Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides
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Solvent-Free and Safe Process for the Quantitative Production of Phosgene from Triphosgene by Deactivated Imino-Based Catalysts
Organic Process Research & Development 2010, 14, 1501–1505 Solvent-Free and Safe Process for the Quantitative Production of Phosgene from Triphosgene by Deactivated Imino-Based Catalysts Heiner Eckert* and Johann Auerweck Department of Chemistry, Technische UniVersitaet Muenchen, Lichtenbergstr. 4, Garching 85747, Germany Abstract: Scheme 1. Decomposition of triphosgene (1a) into carbon tetrachloride, carbon dioxide, and 1 equiv of phosgene (3) Phosgene is quantitatively formed from solid triphosgene in a solvent-free and safe process without any reaction heat, catalyzed by planar N-heterocycles with deactivated imino functions. The rate of phosgene generation is adjustable to the rate of phosgene consumption in the subsequent phosgenation reaction by thermal control, catalyst concentration, and in some cases, specific proper- ties of selected metal phthalocyanines. A thermal runaway reaction of this process is impossible. phosgene in most reactions, yet several phosgenation reactions are advantageously carried out with phosgene, that is, when excessive triphosgene is difficult to remove during the reaction Introduction workup because of its high boiling point of over 200 °C. Its Phosgene (3) is a highly useful and versatile chemical in excess can be destroyed by hydrolysis, when phosgenation performing syntheses.1a Although consisting of only four atoms, products are not sensitive to moisture as are carbonates, four important transformations can be carried out with it in carbamates, ureas, diarylketones, alkylhalides, cyanides, and organic -
Efficient Esterification of Oxidized L-Glutathione and Other Small Peptides
Molecules 2015, 20, 10487-10495; doi:10.3390/molecules200610487 OPEN ACCESS molecules ISSN 1420-3049 www.mdpi.com/journal/molecules Communication Efficient Esterification of Oxidized L-Glutathione and Other Small Peptides Emily R. Vogel, William Jackson and Douglas S. Masterson * Department of Chemistry and Biochemistry, the University of Southern Mississippi, 118 College Drive #5043, Hattiesburg, MS 39406, USA; E-Mails: [email protected] (E.R.V.); [email protected] (W.J.) * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +1-601-266-4714. Academic Editor: Derek J. McPhee Received: 17 May 2015 / Accepted: 4 June 2015 / Published: 8 June 2015 Abstract: Oxidized L-glutathione was esterified to the tetra methyl ester using thionyl chloride in methanol solvent. Other alcohols were tested and the reaction progress was monitored via ESI-MS. This procedure proved to be compatible with other small peptides not containing serine and cysteine residues. In contrast to previously reported methods this procedure provided convenient access to esterified peptides requiring no purification, extended reaction times, or complicated reaction setups. Keywords: esterification; peptide esterification; amino acids; carboxylic acids; esters 1. Introduction The design and synthesis of novel glutathione analogues are studied extensively for their pharmacological properties in the treatment of a wide range of diseases [1–3]. Reduced glutathione (GSH), -L-glutamyl-L-cysteinyl-glycine, is prone to reactivity at the sulfhydryl, terminal amino group, and both carbonyls. Thus, the synthesis of GSH analogues are a synthetic challenge to chemists, and the clever manipulation of protecting groups are needed to prevent unwanted reactions. -
United States Patent Office 3,321,512 Patiented May 23, 1967 2 3,321,512 Peroxide Can Be Prepared in Any Convenient Manner
