DOCSLIB.ORG

United States Patent 19 (11) 4,183,873 Baxamusa Et Al

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
United States Patent 19 (11) 4,183,873 Baxamusa Et Al United States Patent 19 (11) 4,183,873 Baxamusa et al. (45) "Jan. 15, 1980 (54) LIQUID PHASE FLUORINATION PROCESS Attorney, Agent, or Firm-Peter F. Casella; William J. Crossetta, Jr.; Arthur S. Cookfair 75 Inventors: Yusuf A. Baxamusa, Tonawanda; Stephen Robota, North Tonawanda, 57 ABSTRACT both of N.Y. A process for the preparation of compounds of the 73 Assignee: Hooker Chemicals & Plastics Corp., formula: Niagara Falls, N.Y. *) Notice: The portion of the term of this patent subsequent to Jul. 4, 1995, has been disclaimed. comprises contacting compounds of the formula: 21 Appl. No.: 912,629 22 Filed: Jun. 5, 1978 in the liquid phase, with hydrogen fluoride in the pres ence of molybdenum chloride wherein Related U.S. Application Data Ar is aryl 63 Continuation-in-part of Ser. No. 737,626, Nov. 1, 1976, R is a substituent on the aryl nucleus selected from Pat. No. 4,098,832. the group consisting of aryl, substituted aryl, halo gen, alkyl, alkoxy, substituted alkyl, and substituted (51 int.C. ... C07C 25/14 alkoxy; 52 U.S. C. ................................................. 260/651 F n is 0 to 9; (58) Field of Search..................................... 260/651 F X is halogen atom other than fluorine; w is 0 to 2; 56) References Cited 8 p is 1 to 3; U.S. PATENT DOCUMENTS w' is 1 to 3, and is greater than w; 3,131,226 4/1964 Olstowski et al. ................ 260/653.8 p' is 0 to 2, and is less than p; 3,435,082 3/1969 Ager ............... ... 260/653.8 w--p is 3; 3,859,372 l/1975 Robota ............................. 260/651 F w'--p' is 3; 4,079,089 3/1978 Klauke ............................. 260/651 F Z is 1-10; and 4,079,090 3/1978 Bittner et al. ................... 260/651 F 4,093,669 6/1978 Klaukeet al. .................... 260/651 F the maximum value of n--Z is 10. Primary Examiner-C. Davis 16 Claims, No Drawings 4,183,873 2 reaction with hydrogen fluoride, wherein the hydrogen LIQUID PHASE FLUORINATION PROCESS fluoride may be employed in either concentrated or dilute form. It is a still further object to provide a multi This is a continuation-in-part of Ser. No. 737,626, step fluorination process comprising both a vapor phase filed Nov. 1, 1976 and now U.S. Pat. No. 4,098,832. and a liquid phase reaction wherein substantial im BACKGROUND OF THE INVENTION provements in the effective utilization of hydrogen This invention relates to a process for the preparation fluoride reactant are achieved and the amount of hydro of organic fluoride compounds, and in particular, to a gen fluoride waste product is substantially reduced. process for the liquid phase replacement of halogen 10 SUMMARY OF THE INVENTION atoms with fluorine in organic compounds. In accordance with the present invention, there is A variety of fluorination processes are known provided a process for the preparation of fluorinated wherein fluorine replaces substituents of organic com aromatic compounds which comprises reacting a halo pounds, such as halogen atoms, hydrogen atoms, and methyl aromatic compound, wherein the halo is other the like. Such known processes include both vapor 15 phase fluorination reactions and liquid phase fluorina than fluorine, with a fluorinating agent in the presence tion reactions. Typically, such processes involve the of a catalytic amount of molybdenum pentachloride, reaction of an organic halide with hydrogen fluoride, The halomethyl aromatic compound may also contain sometimes in the presence of catalyst, such as antimony stable ring constituents, such as halogen, alkyl, alkoxy, pentachloride, at atmospheric or super-atmospheric substituted alkyl and the like, or other substituents that pressures. Many of the known processes, while suitable will not adversely