DOCSLIB.ORG

Thesis-1952D-S361r.Pdf (3.197Mb)

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Thesis-1952D-S361r.Pdf (3.197Mb) Dat1;3: December 15, 1951 Name!: A. Merrill Schnitzer Position: Student Institution: Oklah<;itna A. & :M •. College Location: Stillwater, Oklahoma Title' of Study: The Reaction of 1,3,5-Trisubstituted Hexahydro-1,3,5- 1 t,riazines with Carbon Disulfide. Number of Pages in Study: 58 Under Direction of What Department: Chemistry. Scope of Study: The original purpose of the invest:Lgation was to determine 'whether N,N 1-disubstituted methylenediamines would react with carbon di­ sulfide and then with formaldehyde in a manner analogoµs to the corres­ ponding N,N'-disubstituted ethylenediamines. The ethylenediamines react with carbon disulfide to give the inner salts of N-alkyl-N-(,$-alkylamino­ ethyl)dithiocarbamic acids. These sal,ts, when treated with formaldehyde, react to form 3,6-disubstituted hexahydro-1,3,6-th;i.adiazepine-2-thiones. 'fhese seven-membered heterocyclic compounds may be the.rmally decomposed to l,J-disubstituted-2-imidazolidinethiones. The investigation was later shifted to the reaction of 1,3,5-trisub:Jtituted hexahydro-1,3,5-triazines with cnrbon disulfide, which produced compounds of the type sought. The pyroly$is of these reaction products was also studied. Find~ngs and· Conclusions: The N, f(' -disubstit uted methy lenes investigated did · not react in the manner expected. The methylenediamines used were aryl substituted, since the alkyl substituted homologs <;1.re not stable. Attempts to prepare N,N'-disubstituted methylenediamines resulted in the formation I of cyclic 1,3,5-t;dsubstituted hexa.hydro-1,3,5-triazines. It was found that i these compounds react w;ith carbon disulfide to produce 3, 5-disubstitvted · tetrahydra-1,3,5-thiadiazine-2-thiones. These latter substances were the compounds expected from the reaction of di.substituted methylenediamines with carbon disulfide,and formaldehyde. The homologs prepared are: ethyl, i isopropyl, cyclohe::i,cyl, /-phenylethyl, benzyl, phenyl, E-tolyl and £-phenetyl. This class of compounds has beep previously reported in the literature, but none of the homologs prepared, with the exception of the ethyl, is recorded. ·These substances were decomposed by pyrolysis and in the cases of the iso­ propyl, cyclohexyl, ,B ~phenylethyl, £-tolyl, and ,2-phenetyl homo logs, the products were 1,3,5-trisubstituted hexahydro-1,3,5-triazine-2-thiones. This , class of co!'.Ilpounds has not been reported in the literature. ADVISER'S THE REACTION OF l,3,5~TRISUBSTITUTED HEXAHYDR0-1,J,5-TRIAZINES WITH CARBON DISULFIDE THE REACTION: OF 1,3,5-TRISUBSTITUTEC HEXAHYI>RO-l,3,5""TRIAZIN.ES WITH CARBON DISULFIDE by A. MERRILL SCHNI~ER /I Master of Science Oklahoma Agricultural and Mechanical College Stillwater, Oklahoma 1949 Submitted to the Department ot Chemistry Oklahoma Agricultural and Mechanical College In Partial Fulfil'.l.ment of the Requirements for the Degree of DOCTOR .OF PHILOSOPHY 1951 OKUllOM~ ii AGRICULTUHL &. h'1ECnAHICAL cm LEGt LIBRARY MAY 1 1952 THE REACTION OF l,3,5-TRISUBSTITUTED rIEXAHYDR0- 1,3,5-TRlAZINES WITH CARBON DISULFIDE A~ MERRILL SCHNITZER MASTER OF SCIENCE 1949 THESIS AND ABSTRACT APPROVED: C/Thesis Adviser Dean ot the Graduate School Head ot the Department 291971 iii ACKNOWLEDGMENT The author wishes to express his sincere gratitude to Dro J. A. Shotton, under whose direction and guidance this work has been done, and to other members of the Department of Chendstr1 for their suggestions and helpful criticism, He also wishes to acknowledge the financial aid rendered by the Oklahoma A, and M, College in the form of a graduate fellowship in the Chemistry Department. iv TABLE OF CONTENTS Introductic;>n 1 Historical 2 Discussion 14 Experimental 33 Summary 55 Bibliography 56 1 INTRODUCTION The original purpose of