EP0000019A1 - N-benzylcycloalkylamines and process for their preparation - Google Patents

N-benzylcycloalkylamines and process for their preparation Download PDF

Info

Publication number
EP0000019A1
EP0000019A1 EP78100031A EP78100031A EP0000019A1 EP 0000019 A1 EP0000019 A1 EP 0000019A1 EP 78100031 A EP78100031 A EP 78100031A EP 78100031 A EP78100031 A EP 78100031A EP 0000019 A1 EP0000019 A1 EP 0000019A1
Authority
EP
European Patent Office
Prior art keywords
atoms
general formula
alkyl
compounds
given above
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Withdrawn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
EP78100031A
Other languages
German (de)
French (fr)
Inventor
Junichi Saito
Tatsuo Tamura
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.)
Bayer CropScience KK
Original Assignee
Nihon Tokushu Noyaku Seizo KK
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 Nihon Tokushu Noyaku Seizo KK filed Critical Nihon Tokushu Noyaku Seizo KK
Publication of EP0000019A1 publication Critical patent/EP0000019A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/32—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing >N—CO—N< or >N—CS—N< groups directly attached to a cycloaliphatic ring

Definitions

  • the invention relates to new N-benzylcycloalkylamines and a process for their preparation.
  • the compounds of formula (I) can be used as intermediates for the production of certain urea and thiourea compounds with excellent fungicidal properties.
  • R 1 is preferably hydrogen or methyl
  • R 2 is an optionally substituted by methyl tetramethylene or pentamethylene group or a hexamethylene group and X is chlorine, bromine, nitro, cyano or methyl.
  • the substituent X is preferably in the 4-position.
  • Suitable benzyl halides of the general formula (II) as starting materials in process variant a) are 4-chlorobenzyl chloride, 4-bromobenzyl chloride, 4-methylbenzyl chloride, 4-nitrobenzyl chloride, 4-cyanobenzyl chloride, 4-chloro-a-methylbenzyl chloride and the corresponding bromides.
  • cycloalkylamines of the general formula (III) which can also be used as starting materials in process variant a) are cyclopentylamine, 3-methylcyclopentylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine and cycloheptylamine.
  • the reaction is preferably carried out using twice the molar amount of amine (based on benzyl halide).
  • the excess of amine serves to bind the acid released in the reaction.
  • Such acid binders are the acid acceptors commonly used, in particular the hydroxides, carbonates, bicarbonates and alcoholates of alkali metals and tertiary amines such as e.g. Triethylamine, diethylaniline and pyridine.
  • N-benzylamines of the general formula (IV) to be used as starting materials in process variant b) are 4-chlorobenzylamine, 4-bromobenzylamine, 4-methylbenzylamine, 4-nitrobenzylamine, 4-cyanobenzylamine and 4-chloro-a-methylbenzylamine.
  • cyclic ketones of the formula (V) which are also suitable as starting materials in process variant b) are cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone and cycloheptanone.
  • Examples of reducing agents for Schiff's Bases of the formula (VI) are sodium borohydride, lithium aluminum hydride, metallic sodium (in alcohol) and metallic magnesium (in alcohol).
  • the Schiff base obtained as an intermediate can be isolated or e.g. be reduced by means of sodium borohydride without isolation in order to obtain the desired N-benzylcycloalkylamine with high purity in good yield.
  • Process variants a) and b) according to the invention are preferably carried out using a solvent or diluent.
  • solvents or diluents are water and inert organic solvents such as aliphatic, alicyclic and aromatic hydrocarbons, which may optionally be chlorinated, such as, for example, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, Carbon tetrachloride, ethylene chloride, trichlorethylene and chlorobenzene, ethers such as diethyl ether, methyl ethyl ether, diispropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl
  • Butanol and ethylene glycol Esters such as ethyl acetate and amyl acetate; Acid amides such as dimethylformamide and dimethylacetamide; Sulfones and sulfoxides such as dimethyl sulfoxide and dimethyl sulfone; and bases such as pyridine.
  • Process variants a) and b) according to the invention can be carried out within a wide temperature range.
  • the. Procedure within a from -20 ° C to the boiling point of the mixture, preferably at temperatures from 0-100 ° C.
  • the reaction is preferably carried out at atmospheric pressure, but it can also be carried out at elevated or reduced pressure.
  • the Schiff base is dissolved in 300 ml of methyl alcohol and 38 g of sodium borohydride are added dropwise with ice cooling. After the addition was completed, the mixture was stirred at 50 ° C for 2 hours to carry out the reaction.
  • the methyl alcohol is distilled off from the reaction mixture, the remaining residue is diluted with water to decompose the borohydrate.
  • the oily material obtained is extracted with ether.
  • the ether layer is dried over anhydrous sodium sulfate, the ether is distilled off under reduced pressure and the residue is distilled under reduced pressure, 15C g-N-4-chlorobenzylcyclopentylamine with a boiling point of 109-110 ° C / 0.2 mm Hg being maintained.
  • the organic phase is dried over anhydrous sodium sulfate and the toluene is distilled off under reduced pressure, 9 'g of 4-4-methylbenzylcyclopentylamine having a boiling point of 102-103 C / 0.3 mm Hg being obtained.
  • the urea or thiourea compounds prepared by reacting the N-benzylcycloalkylamine compounds of the formula (I) with various isocyanates or isothiocyanates have excellent fungicidal properties.
  • urea or thiourea compounds mentioned can be used for the control and control of various plant diseases caused by fungi.
  • the urea or thiourea compounds prepared from the compounds according to the invention can be used against pathogans which affect the part of the plants lying above the ground, and also against pathogens which cause trachacmycosis by attacking the parts of the plants below the ground or the soil of the plants . They are only slightly tonic to warm-blooded animals and well tolerated by Plants, that is to say that at normal application concentrations they have no phytetoxicity to agricultural products. The urea or thiourea compounds according to the invention can therefore be used successfully against the. Pathogens causing fungal diseases on plants can be used in agriculture and gardening.
  • Such ureas and thiourea compounds can be used effectively against plant pathogens such as Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi Imperfecti.
  • Basidiomycetes such as, for example, Pellicularia sasakii, which is one of the most important diseases in rice plants, and Pellicularia filamentosa, which occurs in various agricultural products.
  • the fungicidal activity of the urea or thiourea compounds prepared from the N-benzylcycloalkylamine compounds according to the invention is evident from the bioassay examples given below.
  • the active ingredient, carrier and emulsifier were mixed in the abovementioned amounts to form a wettable powder, which is diluted with water to the prescribed concentration.
  • Rice plants of the Kinnampu variety were grown in Wag pulled pots with 0.0002 Ar each under flood conditions. When young ears were formed, the test compound formulation prepared as described above was sprayed in amounts of 100 ml onto 3 pots each.
  • the rice plants were inoculated at the roots with Pellicularia sasakii, which had previously been grown on a barley bed and had formed sclerotia.
  • the inoculation of the plants was continued for 10 days in a humidity chamber at 28-30 ° C with a relative humidity of 95% or more,

