NZ208933A - Biscyclohexylamine-alkane derivatives and fungicidal compositions - Google Patents

Biscyclohexylamine-alkane derivatives and fungicidal compositions

Info

Publication number
NZ208933A
NZ208933A NZ208933A NZ20893384A NZ208933A NZ 208933 A NZ208933 A NZ 208933A NZ 208933 A NZ208933 A NZ 208933A NZ 20893384 A NZ20893384 A NZ 20893384A NZ 208933 A NZ208933 A NZ 208933A
Authority
NZ
New Zealand
Prior art keywords
hydrogen
carbon atoms
radical
fungicide
radicals
Prior art date
Application number
NZ208933A
Inventor
L Schuster
E Ammermann
E-H Pommer
Original Assignee
Basf Ag
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 Basf Ag filed Critical Basf Ag
Publication of NZ208933A publication Critical patent/NZ208933A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/33—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C211/34—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton
    • C07C211/36—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton containing at least two amino groups bound to the carbon skeleton
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/04—Nitrogen directly attached to aliphatic or cycloaliphatic carbon atoms
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/08—Amines; Quaternary ammonium compounds containing oxygen or sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/33—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C211/34—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton
    • C07C211/38—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton containing condensed ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/52—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups or amino groups bound to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline

Landscapes

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

Abstract

1. Claims for the Contracting states : BE, CH, DE, FR, GB, IT, LI, NL, SE A biscyclohexylamine-alkane of the general formula see diagramm : EP0134499,P13,F2 where R**1 , R**2 , R**4 and R**5 are identical or different and are each alkyl or alkoxy, each of 2 to 5 carbon atoms, R**3 and R**6 are each hydrogen, R**1 and R**3 together and R**4 and R**6 together form a cycloalkyl radical fused to the cyclohexyl radical, and R**1 , R**2 , R**4 and R**5 may furthermore each be hydrogen, with the proviso that only two of the radicals R**1 , R**2 , R**4 and R**5 are simultaneously hydrogen, and R**3 and R**6 may furthermore each be methoxy, with the proviso that two of the radicals R**1 , R**2 , R**4 and R**5 are hydrogen, X is a single bond, a divalent aliphatic radical of 1 to 8 carbon atoms or a cyclohexylene radical, and Y is alkyl of 1 to 4 carbon atoms, and two radicals Y together with N can form a ring, with the exception of the compound in which R**1 , R**2 , R**4 and R**5 are each isopropyl, R**3 and R**6 are each hydrogen, X is methylene and Y is hydrogen. 1. Claims For the Contracting state : AT A fungicide containing a biscyclohexylamine-alkane of the general formula see diagramm : EP0134499,P14,F2 where R**1 , R**2 , R**4 and R**5 are identical or different and are each alkyl or alkoxy, each of 2 to 5 carbon atoms, R**3 and R**6 are each hydrogen, R**1 and R**3 together and R**4 and R**6 together form a cycloalkyl radical fused to the cyclohexyl radical, and R**1 , R**2 , R**4 and R**5 may furthermore each be hydrogen, with the proviso that only two of the radicals R**1 , R**2 , R**4 and R**5 are simultaneously hydrogen, and R**3 and R**6 may furthermore each be methoxy, with the proviso that two of the radicals R**1 , R**2 , R**4 and R**5 are hydrogen, X is a single bond, a divalent aliphatic radical of 1 to 8 carbon atoms or a cyclohexylene radical, and Y is hydrogen or alkyl of 1 to 4 carbon atoms, and two radicals Y together with N can form a ring.

