Opinion on Nitrosamines and Secondary Amines in Cosmetic Products ______
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Nitroso and Nitro Compounds 11/22/2014 Part 1
Hai Dao Baran Group Meeting Nitroso and Nitro Compounds 11/22/2014 Part 1. Introduction Nitro Compounds O D(Kcal/mol) d (Å) NO NO+ Ph NO Ph N cellular signaling 2 N O N O OH CH3−NO 40 1.48 molecule in mammals a nitro compound a nitronic acid nitric oxide b.p = 100 oC (8 mm) o CH3−NO2 57 1.47 nitrosonium m.p = 84 C ion (pKa = 2−6) CH3−NH2 79 1.47 IR: υ(N=O): 1621-1539 cm-1 CH3−I 56 Nitro group is an EWG (both −I and −M) Reaction Modes Nitro group is a "sink" of electron Nitroso vs. olefin: e Diels-Alder reaction: as dienophiles Nu O NO − NO Ene reaction 3 2 2 NO + N R h 2 O e Cope rearrangement υ O O Nu R2 N N N R1 N Nitroso vs. carbonyl R1 O O O O O N O O hυ Nucleophilic addition [O] N R2 R O O R3 Other reaction modes nitrite Radical addition high temp low temp nitrolium EWG [H] ion brown color less ion Redox reaction Photochemical reaction Nitroso Compounds (C-Nitroso Compounds) R2 R1 O R3 R1 Synthesis of C-Nitroso Compounds 2 O R1 R 2 N R3 3 R 3 N R N R N 3 + R2 2 R N O With NO sources: NaNO2/HCl, NOBF4, NOCl, NOSbF6, RONO... 1 R O R R1 O Substitution trans-dimer monomer: blue color cis-dimer colorless colorless R R NOBF OH 4 - R = OH, OMe, Me, NR2, NHR N R2 R3 = H or NaNO /HCl - para-selectivity ΔG = 10 Kcal mol-1 Me 2 Me R1 NO oxime R rate determining step Blue color: n π∗ absorption band 630-790 nm IR: υ(N=O): 1621-1539 cm-1, dimer υ(N−O): 1300 (cis), 1200 (trans) cm-1 + 1 Me H NMR (α-C-H) δ = 4 ppm: nitroso is an EWG ON H 3 Kochi et al. -
Amyl Nitrite Or 'Jungle Juice'
Young People and Other Drugs Amyl Nitrite or ‘Jungle Juice’ Amyl nitrite is an inhalant that belongs to a class As with any drug, the use of nitrites is not risk-free. of chemicals called alkyl nitrites. This group of Some of the harms associated with its use include: drugs can be called ‘poppers’. They are often injuries related to inhaling the vapour referred to by their brand name, with ‘Jungle (e.g., rashes, burns) Juice’ probably being the most well-known of these. allergic reactions accidents and falls Inhaling amyl nitrite relaxes the body and gives vision problems (isopropyl nitrite) a ‘rush’ that lasts for one to two minutes. It is commonly used to enhance sexual pleasure and in rare cases, blood disorders induce a feeling of euphoria and well-being. MOST IMPORTANTLY, AMYL NITRITE OR JUNGLE JUICE MUST NEVER BE DRUNK. Drinking amyl can result in death due to it interfering with the ability of the blood to transport oxygen. What is amyl nitrite? Over the years, to bypass legal restrictions, nitrites have been sold as such things as liquid incense or Amyl nitrite is an inhalant that belongs to a class of room odoriser. Jungle Juice, which can be sold as chemicals called alkyl nitrites. Amyl nitrite is a highly a leather cleaner, is a common product name of flammable liquid that is clear or yellowish in colour. amyl nitrite. It has a unique smell that is sometimes described as ‘dirty socks’. It is highly volatile and when exposed to the air evaporates almost immediately at How is Jungle Juice used? room temperature. -
ATSDR Case Studies in Environmental Medicine Nitrate/Nitrite Toxicity
ATSDR Case Studies in Environmental Medicine Nitrate/Nitrite Toxicity Agency for Toxic Substances and Disease Registry Case Studies in Environmental Medicine (CSEM) Nitrate/Nitrite Toxicity Course: WB2342 CE Original Date: December 5, 2013 CE Expiration Date: December 5, 2015 Key • Nitrate toxicity is a preventable cause of Concepts methemoglobinemia. • Infants younger than 4 months of age are at particular risk of nitrate toxicity from contaminated well water. • The widespread use of nitrate fertilizers increases the risk of well-water contamination in rural areas. About This This educational case study document is one in a series of and Other self-instructional modules designed to increase the primary Case Studies care provider’s knowledge of hazardous substances in the in environment and to promote the adoption of medical Environmen- practices that aid in the evaluation and care of