DOCSLIB.ORG

(12) United States Patent (10) Patent No.: US 6,359,162 B1 Wilms (45) Date of Patent: Mar

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
(12) United States Patent (10) Patent No.: US 6,359,162 B1 Wilms (45) Date of Patent: Mar USOO6359162B1 (12) United States Patent (10) Patent No.: US 6,359,162 B1 Wilms (45) Date of Patent: Mar. 19, 2002 (54) METHOD FOR PRODUCING OTHER PUBLICATIONS GLUFOSINATES AND INTERMEDIATE Mundy, Bradford P.; Ellerd, Michael G. “Name Reactions PRODUCTS FOR THE SAME and Reagents in Organic Syntheses'; John Wiley and Sons: New York, 1988: p. 244.* (75) Inventor: Lothar Wilms, Hofheim (DE) Ivan A. Natchev, J. Chem. Soc. Perkin. Trans. 1, pp. (73) Assignee: Hoechst Schering AgrEvo GmbH, 125-131, 1989. Berlin (DE) * cited by examiner (*) Notice: Subject to any disclaimer, the term of this Primary Examiner Fiona T. Powers patent is extended or adjusted under 35 (74) Attorney, Agent, or Firm-Frommer Lawrence & U.S.C. 154(b) by 0 days. Haug LLP (21) Appl. No.: 09/486,031 (57) ABSTRACT (22) PCT Filed: Aug. 8, 1998 Glufosinate and the 2-methyl analog thereof can be prepared in a multi-step Synthesis from methylphosphorus com (86) PCT No.: PCT/EP98/05053 pounds (II) with unsaturated keto compounds (III) via adducts (IV), Subsequent reaction under the conditions of a S371 Date: Feb. 17, 2000 Strecker synthesis and finally hydrolysis of the aminonitrile S 102(e) Date: Feb. 17, 2000 (V): (87) PCT Pub. No.: WO99/09039 Step 1: PCT Pub. Date: Feb. 25, 1999 (30) Foreign Application Priority Data HC-P -- 21 Aug. 20, 1997 (DE) ......................................... 19736 125 (51) Int. Cl." .............................. C07F 9/30; CO7F 9/32; (II) (III) (IV) CO7F 9/6571 (52) U.S. Cl. ......................... 558/82; 558/179; 558/346; 558/386; 562/11; 562/24 Step 2: (58) Field of Search .......................... 558/82, 179,346, 558/386; 562/11, 24 (56) References Cited Adduct IV - He-H3C P N U.S. PATENT DOCUMENTS bi (s NH2 4.264,532 A * 4/1981 Tsuruoka et al. 4,521,348 A 6/1985 Finke et al. (IV) (V) 4,692,541 A 9/1987 Zeiss et al. FOREIGN PATENT DOCUMENTS Step 3: Hydrolysis of (V) to give glufosinate DE 35 08573 A1 9/1986 Depending on proceSS conditions and Substrates, various EP O009 O22 A1 3/1980 compounds can be identified as adducts (IV). EP O O11 245 A1 5/1980 EP O 292 918 A1 11/1988 19 Claims, No Drawings US 6,359,162 B1 1 2 METHOD FOR PRODUCING process allowing the number of ester precursors to be GLUFOSINATES AND INTERMEDIATE reduced and being Suitable for preparing glufosinate and PRODUCTS FOR THE SAME related compounds. The invention relates to the technical field of the pro The invention provides a process for preparing com ceSSes for preparing biologically active compounds and precursors thereof, preferably of crop protection agents, in pounds of the formula (I), particular the herbicide glufosinate, also known as phosphi nothricin. (I) O Glufosinate (see formula (Ia)) is the common name for | R* the active compound (D.L)-2-amino-4-hydroxy(methyl) HC-P phosphinylbutanoic acid, which is commercially available as monoammonium Salt and is used as foliar herbicide (see OHS1(coon DE-A-2717440, U.S. Pat. No. 4,168.963). NH2 15 (Ia) O in which R* is hydrogen or (C-C)-alkyl, preferably H or | H methyl, or Salts thereof with acids or bases, which comprises HC-P OHN1)(-coon a) (Step 1) NH2 reacting a trivalent methylphosphorus compound of the formula (II) with an unsaturated derivative of the The herbicide can be employed for the non-selective formula (III), if appropriate in the presence of a control of weeds in fruit growing and Viticulture, in planta condensing agent or activator and, if appropriate, tion crops, in vegetable growing prior to Sowing or 25 alcohols, to give an adduct (IV), transplanting, prior to direct Sowing of maize or Soya beans, Step 1: and also on uncultivated land, Such as roadsides, industrial terrain