DE3702964A1 - Aryloxy carboxylic acid derivatives, their preparation and their use - Google Patents

Aryloxy carboxylic acid derivatives, their preparation and their use

Info

Publication number
DE3702964A1
DE3702964A1 DE19873702964 DE3702964A DE3702964A1 DE 3702964 A1 DE3702964 A1 DE 3702964A1 DE 19873702964 DE19873702964 DE 19873702964 DE 3702964 A DE3702964 A DE 3702964A DE 3702964 A1 DE3702964 A1 DE 3702964A1
Authority
DE
Germany
Prior art keywords
formula
aryl
alkyl
compounds according
compound
Prior art date
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.)
Withdrawn
Application number
DE19873702964
Other languages
German (de)
Inventor
Wolfgang Dr Buck
Erich Dr Raddatz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Agrar GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shell Agrar GmbH and Co KG filed Critical Shell Agrar GmbH and Co KG
Priority to DE19873702964 priority Critical patent/DE3702964A1/en
Priority to EP87112370A priority patent/EP0262393B1/en
Priority to AT87112370T priority patent/ATE84298T1/en
Priority to EG497/87A priority patent/EG18578A/en
Priority to DE8787112370T priority patent/DE3783415D1/en
Priority to ES87112370T priority patent/ES2043625T3/en
Priority to NZ221592A priority patent/NZ221592A/en
Priority to CA000545601A priority patent/CA1311240C/en
Priority to HU873791A priority patent/HU203320B/en
Priority to KR1019870009448A priority patent/KR960011716B1/en
Priority to DK198704518A priority patent/DK174902B1/en
Priority to JP62216276A priority patent/JP2632863B2/en
Priority to PT85616A priority patent/PT85616B/en
Priority to BR8704461A priority patent/BR8704461A/en
Priority to IL83684A priority patent/IL83684A/en
Priority to AU77667/87A priority patent/AU610079B2/en
Priority to CN87106006A priority patent/CN1019485B/en
Priority to MYPI87001505A priority patent/MY101353A/en
Publication of DE3702964A1 publication Critical patent/DE3702964A1/en
Priority to GR930400096T priority patent/GR3006845T3/el
Priority to JP8284620A priority patent/JP2884497B2/en
Withdrawn legal-status Critical Current

Links

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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • A01N39/04—Aryloxy-acetic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/22—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton having nitrogen atoms of amino groups bound to the carbon skeleton of the acid part, further acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
    • C07C255/29—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton containing cyano groups and acylated amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/31—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/45—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C255/46—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of non-condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/20—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/39—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
    • C07C323/40—Y being a hydrogen or a carbon atom
    • C07C323/41—Y being a hydrogen or an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Abstract

Compounds of the formula <IMAGE> in which the symbols aryl, Q and R1 to R6 have the meanings given in the description can be prepared by customary methods and used as fungicides against phytopathogenic fungi.

Description

Die Erfindung betrifft neue Aryloxycarbonsäurederivate, die nach üblichen Verfahren erhalten werden können und sich als Wirkstoffe gegen phytopathogene Pilze eignen.The invention relates to new aryloxycarboxylic acid derivatives, which can be obtained by conventional methods and are suitable as active ingredients against phytopathogenic fungi.

Die neuen Verbindungen entsprechen der FormelThe new compounds correspond to the formula

In der Formel I und im folgenden bedeutetIn formula I and below means

Aryleinen unsubstituierten oder ein- bis dreifach durch C₁-C₅-Alkyl, C₁-C₅-Alkoxy, C₁-C₅-Alkyl-SO n (n = 0, 1 oder 2), Halogen, NO₂, CF₃, CN, CH₃OCH₂, (CH₃)₂NCH₂ oder Phenyl substituierten Phenylrest, einen 1- oder 2-Naphthyl-, 2-, 3- oder 4-Pyridyl- oder einen Chinolylrest,Aryleinen unsubstituted or mono- to triple by C₁-C₅-alkyl, C₁-C₅-alkoxy, C₁-C₅-alkyl-SO n (n = 0, 1 or 2), halogen, NO₂, CF₃, CN, CH₃OCH₂, (CH₃ ) ₂NCH₂ or phenyl substituted phenyl radical, a 1- or 2-naphthyl, 2-, 3- or 4-pyridyl or a quinolyl radical,

R₁:H, C₁-C₅-Alkyl, Allyl, R₂ und R₃:H, C₁-C₆-Alkyl (das auch ein O- oder S-Atom in der Kette enthalten kann), C₃-C₇-Cycloalkyl, CH₂-COO-(C₁-C₅-Alkyl), R₂ und R₃ gemeinsam auch -(CH₂)₄-, -(CH₂)₅-,R₁: H, C₁-C₅-alkyl, allyl, R₂ and R₃: H, C₁-C₆-alkyl (which is also an O- or S atom in the chain), C₃-C₇-cycloalkyl, CH₂-COO- (C₁-C₅-alkyl), R₂ and R₃ together also - (CH₂) ₄-, - (CH₂) ₅-,

R₄:CN, CONH₂, R₅:H, CH₃, C₂H₅, R₆:H, CH₃,
mit der Maßgabe, daß "Aryl" nicht 4-Chlor-2-methyl­ phenyl bedeutet, wenn R₁ H oder CH₃ und R₂ H ist.R₄: CN, CONH₂, R₅: H, CH₃, C₂H₅, R₆: H, CH₃,
with the proviso that "aryl" does not mean 4-chloro-2-methylphenyl when R₁ is H or CH₃ and R₂H.

