DOCSLIB.ORG

United States Patent (19) (1) Patent Number: 5,008,396 Krauss (45) Date of Patent: Apr

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
United States Patent (19) (1) Patent Number: 5,008,396 Krauss (45) Date of Patent: Apr United States Patent (19) (1) Patent Number: 5,008,396 Krauss (45) Date of Patent: Apr. 16, 1991 (54) PROCESS FOR THE PREPARATION OF Mechanisms and Structure' 2nd ed. (1977) pp. 5-AMINO-3-CHLOROSULFONYL-1,2,4- 1110-11 11, 1115. TRIAZOLE Primary Examiner-Richard L. Raymond 75 Inventor: Richard C. Krauss, Midland, Mich. Assistant Examiner-Patricia L. Morris 73 Assignee: Dowlanco, Indianapolis, Ind. Attorney, Agent, or Firm-Craig E. Mixan; Ronald G. (21) Appl. No.: 432,289 Brookens (22 Filed: Nov. 6, 1989 57) ABSTRACT (51) Int. Cli............................................ CO7D 249/12 5-Amino-3-chlorosulfonyl-1,2,4-triazole is prepared by (52) U.S. C. .................................................. 548/263.8 the chlor-oxidation of 5-amino-3-mercapto-1,2,4- 58) Field of Search ...................................... 548/263.8 triazole. The process is characterized by the preforma (56) References Cited tion of disulfide from the mercaptan prior to treatment with chlorine. The 5-amino-3-chlorosulfonyl-1,2,4- U.S. PATENT DOCUMENTS triazole reaction mixture can be directly reacted with 4,734,123 3/1988 Monte ..................................... 71/92 substituted anilines to prepare N-(3-(((aryl)amino)sul 4,755,212 7/1988 Kleschick et al. ...................... 71/92 fonyl)-1H-1,2,4-triazol-5-yl)amines which are useful 4,889,553 2/1989 Rowson et al. ......................... 71/92 intermediates for the manufacture of herbicides. OTHER PUBLICATIONS March, "Advanced Organic Chemistry Reactions, 10 Claims, No Drawings 5,008,396 1. 2 PROCESS FOR THE PREPARATION OF H H / / 5-AMINO-3-CHLOROSULFONYL-1,2,4-TRIAZOLE N-N 3Cl2 N - N G) O FIELD OF THE INVENTION - N ^s, --- N ^s, The present invention is directed to a process for the O preparation of 5-amino-3-chlorosulfonyl-1,2,4-triazole (IV) (III) by the chlor-oxidation of 5-amino-3-mercapto-1,2,4- 10 Although the direct chlor-oxidation of 5-amino-3- triazole. More particularly, the present invention is mercapto-1,2,4-triazole to 5-amino-3-chlorosulfonyl 1,2,4-triazole occurs in relatively good yield, the pro directed to a process for accomplishing this conversion cess is plagued by mixing problems associated with which is characterized by the preformation of the corre intractable slurries which complicate scale-up both with sponding disulfide prior to treatment with chlorine. 5 respect to chlorine dispersion and to heat transfer. In addition, the product is contaminated with 3-amino BACKGROUND OF THE INVENTION 1,2,4-triazole (V) Many N-(3-(((aryl)amino)sulfonyl)-1H-1,2,4-triazol 5-yl)amines (I), H 20 / N-N H (I) / N-N - ss, Oi-4 2 25 as a major by-product of the chlor-oxidation process. ANH- N NH2 The discovery of an improved process which would O alleviate the mixing difficulties associated with the in tractable slurries and which would eliminate the forma their preparation, and their value as intermediates in the tion of the major contaminant would be highly desir manufacture of substituted 1,2,4-triazolol,5-alpyrimi 30 able. dine-2-sulfonanilide herbicides (II) SUMMARY OF THE INVENTION The present invention relates to a process for prepar A. (II) 35 ing 5-amino-3-chlorosulfonyl-1,2,4-triazole O NN B a-sh--ra-N- Oi\ N us N - C have been described in U.S. Pat. Nos. 4,734,123 and 4,755,212. Recently, the direct preparation of N-(3- (((aryl)amino)sulfonyl)-1H-1,2,4-triazol-5-yl)amines (I) from 5-amino-3-mercapto-1,2,4-triazole from substituted anilines and from 5-amino-3-chlorosul 45 fonyl-1,2,4-triazole (III) has been reported. H / N-N H / N-N 4 y. in an aqueous acid medium which comprises the consec ArNH2 -- C-5 N NH2 utive steps of: (III) 55 (a) contacting the 5-amino-3-mercapto-1,2,4-triazole with an oxidizing agent to convert it to the correspond H ing disulfide / N - N O as--- N ^n, 60 h N - N O (I) -4 2 S N NH2 2 and The 5-amino-3-chlorosulfonyl-1,2,4-triazole (III) is ob 65 tained by treating 5-amino-3-mercapto-1,2,4-triazole (b) contacting