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The Reaction of Aminonitriles with Aminothiols: a Way to Thiol-Containing Peptides and Nitrogen Heterocycles in the Primitive Earth Ocean
life Article The Reaction of Aminonitriles with Aminothiols: A Way to Thiol-Containing Peptides and Nitrogen Heterocycles in the Primitive Earth Ocean Ibrahim Shalayel , Seydou Coulibaly, Kieu Dung Ly, Anne Milet and Yannick Vallée * Univ. Grenoble Alpes, CNRS, Département de Chimie Moléculaire, Campus, F-38058 Grenoble, France; [email protected] (I.S.); [email protected] (S.C.); [email protected] (K.D.L.); [email protected] (A.M.) * Correspondence: [email protected] Received: 28 September 2018; Accepted: 18 October 2018; Published: 19 October 2018 Abstract: The Strecker reaction of aldehydes with ammonia and hydrogen cyanide first leads to α-aminonitriles, which are then hydrolyzed to α-amino acids. However, before reacting with water, these aminonitriles can be trapped by aminothiols, such as cysteine or homocysteine, to give 5- or 6-membered ring heterocycles, which in turn are hydrolyzed to dipeptides. We propose that this two-step process enabled the formation of thiol-containing dipeptides in the primitive ocean. These small peptides are able to promote the formation of other peptide bonds and of heterocyclic molecules. Theoretical calculations support our experimental results. They predict that α-aminonitriles should be more reactive than other nitriles, and that imidazoles should be formed from transiently formed amidinonitriles. Overall, this set of reactions delineates a possible early stage of the development of organic chemistry, hence of life, on Earth dominated by nitriles and thiol-rich peptides (TRP). Keywords: origin of life; prebiotic chemistry; thiol-rich peptides; cysteine; aminonitriles; imidazoles 1. Introduction In ribosomes, peptide bonds are formed by the reaction of the amine group of an amino acid with an ester function. -
Xylene MSDS # 791.00
Material Safety Data Sheet Page 1 of 2 Xylene MSDS # 791.00 Section 1: Product and Company Identification Xylene Synonyms/General Names: Dimethylbenzene, Xylol Product Use: For educational use only Manufacturer: Columbus Chemical Industries, Inc., Columbus, WI 53925. 24 Hour Emergency Information Telephone Numbers CHEMTREC (USA): 800-424-9300 CANUTEC (Canada): 613-424-6666 ScholAR Chemistry; 5100 W. Henrietta Rd, Rochester, NY 14586; (866) 260-0501; www.Scholarchemistry.com Section 2: Hazards Identification Colorless liquid; benzene-like odor. HMIS (0 to 4) Health 2 WARNING! Flammable liquid, moderately toxic by ingestion and inhalation. Fire Hazard 3 Flammable liquid, keep away from all ignition sources. Reactivity 0 Target organs: Liver, kidneys, heart, auditory system. This material is considered hazardous by the OSHA Hazard Communication Standard (29 CFR 1910.1200). Section 3: Composition / Information on Ingredients Xylene (1330-20-7), 100% Section 4: First Aid Measures Always seek professional medical attention after first aid measures are provided. Eyes: Immediately flush eyes with excess water for 15 minutes, lifting lower and upper eyelids occasionally. Skin: Immediately flush skin with excess water for 15 minutes while removing contaminated clothing. Ingestion: Call Poison Control immediately. Aspiration hazard. Rinse mouth with cold water. Give victim 1-2 tbsp of activated charcoal mixed with 8 oz water. Inhalation: Remove to fresh air. If not breathing, give artificial respiration. Section 5: Fire Fighting Measures IB Flammable Liquid. When heated to decomposition, emits acrid fumes 3 Protective equipment and precautions for firefighters: Use foam or dry chemical to extinguish fire. 2 0 Firefighters should wear full fire fighting turn-out gear and respiratory protection (SCBA). -
Hydrogen Atom Transfer-Mediated Cyclisations of Nitriles
