Review Article Synthesis and Reactions of Five-Membered Heterocycles Using Phase Transfer Catalyst (PTC) Techniques
Total Page:16
File Type:pdf, Size:1020Kb
Load more
Recommended publications
-
A Facile Procedure for the Generation of Dichlorocarbene from the Reaction of Carbon Tetrachloride and Magnesium Using Ultrasonic Irradiation
Molecules 2003, 8, 608-613 molecules ISSN 1420-3049 http://www.mdpi.org A Facile Procedure for the Generation of Dichlorocarbene from the Reaction of Carbon Tetrachloride and Magnesium using Ultrasonic Irradiation Haixia Lin *, Mingfa Yang, Peigang Huang and Weiguo Cao Department of Chemistry, Shanghai University, Shanghai, 200436, P.R. China *Author to whom correspondence should be addressed: e-mail [email protected] Received: 7 April 2003; in revised form: 7 July 2003 / Accepted: 20 July 2003 / Published: 31 July 2003 Abstract: An improved method for the generation of dichlorocarbene was developed that utilizes ultrasound in the reaction of carbon tetrachloride with magnesium. High yields of gem-dichlorocyclopropane derivatives can be obtained in the presence of olefins by this method. Keywords: Dichlorocarbene; gem-dichlorocyclopropanes; ultrasonic irradiation; olefin addition; magnesium Introduction Gem-dichlorocyclopropanes are valuable intermediates in organic synthesis [1,2]. They are typically prepared by the addition of dichlorocarbene to olefins under phase-transfer catalysis conditions [3-5]. Sonochemical generation of dichlorocarbene has also been reported [6-8]. The reactions of dichlorocarbene with olefins in solid-liquid two-phase systems using ultrasonication usually afford high yields of double-bond addition products. In addition, excellent yields of diadducts have been obtained from dienes and dichlorocarbene under ultrasonication and phase-transfer catalyst [9]. Molecules 2003, 8 609 Previously, we reported a novel route for the generation of dichlorocarbene by the reaction of carbon tetrachloride with magnesium in a neutral medium and hypothesized that the mechanism of these reactions might involve a single electron transfer [10]. However, these reactions suffered from several experimental drawbacks: some of the major ones being the sudden exotherm that occurs after an unpredictable induction period, foaming, and in some cases, the use of iodine as the activating agent. -
University of Groningen Reduction of Aldehydes and Ketones by Sodium Dithionite Vries, Johannes G. De
View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by University of Groningen University of Groningen Reduction of Aldehydes and Ketones by Sodium Dithionite Vries, Johannes G. de; Kellogg, Richard M. Published in: Journal of Organic Chemistry DOI: 10.1021/jo01309a011 IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below. Document Version Publisher's PDF, also known as Version of record Publication date: 1980 Link to publication in University of Groningen/UMCG research database Citation for published version (APA): Vries, J. G. D., & Kellogg, R. M. (1980). Reduction of Aldehydes and Ketones by Sodium Dithionite. Journal of Organic Chemistry, 45(21), 4126-4129. https://doi.org/10.1021/jo01309a011 Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons). Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Download date: 12-11-2019 4126 J. Org. Chem. 1980,45,4126-4129 Reduction of Aldehydes and Ketones by Sodium Dithionite Johannes G. -
The Journal of Organic Chemistry 1959 Volume 24 No.8