the disulfide with chlorine. (IV) with chlorine in an aqueous acid medium until the The disulfide may be preformed from the 5-amino-3- reaction is substantially complete. mercapto-1,2,4-triazole or may be prepared in situ prior 3 5,008,396 to chlorination. Preferably, the two steps are conducted without isolation of the intermediate disulfide. One preferred method for quantitatively converting 5-amino-3-mercapto-1,2,4-triazole to the corresponding disulfide is oxidation with hydrogen peroxide. By pre Aqueous acid is generally employed as the initial forming the disulfide prior to treatment with chlorine, reaction medium. Since the subsequent chlorination the 3-amino-1,2,4-triazole contaminant can be avoided. generates hydrochloric acid, aqueous hydrochloric acid In addition, the 5-amino-3-chlorosulfonyl-1,2,4- is the preferred reaction medium. To keep the reaction triazole reaction mixture can be directly reacted with slurry more tractable, the initial oxidation is carried out substituted anilines to prepare intermediates useful for 10 in aqueous HCl of a concentration between about 15 the manufacture of herbicides. and about 30 weight percent. The use of constant boil ing (6.25N) HCl has been found to be quite suitable for DETAILED DESCRIPTION OF THE this purpose. An amount of aqueous acid containing INVENTION medium is generally employed so that the concentration During the direct chlorination of 5-amino-3-mercap 5 of 5-amino-3-mercapto-1,2,4-triazole (or the corre to-1,2,4-triazole, 3-amino-1,2,4-triazole is observed as sponding disulfide) is about 5 to about 30 weight per the major by-product. The appearance of this highly cent of the total reaction mixture. reduced compound in an oxidation reaction is some Because the reaction mixture is a slurry, agitation is what surprising. It has now been found that 2 equiva important to promote contact of the reagents. lents of 5-amino-3-mercapto-1,2,4-triazole react with 20 The temperature is generally maintained in the range 5-amino-3-chlorosulfonyl-1,2,4-triazole under the reac of about the freezing point of the mixture to about 70 tion conditions to produce 3-amino-1,2,4-triazole and C. It is preferably maintained from about 30 to about the SO2 complex of the disulfide of the mercapto 50° C. triazole. After conversion of the mercaptotriazole to the disul 25 fide is complete, the addition of chlorine is commenced. Again, agitation is important to promote contact of the N - NH N - NH reactants. 2 The temperature is generally maintained in the range -*. N 2n NH2 CSO21. Y, of about the freezing point of the mixture to about 50 30 C. It is preferably maintained at about -10 to about 30° C. and more preferably at about -5 to about 25 C. Aq HCl External cooling is generally employed as the reaction is exothermic. The reaction theoretically requires 2.5 moles of chlo N - NH N-NH 35 rine per mole of disulfide. Since any excess peroxide present from the in situ preparation of the disulfide - 2-, -, 2n NH2 + consumes chlorine, allowance must be made for provid 2 ing sufficient chlorine to both decompose the peroxide SO2 + HCl and to oxidize the disulfide to the desired chlorosul fonyltriazole. Slight excesses of from 2 to 5 percent are By converting all of the 5-amino-3-mercapto-1,2,4- often employed. Chlorine is usually added until uptake triazole to disulfide prior to treatment with chlorine, the virtually ceases, since the reaction generally takes place product chlorosulfonyltriazole is never coexistent with about as fast as the chlorine can be added. the starting mercaptotriazole and the formation of the Since the reaction generates hydrochloric acid and by-product 3-amino-1,2,4-triazole is precluded. 