Soweit die Substituenten R₁ bis R₆ Kohlenwasserstoffketten enthalten, können diese gerade oder verzweigt und untereinander gleich oder verschieden sein. Bevorzugt sind Ketten mit bis zu 4, insbesondere bis zu 3 C-Atomen. Als Alkylsubstituent im Arylrest ist CH₃ bevorzugt. Halogen bedeutet Fluor, Chlor, Brom und Jod, bevorzugt Chlor und Fluor. Die Substituenten im Arylrest können gleich oder verschieden sein. CF₃, CN, NO₂, (CH₃)₂NCH₂, Phenyl und C₁-C₅-Alkyl-SO n sind im allgemeinen nur einmal vorhanden. Bedeutet Aryl eine Chinolinylgruppe, so handelt es sich bevorzugt um 8-Chinolinyl.If the substituents R₁ to R₆ contain hydrocarbon chains, these can be straight or branched and the same or different from one another. Chains with up to 4, in particular up to 3, carbon atoms are preferred. CH₃ is preferred as the alkyl substituent in the aryl radical. Halogen means fluorine, chlorine, bromine and iodine, preferably chlorine and fluorine. The substituents in the aryl radical can be the same or different. CF₃, CN, NO₂, (CH₃) ₂NCH₂, phenyl and C₁-C₅-alkyl-SO n are generally present only once. If aryl is a quinolinyl group, it is preferably 8-quinolinyl.

Die neuen Verbindungen werden in an sich bekannter Weise hergestellt.The new compounds are made in a manner known per se produced.

  • 1. Umsetzung von Verbindungen der Formel Aryl - O - Q - COY (II)worin Aryl und Q die obige Bedeutung haben und Y eine Fluchtgruppe ("leaving group") ist, z. B. Halogen (bevorzugt Chlor), OAlkyl, OH, Acyl, mit einer Verbindung der Formel worin R₁-R₄ die obige Bedeutung haben, unter Abspaltung von HY.1. Implementation of compounds of the formula aryl-O-Q-COY (II) in which aryl and Q have the meaning given above and Y is a leaving group, eg. B. halogen (preferably chlorine), alkyl, OH, acyl, with a compound of the formula wherein R₁-R₄ have the above meaning, with the elimination of HY.
  • Die Umsetzung wird vorzugsweise in einem inerten Lösungsmittel, beispielswiese Methylenchlorid, Toluol, Acetonitril, einem Ether, oder in einem Lösungsmittelgemisch bei Temperaturen zwischen Raumtemperatur und der Siedetemperatur des Reaktionsgemischs durchgeführt, wobei ein HY-bindendes Mittel die Reaktion fördert, beispielsweise eine Base, wenn HY eine Säure wie HCl darstellt, Dicyclohexylcarbodiimid oder Carbonyldiimidazol, wenn HY Wasser bedeutet.The reaction is preferably carried out in an inert Solvents, for example methylene chloride, toluene, Acetonitrile, an ether, or in one Solvent mixture at temperatures between Room temperature and the boiling temperature of the Reaction mixture carried out, a HY-binding Agent that promotes the reaction, for example a base, when HY is an acid like HCl, Dicyclohexylcarbodiimide or carbonyldiimidazole if HY means water.
  • Die Ausgangsstoffe sind bekannt oder sonst nach üblichen Verfahren leicht herstellbar. So können Verbindungen der Formel II mit Y = OH z. B. durch Umsetzung entsprechender Phenole Aryl-OH mit 2-Brompropionsäureethylester in Gegenwart einer Base und anschließende Hydrolyse des Esters gewonnen werden. Aus den auf diese Weise erhaltenen Carbonsäuren entstehen, z. B. durch Umsetzung mit Thionylchlorid die entsprechenden Carbonsäurechloride der Formel II.The starting materials are known or otherwise according to usual methods easy to manufacture. So can Compounds of formula II with Y = OH z. B. by Implementation of corresponding phenols with aryl-OH 2-Bromopropionic acid ethyl ester in the presence of a base and subsequent hydrolysis of the ester will. From the so obtained Carboxylic acids arise, e.g. B. by implementation with Thionyl chloride the corresponding carboxylic acid chlorides of formula II.
  • Die α-Aminosäurenitrile (III), R₄ = CN) können nach der Strecker-Synthese aus dem entsprechenden Keton oder Aldehyd, NaCN und NH₄Cl in Wasser bereitet werden (Houben-Weyl, Bd. VIII, S. 274ff (1952)). Die α-Aminosäureamide (III, R₄ = CONH₂) entstehen aus den entsprechenden Nitrilen durch partielle Hydrolyse. The α- amino acid nitriles (III), R₄ = CN) can be prepared in water after the Strecker synthesis from the corresponding ketone or aldehyde, NaCN and NH₄Cl (Houben-Weyl, Vol. VIII, pp. 274ff (1952)). The α- amino acid amides (III, R₄ = CONH₂) arise from the corresponding nitriles by partial hydrolysis.
  • 2. Umsetzung einer Verbindung der Formel Aryl - OM (IV)worin Aryl die obige Bedeutung hat und M Wasserstoff oder ein Alkalikation bedeutet, mit einer Verbindung der Formel in der R₁ bis R₄ und Q die obige Bedeutung haben und Z Halogen oder eine Arylsulfonyloxygruppe darstellt.2. Reaction of a compound of the formula aryl-OM (IV) in which aryl has the above meaning and M is hydrogen or an alkali metalation, with a compound of the formula in which R₁ to R₄ and Q have the above meaning and Z represents halogen or an arylsulfonyloxy group.
  • Die Umsetzung erfolgt in einem inerten polaren Lösungsmittel. Wenn M = H ist, wird eine Base zugesetzt. Bevorzugt sind Bedingungen, unter denen eine Verbindung IV mit M = K oder Na gebildet wird.The reaction takes place in an inert polar Solvent. If M = H, it becomes a base added. Conditions under which are preferred a compound IV with M = K or Na is formed.