THE JOURNAL OF Organic Chemistry © Copyright 1959 Volume 24, Number 8 by the American Chemical Society August 31, 1959 [Contribution from th e C hem istry D epartm ent of Syracuse U n iversity ] Condensation of Thiophenols and Formaldehyde with Some Aromatic Amines GERALD F. GRILLOT and ROBERT E. SCHAFFRATH Received September 85, 1958 N-Arylaminomethyl aryl sulfides and l,3,5-triaryl-l,5-dithia-3-azapentanes have been prepared by condensing primary aromatic amines with formaldehyde and thiophenols. A-Methylanilines condense with formaldehyde and thiophenols to form Ar-methyl-Ar-arylaminomethyl aryl sulfides. Two arylaminoethy 1 aryl sulfides were prepared by condensing 0-chloroethylaniline with the sodium salt of the thiophenol. Basicities of these arylaminoalkyl aryl sulfides have been related to (a) the presence of electrophilic substituents attached to the aryl groups and (b) the number of carbon atoms separating the nitrogen and sulfur atoms. Recently Grillot et a l.1 have demonstrated that Whereas primary aliphatic amines generally the thiophenols condense with secondary aliphatic give a mixture of secondary and tertiary amines in amines and formaldehyde to form dialkylamino- the Mannich reaction, primary aromatic amines methyl aryl sulfides similar in structure to the can be condensed with thiophenols and formalde dialkylaminomethyl alkyl sulfides prepared by hyde in a 1:1:1 mole ratio to give almost exclusively McLeod and Robinson2 3by condensing aliphatic moderately stable usually crystalline W-arylamino- mercaptans with aliphatic -
Chloroform 18.08.2020.Pdf
Chloroform Chloroform, or trichloromethane, is an organic compound with formula CHCl3. It is a colorless, sweet-smelling, dense liquid that is produced on a large scale as a precursor to PTFE. It is also a precursor to various refrigerants. It is one of the four chloromethanes and a trihalomethane. It is a powerful anesthetic, euphoriant, anxiolytic and sedative when inhaled or ingested. Formula: CHCl₃ IUPAC ID: Trichloromethane Molar mass: 119.38 g/mol Boiling point: 61.2 °C Density: 1.49 g/cm³ Melting point: -63.5 °C The molecule adopts a tetrahedral molecular geometry with C3v symmetry. Chloroform volatilizes readily from soil and surface water and undergoes degradation in air to produce phosgene, dichloromethane, formyl chloride, carbon monoxide, carbon dioxide, and hydrogen chloride. Its half-life in air ranges from 55 to 620 days. Biodegradation in water and soil is slow. Chloroform does not significantly bioaccumulate in aquatic organisms. Production:- In industry production, chloroform is produced by heating a mixture of chlorine and either chloromethane (CH3Cl) or methane (CH4). At 400–500 °C, a free radical halogenation occurs, converting these precursors to progressively more chlorinated compounds: CH4 + Cl2 → CH3Cl + HCl CH3Cl + Cl2 → CH2Cl2 + HCl CH2Cl2 + Cl2 → CHCl3 + HCl Chloroform undergoes further chlorination to yield carbon tetrachloride (CCl4): CHCl3 + Cl2 → CCl4 + HCl The output of this process is a mixture of the four chloromethanes (chloromethane, dichloromethane, chloroform, and carbon tetrachloride), which can then be separated by distillation. Chloroform may also be produced on a small scale via the haloform reaction between acetone and sodium hypochlorite: 3 NaClO + (CH3)2CO → CHCl3 + 2 NaOH + CH3COONa Deuterochloroform[ Deuterated chloroform is an isotopologue of chloroform with a single deuterium atom. -
Alphabetical Index of Substances and Articles
ALPHABETICAL INDEX OF SUBSTANCES AND ARTICLES - 355 - NOTES TO THE INDEX 1. This index is an alphabetical list of the substances and articles which are listed in numerical order in the Dangerous Goods List in Chapter 3.2. 2. For the purpose of determining the alphabetical order the following information has been ignored even when it forms part of the proper shipping name: numbers; Greek letters; the abbreviations “sec” and “tert”; and the letters “N” (nitrogen), “n” (normal), “o” (ortho) “m” (meta), “p” (para) and “N.O.S.” (not otherwise specified). 3. The name of a substance or article in block capital letters indicates a proper shipping name. 4. The name of a substance or article in block capital letters followed by the word “see” indicates an alternative proper shipping name or part of a proper shipping name (except for PCBs). 5. An entry in lower case letters followed by the word “see” indicates that the entry is not a proper shipping name; it is a synonym. 