45 since the hydrochloride salt of the product, 5-amino-3- The disulfide may be preformed or may be prepared chlorosulfonyl-1,2,4-triazole forms an extremely thick in situ from 5-amino-3-mercapto-1,2,4-triazole. The slurry at high acid concentrations, it is beneficial to add conversion of the mercaptan to the disulfide is readily water during the latter stages of the oxidation so as to accomplished with mild oxidizing agents and is most finish the reaction at an acid concentration in the range conveniently performed in situ. Many diverse oxidizing 50 of 20-30 weight percent HCl. agents can convert thiols to disulfides, including, for In a typical reaction, 5-amino-3-mercapto-1,2,4- example, iodine, potassium ferricyanide, thallic trifluor triazole, either sieved or milled to promote a free flow oacetate, azobis(N,N-dimethylformamide) and even, in ing slurry, and 6.25N (constant boiling) HCl are some circumstances, just air in the presence of base, but charged to a reaction vessel and vigorously agitated. hydrogen peroxide under acidic conditions is generally 55 Addition of 0.5 equivalents of 30 percent H2O2 at about preferred. Hydrogen peroxide concentrations of from 3 50 C. and at a rate consistent with heat removal pro to 70 percent can be employed. In general, hydrogen duces the disulfide quantitatively and nearly instanta peroxide concentrations of 10 to 50 percent are pre neously. Upon completion of the peroxide addition, the ferred. The use of 30 percent hydrogen peroxide is most flowable slurry of the disulfide is cooled below 5 C.
Load more

Recommended publications
  • INDEX to PESTICIDE TYPES and FAMILIES and PART 180 TOLERANCE INFORMATION of PESTICIDE CHEMICALS in FOOD and FEED COMMODITIES
    US Environmental Protection Agency Office of Pesticide Programs INDEX to PESTICIDE TYPES and FAMILIES and PART 180 TOLERANCE INFORMATION of PESTICIDE CHEMICALS in FOOD and FEED COMMODITIES Note: Pesticide tolerance information is updated in the Code of Federal Regulations on a weekly basis. EPA plans to update these indexes biannually. These indexes are current as of the date indicated in the pdf file. For the latest information on pesticide tolerances, please check the electronic Code of Federal Regulations (eCFR) at http://www.access.gpo.gov/nara/cfr/waisidx_07/40cfrv23_07.html 1 40 CFR Type Family Common name CAS Number PC code 180.163 Acaricide bridged diphenyl Dicofol (1,1-Bis(chlorophenyl)-2,2,2-trichloroethanol) 115-32-2 10501 180.198 Acaricide phosphonate Trichlorfon 52-68-6 57901 180.259 Acaricide sulfite ester Propargite 2312-35-8 97601 180.446 Acaricide tetrazine Clofentezine 74115-24-5 125501 180.448 Acaricide thiazolidine Hexythiazox 78587-05-0 128849 180.517 Acaricide phenylpyrazole Fipronil 120068-37-3 129121 180.566 Acaricide pyrazole Fenpyroximate 134098-61-6 129131 180.572 Acaricide carbazate Bifenazate 149877-41-8 586 180.593 Acaricide unclassified Etoxazole 153233-91-1 107091 180.599 Acaricide unclassified Acequinocyl 57960-19-7 6329 180.341 Acaricide, fungicide dinitrophenol Dinocap (2, 4-Dinitro-6-octylphenyl crotonate and 2,6-dinitro-4- 39300-45-3 36001 octylphenyl crotonate} 180.111 Acaricide, insecticide organophosphorus Malathion 121-75-5 57701 180.182 Acaricide, insecticide cyclodiene Endosulfan 115-29-7 79401
    [Show full text]
  • Synthesis and Herbicidal Activity of Sulfonanilides Having a Pyrimidinyl-Containing Group at the 2-Position
    J. Pestic. Sci., 36(2), 212–220 (2011) DOI: 10.1584/jpestics.G10-87 Original Article Synthesis and herbicidal activity of sulfonanilides having a pyrimidinyl-containing group at the 2؅-position Takumi YOSHIMURA,†* Masao NAKATANI,† Sohei ASAKURA,†† Ryo HANAI,†† Manabu HIRAOKA††† and Shigefumi KUWAHARA†††† † K-I Chemical Research Institute Co., Ltd., Iwata, Shizuoka 437–1213, Japan †† Life Science Research Institute, Kumiai Chemical Industry Co., Ltd., Kikugawa, Shizuoka 439–0031, Japan ††† Formulation Technology Institute, Kumiai Chemical Industry Co., Ltd., Shimizu, Shizuoka 424–0053, Japan †††† Graduate School of Agricultural Science, Tohoku University, Aoba-ku, Sendai 981–8555, Japan (Received October 27, 2010; Accepted November 16, 2010) A novel series of sulfonanilides having a pyrimidinyl-containing group at the 2Ј-position was prepared and their herbicidal activities against paddy weeds and selectivity against rice plants were assessed. The structure-activity relationships were probed by substitution of the sulfonyl group, bridge and benzene ring. Among the sulfon- amides, difluoromethyl compound showed comparatively high activity and a broad spectrum to control weeds, including Echinochloa oryzicola. The most