EP1098881A1 - Compos s de pyridine 3-substitu s et synth se apparent e - Google Patents

Compos s de pyridine 3-substitu s et synth se apparent e

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Publication number
EP1098881A1
EP1098881A1 EP99940022A EP99940022A EP1098881A1 EP 1098881 A1 EP1098881 A1 EP 1098881A1 EP 99940022 A EP99940022 A EP 99940022A EP 99940022 A EP99940022 A EP 99940022A EP 1098881 A1 EP1098881 A1 EP 1098881A1
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European Patent Office
Prior art keywords
formula
acid
mmol
salt
solution
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP99940022A
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German (de)
English (en)
Inventor
Dean Kent Hoglen
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Syngenta Participations AG
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Syngenta Participations AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/76—Nitrogen atoms to which a second hetero atom is attached
    • C07D213/77—Hydrazine radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/65—One oxygen atom attached in position 3 or 5

Definitions

  • the present invention relates to 3-substituted and 2,3-disubstituted pyridine compounds which are useful as intermediates in the synthesis of pyridylsulfonylurea herbicides.
  • the invention also relates to arylation of alcohols using a pyridinediazonium salt. More particularly the arylation process of the instant invention relates to the synthesis of 2,3-disubstituted pyridine compounds via anhydrous diazotization of 3- aminopyridines to form a diazonium salt intermediate that is then reacted with the appropriate alcohol to produce the desired product.
  • the invention additionally relates to pyridine-3-diazonium salt intermediates.
  • 2-chloro-3-hydroxypyridine has been prepared by reacting 3-amino-2- chloropyridine with a nitrite in the presence of acid. Schickh et al., Berichte d. D. Chem. GeseUschaft, 1936, Vol. 69, 2593-2605.
  • 3-aminopyridine moieties are not functionally equivalent to 2-aminopyridine moieties when considered in the context of diazotization-dediazotization reactions.
  • the electronic effects and chemistry are completely different for the diazonium salts prepared from 2-aminopyridines as compared to the diazonium salts prepared from 3-aminopyridines.
  • the most relevant difference is that pyridine-2-diazonium salts are very unstable and can not be isolated. See Heterocyclic Compounds, Volume 14, supplement part 3, page 74 (1974) and R.N.Butler, Chemical Reviews, 1975, Volume 75, No. 2, page 250.
  • Ri is a C ⁇ -C 4 haloalkyl and R is H, halogen or C ⁇ -C alkylthio; and acid addition salts thereof.
  • the haloalkyl groups may be branched or unbranched.
  • the halogen(s) of the haloalkyl group and R when halogen, are independently selected from fiuoro, chloro, bromo and iodo.
  • the degree of halogen substitution of Ri may range from monohalogen substitution to polyhalogen substitution wherein all the hydrogens of the alkyl group have been replaced by halogens (e.g. perfluoroalkyl groups).
  • Compounds of formula la constitute preferred embodiment of the invention:
  • Ri is defined as above. Another preferred embodiment of the invention is wherein Ri is selected from the group consisting of -CH 2 CF 3 ⁇ -CH 2 CC1 3 , and -CH 2 CH 2 C1.
  • An ultimately preferred embodiment of the invention is the compound having the formula:
  • a " is a counter-anion derived from an organic acid or inorganic mineral acid, HA; and Rt is defined as above.
  • a ' is preferably an anion of the formula " OSO 2 R 2 (i.e. the conjugate base of a sulfonic acid), wherein R 2 is C C 4 alkyl, phenyl, C7-C10 alkylaryl, or C 5 -C 10 cycloalkyl (preferably methyl); or an anion of the formula " OOC-R 2a (i.e. the conjugate base of a carboxylic acid) wherein R 2a is C C 4 haloalkyl, preferably trifluoromethyl; and t is defined as above.
  • the pyridinediazonium salt of formula II is useful as an intermediate for the preparation of the compounds of formula I.
  • a preferred pyridinediazonium salt is the pyridinediazonium sulfonate salt of formula II' :
  • R 2 and R 4 are defined as above.
  • a preferred feature of the invention is where R 2 is methyl or a 10-camphoryl group (i.e. a pyridinediazonium 10-camphorsulfonate salt).
  • Another aspect of the invention is the product produced from the process of diazotizing a 3-aminopyridine with an alkyl nitrite and acid under substantially anhydrous conditions.
  • the pyridinediazonium salt of formula II or the product from the process of diazotization are both features of the instantly disclosed invention.
