Synthesis, Anti-Inflammatory Activity of Picen-13-Ylmethylene Derivatives

Total Page:16

File Type:pdf, Size:1020Kb

Load more

The Free Internet Journal Paper for Organic Chemistry Archive for Arkivoc 2017, part v, 67-79 Organic Chemistry Synthesis, anti-inflammatory activity of picen-13-ylmethylene derivatives T. Shanmuganathan,*a,b A. A. M. Prince,b N. Dhatchanamoorthy,a K. Parthasarathy,c and M. Venugopald a Orchid Pharma Ltd, R & D Centre, Chennai 600119, India b Ramakrishna Mission Vivekananda College, Department of chemistry, Mylapore, Chennai 600 004, India c Siddha Central Research Institute, Central Council for Research in Siddha, Chennai 600 106, India d Ven Biotech Private Limited, Chennai, India Email: [email protected] Received 03-19-2017 Accepted 05-27-2017 Published on line 07-09-2017 Abstract A series of picene-13-ylmethylene derivatives (11-17) were synthesized by Knoevenagel condensation of active methylene compounds with picene-13-carbaldehyde. Keywords: Photo cyclization, picene-13-carbaldehyde, picene-13-ylmethylene derivatives, anti-inflammatory DOI: https://doi.org/10.24820/ark.5550190.p010.100 Page 67 ©ARKAT USA, Inc Arkivoc 2017, v, 67-79 Shanmuganathan, T. et al. Introduction Picene or benzo[a]chrysene, is well documented for use in material chemistry.1,2 Picene derivatives were found to be present in abundance as pentacyclic triterpenes and triterpenoids which are often bioactive and present a huge therapeutic potential. Many pentacyclic triterpenes namely oleane, oleanolic acid and ursane are reported to possess promising antitumor,3-5 antiviral,6 antidiabetic,7 anti-inflammatory8 activities. Also a derivative of picene, namely octadecahydro-picene-2,3,14,15-tetranone isolated and purified from the root bark of Zizyphus nummularia, reported to possess anti-cancer and anti-inflammatory activities.9,10 Many polycyclic aromatic compounds such as flavone, quercetin, chrysin and pyrimido[4,5-b]quinolines were reported to possess anti-inflammatory or antioxidant properties.11,12 Because of the close structural similarity with the reported polycyclic compounds, we have envisaged to explore the anti-inflammatory activity of picene analogues. Thus, our interest is to conjugate two naphthalene moieties by cyclization which results in the formation of a picene moiety. Substitution at its alpha position with various esters or amides leads to novel picene methylene derivatives in order to evaluate their biological properties. In order to accomplish our objective, we used a Knoevenagel condensation for the synthesis of novel structures incorporating both the picene moiety and several active methylene compounds, namely, ethyl cyanoacetate, malononitrile, cyanoacetamide, diethyl malonate, ethyl acetoacetate, acetylacetone and 5,6 dimethoxy-1- indanone with picene-13-carbaldehyde. The synthesized picen-13-ylmethylene derivatives were characterized by NMR, IR, mass spectra, elemental analysis. The structures were confirmed by single crystal XRD of a selected example. The compounds were evaluated by in vitro biological tests for their anti-inflammatory properties. Results and Discussion In the present work, we synthesized a new series of picen-13-ylmethylene derivatives 11-17 by condensing active methylene groups with picene-13-carbaldehyde as shown in Scheme 1 and 2. The first step in the Scheme 1 was the condensation of 1-naphthaldehyde 1 with 1-naphthyl acetic acid 2 in the presence of triethylamine and acetic anhydride produced 2,3-di(naphthalen-1-yl)acrylic acid 313,14 with 62% yield after recrystallization from ethyl acetate. Table 1. Reaction conditions and yield of 3 for the esterification using an alcohol Reaction Reaction Reaction Product Yield Solvent condition Time conversion % Ethanol Reflux 3 days 60% 50% of compound 4 Mixture of Ethanol and Toluene Reflux 10 hrs 100% 86% of compound 4 Methanol Reflux 3 days 60% 50% of compound 5 Mixture of Methanol and Reflux 10 hrs 100% 87% of compound 5 Toluene Page 68 ©ARKAT USA, Inc Arkivoc 2017, v, 67-79 Shanmuganathan, T. et al. Compound 3 was then converted to the corresponding ester 4 & 5 using ethanol or methanol and a catalytic amount of sulphuric acid. Esterification of compound 3 with ethanol and sulphuric acid under reflux condition over 3 days gave 50% yield of compound 4. As the starting compound 3 was insoluble in 25 volumes of ethanol under reflux condition, we conducted the experiment using toluene as solvent under Dean Stark conditions. Under continuous removal of water, the esterification reaction was completed in 10 hours with 91% yield of compound 4 without further purification. (Table 1) The ester was cyclized to ethyl or methyl picene-13-carboxylate 6 & 715-19 under irradiation with UV light at 365 nm in the presence of iodine. We studied the oxidative cyclisation of compound 4 with several reactants under different reaction conditions and the results are summarized in Table 2. Treatment