United States Patent Office 3,321,512 Patiented May 23, 1967 2 3,321,512 peroxide can be prepared in any convenient manner. It MANUFACTURE OF PERBENZOIC ACDS is preferred, however, to produce the suspension by dis David James Cooper and Tony Nicholas Gibson, both of tributing the corresponding benzoyl chloride in finely di Whitley Bay, Northumberiand, England, assignors to vided form in an aqueous alkaline solution of hydrogen Thecorporation Procter of & OhioGamble Company, Cincinnati, Cilio, a peroxide having a pH of not less than 10. The benzoyl No Drawing. Fified Jan. 22, 1964, Ser. No. 339,323 chloride reacts with the hydrogen peroxide solution pro Ciains priority, application (Great Britaia, Jan. 31, 1963, ducing the benzoyl peroxide which is obtained in the form 4,012/63 of a fine suspension. This can be achieved by introducing 2. Ciaisas. (C. 260-502) the benzoyl chloride at the periphery of a high speed agi IO tator (for example, an agitator of at least 2 inches in This invention relates to an improved process for the diameter rotating at 1500 to 2000 rp.m.) which is located manufacture of perbenzoic acids. in the solution. Alternatively, the benzoyl chloride can The conventional method of preparing aromatic percar be introduced into the throat of a Venturi mixer through boxylic acids is a two stage process in which the diacyl which the aqueous alkaline solution is passing. peroxide is prepared by reacting the aromatic acyl chlo 15 As stated above, the alkaline solution of hydrogen per ride (e.g., benzoyl chloride) with alkaline hydrogen per oxide must have a pH of at least 10. -
9-2909-00045/02001 Effective Date: 10/16/2014 Expiration Date: 10/15/2019
Facility DEC ID: 9290900045 PERMIT Under the Environmental Conservation Law (ECL) IDENTIFICATION INFORMATION Permit Type: Air State Facility Permit ID: 9-2909-00045/02001 Effective Date: 10/16/2014 Expiration Date: 10/15/2019 Permit Issued To:TWIN LAKE CHEMICAL INC 520 MILL ST PO BOX 411 LOCKPORT, NY 14094-0411 Contact: JAMES D HODAN TWIN LAKE CHEMICAL INC PO BOX 411 LOCKPORT, NY 14095 (716) 433-3824 Facility: TWIN LAKE CHEMICAL INC 520 MILL ST LOCKPORT, NY 14094 Contact: WILLIAM CASWELL TWIN LAKE CHEMICAL INC 520 MILL ST LOCKPORT, NY 14094-1712 (716) 433-3824 Description: This Air State Facility permit incorporates monitoring conditions for Twin Lake Chemical located in Lockport New York. The facility is a manufacturer of various organic acid chlorides used as intermediaries in the production of other compounds and encompasses two main production buildings and 8 reactors. The primary products produced are trimellitic trichloride, trimellitic Anhydride Monoacid chloride,isophthaloyl chloride, orthophthaloyl chloride, terephthaloyl chloride, and phosphorous pentachloride (2-200 gallon nickel reactors). Phosgene and thionyl chloride are used as chlorinating agents. The phosgene is purchased in 1 ton containers from Vandemark Chemical located next to the facility. Raw materials are added to the batch reactors along with a chlorinating agent and a catalyst. Prior to opening the reactor for chemical addition, the reactor is put under vacuum to remove gases. During the reaction process, the reactor is under slight pressure. Reactor temperatures are monitored. After the reaction is completed, the material is transferred to a distillation unit to refine and separate the product. Air strippers remove chlorinated hydrocarbons from wastewater prior to discharge to Lockport WWTP. -
Benzoyl Peroxide
BENZOYL PEROXIDE Prepared at the 63rd JECFA (2004), published in FNP 52 Add 12 (2004) superseding specifications prepared at the 55th JECFA (2000) and published in FNP 52 Add 8 (2000). Treatment of whey with benzoyl peroxide at a maximum concentration of 100 mg/kg does not pose a safety concern (63rd JECFA, 2004). SYNONYMS Benzoyl superoxide, INS No. 928 DEFINITION Benzoyl peroxide is manufactured by the reaction of benzoyl chloride, sodium hydroxide and hydrogen peroxide. Chemical name Dibenzoyl peroxide C.A.S. number 94-36-0 Chemical formula C14H10O4 Structural formula Formula weight 242.23 Assay Not less than 96.0% DESCRIPTION Colourless, crystalline solid having a faint odour of benzaldehyde. Caution: Benzoyl peroxide, especially in the dry form, is a dangerous, highly reactive, oxidizing material and has been known to explode spontaneously FUNCTIONAL USES Bleaching agent CHARACTERISTICS IDENTIFICATION Solubility (Vol. 4) Insoluble in water, slightly soluble in ethanol and soluble in ether. Melting range (Vol. 4) 103 - 106° with decomposition Decomposition to benzoic To 0.5 g of the sample add 50 ml of 0.5 N ethanolic potassium hydroxide, heat acid gradually to boiling and continue boiling for 15 min. Cool and dilute with 200 ml of water. Add sufficient 0.5 N hydrochloric acid to make strongly acidic and extract with ether. Dry the ether solution over anhydrous sodium sulfate, and then evaporate to dryness on a steam bath. The benzoic acid so obtained melts between 121° and 123°. PURITY Lead (Vol. 4) Not more than 2 mg/kg Determine using an atomic absorption technique appropriate to the specified level. -
