DOCSLIB.ORG

UNITED STATES PATENT OFFICE COMPLEX QUATERNARY AMMONIUM SALT Herman A

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
UNITED STATES PATENT OFFICE COMPLEX QUATERNARY AMMONIUM SALT Herman A Patented Oct. 28, 1941 2,260,967 UNITED STATES PATENT OFFICE COMPLEX QUATERNARY AMMONIUM SALT Herman A. Bruson, Philadelphia, Pa., assignor to The Resinous Products & Chemical Company, Philadelphia, Pa. No Drawing. Application December 10, 1938, Serial No. 244,923 14 Claims. (CI. 260-404) This invention relates to new quaternary ann plex nitrogenous condensate of the methylol monium salts derived from complex phenolic es forming phenolic body employed for the process, terbases, and is a continuation in part of copend as described above, the present invention is ap ing application Serial No. 240,009, filed on Novem plicable to any monocarboxylic or polycarboxylic ber 12, 1938 now Patent No. 2,218,739 issued Oc acid halide of the aliphatic, aromatic, allicyclic, tober 22, 1940. of heterocyclic series of the formula R(COX), According to this invention, new Substances wherein R is any organic radical, X is halogen, having useful properties are prepared by con-, and n is a small integer. densing any organic acyl halide with a com Typical acylating agents for the purpose are plex nitrogenous inter-condensation product of O acetyl chloride, chloracetyl chloride, propionyl a methylol-forming phenol, formaldehyde, and chloride, isobutyryl chloride, caproyl chloride, 2- . a strongly basic, non-aromatic secondary amine ethylhexoyl chloride, dodecanoyl chloride, oleic to form an ester hydrohalide salt, and Subse acid chloride, palmitic acid chloride, stearoyl quently reacting upon the free ester base de chloride, crotonyl chloride, acrylyl chloride, rived therefrom, with an alkylating or aralkyl 5 methacrylyl chloride, undecenoyl chloride, naph ating agent capable of converting said ester base thenic acid chloride, ricinoleic acid chloride, into a quaternary ammonium salt. phenylacetyl chloride, tetrahydrofuroyl chloride, Nitrogenous phenolic inter-condensation prod linoleic acid chloride, octyloxyacetyl chloride, ucts of a methylol-forming phenol, formaldehyde, licanic acid chloride, cinnamoyl chloride benzoyl and a strongly basic, non-aromatic Secondary 20 chloride, p-nitrobenzoyl chloride, phenoxyacetyl amine of the kind used for the present purpose chloride, campholic acid chloride, abietic acid have been in part disclosed by the applicant in chloride, ox-bromstearoyl chloride, benzoyl-o-ben U. S. Patents Nos. 2,031,557, 2,033,092, 2,036,916, Zoyl chloride, the corresponding acid bromides 2,040,039, 2040,040, and 2,045,517. These may and homologues or substitution products there be oily, Crystalline or even resinous in nature. 25 of or their obvious equivalents. The compounds obtained directly by the reac Typical complex phenolic-formaldehyde-sec tion of organic acyl halides, and these phenolic . Ondary amine condensates which may be em nitrogenous inter-condensates are hydrohalide ployed include the resinous as well as non-resin salts of phenolic esters containing aliphatically ous tertiary nitrogenous condensation products bound tertiary amine groups. From these hy 30 of methylol-forming phenolic compounds with at drohalide salts, the free nitrogenous bases are least molecular equivalents each of formaldehyde obtained by neutralization of the hydrogen halide and of strongly basic, non-aromatic, secondary radical with alkali. These free bases, in turn, amines of the aliphatic, alicyclic, or heterocyclic combine with alkylating or aralkylating agents Series, including amines having from 2 to 18 car to form quaternary ammonium salts which are 35 bon atoms and upwards. Examples of suitable useful as Wetting, cleansing, emulsifying and dis amines are dimethylamine diethylamine, dibutyl persing agents that may be used in bleaching, amine, diamylamine, diallylamine, methyl-do dyeing, mordanting, mothproofing and surface decylamine, methyl-olleyl amine, dicyclohexyl treating fibrous materials, such as cotton, cellu