of compound 4 with aluminium chloride; or a mixture containing aluminium chloride and sodium chloride20 at 140 °C; or aluminium chloride and stannic chloride21 ;or irradiation with 254 nm in the presence of iodine gave no product. Irradiation of compound 4 with 365 nm light without stirring condition gave 30% yield. The previously reported process22 of vanadium trifluoride oxide in trifluoroacetic acid afforded picene-13-carboxylic acid methyl ester 7 with a yield of 47%. In our present study, it was found that 1 mole of iodine and irradiation with light of 365nm in benzene under stirring are necessary to produce compound 6 & 7 in good yield (86% & 87% respectively) without chromatographic purification. Table 2. Mole ratio of reactants, reaction conditions and yield for the oxidative cyclisation of Compound 4 Reaction time Reactant Solvent Temperature (°C) Yield (%) of 6 (hrs.) AlCl3 (5 mol equiv) & Sodium Chloride Neat 140 °C 6 No product (5 mol equiv) AlCl3 (5 mol equiv) Benzene Reflux 6 No product AlCl3 (5 mol equiv) & Stannic Chloride Benzene Reflux 6 No product (2.5 mol equiv) Iodine (1mol equiv); irradiation at 254 25-30°C, without Benzene 12 No product nm stirring Iodine (1mol equiv); irradiation at 254 25-30°C, with Benzene 12 No product nm stirring Iodine (1mol equiv); irradiation at 365 25-30°C, without Benzene 12 30 nm stirring Iodine (1mol equiv); irradiation at 365 25-30 °C, with Benzene 12 8615-19 nm stirring 3122,15 (after Iodine (3mol equiv); irradiation at 500 cyclohexane Not reported Not reported column nm chromatogra phy) Vanadium Trifluoride oxide (4.4 mol Dichloromet 0 °C Not reported 4722 equiv) hane The picene-13-carboxylic acid ethyl ester 6 was hydrolyzed with sodium hydroxide produced picene-13- carboxylic acid 8 in 88% yield. Page 69 ©ARKAT USA, Inc Arkivoc 2017, v, 67-79 Shanmuganathan, T. et al. Reduction of picene-13-carboxylic acid methyl ester with lithium aluminium hydride has been reported for the preparation of compound 9 with a yield of 97%.23 In our study, mild reducing agents like di-isobutyl aluminium hydride [DIBAL (1M in Toluene)] was used to reduce picene-13-carboxylic acid ethyl ester 6 to picen-13-ylmethanol 924 in 90% yield. It was found that the oxidation of compound 9 with manganese dioxide11 in dichloromethane was not completed even under reflux condition. Therefore, we tried pyridinium chlorochromate as an oxidising agent in dichloromethane at 25-30 °C and obtained the compound 1025,26 in 87% yield without further purification. The picene-13-carbaldehyde 10 was condensed with active methylene compounds using piperidine as a base to give the title compounds 11-17.27,28 O O O H O O A c O /T E A E tO H o r M e O H 2 O H + O R H 2 S O 4 1 2 3 4 R = C 2 H 5 5 R = C H 3 O P C C /D C M h v /I 2 D IB A L O R O H O 6 R = C 2 H 5 9 1 0 7 R = C H 3 N a O H O O H 8 Scheme 1. Synthetic route for Picene-13-carboxylic acid (8) and Picene-13-carbaldehyde (10). Page 70 ©ARKAT USA, Inc Arkivoc 2017, v, 67-79 Shanmuganathan, T. et al. O C H 3 N N O C H 3 O C H 3 N H O O 1 7 1 1 1 2 a b g O C H 3 N f C H 3 O c O N H 2 O 1 6 1 0 1 3 e d O O C H 3 O C H O 3 O O O C H 3 H 3 C 1 5 1 4 Scheme 2. Synthetic route for various picen-13-ylmethylene derivatives (11-17) a) ethyl cyanoacetate b) malononitrile c) cyanoacetamide d) diethylmalonate e) ethyl acetoacetate f) acetyl acetone and g) 5,6 dimethoxy-1-indanone. All the synthesized compounds were characterized by 1H NMR, 13C NMR, IR spectroscopy, Mass and elemental analysis. The structure of 11 was confirmed by single crystal X-ray diffractogram (CCDC No. CCDC 1400968). Based on the single crystal structure, the configuration of the compound was confirmed as the E- isomer. The crystal parameters for compound 11 are given in Table 3 and the ORTEP diagram is shown in Figure 1. Page 71 ©ARKAT USA, Inc Arkivoc 2017, v, 67-79 Shanmuganathan, T. et al. Figure 1. ORTEP diagram of Compound 11. Table 3. Crystal data and structure refinement for Compound 11 Empirical formula C28H19NO2 Formula weight 402.1 Temperature 296(2) K Wavelength 0.71073 Å Crystal system, space group Triclinic, P-1 a = 11.4481(11) Å alpha = 108.889(3)° Unit cell dimensions b = 12.8106(11) Å beta = 97.646(3)° c = 15.4300(13) Å gamma = 90.531(3)° Volume 2118.7(3) Å3 Z, Calculated density 2, 1.259 g/cm3 Absorption coefficient 0.079 mm-1 F(000) 840 Crystal size 0.210 x 0.150 x 0.100 mm Theta range for data collection 1.409 to 21.57° Limiting indices -11<=h<=11, -13<=k<=13, -15<=l<=15 Reflections collected / unique 18796 / 4896 [R(int) = 0.0741] Completeness to theta = 21.570 99.90% Absorption correction None Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4896 / 0 / 561 Goodness-of-fit on F^2 1.007 Final R indices [I>2sigma(I)] R1 = 0.0735, wR2 = 0.2161 R indices (all data) R1 = 0.1930, wR2 = 0.3213 Extinction coefficient n/a Largest diff.
Recommended publications
  • 14 Title: Coal Review of Hydrocarbon Emissions Related to Tar Pitch