potentially tal Medicine exposed patients. The complete series of Case Studies in Environmental Medicine is located on the ATSDR Web site at URL: http://www.atsdr.cdc.gov/csem/csem.html In addition, the downloadable PDF version of this educational series and other environmental medicine materials provides content in an electronic, printable format. Acknowledgements We gratefully acknowledge the work of the medical writers, editors, and reviewers in producing this educational resource. Contributors to this version of the Case Study in Environmental Medicine are listed below. Please Note: Each content expert for this case study has indicated that there is no conflict of interest that would bias the case study content. CDC/ATSDR Author(s): Kim Gehle MD, MPH CDC/ATSDR Planners: Charlton Coles, Ph.D.; Kimberly Gehle, MD; Sharon L. -
Basic Principles and Analytical Application of Derivative Spectrophotometry
13 Basic Principles and Analytical Application of Derivative Spectrophotometry Joanna Karpinska Institute of Chemistry, University of Bialystok, Bialystok Poland 1. Introduction Analytical methods based on measurements of UV or visible light absorption belong to the most popular and most often used in laboratory practice. Commercially available apparatuses are cheap and easy for operation. Spectrophotometric procedures usually are not time- and labour-consuming. The economical aspects of UV-Vis techniques is worth of emphasize too. It is one of the cheapest technique, so spectrophotometers are basic equipment of every laboratory. The main disadvantage and limitation of the spectrophotometry is its low selectivity. The measurement of absorbance is burden by interferences derived from others components of sample. A recorded UV-Vis spectrum is the sum of absorbances of analyte and matrix. Usually, recorded bands are well-defined but more or less distorted by a background. As the background is called absorbance exhibited by matrix (reagents or accompanied compounds). The problem with specific or nonspecific background can be omitted by measurements versus blank. Such procedure can be successfully applied only in the case of simple samples, which composition is stable and well known or when highly selective reagents are used. An isolation of an analyte from matrix is another solution for increasing the selectivity of assay. But every additional operation introduced into sample preparation procedure extents time and costs of single analysis and increases risk of loss or contamination of the analyte. One of the simplest method for an increasing a selectivity is derivatisation of spectra. This operation allows to remove spectral interferences and as a consequence leads to increase selectivity of assay. -
Nomenclature of Carboxylic Acids • Select the Longest Carbon Chain Containing the Carboxyl Group
Chapter 5 Carboxylic Acids and Esters Carboxylic Acids • Carboxylic acids are weak organic acids which Chapter 5 contain the carboxyl group (RCO2H): Carboxylic Acids and Esters O C O H O RCOOH RCO2H Chapter Objectives: O condensed ways of • Learn to recognize the carboxylic acid, ester, and related functional groups. RCOH writing the carboxyl • Learn the IUPAC system for naming carboxylic acids and esters. group a carboxylic acid C H • Learn the important physical properties of the carboxylic acids and esters. • Learn the major chemical reaction of carboxylic acids and esters, and learn how to O predict the products of ester synthesis and hydrolysis reactions. the carboxyl group • Learn some of the important properties of condensation polymers, especially the polyesters. Mr. Kevin A. Boudreaux • The tart flavor of sour-tasting foods is often caused Angelo State University CHEM 2353 Fundamentals of Organic Chemistry by the presence of carboxylic acids. Organic and Biochemistry for Today (Seager & Slabaugh) www.angelo.edu/faculty/kboudrea 2 Nomenclature of Carboxylic Acids • Select the longest carbon chain containing the carboxyl group. The -e ending of the parent alkane name is replaced by the suffix -oic acid. • The carboxyl carbon is always numbered “1” but the number is not included in the name. • Name the substituents attached to the chain in the Nomenclature of usual way. • Aromatic carboxylic acids (i.e., with a CO2H Carboxylic Acids directly connected to a benzene ring) are named after the parent compound, benzoic acid. O C OH 3 -