this investigation was to determing whe ther N,N 1 -disubstitutedmethylenediamines would undergo reactions analogous t o those of the corresponding N,N 1-disubstitutedethylenediamines when treated with certain reagents. N,N'-dialkylethylenediamines react with carbon disulfide and formaldehyde to give heterocyclic compounds that are active vulcanization accelerators. Although some methylenediamines are stable enough to be isolated and kept for considerable periods, most of these compounds are unstable and tend to polymerize or decompose to give more stable compounds. The methylenediamines investigated did not give the desired reactions. It was found in the course of the investigation that the cyclic trimers of substituted methyleneimines (Azomethines, Schiff bases), the 1,3,5-trisubstitutedhexahydro-l,3,5-triazines, react with carbon di­ sulfide to give products of the type desired. A survey of the liter­ ature showed that this type of reaction has been mentioned only briefly. Several of these cyclic trimers were prepared and treated with carbon disulfide, and the reaction products, as well as the compounds resulting from their thermal decomposition, were investigated. 2 HISTORICAL The reaction of dialkylmonoamines and carbon disulfide has been widely studied, largely because the products are useful as vulcan- ization accelerators. The reaction produces the dialkylammonium salts of dialkyldithiocarbamic acids: R S ' N-C-SII - Rf These salts may be oxidized to thiuram disulfides: R, ~ ~ ,,R N-C-S-S-C-N R't 'R 1 In the presence of primary or secondary amines, the product may be dithiocarbamylsulfenamides (1): [o] R S R 11 ' N-v-S-N!l. / R" R) 'R" I '_.....NH R'" which may be thermally decomposed, losing an atom of sulfur, to yield tetrasubstituted thioureas. Donia, Shotton, Bentz, and Smith (2) found that, in general, the reactions of N,N'-dialkylethylenediamines with carbon disulfide are analogous to the reactions of the dialkylmonoamines. However, the ethylenediamines yield cyclic products, owing to the connection between the two nitrogen atoms. Hofmann (3) first reported the reaction of ethylenediamine with carbon disulfide to yield N-~-aminoethyl)dithiocarbamic acid (shown here in the dipolar ion form): 3 He thermally decomposed this acid and obtained hydrogen sulfide and 2-imidazolidinethione: which may be considered as a cyclic derivative of thiourea. Other investigators have extended these reactions to N- substituted- ethylenediamines. Donia, et al., (2) prepared a series of N-alkyl-N­ (,8-alkylaminoethyl)dithiocarbamic acid inner salts by the reaction of N,N'-dialkylethylenediamines with carbon disulfide. They found that these salts could be oxidized in alkaline solution with iodine-potassium iodide reagent to give 2,5-dialkyltetrahydro-1,2,5-thiadiazine-6-thiones: which may be considered to be cyclic dithiocarbamylsulfenamides. These compounds can be thermally decomposed, with the loss of sulfur, to the same 2-imidazolidinethiones as are obtained by decomposing the dithio- carbamic acid inner salts. It was found that the stability of the tetra- hydrothiadiazine ring is related to the size of the alkyl substituents attached to the nitrogen atoms. The isopropyl compound is less stable than the cyclohexyl compound, and the ethyl compound is quite unstable, being obtained only in low yields. Donia and co-workers (4) also studied the reactions of N,N'-dialkyl- diamines with carbon disulfide. These reactions were found to be analogous to those of the dialkylmonoamines, except that ring compounds were formed. These inves tigators prepared a series of 1,3-imidazolidines by condensation 4 of formaldehyde and other aldehydes with N,N'-dialkylethylenediamines. Treatment of the 1,3-dialkylimidazolidines with carbon disulfide in ether or alcohol results in the formation of J,6-dialkylhexahydro-l,J,6- thiadiazepine-2-thiones: These compounds are relatively unstable, and treatment with dilute ammonia water effects removal of the methylene group to form N-alkyl-N-(,6-alkyl­ aminoethyl)dithiocarbamic acid inner salts. They are decomposed also by heat or on standing at room temperature, with the splitting out of thio- formaldehyde and the formation of l,J-dialkyl-2-imidazolidinethiones. Delepine (5) treated the cyclic trimer of methylamine and formalde- hyde, l,3,5-trimethylhexahydro-1,3,5-triazine, with carbon disulfide and obtained a compound that he called 11 dimethylfci'rmocarbothialdine", m.p. 96°c., in the belief that it was an isomer of 11 carbothialdine". The compound long known as "carbothialdine" was first prepared through the action of carbon disulfide on acetaldehyde-ammonia by Redtenbacher and Liebig (6), and was thought to be related to the thialdines. The thialdines, which are 1,3,5-dithiazines, result from the action of hydrogen sulfide on aldehyde-ammonias. "Carbothialdine" was also prepared by Mulder (7) by condensing acetaldehyde with acrunoniwn dithiocarbamate or trithiocarbonate. This compound is thermally unstable, and the decomposition point has been reported as 120°·, by,·Cohn .(8.) and 1.35? by Ainley and co-workers. (9). It is difficult to purify, owing to rapid decomposition in solvents, including water and alcohols. It is soluble in dilute acids, though again with de­ composition. Claus (10) found that iodine, nitrous acid, or mercuric chloride also cause the compound to decompose, with the formation of ammonium thiocyanate, acetaldehyde, ammonia, and carbon disulfide. 5 Guareschi (11) found that ferric thiocyanate is formed when 11 car bothial- dine" is treated with ferric chloride; but that oxidation with ferric chloride in dilute acids, or with chlorine water, produces thiuram di- sulfide, indicating that the dithiocarbamate structure is present within the molecule. Mulder (7) and Levi and Gimignani (12) found that on treatment
Load more

Recommended publications
  • Chemistry Department 32.Pdf (10.36Mb)
    THE FABRICATION OF NANOMETRIC METAL SULFIDES FROM XANTHATE PRECURSORS By ALAN PIQUETTE Bachelor of Arts Western State College of Colorado Gunnison, Colorado 2002 Submitted to the Faculty of the Graduate College of the Oklahoma State University In partial fulfillment of The requirements for The Degree of DOCTOR OF PHILOSOPHY December, 2007 THE FABRICATION OF NANOMETRIC METAL SULFIDES FROM XANTHATE PRECURSORS Thesis Approved: _______________ __Allen Apblett___ ______________ Thesis Advisor ________________ Nicholas Materer_____ __________ _____________ __LeGrande Slaughter___ __________ _______________ ____Jim Smay___ _______________ _____________ __A. Gordon Emslie___ ____________ Dean of the Graduate College ACKNOWLEDGEMENTS It is with my utmost sincere appreciation that I acknowledge my thesis advisor, Dr. Allen W. Apblett, for his support, guidance, and motivation. He provided a research environment that was both friendly and challenging, which made my years in his group enjoyable and rewarding. His broad range of knowledge was something of which I was happy to take advantage. His dedication to teaching and research is something that will be a positive influence on me for the rest of my scientific career. I would like to express gratitude to my committee members: Dr. Nicholas Materer, Dr. LeGrande Slaughter, and Dr. Jim Smay, for their assistance, advice, guidance, and support throughout the years. I am deeply grateful to all my colleagues and friends in the chemistry department. I would specifically like to thank Sulaiman Al-Fadul, Mohammed Al-Hazmi, Zeid Al- Othmann, Mohamed Chehbouni, Satish Kuriyavar, and Tarek Trad for showing me the ropes, for their valuable discussions, continuous encouragement, and for all the help they extended during the course of my stay in the Apblett Group.