and railroad tracks (cf. Z. PflKrankh. PflSchutz, Spe cial Edition IX,431-440, 1981). Also known is the selective use for controlling weeds in crops of useful plants, Such as, inter alia, maize and rapeseed, which have been made resistant by gene technology (cf. EP-A-0242246). A large number of processes for preparing glufosinate (II) (III) (IV) have been disclosed. According to the variant described in EP-A-001 1245 (U.S. Pat. No. 4,521,348), phosphorus 35 containing cyanohydrin derivatives of the formula where in the formulae R" and R independently of one another are halogen, O | R Such as, for example, fluorine, chlorine, bromine or P CN iodine, (C-C)alkoxy with or without Substitution, 40 benzyloxy or phenoxy, which may also be HC1 ORS-nk OR" substituted, or one of the radicals R and R is hydroxyl, and in which R is a hydrocarbon radical Such as alkyl, haloalkyl, R* is as defined in formula (I), cycloalkyl, phenyl or benzyl, with or without Substitution, R 45 b) (Step 2) is hydrogen, alkyl, phenyl or benzyl and R" is hydrogen, the adduct (IV) is, if appropriate after hydrolytic ring acyl, trialkylsilyl or alkylsulfonylalkyl, can be converted opening to aldehydes (R* =H) or ketones (R*=alkyl) into aminonitriles, which in turn can be hydrolyzed to give of the formula (IV) or salt thereof, glufosinate. According to EP-A-001 1245, the preparation of 50 the cyanohydrin derivatives is carried out by reaction of a (IV) monoalkyl methanephosphonate and an acroleincyanohy drin derivative of the formula HC-P O R 55 -k R* OR" in which Z is OH, R' or R, reacted under the in which R" and R" are as defined above. The described 60 conditions of a Strecker Synthesis with ammonia/ proceSS has the disadvantage that the phoshorus-containing ammonium chloride and Sodium cyanide or alterna derivative and its precursors have to be provided in the form tively with mixtures of ammonia and hydrocyanic of esters, whereas in the desired product glufosinate (Ia), the acid or with ammonia and a Salt of hydrocyanic acid, (hydroxy)(methyl)phosphinyl radical is present in hydro Such as, for example, ammonium cyanide or potas lyzed form. 65 sium cyanide, if appropriate in the presence of It is an object of the present invention to provide an ammonium chloride, to give the C-aminonitriles of alternative process to the proceSS described above, Said the formula (V) or a salt thereof, US 6,359,162 B1 4 one or more, preferably 1, 2 or 3, radicals Selected from the group consisting of halogen, alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkyl aminocarbonyl, Substituted amino Such as acylamino, mono or dialkyl-amino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl and haloalkyl, and unsaturated aliphatic radicals corresponding to the abovementioned Saturated hydrocarbon-containing radicals, Such as alkenyl, alkynyl, where in the formulae (IV) and (V) the radical R* is as alkenyloxy, alkynyloxy etc. Preferred radicals having car defined in formula (I) and Z is as defined in formula bon atoms are those having 1 to 4 carbon atoms, in particular (IV) or is OH, and 1 or 2 carbon atoms. Preferred substituents are usually those c) (Step 3) from the group consisting of halogen, for example fluorine the compound of the formula (V) is hydrolyzed under 15 and chlorine, (C-C)alkyl, preferably methyl or ethyl, acidic or basic conditions to give the compound of (C-C)-haloalkyl, preferably trifluoromethyl, (C-C)- the formula (I) or the salt thereof. In the abovementioned formulae and in the formulae used alkoxy, preferably methoxy or ethoxy, (C-C)-haloalkoxy, hereinbelow, the radicals alkyl, alkoxy, haloalkyl, nitro and cyano. Particular preference is given to the Sub haloalkoxy, alkylamino and alkylthio, and also the corre Stituents methyl, methoxy and chlorine. sponding unsaturated radicals and/or radicals which are Phenyl with or without Substitution is preferably phenyl Substituted in