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The compounds of the general formula <IMAGE> in which R<1> denotes hydrogen or alkyl having 1-4 C atoms, R<2> denotes a polymethylene group having 4-7 C atoms, which is optionally substituted by alkyl having 1-4 C atoms, and X denotes halogen, nitro, cyano or alkyl having 1-4 C atoms, are obtained when a benzyl halide is reacted with a cycloalkylamine, if appropriate in the presence of an acid-binding agent, or when a benzylamine is reacted with a cyclic ketone and the Schiff's base obtained is reduced. The compounds of the formula (I) can be used as intermediates for the preparation of certain urea and thiourea compounds having excellent fungicidal properties.

Description

Die Erfindung betrifft neue N-Benzylcycloalkylamine und ein Verfahren zu ihrer Herstellung.The invention relates to new N-benzylcycloalkylamines and a process for their preparation.

Die erfindungsgemäßen Verbindungen entsprechen der allgemeinen Formel

Figure imgb0001
worin

  • R 1 Wasserstoff oder Alkyl mit 1 - 4 C-Atomen,
  • R2 eine Polymethylengruppe mit 4 - 7 C-Atomen, die gegebenenfalls durch Alkyl mit 1 - 4 C-Atomen substituiert ist, und
  • X Halogen, Nitro, Cyan oder Alkyl mit 1 - 4 C-Atomen bedeuten.
The compounds according to the invention correspond to the general formula
Figure imgb0001
 wherein
  • R 1 is hydrogen or alkyl having 1 to 4 carbon atoms,
  • R 2 is a polymethylene group with 4-7 C atoms, which is optionally substituted by alkyl with 1-4 C atoms, and
  • X is halogen, nitro, cyan or alkyl having 1 to 4 carbon atoms.

Die Verbindungen der Formel (I) können als Zwischenprodukte für die Herstellung bestimmter Harnstoff-und Thioharnstoffverbindungen mit ausgezeichneten fungiziden Eigenschaften verwendet werden.The compounds of formula (I) can be used as intermediates for the production of certain urea and thiourea compounds with excellent fungicidal properties.

Vorzugsweise bedeutet R1 Wasserstoff oder Methyl, R2 eine gegebenenfalls durch Methyl substituierte Tetramethylen- oder Pentamethylengruppe oder eine Hexamethylengruppe und X Chlor, Brom, Nitro, Cyan oder Methyl. Bevorzugt steht der Substituent X in der 4-Position.R 1 is preferably hydrogen or methyl, R 2 is an optionally substituted by methyl tetramethylene or pentamethylene group or a hexamethylene group and X is chlorine, bromine, nitro, cyano or methyl. The substituent X is preferably in the 4-position.

Die vorliegende Erfindung betrifft auch ein Verfahren zur Herstellung von Verbindungen der Formel (I), bei dem man

  • a) ein Benzylhalogenid der allgemeinen Formel
    Figure imgb0002
    worin
    • R1 und X die vorstehend angeführte Bedeutung besitzen und
    • Hal Halogen, vorzugsweise Chlor, bedeutet, mit einem Cycloalkylamin der allgemeinen.Formel
      Figure imgb0003
      worin
    • R2 die oben angeführte Bedeutung besitzt, gegebenenfalls in Gegenwart eines Säurebindemittels, umsetzt, oder
  • b) ein Benzylamin der allgemeinen Formel
    Figure imgb0004
    worin
    • R1 und X die vorstehend angeführte Bedeutung aufweisen, mit einem cyclischen Keton der allgemeinen Formel
      Figure imgb0005
      worin
    • R2 die oben angeführte Bedeutung besitzt umsetzt, und die so erhaltene Schiff'sche Base der allgemeinen Formel
      Figure imgb0006
      worin
    • R1,R2 und X die oben angeführte Bedeutung besitzen, reduziert.
The present invention also relates to a process for the preparation of compounds of the formula (I), in which
  • a) a benzyl halide of the general formula
    Figure imgb0002
     wherein
    • R 1 and X have the meaning given above and
    • Hal is halogen, preferably chlorine, with a cycloalkylamine of the general formula
      Figure imgb0003
       wherein
    • R 2 has the meaning given above, optionally in the presence of an acid binder, or
  • b) a benzylamine of the general formula
    Figure imgb0004
     wherein
    • R 1 and X have the meaning given above, with a cyclic ketone of the general formula
      Figure imgb0005
       wherein
    • R 2 has the meaning given above, and the Schiff base of the general formula thus obtained
      Figure imgb0006
       wherein
    • R 1 , R 2 and X have the meaning given above, reduced.

Beispiele für als Ausgangsstoffe in der Verfahrenevariante a) geeignete Benzylhalogenide der allgemeinen Formel (II) sind 4-Chlorbenzylchlorid, 4-Brombenzylchlorid, 4-Methylbenzylchlorid, 4-Nitrobenzylchlorid, 4-Cyanbenzylchlorid, 4-Chlor-a-methylbenzylchlorid und die entsprechenden Bromide.Examples of suitable benzyl halides of the general formula (II) as starting materials in process variant a) are 4-chlorobenzyl chloride, 4-bromobenzyl chloride, 4-methylbenzyl chloride, 4-nitrobenzyl chloride, 4-cyanobenzyl chloride, 4-chloro-a-methylbenzyl chloride and the corresponding bromides.

