CH637917A5 - Cylcoalkanecarboxanilides - Google Patents

Description

The invention relates to novel cycloalkancar boxanilide derivatives which are distinguished by a good herbicidal action. The invention therefore also relates to herbicides which have as active ingredient one or more of the cycloalkane carboxanilide derivatives according to the invention. The invention further relates to a process for the preparation of the compounds according to the invention and their use for controlling unwanted vegetation.

The derivatives of cycloalkane carboxylic acid anilides according to the invention correspond to the following general formula:

-0

where the substituents have the following meaning:

X represents O, S, SO, SO2 or the -NR3 group;

Y represents a fluorine, chlorine or bromine atom or a cyano, a nitro, a C (R3) = NOR3 or a C (0) R3 group or the group -Zp-alkyl-, in which the alkyl part 1 to Contains 6 carbon atoms and can be substituted by one or more fluorine, chlorine or bromine atoms and in which Z represents O, S, SO or SO2;

R1 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, each of these groups being optionally substituted by one or more fluorine, chlorine or bromine atoms; or R1 represents an alkynyl group with 3 to 4 carbon atoms, an alkoxyalkyl group in which each alkyl group contains 1 to 6 carbon atoms, a cycloalkyl or cycloalkylalkyl group with 3 to 7 carbon atoms in the ring, an aralkyl group with 7 to 9 carbon atoms, optionally ring-substituted by 1 or 2 fluorine, chlorine or bromine atoms or by an alkyl group with 1 to 4 carbon atoms or a group of the formula:

R3 O

I II or -CHCR4

R3 O

I II

-CHCNR4R5

or if X represents the group -NR3- R1 for the

Group O

II

-CR «, or -SO2R6

stand; or, if X represents group SO2, R1 can also be for

O

II

-NR4R5, -NR4 -CR6, or-NR4S02R6;

R2 represents an alkyl group with 1 to 6 carbon atoms, a fluorine, chlorine or bromine atom or an alkoxy or alkylthio group, in which the alkyl part contains 1 to 6 carbon atoms; however, if Y is a N02 group and X is an oxygen atom, R1 is not a methyl group; R3, R4 and R5 each independently represent a hydrogen atom or an alkyl or cycloalkyl group with up to 6 carbon atoms and R5 can also represent an alkoxy group with up to 6 carbon atoms;

when X represents the group -NR3-, R1 and R3 can together form part of a heterocyclic ring, e.g.

CHs CH3 -CH2- (CH2) mCH2-, -CH (CH2) 2CH-

or -CH2CH2OCH2CH2-;

when R1 represents the group -NR4R5, then R4 and R5 can together form part of a heterocyclic ring, as shown above for R1 and R3 together;

R6 represents an alkyl group with 1 to 6 carbon atoms or an aryl or aralkyl group with 6 to 10 carbon atoms, which may be substituted by one or more fluorine, chlorine or bromine atoms;

m is 2 or 3; n is 1 or 2 and p is 0 or 1.

As can be seen, the compounds of formula I are derivatives of substituted cyclopropane or substituted cyclobutane carboxylic acids, so that n in formula I is 1 or 2. If R2 in the formula represents an alkyl group, this can be, for example, a methyl, ethyl, propyl or n-butyl group; R2 can also represent a methoxy or methylthio group or their lower alkyl homologues.

As a general rule, the preferred compounds of formula I for the sake of their herbicidal properties are those in which n is 1 and R2 represents a methyl group. The compounds in which R2 represents a chlorine atom are also very active. Compounds in which R2 represents a methoxy group are also useful.

The group Y can represent a chlorine, bromine or fluorine atom, but can also be a cyano, nitro, formyl, hydroxypropionomethyl, trifluoromethyl, trifluoromethoxy, methyl, ethyl, methylsulfonyl or trifluoromethylsulfonyl group .

Because of their good herbicidal properties, preference is given to those compounds of the formula I in which Y represents a trifluoromethyl group. Very effective herbicides are also compounds in which Y represents a chlorine atom or a methyl or nitro group.

R1 can represent a straight chain or preferably a branched alkyl group, e.g. a methyl, ethyl, isopropyl, isobutyl, sec.butyl, tert.butyl, isoamyl, 2-chloroethyl, trifluoromethyl, allyl, phenyl, p-chlorophenyl, naphthyl or Propargyl group. If R1 represents a cycloalkyl group, this can be alkylated or it can be attached to X

s

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be bound via an alkylene group, e.g. a cyclo-propyl, cyclohexyl, methylcyclopropyl, or cyclopropylmethyl group. In addition, R1 can e.g. represent a methoxy-ethyl, benzyl, phenethyl, p-chlorobenzyl or o-methyl-benzyl group or, if X represents the group -NR3, an acetyl, propionyl, caproyl, benzoyl or , Methylsulfonyl, trifluoroacetyl or, if X represents the group SO2, R1 can also represent an unsubstituted amino group, a monomethylamino or dimethylamino group or an acetamido or methylsulfonylamino group.

Compounds in which R1 represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group are generally preferred. Those compounds in which R1 represents an alkyl group with a branched chain, such as an isopropyl or tert-butyl group, are particularly active. Ethyl, methyl and cyclopropylmethyl derivatives and ring-kylated forms also appear to be particularly active. Of course, fluctuations in the effectiveness depend on the particular combination in which the substituents R1, R2, R3, X and Y are present.

R3, R4 and R5 each independently represent a hydrogen atom, an alkyl group such as a methyl or ethyl group, or a cycloalkyl group such as a methylcyclopropyl group; R5 can also represent an alkoxy group, such as a methoxy or ethoxy group. However, if X stands for the group -NR3, then R3 is preferably an isopropyl, n-propyl or tert-butyl group.

R6 can be an alkyl group, e.g. a methyl, ethyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isoamyl or hexyl group; or R6 is an aryl or aralkyl group, e.g. a phenyl, p-chlorophenyl, 2-bromophenyl, naphthyl, phenethyl or benzyl group.

Mention should be made of the compounds according to formula I in which R1, X, Y and R2 have the following meanings: Ì-C3H7.0, CF3, n-CiH «-isoamyl, O, NO2, nC <tH9 -t-butyl , NH, CFj, OCH3 - sulfamoyl, (Ri + X), Et, SCH3 -Ì-C3H7.0, Me, F and Ì-C4H9, SO2, CF3, F.

Compound types in which X represents the O half and Y represents the trifluoromethyl group are e.g. those in which R1 and R2 have the following meanings:

Isobutyl; Methyl isoamyl; Propyl-2-fluorobenzyl; Methyl 2-chlorobenzyl; n-butyl-4-chlorobenzyl; Methyl 2,6-dichlorobenzyl; Ether propargyl; Methyl and sec-butyl or propyl.

Because of their herbicidal properties, preference is given to those compounds of the formula I in which X represents the O-half, while R2 represents a methyl group and R1 represents an alkyl group with 1 to 4 carbon atoms, a cyclopropylmethyl or a 1-methylcyclopropyl group. The alkyl group is preferably a secondary butyl or isopropyl group. Haloalkyl groups, such as 2-chloroethyl groups, are also desirable.

Compounds in which X represents the S, SO or S02 half and Y represents the trifluoromethyl group are those in which R ', X and R2 have the following meanings: CH3OC2H4, S, methyl allyl, S, pentyl -isoamyl, SO, ethyl-i-C4H9, SO2, n-C4H9-cyclopropyl, SO, methyl-2-fluoro-benzyl, SO2, n-C3H7-2-chlorobenzyl, S, methyl-sec.-C-tHi, SO2, methyl-4-chlorobenzyl, SO, nG »H9-2,6-dichlorobenzyl, SO2, methylpropargyl, S-ethyl and sec.-C4H9, SO2, n-C3H7.

Because of their herbicidal properties, those compounds are preferred in which X represents the S, SO or S02 moiety, while R2 represents a methyl group and R1 represents an alkyl group with 1 to 4 carbon atoms, such as a methyl, isopropyl or isobutyl group. Compounds in which R1 represents an isopropyl or an ethyl group seem to be particularly useful.

Possible types of compounds in which X represents the group NR3 and Y represents the trifluoromethyl group are those in which R1, R3 and R2 have the following meaning: t-butyl, H, methylphenyl, H, methoxy-propargyl, H, Methylthio-benzyl, H, F-methylsulfonyl, H, methyl-trifluoromethylsulfonyl, H, methyl-acetyl, H, methyl and trifluoroacetyl, H, methyl.