  • the scope of the invention as to the diazonium salts and the process of preparing the compound of formula I disclosed herein should not be construed to be limited by any particular chemical theory relating to the complexation, equilibration, reaction or acid-base chemistry of the components used to make the diazonium salt or the final product.
  • Static composition denotes 1) the composition composed of components wherein the components have not substantially changed by virtue of their combination or interaction with other composition components, or 2) the composition that has reacted to a point of relative stasis.
  • “Chemically integrated composition” means a composition that results from any equilibration, complexation, dissociation or other chemical transformation (if any) that may occur after combination of the reagents used to prepare the product composition containing the salts of formula II and prior to ultimate use for the preparation of the compounds of formula I. Therefore, the "chemically integrated composition” of the instant invention by definition encompasses the situation where there is an unchanged “static composition” as well as the equilibrated or semi-equilibrated composition existing at any point between initial creation and ultimate use. In other words, the disclosed invention relating to diazonium salts is not limited to a static composition of chemically unaltered constituent components.
  • the invention also includes the process for obtaining the salts of formula II which are useful as intermediates in the process of preparing the compounds of formula I.
  • the compounds of formula I are prepared by reacting a salt of formula II under substantially anhydrous conditions with an alcohol having the formula RiOH wherein Ri is defined above.
  • a preferred process of preparing the compounds of formula I comprises reacting a 3-aminopyridine with an alkyl nitrite in the presence of acid and a solvent/reagent alcohol that reacts with the diazonium salt intermediate generated in situ thereby forming the desired product without isolating the intermediate salt of formula II. See Schemes I and II below. Scheme I:
  • the single-step or "one-pot" procedure depicted in Schemes I and II may be accomplished by adding the alkyl nitrite, preferably t-butyl nitrite, directly to a hot (i.e. 50°C to 75°C) solution of the appropriate 3-amino-pyridine and from 0.5 to 2 equivalents of acid, preferably one equivalent of acid, preferably methanesulfonic acid, in the desired alcohol RiOH, preferably 2,2,2-trifluoroethanol thereby generating the desired 3- substituted-pyridine product.
  • An excess amount of the alcohol may be used so that it thereby acts additionally as the solvent in the reaction.
  • solvents such as methyl-tertiary-butyl ether (MTBE) or chloroform, either alone or in combination with an alcohol solvent.
  • MTBE methyl-tertiary-butyl ether
  • chloroform a compound formed from a hydrocarbonate
  • the solvent or excess alcohol may be removed by distillation, evaporation, under vacuum or otherwise separated from the product using conventional means known in the art.
  • the two-step procedure depicted in Schemes III and IV may be carried out by dissolving the appropriate 3-aminopyridine in the desired alcohol, RiOH, preferably 2,2,2- trifluoroethanol, in the presence of 0.5 to 2 equivalents acid, preferably one equivalent of acid, preferably methanesulfonic acid.
  • RiOH preferably 2,2,2- trifluoroethanol
  • acid preferably one equivalent of acid, preferably methanesulfonic acid.
  • other solvents such as MTBE or chloroform may also be used alone or in combination with an alcohol solvent.
  • the alkyl nitrite, preferably t-butyl nitrite is then added slowly to the 3-aminopyridine solution, preferably at 0°C, thereby generating a diazonium salt.
  • the diazonium salt solution is then either heated followed by addition of the desired alcohol, RiOH or the solution is added directly without heating to a hot solution of the desired alcohol, RiOH thereby generating the 3-substituted-pyridine product.
  • the solvent or excess alcohol may be removed by distillation, evaporation, under vacuum or otherwise separated from the product using conventional means known in the art.
  • the ultimate starting materials such as 3-amino-2-chloropyridine are either commercially available, may be prepared by known procedures or otherwise may be prepared using conventional chemistry knowledge.
  • the alkyl nitrite, acid and alcohol reagents are commercially available, may be prepared by known procedures or may otherwise may be prepared using conventional chemistry knowledge.
  • t- butyl nitrite or isoamyl nitrite are two commercially available nitrites that can be used in the instant invention.
  • alkylaryl is meant an aryl group substituted by one or more alkyl groups, wherein the “aryl” may be either a non-heteroaromatic ring system or heteroaromatic ring system.