Description

New Zealand Paient Spedficaiion for Paient Number £08933 t 2089 33 kM/r* imnrarotV!?! Priority Date(s): ... #1\ .
Complete Specification Filed: !?.' 7. . Ciasc: |o^pi*3;^OH ,.Q& Publication Date: S?. flPV.)???...
P.O. Journal, No: . ....}2!i N.Z. PATENT OFFICE 18 JUL 1984 Patents Form No. 5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION . "BISCYCLOHEXYLAMINE-ALKANES AND THE CONTROL OF FUNGI" WE, BASF Aktiengesellschaft, a German Joint Company organised and existing under the laws of the Federal Republic of Germany, with a registered office at 6700 Ludwigshafen, Federal Republic of Germany, hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be. performed, to be particularly described in and by the following statement:- fa O.Z. 0050/36633 Biscyclohexylamine-alkanes and the control of fungi The present invention relates to biscyclohexyl-amine-alkanes and a method of controlling fungi.
The fungicidal action of N-trichloromethyIthio-5 tetrahydrophthalimide is known (R. W e g I e r , "Chemie der Pf lanzenschutz- und Schad Iingsbek3mpfungsmi11eI", Vol. 2, page 109, Springer Verlag, BerIin/HeideIberg/New York, 1970) .
We have found that biscyclohexylamine-aIkanes of 10 the formula «1 R3 R6 R4 T R2 R5 .Y where R^ , R^, R^ R*1/ R^ and R^ are identical or different and are each hydrogen or alkyl or alkoxy, each of 1 to 5 carbon atoms, or R^ and R^, or R^1 and R^, 1 5 each pair to' ccrplete a cycloalkyl radical fused to each cycJLohexyl radical, X is a single bond, a divalent aliphatic radical of 1 to 8 carbon atoms or a eye lohexy lene radical, and Y is hydrogen or alkyl of 1 to 4 carbon atoms, and the two radicals Y together with N may furthermore form a ring, 20 have a good fungicidal action.
Examples of alkyl radicals of 1 to 5 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, isobutyl, tert.-butyl and pentyl, examples of alkoxy radicals of 1 to 5 carbon atoms are methoxy, ethoxy, propoxy 25 and isopropoxy, and examples of fused cycloalkyl radicals are methylene radicals of 3 to 5 carbon atoms, eg. tri-methylene, tetramethy I ene and pentamethy I ene.
The biscyc lohexylamine-aIkanes occur as mixtures of various stereoisomers. These mixtures are not usually 30 separated, but are used as such. However, it is possible < c f. compounds No. 1 and 2) to concentrate or isolate individual isomers by separation operations, for example /; v 2: n| 28 AUGI986rv 208938 4^ - .2 - O.Z. 0050/36633 by recrystallization, and to subject the remainder of the mixture to a transisomerization procedure followed by a further separation operation.
The pure isomers as well as mixtures of these are 5 embraced by the invention.
The invention is also concerned with the above • compounds as novel substances apart from those wherein Y is hydrogen.
The active ingredients are prepared in general by reacting an aniline which is disubstituted by alkyl with a carbonyl compound, eg. formaldehyde, aceta I dehyde, n-butyraldehyde, acetone, methyl ethyl ketone, diethyl 10 ketone, 2-ethy IhexanaI or eye lohexanone.
The reaction is carried out in an acidic medium, and it is possible to use either a mineral acid or an acidic ion exchanger. The aromatic amines react particularly readily with formaldehyde at from 10 to 100°C; in 15 contrast, aceta Idehyde, higher aliphatic aldehydes and aliphatic ketones react much more slowly, and only at elevated temperatures of about 100 - 180°C, in particular 150°C. In these cases, it is advantageous to carry out the reaction under superatmospheric pressure (1 - 20 bar). 20 When the reaction is complete, the amine is libe rated using an alkali, and is purified by, for example, distillation or crystallization.
The amine is then hydrogenated by a conventional method to give the cyc loa I iphatic compound, and is, if 25 desired, alkylated at the two nitrogen atoms.
Methylation is most advantageously carried out by a well-tried method, using formaldehyde and formic acid (H-T. Clarke et al., Am. Chem. Soc. JS_5^ (1933), 4571).