the carbon Skeleton, may in each case be which is unsubstituted or mono- or poly Substituted, prefer Straight chain or branched. Unless Specifically indicated, ably up to trisubstituted, by identical or different radicals preference for these radicals is given to the lower carbon Selected from the group consisting of halogen, (C-C)- skeletons, for example those having 1 to 4 carbon atoms and, 25 alkyl, (C-C)-alkoxy, (C-C)-haloalkyl, (C-C)halo in the case of unsaturated groups, those having 2 to 4 carbon alkoxy and nitro, for example o-, m- and p-tolyl, atoms. Alkyl radicals, also in the composed meanings Such dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and as alkoxy, haloalkyl, etc., are, for example, methyl, ethyl, n 4-trifluoro- and -trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3- or i-propyl, n-, i-, t- or 2-butyl, pentyls, heXyls, Such as dichlorophenyl, o-, m- and p-methoxyphenyl. n-hexyl, i-hexyl and 1,3-dimethylbutyl, heptyls, Such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl, cycloalkyl An acyl radical is the radical of an organic acid, for is a carbocyclic Saturated ring System, for example having 3 example the radical of a carboxylic acid, and radicals of to 8 ring atoms, for example cyclopropyl, cyclobutyl, acids derived therefrom, Such as the thiocarboxylic acid, cyclopentyl, cyclohexyl, etc.; alkenyl, alkynyl and cycloalk iminocarboxylic acids with or without N-substitution, or the enyl radicals have the meaning of the possible unsaturated 35 radical of carbonic acid monoesters, carbaminic acids with radicals which correspond to the alkyl or cycloalkyl radicals, or without N-Substitution, Sulfonic acids, Sulfinic acids, alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, phosphonic acids, phosphinic acids. Acyl is, for example, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, formyl, alkylcarbonyl Such as (C-C-alkyl)-carbonyl, methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl; cycloalk phenylcarbonyl, where the phenyl ring may be Substituted, enyl is, for example, cyclopentenyl or cyclohexenyl; alkynyl 40 for example as Shown above for phenyl, or is, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, 1-methylbut-3-yn-1-yl.
Load more

Recommended publications
  • Tutorial 2 FORMULAS, PERCENTAGE COMPOSITION
    T-6 Tutorial 2 FORMULAS, PERCENTAGE COMPOSITION, AND THE MOLE FORMULAS: A chemical formula shows the elemental composition of a substance: the chemical symbols show what elements are present and the numerical subscripts show how many atoms of each element there are in a formula unit. Examples: NaCl: one sodium atom, one chlorine atom in a formula unit CaCl2: one calcium atom, two chlorine atoms in a formula unit Mg3N2: three magnesium atoms, two nitrogen atoms in a formula unit The presence of a metal in a chemical formula indicates an ionic compound, which is composed of positive ions (cations) and negative ions (anions). A formula with only nonmetals indicates a + molecular compound (unless it is an ammonium, NH4 , compound). Only ionic compounds are considered in this Tutorial. There are tables of common ions in your lecture text, p 56 (cations) and p 57 (anions). A combined table of these same ions can be found on the inside back cover of the lecture text. A similar list is on the next page; all formulas needed in this and subsequent Tutorial problems can be written with ions from this list. Writing formulas for ionic compounds is very straightforward: TOTAL POSITIVE CHARGES MUST BE THE SAME AS TOTAL NEGATIVE CHARGES. The formula must be neutral. The positive ion is written first in the formula and the name of the compound is the two ion names. EXAMPLE: Write the formula for potassium chloride. The name tells you there are potassium, K+, and chloride, Cl–, ions. Each potassium ion is +1 and each chloride ion is -1: one of each is needed, and the formula for potassium chloride is KCl.