  • addition salts are meant salts of a given compound (or salt) of the invention derived from the chemical interaction with inorganic acids or organic acids. Acid addition salts may also be adducts with an organic solvent or water.
  • Examples of acid addition salts derived from inorganic acids include hydrochlorides, hydrobromides, hydroiodides, sulfates, hydrogensulfates, phosphates, monohydrogenphosphates, dihydrogenphosphates, nitrates, and thiocyanates.
  • Examples of acid addition salts derived from organic acids include carboxylates, sulfonates, and phosphonates.
  • Examples of acid addition salts derived from a carboxylic acid include formates, acetates, propionates, butyrates, cinnamates, benzoates, lactates, oxalates, malonates, succinates, glutarates, adipates, maleates, fumarates, phthalates, citrates, tartarates, salicylates, nicotinates, mandelates and salts from amino acids.
  • Examples of acid addition salts derived from a sulfonic acid include alkylsulfonates (e.g. methanesulfonates, benzenesulfonates (e.g.
  • Substantially anhydrous conditions is defined as conditions sufficient to conduct the diazotization or dediazotization without an undesirable decrease in the efficiency of the process while taking into account the costs and benefits of obtaining the appropriate reagents and reactor design.
  • the diazotization or dediazotization reactions are conducted in the absence of water.
  • Schemes V and VI illustrate certain synthetic routes wherein 2-chloro-3- (2,2,2-trifluoroethoxy)pyridine is used as an intermediate for the production of a known pyridylsulfonylurea which is useful as an herbicide for controlling weeds in corn and sugar cane crops.
  • a known pyridylsulfonylurea which is useful as an herbicide for controlling weeds in corn and sugar cane crops.
  • the individual transformations in Schemes V and VI may be accomplished by using means generally known to one of ordinary skill in the art. See for example U.S. Patents 5,403,814 and 4,522,645, and EP- A- 103543, which are hereby incorporated by reference.
  • the compounds of formula I wherein R is hydrogen can also be used to make the compounds of formula I wherein R 4 is a chloro or bromo.
  • the synthetic transformation may be accomplished via an electrophilic aromatic substitution reaction.
  • Typical chlorinating reagents that may be used are FeCl 3 , AICI 3 , N-chlorosuccinimide or SO 2 Cl 2 .
  • Typical brominating reagents that may be used are FeBr 3 and N-bromosuccinimide.
  • the reactions preferably are run in the absence of light.
  • a reactor vessel is charged with 3-amino-2-chloropyridine (2.7 g, 21 mmol), 2,2,2- trifluoroethanol (15 g, 150 mmol), and trifluoroacetic acid (3.63 g, 31.8 mmol).
  • the solution is cooled to 15°C and magnesium sulfate (2.6 g) is charged to the vessel.
  • the reagent t-butyl nitrite (2.51 g of a 96% solution, 23.4 mmol) is added drop-wise to the vessel while maintaining the temperature in the range 15°C to 20°C.
  • the solution is neutralized with aqueous saturated sodium bicarbonate solution and then extracted with MTBE.
  • the solvent is removed by evaporation to obtain 2-chloro-3-(2,2,2- trifluoroethoxy)pyridine as a crude oil (1.58 g, crude yield 35.6%).
  • a reactor vessel is charged with 3-amino-2-chloropyridine (2.7 g, 21 mmol), 2,2,2- trifluoroethanol (15 g, 150 mmol), and trifluoroacetic acid (3.63 g, 31.8 mmol).
  • the solution is cooled to the range 0°C to 5°C and then the reagent t-butyl nitrite (2.51 g of a 96% solution, 23.4 mmol) is added drop- wise to the vessel maintaining the temperature in the range 0°C to 5°C. After stirring a few minutes the solution is transferred drop-wise to a reactor vessel containing 2,2,2-trifluoroethanol (20 g, 200 mmol) maintained at 55°C.
  • a reactor vessel is charged with 3-amino-2-chloropyridine (2.7 g, 21 mmol), 2,2,2- trifluoroethanol (15 g, 150 mmol), methanesulfonic acid (2.02 g, 21 mmol), and magnesium sulfate (3 g).
  • the solution is cooled to the range 0°C to 5°C and then the reagent t-butyl nitrite (2.51 g of a 96% solution, 23.4 mmol) is added drop- wise to the vessel mamtaining the temperature in the range 0°C to 5°C.
  • a reactor vessel is charged with 3-amino-2-chloropyridine (10 g, 77.8 mmol), 2,2,2-trifluoroethanol (55.6 g, 556 mmol), and after cooling in an ice bath, methanesulfonic acid (7.48 g, 77.8 mmol) is added.
  • the solution is cooled to the range - 5°C to 0°C and then the reagent t-butyl nitrite (2.51 g of a 96% solution, 23.4 mmol) is added drop-wise to the vessel while maintaining the temperature in the range -5°C to 0°C.
  • a reactor vessel is charged with 3-amino-2-chloropyridine (5.4 g, 42 mmol), 2,2,2- trifluoroethanol (50 g, 500 mmol), and methanesulfonic acid (4.1 g, 43 mmol).
  • the solution is heated to the range 55°C to 60°C and then t-butyl nitrite (5.3 g of a 90% solution,46 mmol) is added drop-wise to the vessel while ma taining the temperature at 60°C to 65°C .