Halogenation Reagents
Halogenation Reagents Halogenation is a basic and fundamental transformation in organic chemistry, and halogenated compounds are of extreme importance as building blocks in organic synthesis. The development of modern coupling reactions, such as the [P2140] Suzuki-Miyaura and Mizoroki-Heck reactions, have greatly increased the demand for halogenated compounds as starting materials. P2140 (2.3 eq.) On the other hand, introduction of fluorine into a certain position of bioactive compound such as a pharmaceutical and an agricultural chemical may remarkably reduce the toxicity of the compound, or improve the efficiency of medicine. This is due to the structurally mimic and blocking effect characterized by fluorine. P2140 (3 eq.) In response to this situation, a number of novel halogenation reagents have been developed. 4-tert-Butyl-2,6-dimethylphenylsulfur trifluoride (FLUOLEAD™) [B3664] is introduced as below: B3664 is a novel nucleophilic 1-Fluoro-3,3-dimethyl-1,2-benziodoxole [F0957] is a hypervalent fluorinating agent which was first reported by Umemoto et al.1) iodine derivative developed by Stuart et al.3) F0957 is stable to air Differing from other existing fluorinating agents, such as DAST, and moisture and used as an electrophilic fluorinating reagent for B3664 is a crystalline solid with high thermal stability and less a α-monofluorination of β-ketoesters in the presence of fuming character, which makes it easier to handle. B3664 triethylamine trihydrofluoride. fluorinates a hydroxyl or carbonyl group to afford the corresponding fluorinated compounds in good yields.1) F I O [F0957] O O Ph OEt F0957(2eq.) F O O Et3N-3HF(2.7eq.) [B3664] Ph OEt CH2Cl2 O O 40oC,24h Ph OEt F F Dibromoisocyanuric acid (DBI) [D3753] which was first reported by Gottardi, is a mild and highly effective brominating agent,4a,b,c) and has superior brominating ability when compared with N-bromosuccinimide (NBS), which is frequently used in organic IF5-Pyridine-HF (Hara Reagent) [P2140] is also a novel synthesis. -
Friedel and Crafts' Reaction-The Preparation of Orthobenzoyl-Benzoic Acid and Benzophenone
732 C. R. RUBIDGE AND N. C. QUA. two and five-tenths grams of cyanimidocaxbonic ethyl ester, prepared from bromocyanogen, potassium cyanide, and alcohol1 were added to the suspended alcoholate. Heat was developed, the solution became yellow, and sodium cyanide was precipitated. The reaction mixture was heated for two hours in a flask connected with a reflux condenser, and enough water was added to dissolve the sodium cyanide. After the water solution had been extracted with ether several times, the ether was dried with calcium chloride. Thus, 32 g. of a light yellow oil, possessing a strong basic odor, were obtained when the ether was evaporated. Even at a pressure of 25 mm. the compound could not be distilled without consid- erable decomposition. Therefore, no analysis of the substance was at- tempted. Its identity was established by converting it into the corre- sponding oximido derivative. Preqaration of Oximidocarbonic Ethyl Isoamyl Ester, CZHS@-C~C~HII,- II NOH Eight and four-tenths grams of hydroxylamine, dissolved in a small amount of water, were added to 20 g. of the imido ester dissolved'in 20 cc. of ether. The mixture was shaken thirty minutes, the water layer was drawn off, extracted several times with ether, and the ether dried with sodium sulfate. Twenty grams of a reddish yellow oil were obtained when the ether evaporated. When cooled to -15', white crystals ap- peared which melted when they were spread out on a cold clay plate. 0.1754 g. gave 12.8 cc. Nz at 24.5' and 742 mm. Calc. for CsH1703N: N, 7.99. -
Material Safety Data Sheet HCS Risk Phrases HCS CLASS: Corrosive Liquid