Als Beispiele für Cycloalkylamine der allgemeinen Formel (III), die ebenfalls als Ausgangsstoffe in der Verfahrensvariante a) eingesetzt werden können, seien Cyclopentylamin, 3-Methylcyclopentylamin, Cyclohexylamin, 2-Methylcyclohexylamin, 3-Methylcyclohexylamin, 4-Methylcyclohexylamin und Cycloheptylamin genannt.Examples of cycloalkylamines of the general formula (III) which can also be used as starting materials in process variant a) are cyclopentylamine, 3-methylcyclopentylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine and cycloheptylamine.

Werden in der Verfahrensvariante a) 4-Chlorbenzylchlorid und Cyclopentylamin als Ausgangsstoffe eingesetzt, so kann die Umsetzung durch folgendes Schema dargustellt werden:

Figure imgb0007
If 4-chlorobenzyl chloride and cyclopentylamine are used as starting materials in process variant a), the implementation can be represented by the following scheme:
Figure imgb0007

Bei Durchführung der Verfahrensvariant.e a) wird die Umsetzung vorzugsweise unter Verwendung der doppelten molaren Menge an Amin (bezogen auf Benzylhalogenid) durchgeführt. In diesem Fall dient der Überschuß an Amin dazu, die in der Umsetzung freigesetzte Säure zu binden. Es ist jedoch auch möglich, die molare Menge an Amin in Gegenwart einer äquimolaren Menge an Säurebindemittel einzusetzen.When carrying out process variant e a), the reaction is preferably carried out using twice the molar amount of amine (based on benzyl halide). In this case, the excess of amine serves to bind the acid released in the reaction. However, it is also possible to use the molar amount of amine in the presence of an equimolar amount of acid binder.

Derartige Säurebindemittel sind die üblicherweise eingesetzten Säureakzeptoren, insbesondere die Hydroxide, Carbonate, Bicarbonate und Alkoholate von Alkalimetallen sowie tertiäre Amine wie z.B. Triäthylamin, Diäthylanilin und Pyridin.Such acid binders are the acid acceptors commonly used, in particular the hydroxides, carbonates, bicarbonates and alcoholates of alkali metals and tertiary amines such as e.g. Triethylamine, diethylaniline and pyridine.

Beispiele für die als Ausgangsstoffe in der Verfahrensvariante b) einzusetzenden N-Benzylamine der .allgemeinen Formel (IV) sind 4-Chlorbenzylamin, 4-Brombenzylamin, 4-Methylbenzylamin, 4-Nitrobenzylamin, 4-Cyanobenzylamin und 4-Chlor-a-methylbenzylamin.Examples of the N-benzylamines of the general formula (IV) to be used as starting materials in process variant b) are 4-chlorobenzylamine, 4-bromobenzylamine, 4-methylbenzylamine, 4-nitrobenzylamine, 4-cyanobenzylamine and 4-chloro-a-methylbenzylamine.

Als Beispiele für cyclische Ketone der Formel (V), welche ebenfalls als Ausgangsmaterialien in der Verfahrensvariante b) geeignet sind, seien Cyclopentanon, 3-Methylcyclopentanon, Cyclohexanon, 2-Methylcyclohexanon, 3-Methylcyclohexanon, 4-Methylcyclohexanon und Cycloheptanon genannt.Examples of cyclic ketones of the formula (V) which are also suitable as starting materials in process variant b) are cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone and cycloheptanone.

Beispiele für Reduktionsmittel für die Schiff'schen Basen- der Formel (VI) sind Natriumborhydrid, Lithiumaluminiumhydrid, metallisches Natrium (in Alkohol) und metallisches Magnesium (in Alkohol).Examples of reducing agents for Schiff's Bases of the formula (VI) are sodium borohydride, lithium aluminum hydride, metallic sodium (in alcohol) and metallic magnesium (in alcohol).

Bei Verwendung von 4-Chlorbenzylamin und Cyclopentanon als Ausgangsstoffe in der Verfahrensvariante b) unter Verwendung von Natriumborhydrid als Reduktionsmittel kann die Umsetzung durch folgendes Schema dargestellt werden

Figure imgb0008
Figure imgb0009
 When using 4-chlorobenzylamine and cyclopentanone as starting materials in process variant b) using sodium borohydride as reducing agent, the reaction can be represented by the following scheme
Figure imgb0008
Figure imgb0009

Bei Durchführung der Verfahrensvariante b) kann die als Zwischenprodukt erhaltene Schiff'sche Base isoliert oder z.B. mittels Natriumborhydrid ohne Isolierung reduziert werden, um das gewünschte N-Benzylcycloalkylamin mit hoher Reinheit in guter Ausbeute zu erhalten.When carrying out process variant b), the Schiff base obtained as an intermediate can be isolated or e.g. be reduced by means of sodium borohydride without isolation in order to obtain the desired N-benzylcycloalkylamine with high purity in good yield.

