DOCSLIB.ORG

Amines As Dehalogenating Agents, IQ1 the Fate of N,N-Dimethylaniline in the Reductive Dehalogenation of 3-Bromocamphor

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Amines As Dehalogenating Agents, IQ1 the Fate of N,N-Dimethylaniline in the Reductive Dehalogenation of 3-Bromocamphor Amines as Dehalogenating Agents, IQ1 The Fate of N,N-Dimethylaniline in the Reductive Dehalogenation of 3-Bromocamphor A n g e l o G . G i u m a n i n i * a n d M a r c o M . M u s i a n i Istituto Chimico G. Ciamician and Centro di Gascromatografia-Spettrometria di Massa, University di Bologna, 40126 Bologna, Italy (Z. Naturforsch. 32 b, 1314-1324 [1977]; received June 6, 1977) Debromination, 3-Bromocamphor, N,N-Dimethylaniline, Aniline A product analysis was made for the reaction between some aromatic amines and 3-bromocamphor (2), which was invariably transformed into camphor (3) and eventually aryliminocamphor. The tertiary N,N-dimethylanilines were oxidized through a complex sequence of couplings and rearrangements to a number of diamines of the diphenyl- methane type. Aniline (4) was also successful in the reductive debromination of 2 to 3 and camphor anil (7), but gave only tarry amino compounds. The reaction, carried out at 200 °C, appeared most probably to be triggered by the radicalic dissociation of the C-Br bond. Bromine ended up as bromide ion in quantitative fashion. We have reported the reductive debromination would not be eluted by gas chromatography was of certain a-bromo and a,a-dibromo carbonyl demonstrated by vacuum distillation (0.1 torr) of derivatives, namely ketones2 and esters1 to the the amines mixture which left practically no residue corresponding ketones and esters by the action of (max. temp. 200 °C), although typical pH depending hot N,N-dimethylaniline (1). The fate of bromine colors showed the presence of traces of high molecu­ and the amine was not then investigated and is the lar weight dyes. object of the present work. The more volatile components included aniline (4), N-methylaniline (5), p-bromo-N,N-dimethyl- Results aniline (6) and camphor anil (7). All the higher We have used 3-bromocamphor (2) as the model boiling components showed a dimeric framework, compound, because its reaction with 1 is remarkably namely, that of variously N,N'-polymethylated o- clean, giving camphor (3) in high yield. A standard and p-diaminodiphenylmethanes (DDM’s). They acid base separation allowed to isolate a mixture of are: N,N'-dimethyl-o,o'-DDM (8), N,N'-dimethyl- all basic nitrogen containing compounds. Bromide 2?,p'-DDM (9), N,N,N'-trimethyl-o,p'-DDM (10), ion was found in practically quantitative conver­ N^'.N'-trimethyl-o^'-DDM (11), N,N,N'-trime- sions in the resulting water solution for longer thyl- 2?,p'-DDM (12), N ^N 'jN '-tetram ethyl-o,^'- reaction times (see Table I). At least eleven products DDM (13) and N^N'.N'-tetramethyl-^p'-DDM could be separated by gas chromatography using (14). The mass spectrum of the GC peak with reten­ suitable combinations of stationary phases and tion time ratio 0.57 with respect to 14 in the further identified by mass spectrometry (Table II), analysis with SE 30 as stationary phase and the used both as a preliminary tool for structure mass spectrum of the GC peak with retention time determination and as a fingerprinting method for ratio 1.00 in the analysis with Versamide, respec­ comparison with compounds obtained by different tively belonging mainly to 11 and 14, showed the routes. The relative