    [Show full text]
  • A Comprehensive Investigation on the Formation of Organo-Sulfur Molecules in Dark Clouds Via Neutral-Neutral Reactions
    A&A 395, 1031–1044 (2002) Astronomy DOI: 10.1051/0004-6361:20021328 & c ESO 2002 Astrophysics A comprehensive investigation on the formation of organo-sulfur molecules in dark clouds via neutral-neutral reactions M. Yamada1, Y. Osamura1, and R. I. Kaiser2;? 1 Department of Chemistry, Rikkyo University, 3-34-1 Nishi-ikebukuro, Tokyo 171-8501, Japan 2 Department of Chemistry, University of York, YO10 5DD, UK Received 11 June 2002 / Accepted 9 September 2002 Abstract. Fifteen reactions on the doublet HCnS and singlet/triplet H2CnS(n = 1; 2) potential energy surfaces have been investi- gated theoretically via electronic structure calculations to unravel the formation of hydrogen deficient, sulfur bearing molecules via bimolecular reactions of two neutral species in cold molecular clouds. Various barrierless reaction pathways to synthe- size astronomically observed CnS and hitherto undetected HCnS(n = 1; 2) isomers are offered. These data present important 2 2 guidance to search for rotational transitions of the elusive thioformyl HCS(X A0) and thioketenyl HCCS(X Π) radicals in the interstellar medium. Key words. astrochemistry – ISM: molecules – molecular processes – methods: miscellaneous 1. Introduction terminated counterparts HCnSandCnSH have not been de- tected in the interstellar medium yet. However, these molecules Untangling the synthetic routes to form sulfur-carrying might represent the missing source of molecular-bound sul- molecules in the interstellar medium is a significant instru- fur in the interstellar medium. Hydrogen deficient organosul- ment to understand the chemical evolution and physical con- 2 2 fur molecules like HCS(X A0) and HCCS(X Π) resemble also ditions in star forming regions and in circumstellar envelopes important reaction intermediates which could lead to sulfur (Minh & van Dishoeck 2000).
    [Show full text]
  • United States Patent (113,607,865
    United States Patent (113,607,865 (72) Inventors John Dyer (56) References Cited Media; UNITED STATES PATENTS Lyle H. Phifer, West Chester, both of Pa. 2,694,723 l l 11954 Schramm ..................... 260/455 B 2l Appl. No. 732,551 2,761,247 9/1956 Meadows.... a 260/216 22 Filed May 28, 1968 2,825,655 3/1958 Meadows..................... 260/216 45) Patented Sept. 21, 1971 2,910,466 101959 Watt............................. 260/216 73) Assignee FMC Corporation Philadelphia, Pa. 3.141023,103,507 9/19637/1964 O'Boyle...Knoevenagel. 260/234 Primary Examiner-Lewis Gotts (54) PREPARATION OFXANTHATES Assistant Examiner-Johnnie R. Brown 10 Claims, No Drawings Attorneys-Thomas R. O'Malley, George F. Mueller and Robert G. Hoffmann 52) U.S.C........................................................ 260/234 R, 260/26, 260/455 B 51 int. Cl......................................................... C07c69132 ABSTRACT: A method of forming alcohol xanthates utilizing 50 Field of Search............................................ 260/455 B, a transXanthation reaction between an alcohol xanthate and 234,216 an alcohol, is disclosed herein. 3,607,865 PREPARATION OFXANTHATES erythritol Alcohol xanthic acids and their derivatives are known to be sorbital useful for a variety of applications including mineral flotation glucose agents, sulfidizing agents, rubber vulcanization accelerators, mannitol adhesives and as intermediates in the preparation of shaped 2-methoxyethanol articles, for example, regenerated cellulose fibers and films. 2-ethoxyethanol In general, alcohol xanthates have been derived by reacting 2-butoxyethanol carbon disulfide with simple and complex alcohols under al diethyleneglycol ethylether kaline conditions. Reactions of this type have been known for polyethylene glycols many years and may be seen, for example, in many prior U.S.
    [Show full text]
  • An Improved Method for BTEX Extraction From
    Analytical Methods Accepted Manuscript This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication. Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available. You can find more information about Accepted Manuscripts in the Information for Authors. Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s standard Terms & Conditions and the Ethical guidelines still apply. In no event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains. www.rsc.org/methods Page 1 of 6 Analytical Methods 1 2 Analytical Methods RSC Publishing 3 4 5 TECHNICAL NOTE 6 7 8 9 An improved method for BTEX extraction from 10 charcoal 11 Cite this: DOI: 10.1039/x0xx00000x 12 13 Raffaele Cucciniello a, Antonio Proto a,*, Federico Rossi a, Nadia 14 b c 15 Marchettini , Oriana Motta Received 00th January 2015, 16 Accepted 00th January 2015 17 Abstract In this paper we propose a simple procedure for the extraction of BTEX (benzene, 18 DOI: 10.1039/x0xx00000x toluene, ethylbenzene and xylenes) from activated charcoal. For this purpose synthetic samples 19 www.rsc.org/ were prepared in laboratory and real samples were collected in a polluted environment using 20 21 passive sampling.
