CA1133510A - Cycloalkane- and cycloalkene-carboxylic acid anilides, processes for their preparation and their use as fungicides - Google Patents

Abstract

ABSTRACT
Combating fungi with cycloalkane- and cycloalkene-carboxylic acid anilides of the formula

Description

~335~(~

The present invention relates to certain new cycloalkane- and cycloalkene-carboxylic acid anilides, to a process for their preparation and to their use as fungicides.
It has already been disclosed that certain N-chloroacetyl-N-(2,6-dialkylphenyl)-alanine alkyl esters, for example N-chloroacetyl-N-~2-ethyl-6-methylphenyl)-alanine ethyl ester, can be used with good success for combating fungal diseases of plants (see DE-OS ~Gorman Published Specification) 2,350,944).
However, their action is not always completely satisfactory, especially when small amounts and low concentrations are applied, and in particular in combating 10Phytophthora species.
The present invention now provides, as new compounds, the cycloalkane-and cycloalkene-carboxylic acid anilides of the general formula R~ ~I - C a C - R5 (1) in which Rl represents hydrogen, alkyl or halogen, R2 represents hydrogen or alkyl, R3 represents hydrogen or alkyl, R4 represents hydrogen or alkyl, R5 is hydrogen, alkyl, halogen or phenyl optionally substituted by 20halogen, alkyl or nitro, and R6 is optionally substituted cycloalkyl or cycloalkenyl, the substituents being selected from alkyl, alkenyl, halogenoalXyl with identical or different halogen atoms, halogenalkenyl with identical or different halogen atoms, halogen, alkoxy and a two- to five-membered methylene bridge.
The invention also provides a process for the preparation of a cycloalkane- or cycloalkene-carboxylic acid anilide of ~ ~ ~

-1- :

- l~l33S~

the formula (I) in which (a) an M-propargyl-aniline of the general formula R3 ~ /CH - C C - R5 (II), in which -Rl to R5 have the meanings indicated abo~e, :~
(1) is reacted with an acid chloride, bromide or anhydride of the general formula R6 _ C - Cl(Br) ~,~
o (IIIa) or `
(R - C - )2 ``
o (IIIb), 'i in which R6 has the meaning indicated above, in the presence of a diluent and if appropriate in the : :
presence of an acid-binding agent, or ~.

(2) is reacted with a carboxylic acid of the general formula R6 ~ C - OH
C (IIIc), in which :~
R6 has the meaning indicated above~
~n the presence of an activating agent and if appropriate in the presence of an acid-binding agent, or ~;. -~b) an anilide of the general formula R2 Rl H
- N / (IV), C - R6 -, O

Le A 19 792 1~33SiO

in which Rl to R3 and R6 have the meanings indicated above, is reacted with a propargyl halide of the general formula Hal - CH - C-C - R5 (V), in which R and R have the meanings indicated above and Hal represents chlorine or brom~le, in the presen oe of an acid-binding agent and if appropriate in the presenoe of an organic diluent, or in an aqueous-organic two-phase system in the presenoe of a phase transfer catalyst, or (c) an N-propargyl-anilide acoording to the inventian, of the general formula Rl R4 R3~ \C - R (Ia), H
o ....

in which Rl to R4 have the meanings indicated above, is reac~ed with an aIkali metal hypahalite in the presen oe of a diluent in a nanner which is in itself known.
Process variant (c) is, of course, applicable to the preparatian of anly some of the co~pounds of the formula (I).
The new cycloaIkane- and cycloalkene-carboxylic acid anilides have p~werful fungicidal properties. Surprisingly, the compounds according to the invention exhibit a cansiderably more powerful action than N-chloroaoetyl-N-(2-ethyl-6-methylphenyl)-alanine ethyl ester, which is known frcm the state of

- 3 - ;

.. .. .. .