Hydrogen Atom Transfer-Mediated Cyclisations of Nitriles Oliver J. Turner,*[a,b] John A. Murphy,*[b] David. J. Hirst[a] and Eric P. A. Talbot*[a]† Abstract: Hydrogen atom transfer-mediated intramolecular C-C coupling reactions between alkenes and nitriles, using PhSiH3 and catalytic Fe(acac)3, are described. This introduces a new strategic bond disconnection for ring-closing reactions, forming ketones via imine intermediates. Of note is the scope of the reaction, including formation of sterically hindered ketones, spirocycles and fused cyclic systems. In the early 1960s, Kwiatek and Seyler first reported the use of metal hydrides as catalysts in the hydrogenation of α,β- unsaturated compounds.[1,2] The discovery by Halpern,[3] later elegantly developed by Norton,[4] that metal-hydride hydrogen atom transfer (HAT) proceeded by a free-radical mechanism opened the door to a wide range of alkene hydrofunctionalisation reactions. But it was the pioneering work by Mukaiyama[5] on the catalytic hydration of alkenes, using Co(acac)2 and oxygen, that sparked wider interest in the field of alkene hydrofunctionalisation. As a result, there now exists an extensive ‘toolkit’ for the addition of hydrogen and a functional group to an alkene with Markovnikov selectivity and high chemo-selectivity using cobalt, manganese and iron complexes.[6,7] Efforts have also been made to extend HAT methodologies to C-C bond formation, both in an intra- and intermolecular fashion: Baran’s group developed a general C-C coupling reaction, utilising electron-deficient alkenes as capable radical acceptors (Scheme 1ai).[8–10] Hydropyridylation of alkenes by intramolecular Minisci reaction was recently demonstrated by Starr,[11] which allows for the formation of structures such as Scheme 1. -
Consecutive Reactions of Aromatic–OH Adducts with NO, NO and O : Benzene, Toluene, M- and P-Xylene, Hexamethylbenzene, Phenol
Atmos. Chem. Phys. Discuss., 6, 7623–7656, 2006 Atmospheric www.atmos-chem-phys-discuss.net/6/7623/2006/ Chemistry © Author(s) 2006. This work is licensed and Physics under a Creative Commons License. Discussions Consecutive reactions of aromatic–OH adducts with NO, NO2 and O2: benzene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline R. Koch1,2, R. Knispel1, M. Elend1, M. Siese1,2, and C. Zetzsch1,2 1Fraunhofer-Institute of Toxicology and Experimental Medicine, Hannover, Germany 2Atmospheric Chemistry Research Laboratory, University of Bayreuth, Germany Received: 26 June 2006 – Accepted: 26 July 2006 – Published: 9 August 2006 Correspondence to: C. Zetzsch ([email protected]) 7623 Abstract Consecutive reactions of adducts, resulting from OH radicals and aromatics, with the tropospheric scavenger molecules O2, NO and NO2 have been studied for benzene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline by ob- 5 serving decays of OH at temperatures where the thermal back-decomposition to OH is faster than 3 s−1, typically between 300 and 340 K. The experimental technique was resonance fluorescence with flash photolysis of water as source of OH. Biexponential decays were observed in the presence of either O2 or NO, and triexponential decays were obtained in the presence of NO2. The kinetic analysis was performed by fitting the 10 relevant rate constants of the reaction mechanism to whole sets of decays obtained at various concentrations of aromatic and scavenger. In the case of hexamethylbenzene, the biexponential decays suggest the existence of the ipso-adduct, and the slightly higher necessary temperatures show that it is even more stable. -
Nitrile Synthesis with Aldoxime Dehydratases: a Biocatalytic Platform with Applications in Asymmetric Synthesis, Bulk Chemicals, and Biorefineries
molecules Review Nitrile Synthesis with Aldoxime Dehydratases: A Biocatalytic Platform with Applications in Asymmetric Synthesis, Bulk Chemicals, and Biorefineries Pablo Domínguez de María Sustainable Momentum, SL, Av. Ansite 3, 4–6, 35011 Las Palmas de Gran Canaria, Canary Islands, Spain; [email protected]; Tel.: +34-6-0956-5237 Abstract: Nitriles comprise a broad group of chemicals that are currently being industrially produced and used in fine chemicals and pharmaceuticals, as well as in bulk applications, polymer chemistry, solvents, etc. Aldoxime dehydratases catalyze the cyanide-free synthesis of nitriles starting from aldoximes under mild conditions, holding potential to become sustainable alternatives for industrial processes. Different aldoxime dehydratases accept a broad range of aldoximes with impressive high substrate loadings of up to >1 Kg L−1 and can efficiently catalyze the reaction in aqueous media as well as in non-aqueous systems, such as organic solvents and solvent-free (neat substrates). This paper provides an overview of the recent developments in this field with emphasis on strategies