Another possible method of preparing the active 30 ingredients is to condense an alkylphenol with a ketone under acidic conditions to give a bisphenol, to hyd.ro-genate this to give a biscyclohexanol derivative, and then to react this product with ammonia or a lower dialkylamine and hydrogen over a hydrogenation catalyst at elevated 35 temperatures and under superatmospheric pressure.
A large number of isomers are obtained, the number of isomers depending on the number of substituents on the - 3 - 0.2. 0050/36633 two cyclohexane rings. For one compound, ie. bis-C3,5-diisopropyl-4-N-(dimethylamino)-cyclohexyl3-methane, a coarse separation was carried out using ethyl acetate, a crystalline fraction and a non-crystalline fraction being 5 obtained.
The Examples which follow illustrate the preparation of the active ingredients.
EXAMPLE 1 655 parts by weight of 2,6-diisopropy I ani I ine 10 were dissolved in 3,700 parts by weight of water and 400 parts by weight of concentrated hydrochloric acid, and 170 parts by weight of 30% strength formaldehyde solution in water were added in the course of one hour at from 92 to 100°C, while stirring. After a further 20 minutes, 15 the base was liberated by adding 400 parts by weight of 50% strength sodium hydroxide solution at 100°C. The product was separated off, washed and then distilled to give 605 parts by weight (97% yield) of b i s-C3, 5-d i i so-propyl-4-aminopheny ID-methane of boiling point 200 -20 210°C/0.1 mbar. 600 parts by weight of this product, 100 parts by weight of dioxane and 2 parts by weight of ruthenium oxide hydrate were introduced into <a stirred autoclave, and hydrogenation was carried out at 150 - 200 °C under a 25 pressure of 300 bar of hydrogen. The catalyst was filtered off and the filtrate was distilled under reduced pressure to give 604 parts by weight <97.5% yield) of bis-<3,5-diisop ropy l-4-aminocyc I ohexy I)-methane (No. 13) of boiling point 185°C/0.1 mbar. 30 • EXAMPLE 2 1460 parts by weight of formic acid, 60 parts by weight of water and 698 parts by weight of 30% strength formaldehyde solution were initially taken in a stirred flask. 600 parts by weight of bis-(3,5-diisopropy 1-4-35 ami nocyc lohexyl)-methane, dissolved in 400 parts by weight of dioxane, were run into the stirred mixture in the course of 10 minutes, and the temperature increased to - 4 - O.Z. 0050/36633 6 5°C , vigorous evolution of gas taking place. When the evolution of CO2 was complete, the excess formic acid was evaporated off, the residue was dissolved in ice water, 200 parts by weight of xylene were added and the mixture was rendered alkaline with 850 parts by weight of 50% strength sodium hydroxide solution. The organic phase was separated off and distilled to give 685 parts by weight (99.8% yield) of bis-C3,5-diisopropy 1-4-(dimethyl-am i no)-cy c loh e xy 13-me t h ane of boiling point 200 - 210°C/0.1 mba r.
The compound was separated into a crystalline fraction (No. 1) and a non-crystalline fraction (No. 2) by dissolving in ethyl acetate followed by separation.
The following compounds were obtained analogously: R1 y R3 R6 RA / \ / >v >-Q-n: / R2 No. x -n v y R1 R* R2 R5 ' 1 ch2 n'me *me i-Prop i-Prop 2 ch2 n-me -me i-Prop i-Prop 3 ch2 nh2 1-Prop Me 4 ch2 nh2 Me Me ch2 nh2 i-Prop Eth 6 ch2 nh2 t-But Me 1 ch2 nh2 s-But Eth 8 ch2 n"me Me i-Prop Eth 9 ch2 n'me • Me s-But Eth ch2 N:Me nme Me- Me B.p.°C at mb H [M.p. 100 - 101°C] H 200 0.1 H 190 0.1 H 130 0.1 H 180 0.1 H 170 0.2 H 180 0.1 H 170 0.1 145° 0,1 I Vn I fo 175 0.1 ^ o N O \Jl O N U 0\ 0\ W oo >0 04 GJ No.
R1 R4 R2 R5 11 ch2 12 CH2 13 ch2 14 CH2 CH2 16 CH2 17 CH2 18 CH2 19 21 22 CHj 23 CH, rMe "He N' Me sMe NH<- N'Me v Me N'Me KMe N„n-But Nn-But N,Eth -Eth K Eth vEth sI'Me * Me NHr N'Me Me N^Eth Eth N.Me -Me i-Prop t-But i-Prop Me H H H H Me Me H s-But OMe Me Me i-Prop H H H H Me Me H Eth H B.p.°C at mb H Me H H H H OMe 165 175 185 130 128 200 140 150 125 120 100 215 185 0.1 0.2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.3 i o\ I o o Vjl o V w On 0\ \A u No. X R1 R4 R2 R5 24 -CHo-CHo N Me 2-ono 11 ,, 2 -Me CMe2 NH 26 CMe„ N- 27 CH2 28 CH2 29 CMe2 CH2 31 CEth2 32 CMe2 33 CH2 34 CMe2 CMe0 Me NMe NCMe Me ^Me NMe NHr rMe vMe N N N ■Me Me ✓ Me Me -Eth Eth N' Me •Me ■ Me Me Me Me R1 + R3 tetramethylene i-Pxop i-Prop i-Prop Me i-Prop i-Prop s-But Eth Me Me i-Prop Me i-Prop Eth Eth R3 R6 B.p.