    [Show full text]
  • Mdi), 1,6 Hexamethylene Diisocyanate (Hdi
    4.03.11. PRODUCTION OF ISOCYANATES FOR POLYURETHANE PRO- DUCTION CHEMICALS AND ALLIED APPLICATION NOTE 4.03.11 PRODUCTION OF ISOCYANATES FOR POLYURETHANE PRODUCTION METHYLENE DIPHENYL DIISOCYANATE (MDI), 1,6 HEXAMETHYLENE DIISOCYANATE (HDI) Typical end products Polyurethane foam for different applications, for example, bedding, of materials can be produced to meet the needs for furniture, packaging, coatings and elastomers. specific applications. Chemical curve: R.I. for MDI at Ref. Temp. of 25˚C Application The most commonly used isocyanates for the production of PU are methylene diphenyl diisocyanate (MDI) and toluene diisocyanate (TDI). If color and transparency are important, an aliphatic diisocyanate such as hexamethylene diisocyanate (HDI) is used. The first step in the production of polyurethane is the synthesis of the raw materials. The diisocyanate is typically produced from basic raw materials via nitration, hydrogenation and phosgenation. The feedstock and initial processing steps depend on the Introduction desired isocyanate, but all go through a phosgenation step. Polyurethanes (PUs) are a class of versatile materials with great potential for use in different applications. For instance, for the production of MDI, benzene and They are used in the manufacture of many different nitric acid are reacted to produce nitrobenzene. After items, such as paints, liquid coatings, elastomers, a hydrogeneration step, the nitrobenzene is converted insulators, elastics, foams and integral skins. to aniline. It is then condensed with formaldehyde to produce methylene diphenyl diamine (MDA), the Polyurethanes are produced by polymerization of precursor for MDI. The MDA is fed to a phosgenation a diisocyanate with a polyol. Because a variety of reactor where it reacts with phosgene to produce the diisocyanates and a wide range of polyols can be end-product MDI.
    [Show full text]
  • Chemical Resistance List
    Chemical Resistance List Resistance Substance Permeation Time/Level to Degradation Fluoro- natural chloro- nitrile/ nitrile carbon butyl latex prene chloroprene rubber NR CR CR NBR FKM IIR NR NR CR CR NBR NBR NBR NBR NBR FKM IIR IIR NBR NBR 395 450, 451 720, 722 717 727 730, 732 740, 741 743 754 764 890 897 898 chemical physical 403 706 723, 725 733, 836 742, 757 state 708 726 736 - 739 759 - 0 - 0 0 + 1-methoxy-2-propanol paste 4 2 2 3 4 4 B 1 3 4 6 6 - 0 - 0 0 + 1-methoxy-2-propyl acetate liquid 3 1 1 3 3 A B 2 3 6 6 - 0 0 - 0 + 1-methyl-2-pyrrolidone liquid 5 2 3 3 3 2 A B 1 3 3 6 6 - 0 + + + - 1,1,2-trichlorotrifluoroethane liquid 1 0 5 4 6 6 1 1 2 1 6 1 2 - - - - - - 1.2-epoxy ethane (ethylene oxide) liquid B A A A A 0 0 0 B 1 2 - - - - - - 1.2-epoxy propane (propylene oxide) liquid B A A A 1 A 0 0 0 B 1 2 + + + + + + 1.2-propanediol liquid 6 6 6 6 6 6 6 6 6 6 6 6 6 - + - + + 0 2-ethyl hexyl acrylate liquid 2 1 1 5 6 1 1 2 6 2 3 - 0 0 0 + + 2-mercaptoethanol liquid 3 2 4 4 4 4 1 1 3 6 6 6 - - - 0 0 - 2-methoxy-2-methyl propane liquid 1 B B 2 4 A 1 4 1 3 2 2 - - - - - 0 3-hexanone liquid 1 B 1 1 1 0 0 0 0 0 3 3 - - - - - 0 4-heptanone liquid 1 A 1 1 1 A 0 0 0 B 3 3 - - - - - + acetaldehyde liquid 1 1 1 1 B 0 0 0 A 0 6 6 0 0 0 - - + acetic acid anhydride liquid 6 3 3 3 3 2 A B 1 B 2 6 6 + + + + + + acetic acid, 10 % liquid 6 6 6 6 6 6 6 6 6 6 6 6 6 0 + + + + + acetic acid, 50 % liquid 5 4 6 6 6 2 4 6 6 6 6 - - - - 0 + acetic acid, conc.