that may be of relevance for industry and sustainability. When possible, potential links to biorefineries and to the use of biogenic raw materials are discussed. Keywords: biocatalysis; green chemistry; nitriles; aldoxime dehydratases; sustainability Citation: Domínguez de María, P. Nitrile Synthesis with Aldoxime Dehydratases: A Biocatalytic Platform with Applications in Asymmetric Synthesis, Bulk 1. Aldoxime Dehydratases as Biocatalysts for the Cyanide-Free Synthesis of Nitriles Chemicals, and Biorefineries. Nitriles comprise an important group of chemicals that are widely spread in industry Molecules 2021, 26, 4466. in a broad range of sectors, being used as products, solvents, polymers, commodities, or https://doi.org/10.3390/ as starting materials for the production of other chemicals such as amines, amides, etc. -
Reduction of Organic Functional Groups Using Hypophosphites Rim Mouselmani
Reduction of Organic Functional Groups Using Hypophosphites Rim Mouselmani To cite this version: Rim Mouselmani. Reduction of Organic Functional Groups Using Hypophosphites. Other. Univer- sité de Lyon; École Doctorale des Sciences et de Technologie (Beyrouth), 2018. English. NNT : 2018LYSE1241. tel-02147583v2 HAL Id: tel-02147583 https://tel.archives-ouvertes.fr/tel-02147583v2 Submitted on 5 Jun 2019 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. THESE de DOCTORAT DE L’UNIVERSITE DE LYON EN COTUTELLE AVEC L'UNIVERSITÉ LIBANAISE opérée au sein de l’Université Claude Bernard Lyon 1 École Doctorale de Chimie-École Doctorale des Sciences et Technologies Discipline : Chimie Soutenue publiquement le 07/11/2018, par Rim MOUSELMANI Reduction of Organic Functional Groups Using Hypophosphites Devant le jury composé de Mme. Micheline DRAYE Université Savoie Mont Blanc Rapporteure M. Mohammad ELDAKDOUKI Université Arabe de Beyrouth Rapporteur Mme. Emmanuelle SCHULZ Université Paris 11 examinatrice M. Abderrahmane AMGOUNE Université Lyon 1 Président M. Mahmoud FARAJ Université Internationale Libanaise examinateur Mme. Estelle MÉTAY Université Lyon 1 Directrice de thèse M. Ali HACHEM Université Libanaise Directeur de thèse M. Marc LEMAIRE Université Lyon 1 Membre invité M. -
Example of Tier I SPCC Plan
Auto Service Station Facility Scenario Example Tier I Qualified Facility SPCC Plan Here is an example of an automotive service station facility and how the Step 1: Determine if the Gas owner determines he is covered by the SPCC rule and prepares an SPCC and Care Express needs an Plan. SPCC Plan. Description of Gas and Care Express Jack Smith, owner of the Gas and Care Express, believes he may have Gas and Care Express located in Malham, Pennsylvania is a self-service gasoline to develop, maintain, and implement station and automotive service shop offering basic automotive maintenance and a spill prevention plan under the repair services, including vehicle safety and emission inspections. The facility is SPCC rule. Let’s walk through the owned and operated by Jack Smith and is located at the intersection of Anywhere following scenario to determine if he and Sideways Streets. An empty lot sits adjacent to the back of the facility. A needs an SPCC Plan, and if so, then concrete storm drainage channel runs past one side of the empty lot and conveys we need to determine if he is eligible storm water into an unnamed creek about a 1/4-mile downstream from this location. to self‐certify his SPCC Plan and use The unnamed creek is a tributary of Muddy Creek, which is a tributary to the the Tier I SPCC Plan Template. Susquehanna River. There are four street storm culverts at the intersection where the facility is located. Storm water runoff collected by these culverts is conveyed by Is the facility or part of the facility the storm sewer into Muddy Creek at an outfall about 1 mile away. -
Synthesis of Densely Substituted Pyridine Derivatives from Nitriles by a Non-Classical [4+2] Cycloaddition/1,5-Hydrogen Shift Strategy