affect the reaction. for laboratory investigations and experiments, are un In particular, this invention is directed to a process suitable for commercial use for various reasons, such as for the preparation of compounds of the formula: the low purity of product obtained, the high cost of equipment which must be employed, or the need for 25 frequent replacement of the catalyst, due to loss or which comprises contacting compounds of the formula: deactivation, One of the common difficulties encoun tered in vapor phase fluorination reactions results from RhAr(CFX)2 the highly exothermic nature of such reactions. The heat evolved frequently results in a temperature rise 30 in the liquid phase, with hydrogen fluoride in the pres sufficient to cause thermal decomposition of some of the ence of molybdenum pentachloride wherein organic starting materials and a resultant carbonization Ar is aryl; of the catalyst. Furthermore, such vapor phase reac R is a substituent on the aryl nucleus selected from tions commonly require the use of substantial stoichio the group consisting of aryl, substituted aryl, halo metric excess of hydrogen fluoride with the attendant 35 gen, alkyl, alkoxy and substituted alkyl; problem of disposal of the hazardous hydrogen fluoride n is 0 to 9; containing effluent gases. X is halogen atom other than fluorine; Some of the problems associated with vapor phase w is 0 to 2; fluorination processes may be avoided through the use p is 1 to 3; of liquid phase fluorination. However, although atmo 40 w' is 1 to 3, and is greater than w; spheric liquid phase fluorination processes are known p' is 0 to 2, and is less than p; and are used in laboratory preparations, they have not w--p is 3; received widespread acceptance for larger scale com w'+p' is 3; mercial use for various reasons. Heretofore, the most Z is 1-10; and widely used catalyst for liquid phase fluorinations has 45 the maximum value of n--Z is 10. been antimony pentachloride or a mixture of antimony The designation Ar or aryl represent an aromatic pentachloride and antimony trichloride. However, anti structure such as benzene, naphthalene, anthracene and mony chlorides, although highly effective in the cataly the like, preferably of up to 14 carbon atoms. The pre sis of fluorination reactions, are very volatile materials. ferred compounds prepared in accordance with this To avoid the problems associated with the volatility of 50 invention are those of the above formula wherein Ar is antimony chlorides, such fluorination reactions are benzene. often carried out in closed systems under superatmos Among the R substituents encompassed within the pheric pressure, necessitating the use of pressure equip formula shown above, are alkyl radicals of from 1 to ment. In addition it has been found that to obtain desir about 20 carbon atoms, and preferably of from 1 to ably high yields, antimony chloride catalysts must be 55 about 12 carbon atoms, such as methyl, ethyl, propyl, employed in relatively large concentrations. Thus, al butyl, amyl, octyl, decyl, dodecyl, pentadecyl, eicosyl, though antimony chlorides provide an effective catalyst as well as their various isomer forms, such as isopropyl for fluorination reactions, a need exists for a still more and isobutyl, said alkyl radical being a monovalent radi effective catalyst that will overcome the aforemen cal derivable from an aliphatic hydrocarbon alkane by tioned disadvantages. 