    14 Title: Coal Review of Hydrocarbon Emissions Related to Tar Pitch

    AP42 Section 7.1 Related: 14 Title: Review of Hydrocarbon Emissions Related to Coal Tar Pitch. Includes pitch vapor pressure data and Antoine's coefficients. EF Bart, et al. Allied Chemical Corporation 1980 I ._ ,.. ?i e!,/..'. r'.:.. ,,T.<,ili -:*., $0 ,i .# 1 .... i;.'.,.,: _..:, '">,U<>j. .. .. REVIEW OF HYDROCMSON EMISSIONS RELATED TO COAL TAR PITCH E. F. Bart, S. A. Visnic, P. A. Cerria Allied Chemical Corporation Morristown, New Jersey 07960 Sumnary Coal tar pitch is used primarily as a binder in the manufacture of carbon electrodes for the aluminum and steel industries. The pitch repre- sents the main product from the continuous, high-temperature distillation of coke oven tar. The pitch is produced and generally handled as a liquid at high temperatures, thus resulting in a potential for hydrocarbon emissions during its handling. An ever-increasing need for control of hydrocarbon emissions has resulted for process and storage equipment since amendments were made in 1977 to the Clean Air Act. Within the next several years, most industries will be faced with requirements for the installation of air pollution con- trol equipment. This paper deals with the types of emissions and methods used in quantifying and controlling emissions from coal tar pitch storage equipment. To better understand the nature of coal tar pitch, a brief description is given of its origin, chemistry and physical properties. Coal Tar Distillation Coal tar pitch is the residue from the distillation of coal tar and represents from 30% to 60% of the tar. It is a complex, bituminous sub- stance and has been estimated to contain about 5,000 compounds.
  • Polycyclic Aromatic Hydrocarbon Structure Index