~1~33510 the art and is a closely related oompound chemically and frcm the point of view of its action. The substan oe s according to the invention thus represent an enrichment of the art.
m e formula (I) provides a general definition of the cycloalkane- and cycloalkene-carboxyl;c acid anilides according to the invention. Preferably, in this formula, R2, R3 and R4 are selected independently and each represent hydrogen or straight-chain or branched alkyl with 1 to 4 carbon atcms, Rl represents hydrogen, straight-chain or branched aIkyl with 1 to 4 carbon atoms, or halogen (especially fluorine, chlorine or bromine, R5 represents hydrcgen, straight-chain or branched aIkyl with 1 to 4 carbon atcms, halogen or phenyl which is optionally substituted by halogen, aIkyl with 1 to 4 carbon atoms or nitro, and R6 represents optionally substituted cycloalkyl with 3 to 7 carbon atoms or optionally substituted cycloalkenyl with 4 to 7 carbon atoms, the sub-stituents being selected from alkyl with 1 to 4 carbon atoms, alkenyl with 2 to

4 carbon atoms, halogenoalkyl with 1 to 4 carbon ato~s and up to 5 identical or different halogen atoms (preferred halogens being fluorine, chlorine and bro-mnne), halogenoalkenyl with 2 to 4 carbon atoms and up to 5 identical or differ-ent halogen atoms (preferred halogens being fluorine, chlorine and bromine),halogen, aIkoxy with 1 to 4 carbon atoms and a two- to five-mEmbered methylene bridge.
Very particul æly preferred cycloalkane- and cycloalkene-carboxylic acid anilides of the formLla (I) are those in which; R2 and R3 represent hydrogen, methyl, ethyl, isopropyl, sec.-butyl or tert.-butyl; Rl represents hydrogen, methyl, eth~l, isopropyl, sec.-butyl, tert.-butyl, chlorine or brcmlne;
R represents hydrogen, methyl or ethyl; R5 represents hydrogen, methyl, ethyl, phenyl, bromine, chlo~rine or iodine; and R6 represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo-~: .

133S::~O

heptyl, cyclobutenyl, cyclopentenylJ cyclohexenyl orcycloheptenyl, any of ~hich can be monosu~stit;uted or polysubstituted by identical or different substituents selected from methyl, ethyl, vinyl, allyl, fluorine, chlorine, chloromethyl, trifluoromethyl, dichlorovinyl, dibromovinyl, methoxy, trimethylene and isobutylene.
The following compounds o~ the general formula (I) .ay be mentioned specifically, in addition to the compounds mentioned later in the preparative examples:
T a b 1 e R~
R2 ~ ~ CH - C _ C - Rg R~ ~ - R6 CH3 6-CH3 H CH3 Br Cl 6-CH3 H CH3 H
C2H, 6-CH3 H CH3 H
C2H~ -C2H~ H CH3 H

~0 C2H~ H H CH3 H
Cl - H H CH3 H
i-C3 H7 H H CH3 H
t-C4Hg H H CH3 H ~ ~ -~
CH3 6-CH3 H CH3 ~ Cl ``
Cl Le A 19 792 --` ~133S10 T a b 1 e 1 (continued) Rl R2 R3 R4 ............ R5 R6 CH3 6-CH3 H C~3 H
CH~, 6-CH!, H C2 H~ H

, for example, 3-(2,6-dimethylanilino)-1-butyne and cyclopropanecarboxylic acid chloride are used as starting substances, the course o~ the reaction in process ~ariant (a)tl) can be represented by the ~ollowing equation:
!
,CH3 CH
~` CH3 CH-C--CH ~ + base ,CH3 ~CH-C--CH
~CH \H - HCl (~ \ C~
. . .

If, for example, 3-(2,6-dimethylanilino~ butyne and cyclopentanecarboxylic acid are used as starting substances, the course of the reaction in process variant (a)(2) can be represented by the ~ollowing equation:

CH3 acti~-ating ~NH-CH-C_CH + HO-C{l - HCl CH3 CH-c--CH

CH3 C {
O
'~
::, ~ Le A 19 792 ,, ~1335i~

If, for example, 2,6-dimethyl-cyclopropane-carboxylic acid anilide and propargyl bromide are used as starting substances in process variant (b), the course o~ the reaction can be represented by the following equation:

CH~ ~H
~ N + Br-CH2-C- CH ~
\ c_~1 - HCl CH3 ll-~
~3 ~ CH2-C_ CH

CH~

If, for example, 2,6-dimethyl-N-~l-methyl-2-propynyl)-cyclopropanecarboxylic acid anilide and potassium hypo-bromite are used as starting substances in process variant (c), the course of the reaction can be represented by the following equation:

CH CH3 ~ 3 ~CH-C- C-Br N\ KOBr KOH ~ ~ N \

The formula (II) provides a general definition of the N-propargyl-anilines required as starting substances in carrying out process variant (a). In this formula, Rl, R2, R3, R4 and R5 preferably have those meanings which have already been mentioned as preferred in connection with the description of the substances of the formula (I)~ ~
The N-propargyl-anilines of the formula (II? are, in :
some cases, known (see U.S~ Patent 5peci~ications 3,535,377~ and 4,001,325), or they can be obtained by known processes, for example by reacting corresponding aniline~

Le A l9 792 ...