60 the removal of 1 hydrogen atom; substituted alkyl of It is an object of the present invention to provide an from 1 to about 30 carbon atoms and preferably of from improved process for the liquid phase fluorination of 1 to about 15 carbon atoms, said alkyl group being organic halides. It is a further object to provide an substituted by one or more of aryl, substituted aryl, and improved catalyst for fluorination reactions that is rela the like; alkoxy and substituted alkoxy of from 1 to tively low in cost, of low volatility, and that may be 65 about 20 carbon atoms, and preferably of from 1 to effectively employed at relatively low concentrations. about 12 carbon atoms, such as methoxy, ethoxy, It is a further object to provide an improved process for propoxy, butoxy, pentoxy, octoxy, dodecoxy, pen the fluorination of organic halides in the liquid phase by tadecoxy, eicosoxy, as well as their varius isomer 4,183, 873 3 4. forms, such as iso-propoxy, iso-butoxy, and the like; and halogen. Various other R substituents may be present on the haloalkyl aromatic compound reactants and cor responding products will be obtained. The number (n) 5 of R substituents present on the aromatic nucleus is O Cl O Cln (OCCln from 0 to 9 and preferably from 0 to 5. Where n is more A A A III than 1, the R substituents may be the same or different. The number (Z) substituents on the aromatic nucleus is or mixtures thereof. Similarly, a compound of the above from 1 to 10 and preferably 1 or 2. The maximum num- 0 formula wherein Z is 2, such as, ber of substituents (n+Z) is equal to the total number of positions available on the aromatic nucleus. Thus when CCl3 Ar is benzene, the maximum value of n--Z is 6, and in this instance, for example, if the value of n is 3, the 15 CCl3 maximum value of Z will be 3. Similarly when Ar is Cln naphthalene, the maximum value of n--Z is 8 and when Ar is anthracene the maximum value of n--Z is 10. The wherein n is 0 to 2, is reacted with hydrogen fluoride in preferred compounds which may be fluorinated in ac the presence of molybdenum pentachloride to prepare cordance with this invention are those of the above compounds such as: formula wherein Aris benzene, R is chlorine, n is 0 to 2, and Z is 1 or 2. CFCl2 CF2Cl CFCl2 DESCRIPTION OF PREFERRED 25 EMBODIMENTS CCl3 CCl3 CFCl In a preferred embodiment the present invention is Cl Cln Cln directed to a process for fluorination of compounds of the above formula wherein Aris benzene; Z is 1 or 2; R BI B II B III is a halogen, preferably fluorine, chlorine, or bromine CF CF2Cl CFCl2 and n is 0 to 2.
Load more

Recommended publications
  • Transport of Dangerous Goods
    ST/SG/AC.10/1/Rev.16 (Vol.I) Recommendations on the TRANSPORT OF DANGEROUS GOODS Model Regulations Volume I Sixteenth revised edition UNITED NATIONS New York and Geneva, 2009 NOTE The designations employed and the presentation of the material in this publication do not imply the expression of any opinion whatsoever on the part of the Secretariat of the United Nations concerning the legal status of any country, territory, city or area, or of its authorities, or concerning the delimitation of its frontiers or boundaries. ST/SG/AC.10/1/Rev.16 (Vol.I) Copyright © United Nations, 2009 All rights reserved. No part of this publication may, for sales purposes, be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, electrostatic, magnetic tape, mechanical, photocopying or otherwise, without prior permission in writing from the United Nations. UNITED NATIONS Sales No. E.09.VIII.2 ISBN 978-92-1-139136-7 (complete set of two volumes) ISSN 1014-5753 Volumes I and II not to be sold separately FOREWORD The Recommendations on the Transport of Dangerous Goods are addressed to governments and to the international organizations concerned with safety in the transport of dangerous goods. The first version, prepared by the United Nations Economic and Social Council's Committee of Experts on the Transport of Dangerous Goods, was published in 1956 (ST/ECA/43-E/CN.2/170). In response to developments in technology and the changing needs of users, they have been regularly amended and updated at succeeding sessions of the Committee of Experts pursuant to Resolution 645 G (XXIII) of 26 April 1957 of the Economic and Social Council and subsequent resolutions.