Bevorzugte Bedeutung von Z ist Brom und CH₃-C₆H₄-SO₃-, als bevorzugtes Lösungsmittel dient Acetonitril. Die Reaktion erfolgt in der Wärme, z. B. bei Rückflußtemperatur. Als Basen können beispielsweise Alkalicarbonate, Alkalihydroxide, gegebenenfalls auch hinreichend basische Amide, etwa Triethylamin, verwendet werden.Preferred meaning of Z is bromine and CH₃-C₆H₄-SO₃-, is used as the preferred solvent Acetonitrile. The reaction takes place in the heat, e.g. B. at Reflux temperature. As bases, for example Alkali carbonates, alkali hydroxides, if appropriate also sufficiently basic amides, such as triethylamine, are used will.

Je nach der Bedeutung der R₂ bis R₆ können Verbindungen der Formel I mit einem oder zwei Asymmetriezentren vorliegen. Die Isomeren können gewünschtenfalls nach üblichen Methoden getrennt oder durch Verwendung optisch aktiver Ausgangsprodukte unmittelbar synthetisiert werden. Depending on the importance of R₂ to R₆ can Compounds of formula I with one or two Asymmetry centers are present. The isomers can if desired, separated by customary methods or through the use of optically active raw materials be synthesized immediately.  

Die Verbindungen der Formel I wirken fungitoxisch gegen phytopathogene Pilze. Sie können insbesondere gegen Pilzkrankheiten an Reis angewandt werden. Obwohl sich die neuen Verbindungen z. T. von Herbiziden ableiten (Dichlorprop, 2,4-DB), sind sie überraschenderweise gut pflanzenverträglich.The compounds of formula I act fungitoxically phytopathogenic mushrooms. You can especially against Fungal diseases are applied to rice. Although the new connections e.g. Derive T. from herbicides (Dichlorprop, 2,4-DB), they are surprisingly good plant-friendly.

Für die Anwendung werden die Verbindungen der Formel I mit üblichen Hilfs- und/oder Trägerstoffen zu gebräuchlichen Zubereitungen verarbeitet, die für die Anwendung in Form einer Spritzbrühe mit geeigneten Mengen Wasser verdünnt werden. Solche Zubereitungen sind beispielsweise Emulsions- und Lösungskonzentrate, Suspensionspulver, Stäubemittel, Granulate, die bis zu 80 Gewichtsprozent an Wirkstoff enthalten können.For the application, the compounds of formula I with customary auxiliaries and / or carriers Preparations processed for use in the form a spray liquor diluted with suitable amounts of water will. Such preparations are, for example Emulsion and solution concentrates, suspension powder, Dusts, granules containing up to 80 percent by weight May contain active ingredient.

Beispiele für die Formulierung:Examples of the wording:

1. Emulsionskonzentrat1. Emulsion concentrate

 5,0 Gew.-Teile Wirkstoff gemäß der Erfindung
 3,4 Gew.-Teile epoxidiertes Pflanzenöl
13,4 Gew.-Teile eines Kombinationsemulgators aus Fettalkoholpolyglykoläther und Calcium-Alkylarylsulfonat
40,0 Gew.-Teile Dimethylformamid
38,2 Gew.-Teile Xylol5.0 parts by weight of active ingredient according to the invention
3.4 parts by weight of epoxidized vegetable oil
13.4 parts by weight of a combination emulsifier consisting of fatty alcohol polyglycol ether and calcium alkylarylsulfonate
40.0 parts by weight of dimethylformamide
38.2 parts by weight of xylene

Die Komponenten werden vermischt und für die Anwendung mit Wasser auf eine Wirkstoffkonzentration von 0,01 bis 0,1 Gewichtsprozent verdünnt. The components are mixed and ready for use with water to an active ingredient concentration of 0.01 diluted to 0.1 percent by weight.  