Die erfindungsgemäßen Verfahrensvarianten a) und b) werden vorzugsweise unter Verwendung eines Lösungs- oder Verdünnungsmittels durchgeführt. Beispiele für derartige Lösungs- oder Verdünnungsmittel sind Wasser und inerte organische Lösungsmittel wie aliphatische, alicyclische und aromatische Kohlerwasserstoffe, die gegebenenfalls chloriert sein können, wie z.B. Hexan, Cyclohexan, Petroläther, Ligroin, Benzol, Toluol, Xylol, Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, Äthylenchlorid, Trichloräthylen und Chlorbenzol, Äther wie z.B. Diäthyläther, Methyläthyl- äther, Diiscpropyläther, Dibutyläther, Propylenoxid, Dioxan und Tetrahydrofuran; Ketone wie z.B. Aceton, Methyläthylketon, Methylisopropylketon und Methylisobutylketon; Nitrile wie z.B. Acetonitril, Propionitril und Acrylnitril; Alkohole wie Methanol, Äthanol, Isopropanol, tert. Butanol und Äthylenglycol; Ester wie z.B. Äthylacetat und Amylacetat; Säureamide wie z.B. Dimethylformamid und Dimethylacetamid; Sulfone und Sulfoxide wie z.B. Dimethylsulfoxid und Dimethylsulfon; und Basen wie z.B. Pyridin.Process variants a) and b) according to the invention are preferably carried out using a solvent or diluent. Examples of such solvents or diluents are water and inert organic solvents such as aliphatic, alicyclic and aromatic hydrocarbons, which may optionally be chlorinated, such as, for example, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, Carbon tetrachloride, ethylene chloride, trichlorethylene and chlorobenzene, ethers such as diethyl ether, methyl ethyl ether, diispropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile and acrylonitrile; Alcohols such as methanol, ethanol, isopropanol, tert. Butanol and ethylene glycol; Esters such as ethyl acetate and amyl acetate; Acid amides such as dimethylformamide and dimethylacetamide; Sulfones and sulfoxides such as dimethyl sulfoxide and dimethyl sulfone; and bases such as pyridine.

Die arfindungsgemäßen Verfahrensvarianten a) und b) können innerhalb eines weiten Temperaturbereichs durchgeführt warier. Im allgameinen wird das. Verfahren innerhalb eines

Figure imgb0010
von -20°C bis zum Siedepunkt des Gemisches, vorzugsweise bei Temperaturen von O - 100°C, vorgenommen. Die Umsetzung erfolgt vorzugsweise bei atmosphärischen Druck, sie kann jedoch auch bei erhöhtem oder vermindertem Druck durchgeführt werden.Process variants a) and b) according to the invention can be carried out within a wide temperature range. In general, the. Procedure within a
Figure imgb0010
from -20 ° C to the boiling point of the mixture, preferably at temperatures from 0-100 ° C. The reaction is preferably carried out at atmospheric pressure, but it can also be carried out at elevated or reduced pressure.

Das erfindungsgemäße Verfahren wird anhand der machstehenden Herstellungsbeispiele näher erläutert.The process according to the invention is explained in more detail with reference to the manufacturing examples given.

Beispielexample

Figure imgb0011
Figure imgb0011

Variante a).Option A).

170 g Cyclopentylamin und 40 g Natriumhydroxid werden in 160 ml Wasser gelöst, dann werden unter Rühren und Kühlung 161 g 4-Chlorbenzylchlorid zugetropft. Nach beendeter Zugabe wird die Mischung allmählich erhitzt und bei 60 - 70°C bis zum Ende der Umsetzung 3 Stunden lang gerührt. Die Mischung wird dann bis unter Raumtemperatur gekühlt, die wässerige Phase wird abgetrennt und der Überschuß an Cyclopentylamin bei vermindertem Druck abdestilliert. Nach beendeter Destillation wird der Rückstand mit 200 ml Toluol versetzt und das Gemisch 2 mal mit jeweils 200 ml Wasser gewaschen und darauf über wasserfreiem Natriumsulfat getrocknet. Das Toluol wird unter vermindertem Druckentfernt und der Rückstand unter vermindertem Druck destilliert, wobei 195 g N-4-Chlorbenzylcyclopentylamin mit einem Siedepunkt von 109-110°C/0,2 mm Hg erhalten werden.170 g of cyclopentylamine and 40 g of sodium hydroxide are dissolved in 160 ml of water, then 161 g of 4-chlorobenzyl chloride are added dropwise with stirring and cooling. When the addition is complete, the mixture is gradually heated and stirred at 60-70 ° C. for 3 hours until the reaction has ended. The mixture is then below room temperature cooled, the aqueous phase is separated off and the excess cyclopentylamine is distilled off under reduced pressure. After the distillation has ended, 200 ml of toluene are added to the residue, and the mixture is washed twice with 200 ml of water each time and then dried over anhydrous sodium sulfate. The toluene is removed under reduced pressure and the residue is distilled under reduced pressure to give 195 g of N-4-chlorobenzylcyclopentylamine with a boiling point of 109-110 ° C / 0.2 mm Hg.

Variante b)Variant b)

141,5 g 4-Chlorbenzylamin und 84 g Cyclopentanon werden in 400 ml Toluol gelöst. Die Temperatur des Gemisches wird allmählich erhöht, wobei sich Wasser bilder, welches dann azectrop mittels Toluol vollständig entfernt wird, um die

Figure imgb0012
zu beenden. Das Toluol wird unter vermindertem Druck entfernt, wobei als Kondensat die Schiff'sche Base, erhalten wird.141.5 g of 4-chlorobenzylamine and 84 g of cyclopentanone are dissolved in 400 ml of toluene. The temperature of the mixture is gradually increased, with water forming, which is then completely removed azectropically by means of toluene
Figure imgb0012
to end. The toluene is removed under reduced pressure to give Schiff's base as the condensate.

Die Schiff'sche Base wird in 300 ml Methylalkohol gelöst und 38 g Natriumborhydrid werden unter Eiskühlung zugetropft. Nach beendeter Zugabe wird die Mischung bei 50°C 2 Stunden lang gerührt, um die Umsetzung durchzuführen. Der Methylalkohol wird aus dem Reaktionsgemisch abdestilliert, der verbleibende Rest wird mit Wasser verdünnt, um das Borhydrat zu zersetzen, Das erhaltene ölige Material wird mit Äther extrahiert. Die Ätherschicht wird über wasserfreiem Natriumsulfat getrccknet, der Äther unter vermindertem Druck abdestilliert und der Rückstand unter vermindertem Druck destilliert, wobei 15C g-N-4-Chlorbenzylcyclopentylamin mit einem Siedepunkt von 109-110°C/0,2 mm Hg anhalten werden..The Schiff base is dissolved in 300 ml of methyl alcohol and 38 g of sodium borohydride are added dropwise with ice cooling. After the addition was completed, the mixture was stirred at 50 ° C for 2 hours to carry out the reaction. The methyl alcohol is distilled off from the reaction mixture, the remaining residue is diluted with water to decompose the borohydrate. The oily material obtained is extracted with ether. The ether layer is dried over anhydrous sodium sulfate, the ether is distilled off under reduced pressure and the residue is distilled under reduced pressure, 15C g-N-4-chlorobenzylcyclopentylamine with a boiling point of 109-110 ° C / 0.2 mm Hg being maintained.