    [Show full text]
  • United States Patent O Fice Patented Dec
    2,816,144 United States Patent O fice Patented Dec. 10, 1957 2. conventional manner and the hydrolysis mass is heated until completely free of any side chain chlorine deriva 2,816,144 tives. This can be determined by the use of alcoholic silver nitrate, for example, which will form a cloudy pre PROBEDUCTION OF RBENZALDEHYDE cipitate upon contact with compounds containing a side Robert W. Harris, Silsborough Township, Somerset chain chlorine group. County, N. S. The benzaldehyde which is obtained upon hydrolysis Separates from the aqueous layer and upon washing and No Drawing. Application August 4, 1955, fractionating yields a substantially pure compound which Seria No. 526,574. 0 is totally free from chlorine. 8 Claims. (C. 260-599) The chlorination of toluene is essentially a step-wise reaction and thus the chlorination can be terminated be fore more than two or three percent is converted to the The present invention relates to a process for the pro 5 tri-chloro derivative. This will correspond to a benzal duction of benzaldehyde from toluene. More particu chloride content of no more than about 35%, depending larly, it relates to a process wherein toluene is reacted upon the particular conditions of the reaction, the balance with chlorine and hydrolyzed to produce benzaldehyde being benzyl chloride with a minor amount of unreacted free from chlorine. toluene. Consequently, the reaction is terminated far The chlorination of toluene will result in the introduc 20 short of the maximum formation of benzal chloride so tion of one, two or three chlorine atoms in the methyl that substantially none of the toluene is lost through the side chain.
    [Show full text]
  • Provisional Peer Reviewed Toxicity Values for Benzyl Chloride (Casrn 100-44-7)
    EPA/690/R-08/005F l Final 7-14-2008 Provisional Peer Reviewed Toxicity Values for Benzyl chloride (CASRN 100-44-7) Superfund Health Risk Technical Support Center National Center for Environmental Assessment Office of Research and Development U.S. Environmental Protection Agency Cincinnati, OH 45268 Acronyms and Abbreviations bw body weight cc cubic centimeters CD Caesarean Delivered CERCLA Comprehensive Environmental Response, Compensation and Liability Act of 1980 CNS central nervous system cu.m cubic meter DWEL Drinking Water Equivalent Level FEL frank-effect level FIFRA Federal Insecticide, Fungicide, and Rodenticide Act g grams GI gastrointestinal HEC human equivalent concentration Hgb hemoglobin i.m. intramuscular i.p. intraperitoneal IRIS Integrated Risk Information System IUR inhalation unit risk i.v. intravenous kg kilogram L liter LEL lowest-effect level LOAEL lowest-observed-adverse-effect level LOAEL(ADJ) LOAEL adjusted to continuous exposure duration LOAEL(HEC) LOAEL adjusted for dosimetric differences across species to a human m meter MCL maximum contaminant level MCLG maximum contaminant level goal MF modifying factor mg milligram mg/kg milligrams per kilogram mg/L milligrams per liter MRL minimal risk level MTD maximum tolerated dose MTL median threshold limit NAAQS National Ambient Air Quality Standards NOAEL no-observed-adverse-effect level NOAEL(ADJ) NOAEL adjusted to continuous exposure duration NOAEL(HEC) NOAEL adjusted for dosimetric differences across species to a human NOEL no-observed-effect level OSF oral slope
    [Show full text]
  • Roc Profile: Benzotrichloride
    Report on Carcinogens, Fourteenth Edition For Table of Contents, see home page: http://ntp.niehs.nih.gov/go/roc Benzotrichloride Property Information Molecular weight 195.5a CAS No. 98-07-7 Specific gravity 1.38 at 20°C/4°Ca Melting point –5°Ca Reasonably anticipated to be a human carcinogen Boiling point 221°C at 760 mm Hga Log K 2.92a First listed in the Fourth Annual Report on Carcinogens (1985) ow Water solubility 53 mg/L at 5°Cb Also known as 1-(trichloromethyl)benzene, α,α,α-trichlorotoluene, Vapor pressure 0.414 mm Hg at 25°Ca or benzoic trichloride Vapor density relative to air 6.77a Cl Sources: aHSDB 2009, bChemIDplus 2009. C Cl Use Cl Carcinogenicity Benzotrichloride is used extensively as a chemical intermediate in manufacturing processes. Its most important derivative is benzoyl Benzotrichloride is reasonably anticipated to be a human carcino- chloride (IARC 1999). It has also been used as a dye intermediate in gen based on sufficient evidence of carcinogenicity from studies in the preparation of eight dyes and pigments, including five that have experimental animals. been produced in commercial quantities in the United States. In ad- dition, benzotrichloride has been used to make benzotrifluoride and Cancer Studies in Experimental Animals hydroxybenzophenone ultraviolet-light stabilizers for plastics and in Exposure to benzotrichloride by two routes of administration caused the production of ion-exchange resins, pharmaceuticals, and antimi- tumors at several different tissue sites in mice. When administered crobial agents (IARC 1982b). to female mice by stomach tube, benzotrichloride caused cancer of Production the forestomach (squamous-cell carcinoma) and of the lining of the lung (adenocarcinoma).