2. Suspensionspulver2. Suspension powder

10 Gew.-Teile Wirkstoff gemäß der Erfindung
 3 Gew.-Teile Natrium Fettalkoholsulfonat
 5 Gew.-Teile Salze von Naphthalin-sulfonsäure- Formaldehydkondensat
82 Gew.-Teile Kaolin10 parts by weight of active ingredient according to the invention
3 parts by weight of sodium fatty alcohol sulfonate
5 parts by weight of salts of naphthalene-sulfonic acid-formaldehyde condensate
82 parts by weight of kaolin

Die Wirkung der erfindungsgemäßen Verbindungen, z. B. gegen Piricularia wurde unter tropischen Bedingungen an Saatreis untersucht. 2 Saatreisreihen (I und II) zwischen älteren, mit Piricularia natürlich infizierten Reihen wurden am 41., 45. und 49. Tag nach der Saat mit Spritzbrühen behandelt, die bestimmte Mengen Wirkstoff enthielten. Als Vergleich diente die nur mit Wasser behandelte Kontrolle. Die Bonitierung erfolgte 6, 8, 10 und 13 Tage nach der letzten Spritzung (% befallene Pflanzen).The effect of the compounds of the invention, e.g. B. against Piricularia was planted on seed rice under tropical conditions examined. 2 rows of seed rice (I and II) between older, rows naturally infected with Piricularia were found on 41st, 45th and 49th day after sowing with spray liquors treated that contained certain amounts of active ingredient. As The control treated with water only served as a comparison. The ratings were given 6, 8, 10 and 13 days after the last spraying (% infested plants).

Die erfindungsgemäßen Verbindungen erwiesen sich als gut wirksam gegen Piricularia und als gut pflanzenverträglich.The compounds according to the invention proved to be good effective against Piricularia and well tolerated by plants.

Beispiel 1Example 1 2-(2,4-Dichlorphenoxy)-propionsäure-N-(1-ethyl-1-cyano- propyl)-amid2- (2,4-dichlorophenoxy) propionic acid N- (1-ethyl-1-cyano- propyl) amide

2,2 g 3-Amino-3-cyanopentan und 2,4 g Triethylamin werden in 100 ml Methylenchlorid gelöst. Hierzu gibt man 5,1 g 2-(2,4-Dichlorphenoxy)-propionsäurechlorid und läßt den Ansatz über Nacht bei Raumtemperatur rühren. Die Lösung wird mit Wasser und Natriumhydrogencarbonatlösung ausgeschüttelt, getrocknet und eingeengt. Als Rückstand erhält man 6,3 g (96% d. Th.) eines bräunlichen, viskosen Öls, das beim Verrühren mit Diisopropylether kristallisiert.2.2 g of 3-amino-3-cyanopentane and 2.4 g of triethylamine dissolved in 100 ml of methylene chloride. To do this, add 5.1 g 2- (2,4-dichlorophenoxy) propionic acid chloride and leaves the Stir the mixture overnight at room temperature. The solution with water and sodium bicarbonate solution shaken out, dried and concentrated. As a backlog 6.3 g (96% of theory) of a brownish, viscous are obtained Oil that when mixed with diisopropyl ether crystallized.

Ausbeute: 4,9 g weißer Feststoff (74% d. Th.)
Schmelzpunkt: 100-102°C.Yield: 4.9 g of white solid (74% of theory)
Melting point: 100-102 ° C.

Die Struktur wird durch die spektroskopische Untersuchung bestätigt.The structure is determined by spectroscopic examination approved.

Analyse: C₁₅H₁₈Cl₂N₂O₂  M = 329,23Analysis: C₁₅H₁₈Cl₂N₂O₂ M = 329.23

gef.:C 54,58, H 5,54, Cl 21,06, N 8,35%; ber.:C 54,72, H 5,51, Cl 21,54, N 8,51%.Found: C 54.58, H 5.54, Cl 21.06, N 8.35%; calc .: C 54.72, H 5.51, Cl 21.54, N 8.51%.

Entsprechend können die Verbindungen der nachstehenden Tabellen erhalten werden. Accordingly, the compounds of the following Tables can be obtained.  