    [Show full text]
  • Synthetic Turf Scientific Advisory Panel Meeting Materials
    California Environmental Protection Agency Office of Environmental Health Hazard Assessment Synthetic Turf Study Synthetic Turf Scientific Advisory Panel Meeting May 31, 2019 MEETING MATERIALS THIS PAGE LEFT BLANK INTENTIONALLY Office of Environmental Health Hazard Assessment California Environmental Protection Agency Agenda Synthetic Turf Scientific Advisory Panel Meeting May 31, 2019, 9:30 a.m. – 4:00 p.m. 1001 I Street, CalEPA Headquarters Building, Sacramento Byron Sher Auditorium The agenda for this meeting is given below. The order of items on the agenda is provided for general reference only. The order in which items are taken up by the Panel is subject to change. 1. Welcome and Opening Remarks 2. Synthetic Turf and Playground Studies Overview 4. Synthetic Turf Field Exposure Model Exposure Equations Exposure Parameters 3. Non-Targeted Chemical Analysis Volatile Organics on Synthetic Turf Fields Non-Polar Organics Constituents in Crumb Rubber Polar Organic Constituents in Crumb Rubber 5. Public Comments: For members of the public attending in-person: Comments will be limited to three minutes per commenter. For members of the public attending via the internet: Comments may be sent via email to [email protected]. Email comments will be read aloud, up to three minutes each, by staff of OEHHA during the public comment period, as time allows. 6. Further Panel Discussion and Closing Remarks 7. Wrap Up and Adjournment Agenda Synthetic Turf Advisory Panel Meeting May 31, 2019 THIS PAGE LEFT BLANK INTENTIONALLY Office of Environmental Health Hazard Assessment California Environmental Protection Agency DRAFT for Discussion at May 2019 SAP Meeting. Table of Contents Synthetic Turf and Playground Studies Overview May 2019 Update .....
    [Show full text]
  • 23.5 Basicity and Acidity of Amines
    23_BRCLoudon_pgs5-0.qxd 12/8/08 1:22 PM Page 1122 1122 CHAPTER 23 • THE CHEMISTRY OF AMINES alkylamines, this resonance occurs at rather small chemical shift—typically around d 1. In aromatic amines, this resonance is at greater chemical shift, as in the second of the preceding examples. Like the OH protons of alcohols, phenols, and carboxylic acids, the NH protons of amines under most conditions undergo rapid exchange (Secs. 13.6 and 13.7D). For this reason, split- ting between the amine N H and adjacent C H groups is usually not observed. Thus, in the NMR spectrum of diethylamine,L the N H resonanceL is a singlet rather than the triplet ex- pected from splitting by the adjacent CHL2 protons. In some amine samples, the N H resonance is broadened and, like the OL H protonL of alcohols, it can be obliterated fromL the spectrum by exchange with D2O (the “DL2O shake,” p. 611). The characteristic 13C NMR absorptions of amines are those of the a-carbons—the carbons attached directly to the nitrogen. These absorptions occur in the d 30–50 chemical-shift range. As expected from the relative electronegativities of oxygen and nitrogen, these shifts are somewhat less than the a-carbon shifts of ethers. PROBLEMS 23.4 Identify the compound that has an M 1 ion at mÜz 136 in its CI mass spectrum, an IR 1 + = absorption at 3279 cm_ , and the following NMR spectrum: d 0.91 (1H, s), d 1.07 (3H, t, J 7Hz), d 2.60 (2H, q, J 7Hz), d 3.70 (2H, s), d 7.18 (5H, apparent s).