    [Show full text]
  • Benzotrichloride
    Common Name: BENZOTRICHLORIDE CAS Number: 98-07-7 RTK Substance number: 0212 DOT Number: UN 2226 Date: April 1997 Revision: February 2004 --------------------------------------------------------------------------- --------------------------------------------------------------------------- HAZARD SUMMARY * Benzotrichloride can affect you when breathed in and by * If you think you are experiencing any work-related health passing through your skin. problems, see a doctor trained to recognize occupational * Benzotrichloride is a CARCINOGEN--HANDLE WITH diseases. Take this Fact Sheet with you. EXTREME CAUTION. * Benzotrichloride is a CORROSIVE CHEMICAL and WORKPLACE EXPOSURE LIMITS contact can cause severe skin burns. ACGIH: The recommended airborne exposure limit is * Breathing Benzotrichloride vapor can irritate the nose, 0.1 ppm, which should not be exceeded at any throat and lungs causing coughing, wheezing and/or time. shortness of breath. * Repeated exposure may affect the nervous system causing * Benzotrichloride is a PROBABLE CARCINOGEN in weakness, fatigue, headache, irritability, sleeplessness and humans. There may be no safe level of exposure to a loss of appetite. carcinogen, so all contact should be reduced to the lowest * Benzotrichloride may affect the liver, kidneys and thyroid possible level. gland. * It should be recognized that Benzotrichloride can be absorbed through your skin, thereby increasing your IDENTIFICATION exposure. Benzotrichloride is a colorless to yellow liquid which fumes when exposed to air. It is used to make dyes and other WAYS OF REDUCING EXPOSURE chemicals. * Enclose operations and use local exhaust ventilation at the site of chemical release. If local exhaust ventilation or REASON FOR CITATION enclosure is not used, respirators should be worn. * Benzotrichloride is on the Hazardous Substance List * A regulated, marked area should be established where because it is cited by ACGIH, DOT, NTP, DEP, IARC, Benzotrichloride is handled, used, or stored.
    [Show full text]
  • Benzyl Chloride)
    Screening Assessment for the Challenge Benzene, (chloromethyl)- (Benzyl chloride) Chemical Abstracts Service Registry Number 100-44-7 Environment Canada Health Canada November 2009 Screening Assessment CAS RN 100-44-7 Synopsis Pursuant to section 74 of the Canadian Environmental Protection Act, 1999 (CEPA 1999), the Ministers of the Environment and of Health have conducted a screening assessment of benzene, (chloromethyl)-, also known as benzyl chloride, Chemical Abstracts Service Registry Number 100-44-7. This substance was identified in the categorization of the Domestic Substances List (DSL) as a high priority for action under the Challenge. Benzyl chloride was identified as presenting greatest potential for exposure of individuals in Canada and had been classified by other agencies on the basis of carcinogenicity and genotoxicity. Although the substance met the categorization criteria for persistence, it did not meet the criteria for bioaccumulation potential or inherent toxicity to aquatic organisms; therefore, the focus of this assessment relates primarily to human health aspects. According to data submitted in response to a Notice issued under section 71 of the Act, no persons in Canada reported manufacturing benzyl chloride in a quantity greater than or equal to the reporting threshold of 100 kg for the 2006 calendar year. However, it was reported that 100 000–1 000 000 kg were imported into Canada in that year. The response to the section 71 notice indicated that benzyl chloride is mainly used in Canada as a chemical intermediate for the synthesis of quaternary ammonium compounds, which are used primarily as hard surface sanitizers, corrosion inhibitors, fungicides in industrial cleaners and bactericides in surfactants in household and personal care products.