    [Show full text]
  • (12) Patent Application Publication (10) Pub. No.: US 2011/0027386 A1 Kurihara Et Al
    US 20110027386A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0027386 A1 Kurihara et al. (43) Pub. Date: Feb. 3, 2011 (54) ANTMICROBAL. ZEOLITE AND (30) Foreign Application Priority Data ANTMICROBAL COMPOSITION Feb. 22, 2006 (JP) ................................. 2006-045241 (75) Inventors: Yasuo Kurihara, Nagoya-shi (JP); Kumiko Miyake, Nagoya-shi (JP); Publication Classification Masashi Uchida, Nagoya-shi (JP) (51) Int. Cl. Correspondence Address: AOIN 59/6 (2006.01) NIXON & VANDERHYE, PC COB 39/02 (2006.01) 901 NORTH GLEBE ROAD, 11TH FLOOR AOIP I/00 (2006.01) ARLINGTON, VA 22203 (US) (52) U.S. Cl. .......................... 424/618; 423/701; 423/700 (73) Assignee: Sinanen Zeomic Co., Ltd., (57) ABSTRACT Nagoya-Shi (JP) The present invention relates to antimicrobial zeolite which comprises zeolite whereina hardly soluble zinc salt is formed (21) Appl. No.: 12/923,854 within fine pores present therein and an antimicrobial com position which comprises the foregoing antimicrobial Zeolite (22) Filed: Oct. 12, 2010 in an amount ranging from 0.05 to 80% by mass. The antimi crobial Zeolite according to the present invention can widely Related U.S. Application Data be applied, without causing any color change, even to the (63) Continuation of application No. 1 1/705,460, filed on goods which undergo color changes with the elapse of time Feb. 13, 2007. when the conventional antimicrobial zeolite is added. US 2011/002738.6 A1 Feb. 3, 2011 ANTMICROBAL. ZEOLITE AND 3. An antimicrobial composition comprising the foregoing ANTMICROBAL COMPOSITION antimicrobial zeolite as set forth in the foregoing item 1 or 2 in an amount ranging from 0.05 to 80% by mass.
    [Show full text]
  • Diaminomaleonitrile
    PREBIOLOGICAL PROTEIN SYNTHESIS BY CLIFFORD N. MATTHEWS AND ROBERT E. MOSER CENTRAL RESEARCH DEPARTMENT, MONSANTO COMPANY, ST. LOUIS, MISSOURI Communicated by Charles A. Thomas, July 18, 1966 A major concern of chemical evolution research1 4 is to find an answer to the question: How were proteins originally formed on Earth before the appearance of life? A widely held view stimulated by the speculations of Oparin,5 Haldane,6 Bernal,7 and Urey8 is that the formation of polypeptides occurred via two essential steps, a-amino acid synthesis initiated by the action of natural high-energy sources on the components of a reducing atmosphere, followed by polycondensations in the oceans or on land. The results of a dozen years of simulation experiments1-4 appear to support this view. Experiments in which high-energy radiations were applied to reduced mixtures of gases have yielded many of the 20 a-amino acids commonly found in proteins. The pioneering research of M\iller9 showed that glycine, alanine, aspartic acid, and glutamic acid were among the products obtained by passing electric discharges through a refluxing mixture of hydrogen, methane, ammonia, and water. Exten- sions of these studies by Abelson10 and others'-4 showed that a-amino acid synthesis could be effected by almost any source of high energy so long as the starting mix- ture contained water and was reducing. Since mechanism studies by Miller9 indicated that aldehydes and hydrogen cyanide were transient intermediates during the course of the reaction, it was concluded that the a-amino acids were formed by the well-known Strecker route involving hydrolysis of aminoacetonitriles arising from the interactions of aldehydes, hydrogen cyanide, and ammonia.
    [Show full text]
  • Elemental Impurities: Standards-Setting Record
    Elemental Impurities: Standards-Setting Record December 20, 2012 I. Purpose Current official standards expressed in General Chapter <231> Heavy Metals were last updated in USP 28. This document summarizes the standards-setting activities relative to USP’s new Elemental Impurities (EI) standards, which are designed to replace <231>. The document is divided into four sections: work done prior to 2000, and work in each of the three revision cycles of the 21st century. II. Prior to 2000 Prior to 2000, there were a number of publications which appeared in Pharmacopeial Forum (PF) relating to compendial testing for EI, some of which related to <231> and others of which related to the USP monograph for Magnesium Stearate. These are summarized below. PF Stimuli article [1975] page 861(Attachment 1) This publication made the following recommendations with respect to <231>: a. It is recommended that all articles now tested by Method I be evaluated by the three-tube monitor procedure to confirm the suitability of the method (i.e., no complexation due to the sample, no interfering colors, and no precipitation) or use with each article. Note: It is hoped that each producer of the articles involved will look at his products and report directly to the appropriate Director of Revision (Dr. D. Banes for NF and USP articles; Mr. Duarward Dodgen for FCC articles) concerning the suitability, or lack of suitability, of the method for use with his products. b. It is recommended that the three-tube monitor procedure, with or without the zirconium modification, be given consideration as a replacement for the current Method I procedure.