°C at mb 170 160 170 R4 + R6 tetxamethylene 215 170 0.1 0.1 0.1 0.1 0.1 190 170 0.1 0.1 •vj I 190 220 170 200 200 0.1 0.1 0.1 0.1 0.1 N O o Ul o \ w CT\ <T\ S3 o oo 208933 8 O.Z. 0050/36633 The novel active ingredients have a strong fungitoxic action on phytopathogenic fungi. They are particularly suitable for preventing and curing plant diseases caused by fungi from the Phycomycetes and Deuteromycetes classes, 05 for example Phytophthora infestans in potatoes and tomatoes, Phytophthora capsici in pimientosf Plasmopara viticola in grapes, Peronospora parasitica in broccoli, Pseudoperonospora cubensis in cucumbers and melon's, Pseudo-peronospora humuli in hops, Peronospora tabacina in lO tobacco, Botrytis cinerea in grapes and strawberries, Pyricularia oryzae in rice, Pseudocercosporella herpo-trichoides in wheat and barley Venturia inaequalis in apple trees, Alternaria solani in tomatoes and potatoes, and Cercospora spp.
The novel fungicides are particularly interesting for combatting numerous fungi in various crops, especially cereals, fruit, grapes, cotton, soybeans, vegetables and ornamentals.
The novel active ingredients can be converted into 20 the conventional formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application depends entirely on the purpose for which the agent is to be used; at all events, it should ensure a fine and uniform distribution of the active ingredients. 25 The formulations are prepared in the conventional manner, for example by diluting the active ingredient with solvents and/or carriers, with or without the addition of emulsifiers and dispersants and, where water is used as the diluent, with or without an organic auxiliary solvent. 30 Suitable auxiliaries are, essentially, solvents, for example aromatics, e.g. xylene and benzene, chloro-aromatics, e.g. chlorobenzene, paraffins, e.g. petroleum fractions, alcohols, e.g. methanol and butanol, amines, e.g. ethanolamine, and dimethylformamide and water; carriers, for example natural rock powders, e.g. kaolin, alumina, talc and chalk, and synthetic rock powders, e.g. - 9 - O.Z. 0050/36633 highly disperse silica and silicates; emulsifiers, for example non-ionic and anionic emulsifiers, e.g. polyoxy-ethylene fatty alcohol ethers, alkylsulfonates and aryl-sulfonates, and dispersants, for example lignin, sulfite 05 waste liquors and methylcellulose.
The fungicidal agents generally contain from 0.1 to 95, preferably from 0.5 to 90, wt$ of active ingredient.
The application rates depend on the effect desired, and range from 0.02 to 3 kg of active ingredient per hec-10 tare, or more.
The novel compounds may also be used for protecting materials, e.g., for combatting wood-destroying fungi such as Coniophora puteana and Polystictus versicolor. The novel active ingredients may also be employed as fungi-15 cidally effective components of oily wood preservatives for protecting wood against wood-discoloring fungi. The agents are applied by treating, e.g., impregnating or painting, the wood with them.
The agents and the ready-to-use formulations made 20 therefrom, e.g., solutions, emulsions, suspensions, powders, dusts, pastes or granules, are applied in known manner, for example by spraying, atomizing, dusting, scattering, seed-disinfecting, or watering.
Examples of formulations are given below.
I. 90 parts by weight of compound no. 1 is mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 2 is dis solved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanol-amide, 5 parts by weight of the calcium salt of dodecyl-35 benzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By - 10 - O.Z. 0050/36633 pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.
III. 20 parts by weight of compound no. 5 is dissolved in a mixture consisting of 40 parts by weight of 05 cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and finely distri- buting it therein, an aqueous dispersion is obtained.
IV. 20 parts by weight of compound no. 6 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280°C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.