    [Show full text]
  • How to Use This Guide Dielectric Constant Table
    Dielectric Constant Table.xls Dielectric Constant Table Dielectric Constant (k) is a number relating the ability of a material to carry alternating current to the ability of vacuum to carry alternating current. The capacitance created by the presence of the material is directly related to the Dielectric Constant of the material. Alphabetic Table A B C D Knowing the Dielectric Constant (k) of a material is needed to properly E F G H design and apply instruments such as level controls using radar, RF I J K L admittance, or capacitance technologies. There are also analytical M N O P reasons to know the (k) of a material. Q R S T U V W X How to use this guide Y Z # CLIPPER CONTROLS has compiled an extensive list of products with Dielectric Constants. Many of these Dielectric Constants are given at specific temperatures. If your product's temperature is significantly different from those listed there is a good chance that the Dielectric Constant may be different from the values listed. The products in this reference are listed in alphabetical order and are grouped in sections by the first letter of their name. Proper chemical names were used, and any trade names are the trademark of their respective owners. If you know the correct spelling of the name of the product you wish to review then use the "Search" feature on the web browser to locate the name in the list. You may also click on the letter from the alphabetical table to go directly to the beginning of that alphabetic section.
    [Show full text]
  • Federal Register/Vol. 84, No. 230/Friday, November 29, 2019
    Federal Register / Vol. 84, No. 230 / Friday, November 29, 2019 / Proposed Rules 65739 are operated by a government LIBRARY OF CONGRESS 49966 (Sept. 24, 2019). The Office overseeing a population below 50,000. solicited public comments on a broad Of the impacts we estimate accruing U.S. Copyright Office range of subjects concerning the to grantees or eligible entities, all are administration of the new blanket voluntary and related mostly to an 37 CFR Part 210 compulsory license for digital uses of increase in the number of applications [Docket No. 2019–5] musical works that was created by the prepared and submitted annually for MMA, including regulations regarding competitive grant competitions. Music Modernization Act Implementing notices of license, notices of nonblanket Therefore, we do not believe that the Regulations for the Blanket License for activity, usage reports and adjustments, proposed priorities would significantly Digital Uses and Mechanical Licensing information to be included in the impact small entities beyond the Collective: Extension of Comment mechanical licensing collective’s potential for increasing the likelihood of Period database, database usability, their applying for, and receiving, interoperability, and usage restrictions, competitive grants from the Department. AGENCY: U.S. Copyright Office, Library and the handling of confidential of Congress. information. Paperwork Reduction Act ACTION: Notification of inquiry; To ensure that members of the public The proposed priorities do not extension of comment period. have sufficient time to respond, and to contain any information collection ensure that the Office has the benefit of SUMMARY: The U.S. Copyright Office is requirements. a complete record, the Office is extending the deadline for the extending the deadline for the Intergovernmental Review: This submission of written reply comments program is subject to Executive Order submission of written reply comments in response to its September 24, 2019 to no later than 5:00 p.m.