. . . , . , , , ,- . :: -,,. .. :~: .. ,. : ::: -1133S~

with propargyl halides of the formula (V) or the corres-ponding propargylsulphonates, for example mesylates or tosylates, in the presence of an acid-binding agent, for example sodium carbonate or potassium carbonate, if appropriate in the presence o~ a catalyst, for example copper(I) chloride, and of an inert organic solvent, for example dioxan, at temperatures between 20 and 150C;
preferably, an excess of aniline can also be employed in this reaction.
N-Propargyl-anilines of the formula (II) in which R4 represents methyl can also be obtained by reacting the corresponding anilines with acetylene under pressure in the presence of copper acetylide (in this context, see Liebigs Ann.Chem. 596, 1 (1955)).
Examples of the starting substances of the formula (II) which may be mentioned are:
T a b 1 e 2 .
R, 4 R2 Rl CH - C=C - R~
~) ~ (II) C2 H~ 6-C2 Hg H H H
C2 ~ 6-CH3 H H H
C(CH3 )3 H H H H

Cl 6-CH3 H H H
Cl 6-C(CH3)3 H H H

C8 H3 6-C2 H~ H CH3 H
C2 H, 6-CH, H CH3 Le A 19 792 ~3~i10 T a b 1 e 2 (co~tinued) C2H5 6-CH3 H CH3 CH ;
Cl 6-CH3 H CH3 H

CH3 H H CH3 H ~`

i-C3H7 H H CH3 H
t-C4Hg H H CH3 H
':
m e formulae (IIIa), (IIIb) and (IIIc) provide general definitions of the ~ ;d chlorides, bromides and anhydrides and the carboxylic acids also to be used as starting substances for process variant (a). In these formulae, R6 pre-ferably has those meanings which have already been mentioned as preferred in OQn-nection with the description of the substan oe s of the formula (I).
The acid chlorides, br~mides and anhydrides and the carboxylic acids of the formLlae (IIIa), (IIIb) and (IIIc) are generally known cc~pounds of organic chemistry.

.
;
_ 9 _ 1~335iO

The formula (IV) provides a general definition of the anilides required as starting substances in carrying out process variant (b). In this formula, Rl, R2, R3 and R preferably have those meanings which have already been mentioned as preferred in connection with the des-cription of the substances of the formula (I).
The anilides of the formula (IV) can be obtained in a generally known manner by reacting corresponding anilines with an acid chloride, bromide or anhydride or a carboxylic acid of the formula (IIIa), (IIIb) or (IIIc) according to the conditions of process variant (a), in the presence of an inert or~anic solvent, for example toluene or methylene chloride, if appropriate in the ;~
presence of an acid-binding agent, for example potas.Qium carbonate or triethylamine, or in the presence of a catalyst, for example dimethylformamide, at temperatures between 0 and 100C.
Examples of the starting substances of the ~ormula (IV) which may be mentioned are:
T a b 1 e 3 R2~~ R1 ~H
,~N - ( IV) R3 ~ - R6 CH3 6-CH3 H _~
Cl 6-CH3 H -~
C2 H5 6-CH3 H _~ .`
C2 H, .6-C2 HA; H -< ~ .
CH3 3-CH3 6-CH3 -~
CH3 H H -<

i-C3H7 H H -t-C~H9 H H -~
CH~ 6-CH3 ,' Le A 19 792 ~133Sl(~

T a b 1 e 3 ( continued ) . . .
Rl R2 R3 R6 `
.. .. . . . . - -- --CH3 6-CH3 H C~

CH3 6-CH3 H -~>

CH 6-CH3 H -a CH3 6-CH.~ H -O

CH3 6-CH3 H ~3 , CH3 6-CH3 H {3 .H3 6-CH3 H ~ CH=C~ .
H~ CH3 The formula (V) provides a general definition of the propargyl halides also to be used as starting sub-stances in process variant (b). In this formula, R4 and R5 preferably have those meanings which have already been mentioned as preferred in connection with the description of the substances o~ the formula (I).
The propargyl halides of the formula (V) are generally known compounds of organic chemistry.
The formula (Ia) provides a general de~inition of the N-propargyl-anilides required as starting substances in carrying out process variant (c). These anilides are compounds according to the invention in which R5 represents hydrogen.