Beispiel 2Example 2 2-(4-Methylthiophenyloxy)-propionsäure-N-(1-cyano-1,2- dimethylpropyl)-amid2- (4-methylthiophenyloxy) propionic acid N- (1-cyano-1,2- dimethylpropyl) amide

2,5 g 2-Brompropionsäure-N-(1-cyano-1,2-dimethylpropyl)- amid und 1,4 g 4-Methylmercaptophenol werden in 50 ml Methylisobutylketon gelöst. Nach Zugabe von 1,5 g Pottasche wird der Ansatz 3 Stunden bei 80°C gelöst. Die Lösung wird abgesaugt und eingeengt. Man erhält 2,8 g bräunliches Öl (91,5%), das beim Verrühren mit Diisopropyläther kristallisiert.2.5 g of 2-bromopropionic acid N- (1-cyano-1,2-dimethylpropyl) - amide and 1.4 g of 4-methylmercaptophenol are dissolved in 50 ml Dissolved methyl isobutyl ketone. After adding 1.5 g Potash is dissolved at 80 ° C for 3 hours. The Solution is suctioned off and concentrated. 2.8 g are obtained brownish oil (91.5%), which when mixed with Diisopropyl ether crystallized.

Fp. 83-86°C.Mp 83-86 ° C.

Analyse: C₁₆H₂₂N₂O₂S  M = 306,43Analysis: C₁₆H₂₂N₂O₂S M = 306.43

gef.:C 62,48, H 7,24, N  9,23, S 10,34%; ber.:C 62,71, H 7,24, N  9,14, S 10,46%.Found: C 62.48, H 7.24, N 9.23, S 10.34%; calc .: C 62.71, H 7.24, N 9.14, S 10.46%.

Die Struktur wurde spektroskopisch bestätigt. The structure was confirmed spectroscopically.  

Tabelle I Table I

Verbindungen der Formel Compounds of the formula

Tabelle II Table II

Verbindungen der Formel Compounds of the formula

Claims (8)

1. Verbindungen der Formel In der Formel I und im folgenden bedeutetAryleinen unsubstituierten oder ein- bis dreifach durch C₁-C₅-Alkyl, C₁-C₅-Alkoxy, C₁-C₅-Alkyl-SO n (n = 0, 1 oder 2), Halogen, NO₂, CF₃, CN, CH₃OCH₂, (CH₃)₂NCH₂ oder Phenyl substituierten Phenylrest, einen 1- oder 2-Naphthyl-, 2-, 3- oder 4-Pyridyl- oder einen Chinolylrest, R₁:H, C₁-C₅-Alkyl, Allyl, R₂ und R₃:H, C₁-C₆-Alkyl (das auch ein O- oder S-Atom in der Kette enthalten kann), C₃-C₇-Cycloalkyl, CH₂-COO-(C₁-C₅-Alkyl), R₂ und R₃ gemeinsam auch -(CH₂)₄-, -(CH₂)₅-, R₄:CN, CONH₂, R₅:H, CH₃, C₂H₅, R₆:H, CH₃, mit der Maßgabe, daß "Aryl" nicht 4-Chlor-2-methyl- phenyl bedeutet, wenn R₁ H oder CH₃ und R₂ H ist.gegebenenfalls in Form von Racematen bzw. Gemischen der optischen Isomeren bzw. in Form der reinen Enantiomeren bzw. Diastereomeren.1. Compounds of the formula In the formula I and in the following, aryline means unsubstituted or mono- to triple by C₁-C₅-alkyl, C₁-C₅-alkoxy, C₁-C₅-alkyl-SO n (n = 0, 1 or 2), halogen, NO₂, CF₃ , CN, CH₃OCH₂, (CH₃) ₂NCH₂ or phenyl substituted phenyl, a 1- or 2-naphthyl, 2-, 3- or 4-pyridyl or a quinolyl group, R₁: H, C₁-C₅-alkyl, allyl, R₂ and R₃: H, C₁-C₆-alkyl (which may also contain an O or S atom in the chain), C₃-C₇-cycloalkyl, CH₂-COO- (C₁-C₅-alkyl), R₂ and R₃ together also - (CH₂) ₄-, - (CH₂) ₅-, R₄: CN, CONH₂, R₅: H, CH₃, C₂H₅, R₆: H, CH₃, with the proviso that "aryl" does not mean 4-chloro-2-methylphenyl when R₁ is H or CH₃ and R₂ H. optionally in the form of racemates or mixtures of the optical isomers or in the form of the pure enantiomers or diastereomers. 2. Verbindungen nach Anspruch 1, worin R₁ H, R₂ CH₃, R₃ CH(CH₃)₂ und R₄ CN ist.2. Compounds according to claim 1, wherein R₁ H, R₂ CH₃, R₃ is CH (CH₃) ₂ and R₄ CN. 3. Verbindungen nach Anspruch 1 oder 2, worin Aryl 4-Chlorphenyl, 4-Chlor-2-methylphenyl, 3,4- oder 3,5-Dichlorphenyl ist.3. Compounds according to claim 1 or 2, wherein aryl 4-chlorophenyl, 4-chloro-2-methylphenyl, 3,4- or Is 3,5-dichlorophenyl. 4. Verbindungen nach Anspruch 1, 2 oder 3, worin Q -CH(CH₃)- ist.4. Compounds according to claim 1, 2 or 3, wherein Q -CH (CH₃) - is. 5. Fungizide Mittel, gekennzeichnet durch einen Gehalt an einer Verbindung nach Anspruch 1, 2, 3 oder 4 neben üblichen Hilfs- und/oder Trägerstoffen.5. Fungicidal agents, characterized by a content of a compound according to claim 1, 2, 3 or 4 in addition usual auxiliaries and / or carriers. 6. Verwendung von Verbindungen nach Anspruch 1, 2, 3 oder 4 zur Bekämpfung phytopathogener Pilze.6. Use of compounds according to claim 1, 2, 3 or 4 to combat phytopathogenic fungi. 7. Verwendung von Verbindungen nach Anspruch 1, 2, 3 oder 4 zur Bekämpfung von Pilzkrankheiten an Reis.7. Use of compounds according to claim 1, 2, 3 or 4 to combat fungal diseases in rice. 8. Verfahren zur Herstellung von Verbindungen nach Anspruch 1 bis 4 nach an sich bekannten Methoden, dadurch gekennzeichnet, daß man
  • a) eine Verbindung der Formel Aryl - O - Q - COY (II)worin Aryl und Q die obige Bedeutung haben und Y eine "leaving group" ist, mit einer Verbindung der Formel in der R₁, R₂, R₃ und R₄ die obige Bedeutung haben, umsetzt oder daß man
  • b) eine Verbindung der Formel Aryl - O - M (IV)worin Aryl die obige Bedeutung hat und M Wasserstoff oder ein Alkalikation bedeutet, mit einer Verbindung der Formel in der R₁ bis R₄ und Q die obige Bedeutung haben und Z Halogen oder eine Arylsulfonyloxygruppe bedeutet, umsetzt und daß man gewünschtenfalls vorliegende Gemische von optischen Isomeren nach üblichen Verfahren in die Isomeren bzw. in Diastereomerenpaare auftrennt.
8. A process for the preparation of compounds according to claim 1 to 4 by methods known per se, characterized in that
  • a) a compound of the formula aryl - O - Q - COY (II) in which aryl and Q have the meaning given above and Y is a "leaving group", with a compound of the formula in which R₁, R₂, R₃ and R₄ have the above meaning, implemented or that one
  • b) a compound of the formula aryl-O-M (IV) in which aryl has the above meaning and M is hydrogen or an alkali metalation, with a compound of the formula in which R₁ to R₄ and Q are as defined above and Z is halogen or an arylsulfonyloxy group, and if desired, mixtures of optical isomers present are separated into the isomers or diastereomer pairs by customary processes.
DE19873702964 1986-08-29 1987-01-30 Aryloxy carboxylic acid derivatives, their preparation and their use Withdrawn DE3702964A1 (en)