    [Show full text]
  • A Chemical Study of the Water Extract of Meat
    WILLIAMS Chemical Study of the Water Extract of Meat »**• 5 , J^*—J* . fA fee Chemistry B. S. - v. * 1902 Of w * * * * * * * * * * I > f I * * * * f • " sfglf * * % % .* * * * * H* * f 1 * , , * * * ^ * * * * ^ * ^ ^ ' * * * > ^ + :«t ^ * * , * '/-l^^K' * * * * f ^^^^^^ ^ * * * * * " * * ** * * * * «* i * * * * * * ^ * ^ % ^ m e * * * * * W Criniung anb JTabor. f LIBRARY Illinois. | University of li CLASS. BOOK. volumi;. IBn i ^ Accession No. ' ** ' * S ! H 1 HE* Si * * * * * * * * * .* * * % * * * # * ^ y + ^^^8 1 4 * % * ^ ^ % •- ^ ^ ^» i| **** *** ** ^ * >f t- * + f 4 4* 4v 4k , *fk , • 4 / ^pk 4 s^^^^l^^fc^^lfe7 4 4 4 * * * * i^M^Kv^^r** 4 4» 4 4 * 4 4 ' * JmS^ % 4 * 4 * >ffe^j^|k Us 4 4 , 4* 4 4 4 * >f 4, * *** * || II ^ * * * ^l^i^i^ ^ f ^.4 4. * S^7^fe' * * 4 * 4 fc, 4*-. 4 4- 4 4 * @4 ^444 * 4 «f 4k ' % 4- 4 -4 ^4 ^flPfc ^K; *, 4. 4. 4» * 4 4 *. 4 4 4' 4*' 4* lpl^'4/. vf,:, ... % * 4* 4= 4* 4* 4. * 4 4 . 4- * 4 -4~4^^4%4>4* * * * **** 4 4 4 4 % " 4 4* 4- * * ^ 4 4 4 4 , 4 |^y^p^;>^ 4^.*,- ^,-.4, ,,4 -* ^ 4 4. * * ' * * % I t i 4 # 4- * 4 4 "4 4 * . * ^fV"'^ 1 * * * 4 4- * 4-: * 4* 4 4 % * 4* * * * * 4 4 4 4- . 4 4 * * * 4- 4 % 4 ,". ^H^jw I * 4 * * f * 4 4 4 4 * 4 ; * 4 4^ 4. <** 4,,. 4^ 4 4* 4. 4* 4 4* * 4* 4" ' * 4 * * 4 4. * 4 * * 4 4 * 4 ^ * ^ --4 4v -4 4-4 4 4-4^- % ? 4 4 + ^ 4 4-4 # -A % 4*. 4 4* 4* * . 4- 4 4 4 4 * 4 4'* ^ -4- ^ 4 * * + 4 ^ 4 4 * * *• * ^-^-^^ 4 % * *- * 4* * * ********* % % 4- 4^ 4 4^-^- * * + * ^ % % 4* ^ %^4-%^4.*4 ¥ % * * * * ; 4s '#4^ >|, 4^ 4, : -% * 4, * % 4*4 4^ 4 * 4 ^ 4 4 * 4k 4 4, 4.