  • nitrogen evolution ceases, the solution is cooled, neutralized with aqueous saturated sodium bicarbonate solution and then extracted with MTBE.
  • the solvent is removed by evaporation to obtain 2-chloro-3-(2,2,2-trifluoroethoxy)pyridine as a crude oil (11.1 g) with an actual yield of 67.3%.
  • a reactor vessel is charged with 3-amino-2-isopropylthiopyridine (3.0 g, 18 mmol), 2,2,2-trifluoroethanol (21 g, 210 mmol), and methanesulfonic acid (1.7 g, 18 mmol).
  • the solution is heated to the range 65°C to 70°C and then t-butylnitrite (2.2 g of a 90% solution, 19 mmol) is added drop- wise to the vessel while mamtaining the temperature at 65°C to 70°C .
  • t-butylnitrite 2.2 g of a 90% solution, 19 mmol
  • the solution is cooled, neutralized with aqueous saturated sodium bicarbonate solution and then extracted with MTBE.
  • the solvent is removed by evaporation to obtain 2-isopropyl-3-(2,2,2- trifluoroethoxy)pyridine as a crude oil (4.22 g, crude yield 94%).
  • a reactor vessel is charged with 3-amino-2-bromopyridine (2.0 g, 11.4 mmol), 2,2,2-trifluoroethanol (20 g, 200 mmol), and methanesulfonic acid (1.7 g, 18 mmol).
  • the solution is heated to the range 65°C to 70°C and then t-butylnitrite (1.46 g of a 90% solution, 12.7 mmol) is added drop- wise to the vessel while mamtaining the temperature at 55°C to 70°C .
  • nitrogen evolution ceases, the solution is cooled, neutralized with aqueous saturated sodium bicarbonate solution and then extracted with MTBE.
  • the solvent is removed by evaporation to obtain 2-bromo-3-(2,2,2-trifluoroethoxy)pyridine as a crude oil (2.85 g, crude yield of 96%).
  • a reactor vessel is charged with 3-aminopyridine (2.0 g, 21 mmol), 2,2,2- trifluoroethanol (15 g, 150 mmol), and trifluoroacetic acid (3.63 g, 31.8 mmol).
  • the solution is cooled to 15°C and then t-Butylnitrite (2.51 g of a 96% solution, 23.4 mmol) is added drop-wise to the vessel so that the temperature rises to the range 25°C-30°C.
  • Potassium carbonate (4.4 g) is added to the vessel and the reaction mass is stirred overnight followed by dilution with water and extraction with ethyl acetate.
  • the solvent is evaporated to obtain 3-(2,2,2-trifluoroethoxy)pyridine as a crude oil (3.94 g, crude yield 59.5%) with an actual yield of 56.8%.
  • a reactor vessel is charged with 3-amino-2-chloropyridine (15.0 g, 117 mmol), 2,2,2-trifluoroethanol (21 g, 210 mmol), and methanesulfonic acid (11.2 g, 117 mmol).
  • the solution is heated to the range 50°C to 60°C and then r-butylnitrite (14.7 g of a 90% solution, 128 mmol) is added drop- wise to the vessel while mamtaining the temperature at 50°C to 60°C . After nitrogen evolution ceases, the solution is cooled and ethylene glycol is charged to the reactor.
  • the vessel is put under vacuum and the solvent and other volatiles are distilled off.
  • reaction mass is then neutralized with aqueous saturated sodium bicarbonate solution and extracted with MTBE.
  • the solvent is removed to leave an oil which is stirred several hours with 10% aqueous NaOH (23 g) followed by extraction with MTBE.
  • MTBE is removed under vacuum to obtain 2-chloro-3-(2,2,2- trifluoroethoxy)pyridine as a crude oil (16.83 g) with an actual yield of 65.8%.
  • Analysis by GC indicates the purity of the 2-chloro-3-(2,2,2-trifluoroethoxy)pyridine to be 91.4%.
  • Recovery of the 2,2,2-trifluoroethanol solvent is 88.9% by weight.
  • a reactor vessel is charged with 3-amino-2-chloropyridine (2.7 g, 21 mmol), 2,2,2- trichloroethanol (21 g, 210 mmol), and methanesulfonic acid (2.0 g, 21 mmol).
  • the solution is heated to the range 61°C to 70°C and then f-butylnitrite (2.65 g of a 90% solution, 23 mmol) is added drop-wise to the vessel while maintaining the temperature at 60°C to 70°C .
  • nitrogen evolution ceases, the solution is cooled, neutralized with aqueous saturated sodium bicarbonate solution and then extracted with MTBE.
  • the synthetic transformations described in the examples above were conducted under substantially anhydrous conditions.
  • the actual yield of product was determined using GC analysis and based on internal standards and response factors of standards of known purity. The actual yields recited are based on the theoretical quantity that the starting pyridine could give and represent the actual amount of the desired product formed.
  • a crude product yield in the examples refers to the quantity of isolated material in comparison with the theoretical quantity that the starting pyridine could give. This is only the actual yield of product if the isolated material is 100% product, which is not the case for the un- purified products described in these procedures.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)