Priority Applications (20)

Application Number Priority Date Filing Date Title
DE19873702964 DE3702964A1 (en) 1987-01-30 1987-01-30 Aryloxy carboxylic acid derivatives, their preparation and their use
EP87112370A EP0262393B1 (en) 1986-08-29 1987-08-26 Derivatives of aryloxycarbonic acids, their preparation and their use
AT87112370T ATE84298T1 (en) 1986-08-29 1987-08-26 ARYLOXYCARBONIC ACID DERIVATIVES, THEIR PREPARATION AND USE.
EG497/87A EG18578A (en) 1986-08-29 1987-08-26 Aryloxycarboxylic acid derivatives,the preparation and use thereof
DE8787112370T DE3783415D1 (en) 1986-08-29 1987-08-26 ARYLOXYCARBONIC ACID DERIVATIVES, THEIR PRODUCTION AND USE.
ES87112370T ES2043625T3 (en) 1986-08-29 1987-08-26 ARILOXICARBOXYLIC ACID DERIVATIVES, THEIR PREPARATION AND USE.
NZ221592A NZ221592A (en) 1986-08-29 1987-08-27 Ring substituted amide derivatives and the prevention or combating of piricularia in rice plants
KR1019870009448A KR960011716B1 (en) 1986-08-29 1987-08-28 Derivatives of aryloxycarbonic acids, their preparation and their use
IL83684A IL83684A (en) 1986-08-29 1987-08-28 Fungicidal compositions containing arylcarboxylic acid derivatives,certain such compounds and their preparation
CA000545601A CA1311240C (en) 1986-08-29 1987-08-28 Arylcarboxylic acid derivatives, the preparation and use thereof
DK198704518A DK174902B1 (en) 1986-08-29 1987-08-28 Aryloxycarboxylic acid derivatives, their preparation and use as well as fungicidal agents containing such derivatives
JP62216276A JP2632863B2 (en) 1986-08-29 1987-08-28 Aryloxycarboxylic acid derivatives and their production
PT85616A PT85616B (en) 1986-08-29 1987-08-28 METHOD FOR THE PREPARATION OF ARYLOXYCARBOXYLIC ACID AND COMPOUND FUNGICIDES DERIVATIVES CONTAINING THEM
BR8704461A BR8704461A (en) 1986-08-29 1987-08-28 FUNGICIDAL COMPOUNDS, COMPOUNDS, EMPLOYMENT AND PROCESS FOR THE PREPARATION OF COMPOUNDS
HU873791A HU203320B (en) 1986-08-29 1987-08-28 Fungicide compositions containing aryloxy-carboxylic acid derivatives as active components and process for producing the active components
AU77667/87A AU610079B2 (en) 1986-08-29 1987-08-28 Arylcarboxylic acid derivatives, the preparation and use thereof
CN87106006A CN1019485B (en) 1986-08-29 1987-08-29 Arylcarboxylic acid derivative, preparation and use thereof
MYPI87001505A MY101353A (en) 1986-08-29 1987-09-01 Arylcarboxylic acid derivatives, the preparation and use thereof.
GR930400096T GR3006845T3 (en) 1986-08-29 1993-01-21
JP8284620A JP2884497B2 (en) 1986-08-29 1996-10-08 Aryloxycarboxylic acid derivatives, their production and use