Beispiel 2Example 2

Figure imgb0013
70 g 4-Methylbenzylchlorid werden unter Rühren zu 170 g Cyclopentylamin, welches eine Temperatur von . 40°C aufweist, zugegeben. Nach beendeter Zugabe wird das Gemisch allmählich erhitzt und bei 60°C 2 Stunden lang gerührt, um die Umsetzung zu vollenden. Das Gemisch wird dann auf etwa 15°C gekühlt und in eine Lösung von 24 g Natriumhydroxid in 400 ml Wasser gegossen. Nach gründlichem Rühren wird das gewünschte Produkt einmal mit 300 ml Toluol und zwaimal mit jeweils 100 ml Toluol extrahiert. Die organische Phase wird über wasserfreiem Natriumsulfat getrocknet und das Toluol unter vermindertem Druck abdestilliert, wobei 9' g 4-4-Methylbenzylcyclopentylamin mit einem Siedenunkt von 102-103 C/0,3 mm Hg erhalten werden.
Figure imgb0013
 70 g of 4-methylbenzyl chloride with stirring to 170 g of cyclopentylamine, which has a temperature of. 40 ° C added. When the addition is complete, the mixture is gradually heated and stirred at 60 ° C for 2 hours to complete the reaction. The mixture is then cooled to about 15 ° C and poured into a solution of 24 g sodium hydroxide in 400 ml water. After thorough stirring, the desired product is extracted once with 300 ml of toluene and twice with 100 ml of toluene. The organic phase is dried over anhydrous sodium sulfate and the toluene is distilled off under reduced pressure, 9 'g of 4-4-methylbenzylcyclopentylamine having a boiling point of 102-103 C / 0.3 mm Hg being obtained.

Folgende Verbindungen wurden nach den in den vorstehenden Beispielen analogen Verfahren hergestellt:

Figure imgb0014
Figure imgb0015
 The following compounds were prepared by the methods analogous to those in the preceding examples:
Figure imgb0014
Figure imgb0015

Die durch Umsetzung der N-Benzylcycloalkylaminverbindungen der Formel (I) mit verschiedenen Isocyanaten oder Isothiocyanaten hergestellten Harnstoff- oder Thioharnstoffverbindungen besitzen ausgezeichnete fungizide Eigenschaften.The urea or thiourea compounds prepared by reacting the N-benzylcycloalkylamine compounds of the formula (I) with various isocyanates or isothiocyanates have excellent fungicidal properties.

Die genannten Harnstoff- oder Thioharnstoffverbindungen können für die Kontrolle und Bekämpfung verschiedener, durch Pilze verursachter Pflanzenerkrankungen eingesetzt werden.The urea or thiourea compounds mentioned can be used for the control and control of various plant diseases caused by fungi.

Die aus den erfindungsgemäßen Verbindungen hergestellten Harnstoff- oder Thioharnstoffverbindungen können gegen Pathogane, welche den über dem Erdreich gelegenen Teil der Pflanzen befallen, eingesetzt werden, ferner gegen Pathogene, welche durch Befall der unter dem Erdreich gelegenen Teile der Pflanzen der Samen oder des Erdreichs Trachacmycose verursachen. Sie sind nur geringfügig tonisch gegenüber Warmblütern und gut verträglich für

Figure imgb0016
Pflanzen, d.h. deß sie bei normalen Anwendungskonzentrationan keine Phytetoxizität gegenüber Ackerbauprodukten aufweisen. Die erfindungagemäßen Harnstoff-oder Thioharnstoffverbindungen können daher mit gutem Erfolg gegen die. Erreger von Pilzerkrankungen an Pflanzen in der Landwirtschaft und im Cartenbau eingesetzt werden.The urea or thiourea compounds prepared from the compounds according to the invention can be used against pathogans which affect the part of the plants lying above the ground, and also against pathogens which cause trachacmycosis by attacking the parts of the plants below the ground or the soil of the plants . They are only slightly tonic to warm-blooded animals and well tolerated by
Figure imgb0016
Plants, that is to say that at normal application concentrations they have no phytetoxicity to agricultural products. The urea or thiourea compounds according to the invention can therefore be used successfully against the. Pathogens causing fungal diseases on plants can be used in agriculture and gardening.