V. 80 parts by weight of compound no. 8 is well mixed with 3 parts by weight of the sodium salt of diiso-butylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the sodium salt of a 1ignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.
VI. 3 parts by weight of compound no. 9 is intimately mixed with 9 7 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.
VII. 30 parts by weight of compound no. 1 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence. 2089 33 - 11 - O.Z. 0050/36633 VIII. 40 parts by weight of compound no. 5 is intimately mixed with 10 parts of the sodium salt of a phenol sulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable 05 aqueous dispersion. Dilution in water gives an aqueous dispersion.
IX. 20 parts of compound no. 6 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-form-aldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
In these application forms, the agents according to the invention may also be mixed and applied with other • 15 active ingredients, e.g., herbicides, insecticides, growth regulators, other fungicides and fertilizers. When mixed with other fungicides, the spectrum of fungicidal action is in many cases increased. The following list of fungicides with which the compounds according to the invention 20 may be combined is intended to illustrate and not restrict the combination possibilities. sulfur dithiocarbamates and derivatives thereof, such as ferric dimethyldithiocarbamate 25 zinc dimethyldithiocarbamate manganese ethylenebisdithiocarbamate zinc ethylenebisthiocarbamate tetramethylthiuram disulfide manganese-zinc ethylenediamine-bisdithiocarbamate 30 zinc-(N,N1—propylene-bisdithiocarbamate) ammonia complex of zinc-(N,N'-ethylene)-bisdithiocarbamate and N,N1-polyethylene-bis-(thiocarbamoyl)-disulfide ammonia complex of zinc-(N,N'-propylene-bisdithio-35 carbamate) and N,N1-polypropylene-bis-(thiocarbamoyl)-disulfide 2089 33 O.Z. 0050/36633 nitro derivatives, such as dinitro-(1-methylheptyl)-phenylcrotonate 2-sec-butyl-4,6-dinitrophenyl-3,5-dimethylacrylate 2-sec-buty 1 *-A , 6-dinitrophenyl isopropylcarbonate 05 diisopropyl 5-nitroisophthalate heterocyclic structures, such as 2-heptadecyl-2-imidazoline acetate 2.4-dichloro-6-(o-chloroanilino)-s-triazine 0,O^diethylphthalimidophosphorothionate 5-amino-l-[bis-(dimethylamino)-phosphinyl]-3-phenyl-l,2,4--triazole 2,3-dicyano-l,4-dithiaanthraquinone 2-thio-l,3-dithio-(4,5-b)-quinoxaline methyl 1-(butylcarbamoyl)-2-benzimidazole carbamate 15 2-methoxycarbony1aminobenz imidazole 2-[furyl-(2)]-benzimidazole 2-[thiazolyl-(4)]-benzimidazole N-(1,1,2 ,2-tetrachloroethylthio)-tetrahydrophthalimide N-trichloromethylthiotetrahydrophthalimide 20 N-trichloromethylphthalimide N-dichlorofluoromethylthio-N1,N'-dimethyl-N-phenylsulfuric acid diamide -ethoxy-3-trichloromethyl-l,2,3-thiadiazole 2-thiocyanomethylthiobenzthiazole 25 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone pyridine-2-thio-l-oxide 8-hydroxyquinoline and its copper salt 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-di-30 oxide 2-methyl-5,6-dihydro-4-H-pyran-3-carboxani1ide 2-methyl-furan-3-carboxanilide 2.5-dimethyl-furan-3-carboxanilide 2,4,5-trimethyl-f uran-S-'-carboxanil ide 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide 2-methyl-benzoic acid anilide ZU57 «J - 13 - O.Z. 0050/36633 2-iodobenzoic anilide N-formyl-N-morpholine-2,2,2-trichloroethy1acetal piperazine-1,4-diylbis-(1-(2,2,2-trichloroethy1)-formamide 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichlorethane 05 2,6-dimethyl-N-tridecyl-morpholine and its salts 2,6-dimethyl-N-cyclododecyl-morpholine and its salts N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-di-methylmorpholine N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine lO l-[2-(2,4-dichlorophenyl)-4-ethyl~l,3-dioxolan-2-yl-ethyl]--1-H-l,2,4-triazole l-[2-(2,4-dichlorophenyl)-4-n-propyl-l,3-dioxolan-2-yl--ethyl]-1-H-l,2,4-triazole N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazol-15 -ylurea 1-(4-chlorophenoxy)-3,3-dimethyl-l-(1H-1,2,4-triazol-l-yl)--2-butanone 1-(4-chlorophenoxy)-3,3-dimethyl-l-(1H-1, 2,4-triazol-l-yl)--2-butanol alpha-(2-chlorophenyl)-alpha-(4-chlorophenyl)-5-pyrimidine-methanol -buty1-2-dimethylamino-4-hydroxy-6-methylpyrimidine