' :~
' Le .~ 19 792 __... . ..... - .

~ 33510 Preferred diluents for the reaction of process variant (a~ are inert organic solvents. These include, as preferen oe s, ketones, such as diethyl ketone, and in particular acetone and methyl ethyl ketone; nitriles, such as pro-pionitrile, and in particular aoetonitrile; ethers, such as tetrahydrofuran or dioxan; aliphatic and aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene; halogenated hydrccarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene; and esters, such as ethyl aoetate.
If appropriate, prooess variant ~a) can be carried out in the presence of an acid-binding agent (hydrogen halide acceptor). Any of the customa~y acid-binding agents can be used as these agents. mese include, as preferenoe s,bases, such as tertiary amines, for example triethylamine, or such as pyridine, and furtb=rm~re inorganic bases, for example alkali metal hydroxides and alkali metal carbonates. If appropriate, a catalyst, such as dimethylfor~amide, can cO be used.
me reaction te~,peratures can be varied within a substantial range in carrying out process variant (a). In general, the reaction is carried out at bet~een 0 and 120&, preferably between 20 and 100C.
Equimolar a~ounts of the reactants are preferably used in carrying out process variant (a). Isolation of the resultant oompound of the formula (I) is effected in the c~stomary manner.
Phosphorus oxychloride/pyridine is preferably used as the activating asent in carrying out prcoess variant (a)(2).
Possible diluents for the reaction in process variant (b) are any of the inert organic solvents. These include, as preferenoes, ethers, such as diethyl ether, dioxan or tetrahydrofuran; ammatic hydrocarbons, such as benzene, toluene or xylene; halogenated hydrocarbons, such as msthylene chloride, carbon tetrachloride, chloroform or chlorobenzene; esters, such as ethyl acetate;

~33~iV

ketones, such as methyl isobutyl ketone; nitriles, such as aoetonitrile; and dimethylformamide or dimethylsulphoxide.
The reaction in process variant (b) is carried out in the presen oe of an acid-binding agent. Any of the custamary acid-binding agents can be used as these agents. mese include, as preferenoe s, inorganic bases, for example alk~l; metal hydro~ides and alkali metal carb~nates.
The reactian tem~eratures can be varied within a substantial range in ~ -carrying out process variant (b). In general, the reaction is carried out at between -70 and +100C, preferably between -20 and +80&.
Possible diluents for the reaction in prooess variant (c) are water and organic solvents which are inert towards alkali metal hypohalite. These solvents include, as preferen oes, alcohols, such as methanol or ethanol; ethers, such as diethyl ether, dioxan or tetrahydrofuran; and two-phase mixtures, for example ether/water.
me reaction te~peratures can be varied within a substantial range in ~
process variant (c). In general, the reaction is carried out at between 0 and `
100C, preferably between 0 and 40C.
Ih carrying out prooess variant (c), 1 to 1.5 moles of hypchalite are preferably employed per mole of the ccmpound of the formLla (Ia), the alkali metal hypohalite in general being produced in situ from ~he corresponding halogen and the alkali metal hydroxide (see Houben-Weyl, volume V/2a, pages 608-610 (1977)). Isolation of the end product is effected in the customary m mner.
The active compoun~s according to the invention exhibit a p~werful microbicidal action and can be employed in practice for ccmbating undesired micro,organisms. The active compounds are suitable for use as plant protectian agents.