    [Show full text]
  • 1997-11-12 Carbon Disulfide As Federal Hazardous Air Pollutant
    CARBON DISULFIDE Carbon disulfide is a federal hazardous air pollutant and was identified as a toxic air contaminant in April 1993 under AB 2728. CAS Registry Number: 75-15-0 CS2 Molecular Formula: CS2 Carbon disulfide is a highly refractive, mobile, and very flammable liquid. The purest distillates have a sweet odor. However, the usual commercial and reagent grades of carbon disulfide are foul smelling. It burns with a blue flame to form carbon dioxide and sulfur dioxide. Liquid carbon disulfide will attack some forms of plastics, rubber, and coatings but is non- corrosive to most commercial structural materials at ordinary temperatures. It is miscible in water, alcohol, oils, chloroform, and ether (Merck, 1989). Physical Properties of Carbon Disulfide Synonyms: carbon bisulfide; carbon disulphide; carbon sulfide; sulphocarbonic anhydride; sulphuret of carbon; dithiocarbonic anhydride Molecular Weight: 76.14 Boiling Point: 46.5 oC Melting Point: -111.5 oC Vapor Density: 2.67 (air =1) Flash Point: -30 oC (closed cup) Density/Specific Gravity: 1.2632 at 20/4 oC (water = 1) Critical Temperature: 280 oC Vapor Pressure: 297 mm Hg at 20 oC Log Octanol/Water Partition Coefficient: 1.70 - 4.16 Conversion Factor: 1 ppm = 3.11 mg/m3 (Howard, 1990; HSDB, 1991; Merck, 1989; U.S. EPA, 1994a) SOURCES AND EMISSIONS A. Sources Carbon disulfide is used in the preparation of rayon viscose fibers, and as a solvent for lipids, phosphorus, sulfur, selenium, bromine, iodine, rubber, resins, and waxes (Proctor et al, 1991). Carbon disulfide is also used in the manufacture of carbon tetrachloride, cellophane, flotation Toxic Air Contaminant Identification List Summaries - ARB/SSD/SES September 1997 193 Carbon Disulfide agents, xanthogenates, and numerous other chemicals (HSDB, 1991; Sax, 1987).
    [Show full text]
  • Gasket Chemical Services Guide
    Gasket Chemical Services Guide Revision: GSG-100 6490 Rev.(AA) • The information contained herein is general in nature and recommendations are valid only for Victaulic compounds. • Gasket compatibility is dependent upon a number of factors. Suitability for a particular application must be determined by a competent individual familiar with system-specific conditions. • Victaulic offers no warranties, expressed or implied, of a product in any application. Contact your Victaulic sales representative to ensure the best gasket is selected for a particular service. Failure to follow these instructions could cause system failure, resulting in serious personal injury and property damage. Rating Code Key 1 Most Applications 2 Limited Applications 3 Restricted Applications (Nitrile) (EPDM) Grade E (Silicone) GRADE L GRADE T GRADE A GRADE V GRADE O GRADE M (Neoprene) GRADE M2 --- Insufficient Data (White Nitrile) GRADE CHP-2 (Epichlorohydrin) (Fluoroelastomer) (Fluoroelastomer) (Halogenated Butyl) (Hydrogenated Nitrile) Chemical GRADE ST / H Abietic Acid --- --- --- --- --- --- --- --- --- --- Acetaldehyde 2 3 3 3 3 --- --- 2 --- 3 Acetamide 1 1 1 1 2 --- --- 2 --- 3 Acetanilide 1 3 3 3 1 --- --- 2 --- 3 Acetic Acid, 30% 1 2 2 2 1 --- 2 1 2 3 Acetic Acid, 5% 1 2 2 2 1 --- 2 1 1 3 Acetic Acid, Glacial 1 3 3 3 3 --- 3 2 3 3 Acetic Acid, Hot, High Pressure 3 3 3 3 3 --- 3 3 3 3 Acetic Anhydride 2 3 3 3 2 --- 3 3 --- 3 Acetoacetic Acid 1 3 3 3 1 --- --- 2 --- 3 Acetone 1 3 3 3 3 --- 3 3 3 3 Acetone Cyanohydrin 1 3 3 3 1 --- --- 2 --- 3 Acetonitrile 1 3 3 3 1 --- --- --- --- 3 Acetophenetidine 3 2 2 2 3 --- --- --- --- 1 Acetophenone 1 3 3 3 3 --- 3 3 --- 3 Acetotoluidide 3 2 2 2 3 --- --- --- --- 1 Acetyl Acetone 1 3 3 3 3 --- 3 3 --- 3 The data and recommendations presented are based upon the best information available resulting from a combination of Victaulic's field experience, laboratory testing and recommendations supplied by prime producers of basic copolymer materials.