6. Where an entry is partly in block capital letters and partly in lower case letters, the latter part is considered not to be part of the proper shipping name. 7. A proper shipping name may be used in the singular or plural, as appropriate, for the purposes of documentation and package marking. - 356 - INDEX Name and description Class UN No. Name and description Class UN No. Accumulators, electric, see 4.3 3292 Acid mixture, nitrating acid, see 8 1796 8 2794 8 2795 Acid mixture, spent, nitrating acid, see 8 1826 8 2800 8 3028 Acraldehyde, inhibited, see 6.1 1092 ACETAL 3 1088 -
The Asymmetric Synthesis of Styrene-Oxide and Its Reactions with Dialkylmagnesium Reagents and Boron Hydrides
University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Summer 1971 THE ASYMMETRIC SYNTHESIS OF STYRENE-OXIDE AND ITS REACTIONS WITH DIALKYLMAGNESIUM REAGENTS AND BORON HYDRIDES RONALD LEROY ATKINS Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation ATKINS, RONALD LEROY, "THE ASYMMETRIC SYNTHESIS OF STYRENE-OXIDE AND ITS REACTIONS WITH DIALKYLMAGNESIUM REAGENTS AND BORON HYDRIDES" (1971). Doctoral Dissertations. 964. https://scholars.unh.edu/dissertation/964 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. 72-3736 ATKINS, Ronald Leroy, 1939- THE ASYMMETRIC SYNTHESIS OF STYRENE OXIDE AND ITS REACTIONS WITH DIALKYLMAGNESIUM REAGENTS AND BORON HYDRIDES. University of New Hampshire, Ph.D., 1971 Chemistry, organic University Microfilms, A XEROX Company, Ann Arbor, Michigan © 1971 Ronald LeRoy Atkina ALL RIGHTS RESERVED THE ASYMMETRIC SYNTHESIS OF STYRENE OXIDE AND ITS REACTIONS WITH DIALKYLMAGNESIUM REAGENTS AND BORON HYDRIDES by RONALD L. ATKINS B. S., The University of Wyoming, 1966 M. S., The University of Wyoming, 1968 A THESIS Submitted to the University of New Hampshire In Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Graduate School Department of Chemistry August, 1971 This thesis has been examined and approved. f b w < M & > YUffvyido— The^js Director, James D. Morrison Asspaiate Professor of Chemistry & L DJitdsh-iU. _____ Colin D. -
Gas-Solid Alkali Destruction of Volatile Chlorocarbons
LA-13042-MS Gas-Solid Alkali Destruction of Volatile Chlorocarbons c£lVi •% to BO Los Alamos NATIONAL LABORATORY Los Alamos National Laboratory is operated by the University of California for the United States Department of Energy under contract W-7405-ENG-36- An Affirmative Action/Equal Opportunity Employer This report was prepared as an account of work sponsored by an agency of the United States Government. Neither The Regents of the University of California, the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by The Regents of the University of California, the United States Government, or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of The Regents of the University of California, the United States Government, or any agency thereof. The Los Alamos National Laboratory strongly supports academic freedom and a researcher's right to publish; therefore, the Laboratory as an institution does not endorse the viewpoint of a publication or guarantee its technical correctness. DISCLAIMER Portions of this document may be illegible in electronic image products. Images are produced from the best aTaiiable original document. LA-13042-MS UC-901 Issued: December 1995 Gas-Solid Alkali Destruction of Volatile Chlorocarbons Jerry Foropoulos, Jr. -
Basic Description for Ground and Air Hazardous