preferable substitution position on the benzene ring was in the 6-po- sition and the lower alkyl group showed high herbicidal activity and a broad weed control spectrum, and among the compounds tested, the methoxymethyl group was the best. In respect of the bridge moiety, the hydroxyl group was the best. Among the compounds examined, 2Ј-[(4,6-dimethoxypyrimidin-2-yl)(hydroxy)methyl]-1,1- difluoro-6Ј-(methoxymethyl)methanesulfonanilide, applied at rates between 4 to 16 g a.i./ha, showed excellent pre-emergence herbicidal activity with a broad spectrum against grass, sedge and broadleaf weeds without injury to rice plants.
    [Show full text]
  • IUPAC Provisional Recommendations
    Preferred IUPAC Names 177 Chapter 6, Sect 66 September, 2004 P-66 Amides, imides, hydrazides, nitriles, aldehydes, their chalcogen analogues and derivatives P-66.0 Introduction P-66.1 Amides P-66.2 Imides P-66.3 Hydrazides P-66.4 Amidines, amidrazones, hydrazidines P-66.5 Nitriles P-66.6 Aldehydes P-66.0 Introduction The classes dealt with in this Section have in common the fact that their retained names are derived from those of acids by changing the ‘ic acid’ ending to a class name, for example ‘amide’, ‘ohydrazide’, ‘nitrile’ or ‘aldehyde’. Their systematic names are formed substitutively by the suffix mode using one of two types of suffix, one that includes the carbon atom, for example, ‘carbonitrile’ for −CN, and one that does not, for example, ‘-nitrile’ for −(C)N,. Amidines are named as amides, hydrazidines as hydrazides, and amidrazones as amides or hydrazides. P-66.1 Amides P-66.1.0 Introduction P-66.1.1 Primary amides P-66.1.2 Secondary and tertiary amides P-66.1.3 Chalcogen analogues of amides P-66.1.4 Lactams, lactims, sultams and sultims P-66.1.5 Amides of carbonic, oxalic, cyanic, and polycarbonic acids P-66.1.6 Polyfunctional amides P-66.1.0 Introduction Amides are derivatives of oxoacids in which each hydroxy group has been replaced by an amino or substituted amino group. Chalcogen replacement analogues are called thio-, seleno- and telluroamides. Compounds having one, two or three acyl groups on a single nitrogen atom are generically included and may be designated as primary, secondary and tertiary amides, respectively.
    [Show full text]
  • Standard X-Ray Diffraction Powder Patterns NATIONAL BUREAU of STANDARDS
    NATIONAL INSTITUTE OF STANDARDS & TECHNOLOGY Research Information Center Gaithersburg, MD 20899 NATL INST OF STANDARDS & TECH R.I.C. A1 11 00988606 /NBS monograph QC100 .U556 V25-12;1975 C.1 NBS-PUB-C 19 NBS MONOGRAPH 25 " SECTION 12 U.S. DEPARTMENT OF COMMERCE / National Bureau of Standards Standard X-ray Diffraction Powder Patterns NATIONAL BUREAU OF STANDARDS 1 The National Bureau of Standards was established by an act of Congress March 3, 1901. The Bureau's overall goal is to strengthen and advance the Nation's science and technology and facilitate their effective application for public benefit. To this end, the Bureau conducts research and provides: (1) a basis for the Nation's physical measurement system, (2) scientific and technological services for industry and government, (3) a technical basis for equity in trade, and (4) technical services to promote public safety. The Bureau consists of the Institute for Basic Standards, the Institute for Materials Research, the Institute for Applied Technology, the Institute for Computer Sciences and Technology, and the Office for Information Programs. THE INSTITUTE FOR BASIC STANDARDS provides the central basis within the United States of a complete and consistent system of physical measurement; coordinates that system with measurement systems of other nations; and furnishes essential services leading to accurate and uniform physical measurements throughout the Nation's scientific community, industry, and commerce. The Institute consists of a Center for Radiation Research, an Office of Meas- urement Services and the following divisions: Applied Mathematics — Electricity — Mechanics — Heat — Optical Physics — Nuclear Sciences 2 — Applied Radiation 2 — Quantum Electronics 3 — Electromagnetics 3 — Time 3 3 3 and Frequency — Laboratory Astrophysics — Cryogenics .