A preferred subclass due to its herbicidal properties are those compounds of formula I in which X represents the group NR3, in which R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, such as a methyl, ethyl or propyl group, while in these compounds R1 represents an alkyl group with 1 to 4 carbon atoms, in particular an isopropyl, t-butyl or n-propyl group.

As types of compounds in which R1 represents one of the groups -NR4R5, -NR4S02R6 or -NR4C (0) R6, X represents the SO2 portion and Y represents a trifluoromethyl group, those in which R4, R5 (or R4 and R6) and R2 have the following meanings: H, H, methyl-methoxy, methyl, methyl-t-butyl, H, methyl-1-methylcyclopropyl, H, methyl- (H, methyl), methyl and (H, trifluoromethyl),

Methyl.

A similarly useful subclass of herbicides are the compounds in which Y represents a halogen atom, in particular a bromine or chlorine atom or a methyl group instead of a trifluoromethyl group.

Compounds according to formula I in which Y represents a nitro group are, because of their relatively good accessibility and their good herbicidal properties, a very suitable subclass.

Possible types of compound in which Y represents a nitro group are those in which R'X and R2 have the following meanings:

Propyloxyethylsulfonyl, ethyl isobutylthio, n-C4H9 ethyl sulfinyl, propyl allyloxy, ethyl and 2,6-dichlorobenzylsulfonyl, propyl.

Because of their herbicidal properties, preference is given to those compounds in which Y represents a nitro group and R1 represents an alkyl group having 2 to 4 carbon atoms. Particularly useful compounds appear to be those in which R1 represents an isopropyl group and X represents an O, S, SO or S02 group, since these compounds are distinguished by good selectivity in cereals. Compounds in which X represents an NR3 group are also particularly active.

Suitable compounds in which Y represents an alkyl group are those in which R'X, Y and R2 have the following meanings:

Ethoxy, methyl, methyl-cyclopropylmethoxy, methyl, methyl-1-cyclopropylethoxy, methyl, methyl-1-methylpropoxy, methyl, methyl-isopropoxy, ethyl, methyl-ethylthio, methyl, methyl-ethylsulfonyl, methyl, methyl-methylthio, Methyl, methyl-methylsulfonyl, methyl, methyl-isopropyl-thio, methyl, methyl-isopropylsulfonyl, methyl, methyl-methylthio, isopropyl, methyl-isopropylamino, methyl, methyl-t-butylamino, methyl, methyl- (l-methylcyclo- propyl) amino, methyl, methyl-sulfamoyl, methyl, methyl-methoxy, sec-butyl, methyl- (N-methoxy-N-methyl) amino, methyl, methyl-N- (methylsulfonyl) amino, methyl, methyl-N - (trifluoro-methylsulfonyl) amino, methyl, methyl-aceta-mido, methyl, methyl and trifluoroacetamido, methyl, methyl.

The types of compounds in which Y represents a bromine atom are those in which R'X and R2 have the following meanings:

Ethoxy, methyl-methoxy, methyl-2-methylpropoxy, methyl-1-cyclopropylethoxy, methyl-ethylthio, methyl-methylthio,

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Methyl-isopropylthio, methyl-ethylsulfonyl, methyl-dimethyl-amino, methyl-diethylamino, methylisopropyla-mino, methyl and t-butylamino, methyl.

The corresponding chlorine derivatives are also suitable:

Sulfamoyl, methyl-dimethylsulfamoyl, methyl-t-butyl-sulfamoyl, methyl-N- (acetyl) sulfamoyl, methyl-N- (methyl-sulfonyl) sulfamoyl, methyl- (N-methoxy-N-methyl) amino, methyl-N- (methylsulfonyl) amino, methyl-N- (trifluoromethyl-

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sulfonyl) amino, methyl-acetamide, methyl and trifluoroaceta-mido, methyl;

also the following fluorine derivatives:

Isopropoxy, methyl-isopropylamino, methyl-ethylthio, s methyl-isobutylsulfonyl, methyl and sec-butoxy, methyl. The corresponding bromine derivatives can of course also be used.

The cycloalkane carboxanilides according to the invention can be prepared according to the following scheme:

R1-XNa + Cl - <^ \ -N02

-NaCl

} \ -NOp (la)

0

nh2 + c1c-

CH2 ^ n "X

R '

<CH2) n

(3a)

The above stage la consists in reacting the corresponding sodium alkoxide or mercaptide compound (or the corresponding amine) with a 3-substituted 4-chloronitro-benzene to give a 3,4-disubstituted nitrobenzene, the latter of which then in stage 2a the corresponding aniline is reduced. Step 3a then follows, which consists in converting the aniline and a cycloalkanecarboxylic acid chloride to the desired cycloalkanecarboxanilide according to formula I.

The reaction la is expediently carried out in such a way that the reactants are at room temperature or moderately elevated temperature up to e.g. 150 ° C mixed in a solvent such as an alcohol, dimethyl sulfoxide or dimethylformamide.

The reduction of the 3,4-disubstituted nitrobenzenes in stage 2a is expediently carried out in boiling water which contains iron filings and up to 5% acetic or hydrochloric acid. However, one can also use one of the numerous other reduction methods in which an aromatic, nitro group is reduced to the amino group (see, for example, Schröter and F. Möller in “Methods of Organic Chemistry” [Houben-Weyl], Vol. 11,1, part IV, pp. 341-731,

Georg Thieme Verlag, Stuttgart, 1957).

The corresponding 4'-hydrocarbylsulfinyl or sulfonyl derivatives are prepared by treating the corresponding 4'-hydrocarbylthio derivatives with 85% metachloroperoxybenzoic acid.

When carrying out the acylation reaction (3a), the 3,4-disubstituted aniline is treated with a cycloalkanecarboxylic acid chloride in a suitable solvent, such as

Ether, tetrahydrofuran, benzene, toluene or hexane, in the presence of a molar equivalent of an organic or inorganic base, which can serve as an acceptor for the hydrogen chloride formed in the reaction. For this purpose, organic bases such as tertiary amines (pyridine, triethylamine, collidine, N, N-dimethylaniline, di-45 ethylisopropylamine) or inorganic bases (Na2C03, NaHŒh, K2CO3, CaC03) can be used, which then form those formed during the acylation Collect hydrogen chloride.

The cycloalkane carboxylic acid chlorides used for the reaction or the simple esters from which they are formed 50 are generally known (see, e.g., U.S. Pat. Nos. 3,277,171, 3,211,544 and South American Patent Application 64/1283). The 1-fluorocycloalkanecarboxylic acid chlorides can be prepared simply by treating the ethyl ester of 1-chloroalkanecarboxylic acid with potassium fluoride at elevated temperature, if appropriate in the presence of solvents and / or phase transfer catalysts and converting the ester into the acid chloride in a customary manner. The 1-bromocycloalkanecarboxylic acid chlorides can be prepared by bromination of cycloalkanecarboxylic acid chlorides under reflux in a nitrogen atmosphere.

The 1-ethoxycycloalkanecarboxylic acid chloride used to prepare the above anilides can be prepared by alkali treatment of ethyl 1-bromocyclobutanecarboxylate, a known compound, in which a mixture of 1-bromocyclobutanecarboxylic acid and 1-ethoxycyclobutanecarboxylic acid is liberated, from which one liberates way known per se, eg by treatment with thionyl chloride, the corresponding acid chlorides are obtained.

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The compounds according to the invention, e.g. 4 '- (isopropyl-amino) -3' - (trifluoromethyl) -1-methylcyclopropanecarboxanilide; 4 '- (Isopropoxy) -3' - (trifluoromethyl) -1 -methylcyclopropanecarboxanilide and 4 '- (isopropylthio) -3' - (trifluoromethyl) -1-methylcyclopropanecarboxanilide, have been found to be particularly suitable for combating undesirable plant growth. In particular, certain members of this class have proven to be effective herbicides against a large number of plant species, while others are only active against a limited number of plant species and are therefore to be regarded as selective herbicides. Some of the compounds show a high level of herbicidal activity when it comes to controlling a number of economically important types of weed and broad-leaf weeds. Others are particularly effective as selective herbicides for use in certain important crops.

The compounds according to the invention are also used as active ingredients in agents for regulating plant growth, in which they are present in addition to a carrier or a surface-active agent or both.