amine, morpholine, piperidine, piperazine, pyr lose, rayon, Wool, silk, paper, feathers, hair and 40 rolidine, diethanolamine, triethylene tetramine, leather. Particularly valuable textile assistants and the like. are obtained when either the acyl halide em The phenols which are reacted with formalde ployed or the nitrogenous phenolic inter-conden hyde and the above amines to furnish the com Sate, or both, contain an aliphatic or alicyclic plex nitrogenous condensate, which is to be con hydrocarbon group of 8 to 18 carbon atoms in 45 densed with the acyl halide, are those aromatic clusive but the new compounds are not confined hydroxy compounds which are capable of form to these substituents. ing methylol derivatives with formaldehyde. When the phenol employed contains nuclear The phenols, in a broad way, belong to the class halogen, cyano, thio, thiocyano, nitro, sulfone, of hydroxy or polyhydroxy aromatic compounds alkoxy, aryloxy, or acylamino groups, particularly 50 of either monocyclic or polycyclic structure which valuable products are obtained which are toxic to contain at least one reactive nuclear position insects and lower forms of animal life, and ortho or para to the phenolic hydroxyl group. which may be employed as insecticidal, fungicidal, The phenols which meet these conditions and and bactericidal agents. are operable in this inter-condensation are termed With due regard to the character of the com "methylol-forming" phenols, 2 2,260,967 . Typical examples of such phenols are: phenol, t The following examples illustrate this inven a- or p-naphthol, o-, m-, p-cresol, xylenol (124, O . and 13,5), the various straight or branched chain alkyl phenols, such as propyl, iso-propyl-, butyl-, Eacample 1 amyl-, hexyl-, heptyl-, octyl-, nonyl-, undecyl-, To a solution of 94 g. of phenol in 125 g. of dodecyl-, tetradecyl-, hexadecyl-, oleyl-, octa 5 aqueous 36% commercial dimethylamine solu decyl-phenois; the cycloalkyl or aralkyl phenols, tion (1 mol) there is added dropwise 100 g. of such as cyclohexyl-, bornyl-, camphyl-, benzyl-, aqueous 30% formaldehyde solution (1 mol) or phenyl-phenols, as well as nuclear alkyl, cy with stirring and the reaction mixture main cloalkyl, aryl, aralkyl, hydroxyl, nitro, acyl, acyl tained at 30° C. by cooling. The mixture is amino, halogen, thio, sulfone, aryloxy or alkoxy 10 allowed to stand 24 hours at 25-30° C. and the derivatives thereof, including guaiacol, resorcinol, lower oil layer drawn off and washed several hydroquinone, pyrocatechol, pyrogallol, p-ben times with water. It is then distilled under re zoyl phenol, p-acetyl-aminophenol, o-, m-, p duced pressure and the fraction boiling at 97 chlorphenol, o-, m-, p-bromphenol, pp'-dihy 103 C./13 mm. collected. It is a pale reddish droxydiphenyl dimethylmethane, p-hydroxy 5 oil containing 8.9% nitrogen by analysis. stearophenone, p-dodecanoylphenol, phenolic To a solution of 45.3 g. of this oil dissolved formaldehyde resins in the 'A' stage and other in 125 cc. of methyl ethyl ketone, there is added phenolic compounds Such as p,p'-dihydroxy dropwise with stirring and cooling to about 20° C. 60 g. of cocoanut oil mixed fatty acid chlo diphenyl sulfoxide, p,p'-dihydroxydiphenyl sul 20 rides (obtained by treating mixed fatty acids of fide, p,p'-dihydroxydiphenyl sulfone, hydroxy cocoanut oil with phosphorus trichloride). The anthracenes, hydroxyphenanthrenes, and the like. clear Solution obtained is then evaporated under The reaction between the acyl halide and the reduced pressure on a steam bath to remove complex nitrogenous condensation product of the solvent. The product obtained is a waxy formaldehyde, secondary amine, and the meth 25 mass which is the hydrochloride of the nitrog ylol-forming phenol may be carried out in the enous phenolic ester of mixed cocoanut oil fatty presence or absence of an inert Organic Solvent. acids. It is mixed with water and the phenolic The chief requirement of the process is that the ester base set free at 10-15° C. by the careful acyl halide and the inter-condensation product addition of aqueous 10% sodium hydroxide solu