quantitative unimportance of presence of the molecular ion of another N,N'-poly- products of such extremely high boiling points, that methylated-DDM, i.e., N,N'-dimethyl-o,j9'-DDM (15). This compound was prepared by an independ­ Requests for reprints should be sent to Prof. Dr. ent route and found to have the same GC properties; A. G . G i u m a n i n i , Istituto Chimico G . Ciamician and it showed the same mass spectrum as the one Centro di Gascromatografia-Spettrometria di Massa, Universitd di Bologna, 1-40126 Bologna. reconstructed for the hidden peak. Camphor anil A. G. Giumanini-M. M. Musiani • Amines as Dehalogenating Agents 1315 Table I. Products of the reaction between 3-bromocamphor (2) and aromatic amines*. Amine Time Products [%] [h] B r- Camphor Nitrogen containing compounds N,N-Dimethylaniline (1) 3 29 33 b N,N-Dimethylaniline (1) 8 47 50 Aniline (4, 1) N,Methylaniline (5, 87) p-Bromo-N,N-dimethylaniline ( 6 , 0.5) Camphor anil (7, 1) N,N'-Dimethyl-o,o'-DDM ( 8 1) N.N'-Dimethyl-p.p'-DDM (9, 2) N,N,N'-Trimethyl-o,p'-DDM (10, 1) N,N'N,-Trimethyl-o,p'-DDM (11, 9) N,N,N'-Trimethyl-p,p'-DDM (12, 7) N,N,N',N'-Tetramethyl-o,p'-DDM (13, 3) NjN.N'^'-Tetramethyl-p.p'-DDM (14, 29) N,N'-Dimethyl-o,p'-DDM (15)c N,N-Dimethylaniline (1) 32 1 0 0 76 b N,N-Dimethylaniline (1) and 18 3 c 19 b Aniline (4) 24 98 7 Camphor anil (7, 87) N,N-Diphenylamine (28, 9)d p-Toluidine (22) 24 c 26 Aniline (4, 3)d Camphor anil (7, 1) Camphor p-methylanil (23, 51) N,N-Di-p-tolylamine (42, 3)d N-Phenyl-p-toluidine (43, 0.5)d N,N-Dimethyl-p-toluidine (34) 8 c 58 2,2/-Di(N-methyl-4-toluidino)methane (35, 17) N,N,N'-Trimethyl-2,2'-di(4-toluidino)methane (36, 20) 2,2'-Di(N,N-dimethyl-4-toluidino)methane (37, 5) None 3 c 7 8 1.5 c a Temperature of the thermostatic external bath: 200 °C ± 3 °C. The amine/2 weight ratio was 5:1. b Yields not determined, same qualitative product pattern as in analogous experiments. c Yield not determined. d Yield based on initial amine. Table II. GC-MS data of DDM’s (8-15) from reaction* of 3-bromocamphor (2) and N,N-dimethylaniline (1). DDM GC Rentention ratios 15 Mass spectrometry at 70 eY, m/e (% rel. int . ) 0 Versamide SE 30 N,N'-Dimethyl-o,o'-DDM 0.61 0.35 226 (M+, 100), 120 (67), 107 (56), 118 (50), 106 (40), (8) 91 (35), 194 (26), 227 (19), 180 (18), 119 (16). NjN'-Dimethyl-p.p'-DDM 0 1.98 0 . 8 8 226 (M+, 100), 225 (75), 120 (47), 196 (25), 160 (20), (9) 227 (17), 224 (16), 112 (15), 118 (14), 113 (13). N.NjN'-Trimethyl-o.p'-DDM 0.37 0.30 120 (100), 240 (M+, 8 6 ), 118 (81), 121 (59), 91 (56), (1 0 ) 132 (45), 133 (34), 106 (21), 134 (21), 194 (21). NjN'.N'-Trimethyl-Ojp'-DDM 0 0.70 0.57 240 (M+, 100), 121 (94), 225 (57), 120 (45), 118 (44), (1 1 ) 134 (32), 91 (31), 180 (24), 119 (23), 112 (21). N.NjN'-Trimethyl-p^'-DDM 1.41 0.92 240 (M+, 100), 239 (75), 120 (33), 134 (31), 195 (21), (1 2 ) 119 (19), 241 (18), 209 (17), 118 (15), 223 (11). N,N,N',N'-Tetramethyl-o,p'-DDM 0.44 0.46 134 (100), 254 (M+, 92), 118 (71), 239 (55), 91 (36), (13) 132 (32), 119 (25), 133 (21), 255 (19), 120 (16). N,N,N',N'-Tetramethyl-p,p'-DDMd 1 . 0 0 1 . 0 0 254 (M+, 100), 253 (71), 210 (25), 134 (24), 255 (19), (14) 126 (17), 237 (15), 118 (14), 127 (12), 165 (7). N.N'-Dimethyl-Ojp'-DDM 1 . 0 0 0.57 226 (M+, 100), 57 (61), 211 (60), 120 (59), 118 (55), (15) 107 (52), 224 (52), 209 (47), 55 (47), 223 (41). a Actual experiment described in the experimental section. b Columns: 2 m by 0.25 mm, copper, Versamide 3% on Chromosorb W (80-100 mesh) and SE 30 1% on Chromo- sorb P (80-100 mesh), respectively at 200 °C and at 180 °C; flow rate 30 ml/min (N 2 ), injector at 300 °C, manifold at 300 °C. Compound 14 was taken as internal standard. c Spectra were recorded via the GC inlet, unless specified otherwise. d MS recorded via direct inlet. 