    [Show full text]
  • Sulfonanilide Compounds
    ~" ' Nil II II II Nil 1 1 Nil II MINI II J European Patent Office o «i -» © Publication number: 0 31/ 332 B1 Office europeen* des.. brevets , © EUROPEAN PATENT SPECIFICATION © Date of publication of patent specification: 19.05.93 © Int. CI.5: C07C 311/08, C07D 309/12, C07D 211/46, C07C 317/14, © Application number: 88310899.5 C07C 323/18, C07D 335/02, A61K 31/18, A61K 31/33 (5)nn, Date of filing: 18.11.88AOAAOO ' © Sulfonanilide compounds. ® Priority: 19.11.87 JP 292856/87 Urawa-shi(JP) Inventor: Ohuchi, Yutaka @ Date of publication of application: Azumaso 101, 12-11 Oyaba-2-chome 24.05.89 Bulletin 89/21 Urawa-shl(JP) Inventor: Sekluchl, Kazuto © Publication of the grant of the patent: 2716-4-1-204 Oaza Kawarabukl 19.05.93 Bulletin 93/20 Ageo-shl(JP) Inventor: Salto, Shlujl © Designated Contracting States: Pakusaldo Maehara 202 31-12, Torocho- AT BE CH DE FR GB IT LI LU NL SE 1 - chome Omlya-shl(JP) © References cited: Inventor: Hatayama, Katsuo EP-A- 0 093 591 Danchl 35-3 1200-215, Horlsaklcho FR- A- 2 244 473 Omlya- shl(JP) US- A- 3 725 451 Inventor: Sota, Kaoru US-A- 3840 597 1158- 11, Shlmotoml US- A- 3 856 859 Tokorozawa- shl(JP) © Proprietor: TAISHO PHARMACEUTICAL CO. LTD © Representative: Colelro, Raymond et al 00 24- 1 Takata 3- chome Toshlma- ku MEWBURN ELLIS & CO. 2/3 Cursltor Street CM Tokyo 1 71 (JP) London EC4A 1BQ (GB) CO CO @ Inventor: Yoshlkawa, Kensel IV 2878, Dalmon CO Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted.
    [Show full text]
  • Light in Gold Catalysis Sina Witzel, A
    pubs.acs.org/CR Review Light in Gold Catalysis Sina Witzel, A. Stephen K. Hashmi, and Jin Xie* Cite This: https://dx.doi.org/10.1021/acs.chemrev.0c00841 Read Online ACCESS Metrics & More Article Recommendations ABSTRACT: Within the wide family of gold-catalyzed reactions, gold photocatalysis intrinsically features unique elementary steps. When gold catalysis meets photocatalysis, a valence change of the gold center can easily be achieved via electron transfer and radical addition, avoiding the use of stoichiometric sacrificial external oxidants. The excellent compatibility of radicals with gold catalysts opens the door to a series of important organic transformations, including redox-neutral C−C and C−X coupling, C−H activation, and formal radical−radical cross-coupling. The photocatalysis with gold complexes nicely complements the existing photoredox catalysis strategies and also opens a new avenue for gold chemistry. This review covers the achieved transformations for both mononuclear gold(I) catalysts (with and without a photosensitizer) and dinuclear gold(I) photocatalysts. Various fascinating methodologies, their value for organic chemists, and the current mechanistic understanding are discussed. The most recent examples also demonstrate the feasibility of both, mononuclear and dinuclear gold(I) complexes to participate in excited state energy transfer (EnT), rather than electron transfer. The rare applications of gold(III) photocatalysts, both homogeneous and heterogeneous, are also summarized. CONTENTS Authors AZ Notes AZ 1. Introduction A Biographies AZ 1.1. Redox Au(I)/Au(III) Catalysis A Acknowledgments AZ 1.2. Gold Photoredox Catalysis B References AZ 2. Mononuclear Gold(I) Complexes D 2.1. Dual Gold/Photoredox Catalysis D 2.1.1.