    [Show full text]
  • Evidence of Ammonium Salts in Comet 67P As Explanation for the Nitrogen Depletion in Cometary Comae
    Evidence of ammonium salts in comet 67P as explanation for the nitrogen depletion in cometary comae Authors: K. Altwegg1*, H. Balsiger1, J.-J. Berthelier2, C. Briois3, M. Combi4, H. Cottin5, J. De Keyser6, F. Dhooghe6, B. Fiethe7, S. A. Fuselier8,9, T. I. Gombosi4, N. Hänni1, M. Rubin1, M. Schuhmann1, I. Schroeder1, T. Sémon1, S. Wampfler2 Affiliations: 1Physikalisches Institut, University of Bern, Sidlerstr. 5, CH-3012 Bern, Switzerland. 2Center for Space and Habitability, University of Bern, Sidlerstr. 5, CH-3012 Bern, Switzerland. 2LATMOS/IPSL-CNRS-UPMC-UVSQ, 4 Avenue de Neptune F-94100, Saint-Maur, France. 3Laboratoire de Physique et Chimie de l'Environnement et de l'Espace (LPC2E), UMR CNRS 7328 – Université d'Orléans, France 4Department of Climate and Space Sciences and Engineering, University of Michigan, 2455 Hayward, Ann Arbor, MI 48109, USA. 5 LISA, UMR CNRS 7583, Université Paris-Est-Créteil, Université de Paris, Institut Pierre Simon Laplace (IPSL), Créteil, France 6Royal Belgian Institute for Space Aeronomy, BIRA-IASB, Ringlaan 3, B-1180 Brussels, Belgium. 7Institute of Computer and Network Engineering (IDA), TU Braunschweig, Hans-Sommer- Straße 66, D-38106 Braunschweig, Germany. 8Space Science Directorate, Southwest Research Institute, 6220 Culebra Rd., San Antonio, TX 78228, USA. 9Department of Physics and Astronomy, The University of Texas at San Antonio, San Antonio, TX, 78249 Cometary comae are generally depleted in nitrogen. The main carriers for volatile nitrogen in comets are NH3 and HCN. It is known that ammonia readily combines with many acids like e.g. HCN, HNCO, HCOOH, etc. encountered in the interstellar medium as well as in + - cometary ice to form ammonium salts (NH4 X ) at low temperatures.
    [Show full text]
  • Working with Hazardous Chemicals
    A Publication of Reliable Methods for the Preparation of Organic Compounds Working with Hazardous Chemicals The procedures in Organic Syntheses are intended for use only by persons with proper training in experimental organic chemistry. All hazardous materials should be handled using the standard procedures for work with chemicals described in references such as "Prudent Practices in the Laboratory" (The National Academies Press, Washington, D.C., 2011; the full text can be accessed free of charge at http://www.nap.edu/catalog.php?record_id=12654). All chemical waste should be disposed of in accordance with local regulations. For general guidelines for the management of chemical waste, see Chapter 8 of Prudent Practices. In some articles in Organic Syntheses, chemical-specific hazards are highlighted in red “Caution Notes” within a procedure. It is important to recognize that the absence of a caution note does not imply that no significant hazards are associated with the chemicals involved in that procedure. Prior to performing a reaction, a thorough risk assessment should be carried out that includes a review of the potential hazards associated with each chemical and experimental operation on the scale that is planned for the procedure. Guidelines for carrying out a risk assessment and for analyzing the hazards associated with chemicals can be found in Chapter 4 of Prudent Practices. The procedures described in Organic Syntheses are provided as published and are conducted at one's own risk. Organic Syntheses, Inc., its Editors, and its Board of Directors do not warrant or guarantee the safety of individuals using these procedures and hereby disclaim any liability for any injuries or damages claimed to have resulted from or related in any way to the procedures herein.