    Polycyclic Aromatic Hydrocarbon Structure Index

    NIST Special Publication 922 Polycyclic Aromatic Hydrocarbon Structure Index Lane C. Sander and Stephen A. Wise Chemical Science and Technology Laboratory National Institute of Standards and Technology Gaithersburg, MD 20899-0001 December 1997 revised August 2020 U.S. Department of Commerce William M. Daley, Secretary Technology Administration Gary R. Bachula, Acting Under Secretary for Technology National Institute of Standards and Technology Raymond G. Kammer, Director Polycyclic Aromatic Hydrocarbon Structure Index Lane C. Sander and Stephen A. Wise Chemical Science and Technology Laboratory National Institute of Standards and Technology Gaithersburg, MD 20899 This tabulation is presented as an aid in the identification of the chemical structures of polycyclic aromatic hydrocarbons (PAHs). The Structure Index consists of two parts: (1) a cross index of named PAHs listed in alphabetical order, and (2) chemical structures including ring numbering, name(s), Chemical Abstract Service (CAS) Registry numbers, chemical formulas, molecular weights, and length-to-breadth ratios (L/B) and shape descriptors of PAHs listed in order of increasing molecular weight. Where possible, synonyms (including those employing alternate and/or obsolete naming conventions) have been included. Synonyms used in the Structure Index were compiled from a variety of sources including “Polynuclear Aromatic Hydrocarbons Nomenclature Guide,” by Loening, et al. [1], “Analytical Chemistry of Polycyclic Aromatic Compounds,” by Lee et al. [2], “Calculated Molecular Properties of Polycyclic Aromatic Hydrocarbons,” by Hites and Simonsick [3], “Handbook of Polycyclic Hydrocarbons,” by J. R. Dias [4], “The Ring Index,” by Patterson and Capell [5], “CAS 12th Collective Index,” [6] and “Aldrich Structure Index” [7]. In this publication the IUPAC preferred name is shown in large or bold type.
  • The Study of the Absoiption Spectra of the Hydrocarbons Isolated from the Products of the Action of Alunzinium Chloride on Nup12tkccle.R~E

    The Study of the Absoiption Spectra of the Hydrocarbons Isolated from the Products of the Action of Alunzinium Chloride on Nup12tkccle.R~E

    View Article Online / Journal Homepage / Table of Contents for this issue ABSORPTION SPECTRA OF HYDROCARBONS. 1319 Published on 01 January 1908. Downloaded by University of California - San Diego 12/04/2016 06:21:24. CXXV1.-The Study of the Absoiption Spectra of the Hydrocarbons isolated from the Products of the Action of Alunzinium Chloride on Nup12tkccle.r~e. By ANNIEHOMER, Fellow of Newnham College, and JOHNEDWARD PURVIS, M.A. FROMthe products of the action of aluminium chloride on naphthalene, besides PP-dinaphthyl previously isolated by Friedel and Crafts from the same reaction, there have been isolated three new hydrocarbons which have been described in detail by one of us (Homer, Trans., 1907, 9 1, 1103). The substances isolated were : (.i) CI4Hl6, a homologue of naphthalene, either tetramethyl- or 4s2 View Article Online 1320 HOMER AND PURVIS: THE STUDY OF THE diethyl-naphthalene, more probably the former ; (ii) CZ0Hl4, /3@-dinaphthyl; (iii) c26H22, a substance supposed to be a homologue of dinaphthanthracene, C,,H14 ; and (iv) C40H26, probably tetra- naph t h yl. @B-Dinaphthylis formed by the condensation of two naphthalene molecules. It was thought that the hydrocarbon C,,HZ6 was formed by the condensation of either two PP-dinaphthgl or four naphthalene molecules, more probably by the former, as an increase in the time allowed for the action of aluminium chloride on naphthalene, or a rise in the temperature at which the reaction was conducted, caused a decrease in the amount of the hydrocarbon aad an increase in the amount of the hydrocarbon C,,H,, produced. It was suggested that the substance C261322was a homologue of dinaphthanthracene, CZ2Hl4,and its formation from alkylnaphthalenes, which are also formed during the reaction, was given as follows : The intense fluorescence of the substance suggested the presence of an anthracenoid linking, In the method of formation thus proposed, hydrogen would be eliminated from a /3-methyl group of trimethylnaphthalene.
  • Absence of Photoemission from the Fermi Level in Potassium Intercalated Picene and Coronene films: Structure, Polaron Or Correlation Physics?

