WO2000034288A1 - Procede permettant l'elimination de cyanide dans les reactions produisant 1,3 diones - Google Patents

Procede permettant l'elimination de cyanide dans les reactions produisant 1,3 diones Download PDF

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Publication number
WO2000034288A1
WO2000034288A1 PCT/US1998/026015 US9826015W WO0034288A1 WO 2000034288 A1 WO2000034288 A1 WO 2000034288A1 US 9826015 W US9826015 W US 9826015W WO 0034288 A1 WO0034288 A1 WO 0034288A1
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Prior art keywords
alkyl
alkoxy
independently
haloalkyl
cyano
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PCT/US1998/026015
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English (en)
Inventor
Steven Arnold Dombchik
Kanu Maganbhai Patel
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E.I. Du Pont De Nemours And Company
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Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to PCT/US1998/026015 priority Critical patent/WO2000034288A1/fr
Priority to AU17167/99A priority patent/AU1716799A/en
Publication of WO2000034288A1 publication Critical patent/WO2000034288A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/10—Spiro-condensed systems

Definitions

  • This invention relates to a process for removing cyanide from reactions producing acylated 1,3-dicarbonyl compounds. More particularly, this invention relates to a process using a peroxide source and a base to remove cyanide from the acylated 1,3-dicarbonyl reaction products produced by the reaction of cyanide with precursors, or the reaction of cyanide moiety containing precursors.
  • 2-(substituted benzoyl)-l,3-cyclohexane diones are known as herbicides. Processes for making such compounds are disclosed in for example, U.S. Patent nos.
  • the process of the present invention involves treatment of acylated 1,3-dicarbonyl products containing cyanide as an impurity with a peroxide source and a base.
  • the product of this process contains less than about 0.1 ppm cyanide or an amount of cyanide which is non-detectable by calorimetric method, as described in Standard Methods for the
  • EP 527,614 describes the removal of cyanide from tricarbonyl compounds using enzymes. Enzyme methods are often expensive and difficult to scale up. Therefore, there is a need for a method for effective removal of cyanide from dione reactions.
  • This invention relates to a process for removing cyanide from a reaction product produced by the rearrangement of an enol ester catalyzed by a cyanide source or the reaction of an acyl-cyanide with a 1,3-diketone, wherein said removal is carried out in the presence of an effective amount of a peroxide source.
  • this invention relates to removal of cyanide where the reaction product has the formula:
  • R 1 is H, C r C 4 alkyl, C r C 4 haloalkyl, C r C 4 alkoxy, C r C 4 haloalkoxy, C r C 6 alkylthio, C ⁇ -Cg haloalkylthio, halogen or cyano;
  • R 2 is C r C alkyl, C r C haloalkyl, C r C 4 alkoxy, C r C 4 haloalkoxy, C r C 6 alkylthio,
  • each R 6 is independently halogen, Cj-C 4 alkoxy, C ⁇ -C haloalkoxy, C j - alkyl,
  • R 6a is halogen, C r C 4 alkoxy, C r C 4 haloalkoxy, C r C 4 haloalkyl, C r C 3 alkoxycarbonyl, S(O) n R 16 , S(O) 2 NR 14 R 15 , nitro or cyano;
  • R 7 is H or M; each R 8 is independently H, C r C3 alkyl, C3-C alkenyl, C 3 -C alkynyl, C1-C3 alkoxy, formyl, C 2 -C 4 alkoxycarbonyl, -CH(C 1 -C 3 alkoxy) 2 , C r C 3 alkylthio, C 2 -C 4 alkylthioalkyl, cyano or halogen; or when two R 8 are attached to the same carbon atom
  • R 10 is phenyl or benzyl, each optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano or nitro;
  • R 1 1 is H, C r C 4 alkyl, C r C 4 haloalkyl, C r C 4 alkoxy, C r C 4 haloalkoxy, halogen, cyano or nitro;
  • R 12 is H or C r C 4 alkyl; each R 14 is independently H or C C 4 alkyl;
  • R 15 is C j -C 4 alkyl or Cj-C 4 alkoxy; or R 14 and R 15 can be taken together as -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH2CH2CH 2 CH 2 ,
  • each R 16 is independently C C 4 alkyl or Cj-C 4 haloalkyl;
  • X 1 and X 2 are independently O or S;
  • M is an alkali or alkaline earth metal; or M is HN(C ⁇ -Cg alkyl) 3 ; m is 0, 1, 2 or 3; each n is independently 0, 1 or 2; p is O, 1, 2, 3 or 4; r is 0, 1, 2, 3 or 4; t is 2 or 3; and w is 0, 1 or 2.