BASIC DESCRIPTION FOR GROUND AND AIR GROUND AND AIR HAZARDOUS MATERIALS SHIPMENTS GROUND SHIPMENTS AIR SHIPMENTS SHIPMENTS HAZARD DOT DOT CLASS OR MAXIMUM EXEMPTION, GROUND EXEMPTION, HAZARDOUS MATERIALS DESCRIPTIONS DIVISION I.D. NUMBER LABEL(S) REQUIRED OR QUANTITY PER SPECIAL SERVICE TO LABEL(S) REQUIRED OR MAXIMUM NET CARGO SPECIAL NON-BULK AND PROPER SHIPPING NAME (Subsidiary if (ALSO MARK PACKING EXEMPTION, SPECIAL PERMIT INNER PERMIT CANADA EXEMPTION, SPECIAL PERMIT QUANTITY PER AIRCRAFT PERMIT SPECIAL EXCEPTIONS PACKAGING (ALSO MARK ON PACKAGE) applicable) ON PACKAGE) GROUP OR EXCEPTION RECEPTACLE OR 173.13 PERMITTED OR EXCEPTION PACKAGE** QUANTITY OR 173.13 PROVISIONS §173.*** §173.*** (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) Accellerene, see p-Nitrosodimethylaniline Accumulators, electric, see Batteries, wet etc Accumulators, pressurized, pneumatic or hydraulic (containing non-flammable gas), see Articles pressurized, pneumatic or hydraulic (containing non-flammable gas) FLAMMABLE FLAMMABLE Acetal 3 UN1088 II LIQUID * YES LIQUID * 5 L 150 202 FLAMMABLE Acetaldehyde 3 UN1089 I LIQUID YES Forbidden None 201 May not be regulated when shipped via UPS Acetaldehyde ammonia 9 UN1841 III ground YES CLASS 9 * 30 kg 30 kg 155 204 FLAMMABLE FLAMMABLE Acetaldehyde oxime 3 UN2332 III LIQUID * YES LIQUID * 25 L 150 203 CORROSIVE, CORROSIVE, Acetic acid, glacial or Acetic acid solution, FLAMMABLE FLAMMABLE A3, A6, with more than 80 percent acid, by mass 8 (3) UN2789 II LIQUID * YES LIQUID * 1 L A7, A10 154 202 Acetic -
A Study for Health Hazard Evaluation of Methylene Chloride Evaporated from the Tear Gas Mixture
Saf Health Work 2010;1:98-101 | DOI:10.5491/SHAW.2010.1.1.98 pISSN : 2093-7911 eISSN : 2093-7997 Case Report A Study for Health Hazard Evaluation of Methylene Chloride Evaporated from the Tear Gas Mixture Seung-Hyun PARK, Eun-Kyo CHUNG, Gwang-Yong YI, Kwang-Jae CHUNG, Jung-Ah SHIN and In-Seop LEE Department of Occupational Environment Research, Occupational Safety and Health Research Institute, KOSHA, Incheon, Korea This study explored the health hazard of those exposed to methylene chloride by assessing its atmospheric concentration when a tear gas mixture was aerially dispersed. The concentration of methylene chloride ranged from 311.1–980.3 ppm (geometric mean, 555.8 ppm), 30 seconds after the dispersion started. However, the concentration fell rapidly to below 10 ppm after dispersion was completed. The concentration during the dispersion did not surpass the National Institute for Occupational Safety and Health ‘immediately dangerous to life or health’ value of 2,300 ppm, but did exceed the American Conference of Governmental Industrial Hygienists excursion limit of 250 ppm. Since methylene chloride is highly volatile (vapor pressure, 349 mmHg at 20oC), the post- dispersion atmospheric concentration can rise instantaneously. Moreover, the o-chlorobenzylidenemalononitrile formulation of tear gas (CS gas) is an acute upper respiratory tract irritant. Therefore, tear gas mixtures should be handled with delicate care. Key Words: Methylene chloride, CS tear gas, Tear gas mixture, Health hazard evaluation Introduction Despite this long history of use, CS gas has recently come under greater scrutiny since it can be applied as a mixture that Tear gases such as o-chlorobenzylidenemalononitrile (CS), contains a suspected human carcinogen, methylene chloride. -
Hazardous Chemicals Vapor Phase Library
Hazardous Chemicals Vapor Phase Library Index Number Compound Name Index Number Compound Name 1 (Chloromethyl)trichlorosil 28 4,4'- ane Isopropylidenediphenol; 2 Benzyl chloride; a- Bisphenol A Chlorotoluene 29 2-Phenylphenol; 2- 3 1,3-Dichlorobenzene Hydroxybiphenyl 4 N,N-Dimethylaniline 30 Phenyltrichlorosilane 5 Cumene; 31 Resorcinol; 1,3- Isopropylbenzene Dihydroxybenzene 6 Naphthalene 32 Phenanthrene 7 1,2,4-Trichlorobenzene 33 Fluoranthene 8 4-Allyl-1,2- 34 Acenaphthylene (methylenedioxy)benzen 35 Ethyl thiocyanate e; Safrole 36 1,4-Dichloro-2-butene, 9 Tolylene 2,6- (E) + (Z) diisocyanate; 2-Methyl- 37 2,4,6-Trifluoro-1,3,5- 1,3-phenylene triazine; Cyanuric fluoride diisocyanate 38 3- 10 Triethoxysilane Hydroxypropanesulfonic 11 Butyraldehyde; Butanal acid sultone; 1,3- 12 Acrolein; Propenal Propane sultone 13 2-Methylpropionic acid; 39 Formic acid Isobutyric acid 40 Acetic acid; Ethanoic 14 Biphenyl acid 