    Absence of Photoemission from the Fermi Level in Potassium Intercalated Picene and Coronene films: Structure, Polaron Or Correlation Physics?

    Absence of photoemission from the Fermi level in potassium intercalated picene and coronene films: structure, polaron or correlation physics? Benjamin Mahns,1 Friedrich Roth,1 and Martin Knupfer1 IFW Dresden, P.O. Box 270116, D-01171 Dresden, Germany (Dated: 13 September 2018) The electronic structure of potassium intercalated picene and coronene films has been studied using photoemission spectroscopy. Picene has additionally been intercalated using sodium. Upon alkali metal addition core level as well as valence band pho- toemission data signal a filling of previously unoccupied states of the two molecular materials due to charge transfer from potassium. In contrast to the observation of superconductivity in Kxpicene and Kxcoronene (x ∼ 3), none of the films studied shows emission from the Fermi level, i. e. we find no indication for a metallic ground state. Several reasons for this observation are discussed. arXiv:1203.4728v1 [cond-mat.supr-con] 21 Mar 2012 1 I. INTRODUCTION Superconductivity always has attracted a large number of researchers since this phe- nomenon harbors challenges and prospects both under fundamental and applied points of view. Very recently, it has been discovered that some molecular crystal consisting of poly- cyclic aromatic hydrocarbons demonstrate superconductivity upon alkali metal addition. Furthermore, these compounds are characterized by rather high transition temperatures into 1 2 the superconducting state, for instance K3picene (Tc=18 K) and K3coronene (Tc=15 K) . Most recently, superconductivity with a transition temperature of 33 K has been reported 3 for K3dibenzopentacene . These doped aromatic hydrocarbons thus represent a class of or- ganic superconductors with transition temperatures only slightly below that of the famous 4{8 alkali metal doped fullerenes with Tc's up to 40 K .
  • Prcn.Uppderlimit Of

    Prcn.Uppderlimit Of

    564 MARCH 29, THE CANCER-PRODUCING FACTOR IN TAR. rTRBTETISU 19241 IMDICAIJOURNAr. I wlhiel eacll fraction is produced; the figures are onlv very ON THE CANCER-PRODUCING FACTOR rouglh, for the practice varies considerably in different tar- IN TAR. works, and also in the same works in accordance with fluctuiations in the BY miiarket for different products. Tlhus the proportion of creosote oil produced may vary from 9 per E. L. KENNAWAY, M.D., D.Sc. cent. to 25 per cent. of the crude tar. (From the Cancer Hospital Research Institute, London.) TABLE I.-Fi'ractions of Gasworks Tar. TH.AT tar can produce cancer has been known for nearly fifty years, but no systematic attemipt to tlle par- Limit of idenitify Fraction. PrCn.UppDer ticular comiipounds responsible for this effect was possible Pof TCar. Temperature until tlleexperimental productionof cancer in lower animals a became practical method. In thle absence of such experi- 1. Ammoniacal liquor ... ... 2 nmenltal evidence from the laboratory, th'e capacity of any 2. Crude naphtha ... ... ... 2 material to produce cancer must be learned from those accidental experiments on man which are the cause of 3. Light oil ... ... ... ... 9 2250 "industrial diseases." When a new cancer-producing 4. Middle or carbolic oil ... ... 5 2550 substance comes into industrial use on a large scale no danger will be detected during the long latent period, 5. Creosote oil ... ... ... ... 14 2750 whieh in man is probably of many years' duration; the 6. Anthracene oil ... ... 3 320P* effect of the will then become apparent, as we substaneo 7. Pitch ... ... ... ... ... ...63 have seen recently in the case of mule-spinners.
  • Certificate of Analysis