  • this invention relates to removing cyanide from reaction products where the product has the following chemical formula:
  • R 1 is H, C r C 4 alkyl, C r C 4 haloalkyl, C r C 4 alkoxy, C r C 4 haloalkoxy, C r C 6 alkylthio, C ⁇ -Cg haloalkylthio, halogen or cyano;
  • R 2 is C r C 4 alkyl, C r C 4 haloalkyl, Cj-C 4 alkoxy, C r C 4 haloalkoxy, C r C 6 alkylthio,
  • R 10 is H, C r C 4 alkyl, C r C 4 haloalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl or
  • R 10 is phenyl or benzyl, each optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano or nitro;
  • R 1 1 is H, C j -C 4 alkyl, Cj-C haloalkyl, C ⁇ -C 4 alkoxy, Cj-C 4 haloalkoxy, halogen, cyano or nitro;
  • R 12 is H or C r C 4 alkyl; each R 16 is independently C C 4 alkyl or Cj-C 4 haloalkyl;
  • X 1 and X 2 are independently O or S;
  • M is an alkali or alkaline earth metal; or M is HNCC j -C ⁇ alkyl) 3 ; m is 0, 1, 2 or 3; each n is independently 0, 1 or 2; p is 0, 1, 2, 3 or 4; r is 0, 1, 2, 3 or 4; t is 2 or 3; and w is 0, 1 or 2.
  • this invention relates to removing cyanide from reaction products where the product has the chemical formula:
  • This invention relates to a process for removing cyanide from a compound having the formula:
  • each R 6 is independently halogen, C ⁇ -C alkoxy, C r C 4 haloalkoxy, C j - alkyl, C j -C haloalkyl, C 1 -C3 alkoxycarbonyl, S(O) n R 16 , nitro or cyano;
  • R 6a is halogen, alkoxycarbonyl, S(O) n R 16 , S(O) 2 NR 1 Rl5, nitro or cyano;
  • R 15 is C r C 4 alkyl or C r C 4 alkoxy
  • R 14 and R 15 can be taken together as -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 - , -CH 2 CH 2 CH 2 CH 2 - or -CH 2 CH 2 OCH 2 CH 2 -; each R 16 is independently Cj-C 4 alkyl or C C 4 haloalkyl;
  • M is an alkali or alkaline earth metal; or M is HN(C ⁇ -Cg alkyl) 3 ; m is 0, 1, 2 or 3; each n is independently 0, 1 or 2; r is O, 1, 2, 3 or 4.
  • This invention relates to a process for removing cyanide from a compound having the formula
  • each R 6 is independently halogen, C C 4 alkoxy, C j -C 4 haloalkoxy, C j -C 4 alkyl,
  • R 6a is halogen, C j - . alkoxy, C j - haloalkoxy, C C 4 haloalkyl, C1-C3 alkoxycarbonyl, S(O) n R 16 , S(O) 2 NR 14 R 15 , nitro or cyano;
  • R 7 is H or M;
  • R 10 is H, C r C 4 alkyl, C r C 4 haloalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl or
  • R 10 is phenyl or benzyl, each optionally substituted on the phenyl ring with CJ-C3 alkyl, halogen, cyano or nitro;
  • R 1 1 is H, Cj-C 4 alkyl, Cj-C 4 haloalkyl, C C 4 alkoxy, C C 4 haloalkoxy, halogen, cyano or nitro;
  • R 12 is H or C r C 4 alkyl; each R 14 is independently H or C r C 4 alkyl;
  • R 15 is Ci"C 4 alkyl or C C 4 alkoxy; or R 14 and R 15 can be taken together as -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -
  • each R 16 is independently C C 4 alkyl or C C 4 haloalkyl
  • M is an alkali or alkaline earth metal; or M is HN(C ⁇ -C 6 alkyl ⁇ ; m is 0, 1, 2 or 3; each n is independently 0, 1 or 2; r is O, 1, 2, 3 or 4.