“Carrier” is to be understood as a solid or liquid material which can be inorganic or organic and of synthetic or natural origin; the active ingredient is mixed or formulated with the carrier in order to facilitate its application to the plant, the seed, the soil or other objects to be treated or its storage, transport and handling.

Suitable solid carriers are natural and synthetic clays and silicates, e.g. natural silica such as diatomaceous earth; Magnesium silicates, e.g. Talke; Magnesium aluminum silicates, e.g. Attapulgite and vermiculite; Aluminum silicates, e.g. Kaolinites, montmorillinites and mica; Calcium carbonates; Calcium sulfate; synthetic silicon oxide hydrates and synthetic calcium or aluminum silicates; Elements such as carbon and sulfur; natural and synthetic resins, e.g. Coumarone resins, polyvinyl chloride and styrene polymers and copolymers; solid polychlorophenols; Bitumen, waxes such as beeswax, paraffin and chlorinated mineral waxes; as well as solid fertilizers, e.g. Superphosphates.

Examples of suitable liquid carriers are water, alcohols, e.g. Isopropanol, glycols; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Ether; aromatic hydrocarbons such as benzene, toluene and xylene; Petroleum fractions, e.g. Kerosene or light oil; chlorinated hydrocarbons, such as carbon tetrachloride, perchlorethylene or trichloroethane, each including liquefied, usually vapor or gaseous products. Mixtures of different liquids are also often suitable.

The surfactant can be an emulsifying or dispersing agent or a wetting agent; it can be non-ionic or ionic. Any surfactant suitable for building herbicides or insecticides can be used, e.g. the sodium or calcium salts of polyacrylic acids and lignin sulfonic acids; the condensation products of fatty acids or aliphatic amines or amides with at least 12 carbon atoms in the molecule with ethylene oxide and / or propylene oxide; Fatty acid esters of glycerin, sorbitol, sucrose or pentaerythritol; Condensates of these with ethylene oxide and / or propylene oxide; Condensation products of fatty alcohols or alkyl phenols, e.g. p-octylphenol or p-octyl cresol, with ethylene oxide and / or propylene oxide; Sulfates or sulfonates of these condensation products, alkali metal or alkaline earth metal salts, preferably sodium salts of sulfuric or sulfonic acid esters with at least 10 carbon atoms in the

Molecule, e.g. Sodium lauryl sulfate, sodium sec-alkyl sulfates, sodium salts of sulfonated castor oil and sodium alkylarylsulfonates such as sodium dodecylbenzenesulfonate; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

The agents produced with the active ingredients according to the invention can be wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates or aerosols. Wettable powders are usually prepared in such a way that they contain 25.50 or 75% of active ingredient and usually also a solid carrier, 3 to 10% by weight of dispersing agent, 1 to 5% by weight of wetting agent and

if necessary, contain up to 10% by weight of stabilizers and / or other additives, such as agents for facilitating the introduction or adhesion. Dusts are usually concentrates, the composition of which corresponds to that of the wettable powders, but the dispersant or wetting agent has been omitted. They are diluted on the spot with other solid carriers, so that a 20 agent is obtained which generally contains 0.5 to 10% by weight of active ingredient. Granules usually have a grain diameter of approximately 0.15 to 1.7 mm and can be produced using agglomeration or impregnation methods. They usually contain 0.5 to 25% by weight of active ingredient and up to 10% by weight of additives such as stabilizers, retardants and binders. In addition to the solvent and optionally an auxiliary solvent, emulsifiable concentrates usually contain 10 to 50% w / v active ingredient, 2 to 20% w / v emulsifier 30 and up to 20% w / v additive, such as stabilizers or agents to facilitate penetration or to prevent corrosion. Suspension concentrates are prepared in such a way that a stable, non-settling, flowable product is obtained and usually contain 35 to 10 to 75% by weight of active ingredient, 0.5 to 5% by weight of dispersant, 1 to 5% by weight of surface-active agent 0.1 to 10% by weight of suspending agents, such as protective colloids and thixotropic agents, and up to 10% by weight of suitable additives, such as defoamers, corrosion inhibitors, stabilizers 40 or agents to facilitate penetration or adhesion; water or an organic liquid in which the active ingredient is practically insoluble is present as the carrier, it being possible, if appropriate, for certain organic solids or inorganic salts to be dissolved in the carrier which prevent settling or, if water is present, freezing.

The use of aqueous dispersions and emulsions, e.g. Those obtained by diluting a wettable powder or concentrate according to the invention also fall under the invention. The emulsions can be of the water-in-oil or oil-in-water type and have a thick, mayonnaise-like consistency.

The agents according to the invention can also contain other admixtures, e.g. contain other compounds with pesticide, in particular 55 insecticide, acaricide, herbicide or fungicide properties.

When used, the compound according to the invention is applied as such or as part of one of the means described in more detail above in an amount 60 which guarantees success.

The amount of active ingredient to be used for the purpose in question depends of course on a number of factors, e.g. The type and condition of the vegetation, the type of effectiveness desired, the type of application, the climate, the season, etc. Recommendations regarding the exact amount of use cannot therefore be given. However, it should be noted that generally an amount of active ingredient from 0.11 to 11.0 kg / ha leads to good results.

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The following examples serve to explain the invention in more detail. It should be noted that the identity of all compounds, whether intermediate or end product, has been verified by elemental analysis, infrared analysis and nuclear magnetic spectral analysis.

example 1

4'-Isopropoxy-3 '- (trifluoromethyl) -1-methyl-cyclopropane-carboxanilide a) Preparation of 3- (trifluoromethyl) -4-isopropoxynitro-benzene

A solution of 41 g (0.5 mol) of sodium isopropoxide in 300 was added dropwise to a solution of 118 g (0.5 mol) of 3- (trifluoromethyl) -4-chloronitrobenzene, cooled to 5 ° C., in 100 ml of dimethyl sulfoxide (DMSO) ml of dimethyl sulfoxide added. The dark reaction mixture was stirred at ambient temperature for one hour, poured out into water and taken up in ether. The ether extracts were washed with water, dried and concentrated. After recrystallization of the remaining liquid from hexane, 115.5 g (92.7%) of a white crystalline solid were obtained; M. 34-36 ° C (la).

b) Preparation of 3- (trifluoromethyl) -4-isopropoxyaniline

To a refluxed mixture of 113.3 g

(0.455 mol) of substance la in 1200 ml of 5% aqueous acetic acid and 50 ml of methanol were added in portions with stirring 137.5 g of iron filings. The reaction mixture was refluxed for one hour, filtered hot, cooled and extracted with ether. After drying and concentrating, 72.3 g (72.6%) of an amber oil (lb) were obtained from the ether extracts.

c) Preparation of 4'-isopropoxy-3 '- (trifluoromethyl) -l-methylcyclopropanecarboxanilide

To a solution of 10.9 g (0.05 mol) of substance Ib and 5.0 g (0.05 mol) of triethylamine in 100 ml of tetrahydrofuran was added dropwise 5.9 g (0.05 mol) of 1- Methylcyclopropanecarboxylic acid chloride too. The temperature rose to 55 ° C due to the exothermic reaction. The reaction mixture was stirred and refluxed for 30 minutes and then concentrated under reduced pressure. The resulting solid was washed with water, dried and recrystallized from ether; 14.5 g (97%) of white crystals of mp 106-109 ° C. were obtained.