bis-(p-chlorophenyl)-3-pyridinemethanol l,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene 25 1,2-bis-(3-methoxycarbonyl)-2-thioureido)-benzene and various substances, such as dodecylguanidine acetate 3-[2-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutar-imide hexachlorobenzene D,L-methyl-N-(2,6-dimethylphenyl)-N-(2-furoyl)-alanate methyl D,L-N-(2,6-dimethylphenyl)-N-(2-methoxyacetyl)--alanate N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyro-35 lactone methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate 2089 33 - 14 - O.Z. 0050/36633 -methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-l,3-oxa-zolidine 3-(3,5-dichlorophenyl)-5-methyl-5-methoxymethyl-l,3-oxa-zolidin-2,4-dione 05 3-(3,5-dichlorophenyl)-1-isopropyl-carbamoylhydantoin N-{3,5-dichlorophenyl)-1,2-dimethyl-cyclopropane-l,2-di-carboximide.
The following experiments demonstrate the biological action of the compounds. Comparative agent A is the prior lO art active ingredient N-trichloromethylthiotetrahydro-phthalimide.
Experiment 1 Action on Botrytis cinerea in pimientos Pimiento seedlings of the "Neusiedler Ideal Elite" 15 variety were sprayed, after 4 to 5 leaves were well developed, to runoff with aqueous suspensions containing (dry basis) 80ft of active ingredient and 20ft of emulsi-fier. After the sprayed-on layer had dried, the plants were sprinkled with a conidial suspension of the fungus 20 Botrytis cinerea, and placed at 22° to 24°C in a chamber of high humidity. After 5 days, the disease had spread to such a great extent on the untreated plants that the necroses covered the major portion of the leaves.
The results of this experiment show that for instance 25 compounds nos. 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 13, 22, 28 and 29, applied as 0.05$ spray liquors, had a better fungicidal action (e.g., 97ft) than prior art compound A (e.g., 70ft).
Experiment 2 30 Action on Alternaria solani in tomatoes Potted tomato plants of the "Grofie Fleischtomate" variety cultivated in the greenhouse were sprayed at the 4-leaf stage with aqueous suspensions containing (dry basis) 80ft of active ingredient and 20ft of emulsifier.
After the sprayed-on layer had dried, the leaves were inoculated with an aqueous spore suspension of the fungus m 2089 U - 15 - O.Z. 0050/36633 Alternaria solani. The plants were then placed in a water vapor-saturated chamber kept at 22° to 24°C. After 4 days, the disease on the untreated but inoculated plants had spread to such a great extent that the fungicidal action 05 of the compounds was able to be assessed.
The results of this experiment show that for example compounds nos. 1, 6, 9, 13 and 22, applied as 0.1ft spray liquors, had a good fungicidal action (e.g., 93ft). Experiment 3 Action of Phytophthora infestans in tomatoes Leaves of potted tomatoes of the "Grofie Fleisch-tomate" variety were sprayed with aqueous liquors containing (dry basis) 80ft of active ingredient and 20ft of emulsi-fier. After the sprayed-on layer had dried, the leaves 15 were infected with a zoospore suspension of Phytophthora infestans. The plants were then placed for 5 days in a steam-saturated chamber kept at 16° to 18°C. After this period, the disease had spread on the untreated control plants to such an extent that the fungicidal action of the 20 compounds was able to be assessed.
The results of this experiment show that for example compounds nos. 1, 2, 3, 5, 6, 7, 8, 9, 13, 27, 28 and 29, applied as 0.25ft sprays, had a better fungicidal action (e.g., 93ft) than prior art compound A (e.g. 60ft). 25 Experiment 4 Action on Plasmopara viticola Leaves of potted vines of the Muller-Thurgau variety were sprayed with aqueous suspensions containing (dry basis) 80ft of active ingredient and 20ft of emulsifier. To 30 assess the duration of action, the plants were set up, after the sprayed-on layer had dried, for 10 days in the greenhouse. Then the leaves were infected with a zoospore suspension of Plasmopara viticola. The plants were first placed for 16 hours in a water vapor-saturated chamber at 35 24°C, and then in a greenhouse for 8 days at from 20° to 30°C. To accelerate and intensify the sporangiophore

