recently been placed under is allowed to passively diffuse through the warren (this is review by the Australian Pesticides and Veterinary the preferred method)1. Medicines Authority (APVMA) because of environmental, There are strict regulations around the use of fumigants human health and human safety concerns. It is not for rabbit control that reduce the risk of harm to recommended for use, even though it is still registered operators. For this reason, users may also require training in some states. Pressure fumigation using chloropicrin ® or accreditation before using approved fumigants. -
High-Threat Chemical Agents: Characteristics, Effects, and Policy Implications
Order Code RL31861 CRS Report for Congress Received through the CRS Web High-Threat Chemical Agents: Characteristics, Effects, and Policy Implications Updated September 9, 2003 Dana A. Shea Analyst in Science and Technology Policy Resources, Science, and Industry Division Congressional Research Service ˜ The Library of Congress High-Threat Chemical Agents: Characteristics, Effects, and Policy Implications Summary Terrorist use of chemical agents has been a noted concern, highlighted after the Tokyo Sarin gas attacks of 1995. The events of September 11, 2001, increased Congressional attention towards reducing the vulnerability of the United States to such attacks. High-threat chemical agents, which include chemical weapons and some toxic industrial chemicals, are normally organized by military planners into four groups: nerve agents, blister agents, choking agents, and blood agents. While the relative military threat posed by the various chemical types has varied over time, use of these chemicals against civilian targets is viewed as a low probability, high consequence event. High-threat chemical agents, depending on the type of agent used, cause a variety of symptoms in their victims. Some cause death by interfering with the nervous system. Some inhibit breathing and lead to asphyxiation. Others have caustic effects on contact. As a result, chemical attack treatment may be complicated by the need to identify at least the type of chemical used. Differences in treatment protocols for the various high-threat agents may also strain the resources of the public health system, especially in the case of mass casualties. Additionally, chemical agents trapped on the body or clothes of victims may place first responders and medical professionals at risk. -
Toxicological Profile for Cyanide
CYANIDE 141 5. PRODUCTION, IMPORT/EXPORT, USE, AND DISPOSAL 5.1 PRODUCTION The demand for hydrogen cyanide in the United States during 2000 was 1.615 billion pounds, up slightly from 1.605 billion pounds in 1999 (CMR 2001). Production of hydrogen cyanide in 2003 was 2.019 billion pounds in the United States (FAS 2005). The demand for hydrogen cyanide was projected to be 1.838 billion pounds in 2004 (CMR 2001; NYSDOH 2005). Major producers of hydrogen cyanide are Adisseo USA, Inc. (Institute, West Virginia); Cyanco Co. (Winnemucca, Nevada); Cytec Industries (Waggoman, Louisiana); Degussa Corp. (Theodora, Alabama); The Dow Chemical Company (Freeport, Texas); E.I. du Pont de Neumours and Company (Memphis, Tennessee; Beaumont, Texas); Innovene (Green Lake, Texas and Lima, Ohio); Invista, Inc. (Orange, Texas and Victoria, Texas); Rhom and Haas Texas Inc. (Deer Park, Texas); Solutia, Inc. (Alvin, Texas); Sterling Chemicals, Inc. (Texas City, Texas); and Syngenta Crop Protection (St. Garbiel, Louisiana) (SRI 2005). The combined annual production capacity of these plants is approximately 2.036 billion pounds (SRI 2005). As of February 2005, the following companies produced other cyanide compounds in the United States (SRI 2005): ammonium Crompton, Taft, Louisiana; and Mallinckrodt, Inc., St. Louis, Missouri thiocyanate: cyanogen: Matheson Gas Products, Inc., Gloucester, Massachusetts potassium cyanide: DuPont Chemical Company, Memphis, Tennessee; and The Dow Chemical Company, Nashua, New Hampshire potassium silver Engelhard Corporation, Union, New Jersey; and Metalor Technologies USA, North cyanide: Attleboro, Massachusetts Facilities in the United States producing sodium cyanide and their annual capacity (in millions of pounds) in 2005 include: Cyanco Co., Winnemucca, Nevada (86); and E.I. -
Combustion and Pyrolysis Kinetics of Chloropicrin J.-C