1316 A. G. Giumanini-M. M. Musiani • Amines as Dehalogenating Agents (7), 9 and 14 were prepared according to known N,N,N',N'-tetrainethyl-o,o'-DDM is not present, methods3-5. Partial methylation of 9 with methyl most probably because of steric reasons, and in iodide gave 12. o-(N-Methylamino)benzyl alcohol force of an extrapolation of the rationale explaining (16) was condensed with N,N-dimethylaniline (1) the relative variation of the m/e 134 and 120 peak and N,N-dimethylanilinium bromide (17) to give intensity in the mass spectrum, as could be learnt mainly 11 and some 13: the ratio of these two from the mass spectra of 11 and 12 (quem vide, products was found to depend on the reaction tem­ Table II): in fact release of steric compression perature. Compound 13 appeared to be produced facilitated the formation of the ion at mje 120 for 10. via N-methylation by 17. The same alcohol 16 with N-methylaniline (5) and N-methylanilinium bromide Discussion (18) gave as the major product 15 with minor The product analysis of the reaction between 1 amounts of 8. No N-methylation took place in this and 2 appeared to be rather satisfactoy: e.g., in an instance. A priori, compound 10, present in small experiment with 50% yield of camphor (3), we amount in the mixture of the reaction of 1 with 2, obtained bromide ion and oxidized N,N-dimethyl- and for which no independent synthesis was made, aniline products of the DDM type respectively in with its molecular weight 240 could have either the 47% and 52% yield.
Load more

Recommended publications
  • Synthesis and Toxicity
    Molecules 2008, 13, 986-994 molecules ISSN 1420-3049 © 2008 by MDPI www.mdpi.org/molecules Full Paper Fluorinated Analogs of Malachite Green: Synthesis and Toxicity George A. Kraus 1,*, Insik Jeon 1, Marit Nilsen-Hamilton 2, Ahmed M. Awad 2, Jayeeta Banerjee 2 and Bahram Parvin 3 1 Iowa State University Department of Chemistry, Ames, IA 50011, USA; Tel. +1 515-294-7794; Fax: +1 515-294-0105 2 Iowa State University Department of Biochemistry, Biophysics and Molecular Biology, Ames, IA 50011, USA; Tel. +1 515-9996; Fax: +1 515-294-0453 3 Lawrence Berkeley Laboratory Department of Cancer Biology, Berkeley, CA 94720, USA; Tel. +1 510-486-6203; Fax: +1 510-486-6363 * Author to whom correspondence should be addressed; E-mail: [email protected] Received: 21 March 2008; in revised form: 22 April 2008 / Accepted: 22 April 2008 / Published: 27 April 2008 Abstract: A series of fluorinated analogs of malachite green (MG) have been synthesized and their toxicity to Saccharomyces cerevisiae and a human ovarian epithelial cell line examined. The toxicity profiles were found to be different for these two species. Two analogs, one with 2,4-difluoro substitution and the other with 2-fluoro substitution seem to be the most promising analogs because they showed the lowest toxicity to the human cells. Keywords: Malachite Green; Malachite Green analogs; Bathochromic shift; Toxicity; Saccharomyces cerevisiae; human ovarian epithelial cells. Introduction We are developing a new procedure for real-time imaging of gene expression. It involves a nucleic acid probe that can be used in conjunction with a 18F-labeled target molecule to image gene expression in vivo [1].