Fungicidal agents in plant protection are employed -for combating PlasTAdUophoromycetes, Oomycet s! Chytridiomyoetes, Zygom~cetes! Ascomyoetes, Basidiomycetes and Deuteromyoetes.
The good toleration, ky plants, of the active compounds, at the concen-trations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agents, the active compounds according to the invention can be employed with particularly good sucoess for combating Com~cetes, for example the blight and brcwn rot of tomato and potato causative organism (Phytophthora infestans). It should be particularly emphasised that the active compounds according to the invention display not only a protective action but also a ative/eradicative action. They also have systemic properties. Thus, it is possible to protect plants from fungal attack if the active co~pound is fed to the above-ground parts of the plants via the soil and the root or via the seed.
me active co~pounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, dusting agents, foams, pastes, soluble p~wders, granules, aerosols, suspension-emLlsion con oentrates, seed-treatment pcwders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substanoe s, coating ccmpositions for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV cold mist and warn mist formNlations.
mese formulations may be produoe d in known manner, for example by -mixing the active ccmpounds with extends, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming , : .. , . - -... .. :, ~ 3S:~

agents. In the case o~ the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphtha-lenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenæenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydro-carbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or ;
glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethylsulphoxide,as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal tempera-ture and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogeh and carbon dioxide.
As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
As emulsifying and/or foam-forming agents there ~
may be used non-ionic and anionic emulsi~iers, such `;
as polyoxyethylene-fatty acid esters, polyoxyethylene-Le A 19 792 .:
.. _. . . . . .. _ _ _ .. _ .. ... ., .. _ .. .. . . ..... .. . ...... ...

fatty alcohol ethers, for example al~ylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sul-phonates as well as albumin hydrolysis products.
Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formu- -10 lationS.
It is possible to use co]orants such as inorganic pigments, for example iron oxide, titanium oxide and Prusisian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dye-15 stuffs, and trace nutrients, such as salts of iron, ;~
manganese, boron, copper, cobalt, molybdenum and zinc.
I'he formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention can be present in the formulations, or in the ~arious ``
use forms,as a ~ixture with other active compounds, such as fungicides, bactericides, insecticides, acaricides~
nematicides, herbicides, bird repellants, growth factors, plant nutrients and agents for improving soil structure.
The active compounds can be used as such, as theirformulations or as the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules.
They may be used in the customary manner, for example by watering, immersion, spraying, atomising, misting, vaporising, injecting, brushing on, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.

Le A 19 792 .

.
'. , ' ., .. ` , " ' ' " ! ~

- 3 ~33~1~

Especially in the treatment of parts of plants, the active campound cQncentrations in the use forms can be varied within a substantial range. They are, in general, between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.
In the treatment of seed, amounts of active compound of 0.001 to 50 g, preferably 0.01 to 10 g, are generally employed per kilogram of seed.
For the treatment of soil, active compound conoentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are generally employed at the plaoe of action.
The present invention also provides a fungicidal conposition contain-ing as active ingredient a co~pcund of the present invention in admixtNre with ~`
a solid or liquefied gaseous diluent or carrier or in admixture with a liquid ~;luent or carrier containing a surface-active agent.
The present inventian also provides a method of combating fungi which oomprises applying to the fvngi, or to a habitat thereof, a oompound of the pre-sent invention alone or in the fonm of a comFositiQn containing as active ingred-ient a compound of the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by fungi by being grcwn in areas in which immediately prior to and/or during the time of the growing a co~pound of the present invention was applied alone or in admdxture with a diluent or carrier.
It will be sePn that the us~al methods of providing a harvested crop may be improved by the present invention.
The fungicidal activitv of the ccmpounds of this invention is illus-trated by the follcwing biotest Examples.
In these Exa~ples, the ocmpounds according to the present invention are each identified by the number (given in brackets) of the corresponding pre-parative Example, which will be found later in this specification.
m e known ccmparison oo~pound is identified as follows~