  • the process of cyanide removal is carried out under basic conditions with a molar excess of peroxide relative to cyanide
  • the peroxide source is selected from the group consisting of hydrogen peroxide, benzoyl peroxide, peracetic acid, or 1,1,1-trifluoromethyl peracetic acid, and the process is carried out at a temperature of about -10 to 60° C and a pressure of -10 to 10 bar.
  • the process of cyanide removal is carried with a ratio of cyanide to H2O2 of about 1:50 to about 1:200, and in the presence of a solvent selected from the group consisting of methanol, ethanol, acetonitrile, ethyl acetate, toluene and water.
  • This invention relates to a process for removal of cyanide from acylated 1,3-dicarbonyl compounds produced by rearrangement of corresponding enol esters using a cyanide source or by the treatment of an acyl cyanide with a dione.
  • acylated 1,3-dicarbonyl compounds have the general formula 1 ,
  • R 1 is H, C r C 4 alkyl, C r C 4 haloalkyl, C r C 4 alkoxy, C r C 4 haloalkoxy, C r C 6 alkylthio, C 2 -C6 haloalkylthio, halogen or cyano;
  • R 2 is C ⁇ -C 4 alkyl, Cj-C4 haloalkyl, Cj-C alkoxy, Cj- haloalkoxy, C j -C 6 alkylthio,
  • each R 6 is independently halogen, C j - alkoxy, C ⁇ -C 4 haloalkoxy, C j -C 4 alkyl,
  • R 6a is halogen, Cj-Q alkoxy, Cj-C haloalkoxy, Cj-C 4 haloalkyl, C j -C 3 alkoxycarbonyl, S(O) n R 16 , S(O) 2 NR 14 R 15 , nitro or cyano;
  • R 7 is H or M; each R 8 is independently H, C1-C3 alkyl, C3-C 4 alkenyl, C 3 -C 4 alkynyl, C1-C3 alkoxy, formyl, C 2 -C alkoxycarbonyl, -CH(C ] -C3 alkoxy) 2 , C j -C-3 alkylthio, C 2 -C 4 alkylthioalkyl, cyano or halogen; or when two R 8 are attached to the same carbon
  • R 10 is H, C r C 4 alkyl, C r C 4 haloalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl or
  • R 10 is phenyl or benzyl, each optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano or nitro;
  • R 1 1 is H, C C 4 alkyl, Cj-C 4 haloalkyl, C r C alkoxy, C r C 4 haloalkoxy, halogen, cyano or nitro;
  • R 1 is H or C r C 4 alkyl; each R 14 is independently H or C j -C 4 alkyl;
  • R 15 is C j -C 4 alkyl or C j -C alkoxy; or R 14 and R 15 can be taken together as -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -
  • each R 16 is independently C r C 4 alkyl or C r C haloalkyl;
  • X 1 and X 2 are independently O or S;
  • M is an alkali or alkaline earth metal; or M is HN(C ⁇ -C 6 alkyl) 3 ;
  • m is 0, 1, 2 or 3;
  • each n is independently 0, 1 or 2;
  • p is 0, 1, 2, 3 or 4;
  • r is 0, 1, 2, 3 or 4;
  • t is 2 or 3; and
  • w is 0, 1 or 2.
  • a process is provided to remove cyanide impurity from Formula 1 compounds in a suitable solvent.
  • suitable solvent is meant a liquid wherein the reactants can be dissolved or suspended and the process proceeds.
  • suitable solvents include alcohols such as methanol, ethanol, isopropanol and the like, water, acetonitrile, tetrahydrofuran, dioxane, dimethylsulfoxide and NN-dimethyl formamide.
  • the reaction temperature is typically from -25 °C to 100 °C.
