EP0000019A1 - N-Benzylcycloalcoylamines et procédé pour leur préparation - Google Patents

N-Benzylcycloalcoylamines et procédé pour leur préparation Download PDF

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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Withdrawn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)
English (en)
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/fr
Withdrawn legal-status Critical Current

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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)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (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)
EP78100031A 1977-06-03 1978-06-01 N-Benzylcycloalcoylamines et procédé pour leur préparation Withdrawn EP0000019A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP64633/77 1977-06-03
JP52064633A JPS5822099B2 (ja) 1977-06-03 1977-06-03 Ｎ−ベンジル−シクロアルキルアミン系化合物および該化合物の製造方法

Publications (1)

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

Family

ID=13263858

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100031A Withdrawn EP0000019A1 (fr) 1977-06-03 1978-06-01 N-Benzylcycloalcoylamines et procédé pour leur préparation

Country Status (5)

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2403138A1 (de) * 1974-01-23 1975-07-31 Hoechst Ag Benzylaminderivate und verfahren zu ihrer herstellung
FR2359123A1 (fr) * 1976-07-20 1978-02-17 Nihon Tokushu Noyaku Seizo Kk Nouvelles urees ou thiourees, leur procede de preparation et leur application comme fongicides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2403138A1 (de) * 1974-01-23 1975-07-31 Hoechst Ag Benzylaminderivate und verfahren zu ihrer herstellung
FR2359123A1 (fr) * 1976-07-20 1978-02-17 Nihon Tokushu Noyaku Seizo Kk Nouvelles urees ou thiourees, leur procede de preparation et leur application comme fongicides

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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JPS53149949A (en) 1978-12-27
JPS5822099B2 (ja) 1983-05-06
DK248578A (da) 1978-12-04
IT7824124A0 (it) 1978-06-01
BR7803521A (pt) 1979-02-13

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