    [Show full text]
  • Aniline and Aniline Hydrochloride
    SOME AROMATIC AMINES AND RELATED COMPOUNDS VOLUME 127 This publication represents the views and expert opinions of an IARC Working Group on the Identification of Carcinogenic Hazards to Humans, which met remotely, 25 May–12 June 2020 LYON, FRANCE - 2021 IARC MONOGRAPHS ON THE IDENTIFICATION OF CARCINOGENIC HAZARDS TO HUMANS ANILINE AND ANILINE HYDROCHLORIDE 1. Exposure Characterization 1.1.2 Structural and molecular formulae, and relative molecular mass 1.1 Identification of the agent (a) Aniline 1.1.1 Nomenclature NH2 (a) Aniline Chem. Abstr. Serv. Reg. No.: 62-53-3 EC No.: 200-539-3 Molecular formula: C H N IUPAC systematic name: aniline 6 7 Relative molecular mass: 93.13 (NCBI, 2020a). Synonyms and abbreviations: benzenamine; phenylamine; aminobenzene; aminophen; (b) Aniline hydrochloride aniline oil. NH2 (b) Aniline hydrochloride Chem. Abstr. Serv. Reg. No.: 142-04-1 EC No.: 205-519-8 HCl IUPAC systematic name: aniline hydro - Molecular formula: C6H8ClN chloride Relative molecular mass: 129.59 (NCBI, Synonyms: aniline chloride; anilinium chlo- 2020b). ride; benzenamine hydrochloride; aniline. HCl; phenylamine hydrochloride; phenylam- monium chloride. 1.1.3 Chemical and physical properties of the pure substance Aniline is a basic compound and will undergo acid–base reactions. Aniline and its hydrochlo- ride salt will achieve a pH-dependent acid–base equilibrium in the body. 109 IARC MONOGRAPHS – 127 (a) Aniline Octanol/water partition coefficient (P): log Kow, 0.936, predicted median (US EPA, 2020b) Description: aniline appears as a yellowish Conversion factor: 1 ppm = 5.3 mg/m3 [calcu- to brownish oily liquid with a musty fishy lated from: mg/m3 = (relative molecular odour (NCBI, 2020a), detectable at 1 ppm 3 mass/24.45) × ppm, assuming temperature [3.81 mg/m ] (European Commission, 2016; (25 °C) and pressure (101 kPa)].
    [Show full text]
  • Nitrosamines EMEA-H-A5(3)-1490
    25 June 2020 EMA/369136/2020 Committee for Medicinal Products for Human Use (CHMP) Assessment report Procedure under Article 5(3) of Regulation EC (No) 726/2004 Nitrosamine impurities in human medicinal products Procedure number: EMEA/H/A-5(3)/1490 Note: Assessment report as adopted by the CHMP with all information of a commercially confidential nature deleted. Official address Domenico Scarlattilaan 6 ● 1083 HS Amsterdam ● The Netherlands Address for visits and deliveries Refer to www.ema.europa.eu/how-to-find-us Send us a question Go to www.ema.europa.eu/contact Telephone +31 (0)88 781 6000 An agency of the European Union © European Medicines Agency, 2020. Reproduction is authorised provided the source is acknowledged. Table of contents Table of contents ...................................................................................... 2 1. Information on the procedure ............................................................... 7 2. Scientific discussion .............................................................................. 7 2.1. Introduction......................................................................................................... 7 2.2. Quality and safety aspects ..................................................................................... 7 2.2.1. Root causes for presence of N-nitrosamines in medicinal products and measures to mitigate them............................................................................................................. 8 2.2.2. Presence and formation of N-nitrosamines
    [Show full text]
  • Sds – Safety Data Sheet
    Effective Date: 02/02/16 Replaces Revision: 01/01/13, 12/22/10 NON-EMERGENCY TELEPHONE 24-HOUR CHEMTREC EMERGENCY TELEPHONE 610-866-4225 800-424-9300 SDS – SAFETY DATA SHEET 1. Identification Product Identifier: N, N – DIMETHYLANILINE Synonyms: Xylidine; N,N-Dimethylbenzenamine; Benzenamine,N,N-Dimethyl-; Dimethylphenylamine Chemical Formula: C6H5N(CH3)2 Recommended Use of the Chemical and Restrictions On Use: Laboratory Reagent Manufacturer / Supplier: Puritan Products; 2290 Avenue A, Bethlehem, PA 18017 Phone: 610-866-4225 Emergency Phone Number: 24-Hour Chemtrec Emergency Telephone 800-424-9300 2. Hazard(s) Identification Classification of the Substance or Mixture: Flammable liquids (Category 4) Acute toxicity, Oral (Category 3) Acute toxicity, Inhalation (Category 3) Acute toxicity, Dermal (Category 3) Skin irritation (Category 3) Eye irritation (Category 2A) Carcinogenicity (Category 2) Acute aquatic toxicity (Category 2) Chronic aquatic toxicity (Category 2) Risk Phrases: Symbol: T, N R23/24/25: Toxic by inhalation, in contact with skin and if swallowed. R40: Limited evidence of a carcinogenic effect. R51/ 53: Toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment. Label Elements: Trade Name: N, N – DIMETHYLANILINE Signal Word: Danger N, N - DIMETHYLANILINE Page 1 of 6 Hazard Statements: H227: Combustible liquid. H301 + H311: Toxic if swallowed or in contact with skin. H316: Causes mild skin irritation. H319: Causes serious eye irritation. H331: Toxic if inhaled. H351: Suspected of causing cancer. H411: Toxic to aquatic life with long lasting effects. Precautionary Statements: P261: Avoid breathing dust / fume / gas / mist / vapors / spray. P273: Avoid release to the environment. P280: Wear protective gloves / protective clothing.