Example 2

4 '- (Benzyloxy) -3' -trifluoromethyl-1-methylcyclopropane-carboxanilide a) Preparation of 3- (trifluoromethyl) -4- (benzyloxy) nitrobenzene

To a solution of 45.1 g (0.2 mol) of 3- (trifluoromethyl) -4-chloronitrobenzene in 100 ml of DMSO was added dropwise a solution of 26 g (0.2 mol) of sodium benzyl oxide in 75 ml of benzyl alcohol at ambient temperature, whereby the temperature rose to 40 ° C. After 48 hours at ambient temperature, the reaction mixture was poured into ice water and extracted with ether, the extract was dried and concentrated to about 200 ml. 200 ml of hexane were added to the concentrated solution and the mixture was cooled. After filtration, 51.5 g (87%) of colorless crystals of mp 112-114 ° C remained (2a).

b) Preparation of 3- (trifluoromethyl) -4-benzyloxy-aniline

To a refluxed mixture of 64.5 g

(0.217 mol) of substance 2a in 700 ml of 5% acetic acid and

30 ml of methanol 65.5 g of iron filings were added in portions over 15 minutes. The mixture was stirred for a further 30 min and kept under reflux, filtered hot, cooled and extracted with ether. After washing with water, drying and concentrating, the ether extract gave 56.0 g (97%) of a light amber-colored oil which crystallized on standing (2b).

c) Preparation of 4 '- (benzyloxy) -3' - (trifluoromethyl) -l-methylcyclopropanecarboxanilide

To a solution of 2.7 g (0.01 mol) of substance 2b and 2.7 g (0.01 mol) of triethylamine in 50 ml of tetrahydrofuran were added 1.2 g (0.01 mol) of 1- Methylcyclopropanecarboxylic acid chloride added. After standing for one hour, the reaction mixture was poured out over ice and water and extracted with 200 ml of ether. The ether extract was dried and concentrated. After recrystallization of the resulting solid from ether, 3.6 g of solid of melting point 120-122 ° C. were obtained.

Example 3

4 '- (Cyclopropylmethoxy) -3' - (trifluoromethyl) -1-methylcy-clopropanecarboxanilide a) Preparation of 3- (trifluoromethyl) -4- (cyclopropyl-methoxy) nitrobenzene

To a solution of 22.5 g (0.1 mol) cooled to 10 ° C

3- (Trifluoromethyl) -4-chloronitrobenzene in 100 ml DMSO was stirred at ambient temperature with a solution of 0.11 mol sodium cyclopropyl methoxide (prepared by dissolving 4.9 g 57% sodium hydride in 7.9 g cyclopropyl methanol and 50 ml tetrahydrofuran) added in 100 ml DMSO. The reaction mixture was warmed to 50 ° C for one hour, then poured out into ice water and filtered. After recrystallization from hexane, 11.0 g (42%) of a white crystalline solid with a melting point of 41-44 ° C. (3a) were obtained.

b) Preparation of 3- (trifluoromethyl) -4- (cyclopropyl-methoxy) aniline

28 g of iron filings and 10 ml of methanol were added to a stirred and refluxed mixture of 11.0 g (0.042 mol) of substance 3a in 150 ml of 5% aqueous acetic acid. The mixture was stirred vigorously under reflux for one hour, cooled and extracted with ether. After washing with aqueous sodium bicarbonate, drying and concentrating, 9.5 g (98%) of an amber-colored oil (3b) were obtained from the ether extract.

c) Preparation of 4 '- (cyclopropylmethoxy) -3' - (trifluoromethyl) - 1 -methylcyclopropanecarboxanilide

2.4 g (0.02 mol) of 1-methylcyclopropanecarboxylic acid chloride were added to a solution of 4.6 g (0.02 mol) of substance 3b and 2.0 g (0.02 mol) of triethylamine in 30 ml of tetrahydrofuran . The mixture was refluxed for one hour, poured into ice water and extracted with ether. After drying and concentrating the extract and recrystallizing the residue from hexane, 5.0 g (79%) of white crystals of mp 84-85 ° C. were obtained.

Example 4

4 '- (Methylthio) -3' - (trifluoromethyl) -1 -methylcyclopropanecarboxanilide a) Preparation of 3- (trifluoromethyl) -4- (methylthio) nitrobenzene

To a solution of 45.1 g (0.20 mol) of 3- (trifluoromethyl) -

4-chloronitrobenzene and 15 g (0.30 mol) methyl mercaptan in

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150 ml of DMSO was added dropwise at ambient temperature while stirring a solution of 8.0 g (0.2 mol) of sodium hydroxide in 20 ml of water, the temperature rising to 60 ° C. due to the exothermic reaction. After one hour the reaction mixture was poured into water, the product was filtered off and dried; 45.0 g (95%) of a yellow solid, melting at 50 ° C. (4a), were obtained.

b) Preparation of 3- (trifluoromethyl) -4- (methylthio) aniline

61 g of iron powder were added to 45.0 g (0.19 mol) of substance 4a in 5% aqueous acetic acid, and the mixture was refluxed for three hours and filtered while hot through Celite (filter aid). The cooled filtrate was extracted with ether. The ether extract was washed with 10% aqueous sodium bicarbonate and then with water, dried over anhydrous MgSÛ4 and concentrated under reduced pressure; 31.8 g (81%) of a light yellow oil (4b) were obtained.

c) Preparation of 4 '- (methylthio) -3' - (trifluoromethyl) -1 -methylcyclopropanecarboxanilide

To a solution of 31.8 g (0.154 mol) of substance 4b and 15.6 g (0.154 mol) of triethylamine in 200 ml of tetrahydrofuran, 18.2 g (0.154 mol) of 1-methylcyclopropanecarboxylic acid chloride were added dropwise with stirring. The temperature rose to 65 ° C due to the exothermic reaction. The mixture was stirred and refluxed for 1 h, then poured into ice water and filtered. After washing with water and drying, 43.5 g (98%) of a yellow dye with a melting point of 97-98 ° C. were obtained from the filter cake.

Example 5

4 '- (Methylsulfinyl) -3' - (trifluoromethyl) -1 -methylcyclopropanecarboxanilide

A solution of 14.5 g (0.05 mol) of 4 '- (methylthio) -3' - (trifluoromethyl) -1 -methylcyclopropanecarboxanilide (prepared according to Example 4) in 150 ml of chloroform was cooled to 5 ° C. in the course of 20 min A solution of 10.2 g (0.05 mol) of 85% metachloroperoxybenzoic acid in 150 ml of chloroform was added dropwise with stirring. The reaction solution was allowed to gradually balance to 25 ° C, which took 16 hours; the solution was then washed well with 10% sodium carbonate and water, dried and concentrated. The solid residue was recrystallized from methanol and gave 13.0 g (86%) of a light cream-colored solid; Mp 181-184 ° C.

Example 6

4 '- (Methylsulfonyl) -3' -trifluoromethyl-1 -methyl-cyclopro-pancarboxanilide

To a solution of 7.0 g (0.024 mol) of 4 '- (methylthio) -3' - (trifluoromethyl 1) -1-methylcyclopropane-carboxanilide (prepared according to Example 4) in 200 ml of chloroform was added dropwise over 10 minutes at ambient temperature 10.2 g (0.05 mol) of 85% metachloroperoxybenzoic acid were added with stirring. The exothermic reaction raised the temperature to 50 ° C. and the reaction mixture was stirred for 16 hours and washed out with 10% aqueous sodium carbonate and then with water. The chloroform layer was dried and evaporated to dryness. After recrystallization from methanol, the residue gave 7.5 g (97%) of a light cream-colored solid; Mp 135-138 ° C.

Example 7

4 '- (4-chlorophenoxy) -3' - (trifluoromethyl) -1 -methylcyclopropanecarboxanilide

5 a) Preparation of 4 '- (4-chlorophenoxy) -3' - (trifluoromethyl) nitrobenzene

A solution of 64.2 g (0.5 mol) of 4-chlorophenol and 112.7 g (0.5 mol) of 2-chloro-5-nitrobenzotrifluoride in 400 ml of DMSO was added dropwise at 30 to 35 ° C. with stirring Solution of 20 g (0.5 mol) sodium hydroxide in 20 ml water added. After 1 Vi hours the reaction mixture was poured into cold water and extracted with 800 ml of ether. After drying and concentrating under reduced pressure, the ether solution gave 158 g (99%) of a product which crystallized on standing; Mp 46-48 ° C (from hexane) (7a).

b) Preparation of 4 '- (4-chlorophenoxy) -3' - (trifluoromethyl) aniline

140 g of iron powder were added in portions to a refluxed mixture of 165 g (0.492 mol) of nitro compound 7a in 1180 ml of 5% aqueous acetic acid. After 2 hours the reaction mixture was filtered through a filter aid and the residue washed with methanol. The combined filtrates were extracted seven times with 300 ml ether each. The combined ether extracts, after washing with aqueous sodium bicarbonate, drying and concentrating, gave 141.5 g of a product which, after recrystallization from hexane, melted at 43 to 45 ° C. (7b).