Doctor of Philosophy University of London
ASPECTS OF THIONITRITES AND NITRIC OXIDE IN CHEMISTRY AND BIOLOGY A Thesis Presented by Marta Cavero Tomas In Partial Fulfilment of the Requirements for the Award of the Degree of DOCTOR OF PHILOSOPHY OF THE UNIVERSITY OF LONDON Christopher Ingold Laboratories, Department of Chemistry, University College London, London WC IN OAJ October 1999 ProQuest Number: 10797749 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 com plete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 10797749 Published by ProQuest LLC(2018). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C ode Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 ABSTRACT This thesis is divided into three parts: Part one is comprised of six chapters and provides a topical review of the main aspects of the chemistry and biology of nitric oxide and of thionitrites. The first chapter is a general introduction to the topic. The second chapter reviews the biology of nitric oxide. The third chapter provides a survey of some of the known chemistry of nitric oxide, with particular emphasis on those aspects which might be relevant in biological systems. The fourth chapter describes the biology of thionitrites in relation to NO. -
Functional Group Transformations in Derivatives Of
Article pubs.acs.org/joc Functional Group Transformations in Derivatives of 1,4- Dihydrobenzo[1,2,4]triazinyl Radical † § † ∥ † ‡ † ⊥ Agnieszka Bodzioch, , Minyan Zheng, , Piotr Kaszynski,́ *, , and Greta Utecht , † Organic Materials Research Group Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235, United States ‡ Faculty of Chemistry, University of Łodź,́ Tamka 12, 91403 Łodź,́ Poland *S Supporting Information ABSTRACT: Transformations of functional groups OCOPh, ’ − OCH2Ph, I, NO2, and CO2Me in Blatter s radical derivatives 1 5 were investigated in order to develop synthetic tools for incorporation of the benzo[1,2,4]triazinyl system into complex molecular architectures. Thus, basic hydrolysis of OCOPh or Pd-catalyzed debenzylation of OCH2Ph gave phenol functionality, which was acylated and alkylated. Pd-catalyzed Suzuki, Negishi, Sonogashira, and Heck C−C cross-coupling reactions of iodo derivatives 1c, 1d, and 2d ffi were also successful and e cient. Reduction of NO2 in 1e led to aniline derivative 1t, which was reductively alkylated with hexanal and coupled to L-proline. Selected benzo[1,2,4]triazinyl radicals were characterized by EPR and electronic absorption spectroscopy, and the results were analyzed in tandem with DFT computational methods. Lastly, the mechanism for formation of the 1,4- dihydrobenzo[1,2,4]triazine ring was investigated using the B3LYP/6-31G(2d,p) method. ■ INTRODUCTION little attention, and only a handful of derivatives have been Stable π-delocalized radicals are becoming important structural reported in the literature. This situation changed several years elements of materials for solar cells,1 energy storage,2 ago when Koutentis began systematic development of synthetic − electronic,3,4 and biological5 8 applications.9,10 Their incorpo- access to this class of radicals. -
Systems Biology Reveals Reprogramming of the S-Nitroso
www.nature.com/scientificreports OPEN Systems biology reveals reprogramming of the S‑nitroso‑proteome in the cortical and striatal regions of mice during aging process Maryam Kartawy, Igor Khaliulin & Haitham Amal* Cell aging depends on the rate of cumulative oxidative and nitrosative damage to DNA and proteins. Accumulated data indicate the involvement of protein S‑nitrosylation (SNO), the nitric oxide (NO)-mediated posttranslational modifcation (PTM) of cysteine thiols, in diferent brain disorders. However, the changes and involvement of SNO in aging including the development of the organism from juvenile to adult state is still unknown. In this study, using the state‑of‑the‑ art mass spectrometry technology to identify S‑nitrosylated proteins combined with large‑scale