15 Acenaphthene 41 Adipic acid; Hexanedioic 16 Fluorene acid 17 1,3-Dinitrobenzene 42 Acetamide 18 1,2-Dinitrobenzene 43 Acrylamide; 19 Piperylene, (E) + (Z); Propenoamide 1,3-Pentadiene, (E) + (Z) 44 Urethane; Ethyl 20 1,2- carbamate Dibromotetrafluoroethan 45 1,2,3,4,5,6- e Hexachlorocyclohexane, 21 Bis(2-ethylhexyl) adipate; g-isomer; Lindane Bis(2-ethylxexyl) 46 Ethyltrichlorosilane hexanedioate 47 (E)-1,4-Dichloro-2- 22 1,2,4,5- butene Tetrachlorobenzene 48 3-Nitrophenol 23 Pentachlorobenzene 49 2,4,5-Trichlorophenol 24 Isobutyraldehyde; 2- 50 4-Nitrobenzyl chloride; a- Methylpropanal Chloro-4-nitrotoluene 25 2-Methylaziridine -
United States Patent (19) 11) 4,339,589 Steglich Et Al
United States Patent (19) 11) 4,339,589 Steglich et al. 45) Jul. 13, 1982 54 PREPARATION OF 4-SUBSTITUTED 52 U.S. C. .................................... 548/228; 548/352; OXAZOLIDIN-5-ONES 562/441; 562/442; 562/443; 562/444; 562/445; (75) Inventors: Wolfgang Steglich, Berlin; Rudolf 562/446,562/553; 562/567; 562/568; 562/571; Hurnaus; Peter Gruber, both of 562/575; 562/433 Biberach; Boerries Kuebel, Berlin, all 58) Field of Search......................................... 548/228 of Fed. Rep. of Germany (56) References Cited 73) Assignee: BASF Aktiengesellschaft, Fed. Rep. U.S. PATENT DOCUMENTS of Germany 3,676,453 7/1972 Pines et al........ ... 548/228 (21) Appl. No.: 175,593 4,264,771 4/1981 Stealich et al. ..................... 548/228 22 Filed: Aug. 5, 1980 Primary Examiner-David B. Springer Attorney, Agent, or Firm-Keil & Witherspoon Related U.S. Application Data 57 ABSTRACT 63 Continuation of Ser. No. 891,456, Mar. 29, 1978, Pat. Manufacture of 4-substituted oxazolinone-(5) com No. 4,264,771, which is a continuation of Ser. No. pounds, which are intermediates for substituted aminoa 484,068, Jul. 16, 1974, abandoned. cids, by alkylation of 2-substituted or 3,4-disubstituted (30) Foreign Application Priority Data oxazolinone-(5) compounds in an aprotic solvent in the Jul. 19, 1973 (DE) Fed. Rep. of Germany ....... 2336718 presence of a tertiary amine. 51) Int. Cl. ............................................ C07D 265/10 7 Claims, No Drawings 4,339,589 1. 2 zyl, diacetoxybenzyl, methylenedioxybenzyl and p PREPARATION OF 4-SUBSTITUTED chlorobenzyl. OXAZOLDIN-5-ONES Further possible substituents of the alkyl radicals are alkoxy, alkylthio, acylamino and carbethoxy radicals, This is a continuation of application Ser. -
Lecture 13 Electrophilic Aromatic Substitution I 5.1 Principles
NPTEL – Chemistry – Principles of Organic Synthesis Lecture 13 Electrophilic Aromatic Substitution I 5.1 Principles The reaction occurs in two stages: the electrophile adds to one carbon atom of the aromatic ring, yielding a carbocation in which the positive charge is delocalized, and a proton is then eliminated from the adduct. H E H E H E E -H E 5.2 Formation of Carbon-Carbon Bonds 5.2.1 Friedel-Crafts Acylation Acylation of aromatic rings is generally peroformed using acid chloride or acid anhydride as an acylating agent in the presence of Lewis acid. O Z RCOCl, AlCl Z 3 R H2O Mechanism AlCl3 RCOCl RC=O + AlCl4 H H RC=O COR Z Z COR Z Joint initiative of IITs and IISc – Funded by MHRD Page 1 of 26 NPTEL – Chemistry – Principles of Organic Synthesis In some circumstances, carboxylic acid is used as an acylating agent in the presence of a proton acid. HO OH O 2 PhOH, H2SO4 O O -H2O O O Phenolphthalein Indicator Intramolecular reactions are of particular value to construct cyclic systems. These reactions are usually carried out using dibasic acid anhydrides. For example, the synthesis -tetralone has been accomplished from benzene and succinic anhydride using AlCl3 in 80% yield. O O OH OH AlCl3 reduction + O O O O SOCl2 Cl AlCl3 O O Joint initiative of IITs and IISc – Funded by MHRD Page 2 of 26 NPTEL – Chemistry – Principles of Organic Synthesis Examples: 5 mol% Tb(OTf)3 CO H 2 PhCl O D.-M. Cui, C. Zhang, M. Kawamura, S.