    [Show full text]
  • H2CS) and Its Thiohydroxycarbene Isomer (HCSH
    A chemical dynamics study on the gas phase formation of thioformaldehyde (H2CS) and its thiohydroxycarbene isomer (HCSH) Srinivas Doddipatlaa, Chao Hea, Ralf I. Kaisera,1, Yuheng Luoa, Rui Suna,1, Galiya R. Galimovab, Alexander M. Mebelb,1, and Tom J. Millarc,1 aDepartment of Chemistry, University of Hawai’iatManoa, Honolulu, HI 96822; bDepartment of Chemistry and Biochemistry, Florida International University, Miami, FL 33199; and cSchool of Mathematics and Physics, Queen’s University Belfast, Belfast BT7 1NN, Northern Ireland, United Kingdom Edited by Stephen J. Benkovic, The Pennsylvania State University, University Park, PA, and approved August 4, 2020 (received for review March 13, 2020) Complex organosulfur molecules are ubiquitous in interstellar molecular sulfur dioxide (SO2) (21) and sulfur (S8) (22). The second phase clouds, but their fundamental formation mechanisms have remained commences with the formation of the central protostars. Tempera- largely elusive. These processes are of critical importance in initiating a tures increase up to 300 K, and sublimation of the (sulfur-bearing) series of elementary chemical reactions, leading eventually to organo- molecules from the grains takes over (20). The subsequent gas-phase sulfur molecules—among them potential precursors to iron-sulfide chemistry exploits complex reaction networks of ion–molecule and grains and to astrobiologically important molecules, such as the amino neutral–neutral reactions (17) with models postulating that the very acid cysteine. Here, we reveal through laboratory experiments, first sulfur–carbon bonds are formed via reactions involving methyl electronic-structure theory, quasi-classical trajectory studies, and astro- radicals (CH3)andcarbene(CH2) with atomic sulfur (S) leading to chemical modeling that the organosulfur chemistry can be initiated in carbonyl monosulfide and thioformaldehyde, respectively (18).
    [Show full text]
  • MDI Process Update Process Economics Program Review 2016-13
    ` IHS CHEMICAL MDI Process Update Process Economics Program Review 2016-13 March 2017 ihs.com PEP Review 2016-13 MDI Process Update Ron Smith Senior Principal Analyst Downloaded 20 March 2017 08:28 AM UTC by Anandpadman Vijayakumar, IHS ([email protected]) IHS Chemical | PEP Review 2016-13 MDI Process Update PEP Review 2016-13 MDI Process Update Ron Smith, Senior Principal Analyst Abstract Isocyanates are a major ingredient for the production of polyurethane products that are formed by the reactive polymerization of isocyanates with polyols. A long and difficult search for a reasonable economic pathway to produce isocyanates by vapor-phase phosgenation of diphenylmethane diamine (MDA) in place of liquid-phase phosgenation of MDA has been developed and commercialized since our last report on isocyanates (PEP Report 1E) was published in August 1992. In this review, we investigate large-scale, single-train integrated technology and economics for the production of methylene diphenyl diisocyanate (MDI), including condensation of aniline with formaldehyde to produce MDA, production of phosgene from carbon monoxide and chlorine, gas-phase phosgenation of MDA to produce crude MDI, and separation/recovery of MDI products. The key gas-phase phosgenation step produces isocyanates from MDA at high pressure and temperature, enabling a significant shortening of residence time in the reactor. The rate determining step is the dissociation of the polymeric MDA–carbonyl chloride intermediate into polymeric MDI and HCl followed by HCl removal. A summary of the process economics for the production of 373 million lbs/yr of crude MDI and 336 million lbs/yr of polymeric MDI (PMDI) and 37 million lbs/yr of pure MDI for continuous vapor-phase isocyanate production shows that on a US Gulf Coast basis, the world-scale, single-train, integrated vapor-phase technology–based plant will meet plant gate costs.
    [Show full text]