    [Show full text]
  • The Conversion of N – Methylaniline and N –, 2 – Dimethylaniline by Using Different Catalysts
    View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by KHALSA PUBLICATIONS I S S N 2 3 2 1 - 8 0 7 X Volume 13 Number8 Journal of Advances in chemistry THE CONVERSION OF N – METHYLANILINE AND N –, 2 – DIMETHYLANILINE BY USING DIFFERENT CATALYSTS Aghayev Akbar Ali1, Musfatayeva Naila Abdulla2, Shahtakhtinskaya Pari Turabkhan3, Muradov Mahal Mayil4, Nasirova Irada Mammad5 1 Doctor of Chemical Sciences, Professor, the Head of the Department of “Petrochemistry and Chemical Technologies”, Sumgait State University, Sumgait, Azerbaijan [email protected] 2 Lead Teacher of the Department of “Chemistry of High Molecular Compounds and Analytical Chemistry”, Sumgait State University, Sumgait, Azerbaijan [email protected] 3 Associate Professor of the Department of “Petroleum Chemistry and Chemical Technologies”, Sumgait State University, Sumgait, Azerbaijan 4 Associate Professor of the Department of “Petroleum Chemistry and Chemical Technologies”, Sumgait State University, Sumgait, Azerbaijan [email protected] 5 Lead Teacher of the Department of “Petroleum Chemistry and Chemical Technologies”, Sumgait State University, Sumgait, Azerbaijan ABSTRACT The catalytic conversion of N – methylaniline and N –, 2 – dimethylaniline in the presence of Pd – HSHM, CuFe2O4·γ·Al2O3 and vanadium – chromium – aluminium (VChA) oxide systems has been investigated. The comparative analysis of the results of the conversion of three different feedstocks with VChA catalyst shows that the xylidines, especially 2,6 – dimethylaniline is formed
    [Show full text]
  • (((4-Methoxyphenyl)Amino)Methyl)-N,N-Dimethylaniline and 2-Methoxy-5-((Phenylamino)Methyl)Phenol
    molbank Communication 4-(((4-Methoxyphenyl)amino)methyl)-N,N-dimethylaniline and 2-Methoxy-5-((phenylamino)methyl)phenol Peter A. Ajibade * and Fartisincha P. Andrew School of Chemistry and Physics, University of KwaZulu-Natal, Private Bag X01, Pietermaritzburg 3209, South Africa; [email protected] * Correspondence: [email protected] Abstract: Molecular structures of 4-(((4-methoxyphenyl)amino)methyl)-N,N-dimethylaniline and 2-methoxy-5-((phenylamino)methyl)phenol synthesized via Schiff bases reduction route are reported. The compounds consist of asymmetric units of C16H20N2O(1) and C14H15NO2 (2) in orthorhombic and monoclinic crystal systems, respectively. Compound 1 consist of intermolecular C11—H11···N2 hydrogen bonding with C11···N21 = 3.463(4) Å. The hydroxyl group in 2 is also involved in inter- molecular O2—H2···O2 and O2—H2···O21 hydrogen bonding with O2···O11 = 2.8885(15) Å and O1···O21 = 2.9277(5) Å. The molecular structures of the compounds are stabilized by secondary intermolecular interactions of C1—H1B···O11 and C5—H···(C41, C51, C61, C71) for 1 and H···C, C—H···O and N—H···C for 2. The reported compounds are important starting material for the synthesis of many compounds such as azo dyes and dithiocarbamate. Keywords: secondary amines; crystal structure; sodium borohydride; supramolecular structure Citation: Ajibade, P.A.; Andrew, F.P. 1. Introduction 4-(((4-Methoxyphenyl)amino) N-alkylation of primary amines and ammonia, reduction of nitriles and amides in methyl)-N,N-dimethylaniline and the presence of catalyst such as LiAlH4 and NaBH4, tin, or iron have been used for the 2-Methoxy-5-((phenylamino)methyl) preparation of secondary amines [1–5].