computational biology, we tested the S‑nitroso‑proteome in juvenile and adult mice in both cortical and striatal regions. We found reprogramming of the S‑nitroso‑proteome in adult mice of both cortex and striatum regions. Signifcant biological processes and protein–protein clusters associated with synaptic and neuronal terms were enriched in adult mice. Extensive quantitative analysis revealed a large set of potentially pathological proteins that were signifcantly upregulated in adult mice. Our approach, combined with large scale computational biology allowed us to perform a system‑level characterization and identifcation of the key proteins and biological processes that can serve as drug targets for aging and brain disorders in future studies. Nitric oxide (NO) is produced in diferent organs and tissues, including the central and peripheral nervous sys- tem, and is one of the most important signaling molecules in the body1,2. At low concentrations, it participates in cell signaling and may have therapeutic value for brain injury 3. -
C-Nitroso-Substituted Ligands of Poly(ADP-Ribose) Polymerase (Zinc Rmger/Drug-Induced Cell Death) WILLIAM G
Proc. Nati. Acad. Sci. USA Vol. 89, pp. 7703-7707, August 1992 Pharmacology Induction of endonuclease-mediated apoptosis in tumor cells by C-nitroso-substituted ligands of poly(ADP-ribose) polymerase (zinc rmger/drug-induced cell death) WILLIAM G. RICE*t, CHRISTOPHER D. HILLYERt, BRAD HARTEN*, CATHERINE A. SCHAEFFER*, MARK DORMINY*, DIXON A. LACKEY III*, EVA KIRSTEN§, JEROME MENDELEYEV§, KALMAN G. BUKI§, ALAEDDIN HAKAM§, AND ERNEST KUNt§ *Division of Hematology and Oncology, Department of Pediatrics, and tDepartment of Pathology and Laboratory of Medicine and the Winship Cancer Center, Emory University School of Medicine, Atlanta, GA 30322; and §Laboratory for Environmental Toxicology and Chemistry, The Romberg Tiburon Center, San Francisco State University, P.O. Box 855, Tiburon, CA 94920 Communicated by John Baldeschwieler, May 19, 1992 ABSTRACT 6-Nitroso-1,2-benzopyrone and 3-ni- Assays. For cell proliferation tests, cells were cultured in trosobenzamide, two C-nitroso compounds that inactivate the 96-well tissue culture plates at 3 x 103 cells per well (250-gl eukaryotic nuclear protein poly(ADP-ribose) polymerase total volume per well) for 2 hr (or the indicated length oftime) [NAD+:poly(adenosine diphosphate D-ribose) ADP-D-ribosyl- in the absence or presence of various concentrations of transferase, ADPRT, EC 2.4.2.30] at one zinc-ringer site, NOBA or NOBP; thereafter 0.5 ,uCi of [methyl-3H]thymidine completely suppressed the proliferation of leukemic and other (85 Ci/mmol; 1 Ci = 37 GBq) was added per well and its malignant human cells and subsequently produced cell death. incorporation into DNA following an 18-hr incubation was Tumoricidal concentrations of the drugs were relatively harm- determined radiochemically (6). -
A Binuclear Ruthenium(I) Carbonyl Complex Containing a Bridging Benzene-1,2-Dithiolate Ligand
FULL PAPER Derivative Chemistry of [Ru2(µ-bdt)(CO)6], a Binuclear Ruthenium(I) Carbonyl Complex Containing a Bridging Benzene-1,2-dithiolate Ligand Javier A. Cabeza,*[a] M. Angeles Martı´nez-Garcı´a,[a] Vı´ctor Riera,[a] Diego Ardura,[b] Santiago Garcı´a-Granda,[b] and Juan F. Van der Maelen[b] Keywords: Ruthenium / Thiolate ligands / Dithiolate ligands / Substitution reactions / Electrophilic additions The known dithiolate-bridged ruthenium(I) complex [Ru2(µ- bdt)(CO)4}(µ-dppm)]n, which consists of binuclear {Ru2(µ- bdt)(CO)6](1) (bdt = benzene-1,2-dithiolate) has been bdt)(CO)4} units linked to each other by bridging dppm prepared in fair yield (55%) by the sequential treatment of ligands. The use of two equivalents of dppm leads to [Ru2(µ- 1 RuCl3·nH2O with carbon monoxide, benzene-1,2-dithiol and bdt)(CO)4(η -dppm)2] in quantitative yield. The X-ray zinc in a one-pot reaction. Complex 1 reacts readily with diffraction structure of [Ru2(µ-bdt)(CO)4(PiPr3)2](3c) confirms monodentate phosphanes to give, stepwise, the penta- and that the phosphane ligands are located in axial positions, cis tetracarbonyl derivatives [Ru2(µ-bdt)(CO)6–n(PR3)n](n= 1, 2; to both sulfur atoms, and that the Ru–Ru distance is short R = Ph, Cy, iPr). However, the reaction of 1 with one [2.6753(7) A˚ ]. A comparative study of the reactivity of + + equivalent of bis(diphenylphosphanyl)methane (dppm) complexes 1 and 3c with the electrophiles H , [Au(PPh3)] , affords a mixture of complex 1 and the disubstituted and HgCl2 has allowed the isolation of the derivatives [Ru2(µ- 1 derivative [Ru2(µ-bdt)(CO)4(η -dppm)2], in which the dppm H)(µ-bdt)(CO)6–n(PiPr3)n][BF4](n= 0, 2), [Ru2Au(µ-bdt)(CO)6–n- ligands are monodentate. -