Darartige Harnstoffe und Thioharnstoffverbindungen können wirksam gegen Pflanzenerkrankungserreger wie Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes und Fungi Imperfecti eingesetzt werden. Insbesondere sind sie wirksam gegenüber Basidiomyceten wie z.B. Pellicularia sasakii, welche eine der wichtigsten Xrankheiten bei Reispflanzen ist, und Pellicularia filamentosa, die bei verachiedenen Ackerbauprodukten auf- tritt, Außardem besitzen sie aussazeichnete Wirksamkeit zegenüber Gorticium centrifungrum bei verschiedenen Ackerbauprodukten, Pyticularia oryzae und Xanthomonas oryzae, welche Reispflanzen befallen, Erwinia aroideae an Chinakohl, Xanthomonas citri an Zitrusfrüchten, Cochliobolus miyabeanus an Reispflanzen, Mycosphaerella musicola an Bananen, Botrytis cinerea an verschiedenen Ackerbauprodukten einschließlich Erdbeeren, Plasmopara viticola an Weintrauben, Glomerella cingulata an Weintrauben, Äpfeln und Birnen, Sclerotinia aclerotiorum an Gemüsen, Colletotrichum lagenarium an Gurken, Diaporthe citri an Zitrusfrüchten, Podosphaera leucotricha an Äpfeln, Sphaeroteca fuliginea an Gurken, Pilzerkrankungen, welche schwarzen Blattbrand verursachen, wie z.B. Alternaria mali an Äpfeln, Alternaria solani an Kartoffeln, Alternaria kikuchiana an Birnen und Pilzen welche Schorf verursachen, wie z.B. Venturia inaequalis an Äpfeln und Venturia pirina an Birnen.Such ureas and thiourea compounds can be used effectively against plant pathogens such as Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi Imperfecti. In particular, they are effective against Basidiomycetes such as, for example, Pellicularia sasakii, which is one of the most important diseases in rice plants, and Pellicularia filamentosa, which occurs in various agricultural products. In addition, they have excellent activity against Gorticium centrifungrum in various agricultural products, Pyticularia ora and Pyticularia oras oryzae, which infest rice plants, Erwinia aroideae on Chinese cabbage, Xanthomonas citri on citrus fruits, Cochliobolus miyabeanus on rice plants, Mycosphaerella musicola on bananas, Botrytis cinerea on various arable crops including strawberries, Plasmopara viticola on grapes, Selnclerotina ape cloves, Glomerella ananas, Glomerella on vegetables, Colletotrichum lagenarium on cucumbers, Diaporthe citri on citrus fruits, Podosphaera leucotricha on apples, Sphaeroteca fuliginea on cucumbers, fungal diseases which cause black leaf fire, such as Alternaria mali on apples, Alternaria solani on potatoes, Alternaria kikuchiana on Birorf cause, such as Venturia inaequalis on apples and Venturia pirina on pears.

Die fungizide Wirksamkeit der aus den erfindungs- zemäβen N-Benzylcycloalkylaminverbindungen hergestellten Harnstoff- oder Thioharnstoffverbindungen geht aus den rachstehend angeführten Biotestbeispielen hervor.The fungicidal activity of the urea or thiourea compounds prepared from the N-benzylcycloalkylamine compounds according to the invention is evident from the bioassay examples given below.

Beispiel AExample A

Bekämpfung von Blattscheidenbrand an Reispflanzen (Topftest)Fighting leaf sheath fire on rice plants (pot test)

Herstellung der WirkstofformulierungProduction of the active ingredient formulation

Figure imgb0017
Figure imgb0017

Wirkstoff, Trägermittel und Emulgator wurden in den oben angeführten Mengen zu einem benetzbaren Pulver vermischt, welches mit Wasser auf die vorgeschriebene Konzentration verdünnt wird.The active ingredient, carrier and emulsifier were mixed in the abovementioned amounts to form a wettable powder, which is diluted with water to the prescribed concentration.

TestverfahrenTest procedure

Reispflanzen der Varietät Kinnampu wurden in Wagnertöpfen mit je 0,0002 Ar unter Überschwemmungsbedingungen gezogen, Bei der Bildung junger Ähren wurde die wie vorstehend beschrieben hergestellte Formulierung der Testverbindung in Mengen von 100 ml auf jeweils 3 Töpfe aufgesprüht.Rice plants of the Kinnampu variety were grown in Wag pulled pots with 0.0002 Ar each under flood conditions. When young ears were formed, the test compound formulation prepared as described above was sprayed in amounts of 100 ml onto 3 pots each.

Am folgenden Tag wurden die Reispflanzen an den Wurzeln mit Pellicularia sasakii beimpft, die vorher auf einem Gerstennährboden gezogen worden war und Sklerotien gebildet hatte. Die Beimpfung der Pflanzen wurde in einer Feuchtekammer bei 28-30°C bei einer relativen Luftfeuchtigkeit von 95 % oder mehr 10 Tage lang fortgesetzt,The following day, the rice plants were inoculated at the roots with Pellicularia sasakii, which had previously been grown on a barley bed and had formed sclerotia. The inoculation of the plants was continued for 10 days in a humidity chamber at 28-30 ° C with a relative humidity of 95% or more,

Nach Ablauf dieses Zeitraums wurden der Befallsgrad und das Ausmaß der Phytotoxizität bestimmt. Die Prüfung wurde durch Bemessen des Ausbreitungsgrades der Infektionsflecken von der Beimpfungsstelle von der Wurzel

Figure imgb0018
vorgenommen und der Befallsgrad wurde wie folgt bewerset.
Figure imgb0019
worin

  • N = Gesamtzahl der geprüften Reisstengel
  • n1 Anzahl der Stengel ohne Anzeichen von Befall
  • n1 Anzahl der Stengel, die von unten an bis zur ersten Blattscheide befallen waren
  • n2 Anzahl der Stengel, die von unten an bis zur zweiten Blattscheide befallen waren
  • n3 Anzahl der Stengel, die von unten an bis zur dmitten Blattscheide befallen waren
After this period, the degree of infestation and the level of phytotoxicity were determined. The test was carried out by measuring the degree of spread of the infection spots from the inoculation site from the root
Figure imgb0018
and the degree of infestation was assessed as follows.
Figure imgb0019
 wherein
  • N = total number of rice stems tested
  • n 1 Number of stems with no signs of infection
  • n 1 Number of stems that were affected from the bottom to the first leaf sheath
  • n 2 Number of stems that were affected from the bottom to the second leaf sheath
  • n 3 Number of stems that were affected from the bottom to the middle leaf sheath

Die Ergebnisse der Tests sind aus Tabelle A ersichtlich:

Figure imgb0020
Figure imgb0021
Figure imgb0022
 The results of the tests are shown in Table A:
Figure imgb0020
Figure imgb0021
Figure imgb0022

Beispiel BExample B Bekämpfung von Rhizopus oryzae (Umfallkrankheit der Keimlinge)Control of Rhizopus oryzae (seedling disease) Wirks tofformulierung:Active substance formulation:

Figure imgb0023
Figure imgb0023

Testverfahren:Test procedure:

In einem Autoklaven sterilisiertes Hochlanderdreich (organisches Erdreich) wurde mit Rhizopus oryzae beimpft, der auf Weizenkleienährboden 5 Tage lang gezogen worden war, der Mikroorganismus wurde durch Halten des Erdreichs in einer Feuchtkammer während 48 Stunden zum Vermehren gebracht, um das Erdreich zu infizieren. Das wie vorstehend beschrieben infizierte Erdreich wurde in einen Setzkasten mit den Abmessungen 58 cm x 28 cm eingebracht und 2 cm tief verteilt, dann wurden etwa 350 ml ungeschälter Reis der Varietät Asahi, der 48 Stunden in Wasser angequollen und damit zur beginnenden Keimung gebracht worden war, in den Kasten gesät und mit Erdreich bedeckt..Highland soil (organic soil) sterilized in an autoclave was inoculated with Rhizopus oryzae grown on wheat bran culture medium for 5 days, the microorganism was propagated by keeping the soil in a humid chamber for 48 hours to infect the soil. The soil infected as described above was placed in a 58 cm x 28 cm seed box and distributed 2 cm deep, then about 350 ml of unpeeled rice of the Asahi variety, which had been swollen in water for 48 hours and brought to the onset of germination , sown in the box and covered with soil ..

Das Erdreich wurde darauf mit einer verdünnten, wässerigen Lösung der Wirkstofformulierung in der vorgeschriebenen Konzentration in Mengen von 500 ml pro Kasten berieselt. Die Setzkästen wurden in einer Feuchtkammer 4 Tage lang bei Temperaturen von 33-35°C gehalten, um die Keimung einzuleiten. Nach Entnahme aus der Feuchtkammer wurden die Setzlinge auf herkömmliche Weise zum Ergrünen und Erhärten gebracht und in einem Treibhaus mit der üblichen Sorgfalt gezogen. 15 Tage nach Beginn der Keimung wurden insgesamt 100 Setzlinge von zwei Stellen in der Mitte jedes Setzkastens entnommen und der Wurzelbafall und der Befallsgrad mit Umfallkrankheit der Keimlinge wurde nach der nachstehenden Norm bewertet:

  • (A) schwerer Befall: alle Wurzeln abgestorben oder verkümmertes Wurzelwachstum, oder alle Wurzelhauben gehemmt.
  • (B) leichter Befall: normales Wachstum 1-2 Wurzelhauben und Hauptwurzeln.
  • (C) gesund: normales Wachstum von 3 oder mehr Wurzelhauben und Hauptwurzeln.
The soil was then sprinkled with a dilute, aqueous solution of the active compound formulation in the prescribed concentration in amounts of 500 ml per box. The type cases were kept in a humid chamber at temperatures of 33-35 ° C for 4 days to initiate germination. After removal from the wet room, the seedlings were greened and hardened in a conventional manner and grown in a greenhouse with the usual care. 15 days after the start of germination, a total of 100 seedlings were removed from two places in the middle of each seed box and the root fall and the The degree of infestation with seeding disease of the seedlings was assessed according to the following standard:
  • (A) severe infestation: all roots have died or stunted root growth, or all root canals have been inhibited.
  • (B) mild infestation: normal growth 1-2 root caps and main roots.
  • (C) healthy: normal growth of 3 or more root canals and main roots.

Der Befallsgrad wurde gemäß nachstehender Gleichung berechnet:

Figure imgb0024
worin

  • An die Zahl der schwer befallenen Stengel
  • Bn die Zahl der leicht befallenen Stengel
  • Cn die Zahl der gesunden Stengel
    bedeutet und

N : An x Bn + Cn = 100 ist.The degree of infestation was calculated according to the following equation:
Figure imgb0024
 wherein
  • The number of severely infested stems
  • Bn the number of slightly infected stems
  • Cn the number of healthy stems
    means and

N: An x Bn + Cn = 100.

Die Testergebnisse sind aus der nachstehenden Tabelle B ersichtlich.

Figure imgb0025
The test results are shown in Table B below.
Figure imgb0025

Claims (2)

1, N-Benzylcycloalkylamine der allgemeinen Formel
Figure imgb0026
worin R1 Wasserstoff oder Alkyl mit 1 - 4 C-Atomen, R2 eine Polymethylengruppe mit 4 - 7 C-Atomen, die gegebenenfalls durch Alkyl mit 1 - 4 C-Atomen substituiert ist, und X Halogen, Nitro, Cyan oder Alkyl mit 1 - 4 C-Atomen bedeuten. 1, N-Benzylcycloalkylamine of the general formula
Figure imgb0026
 wherein R 1 is hydrogen or alkyl having 1 to 4 carbon atoms, R 2 is a polymethylene group with 4-7 C atoms, which is optionally substituted by alkyl with 1-4 C atoms, and X is halogen, nitro, cyan or alkyl having 1 to 4 carbon atoms. 2. Verfahren zur Herstellung von N-Benzylcycloalkylaminen, dadurch gekennzeichnet, daß man a) ein Bezylhalogenid der allgemeinen Formel
Figure imgb0027
worin R1 und X die vorstehend angeführte Bedeutung besitzen und Hal Halogen, vorzugsweise Chlor, bedeutet, mit einem Cycloalkylamin der allgemeinen Formel
Figure imgb0028
worin R2 die oben angeführte Bedeutung besitzt, gegebenefalls in Gegenwart eines Säurebindemittels, umsetzt oder b) ein benzylamin der allgemeinen Formel
Figure imgb0029
worin R1 und X die vorstehend angeführte Bedeutung aufweisen, mit einem cyclischen Keton der allgemeinen Formel
Figure imgb0030
worin R2 die oben angeführte Bedeutung besitzt umsetzt und die so erhaltene Schiff'sche Base der
Figure imgb0031
Formel worin
Figure imgb0032
 R1, R2 und X die oben angeführte Bedeutung besitzen, reduziert. 2. Process for the preparation of N-benzylcycloalkylamines, characterized in that a) a bezyl halide of the general formula
Figure imgb0027
 wherein R 1 and X have the meaning given above and Hal is halogen, preferably chlorine, with a cycloalkylamine of the general formula
Figure imgb0028
 wherein R 2 has the meaning given above, optionally in the presence of an acid binder, or b) a benzylamine of the general formula
Figure imgb0029
 wherein R 1 and X have the meaning given above, with a cyclic ketone of the general formula
Figure imgb0030
 wherein R 2 has the meaning given above and the Schiff base thus obtained
Figure imgb0031
Formula where
Figure imgb0032
 R 1 , R 2 and X have the meaning given above, reduced.
EP78100031A 1977-06-03 1978-06-01 N-benzylcycloalkylamines and process for their preparation Withdrawn EP0000019A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP64633/77 1977-06-03
JP52064633A JPS5822099B2 (en) 1977-06-03 1977-06-03 N-benzyl-cycloalkylamine compound and method for producing the compound