30 c) Preparation of 4 '- (4-chlorophenoxy) -3' - (trifluoromethyl) - 1 -methylcyclopropanecarboxanilide

2.4 g (0.02 mol) of 1-methyl-cyclopropylcarboxylic acid chloride were added dropwise to a solution of 5.75 g (0.02 mol) of amine 7b in 40 ml of tetrahydrofuran. The

The mixture was heated to 60 ° C. for an hour with stirring, poured out into ice water and filtered. After recrystallization from ether-hexane (1: 3), 6.5 g (88%) of a product which melted at 115 to 117 ° C. were obtained from the filter cake.

40 Example 8

4 '- (4-chlorophenoxy) -3' - (trifluoromethyl) -1-butylcyclo-propanecarboxanilide

To a solution of 2.9 g (0.01 mol) of the amine obtained according to Example 7b and 1.0 g (0.01 mol) of triethylamine in 50 ml of tetrahydrofuran was added dropwise 1.7 g (0.01 mol) of 1- Butyl-cyclopropanecarboxylic acid chloride added. The mixture was kept at 60 ° C. with stirring for an hour, poured out into ice water and extracted with ether. After drying the ether extract and evaporating under reduced pressure, a yellow syrup remained as residue, which after recrystallization from hexane gave 3.3 g (80%) of a brownish solid; M. 104-106 ° C.

Example 9

ss 4 '- (isopropylthio) -3' - (trifluoromethyl) -1 -methylcyclopropanecarboxanilide a) Preparation of 4 '- (isopropylthio) -3' - (trifluoromethyl) nitrobenzene

60 To a solution of 112.8 g (0.5 mol) of 2-chloro-nitrobenzotrifluoride and 46 g (0.6 mol) of isopropyl mercaptan in 400 ml of DMSO was added dropwise 40 g of 50% aqueous sodium hydroxide solution over the course of half an hour , the temperature rising to 50 ° C. After 24 hours, the reaction

65 mixed poured into ice water and extracted three times with 200 ml of methylene chloride. The combined extracts were washed with water, dried and concentrated to give 132 g (99%) of an orange-yellow liquid (9a).

15

20th

45

50

9

637 917

b) Preparation of 4 '- (isopropylthio) -3' - (trifluoromethyl) aniline

132.5 g (0.5 mol) of nitro compound 9a in 800 ml of 5% aqueous acetic acid were heated to the reflux temperature with stirring. After removing the heating jacket, 150 g of iron powder were then added in such a way that the reflux was maintained. After all was added, the mixture was stirred and refluxed for an hour and then filtered while hot. The filtrate was extracted three times with 300 ml of ether each time. The combined extracts were washed with 10% sodium carbonate and then with water. After drying, the solution was evaporated to dryness under reduced pressure to give 70.5 g (60%) of a yellow oil (9b).

c) Preparation of 4 '- (isopropylthio) -3' - (trifluoromethyl) -1-methylcyclopropanecarboxanilide

To a solution of 23.5 g (0.1 mol) of the amine 9b and 10.1 g (0.1 mol) of triethylamine in 150 ml of tetrahydrofuran was added dropwise 11.9 g (0.1 mol ) 1-Methylcyclopropylcarboxylic acid chloride added, the temperature rising to 55 ° C. The mixture was refluxed for one hour, poured out into ice water and filtered. After recrystallization from hexane, 25 g (79%) of colorless crystals of mp 103-105 ° C. were obtained from the filter cake.

Examples 10 to 42 A further 15 cyclopropanecarboxanilides, which are listed in Table 1, were prepared analogously to the preceding examples.

Table 1 Cyclopropane carboxanilides

10th

O

chs-

ch3

96

106-108

11

O

c2h5-

ch3

98

83-85

12

0

ch30ch2ch2-

ch3

98

83-85

13

o ch2 = chch2-

ch3

89

58-60

14

0

c2hsch (CH3) -

ch3

89

93-95

15

0

(ch3) 2chch2-

ch3

95

91-93

16

0

ch3 (ch2) s-

ch3

72

68-70

17th

S-0

(ch3) 2ch-

chs

91

143-145

18th

n, 0

(chs ^ ch-

ch3

75

140-143

19th

S

(ch3) 2chch2-

ch3

94

95-97

20th

S-0

(ch3) 2chch2-

ch3

67

oil

21st

SO

(ch3) 2chch2-

ch3

91

oil

22

s c2h5-

ch3

86

68-69

23

S-0

c2h5-

ch3

81

136-139

24th

S / O ö

c2h5-

ch3

83

140-143

25th

S

(ch3) 2chch2ch2-

ch3

90

78-80

26

S-0

(ch3) 2chch2ch2-

ch3

69

oil

27th

S 'O

%O

(ch3) 2chch2ch2-

ch3

100

oil

28

S

n-CsHu-

ch3

88

60-62

29

S-0

n-CsHn-

CHs

69

oil

30th

ç, 0

S ^ O

n-CsHn-

CHs

100

oil

31

s ch2 = chch2-

ch3

48

oil

32

s

(ch3) 3c-

ch3

92

144-146

33

s c2hS (CH3) ch-

CHs

88

100-102

34

s n-CóHn-

ch3

89

67-69

35

s n-CvHis-

ch3

89

60-62

36

s

(CH3> CHCH2

n-c4hs

68

88-91

37

s

C6H5CH2-

CHs

85

100-102

38

S-0

C6H5CH2

ch3

98

oil

39

s <°

C6H5CH2-

ch3

96

oil

40

s c2h5-

c2hs

40

oil

41

O

(ch3) 2ch-

c2h5

59

89-90

42

0

cich2ch-

chs

97

83-86

637917

Example 43

4 '- (Isopropylthio) -3' -nitro-1 -methylcyclopropanecarboxanilide a) Preparation of 4 '- (Isopropylthio) -3-nitroaniline To a solution of 34.5 g (0.2 mol) of 4-chloro-3-nitroaniline and 24 g (0.3 mol) of isopropyl mercaptan in 200 ml of DMSO was added at room temperature with stirring a solution of 8.0 g (0.2 mol) of sodium hydroxide in 10 ml of water. As a result of the exothermic reaction, the temperature rose to 60 ° C. and the mixture assumed a deep red color. After three days, the reaction mixture was poured into water and extracted with methylene chloride. The combined extracts were washed with water, dried with anhydrous MgSÛ4, filtered and concentrated to give 41.1g (97%) of a red-brown syrup (43a).

10th

b) Preparation of 4 '- (isopropylthio) -3' nitro-1-methylcyclopropanecarboxanilide

To a solution of 16.0 g (0.75 mol) of substance 43a and 7.6 g (0.75 mol) of triethylamine in 150 ml of tetrahydrofuran s were added dropwise 8.9 g (0.075 mol) of 1-methylcyclopropanecarboxylic acid chloride with stirring , the temperature rising to 60 ° due to the exothermic reaction. The mixture was refluxed for one hour, poured out over ice water and extracted with ether. After drying and concentrating, the ether extract gave 20.7 g of a dark, red-brown oil. After purification by silica chromatography, 10.5 g (48%) of a light yellow solid was obtained, which melted at 92 to 94 ° C.

15 Examples 44 to 46

Analogously to Example 43, further cyclopropane carboxanilides were prepared, which are listed in Table 2.

Table 2 Cyclopropanecarboxanilide no2

Example No. X R1 yield in% mp-, ° C.

44 S-O (ch3> ch- 73 143-145

45 S <q (ch3> ch- 90 103-105

46 O (CH3> CH 47 100-101

Example 4 7 stirred under reflux and filtered while warm. After cooling

4 '- (Cyclopropylmethoxy) -3' -chloro-1-methylcyclopropane 45 it was extracted with ether, the ether extract was washed with aqueous carboxanilide sodium bicarbonate, dried and concentrated; 22.8 g (99%) of a melt at 54 to 55 ° C.

a) Preparation of 3-chloro-4- (cyclopropylmethoxy) - zenden solid (47b).

nitrobenzene

17.3 g of cyclopropylmethanol were added to a solution of 38.4 g of 3,4-dichloronitrobenzene in 50 c). Preparation of 4 '- (cyclopropylmethoxy) -3'-chloro-1-150 ml of DMSO, and methylcyclopropane carboxanilide were then added to the solution Stir dropwise 92 g to a solution of 4.9 g of substance 47b and 2.5 g

Sodium hydroxide dissolved in 10 ml of water was added, whereby triethylamine in 50 ml of tetrahydrofuran was added dropwise to a temperature of 45 ° C. The mixture was then added to 18 3.0 g of 1-methylcyclopropane carboxylic acid chloride. The hour at 75 to 80 ° C stirred, poured over ice water ss mixture was refluxed for 30 min, in ice water and filtered. After recrystallization, the filter cake was poured out and filtered, whereupon the filtrate from methanol / stall from methanol was recrystallized from 27 g (59%) of a slightly brownish water (4: 1). 6.5 g of a solid of mp 42-44 ° C. (47a) were obtained. (92%) white crystals of mp 111-113 ° C.

b) Preparation of 3-chloro-4- (cyclopropylmethoxy) aniline 60

To 26.7 g of substance 47a in 300 ml of 5% aqueous examples 48 to 55

56 g of iron filings and 15 ml of methanol were added to acetic acid. According to Example 47, those listed in Table 3 were added. The mixture was made vigorously with additional cyclopropane carboxanilides for one hour.