CH O
(A) = CH3 ~ 1 3 11 _ O
~ N ~ 2 5 C2H5 o N-CHloroaoetyl-N-(2-ethyl-6-methyl-phenyl)-alanine ethyl ester Example A
Phytophthora test (tcmato)/protective Solvent: 4.7 parts by weight of aoe tone Emulsifier: 0.4 part by weight of aIkylaryl polyglycol ether ~ateI~ 95 parts by weight me amount of the active ccmpo~nd required for the desired conoentra-tian of the active co~pound in the spray liquid was mixed with the stated amountof solvent and the oonoentrate was diluted with the stated amount of water whichoontained the stated amount of emulsifier. ;
Young tomato plants with 2 to 4 foliage leaves were sprayed with the spray liquid until dripping wet. m e plants remained in a greenhouse for 24 hours at 20 deg. C and at a relative atmospheric humidity of 70%. me tomato plants were then inoculated with an aqueous spore suspension of Phytophthora infestans. me plants were brought into a mDist chamber with an atmospheric humidity of 100% and a temperature of 18-20 deg. C.
After 5 days the infection of the tomato plants was determlned. The assessment data were oonverted to per oent infection: 0~ meant no infection;
100% ~eant that the plants were totally infected. `
The active oompounds, the conoe ntrations of the active compound and and the results can be seen from the follcwing table:

: "' ~33Si~

T a b 1 e A
Phytophthora test (to~atoes)/protective Active co~pound Infection in % at an active compound con-centration of 0.0005%

(A~ 59 (1~ 11 ;
Example B
Phytophthora test (tomato)/systemic Solvent: 4.7 parts by weight of acetone EmLlsifier: 0.3 part by weight of alkylaryl polyglycol ether ~ater: 95 parts by weight The a~ount of active compound required for the desired concentration of the active compound in the watering liquid was mixed with the stated amount of solvent and the ooncentrate was diluted with the stated amount of water which oontained the stated amount of the emulsifier.
Tomato plants grown in standard soil and having 2 to 4 foliage leaves were watered three tLmes in the course of one week with 10 ml of the watering liquid, having the stated concentration of active compound, per 100 ml of soil The plants treated in this way were inoculated, after the treatment, ~ith an aqueous spore susp_nsion of Phytophthora infestans. The plants were brought into a humidity cha~ber at an atmospheric humidity of 100% and a tempera-ture of 18 to 20 deg. C. After 5 days, the infection of the to~ato plants was deternined. The assessment data obtained were converted to percent infection.
0% denoted no infection and 100% denoted that the plants were totally infected.
The active ocmeounds, the concentrations of the active co~ound and the results can be seen from the following table:

t,.~

~ 33~

T a b 1 e B
. .
Phytophthora test (ta~atoes)/systemic Active compound InfectiQn in % at an active oompound con-oentration of 100 ppm (A) 71 (1) Prep~rative Examples EXample 1 CH :

3 (1) O

. ~

8.0 g (0.075 m~l) of cyclopropanecarbQxylic acid chloride were added `

drcpwise to a boiling solution of 9.0 g (0.05 mDl) of 3-(2,6-dimethylanilino)-1-butyne and 5.95 g (0.075 mol) of pyridine in 50 ml of tetrahydrofuran in the ccorse of 5 minutes and the mixture was heated under reflux for 5.5 hours. me : :

solvent was distilled off in vacuo, the residue was partitioned between ethyl aoetate and dilute hydrochloric acid and the organic phase was washed with 5%

strength sodium hydroxide solution and water, dried over sodium sulphate and evaporated. The black oily residue (9.7 g) was dissolved in chloroform, the ;

cblorDform solution was discharged anto a silica gel column (24x3c~) and the -~

:`

,: , ~.

:

~ ~133S10 column was eluted wlth 250 ml of chloroform. After evaporating off the solvent from the eluate, 8.9 9 (73.9O of theory) of 2,6-dimethyl-N-(l-methyl-2-propynyl)-cyclopropanecarboxylic acid anilide remained as a brown oil with a refractive index of n24: 1.5263.
Th~ following compounds of the gen~ral formula .
R~
R R~ ~ CH - C--C - R5 t I ) R3~ ~ C - R6 O :
were obtained in an analogous manner and according to process variants (a), (b) and (c):

10 Ex- 1 2 3 4 5 6 Melting ample R R R R R R point (C) No. or refractive ~.
index '.

2 CH3 6-CH3 H CH3 . H ~ 80-83 3 CH3 6-CH3 H CH3 H ~ n~: 1,5389 ,,- CH=Ccl2 4 CH3 6-CH., H CH3 H -<I lOl -1 02 - ~CHH3 - .
CH3 6-CH3 H CH3 H ~ 112-113 .
6 CH3 6-CH3 H CH3 H _0 72-73 7 CH~, 6-CH.... H H H ~ 72-76 8 CH~ 6-CH~ H H H ~ nD: l ~ 5400 ~. :

:
Le A 19 792 :~ .