are mixed in such a way that the reaction be 30 tion till the solution is faintly pink to phenol tween them is controlled. The permissible rate phthalein indicator. The free phenolic ester of addition of one reactant to the other Will de base separates as a pale yellow oil containing pend upon the temperature as well as on the 4.14% nitrogen by analysis. It is soluble in nature of the particular reactants. In general, dilute lactic or acetic acids to give foamy, Soapy there is a wide range of temperatures at which 35 solutions. It is converted into quaternary am the reaction may be carried out, so long as no monium Salts as follows: appreciable amount of insoluble resinous mate (a) Twenty parts of the above free base of rial results. The proportion of acyl halide re the phenolic ester is heated with 7.6 parts of quired is at least one acyl halide group for each benzyl chloride at 90-95 C. for three hours. hydroxyl group to be esterified. As a result of 40 The product obtained is a viscous resin which, the reaction, a product is obtained which is the when dissolved in water, is capable of forming hydrohalide salt of a phenolic tertiary amine, insoluble precipitates with direct dyestuffs con the phenolic hydroxyl of which is esterified by taining sulfonic acid groups and may be used the acyl group. These complex ester salts are therefore for fixing dyestuffs to textile fibers. usually water-soluble compounds, the higher; al 45 It may also be used to give rayon a soft, Supple kylated members of which in aqueous solution feel, and for "animalizing' cotton or rayon fibers foam when shaken and show typical soap-like so that they will take the usual silk dyestuffs. properties. Upon neutralization with a strong (b) By using 10 parts of diethyl sulfate in alkali hydroxide, the salt-forming radical is re place of the benzyl chloride as in (a) above, moved and the free acylated complex phenolic 50 the corresponding quaternary ammonium sul bases are formed. These ester bases can, in the furic ester is obtained as a pale yellow oil. It case of the lower members, be distilled under dissolves in water to give a foamy solution useful reduced pressure without decomposition.
Load more

Recommended publications
  • Organic Chemistry
    Wisebridge Learning Systems Organic Chemistry Reaction Mechanisms Pocket-Book WLS www.wisebridgelearning.com © 2006 J S Wetzel LEARNING STRATEGIES CONTENTS ● The key to building intuition is to develop the habit ALKANES of asking how each particular mechanism reflects Thermal Cracking - Pyrolysis . 1 general principles. Look for the concepts behind Combustion . 1 the chemistry to make organic chemistry more co- Free Radical Halogenation. 2 herent and rewarding. ALKENES Electrophilic Addition of HX to Alkenes . 3 ● Acid Catalyzed Hydration of Alkenes . 4 Exothermic reactions tend to follow pathways Electrophilic Addition of Halogens to Alkenes . 5 where like charges can separate or where un- Halohydrin Formation . 6 like charges can come together. When reading Free Radical Addition of HX to Alkenes . 7 organic chemistry mechanisms, keep the elec- Catalytic Hydrogenation of Alkenes. 8 tronegativities of the elements and their valence Oxidation of Alkenes to Vicinal Diols. 9 electron configurations always in your mind. Try Oxidative Cleavage of Alkenes . 10 to nterpret electron movement in terms of energy Ozonolysis of Alkenes . 10 Allylic Halogenation . 11 to make the reactions easier to understand and Oxymercuration-Demercuration . 13 remember. Hydroboration of Alkenes . 14 ALKYNES ● For MCAT preparation, pay special attention to Electrophilic Addition of HX to Alkynes . 15 Hydration of Alkynes. 15 reactions where the product hinges on regio- Free Radical Addition of HX to Alkynes . 16 and stereo-selectivity and reactions involving Electrophilic Halogenation of Alkynes. 16 resonant intermediates, which are special favor- Hydroboration of Alkynes . 17 ites of the test-writers. Catalytic Hydrogenation of Alkynes. 17 Reduction of Alkynes with Alkali Metal/Ammonia . 18 Formation and Use of Acetylide Anion Nucleophiles .