Synthesis of densely substituted pyridine derivatives from nitriles by a non-classical [4+2] cycloaddition/1,5-hydrogen shift strategy Wanqing Wu ( [email protected] ) South China University of Technology https://orcid.org/0000-0001-5151-7788 Dandan He South China University of Technology Kanghui Duan South China University of Technology Yang Zhou South China University of Technology Meng Li South China University of Technology Huanfeng Jiang South China University of Technology Article Keywords: pyridine derivatives, organic synthesis, medicinal chemistry. Posted Date: March 3rd, 2021 DOI: https://doi.org/10.21203/rs.3.rs-258126/v1 License: This work is licensed under a Creative Commons Attribution 4.0 International License. Read Full License Page 1/18 Abstract A novel strategy has been established to assemble an array of densely substituted pyridine derivatives from nitriles and o-substituted aryl alkynes or 1-methyl-1,3-enynes via a non-classical [4 + 2] cycloaddition along with 1,5-hydrogen shift process. The well-balanced anities of two different alkali metal salts enable the C(sp3)-H bond activation as well as the excellent chemo- and regioselectivities. This protocol offers a new guide to construct pyridine frameworks from nitriles with sp3-carbon pronucleophiles, and shows potential applications in organic synthesis and medicinal chemistry. Introduction Compounds containing pyridine core structures, not only widely exist in natural products, pharmaceuticals, and functional materials,1–7 but also serve as useful and valuable building blocks for metal ligands.8,9 For instance, pyridine derivative Actos I10 is a famous drug for the treatment of type 2 diabetes; Bi-(or tri-)pyridines II11–15 are often used as ligands in metal-catalyzed reactions; Kv1.5 antagonist III16 and alkaloid papaverine IV17 are two representative isoquinolines as a promising atrial- selective agent and a smooth muscle relaxant, respectively (Fig. -
Internal Revenue Service, Treasury § 48.4081–2
Internal Revenue Service, Treasury § 48.4081±2 practical and commercial fitness solely sentence in the definition of terminal by reason of its possible or rare use as are effective January 2, 1998. a fuel in the propulsion engine of a [T.D. 8659, 61 FR 10453, Mar. 14, 1996, as highway vehicle, train, or boat. amended by T.D. 8748, 63 FR 25, Jan. 2, 1998] (iii) Cross reference. For the tax on blended taxable fuel, see § 48.4081±3(g). § 48.4081±1T Taxable fuel; definitions For the back-up tax on certain uses of (temporary). liquids other than diesel fuel, see (a) [Reserved] § 48.4082±4. (b) Definitions. (3) Gasoline blendstocksÐ(i) In general. Kerosene means, after June 30, 1998Ð Except as provided in paragraph (1) The two grades of kerosene (No. 1± (c)(3)(ii) of this section, gasoline K and No. 2±K) described in ASTM blendstocks meansÐ Specification D 3699; and (A) Alkylate; (2) Kerosene-type jet fuel described in (B) Butane; ASTM Specification D 1655 and mili- tary specifications MIL±T±5624R and (C) Butene; MIL±T±83133D (Grades JP±5 and JP±8). (D) Catalytically cracked gasoline; For availability of ASTM and military (E) Coker gasoline; specification material, see § 48.4081± (F) Ethyl tertiary butyl ether 1(c)(2)(i). (ETBE); (G) Hexane; [T.D. 8774, 63 FR 35801, July 1, 1998] (H) Hydrocrackate; § 48.4081±2 Taxable fuel; tax on re- (I) Isomerate; moval at a terminal rack. (J) Methyl tertiary butyl ether (a) Overview. This section provides (MTBE); the general rule that all removals of (K) Mixed xylene (not including any taxable fuel at a terminal rack are sub- separated isomer of xylene); ject to tax and the position holder with (L) Natural gasoline; respect to the fuel is liable for the tax. -
Fluid Handling
FLUID HANDLING Pumps Fluid Siphon Pump Battery-Operated Polypropylene Multi-Use Fluid Transfer Pump SKU 568475 99 Liquid Transfer Pump Lever-Action Pump SKU 094647 99 24863 14 SKU 471071 99 SKU 688036 99 25713 9 • Transfers Fluids Easily 25712 14 24471 29 • Small and Lightweight • Use to Transfer Gas, Water, Oil and Other Non-Corrosive • Move Liquids Safely and Easily with • Ideal for Diesel, Kerosene, Liquids • Intake and Discharge This Convenient Handheld Pump Lubricants and Other Oils Transfer System • Hose Reaches 6 Ft. • Pumps Gas, Water, Oil and Other • Not for Gasoline, Water-Based with 1/2" Diameter • Pumps Air into Inflatables Non-Corrosive Liquids Chemicals or DEF • Includes: (2) 50" • Pumps Up to 6 Quarts of (127 cm) Long Hoses Liquid per Minute Polypropylene Hand Oil Pump Ryton® Rotary Polypropylene Lever-Action Pump with Lever-Action Pump Barrel Pump Rotary Drum Pump SKU 462495 99 DEF Stainless Steel Rod 24381 27 with Stainless COMPATIBLE SKU 462486 99 SKU 688035 99 SKU 688038 • Oil Pump for Use with Steel