Claims (11)

ZU8V J - 16 - JQ..&<£^0^3< discharge, the plants were then again placed in the moist chamber for 16 hours. The extent of fungus attack was then assessed on the undersides of the leaves. The results of the experiment show that for instance 05 compounds nos. 1, 2, 3, 5, 6, 8 and 13, applied as 0.025ft sprays, had a good fungicidal action (e.g., 97$). 208933 - 17 - O.Z. 0050/36633 WHAT JtfWE ri AIM !<:•-
1. A biscyclohexylamine-alkane of the formula K1 R3 R6 RA R2 R5 12 4 5 where R , R , R and R are identical or different and are each alkyl or alkoxy, each of 2 to 5 carbon atoms, R3 and lO R6 are each hydrogen, R^, R2, R4 and R"* may furthermore each be hydrogen, with the proviso that only two of the 12 4 5 radicals R , R , R and R are simultaneously hydrogen, R3 and R^ may each furthermore be methoxy, with the 12 4 5 proviso that two of the radicals R , R , R and R are or 1 3 A 15 then hydrogen/ R and R , and/or R^ and Rb, each pair to complete a cycloalkyl radical fused to each cyclohexyl radical, X is a single bond, a divalent aliphatic radical of 1 to 8 carbon atoms or a cyclohexylene radical, Y is hydrogen er alkyl of 1 to 4 carbon atoms, and two radicals Y together with N 20 can form a ring.
2. A process for combatting fungi, wherein the fungi or the materials, plants, seed or soil to be protected 30 against fungus attack are treated with a biscyclohexylamine-alkane of the formula R1 R3 R6 R4 ) ( )—( /Y 35 Y ^N^ Y R2 R5 where R1, R2, R3, R4, R5 and R6 are identical or different and are each hydrogen or alkyl or alkoxy, each of 1 to 5 carbon atoms, or R^" and R3, ahd/or R^ and R6f*Heach pair to complete form a cycloalkyl radical fused to the cyclohexyl radical, 05 X is a single bond, a divalent aliphatic radical of 1 to 8 carbon atoms or a cyclohexylene radical, and Y is hydrogen or alkyl of 1 to 4 carbon atoms, and the two radicals Y together with N may furthermore form a ring.
3. A fungicide containing a solid or liquid carrier and a biscyclohexylamine-alkane as claimed in claim 2. 25 -
4. A process for manufacturing a fungicide, wherein a,,, solid or liquid carrier is mixed with a biscyclohexyl- /Av amine-alkane as claimed in claim 2. 18 20*983
5. A compound as claimed in claim 1 as specifically set forth herein.
6. A fungicide as claimed in claim 3 containing a biscyclohexylamine alkane as specifically set forth herein.
7. A process for combatting fungi as claimed in claim 2 wherein the biscyclohexylamine alkane is a compound specifically set forth herein.
8. A fungicide as claimed in claim 3 or 6 additionally containing at least one other fungicide.
9. A fungicide as claimed in claim 8 wherein the or each other fungicide is selected from such fungicides specifically set forth herein.
10. A process for combatting fungi wherein the fungi or materials, plants, seed or soil to be protected against funguous attack are treated with a fungicide as claimed in claim 8 or 9.
11. A process for producing a compound as claimed in claim 1 substantially as herein described. BASF AKTIENGESELLSCHAFT By their Attorneys BALDWIN, SON ,& CAREY
NZ208933A 1983-07-19 1984-07-18 Biscyclohexylamine-alkane derivatives and fungicidal compositions NZ208933A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19833325895 DE3325895A1 (en) 1983-07-19 1983-07-19 BISCYCLOHEXYLAMINAL CHANES AND METHOD FOR CONTROLLING MUSHROOMS