    Certificate of Analysis

    National Institute of Standards & Technology Certificate of Analysis Standard Reference Material® 1597a Complex Mixture of Polycyclic Aromatic Hydrocarbons from Coal Tar This Standard Reference Material (SRM) is intended for use in the evaluation and validation of analytical methods for the determination of a natural, combustion-related mixture of polycyclic aromatic hydrocarbons (PAHs). SRM 1597a is isolated from a coal tar sample and dissolved in toluene. It is suitable for direct analysis (i.e., without sample cleanup or concentration) in the determination of PAHs using analytical techniques such as gas chromatography (GC), liquid chromatography (LC), or gas chromatography/mass spectrometry (GC/MS). This SRM may also be used to evaluate procedures for measurement of mutagenic activity of combustion-related mixtures of PAHs and related compounds. A unit of SRM 1597a consists of one 5 mL ampoule, containing 1.3 mL of material. Certified Mass Fraction Values: Certified values for concentrations, expressed as mass fractions, for 34 PAHs are provided in Table 1. The certified values are based on the agreement of results obtained at NIST from two or more chemically independent analytical techniques [1,2]. A NIST certified value is a value for which NIST has the highest confidence in its accuracy in that all known or suspected sources of bias have been investigated or accounted for by NIST. Reference Mass Fraction Values: Reference values for concentrations, expressed as mass fractions, are provided for 36 additional PAHs in Table 2 and for 10 polycyclic aromatic sulfur heterocycles (PASH) in Table 3. Reference values are given in Table 4 for the mutagenic activity of SRM 1597a.
  • DP70323.Pdf (5.434Mb)

    DP70323.Pdf (5.434Mb)

    PART I THE SELEHXUM DKHYDKOOKNATIOH OF URSOLIC ACIB PART II THE PREPARATION OF MBTBOXY AC 8 TAL&EBYCB BY BARRY II * DUVALL01 Cl n€ m LD o7 ? 3 , Ml od X V v a U , H - M r+i; &- Thesis submitted to the Faculty of the Graduate School of the University of Merylend In partial fulfillment of the requirements for the degree of Doctor of Philosophy* CHEMISTRY LIBRARY 1956 * jjniverslty o p m a r y l a h d UMI Number: DP70323 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. UMI Dissertation Publishing UMI DP70323 Published by ProQuest LLC (2015). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 ACKNOWLEDGMENT The writer wished to express his appreciation to Dr* N* L. Drake for suggesting these problems and for his constant advice and attention during the course of this research. TABLE OF C0HTE8TS FART I The Selenium Dehydrogenation of Orsolie Acid Page 1* Historical Introduction 1 A. Ursolic Acid ....... ............ 1 B« Selenium Dehydrogenation .......... 25 2* Experimental Part ......... ...... 41 A* Purification of Ursolic Acid ........... 41 B. Dehydrogenation Experiments ...... 44 5* Discussion of Results .....................
  • United States Patent Office. Harry F