    [Show full text]
  • Korea Industrial Tariff Schedule
    DRAFT Subject to Legal Review for Accuracy, Clarity, and Consistency Annex 2-B Industrial Schedule for the Republic of Korea Staging HSK 10 Description Base Rate Category 0301101000 Gold carp 10 C 0301102000 Tropical fish 10 C 0301109000 Other 10 A 0301911000 Salmo trutta, Oncorhynchus mykiss,Oncorhynchus clarki, Oncorhynchus 10 C aguabonita,Oncorhynchus gilae 0301912000 Oncorhynchus apache and Oncorhynchus chrysogaster 10 C 0301921000 Glass eel 10 A 0301929000 Other 30% or I ￦1,908/kg 0301930000 Carp 10 C 0301992000 Yellow tail 10 A 0301994000 Sea-bream 45% or G ￦3,292/kg 0301995000 Conger eel 10 G 0301996000 Sharp toothed eel 10 G 0301997000 Salad eel 10 C 0301998000 Flat fish 10 C 0301999010 True bass 10 G 0301999020 Puffers 10 G 0301999030 Tilapia 10 C 0301999040 Rock fish(including pacific ocean perch) 10 C 0301999050 Sea bass 40 C 0301999060 Mullets 10 C 0301999070 Loaches 10 C 0301999080 Cat fishes 10 A 0301999091 Rock Trout(Hexagrammos spp., Agrammus spp.) 10 C 0301999092 Crusian carp 10 C 0301999093 Salmon 10 A 0301999094 Grass carp 10 A 0301999095 Croakers 36 G 0301999099 Other 10 G 0302111000 Salmo trutta, Oncorhynchus mykiss, Oncorhynchus clarki,Oncorhynchus 20 G aquabonita, Oncorhynchus gilae 0302112000 Oncorhynchus apache and Oncorhynchus chrysogaster 20 A 0302120000 Pacific salmon(Oncorhynchus nerka, Oncorhynchus gorbuscha, Oncorhynchus 20 A keta, Oncorhynchus tschawytscha, Oncorhynchus kisutch, Oncorhynchus masou and Oncorhynchus rhodurus), Atlantic salmon(Salmo salar)and Danube salmon(Hucho hucho) 0302190000 Other 20
    [Show full text]
  • Alkyl Mercury-Induced Toxicity: Multiple Mechanisms of Action
    Alkyl Mercury-Induced Toxicity: Multiple Mechanisms of Action John F. Risher and Pamela Tucker Contents 1 Preface 1.1 How Alkyl Mercury Compounds Get into the Food Web 2 Introduction 3 Methylmercury: Mechanisms of Toxic Action 3.1 Altered Membrane Permeability 3.2 Altered Intracellular Calcium Homeostasis 3.3 Oxidative Stress/Reactive Oxygen Species (ROS) 3.4 Effects on Receptor Binding/Neurotransmitter Release 3.5 Effects Involving Arachidonic Acid 3.6 Effects on Cell Cycle/Cell Division 3.7 Effects on Glutathione (GSH) Activity 3.8 Involvement with Nitric Oxide Synthetase 3.9 Effects on Glial Cells and Glutamate-Glutamine Uptake and Homeostasis 3.10 Other Mechanisms 4 Ethylmercury: Mechanisms of Toxic Action 4.1 Mobilization of Intracellular Ca++ 4.2 Effects on Mitochondria (Membrane and ROS) 4.3 Effects on Arachidonic Acid, Leukotriene Synthesis, and Membrane Integrity 4.4 Effects on Glutathione (GSH) 4.5 Effects on Glutamate Transport 4.6 Effects on Neurotransmitter Availability 5 Summary and Conclusions References J.F. Risher (*) • P. Tucker Division of Toxicology and Human Health Sciences, Agency for Toxic Substances and Disease Registry, 1600 Clifton Road (MS F-58), Atlanta, GA 30333, USA e-mail: [email protected]; [email protected] © Springer International Publishing 2016 Reviews of Environmental Contamination and Toxicology, DOI 10.1007/398_2016_1 J.F. Risher and P. Tucker Abstract There are a number of mechanisms by which alkylmercury compounds cause toxic action in the body. Collectively, published studies reveal that there are some similarities between the mechanisms of the toxic action of the mono-alkyl mercury compounds methylmercury (MeHg) and ethylmercury (EtHg).