Material Safety Data Sheet HCS Risk Phrases HCS CLASS: Corrosive liquid. HCS CLASS: Combustible liquid IIIA having a flash point between 60.0°C (140°F) and 93.3°C (200°F) Section I. Chemical Product and Company Identification Common Name/ Benzoyl Chloride In Case of Trade Name Emergency In the continental U.S.A. call CHEMTREC 800-424-9300 (24 hours) Outside the continental U.S.A. call CHEMTREC 703-527-3887 (24 hours) Supplier Velsicol Chemical Corporation Manufacturer Velsicol Chemical Corporation 10400 W. Higgins Road 10400 W. Higgins Road Rosemont, IL 60018 U.S.A. Rosemont, IL 60018 U.S.A. Phone: 847-298-9000 Phone: 847-298-9000 Fax: 847-298-9015 Fax: 847-298-9015 Synonym Benzenecarbonyl Chloride Material Uses Agricultural Industry: Chloramber Chemical Name Benzoyl Chloride (herbicide). Intermediate for pesticides. Chemical Family Acyl Halide Industrial Applications: Acylation. Chemical C7 H5 CL 0 Polymerization initiator of benzophenone. Formula Intermediate for stabilizers. Acetic anhydride production. Textile Industry: Cellulosic yarn treatment agent. Fastness improver. Other Non-Specified Industry: Organic analysis. Dyes. Perfumes. Section II. Composition and Information on Ingredients Name CAS# % by Weight TLV/PEL OSHA Hazardous Ingredients 1) Benzoyl Chloride 98-88-4 >99.5 STEL: 2.8 (mg/m3) from Yes ACGIH (TLV) 2) Benzotrichloride 98-07-7 <0.02 STEL: 0.1 ppm from Yes ACGIH; Skin designation. 3) Benzyl Alcohol 100-44-7 <0.01 TWA: 1 (ppm) from Yes ACGIH (TLV) Section III. Hazards Identification Emergency Overview Clear. Liquid. Pungent. Acrid odor. DANGER! CAUSES SEVERE EYE, SKIN AND RESPIRATORY TRACT BURNS. MAY CAUSE BLINDNESS. -
1 Chapter 15: Alcohols, Diols, and Thiols 15.1: Sources of Alcohols
Chapter 15: Alcohols, Diols, and Thiols 15.1: Sources of Alcohols (please read) Hydration of alkenes (Chapter 6) 1. Acid catalyzed hydration 2. Oxymercuration 3. Hydroboration Hydrolysis of alkyl halides (Chapter 8) nucleophilic substitution Reaction of Grignard or organolithium reagents with ketones, aldehydes, and esters. (Chapter 14) Reduction of alehydes, ketones, esters, and carboxylic acids (Chapter 15.2 - 15.3) Reaction of epoxides with Grignard Reagents (Chapter 15.4) Diols from the dihydroxylation of alkenes (Chapter 15.5)320 15.2: Preparation of Alcohols by Reduction of Aldehydes and Ketones - add the equivalent of H2 across the π-bond of the carbonyl to yield an alcohol H O [H] O aldehyde (R or R´= H) → 1° alcohol C C ketone (R and R´≠ H) → 2° alcohol R H R R' R' Catalytic hydrogenation is not typically used for the reduction of ketones or aldehydes to alcohols. Metal hydride reagents: equivalent to H:– (hydride) sodium borohydride lithium aluminium hydride (NaBH4) (LiAlH4) H H Na+ H B H Li+ H Al H H H B H Al H 321 electronegativity 2.0 2.1 1.5 2.1 1 synthons precursors R1 R1 R1 + H: R2 C OH C OH = C O + NaBH4 H R2 R2 NaBH4 reduces aldehydes to primary alcohols O H H NaBH O2N 4 O N H 2 OH HOCH2CH3 NaBH4 reduces ketones to secondary alcohols H OH O NaBH4 HOCH2CH3 ketones 2° alcohols NaBH4 does not react with esters or carboxylic acids O HO H NaBH4 H CH CO H3CH2CO 3 2 HOCH2CH3 O O 322 Lithium Aluminium Hydride (LiAlH4, LAH) - much more reactive than NaBH4. -
Bringing Order to Organic Chemistry
Radicals and Types: Bringing Order to Organic Chemistry Organic Chemistry can now make you completely mad. It seems like a primeval forest in a tropical country where we hate to venture, full of the most peculiar things, an enormous thicket with no end and no way out. Friedrich Wöhler to Jakob Berzelius, January 28, 1835 Monday, October 4, 2010 Transformation of Organic Chemistry, 1820-1850 Reasons for this transformation: • Recognition of isomerism. • Explanation of isomerism by “arrangement.” • The rapid adoption of Berzelian notation as “paper tools” • Justus Liebig’s invention of the Kaliapparat for organic analysis Monday, October 4, 2010 Justus von Liebig (1803-1873) Friedrich Wöhler (1800-1882) Monday, October 4, 2010 Compounds with Identical Molecular Formulas • Liebig: Silver fulminate: 77.53% AgO, 22.47% cyanic acid • Wöhler: Silver cyanate: 77.23% AgO, 22.77% cyanic acid • Wöhler, 1828: • Cyanic acid + ammonia –––> ammonium cyanate –––> urea • Berzelius: • Isomers: compounds with different properties, but identical elemental composition. Monday, October 4, 2010 Liebig, Wöhler and the Oil of Bitter Almonds (1834) • C14H12O2 + oxidant --> C14H12O4 (benzoic acid) • C14H12O2 + chlorine --> C14H12O2Cl2 • C14H12O2 + bromine --> C14H12O2Br2 • (Many other reactions with iodine, ammonia, etc.) • Benzoyl Hydrogen: C14H10O2 • H2 • Benzoyl chloride: C14H10O2 • Cl2 • Benzoyl iodide: C14H10O2 • I2 • Benzoic acid: C14H10O2 • OH2 • Constant set of atoms: C14H12O2 Benzoyl radical Monday, October 4, 2010 Liebig, Wöhler and the Oil of Bitter Almonds (1834) Role of Berzelian formulas in creating the concept of the benzoyl radical • Elemental analysis results must be converted into integral numbers of “atoms” (C14H10O2 • H2 for oil of bitter almonds) • Formulas represent the benzoyl radical, but are also the means of “discovering” it, by manipulating symbols on paper. -
Reactions of Alcohols
Reactions of Alcohols Alcohols are versatile organic compounds since they undergo a wide variety of transformations – the majority of which are either oxidation or reduction type reactions. Normally: Oxidation is a loss of electrons; Reduction is a gain of electrons. But in organic terms: Oxidation: loss of H2; addition of O or O2; addition of X2 (halogens). Reduction: - addition of H2 or H ; loss of O or O2; loss of X2. Neither an oxidation nor reduction: Addition or loss of H+, H2O, HX. Ch11 Reacns of Alcohols (landscape).docx Page 1 Oxidation of Alcohols Primary and secondary alcohols are easily oxidized by a variety of reagents. Secondary Alcohols The most common reagent used for oxidation of secondary alcohols to ketones is chromic acid, H2CrO4. Chromic acid is produced in situ by reaction of sodium dichromate, sulfuric acid and water. Na2Cr2O7 + H2O + 2H2SO4 2 H2CrO4 + 2 NaHSO4 Ch11 Reacns of Alcohols (landscape).docx Page 2 Mechanism of oxidation The alcohol and chromic acid produce a chromate ester, which then reductively eliminates the Cr species. The Cr is reduced (VI IV), the alcohol is oxidized. Oxidation of Primary Alcohols Primary alcohols are easily oxidized just like secondary alcohols, and the INITIAL product of oxidation is an aldehyde. Ch11 Reacns of Alcohols (landscape).docx Page 3 However, the aldehyde can also be easily oxidized to an acid, and this ‘over-oxidation’ is a practical problem. E.g. A common reagent that selectively oxidizes a primary alcohol to an aldehyde (and no further) is pyridinium chlorochromate, PCC. N: CrO3, HCl (PCC) E.g. Tertiary Alcohols These are resistant to oxidation because they have no hydrogen atoms attached to the oxygen bearing carbon (carbinol carbon). -
Benzoyl Peroxide
criteria for a recommended standard. OCCUPATIONAL EXPOSURE TO BENZOYL PEROXIDE U.S. DEPARTMENT OF HEALTH, EDUCATION, AND WELFARE Public Health Service Center for Disease Control National Institute for Occupational Safety and Health Ju n e 1977 For sate by the Superintendent of Documents,Government U.S. Printing Office, Washington, D.C. 20402 DHEW (NIOSH) Publication No. 77-166 PREFACE The Occupational Safety and Health Act of 1970 emphasizes the need for standards to protect the health and safety of workers exposed to an ever-increasing number of potential hazards at their workplace. The National Institute for Occupational Safety and Health has projected a formal system of research, with priorities determined on the basis of specified indices, to provide relevant data from which valid criteria for effective standards can be derived. Recommended standards for occupational exposure, which are the result of this work, are based on the health effects of exposure. The Secretary of Labor will weigh these recommendations along with other considerations such as feasibility and means of implementation in developing regulatory standards. It is intended to present successive reports as research and epidemiologic studies are completed and as sampling and analytical methods are developed. Criteria and standards will be reviewed periodically to ensure continuing protection of the worker. I am pleased to acknowledge the contributions to this report on benzoyl peroxide by members of the NIOSH staff, by the Review Consultants on Benzoyl Peroxide, by the ad hoc committees of the American Medical Association and the American Conference of Governmental Industrial Hygienists, and by Robert B. O'Connor, M.D., NIOSH consultant in occupational medicine.