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19873702964 DE3702964A1 (en) 1987-01-30 1987-01-30 Aryloxy carboxylic acid derivatives, their preparation and their use

Publications (1)

Publication Number Publication Date
DE3702964A1 true DE3702964A1 (en) 1988-08-11

Family

ID=6319995

Family Applications (1)

Application Number Title Priority Date Filing Date
DE19873702964 Withdrawn DE3702964A1 (en) 1986-08-29 1987-01-30 Aryloxy carboxylic acid derivatives, their preparation and their use

Country Status (1)

Country Link
DE (1) DE3702964A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998033765A1 (en) * 1997-02-04 1998-08-06 E.I. Du Pont De Nemours And Company Fungicidal carboxamides
WO2004048316A1 (en) * 2002-11-26 2004-06-10 Syngenta Limited N-alkynyl-2- (substituted phenoxy) alkylamides and their use as fungicides
US7371764B2 (en) 2002-11-26 2008-05-13 Syngenta Limited Quinolin-isoquinolin-and quinazolin-oxyalkylamides and their use as fungicides
US7420090B2 (en) 2002-11-26 2008-09-02 Syngenta Limited Fungicides
US7511151B2 (en) 2002-11-26 2009-03-31 Syngenta Limited Substituted pyridyloxyalkylamides and their use as fungicides
US8067592B2 (en) 2003-06-04 2011-11-29 Syngenta Limited N-alkyny-2-(substituted aryloxy) alkylthioamine derivatives as fungicides
WO2011087837A3 (en) * 2009-12-22 2012-01-12 E. I. Du Pont De Nemours And Company Fungicidal 2-(bicyclic aryloxy)carboxamides
EP2314568A3 (en) * 2001-11-16 2012-02-29 Syngenta Participations AG Novel alpha-oxygenated or alpha-thiolated carboxylic acid phenethylamide derivatives
WO2012087372A1 (en) * 2010-12-22 2012-06-28 E. I. Du Pont De Nemours And Company Fungicidal 2-(bicyclic aryloxy)carboxamides

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2229211A1 (en) * 1971-06-25 1972-12-28 Stauffer Chemical Co., New York, N.Y. (V.StA.) N-acetonitrilo-alpha-phenoxyalkylamides and their use as herbicides
US3932168A (en) * 1971-11-17 1976-01-13 Abbott Laboratories Substituted aryloxyacetamido nitrile derivatives as carbohydrate deposition agents
US4001427A (en) * 1975-06-26 1977-01-04 Stauffer Chemical Company N-dimethylacetonitrile-α-(substituted phenoxy) alkylamides and their use as miticides
US4119433A (en) * 1977-07-05 1978-10-10 Stauffer Chemical Company 3-Halo-5-(lower alkoxy) phenoxy alkyl amides
US4154849A (en) * 1977-10-26 1979-05-15 Stauffer Chemical Company N-Cyano-2-(substituted phenoxy) butyramides and their use as mildewicides
CA1071233A (en) * 1975-06-26 1980-02-05 Don R. Baker Phenoxy alkylamides and their use as miticides
DE3629441A1 (en) * 1986-08-29 1988-03-03 Celamerck Gmbh & Co Kg Novel phenoxycarboxylic acid derivatives, their preparation and their use

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2229211A1 (en) * 1971-06-25 1972-12-28 Stauffer Chemical Co., New York, N.Y. (V.StA.) N-acetonitrilo-alpha-phenoxyalkylamides and their use as herbicides
US3932168A (en) * 1971-11-17 1976-01-13 Abbott Laboratories Substituted aryloxyacetamido nitrile derivatives as carbohydrate deposition agents
US4001427A (en) * 1975-06-26 1977-01-04 Stauffer Chemical Company N-dimethylacetonitrile-α-(substituted phenoxy) alkylamides and their use as miticides
CA1071233A (en) * 1975-06-26 1980-02-05 Don R. Baker Phenoxy alkylamides and their use as miticides
US4119433A (en) * 1977-07-05 1978-10-10 Stauffer Chemical Company 3-Halo-5-(lower alkoxy) phenoxy alkyl amides
US4154849A (en) * 1977-10-26 1979-05-15 Stauffer Chemical Company N-Cyano-2-(substituted phenoxy) butyramides and their use as mildewicides
DE3629441A1 (en) * 1986-08-29 1988-03-03 Celamerck Gmbh & Co Kg Novel phenoxycarboxylic acid derivatives, their preparation and their use