    [Show full text]
  • (12) United States Patent (10) Patent No.: US 8,298,992 B2 Stern Et Al
    US008298.992B2 (12) United States Patent (10) Patent No.: US 8,298,992 B2 Stern et al. (45) Date of Patent: Oct. 30, 2012 (54) LOW ODOR, LOW VOLATILITY SOLVENT (56) References Cited FOR AGRICULTURAL CHEMICALS U.S. PATENT DOCUMENTS (75) Inventors: Alan J. Stern, Magnolia, TX (US); 2,778,826 A * 1/1957 Schmidle ...................... 546,192 David Ferguson, Spring, TX (US); 3,074,940 A * 1/1963 Benzing ............. ... 544,178 Howard Stridde, George West, TX (US) 3,342,673 A * 9, 1967 Kaufman et al. ............. 514,443 5,283,229 A 2/1994 Narayanan et al. (73) Assignee: Huntsman Petrochemical LLC. The 2005, 0137091 A1 6, 2005 Herold et al. Woodlands, TX (US) 2005/0215433 A1 9, 2005 Benitez et al. (*) Notice: Subject to any disclaimer, the term of this OTHER PUBLICATIONS patent is extended or adjusted under 35 Masuyama A. Preparation and Surface Active Properties of Terminal U.S.C. 154(b) by 743 days. Amide Type of Alcohol Ethoxylates, Jun. 1989, JAOCS, vol. 66, No. (21) Appl. No.: 12/300,482 6, pppp. 834-837.* * cited by examiner (22) PCT Filed: May 25, 2007 86) PCT No.: PCT/US2007/069793 Primary Examiner — Brian-Yong S Kwon (86) O Assistant Examiner — Andriae M Holt S371 (c)(1), (74) Attorney, Agent, or Firm — Huntsman International (2), (4) Date: Nov. 12, 2008 LLC (87) PCT Pub. No.: WO2007/140332 (57) ABSTRACT PCT Pub. Date: Dec. 6, 2007 A composition includes an agricultural component in an (65) Prior Publication Data amount of at least about 27% by weight and a solvent com position in an amount not greater than about 55% by weight.
    [Show full text]
  • The Preparation of Derivatives Related to Novocain
    University of Louisville ThinkIR: The University of Louisville's Institutional Repository Electronic Theses and Dissertations 1-1927 The preparation of derivatives related to novocain. Helen Peil University of Louisville Follow this and additional works at: https://ir.library.louisville.edu/etd Recommended Citation Peil, Helen, "The preparation of derivatives related to novocain." (1927). Electronic Theses and Dissertations. Paper 1108. https://doi.org/10.18297/etd/1108 This Master's Thesis is brought to you for free and open access by ThinkIR: The University of Louisville's Institutional Repository. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of ThinkIR: The University of Louisville's Institutional Repository. This title appears here courtesy of the author, who has retained all other copyrights. For more information, please contact [email protected]. UNIVERSITY OF LOUISVILLE THE PREPARATION OF DERIVATIVES RELATED TO NOVOCAIN A Dissertation Submitted to the Faculty Of the Graduate School of the College of Liberal Arts In Partial Fulfillment of the Requirements for the Degree Of Master of Science Department of Chemistry By Helen Peil 1927 COYTENTS Part 1 THE PREP RATION OF DERIVA.TIVES REUTED TO NOVOCAIN Page 1 . Introduction 1 2. Experiments 7 3 . Conclusions 17 4. Bibliography 18 Part 2 THE OXIDII. TION OF n- BUTYL THIOCYA.NA TE WITH NITRIC ACID Page 1. Introduction 19 2. Experiments 20 3. Conclusions 28 4. BIbliography 29 INTRODUCTION \ I • 1. PREP/~RA'l'IUN OF DlillIVATIV.I!:S REL.A,Tl.;D TO NOVOCAIN The study of the relationship between chemica.l constitution - snd physiological effect emb~ cas m~ ny very interesting pro­ blems which are, however, frequently difficuJt to solve In the investigation of any dru the first step i s to determine the princ~ple to which the physiological effect is due, and then b:' ane.lysis and synthesis assign t 1e correct chemic" 1 constitution t o this principle.