    [Show full text]
  • Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides
    Proceedings of the Iowa Academy of Science Volume 61 Annual Issue Article 26 1954 Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides B. R. Bluestein Coe College Albert Hybl Coe College Yoshimi Al Nishioka Coe College Let us know how access to this document benefits ouy Copyright ©1954 Iowa Academy of Science, Inc. Follow this and additional works at: https://scholarworks.uni.edu/pias Recommended Citation Bluestein, B. R.; Hybl, Albert; and Nishioka, Yoshimi Al (1954) "Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides," Proceedings of the Iowa Academy of Science, 61(1), 225-232. Available at: https://scholarworks.uni.edu/pias/vol61/iss1/26 This Research is brought to you for free and open access by the Iowa Academy of Science at UNI ScholarWorks. It has been accepted for inclusion in Proceedings of the Iowa Academy of Science by an authorized editor of UNI ScholarWorks. For more information, please contact [email protected]. Bluestein et al.: Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlor Reaction Kinetics of the Alcoholysis of Substituted Benzoyl Chlorides By B. R. BLUESTEIN, ALBERT HYBL* AND YosHIMI AL NISHIOKA INTRODUCTION The reaction kinetics of the alcoholysis of substituted benzoyl chlorides was studied. The mechanism of the alcoholysis reaction, which is most generally accepted ( 1), shows that the overall re­ action should be second-order and that the reaction should be first-order with respect to the acid chloride and first-order with respect to the alcohol. This rate study was carried out using a large excess of alcohol as the solvent, thus obtaining pseudo-first order rate constants, first-order with respect to the acid chloride only.
    [Show full text]
  • Chip Incompatibility Filters
    ChIP Incompatibility Filters Filter Name Type Description includes carboxylic acid halides and >1 acyl halide and related SMARTS derivatives like chloroformates, carbamoyl- , imidoyl halides, etc. >1 aldehyde SMARTS R no heteroatom no isocyanate, ketene, etc. >1 alkyl bromide / iodide SMARTS no acyl halide or related or vinyl halide >1 amine aromatic primary SMARTS aromatic carbon bound to N, N not charged >1 amines (aromatic/aliphatic, primary no amide, enamine, etc., no heteroatom SMARTS or secondary) bound to N, N not charged no amide, enamine, etc, no heteroatom >1 amines nucleophilic (aliphatic SMARTS bound to N, no aromatic carbon bound to primary or secondary) N, N not charged >1 aryl bromide / iodide SMARTS any aryl bromide / iodide >1 aryl halide SMARTS any aryl halide any boronic acid derivative, aromatic or >1 boronic acid derivative SMARTS aliphatic >1 carbonyl acid SMARTS any carboxylic or carbamic acid, etc. >1 carboxylic acid anhydrides SMARTS carbon must be bound to carbonyl no heteroatom bound to carbonyl or >1 carboxylic acid ester SMARTS oxygen, no acid, no anydride, etc >1 isocyanate / isothiocyanate SMARTS no restrictions to nitrogen substituents R no heteroatom, no isocyanate, ketene, >1 ketone or aldehyde SMARTS etc. >1 NH any SMARTS R can be anything >1 thioamide and related (any) SMARTS any substitution >1 thiol and related (nucleophic) SMARTS any SH or negative S >2 NH any SMARTS R can be anything acidic compounds I combination sulfonyl acids and carboxylic acids anhydrides, bicarbonates, thio and imino acyl anhydrides and derivatives SMARTS derivatives, etc. includes carboxylic acid halides and acyl halide and related SMARTS derivatives like chloroformates, carbamoyl- , imidoyl halides, etc.
    [Show full text]
  • 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.
    [Show full text]
  • 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.