  • the reaction times are from 0.5 h to 24 h.
  • the cyanide to peroxide ratio is 1 :500.
  • the pressure is from about -2 to +25 atm.
  • Suitable bases include both organic bases such as trialkylamines and inorganic bases such as alkali metal alkoxides or hydroxides.
  • the trialkylamines preferably have from 1-6, or more preferably 1-4 carbon atoms per alkyl group.
  • a particularly preferable amine is triethylamine.
  • the base is used in the amount of from about 1 to about 2 mol per mol of tricarbonyl compound, preferably 1.25 to 1.5 mol per mol.
  • Suitable peroxide sources include, but are not limited to, aqueous hydrogen peroxide, peracetic acid, trifluoromethyl peracetic acid, m-chloroperbenzoic acid and the like.
  • the preferred ratio of cyanide to peroxide is between 1 :25 to 1 :200.
  • the peroxide should exceed the molar quantity of cyanide by at least 25 fold.
  • the peroxide source is 35% aqueous hydrogen peroxide.
  • a preferred process to remove cyanide from Formula 1 is at temperatures from about -10 to 100 °C, reaction times of 0.5 to 6h, pressures of about one atmosphere, mole ratios of Formula 1 compounds to alkoxide or hydroxide is 1:1, the mole ratio of cyanide to peroxide is 1:200, and the solvent is methanol.
  • Particularly preferred for achieving high yield of cyanide free compounds of Formula 1 is where the reaction temperature is from 0-25 °C, reaction time is 1-2 h, pressure is 1 atmosphere and the solvent is methanol.
  • the alkoxide or hydroxide is typically added to a suspension of Formula 1 in solvent with mixing.
  • the hydrogen peroxide can be added first to the reaction mixture followed by base or the base can be added before the hydrogen peroxide.
  • the preferred process is to add base in a solvent followed by hydrogen peroxide.
  • the reaction temperature is maintained during and after the addition is complete and until the reaction has gone to completion.
  • Isolation of the cyanide free* product of Formula 1 can be accomplished by standard workup procedures such as filtration to obtain salts of compounds of Formula 1.
  • the salt free compounds can be obtained by acidic workup using dilute hydrochloric acid or acetic acid. (*Cyanide determination for filtrate and product is by the calorimetric method previously described, levels under 0.1 ppm or non-detectable are defined as cyanide free.)
  • This invention further pertains to a process for making cyanide free preparations of compounds selected from Formula la (Formula 1 wherein J is J-l)
  • R 1 is H, C r C 4 alkyl, C r C 4 haloalkyl, C r C 4 alkoxy, C r C 4 haloalkoxy, C r C 6 alkylthio, C -Cg haloalkylthio, halogen or cyano;
  • R 2 is C r C alkyl, C r C 4 haloalkyl, C r C 4 alkoxy, C ⁇ -C 4 haloalkoxy, Cj-Cg alkylthio,
  • R 1 and R 2 are taken together to form -X 1 -(CH 2 ) t -X 2 -, optionally substituted with 1-4
  • R 10 is H, C r C 4 alkyl, C r C 4 haloalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl or -CH 2 CH OR 12 ; or R 10 is phenyl or benzyl, each optionally substituted on the phenyl ring with C 1 -C3 alkyl, halogen, cyano or nitro; R 1 1 is H, Ci-C alkyl, C C 4 haloalkyl, C j -C 4 alkoxy, C C 4 haloalkoxy, halogen, cyano or nitro; R 12 is H or C r C 4 alkyl; each R 16 is independently C ⁇ -C 4 alkyl or C1-C 4 haloalkyl;
  • X 1 and X 2 are independently O or S;
  • M is an alkali or alkaline earth metal; or M is HN(C j -C6 alkyl) 3 ; m is 0, 1, 2 or 3; each n is independently 0, 1 or 2; p is 0, 1, 2, 3 or 4; r is 0, 1, 2, 3 or 4; t is 2 or 3; and w is 0, 1 or 2.