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998033765A1 (en) * 1997-02-04 1998-08-06 E.I. Du Pont De Nemours And Company Fungicidal carboxamides
US6251947B1 (en) 1997-02-04 2001-06-26 Board Of Trustees Of The University Of Arkansas Fungicidal carboxamides
EP2314568A3 (en) * 2001-11-16 2012-02-29 Syngenta Participations AG Novel alpha-oxygenated or alpha-thiolated carboxylic acid phenethylamide derivatives
WO2004048316A1 (en) * 2002-11-26 2004-06-10 Syngenta Limited N-alkynyl-2- (substituted phenoxy) alkylamides and their use as fungicides
US7271130B2 (en) 2002-11-26 2007-09-18 Syngenta Limited N-alkynyl-2-(substituted phenoxy) alkylamides and their use as fungicides
US7371764B2 (en) 2002-11-26 2008-05-13 Syngenta Limited Quinolin-isoquinolin-and quinazolin-oxyalkylamides and their use as fungicides
US7420090B2 (en) 2002-11-26 2008-09-02 Syngenta Limited Fungicides
US7511151B2 (en) 2002-11-26 2009-03-31 Syngenta Limited Substituted pyridyloxyalkylamides and their use as fungicides
US8067592B2 (en) 2003-06-04 2011-11-29 Syngenta Limited N-alkyny-2-(substituted aryloxy) alkylthioamine derivatives as fungicides
WO2011087837A3 (en) * 2009-12-22 2012-01-12 E. I. Du Pont De Nemours And Company Fungicidal 2-(bicyclic aryloxy)carboxamides
WO2012087372A1 (en) * 2010-12-22 2012-06-28 E. I. Du Pont De Nemours And Company Fungicidal 2-(bicyclic aryloxy)carboxamides

Similar Documents

Publication Publication Date Title
EP0262393B1 (en) Derivatives of aryloxycarbonic acids, their preparation and their use
DE69324552T4 (en) N&#39;-substituted-N, insecticides N&#39;Diacylhydrazin
CH650493A5 (en) D-(+)-alpha-phenoxypropionic acid derivatives
DE3109035A1 (en) N-SUBSTITUTED (DELTA) (HIGH ARROW) 1 (HIGH ARROW) TETRAHYDROPHTHALIMIDE DERIVATIVES, HERBICIDE COMPOSITION THEREOF, AND METHOD FOR USE THEREOF
DE2643477C2 (en)
DE3702964A1 (en) Aryloxy carboxylic acid derivatives, their preparation and their use
DE2500265A1 (en) NEW MICROBICIDES
EP0175188A1 (en) Carbamoylimidazole derivatives
DE2543888B2 (en) l-Phenyl-S-alkyl-S-benzylureas, process for their preparation and their use as fungicides
CH637386A5 (en) BENZOXAZOLE AND BENZOTHIAZOLE DERIVATIVES.
CH520128A (en) Process for the preparation of thioureidobenzenes and their use in fungicidal and acaricidal agents
DE2717280A1 (en) TRIAZAPENTADIENE, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE AS A MITE AGENT
DE2643403A1 (en) MICROBICIDAL AGENTS
DD147610A5 (en) FUNGICIDAL AGENT
DE2919825C2 (en)
DE2836945A1 (en) DERIVATIVES OF 1,2,4-TRIAZOLE
DE3629441A1 (en) Novel phenoxycarboxylic acid derivatives, their preparation and their use
DD262359A5 (en) GYANOACETAMIDE DERIVATIVES WITH FUNGICIDE EFFICACY
DE2242785A1 (en) 1-ALKYLSULFONYL-2-TRIFLUOROMETHYLBENZIMIDAZOLE, METHOD FOR MANUFACTURING AND USING IT AS AN EECTOPARASITE AGENT
EP0007066A1 (en) 4-Alkyl- and 4-allyl-thio-, sulfinyl- and sulfonyl-methyl-2-amino-6-N,N&#39;-dimethylcarbamoyloxy pyrimidines, process for their preparation, compositions containing them and their use as insecticides
DE4120904A1 (en) ACYLATED AMINOPHENOL DERIVATIVES
EP0398059A1 (en) Cyclopropanoylaminoacid amide derivatives
EP0148442B1 (en) Halogenated sulfides, process for their preparation and their use in microbicidal compositions
DE2643445A1 (en) MICROBICIDAL AGENTS
DE1768041C3 (en) ß-Alkoxyacrylic acid amides and their use for combating insects and acarids

Legal Events

Date Code Title Description
8127 New person/name/address of the applicant

Owner name: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V., D

8128 New person/name/address of the agent

Representative=s name: JUNG, E., DIPL.-CHEM. DR.PHIL. SCHIRDEWAHN, J., DI

8110 Request for examination paragraph 44
8130 Withdrawal