    [Show full text]
  • United States Patent Office
    Patented Dec. 23, 1947 2432,991 UNITED STATES PATENT OFFICE ACYLATION OF THOPHENE Howard D. Hartough, Pitman, and John J. Sar della, Woodbury, N. J., assigners to Socony Wacuum Oil Company, incorporated, a corpo ration of New York No Drawing. Application January 8, 1946, Seria No. 642.13 12 Claims, (C. 260-329) 2 This invention relates to a catalytic acylation in carbon disulfide to a suspension of aluminum process for thiophenes and, more particularly, is chloride in the same solvent. If, however, a car directed to a method for acylating thiophene and oon disulfide solution of the acid chloride was its derivatives in the presence of glauconite as a added to a suspension of thiophene and alumi catalyst. r nun chloride, much tar was formed and a low The acylation of thiophene. and thiophene de yield of ketone resulted. The acylation of thio rivatives has previously been carried out employ phene has, accordingly, been an exceedingly dif ing Organic acid anhydrides, acyl halides, and fictly reaction to carry out, the usual acylation acyl nitriles as acylating agents and in the pres catalysts causing excessive resinification of the eace of various catalysts, including aluminun thiophene reactant. The resinification usually chloride, stannic chloride, titanium tetrachloride, occurs before acylation can be effected, and if phosphorus pentoxide and 2-chloronercurithio 'the expected reaction product is formed, it is phene. Other methodis of inaking acylated thio generally only in relatively Small amounts. phene include the dry distillation of calcium It has now been discovered that acylated thio salts of thiophene carboxylic acids and the action s phenes may be obtained in an efficient manner of nitriles on thienyiragnesium iodide.
    [Show full text]
  • 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.
    [Show full text]
  • 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.
    [Show full text]
  • C:\Documents and Settings\Steve Murov\My
    125 Exercise 15 - Preparation of a Key for Reaction-Map of Organic Chemistry (see Appendix C in student manual) Abstract: The Reaction -Map of Organic Chemistry has been designed to give organic chemistry students an overview of most of the reactions needed for the organic chemistry course. The chart has been partially organized according to the periodic table on the horizontal axis and according to carbon oxidation level on the vertical axis. In addition the carboxyls are grouped vertically according to decreasing reactivity and carbon - carbon bond forming reactions are emphasized with bold arrows. The chart provides a study aide for students and should help students develop synthetic routes from one functional group to another. The chart should be especially useful for students studying for the final examination for the two semester organic chemistry course. In addition to the chart, three keys are available that organize the reactions according to mechanism, functional group preparations and functional group reactions. Chemistry can be thought of a search for order in matter and this chart attempts to provide some insight into the order that exists in organic chemistry. Please note, “Supporting information reprinted with permission from J. Chem. Ed. 2007, 84(7), 1224. Copyright 2007 American Chemical Society.” Reaction-Map as a Study Aid At the end of a two semester course in organic chemistry, a student should be able to perform the exercises below. (Note: In addition to the exercises below, a student of organic chemistry should be able to demonstrate competency with spectroscopic, stereochemical and multistep synthetic challenges.) By performing the exercises below should result in the preparation of three keys for the Reaction-Map of Organic Chemistry.
    [Show full text]
  • 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.
    [Show full text]
  • 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.
    [Show full text]
  • Before Radicals Were Free – the Radical Particulier of De Morveau
    Review Before Radicals Were Free – the Radical Particulier of de Morveau Edwin C. Constable * and Catherine E. Housecroft Department of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, Switzerland; [email protected] * Correspondence: [email protected]; Tel.: +41-61-207-1001 Received: 31 March 2020; Accepted: 17 April 2020; Published: 20 April 2020 Abstract: Today, we universally understand radicals to be chemical species with an unpaired electron. It was not always so, and this article traces the evolution of the term radical and in this journey, monitors the development of some of the great theories of organic chemistry. Keywords: radicals; history of chemistry; theory of types; valence; free radicals 1. Introduction The understanding of chemistry is characterized by a precision in language such that a single word or phrase can evoke an entire back-story of understanding and comprehension. When we use the term “transition element”, the listener is drawn into an entire world of memes [1] ranging from the periodic table, colour, synthesis, spectroscopy and magnetism to theory and computational chemistry. Key to this subliminal linking of the word or phrase to the broader context is a defined precision of terminology and a commonality of meaning. This is particularly important in science and chemistry, where the precision of meaning is usually prescribed (or, maybe, proscribed) by international bodies such as the International Union of Pure and Applied Chemistry [2]. Nevertheless, words and concepts can change with time and to understand the language of our discipline is to learn more about the discipline itself. The etymology of chemistry is a complex and rewarding subject which is discussed eloquently and in detail elsewhere [3–5].
    [Show full text]