11 637917

Table 3 Cyclopropane carboxanilides

Example No. X R 'Yield in% mp, ° C

48 O <= T> CH2- 89 107-109

49 O 86 146-149

50 O Cl <Zj> CH2-80 135-137

Cl

51 O ^ H> CH2-95 150-152

Cl

52 O CH3OC2H2- 75 74- 75

53 O (CH3) 2CH- 67 107-110

54 O CHs 92 128-130

CHs

55 O / \ I 87 87- 89

^ —CH-

Example 56

4'-Piperidinyl-3 '- (trifluoromethyl) -1-methylcyclopropanecarboxanilide a) Preparation of 4-nitro-1-piperidinyl-2- (trifluoromethyl) benzene

17 g of piperidine were added dropwise to a solution of 4-nitro-2- (trifluoromethyl) chlorobenzene in 150 ml of DMSO. The mixture was stirred at ambient temperature but protected from the influence of air and moisture, stirred for several days, then poured out over ice water and extracted with methylene chloride. After washing with cold water, drying and concentrating, the extract gave 27.4 g (100%) of a tan oil (56a).

b) Preparation of 4-piperidinyl-3- (trifluoromethyl) -benzolamine

26 g of substance 56a were heated to 95 ° C in about 500 ml of 5% acetic acid, whereupon 17 g of iron powder were added to the mixture in portions such that the reflux was maintained without external heat supply. After all was added, the mixture was stirred for 1½ hours and warmed to reflux and filtered while warm; the cooled filtrate was extracted with ether. After washing with 10% aqueous sodium bicarbonate and then with water, drying and concentrating the ether extract, 22 g (96%) of a yellow-brown oil (56b) were obtained.

c) Preparation of 4'-piperidinyl-3 '- (trifluoromethyl) -1-methylcyclopropanecarboxanilide

5.3 g of 1-methylcyclo-propanecarboxylic acid chloride were added dropwise to 11 g of substance 56b in 75 ml of tetrahydrofuran and 4.6 g of triethylamine, the reaction

35 temperature rose to 55 ° C. The mixture became l'A

Heated to 64 ° C with stirring, poured out over ice water and extracted with ether. After washing with water, drying and concentrating, 13 g (88%) of a yellow syrup were obtained from the ether extract, which after recrystallization from hexane gave 12 g (82%) of an off-white solid of mp 109-111 ° C.

Example 57

4 '- (Isopropylamino) -3' - (trifluoromethyl) -1-methylcyclo-45 propane carboxanilide a) Preparation of N-isopropyl-4-nitro-2- (trifluoromethyl) benzene amine

13 g of isopropylamine were added to a solution of 45 g of 3- (trifluoromethyl) -4-chloronitro-50 benzene in 150 ml of DMSO. The mixture was kept at 80 to 90 ° C for 2 hours, then poured out over ice water, acidified and filtered. The dried, evaporated filtrate gave 49.6 g of a product which melted at 35 to 36 ° C (57a).

55

b) Preparation of 4- (isopropylamino) -3- (trifluoromethyl) benzene amine

49.6 g of substance 57a were added to about 565 ml of 5% acetic acid heated to 90 ° C., after which 123 g of 60 iron powder were added in portions. The mixture was then refluxed for one hour and filtered hot, after which the cooled filtrate was extracted with ether. After washing with 10% aqueous sodium bicarbonate and then with water, drying and evaporating, the ether extract gave 38.7 g (89%) of a light amber oil (57b).

c) Preparation of 4 '- (isopropylamino) -3' - (trifluoro-

637917

12

methyl) -1 -methylcyclopropanecarboxanilide

118.5 g of 1-methylcyclopropanecarboxylic acid chloride were added dropwise to a solution of about 19 g of substance 57b in 150 ml of tetrahydrofuran and 8.8 g of triethylamine in the course of 5 minutes at 25 to 64 ° C. The reaction mixture was refluxed with stirring for 30 min, then poured out over ice water and extracted with ether. The ether extract was dried and concentrated and the

Residue recrystallized from ether / petroleum ether; 22 g (84%) of a gray dye with a melting point of 100-102 ° C. were obtained.

Examples 58 to 70 Further cyclopropanecarboxanilides, which are listed in Table 4, were prepared analogously to Examples 56 and 57.

Table 4 Cyclopropane carboxanilides

R

^ n - <(y- - nc — t-

^ W H 1H.

I.

Example No.

R3

R '

Yield%

Mp "° C

58

59

60

61

62

63

H H

CHs CHs H

H

OCHs

III

CHsHNCCH-H

CHs

(ch3) 2ch- (ch3> C-

Z \.

cf3

cf3 cf3

cf3 cf3

cf3

58

9 85 84 93

68

223-226

136-141 89- 91 98-100 105-108

126-128

64

65

66

H

CsHr

C.

CHs c3h7

cf3 cf3 cf3

79 68 77

120-122 74- 76 102-104

67

68

69

70

ch3

h c3h7 h

(ch3) 2ch

(CH3) 3c-

c3h7

cf3

no2 no2 no2

98

2 4 31

oil

172-174 211-214 77- 79

Example 71

4 '- (Isopropoxy) -3' - (trifluoromethyl) -1-chlorocyclopropane carboxanilide

To a solution of 10.95 g of substance Ib in 100 ml of tetrahydrofuran and 5.05 g of triethylamine, 6.95 g of 1-chlorocyclopropane-carboxylic acid chloride were added dropwise at ambient temperature. After standing for 2 days, the reaction mixture was evaporated to dryness. The resulting solid was washed with water and recrystallized from 80% aqueous methanol; 10 g (62%) of a white solid of mp 106-108 ° C. were obtained.

Example 72

4'-isopropoxy-3 '- (trifluoromethyl) - 1-ethoxycyclobutancar-boxanilide and 4'-isopropoxy-3' - (trifluoromethyl) -l-bromcy-clobutanecarboxanilide a) Preparation of 1-ethoxycyclobutanecarboxylic acid-

50 chloride and 1-bromocyclobutane carboxylic acid chloride

A solution of 82.8 g of ethyl 1-bromocyclobutane carboxylate and 28 g of potassium hydroxide in 250 ml of 85% aqueous ethanol was refluxed for 15 minutes. Then the reaction mixture was evaporated to dryness under reduced pressure, taken up in cold hydrochloric acid and extracted with ether. After drying and evaporation, 53 g of a viscous mixture of acids were obtained from the ether extract. Treatment of this mixture with excess thionyl chloride under reflux conditions followed by distillation gave 18 g of a colorless liquid boiling at 70 to 75 ° C (16 mm). Gas-liquid chromatography showed the presence of 1-bromo-cyclobutanecarboxylic acid chloride and 1-ethoxycyclobutanecarboxylic acid chloride in a ratio of about 4; 1 on.

65

b) Preparation of 4 '- (isopropoxy) -3' - (trifluoromethyl) -1-ethoxycyclobutane carboxanilide and 4'-isopropoxy-3 '"(trifluoromethyl) -1-bromocyclobutane carboxanilide

13

637 917

To a solution of 10.9 g of substance Ib and 5.1 g of triethylamine in 175 ml of tetrahydrofuran were added dropwise at 10 to 20 ° C. 12.1 g of substance 72a. After standing overnight, the reaction mixture was evaporated to dryness, washed with water and extracted with ether. After blowing off the ether, the residue was purified by silica chromatography. The first fraction consisted of 3.0 g (16%) of the 1-ethoxycy-clobutane ester as a brownish solid, mp 48-50 ° C. The second fraction consisted of 2.8 g (13%) 1-bromocyclobutane ester as a white solid, mp 82-84 ° C.