    [Show full text]
  • March 20, 2008 HAZARDOUS AIR POLLUTANTS – Sorted Alphabetically
    HAZARDOUS AIR POLLUTANTS – sorted alphabetically CAS CAS Number Chemical Name VOC/PM Number Chemical Name VOC/PM 75-07-0 Acetaldehyde VOC 91-94-1 3,3'-Dichlorobenzidine VOC1 60-35-5 Acetamide VOC 111-44-4 Dichloroethyl ether (Bis(2-chloroethyl) ether) VOC 75-05-8 Acetonitrile VOC 542-75-6 1,3-Dichloropropene VOC 98-86-2 Acetophenone VOC 62-73-7 Dichlorvos VOC 53-96-3 2-Acetylaminofluorene VOC1 111-42-2 Diethanolamine VOC 107-02-8 Acrolein VOC 64-67-5 Diethyl sulfate VOC 79-06-1 Acrylamide VOC 119-90-4 3,3'-Dimethoxybenzidine VOC1 79-10-7 Acrylic acid VOC 60-11-7 4-Dimethylaminoazobenzene VOC1 107-13-1 Acrylonitrile VOC 121-69-7 N,N-Dimethylaniline VOC 107-05-1 Allyl chloride VOC 119-93-7 3,3'-Dimethylbenzidine VOC1 92-67-1 4-Aminobiphenyl VOC1 79-44-7 Dimethylcarbamoyl chloride VOC 62-53-3 Aniline VOC 68-12-2 Dimethylformamide VOC 90-04-0 o-Anisidine VOC 57-14-7 1,1-Dimethylhydrazine VOC 0 Antimony Compounds PM 131-11-3 Dimethyl phthalate VOC 0 Arsenic Compounds PM2 77-78-1 Dimethyl sulfate VOC 1332-21-4 Asbestos (friable) PM 534-52-1 4,6-Dinitro-o-cresol (including salts) VOC1 71-43-2 Benzene VOC 51-28-5 2,4-Dinitrophenol VOC1 92-87-5 Benzidine VOC1 121-14-2 2,4-Dinitrotoluene VOC 98-07-7 Benzotrichloride VOC 123-91-1 1,4-Dioxane (1,4-Diethylene oxide) VOC 100-44-7 Benzyl chloride VOC 122-66-7 1,2-Diphenylhydrazine VOC 0 Beryllium Compounds PM 106-89-8 Epichlorohydrin (l-Chloro-2,3-epoxypropane) VOC 92-52-4 Biphenyl VOC 106-88-7 1,2-Epoxybutane (1,2-Butylene oxide) VOC 542-88-1 Bis(chloromethyl) ether VOC 140-88-5 Ethyl acrylate VOC
    [Show full text]
  • Localories Per Mole
    LOS ALAMOS SERIES ON DYNAMIC MATERIAL PROPERTIES LOS ALAMOS DATA CENTER FOR DYNAMIC MATERIAL PROPERTIES TECHNICAL COMMITTEE Charles L. Mader Program Manager Terry R. Gibbs Explosive Data Editor Charles E. Morris Shock Wave Profile Editor Stanley P. Marsh Equation of State Editor Alphonse Popolato Explosive Data Editor Martha S. Hoyt Computer Applications Analyst Kasha V. Thayer Technical Editor Sharon L. Crane Technical Editor John F. Barnes Richard D. Dick John W. Hopson, Jr. James N. Johnson Elisabeth Marshall Timothy R. Neal Suzanne W. Peterson Raymond N. Rogers John W. Taylor Melvin T. Thieme Jerry D. Wackerle John M. Walsh . 111 LASL EXPLOSIVE PROPERTY DATA Editors - Terry R. Gibbs Alphonse Popolato CONTRIBUTORS John F. Baytos Bobby G. Craig Arthur W. Campbell William E. Deal Jerry J. Dick Robert H. Dinegar Raymond P. Engelke Thomas E. Larson Elisabeth Marshall John B. Ramsay Raymond N. Rogers Diane Soran Manuel J. Urizar Jerry D. Wackerle UNIVERSITY OF CALIFORNIA PRESS Berkeley l Los Angeles l London University of California Press Berkeley and Los Angeles, California University of California Press, Ltd. London, England Copyright @ 1980 by The Regents of the University of California ISBN o-520-040 12-O Series ISBN O-520-04007-4 Library of Congress Catalog Card Number: 80-53635 Printed in the United States of America 123456789 vi CONTENTS PART I. EXPLOSIVES PROPERTIES BY EXPLOSIVES ................ 1 Baratol ............................................................. 3 Composition B ......................................................