    [Show full text]
  • Korea Tariff Schedule
    Annex 2-B Tariff Schedule of Korea HSK Description Base rate Staging Category Safeguard 0101101000 Horses 8 D 0101109000 Other 8 D 0101901010 Horses for racing 8 D 0101901090 Other 8 D 0101909000 Other 8 G 0102101000 Milch cows 89.1 A 0102102000 Beef cattle 89.1 A 0102109000 Other 89.1 A 0102901000 Milch cows 40 M 0102902000 Beef cattle 40 H 0102909000 Other 0 K 0103100000 1. Pure-bred breeding animals 18 A 0103910000 Weighing less than 50kg 18 G 0103920000 Weighing 50kg or more 18 G 0104100000 Sheep 8 A 0104201000 Milch goats 8 G 0104209000 Other 8 A 0105111000 Pure-bred breeding animals 9 A 0105119000 Other 9 A 0105120000 B. Turkeys 9 A 0105191000 Ducks 18 G 0105199000 Other 9 A 0105921000 (1) Pure-bred breeding animals 9 A 0105929000 (2)Other 9 A 0105931000 (1) Pure-bred breeding animals 9 A 0105939000 (2) Other 9 A 0105991000 Ducks 18 G 0105992000 Turkeys 9 A 0105999000 Other 9 A 0106110000 Primates 8 A Whales, dolphins and porpoises(mammals 0106120000 of the order Cetacea); manatees and 8A dugongs(mammals of the order Sirenia) 0106191000 Dogs 8 D 0106192000 Rabbits and hares 8 D 0106193000 Deer 8 G 0106194000 Bears 8 A 0106199000 Other 8 D 0106201000 Snakes 8 A 0106202000 Fresh-water tortoises 8 D 0106203000 Turtles 8 A 0106209000 Other 8 A 0106310000 Birds of prey 8 D Psittaciformes (including parrots, 0106320000 8D parakeets, macaws and cockatoos) 0106390000 Other 8 A 0106901000 Amphibia 8 A 0106902010 Honey bees 8 D 0106902090 Other 8 A 0106903010 Lug worms 8 A 0106903020 Yarn earth worms 8 A 0106903090 Other 8 A 0106909000 Other
    [Show full text]
  • Multidirectional Efficacy of Biologically Active Nitro Compounds Included in Medicines
    Review Multidirectional Efficacy of Biologically Active Nitro Compounds Included in Medicines Dorota Olender, Justyna Żwawiak * and Lucjusz Zaprutko Department of Organic Chemistry, Pharmaceutical Faculty, Poznan University of Medical Sciences, Grunwaldzka 6, 60-780 Poznan, Poland; [email protected] (D.O.); [email protected] (L.Z.) * Correspondence: e-mail: [email protected]; Tel.: +48-618-546-678 Received: 8 May 2018; Accepted: 25 May 2018; Published: 29 May 2018 Abstract: The current concept in searching for new bioactive products, including mainly original active substances with potential application in pharmacy and medicine, is based on compounds with a previously determined structure, well-known properties, and biological activity profile. Nowadays, many commonly used drugs originated from natural sources. Moreover, some natural materials have become the source of leading structures for processing further chemical modifications. Many organic compounds with great therapeutic significance have the nitro group in their structure. Very often, nitro compounds are active substances in many well-known preparations belonging to different groups of medicines that are classified according to their pharmacological potencies. Moreover, the nitro group is part of the chemical structure of veterinary drugs. In this review, we describe many bioactive substances with the nitro group, divided into ten categories, including substances with exciting activity and that are currently undergoing clinical trials. Keywords: nitro group; nitro compounds; drugs with the nitro group; veterinary medicines with the nitro group 1. Introduction Drugs exert a local action, or, after being absorbed into the body, a general effect. The chemical structure of the active substance is fundamental because of its therapeutic effect on the body.
    [Show full text]