    United States Patent Office. Harry F

    ul Patented July 6, 1926. 1,591,712 UNITED STATES PATENT OFFICE. HARRY F. T.EWIS, OE BUFFALO, NEW YORK, ASSIGNOR, to NATIONAL ANILINE & CHEMICAL COMPANY, INC., OF NEW YORK, N. Y., A. CORPORATION OF NEW YORK. PURIFICATION OF ANTHRAQUINONE. No Drawing. Application filed IIarch 4, 1920. Serial No. 363,261. This invention relates to the purification lar alkali employed. The strength of the of anthraquinone, and more particularly to alkali solution can also be varied, from rela the purification of anthraquinone admixed tively dilute solutions to concentrated solu With other oxidation products, such as the tions. The purification is best effected at oxidation products of carbazol and other a temperature between about 50 and 100° C., nitrogen bases and the carboxy and phenolic but lower temperatures may be used. The 60 Oxidation products of other hydrocarbons. inpurities particularly removed by such In the production of anthraquinone by alkaline treatment are those above indicated, Oxidizing anthracene, for example, with a namely, the oxidation products of carbazol O Solution of chromic acid, or with an acid and other nitrogen bases, as well as the Solution of sodium or potassium dichro carboxy and phenolic oxidation products of mate, such impurities as are admixed with Such hydrocarbons as methylanthracene. the anthracene are subjected to the same phenanthrene, acenaphthene, etc., and oxida Oxidizing agent or agents as is the anthra tion products which contain chromium as a s cene itself. As a result, the anthraquinone constituent. produced, after separating the constituents In the preferred practice of the inven O which are soluble in Water or in the acid tion, the crude anthraquinone is extracted Solution, contains various impurities in ad with hot alkaline solution in amount, from mixture therewith.
  • Toxicological Profile for Wood Creosote, Coal Tar Creosote, Coal Tar, Coal Tar Pitch, and Coal Tar Pitch Volatiles

    Toxicological Profile for Wood Creosote, Coal Tar Creosote, Coal Tar, Coal Tar Pitch, and Coal Tar Pitch Volatiles

    TOXICOLOGICAL PROFILE FOR WOOD CREOSOTE, COAL TAR CREOSOTE, COAL TAR, COAL TAR PITCH, AND COAL TAR PITCH VOLATILES U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES Public Health Service Agency for Toxic Substances and Disease Registry September 2002 CREOSOTE ii DISCLAIMER The use of company or product name(s) is for identification only and does not imply endorsement by the Agency for Toxic Substances and Disease Registry. CREOSOTE iii UPDATE STATEMENT Toxicological profiles are revised and republished as necessary, but no less than once every three years. For information regarding the update status of previously released profiles, contact ATSDR at: Agency for Toxic Substances and Disease Registry Division of Toxicology/Toxicology Information Branch 1600 Clifton Road NE, E-29 Atlanta, Georgia 30333 V FOREWORD This toxicological profile is prepared in accordance with guidelines" developed by the Agency for Toxic Substances and Disease Registry (ATSDR) and the Environmental Protection Agency (EPA). The original guidelines were published in the Federal Register on April 17, 1987. Each profile will be revised and republished as necessary. The ATSDR toxicological profile succinctly characterizes the toxicologic and adverse health effects information for the hazardous substance described therein. Each peer-reviewed profile identifies and reviews the key literature that describes a hazardous substance's toxicologic properties. Other pertinent literature is also presented, but is described in less detail than the key studies. The profile is not intended to be an exhaustive document; however, more comprehensive sources of specialty information are referenced. The focus of the profiles is on health and toxicologic information; therefore, each toxicological profile begins with a public health statement that describes, in nontechnical language, a substance's relevant toxicological properties.
  • Environmental Health Criteria 171