    [Show full text]
  • MECHANISTIC EVALUATION of N-DEALKYLATION by CYTOCHROME P450 USING N,N-DIMETHYLANILINE N-OXIDES and KINETIC ISOTOPE EFFECTS by KE
    MECHANISTIC EVALUATION OF N-DEALKYLATION BY CYTOCHROME P450 USING N,N-DIMETHYLANILINE N-OXIDES AND KINETIC ISOTOPE EFFECTS By KENNETH M. ROBERTS A dissertation submitted in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY WASHINGTON STATE UNIVERSITY School of Molecular Biosciences DECEMBER 2009 To the Faculty of Washington State University: The members of the Committee appointed to examine the dissertation of KENNETH M. ROBERTS find it satisfactory and recommend that it be accepted. ___________________________________ Jeffrey P. Jones, Ph.D., Chair ___________________________________ William B. Davis, Ph.D. ___________________________________ Lisa M. Gloss, Ph.D. ___________________________________ ChulHee Kang, Ph.D. ii MECHANISTIC EVALUATION OF N-DEALKYLATION BY CYTOCHROME P450 USING N,N-DIMETHYLANILINE N-OXIDES AND KINETIC ISOTOPE EFFECTS Abstract by Kenneth M. Roberts, Ph.D. Washington State University December 2009 Chair: Jeffrey P. Jones Cytochrome P450 enzymes (P450) are a large family of heme-containing monooxygenases found throughout nature. Five isoforms in humans have gained the attention of the pharmaceutical industry due to their responsibility for the oxidation of the majority of pharmaceutical compounds. Due to unconstrained active sites which permit multiple orientations of a given substrate and an arsenal of oxidations attributed to the enzyme, the drug-metabolizing P450s are promiscuous enzymes. Development of predictive models for the oxidation of a given compound by P450 is a major goal for drug development. Since a drug may be oxidized in several ways, prediction of P450-mediated metabolism requires understanding the mechanisms of the possible oxidations that can be performed. This work is focused on evaluating the mechanism of N-dealkylation by P450s using N-oxides as competent models of the native P450 oxidant.
    [Show full text]
  • Regulation 5.23, Toxic Air Contaminants
    REGULATION 5.23 Categories of Toxic Air Contaminants Air Pollution Control District of Jefferson County Jefferson County, Kentucky Relates To: KRS Chapter 77 Air Pollution Control Pursuant To: KRS Chapter 77 Air Pollution Control Necessity and Function: KRS 77.180 authorizes the Air Pollution Control Board to adopt and enforce all orders, rules, and regulations necessary or proper to accomplish the purposes of KRS Chapter 77. This regulation identifies the categories of toxic air contaminants to be addressed in these regulations. SECTION 1 Category 1 Toxic Air Contaminants 1.1 The Category 1 Toxic Air Contaminants list includes the compounds monitored in the 2000 to 2001 West Louisville Air Toxics Study at a concentration representative of a cancer risk greater than 1.010-6 or a non-cancer Hazard Quotient (HQ) greater than 1.0. 1.2 The Category 1 Toxic Air Contaminants list reads as follows: Category 1 Toxic Air Contaminants CAS No. Compound 1. 107-13-1..............................Acrylonitrile 2. 7440-38-2..............................Arsenic & various and arsenic compounds 3. 71-43-2..............................Benzene 4. 75-25-2..............................Bromoform 5. 106-99-0..............................1,3-Butadiene 6. 7440-43-9..............................Cadmium & various and cadmium compounds 7. 56-23-5..............................Carbon tetrachloride 8. 67-66-3..............................Chloroform 9. 126-99-8..............................Chloroprene [2-Chloro-1,3-butadiene] 10. 7440-47-3..............................Chromium & various and chromium compounds 11. 106-46-7..............................1,4-Dichlorobenzene 12. 50-00-0..............................Formaldehyde 13. 75-09-2..............................Methylene chloride [Dichloromethane] 14. 7440-02-0..............................Nickel & various and nickel compounds 15. 127-18-4..............................Perchloroethylene [Tetrachloroethylene] 16.