Publications (1)

Publication Number Publication Date
NZ208933A true NZ208933A (en) 1986-11-12

Family

ID=6204281

Family Applications (1)

Application Number Title Priority Date Filing Date
NZ208933A NZ208933A (en) 1983-07-19 1984-07-18 Biscyclohexylamine-alkane derivatives and fungicidal compositions

Country Status (5)

Country Link
EP (1) EP0134499B1 (en)
JP (1) JPS6075450A (en)
AT (1) ATE25514T1 (en)
DE (2) DE3325895A1 (en)
NZ (1) NZ208933A (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3640247A1 (en) * 1986-11-25 1988-05-26 Basf Ag FUNGICIDAL CYCLOHEXYLAMINE
CA2008089A1 (en) * 1989-01-25 1990-07-25 Herbert F. Strohmayer Bridged bis(cyclohexylamine) curing agents for epoxy resins
US4946925A (en) * 1989-01-25 1990-08-07 Air Products And Chemicals, Inc. Bridge bis(cyclohexylamine) curing agents for epoxy resins
JP5449193B2 (en) * 2008-01-18 2014-03-19 ビーエーエスエフ ソシエタス・ヨーロピア Method for producing alicyclic amine
AU2010283879B9 (en) 2009-08-13 2015-10-08 Basf Se Porous gels based on aromatic and cycloaliphatic amines

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE907294C (en) * 1942-06-23 1954-03-22 Hoechst Ag Process for the preparation of compounds of the diamino-dicyclohexylmethane series
US2606928A (en) * 1947-11-18 1952-08-12 Du Pont Preparation of amino alicyclic compounds
DE2401014C3 (en) * 1974-01-10 1980-07-24 Th. Goldschmidt Ag, 4300 Essen Microbicidal preparation
GB1550051A (en) * 1976-07-22 1979-08-08 Bayer Ag Tetraalkylated biscyclohexylamine derivatives

Also Published As

Publication number Publication date
DE3462397D1 (en) 1987-04-02
ATE25514T1 (en) 1987-03-15
JPS6075450A (en) 1985-04-27
EP0134499A1 (en) 1985-03-20
EP0134499B1 (en) 1987-02-25
DE3325895A1 (en) 1985-01-31

Similar Documents

Publication Publication Date Title
CS195346B2 (en) Fungicide
HU204396B (en) Fungicide compositions containing 4-substituted cyclohexyl-amine derivatives and process for producing the active components
CS199732B2 (en) Fungicide
CS208669B2 (en) Fungicide means
CS199223B2 (en) Fungicide
EP0130366B1 (en) Arylalkylimidazolium and triazolium salts, process for their preparation and their use as microbicides
NZ208933A (en) Biscyclohexylamine-alkane derivatives and fungicidal compositions
CZ466989A3 (en) Oximether derivative, fungicidal agent containing thereof and method of fighting fungi
US4284791A (en) Combating fungi with N-chloroacetyl-N-(2,6-di-substituted phenyl)-alanine esters
US2971884A (en) Method for the control of fungal organisms
CA1220211A (en) Triazolyl alcohols, their preparation and their use as fungicides
EP0014999B1 (en) Optically active forms of 4-(3-(p-tert.-butylphenyl)-2-methylpropyl)-cis-2,6-dimethylmorpholine and their salts; fungicides containing these compounds and process for their preparation
US4661632A (en) Halogenopropargylformamide pesticides
CA1252107A (en) N-(arylpropyl)-azolylureas, and fungicides containing these compounds
US4457930A (en) Todopropargylsulphamides, microbicidal compositions and use
US4560694A (en) Fungicidal alkylene(cycloalkylene)-bis-heterocyclyl-biguanides
US4628058A (en) N-(2,3-dihydrobenzofuran-2-yl)-azolylureas and fungicides containing these compounds
US4496575A (en) Fungicidal N-sulphenylated hydantoins
CS214710B2 (en) Fungicide means
CS268836B2 (en) Fungicide and method of its effective substances production
US4515801A (en) Fungicidally active pyrano-pyrazole derivatives
US4397869A (en) Combating fungi with N-sulphenylated ureas
EP0094562B1 (en) Diamine derivatives, process for their production and their use as fungicides
US4469902A (en) 1-Iodoprop-1-yn-3-ols as plant protection agents
US4291046A (en) Preparation of novel fungicidally active spiro derivatives of 3-(3,5-dihalogenophenyl)-oxazolidine-2-thion-4-ones