Example 73

4 '- (Isopropoxy) -3' -methyl-1-methylcyclopropanecarboxanilide a) Preparation of isopropyl orthotolyl ether

12 g of 57% sodium hydroxide solution were added in portions to a solution of 54.1 g (0.5 mol) of orthocresol in 150 ml of DMSO, with stirring, the temperature rising to 45.degree. After 2 hours at ambient temperature, 51.5 g (0.5 mol) of isopropyl bromide in 50 ml of DMSO was added dropwise to the mixture with stirring. After a further 2 hours, the reaction mixture was poured into 1000 ml of ice water and extracted with ether. Distillation of the dried extract gave 53.9 g of the reaction product as a colorless liquid; Bp 94-96 ° C (30mm) (73a).

b) Preparation of 2-isopropoxy-5-nitrotoluene

A solution of 13.9 g (0.22 mol) of 90% nitric acid was added dropwise to a solution of 31.8 g (0.2 mol) of ether 73a and 28.7 g of acetic anhydride in 200 ml of glacial acetic acid, cooled to 6 ° C. added in 100 ml of glacial acetic acid. The reaction mixture was left to stand at ambient temperature for 12 hours, poured out into water and extracted with methylene chloride. After washing with 5% sodium carbonate and water, drying and concentrating, the extract gave 21.8 g of an amber oil (73b).

c) Preparation of 4 '- (isopropoxy) -3' methyl-1-methylcyclopropane carboxanilide

21.8 g (0.11 mol) of substance 73b and 2 g of 10% palladium-carbon catalyst in 150 ml of tetrahydrofuran were placed in a Parr shaker. The glass cylinder was charged with hydrogen at 2.8 kg / cm 2 and shaken until no more hydrogen was taken up, after which the catalyst was filtered off. 11.2 g of triethylamine and 12.6 g of 1-methylcyclopropanecarboxylic acid chloride were added to the resulting solution, causing the temperature to rise to 35 ° C. After 1 hour the reaction mixture was evaporated to dryness and washed with water. Purification by silica chromatography gave 0.8 g of white crystals of mp 99-101 ° C.

Example 74

4 '- (Dimethylsulfamoyl) -3' - (trifluoromethyl) -1 -methylcyclopropanecarboxanilide a) Preparation of 4-nitro-3- (trifluoromethyl) -benzenesulphonyl chloride

A mixture of 57.5 g (0.28 mol) of 4-nitro-2- (trifluoromethyl) aniline in 200 ml of concentrated hydrochloric acid was heated to 90 ° C. for 15 minutes and at 18 hours

Ambient temperature continued to stir. The resulting mixture was cooled to 4 ° C and diazotized with 21.4 g (0.31 mol) of sodium nitrite in 50 ml of water. After 1 hour, the solution of the diazonium salt was introduced dropwise over the course of 5 1/2 hours with stirring into a solution which had been cooled to 5 ° to 10 ° C. and contained 13 g of copper (II) chloride and 64 g of sulfur dioxide in 250 ml of glacial acetic acid. After 2 hours the mixture was filtered and the filter cake washed well with water and dried; 68 g (84%) of a light brown solid of mp 77-79 ° C. (74a) were obtained.

b) Preparation of N, N-dimethyl-4-nitro-2- (trifluoromethyl) benzenesulfonamide

To a solution of 14 g (0.05 mol) of the sulfonyl chloride 15 7 4a in 100 ml of tetrahydrofuran, an excess of anhydrous dimethylamine was added with stirring through a gas inlet tube, as a result of which the internal temperature rose to 60.degree. The mixture was stirred for Vi hour at ambient temperature, poured into 500 ml of ice water and triturated 01-20. After washing with water and drying, 14 g (94%) of a light brown solid were obtained from the filter cake; Mp 95-97 ° C (74b).

c) Preparation of 4-dimethylsulfamoyl-3- (trifiuor-25 methyl) aniline

After heating with stirring, 12 g of iron powder were added in portions to a mixture of 13.5 g (0.045 mol) of amide 74b in 250 ml of 5% acetic acid and the mixture was kept under reflux for 6 hours. After Abfil-30 freeze in the hot state and extract the cooled filtrate with ether, the ether extract was washed with aqueous sodium bicarbonate, dried, evaporated and recrystallized from ether-hexane (1: 2); 10.1 g (83%) of a colorless solid were obtained; M. 140-142 ° C (74c).

35

d) Preparation of 4 '- (dimethylsulfamoyl) -3' - (trifluoromethyl) -1 -methylcyclopropanecarboxanilide

To a solution of 6.7 g (0.025 mol) of the aniline 74c and 2.5 g of triethylamine in 50 ml of tetrahydrofuran was added 40 drops of 3.0 g (0.25 mol) of 1-methylcyclopropanecarboxylic acid chloride. The mixture was refluxed for 1 hour, poured into ice water, filtered and recrystallized from methanol; 7.5 g (86%) of white crystals of mp 153-156 ° C. were obtained.

45

Example 75

4 '- (Isopropoxy) -3' -chloro-1-methoxycyclopropanecarbox-anilide so A mixture of 5.6 g of 3-chloro-4-isopropoxyaniline, 3.9 g of methyl 1-methoxycyclopropanecarboxylate and 1.8 g of sodium methoxide in 50 ml of benzene was refluxed for 3 hours. After evaporation to a volume of 25 ml, the reaction mixture was then poured out over ice water, acidified with hydrochloric acid and extracted with ether. The ether extract was dried, filtered and concentrated. When the residue was purified by silica chromatography, 1.8 g of white crystals of F. 86-87 ° C.

60

Examples 76-93

Further cyclopropanecarboxanilides which were prepared analogously to the examples above are listed in Tables 5 and 6.

637917

14

Table 5 Cyclopropanecarboxanilides

Example No.

Yield%

Mp, ° C

76

O

CF3

czhs

82

85-87

77

S

CF3

C2H5

80

56-58

78

s cf3

CH2 = CHCH2

60

oil

CH B

79

0

Cl

^ -CH-

67

51-52

80

0

Cl

67

70-72

81

0

Cl

CHs

76

95-98

82

NCH3

S02CH3

(CHs> CH-

80

145-148

83

NCH3

CF3

(CHs) 2CH-

65

55-57

84

O

CF3

C1 (CH2) 2-

100

oil

Table 6 Cyclopropanecarboxanilides

Example No.

Y

X

R '

R2

Yield in%

Mp, ° C

85

CN

O

(CHs> -CH-

CHs

49

130-132

86

shcm

NCHs

(CHS) 2CH-

CHs

95

175-177

87

Br

NH

(CHs) 2CH-

CH3

26

89-90

88

so2ch3

s

C2H5-

CHs

56

130-134

89

CFs see

(CHs> CH-

Cl

60

62-64

90

CF3

NCHs

(CHs) 2CH-

C2H5

38

oil

91

Br o

(CHs ^ CH-

CH3

32

99-101

92

CN

O

CHs

CHs

16

129-131

93

SCHs o

C2H5

CHs

1

114-116

Example 94 Detection of the Herbicidal Activity The herbicidal activity of the compounds according to the invention before emergence was determined by introducing seeds from garden cress, downy bristle, wild mustard, velvet leaf, soybean, wheat and cotton into test tubes of 25 × 200 mm, in which soil was contained with the compound to be tested in an amount of 0.1 and 1 mg per tube (designated in Table I with the Roman numerals I and II respectively). The tubes loaded with seeds were kept under controlled conditions (temperature, humidity, light) for 13 to 14 days. The amount of germination and growth in each tube was rated on a scale from 0 to 9, where 0 means no herbicidal activity and 9 means seedling death or no germination.

The efficacy of the compounds according to the invention after emergence was determined by adding 7-day-old cinquefoil plants, 10-day old goosefoot plants, 7-day-old fluffy trespa plants, 10-day old wild mustard plants, 10-day old velvet leaf plants, 14-day old soybean plants, Sprayed 7 day old wheat plants and 14 day old cotton plants extensively with a liquid preparation of the compounds to be tested; 0.62 ml of a 0.05% solution (designated I in Table I) and 0.56 ml of a 0.5% solution (referred to II in Table I) were used for this. The sprayed plants were kept under controlled conditions for 10 to 11 days, after which the effect of the compound to be examined was determined visually; the results are rated 0 to 9 on the scale above. 60 Table I shows the results of the tests before and after emergence.