    Environmental Health Criteria 171

    Environmental Health Criteria 171 DIESEL FUEL AND EXHAUST EMISSIONS Please note that the layout and pagination of this web version are not identical with the printed version. Diesel fuel and exhaust emissions (EHC 171, 1996) UNITED NATIONS ENVIRONMENT PROGRAMME INTERNATIONAL LABOUR ORGANISATION WORLD HEALTH ORGANIZATION INTERNATIONAL PROGRAMME ON CHEMICAL SAFETY ENVIRONMENTAL HEALTH CRITERIA 171 DIESEL FUEL AND EXHAUST EMISSIONS This report contains the collective views of an international group of experts and does not necessarily represent the decisions or the stated policy of the United Nations Environment Programme, the International Labour Organisation, or the World Health Organization. Environmental Health Criteria 171 DIESEL FUEL AND EXHAUST EMISSIONS First draft prepared by the staff members of the Fraunhofer Institute of Toxicology and Aerosol Research, Germany, under the coordination of Dr. G. Rosner Published under the joint sponsorship of the United Nations Environment Programme, the International Labour Organisation, and the World Health Organization, and produced within the framework if the Inter-Organization Programme for the Sound Management of Chemicals. World Health Organization Geneva, 1996 The International Programme on Chemical Safety (IPCS) is a joint venture of the United Nations Environment Programme, the International Labour Organisation, and the World Health Organization. The main objective of the IPCS is to carry out and disseminate evaluations of the effects of chemicals on human health and the quality of the environment. Supporting activities include the development of epidemiological, experimental laboratory, and risk-assessment methods that could produce internationally comparable results, and the Page 1 of 287 Diesel fuel and exhaust emissions (EHC 171, 1996) development of manpower in the field of toxicology.
  • Part I the Selenium Dehydrogenation Op

    Part I the Selenium Dehydrogenation Op

    PART I THE SELENIUM DEHYDROGENATION OP PRIEDELINOL PART II THE BROMINATION OP FRIEDELIN BY . \ WILLARD TV HASKINS \ \ Thesis submitted to the Faculty of the Graduate School of the University of Maryland In partial fulfillment of the requirements for the degree of Doctor of Philosophy* 1936 • UMI Number: DP70114 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. Dissertation Publishing UMI DP70114 Published by ProQuest LLC (2015). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code uest ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 ACKNOWLEDGMENT The writer Is Indebted to Dr* N* L# Drake, under whose direction and advice this work was carried out* TABLE OF CONTENTS Page PART I Review or Literature ...••.•» 1 Introduction ... 11 Experimental ...... 15 Conclusions ....... ... 28 Summary ............................... 29 Bibliography ..................... 50 PART XI Introduction * • •.... 51 Experimental...... 55 Conclusions •. * 55 REVIEW OP LITERATURE ON TRITERPENES PROM 1933 TO DATE* Ruzicka, previous to 1933, had proposed a structural formula (I) for the carbon skeleton of the trlterpenes based
  • Nationwide Increase of Polycyclic Aromatic Hydrocarbons in Ultrafine

    Nationwide Increase of Polycyclic Aromatic Hydrocarbons in Ultrafine

    Atmos. Chem. Phys., 20, 14581–14595, 2020 https://doi.org/10.5194/acp-20-14581-2020 © Author(s) 2020. This work is distributed under the Creative Commons Attribution 4.0 License. Nationwide increase of polycyclic aromatic hydrocarbons in ultrafine particles during winter over China revealed by size-segregated measurements Qingqing Yu1, Xiang Ding1,4, Quanfu He1, Weiqiang Yang5, Ming Zhu1,2, Sheng Li1,2, Runqi Zhang1,2, Ruqin Shen1, Yanli Zhang1,3,4, Xinhui Bi1,4, Yuesi Wang3,6, Ping’an Peng1,4, and Xinming Wang1,2,3,4 1State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China 2University of Chinese Academy of Sciences, Beijing 100049, China 3Center for Excellence in Regional Atmospheric Environment, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021, China 4Guangdong-Hong Kong-Macao Joint Laboratory for Environmental Pollution and Control, Guangzhou Institute of Geochemistry, Chinese Academy of Science, Guangzhou 510640, China 5Guangdong Provincial Academy of Environmental Science, Guangzhou 510045, China 6State Key Laboratory of Atmospheric Boundary Layer Physics and Atmospheric Chemistry, Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing 100029, China Correspondence: Xinming Wang ([email protected]), and Xiang Ding ([email protected]) Received: 10 June 2020 – Discussion started: 22 June 2020 Revised: 13 October 2020 – Accepted: 14 October 2020 – Published: 1 December 2020 3 Abstract. Polycyclic aromatic hydrocarbons (PAHs) are BaPeq (8.48 vs. 1.34 ng/m / and PAHs’ inhalation cancer risk toxic compounds in the atmosphere and have adverse effects (7.4 × 10−4 vs.