    [Show full text]
  • Α-Chlorinated Toluenes and Benzoyl Chloride
    α-CHLORINATED TOLUENES AND BENZOYL CHLORIDE Data were last reviewed in IARC (1982) and the compounds were classified in IARC Monographs Supplement 7 (1987a). 1. Exposure Data Benzyl chloride 1.1 Chemical and physical data 1.1.1 Nomenclature Chem. Abstr. Serv. Reg. No.: 100-44-7 Chem. Abstr. Name: (Chloromethyl)benzene IUPAC Systematic Name: α-Chlorotoluene Synonyms: Chloromethyl benzene; chlorophenylmethane; α-tolyl chloride 1.1.2 Structural and molecular formulae and relative molecular mass CH2Cl C7H7Cl Relative molecular mass: 126.6 1.1.3 Chemical and physical properties of the pure substance From Lide (1997), unless otherwise specified (a) Description: Colourless liquid with a pungent odour (Lewis, 1993) (b) Boiling-point: 179°C (c) Melting-point: –45°C 20 (d) Density: d10 1.10 (e) Solubility: Insoluble in water; slightly soluble in carbon tetrachloride; miscible with chloroform, diethyl ether and ethanol (Budavari, 1996) (f) Vapour pressure: 133 Pa at 22°C; relative vapour density (air = 1), 4.36 (Ver- schueren, 1996) (g) Stability: Decomposes in hot water to benzyl alcohol (United States Environ- mental Protection Agency, 1980); decomposes rapidly when heated in the pre- sence of iron (Budavari, 1996); combustible (Lewis, 1993) (h) Reactivity: Undergoes reactions both at the side-chain containing the chlorine and at the aromatic ring (Gelfand, 1979) –453– 454 IARC MONOGRAPHS VOLUME 71 (i) Flash-point: 67°C (closed cup); 74°C (open cup) (Lin & Bieron, 1993) (j) Explosive limit: Lower, 1.1% by volume of air (Lin & Bieron, 1993) (k) Octanol/water partition coefficient (P): log P, 2.30 (Verschueren, 1996) (l) Conversion factor: mg/m3 = 5.18 × ppm 1.2 Production and use The chemical processes associated with the manufacture of chlorinated toluenes are summarized in Figure 1.
    [Show full text]
  • The Mechanism of the Hydrolysis of Benzotrichloride
    Title THE MECHANISM OF THE HYDROLYSIS OF BENZOTRICHLORIDE Author(s) TANABE, Kozo; SANO, Tomoko Citation JOURNAL OF THE RESEARCH INSTITUTE FOR CATALYSIS HOKKAIDO UNIVERSITY, 13(2), 110-118 Issue Date 1966-01 Doc URL http://hdl.handle.net/2115/24797 Type bulletin (article) File Information 13(2)_P110-118.pdf Instructions for use Hokkaido University Collection of Scholarly and Academic Papers : HUSCAP J. Res. Inst. Catalysis, Hokkaido Univ., Vol. 13, No.2, pp. 110 to 118 (1965) THE MECHANISM OF THE HYDROLYSIS OF BENZOTRICHLORIDE By Kozo T ANABE*) and Tomoko SANO*) (Received September 30, 1965) Abstract The rate of the hydrolysis of benzotrichloride was determined at 5, 20 and 30°C over a pH range from 0 to 14. The rate was found to be constant independently of pH. It was also found that the nucleophilic reagents such as piperidine and thiophenol have no appreciable effect on the hydrolysis rate and that the rate decreases with increase of chloride ion concentra­ tion in solution. On the basis of these results together with those on the chlorine exchange reported in the foregoing paper, the mechanism of the hydrolysis is discussed. Introduction In the foregoing paper, the chlorine exchange of benzotrichloride with aqueous chloride solution was studied!). The hydrolysis of benzotrichloride is now investigated under the same experimental condition as those in the exchange reaction to elucidate the mechanism. § 1. Experimental The reaction was carried out in the same way as in the case of benzal chloride2l. The purification of benzotrichloride has been described in the foregoing paperll. All other chemicals used were guaranteed reagents of Kanto Chemical Co.