Continuous-Flow Production of Alkyl Nitrites, Originally Designed by BIOS Chemicals
FLOW CHEMISTRY Industry Perspective ● Peer reviewed Jean-Christophe M. Continuous-flow production Monbaliu of alkyl nitrites JEAN-CHRISTOPHE M. MONBALIU1*, JEREMY JORDA2, BÉRENGÈRE CHEVALIER2, CHRISTIAN V. STEVENS1, BERNARD MORVAN3 *Corresponding author 1. Ghent University, SynBioC Research Group, Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Coupure links 653, Gent, B-9000, Belgium 2. CORNING S.A.S, Corning European Technology Center, Avenue de Valvins 7 bis, Avon, F-77210, France 3. BIOS Chemicals, Plateforme technologique DELTA Sud, Verniolle, F- 09340, France the oxidation of olefins (6f, 7c). Recent publications reported ABSTRACT their use for the production of diazonium intermediates in the Alkyl nitrites are important building blocks for the chemical continuous production of synthesis of azo dyes (6c). and pharmaceutical industries. In this article, we report a case study for the continuous-flow production of alkyl nitrites, originally designed by BIOS Chemicals. The PREPARATION OF ALKYL NITRITES intrinsic advantages of a Corning® Advanced-Flow™ reactor system, including high versatility, high mixing, and Numerous methods have been developed at the lab scale heat-exchange efficiency under corrosive conditions, for preparing alkyl nitrites from alcohols: esterification with allowed the development of an economically viable and nitrous acid; transesterification from tert-butyl nitrite (8a) or from user-friendly process in a short period of time, leading to N-nitrosoamines (8b); and nitrosation with various nitrosating a throughput of 10t/year of processed material with high agents such as nitrosyl chloride (8c). Thiols and trimethylsilyl ethers purity (93-98 percent). can also be transformed in the corresponding nitrites (8d). Industrial processes can be divided into two categories: (a) 50 liquid phase processes and (b) vapour phase processes. -
N-Nitroso Compounds in the Diet
Mutation Research 443Ž. 1999 129±138 www.elsevier.comrlocatergentox Community address: www.elsevier.comrlocatermutres N-Nitroso compounds in the diet William Lijinsky 11398 High Hay DriÕe, Columbia, MD 21044, USA Received 7 October 1998; received in revised form 12 February 1999; accepted 12 February 1999 Abstract N-Nitroso compounds were known almost 40 years ago to be present in food treated with sodium nitrite, which made fish meal hepatotoxic to animals through formation of nitrosodimethylamineŽ. NDMA . Since that time, N-nitroso compounds have been shown in animal experiments to be the most broadly acting and the most potent group of carcinogens. The key role of nitrite and nitrogen oxides in forming N-nitroso compounds by interaction with secondary and tertiary amino compounds has led to the examination worldwide of foods for the presence of N-nitroso compounds, which have been found almost exclusively in those foods containing nitrite or which have become exposed to nitrogen oxides. Among these are cured meats, especially baconÐand especially when cooked; concentrations of 100 mgkgy1 have been found or, more usually, near 10 mgkgy1. This would correspond to consumption of 1 mg of NDMA in a 100-g portion. Much higher concentrations of NDMAŽ. but lower ones of other nitrosamines have been found in Japanese smoked and cured fish Ž more than 100 mg kgy1. Beer is one source of NDMA, in which as much as 70 mg ly1 has been reported in some types of German beer, although usual levels are much lowerŽ 10 or 5 mg ly1. ; this could mean a considerable intake for a heavy beer drinker of several liters per day.