Publications (1)

Publication Number Publication Date
EP0000019A1 true EP0000019A1 (en) 1978-12-20

Family

ID=13263858

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100031A Withdrawn EP0000019A1 (en) 1977-06-03 1978-06-01 N-benzylcycloalkylamines and process for their preparation

Country Status (5)

Country Link
EP (1) EP0000019A1 (en)
JP (1) JPS5822099B2 (en)
BR (1) BR7803521A (en)
DK (1) DK248578A (en)
IT (1) IT7824124A0 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0072528A2 (en) * 1981-08-19 1983-02-23 Bayer Ag (Thio)ureas, their preparation and their use as plant protecting agents

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2403138A1 (en) * 1974-01-23 1975-07-31 Hoechst Ag BENZYLAMINE DERIVATIVES AND PROCESS FOR THEIR PRODUCTION
FR2359123A1 (en) * 1976-07-20 1978-02-17 Nihon Tokushu Noyaku Seizo Kk NEW UREA OR THIOURE, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS FUNGICIDES

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2403138A1 (en) * 1974-01-23 1975-07-31 Hoechst Ag BENZYLAMINE DERIVATIVES AND PROCESS FOR THEIR PRODUCTION
FR2359123A1 (en) * 1976-07-20 1978-02-17 Nihon Tokushu Noyaku Seizo Kk NEW UREA OR THIOURE, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS FUNGICIDES

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
EXPERIENTIA, vol. 33, Januar 1977, Basel, A.BASHA und A.RAHMAN "A new method for the reduction of amides with zincethanol", Seiten 101-102 *
TETRAHEDRON LETTERS, Januar 1976, Oxford, ATTA-ur-RAMAN, A.BASHA und N.WAHEED "A new method for the reduction of amides to amines with sodium borohydride", Seiten 219-222 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0072528A2 (en) * 1981-08-19 1983-02-23 Bayer Ag (Thio)ureas, their preparation and their use as plant protecting agents
EP0072528A3 (en) * 1981-08-19 1983-11-16 Bayer Ag (thio)ureas, their preparation, their use as plant protecting agents and intermediates for their production
US4487783A (en) * 1981-08-19 1984-12-11 Bayer Aktiengesellschaft Combating fungi with novel (thio-)ureas, and novel intermediates therefor

Also Published As

Publication number Publication date
DK248578A (en) 1978-12-04
JPS5822099B2 (en) 1983-05-06
BR7803521A (en) 1979-02-13
IT7824124A0 (en) 1978-06-01
JPS53149949A (en) 1978-12-27

Similar Documents

Publication Publication Date Title
DE2732257C3 (en) Phenylureas or phenylthioureas, process for their preparation and their use for combating fungi
EP0206999A2 (en) Microbiocide compounds
DE2543888C3 (en) l-Phenyl-S-alkyl-S-benzylureas, process for their preparation and their use as fungicides
DE1955750A1 (en) Ureidophenylguanidines, process for their preparation and their fungicidal use
EP0000376B1 (en) Ureas and thioureas, processes for their preparation and their use as fungicides
DD222766A5 (en) MICROBICIDE MEDIUM
EP0065483B1 (en) Acyl aniline and acylnaphthyl amine microbicides, processes for preparing them and their use
DE2940765A1 (en) SUBSTITUTED ALKYLAMONIUM SALTS, THEIR PRODUCTION, THEIR USE FOR REGULATING THE PLANT GROWTH AND MEANS THEREFORE
EP0144895B1 (en) Thiolan-2,4-dion-3-carboxamides
DE3226009A1 (en) 2,4-HEXADIENE ACID DERIVATIVES SUITABLE FOR WEED KILLING AND PLANT GROWTH REGULATORS
EP0000019A1 (en) N-benzylcycloalkylamines and process for their preparation
DE1955749A1 (en) Amidophenylguanidines, process for their preparation and their fungicidal use
DE2545569C3 (en) 13-Dithiacyclopenten-2-ylidenemalonic acid dialkyl ester, process for their preparation and fungicidal agents containing them
DE2557406A1 (en) NEW THIOURA COMPOUNDS, METHODS FOR THEIR MANUFACTURING AND THEIR USE AS FUNGICIDES
EP0237912A1 (en) Sulfonyl azoles
DE68916468T2 (en) 1-Dimethylcarbamoyl-3-substituted-5-substituted-1H-1,2,4-triazoles.
EP0257448B1 (en) Optically active cyclopropanecarboxamides
EP0014887B1 (en) Spiro derivatives of 3-(3,5-dihalophenyl)-oxazolidine-2-thion-4-ones, processes for their preparation and their use as fungicides
DE2114882A1 (en) Cyclohexyhdeniminophenyl thioureas, process for their preparation and their fungicidal use
DE3414881A1 (en) ALLOPHANATE DERIVATIVES
DE3032327A1 (en) N-SULFENYLATED UREA SUBSTANCES, METHOD FOR THE PRODUCTION THEREOF, THE FUNGICIDES CONTAINING THEM AND THEIR USE
EP0239927A1 (en) Cyclic carbamates
DE2101149A1 (en) Fungicides
DE2111589A1 (en) Insecticides
EP0043348A1 (en) Imidazolidine-2,4-dione derivatives, process for their preparation and their microbicidal application

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE CH DE FR GB NL

Kind code of ref document: A1

Designated state(s): BE CH DE FR GB NL

17P Request for examination filed
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn
RIN1 Information on inventor provided before grant (corrected)

Inventor name: TAMURA, TATSUO

Inventor name: SAITO, JUNICHI