    [Show full text]
  • Circular of the Bureau of Standards No
    DEPARTMENT OF COMMERCE BUREAU OF STANDARDS George K. Burgess, Director CIRCULAR OF THE BUREAU OF STANDARDS, No. 14S SUMMARY OF TECHNICAL METHODS FOR THE UTILIZATION OF MOLASSES COLLATED FROM PATENT LITERATURE January 28, 1924 PRICE, IS CENTS Sold only by the Superintendent of Documents, Government Ptintine Office Washineton, D. C. WASHINGTON GOVERNMENT PRINTING OFFICE 1924 DEPARTMENT OF COMMERCE BUREAU OF STANDARDS George K. Burgess, Director CIRCULAR OF THE BUREAU OF STANDARDS, No. 145 SUMMARY OF TECHNICAL METHODS FOR THE UTILIZATION OF MOLASSES , COLLATED FROM PATENT LITERATURE January 28, 1924 PRICE, 15 CENTS Sold only by the Superintendent of Documents, Government Printing Office Washington, D. C. WASHINGTON GOVERNMENT PRINTING OFFiCE 1924 SUMMARY OF TECHNICAL METHODS FOR THE UTILI¬ ZATION OF MOLASSES. COLLATED FROM PATENT LITERATURE. ABSTRACT. Economic conditions the world over have made it generally recognized that the future of the American beet-sugar industry is to a great extent dependent on the profitable utilization of the molasses produced. The latter contains numerous val¬ uable substances which have never been successfully recovered outside of Germany. For many years that country has seen fit to veil its developments and discoveries and to maintain the strictest secrecy regarding the operation of its molasses plants. The scientific literature on the subject is practically barren, so far as the actual results achieved in Germany are concerned. In order to carry out the necessary experi¬ mental work for the American industry every possible source of information has been investigated. After a few clues were obtained the United States Patent Office liter¬ ature was searched and eventually over 1,000 German patents on molasses utilization and associated subjects were uncovered.
    [Show full text]
  • 140 ORGANIC ANALYSIS. Elementary Micro-Analysis Of
    140 ABSTEiACTS OF CHEMICAL PAPERR ORGANIC ANALYSIS. Elementary Micro-Analysis of Organic Substances. J. V. Dubsky. (Helv. Chirn. Acta, 1919, 2, 63-75,)-Gas- Volumetric Estimatiort of Nitrogen : The use of Kipp's apparatus for the preparation of air-free carbon dioxide has the draw- back that, owing to the adsorption of the air on the aides of the flask and the marble fragments, tbe gas is unsuitable for the purpose until after one or two days. A more simple and rapid method is to prepare the gas by heating sodium bicarbonate for six to eight minutes in a micro-bicarbonate tube 8 crns. long by 10 to 16 mm. in diameter, cloeed by a cork through which passes a capillary tube. This must fit perfectly into the perforation, or air will be drawn into the - tube. A new form of micro-nitrometer is described. It has a capacity of 1.9 crns., and is sealed by a small amount of mercury, whilst the carbon dioxide is introduoed directly at the base (see diagram). The combustion tube is charged in the manner previously described (Chem. Zeit., 1916, M, 201), but care must be taken that the reduced copper spiral is carefully heated in the Oven to expel the last traces of methyl alcohol. When once reduced, the same spiral may be used for a, series of analyses, provided that tho combustion tube is always allowed to cool in a current of carbon dioxide. It is essential to have a sufficiently long layer of copper oxide in the tube, and for this reason a tube 43 cms.
    [Show full text]
  • Cyanide-Containing Hemoglobin Reagent Composition and Method
    * — llllllllllllllllllllllllllllll OJII Eur°Pean Patent Office <*S Office europeen des brevets (11) EP 0 878 715 A1 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) int. CI.6: G01N 33/72 18.11.1998 Bulletin 1998/47 (21) Application number: 98108384.3 (22) Date of filing: 08.05.1998 (84) Designated Contracting States: (72) Inventor: Malin, Michael J. AT BE CH CY DE DK ES Fl FR GB GR IE IT LI LU Park Ridge, New Jersey 07056 (US) MCNLPTSE Designated Extension States: (74) Representative: AL LT LV MK RO SI Burkert, Frank et al Bayer AG, (30) Priority: 13.05.1997 US 854914 Konzernbereich RP Patente und Lizenzen (71) Applicant: Bayer Corporation 51368 Leverkusen (DE) Pittsburgh, PA 15205-9741 (US) (54) Cyanide-containing hemoglobin reagent composition and method providing acceptable precision, accuracy and freedom from white cell interference on automated hematology analyzers (57) The invention describes an improved stable reagent composition and method for the determination of hemoglobin (Hb) using whole blood samples and automated hematology analyzers, for example, the TECHNICON H*™ series of instruments as sold by the assignee hereof. The Hb reagent comprises an inor- ganic cyanide salt, at least one surfactant and a base and has a final pH of about 10.0 to about 1 1 .2, prefera- bly about 1 0.4 to about 1 1 .2 or less and more preferably about 10.8 to about 11.2 or less. This reagent is intended for use as a universal Hb determination rea- gent for all of the instruments in the aforementioned series and will provide accurate and precise results without accompanying interference from elevated num- bers of white blood cells, especially as found in abnor- mal blood specimens, and without system-to-system variation in the results obtained.