, . .
.. ..

- 3~

Melting ampleRl R2 R3 R4 R5R6 point ( C ) No. fractive index CH=CCl2 9 CH3 6-CH3 H H H~;_ CH3 62-63 C 3 6 CH3 HCH3 H ~ nD: 1 ,.5232 11 CH3 6-Ctl3 H- H ~ Cl 155-~6 ~`.

. .

Le A 19 792 `
,,,,",.,) . .. :

Claims (14)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A cycloalkane- or cycloalkene-carboxylic acid anilide of the formula in which R1 is hydrogen, alkyl or halogen, R2 is hydrogen or alkyl, R3 is hydrogen or alkyl, R4 is hydrogen or alkyl, R5 is hydrogen, alkyl, halogen or phenyl optionally substituted by halogen, alkyl or nitro, and R6 is optionally substituted cycloalkyl or cycloalkenyl, the substituents being selected from alkyl, alkenyl, halogenoalkyl with identical or different halogen atoms, halogenoalkenyl with identical or different halogen atoms, halogen, alkoxy and a two-to five-membered methylene bridge.

2. A compound according to claim 1, in which R1 is hydrogen, alkyl with 1 to 4 carbon atoms, or halogen, R2, R3 and R4 each independently is hydrogen or alkyl with 1 to 4 carbon atoms, R5 is hydrogen, alkyl with 1 to 4 carbon atoms, halogen or phenyl optionally substituted by halogen, alkyl with 1 to 4 carbon atoms or nitro, and R6 is optionally substituted cycloalkyl with 3 to 7 carbon atoms or optionally substituted cycloalkenyl with 4 to 7 carbon atoms, the substituents being selected from alkyl with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms, halogenoalkyl with 1 to 4 carbon atoms and up to 5 identical or dif-ferent halogen atoms, halogenoalkenyl with 2 to 4 carbon atoms and up to 5 identical or different halogen atoms, halogen, alkoxy with 1 to 4 carbon atoms and a two- to five-membered methylene bridge.

3. A compound according to claim 1, in which R1 is hydrogen, methyl, ethyl, isopropyl, sec.-butyl, tert.-butyl, chlorine or bromine, R2 and R3 each independently is hydrogen, methyl, ethyl, isopropyl, sec.-butyl or tert.-butyl, R4 is hydrogen, methyl or ethyl, R5 is hydrogen, methyl, ethyl, phenyl, bromine, chlorine or iodine, and R6 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclobutenyl, cyclopentenyl, cyclohexenyl or cycloheptenyl, any of which may be substituted by methyl, ethyl, vinyl, allyl, fluorine, chlorine, chloro-methyl, trifluoromethyl, dichlorovinyl, dibromovinyl, methoxy, trimethylene or isobutylene.

4. 2,6-Dimethyl-N-(1-methyl-2-propynyl)-cyclopropane-carboxylic acid anilide of the formula

5. A method of combating fungi comprising applying to the fungi, or to a habitat thereof- a fungicidally effective amount of a compound according to claim 1.

6. A method according to claim 5, wherein the compound is applied in the form of a composition containing such compound as active ingredient in admixture with a suitable diluent or carrier.

7. A method according to claim 6, wherein a composition is used con-taining from 0.0001 to 1% of said compound, by weight.

8. A method according to claim 7, wherein a composition is used con-taining from 0.001 to 0.5% of said compound, by weight.

9. A method according to claim 5, wherein said compound is applied to soil in an amount of 0.00001 to 0.1 percent by weight.

10. A method according to claim 9, wherein said compound is applied to soil in an amount of 0.0001 to 0.02 percent by weight.

11. A method according to claim 5, wherein said compound is applied to seed in an amount of 0.001 to 50 g per kg of seed.

12. A method according to claim 11, wherein said compound is applied to seed in an amount of 0.01 to 10 g per kg of seed.

13. The method according to claim 5, 6 or 8, wherein the compound is 2,6-dimethyl-N-(1-methyl-2-propynyl)-cyclopropanecarboxylic acid anilide.

14. The method according to claim 10 or 12, wherein the compound is 2,6-dimethyl-N-(1-methyl-2-propynyl)-cyclopropanecarboxylic acid anilide.