    [Show full text]
  • Particularly Hazardous Substances Human Reproductive Page 1 of 25 March 2011 Carcinogen Hazard
    Particularly Hazardous Substances Human Reproductive Page 1 of 25 March 2011 Carcinogen Hazard CAS Number order Acutely Probable Reactive Female Known Toxic Male CAS Fetal Number Chemical 00–00–1 Nickel compounds 00–00–2 Chromium [VI] Compunds 00–00–3 Cadmium compounds 00–00–4 Chlorophenols (polychlorophenols) 00–00–5 Hexachlorocyclohexanes 00–00–6 Lead compounds, inorganic 00–00–7 Methyl and other organic mercury compounds 00–01–0 Polychlorinated biphenyls (PCBs) ‐ all forms 00–01–1 Organolithium compounds 00–01–3 Botulinum Toxins 00–01–4 Clostridium perfringens, epsilon toxin 00–01–5 Conotoxins 00–01–6 Ricin isolates 00–01–7 Saxitoxins 00–01–8 Staphylococcal enterotoxins 00–01–9 Tetrodotoxins 00–02–0 Tricothecene mycotoxins 50–00–0 Formaldehyde (Formalin) (Paraformaldeyde) 50–06–6 Phenobarbital 50–07–7 Mitomycin C 50–18–0 Cyclophosphamide 50–29–3 DDT [p,p'‐DDT] 50–32–8 Benzo[a]pyrene 50–35–1 Thalidomide 50–55–5 Reserpine 51–21–8 5‐Fluorouracil 51–28–5 Dinitrophenol Particularly Hazardous Substances Human Reproductive Page 2 of 25 March 2011 Carcinogen Hazard CAS Number order Acutely Probable Reactive Female Known Toxic Male CAS Fetal Number Chemical 51–52–5 Propylthiouracil 51–75–2 HN2 (nitrogen mustard‐2) 51–79–6 Ethyl carbamate (Urethane) 52–24–4 Thiotepa 52–67–5 Valine, 3‐mercapto‐, D‐ 53–70–3 Dibenz [a,h]anthracene 53–96–3 2‐acetylaminofluorene 54–62–6 Aminopterin 55–18–5 N‐Nitrosodiethylamine 55–63–0 Nitrogycerine 55–86–7 Nitrogen Mustard Hydrochloride 55–98–1 1,4‐Butanediol dimethanesulfonate (Busulfan; Myleran) 56–04–2 Methylthiouracil
    [Show full text]
  • Thesis-1955D-S632n.Pdf (12.10Mb)
    NEW ADDITION REACTIONS OF ETHYLENE OXIDE By FRANK BIER SLEZAK 11 Bachelor of Science Antioch College Yellow Springs, Ohio 1951 Master of Science Oklahoma Agricultural and Mechanical College Stillwater, Oklahoma 1953 Submitted to the faculty of the Graduate School of the Oklahoma Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of DCX::TOR OF HIILOSOPHY May, 1955 i NEW ADDITION REACTIONS OF ETHYLENE OXIDE Thesis Approved: Thesis Adviser eanofthe Graduate School ;; ACKNOWLEDGEMENT The author is deeply grateful to Dr. o.c. Dermer for his continuous guidance during the course of this work. The author also wishes to thank other members of the Chemistry Department for their suggestions and com= roonts on various phases of the research described herein. This work was made possible by the Chemistry Department i n the form of a Graduate Fellowship and by the Cities Service Research and Develop= ment Company, sponsors of part of the worko TABLE OF CONTENTS Page I. INTRODUCTION 1 II. HISTORICAL 2 Preparation of Ethylene Oxide • 2 Physical Pro~rties of Ethylene Oxide 2 Mechanism of Reaction of Ethylene Oxide 2 Reaction of Ethylene Oxide with Co~pounds Containing Active Hydrogen 4 Reaction of Ethylene Oxide with Compounds Containing No Active Hydrogen • 13 III. EXPERIMENTAL PART A. Preparation of Methoxymethyl Acetate and Methylene Diacetate Introduction •• 18 Procedure and Results • 20 Discussion • 0 26 PART B. Acid-Catalyzed Reactions of Ethylene Oxide with Esters and Acetal Analogs Introduction •• • 27 Procedure and Results. 28 Discussion 56 PART C. Reac.tion of Ethylene Oxide with Com­ pounds Capable of Forming Enolates Introduction.
    [Show full text]