    [Show full text]
  • Method for Inhibiting Fatigue of Aluminum
    Patentamt JEuropaischesJ European Patent Office @ Publication number: 0 042 205 ^ ^ Office europeen des brevets g) EUROPEAN PATENT APPLICATION g) Application number: 81301540.1 © Int. CI.3: C 23 F X/ C 23 F 11/18 g) Date of filing: 08.04.81 (§) Priority: 13.06.80 US 159128 @ Applicant: EARLY CALIFORNIA INDUSTRIES, INC., P.O. Drawer 21 568, Phoenix Arizona 85036 (US) Crouch Robert L 1509 W. ® Date of publication of application : 23.12.81 @ Lnhvent?r Pierson, No. 3, Bulletin 81/51 Phoenix Arizona 85015 (US) @ Representative: Newens, Leonard Eric et al, F.J. CLEVELAND CO. 40/43 Chancery Lane, London @ Designated Contracting States : FR IT WC2A 1 JQ (GB) @ Method for inhibiting fatigue of aluminum. A method of inhibiting the fatigue of aluminum comprising the steps of immersing aluminum in an aque- ous solution of a water soluble cyanide compound at room temperature and continuously maintaining the alu- minum in contact with the aqueous solution. The aque- ous solution is substantially free of chromium. This invention concerns a method for inhibiting fatigue. More particularly, the invention relates to a method for inhibiting the fatigue of aluminum and aluminum alloys. According to a further aspect, the invention relates to inhibiting fatigue corrosion in aluminum and aluminum alloys. A number of aluminum corrosion inhibitors are well known in the art. Chromates, in particular sodium dichromate, have long been recognized as one of the better corrosion inhibitors of aluminum. Another known aluminum corrosion inhibitor is comprised of an aqueous solution of chromic acid or a water soluble chromic salt and, of ferricyanic or ferrocyanic acid or a water soluble salt thereof.
    [Show full text]
  • United States Patent (19) (11) Patent Number: 5,037,977 Tan Et Al
    United States Patent (19) (11) Patent Number: 5,037,977 Tan et al. (45) Date of Patent: Aug. 6, 1991 54 METHOD FOR PRODUCTION OF DIMERIC 4,778,885 10/1988 Vukovic et al..................... 540/478 ALKALOIDS FOREIGN PATENT DOCUMENTS 75 Inventors: Hiroaki Tan; Naoya Sakamoto; 3801450 8/1988 Fed. Rep. of Germany ...... 540/478 Eiichiro Hata; Takeshi Ishitoku; 2544319 10/1984 France ................................ 540/478 Noriaki Kihara, all of Yamaguchi, Japan Primary Examiner-Diana Rivers Attorney, Agent, or Firm-Nixon & Vanderhye 73) Assignee: Mitsui Petrochemical Industries Ltd., Tokyo, Japan (57) ABSTRACT (21) Appl. No.: 390,903 This invention concerns a method for the production of dimeric alkaloids, characterized by reacting of catha 22 Filed: Aug. 8, 1989 ranthine with vindoline in the presence of Fe3+ and (1) (30) Foreign Application Priority Data removing or inactivating the Fe3+ and allowing the Aug. 11, 1988 JP Japan ................................ 63-1988.97 reaction product to react with a reducing agent or (2) Aug. 11, 1988 JP Japan ................................ 63-198898 allowing presence of oxygen and a dicarboxylic acid or a derivative thereof in the reaction system and allowing I51) Int. Cl............................................. C07D 51.9/04 the reaction product to react with a hydride source. (52) U.S. Cl. ....................................... 540/478; 546/51 In accordance with this invention, such dimeric alkaloid 58) Field of Search......................................... 540/478 as vinblastine, leurosidin, and 3',4'-anhydrovinblastine (56) References Cited which are useful as antineoplastic drugs can be pro U.S. PATENT DOCUMENTS duced in high yields. 4,279,817 7/1981 Kutney ................................ 540/478 4,737,586 4/1988 Potier et al.
    [Show full text]