Rod 24382 29 24470 79 99 Oil-Based Fluids, Heating 24472 29 SKU 688037 • Fluid Transfer • Ideal for Pumping Diesel, Oils, Motor Oils, Heavy 99 Pump for Use with Oils, Kerosene, Water-Based • Ideal for Pumping and Light Oils, Diesel 24473 39 Diesel, Oils, Kerosene, Oil-Based Fluids, Chemicals, Bases and and Kerosene • Ideal for Pumping Heating Oils, Mild Acids Water-Based Chemicals, • Built-in 1-1/2" and 2" Bung Diesel, Oils, Kerosene, Bases and Mild Acids Motor Oils, ATF, • Not for Gasoline or DEF for Use on 16 to 55 Gallon Water-Based Chemicals, Diesel and • Not for Gasoline or DEF Drums with Either Opening Bases and Acids Including DEF Kerosene • Not for Gasoline • Not for Gasoline • Not for Gasoline Lever-Action Manual Gear Lube Manual Rotary Pump with Hose for 55 Gallon Drums* BONUS Barrel Pump Dispenser SKU 265089 99 5 Qt. -
General Tax Information Bulletin #300 Page 2
INFORMATION BULLETIN #300 GENERAL TAX JUNE 2021 (Replaces Bulletin #300 dated June 2020) Effective Date: July 1, 2021 SUBJECT: Sales of Compressed Natural Gas (CNG) and Liquefied Natural Gas (LNG) REFERENCES: IC 6-2.5-5-51; IC 6-6-2.5-1; IC 6-6-2.5-16.5; IC 6-6-2.5-22; IC 6-6-2.5- 22.5; IC 6-6-2.5-28; IC 6-6-4.1-1; IC 6-6-4.1-4; IC 6-6-4.1-4.5. DISCLAIMER: Commissioner’s directives are intended to provide nontechnical assistance to the general public. Every attempt is made to provide information that is consistent with the appropriate statutes, rules, and court decisions. Any information that is not consistent with the law, regulations, or court decisions is not binding on either the department or the taxpayer. Therefore, the information provided herein should serve only as a foundation for further investigation and study of the current law and procedures related to the subject matter covered herein. SUMMARY OF CHANGES The bulletin was updated to provide the new special fuel tax rate effective July 1, 2021. I. DEFINITIONS “Natural gas” means compressed or liquid natural gas. “Natural gas product” means: (1) A liquid natural gas (LNG) or compressed natural gas (CNG) product; or (2) A combination of liquefied petroleum gas and a compressed natural gas product; used in an internal combustion engine or a motor to propel any form of vehicle, machine, or mechanical contrivance. “Alternative fuel” means a liquefied petroleum gas, not including a biodiesel fuel or biodiesel blend, used in an internal combustion engine or a motor to propel any form of vehicle, machine, or mechanical contrivance. -
Microflex Gloves Chemical Compatibility Chart
1 1 1 2 2 3 1 CAUTION (LATEX): This product contains natural rubber 2 CAUTION (NITRILE: MEDICAL GRADE): Components used 3 CAUTION (NITRILE: NON-MEDICAL GRADE)): These latex (latex) which may cause allergic reactions. Safe use in making these gloves may cause allergic reactions in gloves are for non-medical use only. They may NOT be of this glove by or on latex sensitized individuals has not some users. Follow your institution’s policies for use. worn for barrier protection in medical or healthcare been established. applications. Please select other gloves for these applications. Components used in making these gloves may cause allergic reactions in some users. Follow your institution’s policies for use. For single use only. NeoPro® Chemicals NeoPro®EC Ethanol ■NBT Ethanolamine (99%) ■NBT Ether ■2 Ethidium bromide (1%) ■NBT Ethyl acetate ■1 Formaldehyde (37%) ■NBT Formamide ■NBT Gluteraldehyde (50%) ■NBT Test Method Description: The test method uses analytical Guanidine hydrochloride ■NBT equipment to determine the concentration of and the time at which (50% ■0 the challenge chemical permeates through the glove film. The Hydrochloric acid ) liquid challenge chemical is collected in a liquid miscible chemical Isopropanol ■NBT (collection media). Data is collected in three separate cells; each cell Methanol ■NBT is compared to a blank cell which uses the same collection media as both the challenge and Methyl ethyl ketone ■0 collection chemical. Methyl methacrylate (33%) ■0 Cautionary Information: These glove recommendations are offered as a guide and for reference Nitric acid (50%) ■NBT purposes only. The barrier properties of each glove type may be affected by differences in material Periodic acid (50%) ■NBT thickness, chemical concentration, temperature, and length of exposure to chemicals.