    [Show full text]
  • Amines As Dehalogenating Agents, IQ1 the Fate of N,N-Dimethylaniline in the Reductive Dehalogenation of 3-Bromocamphor
    Amines as Dehalogenating Agents, IQ1 The Fate of N,N-Dimethylaniline in the Reductive Dehalogenation of 3-Bromocamphor A n g e l o G . G i u m a n i n i * a n d M a r c o M . M u s i a n i Istituto Chimico G. Ciamician and Centro di Gascromatografia-Spettrometria di Massa, University di Bologna, 40126 Bologna, Italy (Z. Naturforsch. 32 b, 1314-1324 [1977]; received June 6, 1977) Debromination, 3-Bromocamphor, N,N-Dimethylaniline, Aniline A product analysis was made for the reaction between some aromatic amines and 3-bromocamphor (2), which was invariably transformed into camphor (3) and eventually aryliminocamphor. The tertiary N,N-dimethylanilines were oxidized through a complex sequence of couplings and rearrangements to a number of diamines of the diphenyl- methane type. Aniline (4) was also successful in the reductive debromination of 2 to 3 and camphor anil (7), but gave only tarry amino compounds. The reaction, carried out at 200 °C, appeared most probably to be triggered by the radicalic dissociation of the C-Br bond. Bromine ended up as bromide ion in quantitative fashion. We have reported the reductive debromination would not be eluted by gas chromatography was of certain a-bromo and a,a-dibromo carbonyl demonstrated by vacuum distillation (0.1 torr) of derivatives, namely ketones2 and esters1 to the the amines mixture which left practically no residue corresponding ketones and esters by the action of (max. temp. 200 °C), although typical pH depending hot N,N-dimethylaniline (1). The fate of bromine colors showed the presence of traces of high molecu­ and the amine was not then investigated and is the lar weight dyes.
    [Show full text]
  • HAZARDOUS AIR POLLUTANTS Per 1990 Clean Air Act Amendments, §112(B)
    Appendix 1 HAZARDOUS AIR POLLUTANTS per 1990 Clean Air Act Amendments, §112(b) HAZARDOUS AIR POLLUTANTS 7647010 Hydrochloric acid 7664393 Hydrogen fluoride (Hydrofluoric acid) 75070 Acetaldehyde (voc) 123319 Hydroquinone (voc) 60335 Acetamide (voc) 78591 Isophorone (voc) 75058 Acetonitrile (voc) 58899 Lindane (all isomers) (voc) 98862 Acetophenone (voc) 108316 Maleic anhydride (voc) 53963 2-Acetylaminofluorene (voc) 67561 Methanol (voc) 107028 Acrolein (voc) 72435 Methoxychlor (voc) 79061 Acrylamide (voc) 74839 Methyl bromide (Bromomethane) (voc) 79107 Acrylic acid (voc) 74873 Methyl chloride (Chloromethane) (voc) 107131 Acrylonitrile (voc) 71556 Methyl chloroform (1,1,1-Trichloroethane) 107051 Allyl chloride (voc) 78933 Methyl ethyl ketone (2-Butanone) (voc) 92671 4-Aminobiphenyl (voc) 60344 Methyl hydrazine (voc) 62533 Aniline (voc) 74884 Methyl iodide (Iodomethane) (voc) 90040 o-Anisidine (voc) 108101 Methyl isobutyl ketone (Hexone) (voc) 1332214 Asbestos (TSP) 624839 Methyl isocyanate (voc) 71432 Benzene (including benzene from gasoline) (voc) 80626 Methyl methacrylate (voc) 92875 Benzidine (voc) 1634044 Methyl tert butyl ether (voc) 98077 Benzotrichloride (voc) 101144 4,4-Methylene bis(2-chloroaniline) (voc) 100447 Benzyl chloride (voc) 75092 Methylene chloride (Dichloromethane) 92524 Biphenyl (voc) 101688 Methylene diphenyl diisocyanate (MDI) (voc) 117817 Bis(2-ethylhexyl)phthalate (DEHP) (voc) 101779 4,4-Methylenedianiline (voc) 542881 Bis(chloromethyl)ether (voc) 91203 Naphthalene (voc) 75252 Bromoform (voc) 98953 Nitrobenzene
    [Show full text]