Combustion and Pyrolysis Kinetics of Chloropicrin J.-C. Lizardo-Huerta, B. Sirjean, L. Verdier, R. Fournet, Pierre-Alexandre Glaude To cite this version: J.-C. Lizardo-Huerta, B. Sirjean, L. Verdier, R. Fournet, Pierre-Alexandre Glaude. Combustion and Pyrolysis Kinetics of Chloropicrin. Journal of Physical Chemistry A, American Chemical Society, 2018, 122 (26), pp.5735 - 5741. 10.1021/acs.jpca.8b04007. hal-01921757 HAL Id: hal-01921757 https://hal.univ-lorraine.fr/hal-01921757 Submitted on 14 Nov 2018 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Combustion and Pyrolysis Kinetics of Chloropicrin J.-C. Lizardo-Huerta1, B. Sirjean1, L. Verdier2, R. Fournet1, P.-A. Glaude1* 1 Laboratoire Réactions et Génie des Procédés, CNRS, Université de Lorraine 1 rue Grandville BP 20451 54001 Nancy Cedex, France 2 DGA Maîtrise NRBC, Site du Bouchet, 5 rue Lavoisier, BP n°3, 91710 Vert le Petit, France Corresponding author : Pierre-Alexandre Glaude Laboratoire Réactions et Génie des Procédés 1 rue Grandville BP 20451 54001 Nancy Cedex, France Email:[email protected] 1 Abstract Chloropicrin (CCl3NO2) is widely used in agriculture as a pesticide, weed-killer, fungicide or nematicide. -
Chemical Warfare Agents
Manuscript for Kirk-Othmer Encyclopedia of Chemical Technology August 2019 CHEMICAL WARFARE AGENTS This is the pre-print manuscript of an article published in the Kirk-Othmer Encyclopedia of Chemical Technology: https://onlinelibrary.wiley.com/doi/book/10.1002/0471238961 The published version of the article is available at the Wiley website: https://onlinelibrary.wiley.com/doi/10.1002/0471238961.0308051308011818.a01.pub3 How to cite: Costanzi, S. (2020). Chemical Warfare Agents. In Kirk‐Othmer Encyclopedia of Chemical Technology, (Ed.). doi:10.1002/0471238961.0308051308011818.a01.pub3 Stefano Costanzi Department of Chemistry and Center for Behavioral Neuroscience American University, Washington, D.C. [email protected] Chemical weapons are weapons that exploit the toxicity of chemicals to bring about death or harm. The toxic chemicals on which chemical weapons are based are known as chemical warfare agents. The elimination of this entire category of weapons is the aim of the Convention on the Prohibition of the Development, Production, Stockpiling and Use of Chemical Weapons and on their Destruction, also known as Chemical Weapons Convention or CWC, which was opened for signature in 1993 and entered into force in 1997. Administered and implemented by the Hague- based Organisation for the Prohibition of Chemical Weapons (OPCW), the CWC is an international treaty that enjoys almost universal embracement, having been ratified or acceded by 193 States Parties. Importantly, the CWC poses a complete and absolute ban on chemical weapons, mandating State Parties to renounce “(a) to develop, produce, otherwise acquire, stockpile or retain chemical weapons, or transfer, directly or indirectly, chemical weapons to anyone; (b) to use chemical weapons; (c) to engage in any military preparations to use chemical weapons; (d) to assist, encourage or induce, in any way, anyone to engage in any activity prohibited to a State Party” under the Convention (CWC Article II, Paragraph 1) (1-3). -
Safe Handling and Disposal of Chemicals Used in the Illicit Manufacture of Drugs
Vienna International Centre, PO Box 500, 1400 Vienna, Austria Tel.: (+43-1) 26060-0, Fax: (+43-1) 26060-5866, www.unodc.org Guidelines for the Safe handling and disposal of chemicals used in the illicit manufacture of drugs United Nations publication USD 26 Printed in Austria ISBN 978-92-1-148266-9 Sales No. E.11.XI.14 ST/NAR/36/Rev.1 V.11-83777—September*1183777* 2011—300 Guidelines for the Safe handling and disposal of chemicals used in the illlicit manufacture of drugs UNITED NATIONS New York, 2011 Symbols of United Nations documents are composed of letters combined with figures. Mention of such symbols indicates a reference to a United Nations document. ST/NAR/36/Rev.1 UNITED NATIONS PUBLICATION Sales No. E.11.XI.14 ISBN 978-92-1-148266-9 eISBN 978-92-1-055160-1 © United Nations, September 2011. All rights reserved. The designations employed and the presentation of material in this publication do not imply the expression of any opinion whatsoever on the part of the Secretariat of the United Nations concerning the legal status of any country, territory, city or area, or of its authorities, or concerning the delimitation of its frontiers or boundaries. Requests for permission to reproduce this work are welcomed and should be sent to the Secretary of the Publications Board, United Nations Headquarters, New York, N.Y. 10017, U.S.A. or also see the website of the Board: https://unp.un.org/Rights.aspx. Governments and their institutions may reproduce this work without prior authoriza- tion but are requested to mention the source and inform the United Nations of such reproduction.