  • this invention pertains to removing cyanide from mixtures containing compounds of formula 2a or 2b,
  • This invention further pertains to making cyanide-free preparations of compounds selected from formula lb (formula 1 wherein J is J-2),
  • each R 6 is independently halogen, C C 4 alkoxy, Cj-C 4 haloalkoxy, Cj-C 4 alkyl, C j -C 4 haloalkyl, C 1 -C3 alkoxycarbonyl, S(O) n R 16 , nitro or cyano;
  • R 6a is halogen, C ⁇ -C 4 alkoxy, C r C 4 haloalkoxy, C r C 4 haloalkyl, -C3 alkoxycarbonyl, S(O) n R 16 , S(O) 2 NR 14 R 1 5, nitro or cyano;
  • R 7 is H or M;
  • each R 8 is independently H, C r C 3 alkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, C r C 3 alkoxy, formyl, C 2 -C alkoxycarbonyl, -CH(C ⁇ -C 3 alkoxy) 2 ,
  • R 10 is phenyl or benzyl, each optionally substituted on the phenyl ring with C 1 -C3 alkyl, halogen, cyano or nitro;
  • R 1 1 is H, Cj-C 4 alkyl, C1-C4 haloalkyl, C r C 4 alkoxy, C r C 4 haloalkoxy, halogen, cyano or nitro;
  • R 12 is H or C r C 4 alkyl; each R 14 is independently H or C C 4 alkyl;
  • R 15 is C j -C4 alkyl or C ⁇ -C 4 alkoxy
  • R 14 and R 15 can be taken together as -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -,
  • each R 16 is independently Cj-C alkyl or C C 4 haloalkyl
  • M is an alkali or alkaline earth metal; or M is HN(C ⁇ -C 6 alkyl) 3 ; m is 0, 1, 2 or 3; each n is independently 0, 1 or 2; r is O, 1, 2, 3 or 4. More preferably this invention relates to removal of cyanide from mixtures containing a compound of Formula 3.
  • Free cyanide was determined via a calorimetric method based upon the reaction of chloramine T with any cyanide present to form cyanogen chloride.
  • the cyanogen chloride forms a red-blue color upon addition of a pyridine-barbituric acid reagent.
  • the UV- visible spectra was recorded at or near 582 nm and cyanide content was calculated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé utilisant une source de peroxyde pour éliminer le cyanide dans les produits réactionnels acylés 1,3-dicarbonyles de formule (I) produit par la réaction entre le cyanide et les précurseurs ou la réaction du groupe caractéristique du cyanide contenant des précurseurs. J est (J-1) ou (J-2), Q est (Q-1) ou (Q-2). Toutes les définitions sont celles précisées dans le descriptif.
PCT/US1998/026015 1998-12-08 1998-12-08 Procede permettant l'elimination de cyanide dans les reactions produisant 1,3 diones WO2000034288A1 (fr)

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Application Number Priority Date Filing Date Title
PCT/US1998/026015 WO2000034288A1 (fr) 1998-12-08 1998-12-08 Procede permettant l'elimination de cyanide dans les reactions produisant 1,3 diones
AU17167/99A AU1716799A (en) 1998-12-08 1998-12-08 Process for removal of cyanide from reactions producing 1,3 diones

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PCT/US1998/026015 WO2000034288A1 (fr) 1998-12-08 1998-12-08 Procede permettant l'elimination de cyanide dans les reactions produisant 1,3 diones

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Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3835047A (en) * 1971-02-11 1974-09-10 Ugine Kuhlmann Method for treating solutions containing cyanohydrins
GB1526190A (en) * 1976-04-07 1978-09-27 Erdoelchemie Gmbh Process for removing nitrogen compounds from waste water from the preparation of acrylonitrile
JPS5464672A (en) * 1977-10-29 1979-05-24 Noboru Nakamura Production of raw beanjam not containing cyanic compound from beans containing cyanic compound
US4220529A (en) * 1975-08-22 1980-09-02 Produits Chimiques Ugine Kuhlmann Oxidative purification of water