Abstract

La présente invention concerne des composés de pyridine 3-substitués et 2,3-disubstitués de formule (I), dans laquelle R1 représente haloalkyle C1-C4 et R4 désigne H, halogène, ou alkylthio C1-C4. L'invention concerne également des sels d'addition acide de ces composés, ces sels pouvant être utilisés comme produits intermédiaires dans la synthèse d'herbicides de pyridylsulfonylurée. Cette invention concerne également l'arylation d'alcools à l'aide d'un sel de pyridinediazonium. Plus particulièrement, le processus d'arylation de la présente invention concerne la synthèse de composés de pyridine 2,3-disubstitués par une diazotation anhydre de 3-aminopyridines permettant de former un produit intermédiaire salin diazoïque, que l'on fait ensuite réagir avec un alcool approprié de manière à obtenir le produit souhaité. Cette invention concerne enfin des produits intermédiaires salins de pyridine-3-diazonium.
EP99940022A 1998-07-21 1999-07-19 Compos s de pyridine 3-substitu s et synth se apparent e Withdrawn EP1098881A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US120291 1980-02-11
US12029198A 1998-07-21 1998-07-21
PCT/EP1999/005130 WO2000005212A1 (fr) 1998-07-21 1999-07-19 Composés de pyridine 3-substitués et synthèse apparentée

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EP1098881A1 true EP1098881A1 (fr) 2001-05-16

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EP99940022A Withdrawn EP1098881A1 (fr) 1998-07-21 1999-07-19 Compos s de pyridine 3-substitu s et synth se apparent e

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EP (1) EP1098881A1 (fr)
JP (1) JP2002521366A (fr)
AU (1) AU5411799A (fr)
IL (3) IL140750A0 (fr)
WO (1) WO2000005212A1 (fr)
ZA (1) ZA200100474B (fr)

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Publication number Priority date Publication date Assignee Title
CN103910668B (zh) * 2013-01-07 2016-12-28 上海医药工业研究院 一种3‑烷基吲哚的制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3828056A (en) * 1972-09-11 1974-08-06 Searle & Co (2-(2-methyl-5-nitro-1-imidazolyl)ethyl)heteroaryloxy ethers
DE3545570A1 (de) * 1985-12-21 1987-06-25 Hoechst Ag Neue pyridin-derivate und deren n-oxide, verfahren zu ihrer herstellung und ihre verwendung als zwischenprodukte
CA2080249C (fr) * 1990-05-31 1996-11-19 Dennis M. Godek Obtention de piperidines a substituant
JPH04364168A (ja) * 1990-08-08 1992-12-16 Taisho Pharmaceut Co Ltd スルホンアミドピリジン化合物
US5403814A (en) * 1991-03-25 1995-04-04 Ciba-Geigy Corporation Sulfonylureas
EP0540697B1 (fr) * 1991-03-25 1998-06-03 Novartis AG Sulfonylurees
DE59200283D1 (de) * 1992-07-30 1994-08-18 Ciba Geigy Ag Sulfonylharnstoffe als Herbizide.
JPH08245590A (ja) * 1995-03-09 1996-09-24 Terumo Corp スルホンアミド誘導体及びこれを含有する医薬製剤

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0005212A1 *

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IL140750A (en) 2006-08-20
ZA200100474B (en) 2002-05-16
WO2000005212A1 (fr) 2000-02-03
AU5411799A (en) 2000-02-14
IL172228A (en) 2006-04-10
JP2002521366A (ja) 2002-07-16
IL140750A0 (en) 2002-02-10

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