EP0068458A2 (fr) * 1981-06-29 1983-01-05 Degussa Aktiengesellschaft Procédé pour le traitement par l'hydropéroxyde de courants continus d'eau usée contenant une quantité variable de matières oxydables
US4695673A (en) * 1985-11-20 1987-09-22 Stauffer Chemical Company Process for the production of acylated 1,3-dicarbonyl compounds
US4946981A (en) * 1982-03-25 1990-08-07 Ici Americas Inc. Certain 2-(2-substituted benzoyl)-1,3-cyclohexanediones
EP0398234A1 (fr) * 1989-05-19 1990-11-22 Degussa Aktiengesellschaft Procédé pour éliminer des cyanures d'eaux usées
US5069787A (en) * 1990-02-23 1991-12-03 Geo-Microbial Technologies, Inc. Method and apparatus for removing cyanide from a fluid
US5137642A (en) * 1992-01-21 1992-08-11 Fmc Corporation Detoxification of aqueous cyanide solutions
US5364605A (en) * 1991-06-05 1994-11-15 Fmc Corporation Recovery of cyanide from precious metal tailings
WO1995002615A1 (fr) * 1993-07-12 1995-01-26 Basf Aktiengesellschaft Procede permettant d'eliminer des impuretes renfermant des groupes nitrile contenues dans des polymerisats
WO1995004054A1 (fr) * 1993-08-02 1995-02-09 Idemitsu Kosan Co., Ltd. Derive de pyrazole
WO1996026206A1 (fr) * 1995-02-24 1996-08-29 Basf Aktiengesellschaft Derives de pyrazol-4-yl-benzoyle et leur utilisation comme herbicides
WO1997001550A1 (fr) * 1995-06-29 1997-01-16 E.I. Du Pont De Nemours And Company Cetals et spirocycles herbicides

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3835047A (en) * 1971-02-11 1974-09-10 Ugine Kuhlmann Method for treating solutions containing cyanohydrins
US4220529A (en) * 1975-08-22 1980-09-02 Produits Chimiques Ugine Kuhlmann Oxidative purification of water
GB1526190A (en) * 1976-04-07 1978-09-27 Erdoelchemie Gmbh Process for removing nitrogen compounds from waste water from the preparation of acrylonitrile
JPS5464672A (en) * 1977-10-29 1979-05-24 Noboru Nakamura Production of raw beanjam not containing cyanic compound from beans containing cyanic compound
EP0068458A2 (fr) * 1981-06-29 1983-01-05 Degussa Aktiengesellschaft Procédé pour le traitement par l'hydropéroxyde de courants continus d'eau usée contenant une quantité variable de matières oxydables
US4946981A (en) * 1982-03-25 1990-08-07 Ici Americas Inc. Certain 2-(2-substituted benzoyl)-1,3-cyclohexanediones
US4695673A (en) * 1985-11-20 1987-09-22 Stauffer Chemical Company Process for the production of acylated 1,3-dicarbonyl compounds
EP0398234A1 (fr) * 1989-05-19 1990-11-22 Degussa Aktiengesellschaft Procédé pour éliminer des cyanures d'eaux usées
US5069787A (en) * 1990-02-23 1991-12-03 Geo-Microbial Technologies, Inc. Method and apparatus for removing cyanide from a fluid
US5364605A (en) * 1991-06-05 1994-11-15 Fmc Corporation Recovery of cyanide from precious metal tailings
US5137642A (en) * 1992-01-21 1992-08-11 Fmc Corporation Detoxification of aqueous cyanide solutions
WO1995002615A1 (fr) * 1993-07-12 1995-01-26 Basf Aktiengesellschaft Procede permettant d'eliminer des impuretes renfermant des groupes nitrile contenues dans des polymerisats
WO1995004054A1 (fr) * 1993-08-02 1995-02-09 Idemitsu Kosan Co., Ltd. Derive de pyrazole
WO1996026206A1 (fr) * 1995-02-24 1996-08-29 Basf Aktiengesellschaft Derives de pyrazol-4-yl-benzoyle et leur utilisation comme herbicides
WO1997001550A1 (fr) * 1995-06-29 1997-01-16 E.I. Du Pont De Nemours And Company Cetals et spirocycles herbicides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 7927, Derwent World Patents Index; AN 49822b, XP002111088 *

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