The herbicidal activity of the compounds according to the invention in relation to some common weed species was further determined by spraying a preparation of the compound to be investigated on the soil into which the weed seed in question had been introduced (trial before emergence) or by leafing the already developed weed plants

50

15

637917

(Try after emergence). In both test series, the plants were housed in narrow bowls and were sprayed with the appropriate compound. The solution of the test compound was sprayed from end to end over the dish, the concentration of the test compound in the preparation being varied logarithmically from a higher value at one end of the band to a lower value at the other end. The effect of the compound to be tested was determined visually and stated as a nominal application amount in lb / acre (1.12 kg / ha), calculated on the floor area of the belt, at which weed growth was prevented by 90%; this value is referred to in the table as “GIDoo” and means that growth is suppressed by 90% at this dosage.

The weed species concerned and the results of the tests before and after emergence are shown in Tables II and III, to which the following should also be noted:

a) The test plants are abbreviated as follows:

G.K.

=

Garden cress f.T.

=

downy trespe w.S.

=

wild mustard

5 Sbl.

=

Velvet leaf

Soya

=

Soybean

Wz.

=

wheat

Bw.

=

cotton

F.K.

=

Cinquefoil io G.F.

=

Goose foot g-F.

=

yellow foxtail

H.H.

=

Herbsthetse b) The Arabic numerals are the GIDso values, given in lb / acre; for the conversion into kg / ha the

Numbers are multiplied by 1.12. However, since these are comparative values that can be seen more clearly from whole numbers, no conversion has been carried out.

c) The Roman numerals I and II are explained above.

Table I Herbicidal Efficacy - Trial Results

Before emergence (bottom)

After emergence (leaves)

G.K. f.T.

w.S.

Sbl.

Soya Wz. Bw. F.K. G.F. f.T. w.S.

Sbl.

Soya Wz. Bw.

Example I I I I I I I 1

II II II II II II II II II II II II II II II

10 9396 784-5

9799865 999-952 3

11

7

7

4th

5

8th

9

4th

8th

3rd

5

0

7

7

9

9

7

8th

7

9

6

9

6

5

2nd

1

8th

8th

0

2nd

9

9

0

1

4th

3rd

0

8th

9

7

9

8th

9

8th

9

9

9

7

6

9

12

6

9

1

4th

9

9

4th

8th

3rd

4th

0

0

2nd

0

7

0

2nd

1

9

2nd

7

2nd

3rd

2nd

2nd

0

8th

0

0

0

2nd

0

0

0

0

0

8th

9

7

8th

3rd

3rd

9

9

3rd

9

4th

2nd

7

3rd

7

8th

0

0

6

8th

0

0

0

0

0

7

7

4th

8th

7

7

8th

9

6

9

4th

9

7

13

8th

9

0

0

4th

8th

0

0

0

2nd

0

3rd

7

2nd

9

6

6

8th

8th

7

9

6

3rd

8th

15

0

8th

0

0

0

0

0

0

0

0

0

3rd

6

3rd

8th

4th

6

7

9

9

9

5

4th

8th

14

0

8th

0

0

0

9

0

■ 0

0

0

0

7

8th

8th

9

0

8th

8th

9

9

9

6

1

9

16

0

4th

0

0

0

0

0

0

0

2nd

0

5

6

0

2nd

2nd

7

8th

8th

7

8th

6

0

8th

4th

3rd

9

0

2nd

8th

9

0

5

7

5

0

4th

6

8th

9

1

5

7

9

7

8th

6

0

7

5

9

9

1

5

9

9

7

7

7

7

0

0

2nd

7

8th

0

2nd

0

4th

3rd

5

4th

6

7

6 9397 06067

9697670 1 8 1 9 875 7

9 9090 59287

9 3 9 8003 7 9 7 9 889 8

637917

16

Table I (continued)

Before emergence (bottom) After emergence (leaves)

G.K.

f.T.

w.S.

Sbl.

Soya

Wz.

Bw.

F.K.

G.F.

f.T.

w.S.

Sbl.

Soya

Wz.

Bw.

example

I.

II

I.

II

I.

II

I.

II

II

II

II

I.

II

I.

II

I.

II

I.

II

I.

II

II

II

II

17th

9

9

6

6

9

9

9

9

7

7

6

1

4th

5

9

1

5

5

9

9

9

6

6

7

18th

9

9

6

6

9

9

9

9

7

6

0

4th

6

9

9

4th

9

5

9

9

9

6

6

7

19th

0

0

0

0

0

0

0

0

0

0

0

6

8th

9

9

4th

5

9

9

8th

8th

8th

4th

8th

20th

9

9

5

7

9

9

5

9

7

5

4th

2nd

7

9

9

3rd

5

7

9

8th

8th

8th

7

8th

21st

8th

9

0

7

9

9

7

9

6

4th

6

7

7

9

9

0

5

8th

9

8th

8th

5

5

9

29

7

9

0

4th

9

9

0

9

1

1

0

0

0

0

5

0

4th

7

9

3rd

8th

8th

4th

9

30th

6

9

0

3rd

9

9

0

7

1

1

0

0

0

0

1

2nd

3rd

8th

9

8th

9

9

8th

8th

26

9

9

0

8th

9

9

7

9

5

5

0

0

2nd

1

7

0

3rd

8th

8th

8th

9

9

4th

9

27th

8th

8th

0

4th

9

9

3rd

9

2nd

2nd

0

0

6

3rd

9

4th

7

9

9

9

9

9

8th

9

31

0

9

0

0

2nd

9

0

0

0

0

0

8th

9

9

9

5

8th

9

9

9

0

9

8th

8th

9

22

9

9

5

7

8th

9

8th

9

8th

6

0

9

9

9

9

8th

9

9

9

9

9

7

3rd

8th

23

9

9

7

7

9

9

9

9

8th

7

7

2nd

8th

9

9

9

9

9

9

9

9

5

2nd

9

24th

9

9

8th

8th

9

9

9

9

8th

8th

0

2nd

8th

9

9

8th

9

9

9

9

9

5

1

8th

28

0

1

0

0

0

0

0

0

0

0

0

6

6

3rd

9

2nd

2nd

8th

9

8th

8th

8th

2nd

9

34

0

0

0

0

0

0

0

0

0

0

0

7

8th

4th

9

0

0

8th

9

3rd

7

7

2nd

9

35

0

0

0

0

0

0

0

0

0

0

0

5

5

7

7

0

9

7

7

5

8th

8th

2nd

9

33

5

8th

0

0

0

8th

0

0

0

0

0

7

8th

4th

9

0

5

8th

8th

8th

9

9

2nd

9

32

0

0

0

0

0

0

0

0

0

0

0

0

0

0

7

5

5

6

7

3rd

9

8th

3rd

4th

25th

0

1

0

0

0

0

0

0

0

0

0

6

7

3rd

8th

1

1

9

9

8th

8th

8th

0

9

37

0

0

0

0

-

-

0

0

5

0

0

7

9

9

9

5

5

-

-

6

9

4th

0

5

38

0

8th

0

2nd

-

-

0

6

0

0

0

2nd

8th

8th

9

3rd

7

-

-

9

9

3rd

0

3rd

17 637917

Table I (continued)

Before emergence (bottom)

After emergence (leaves)

G.K.

f.T.

w.S.

Sbl.

Soya

Wz.

Bw.

F.K.

G.F.

f.T.

w.S.

Sbl.

Soya

Wz.

Bw.

example

I.

II

I.

II

I.

II

I.

II

II

II

II

I.

II

I.

II

1

II

I.

II

I.

II

II

II

II

39

2nd

9

0

0

-

0

3rd

0

0

0

1

6

8th

9

4th

7

-

3rd

4th

0

0

0

40

2nd

2nd

0

0

-

-

0

0

0

0

0

0

7

4th

7

0

3rd

-

-

0

7

5

0

0

41

7

7

0

0

-

-

0

0

0

0

0

3rd

3rd

0

8th

0

3rd

-

-

3rd

6

4th

0

2nd

56

0

0

0

0

-

-

0

0

0

0

0

0

0

6

9

0

0

-

-

7

9

4th

0

0

66

3rd

6

0

0

-

-

0

4th

0

0

0

2nd

4th

4th

9

2nd

7

-

-

4th

9

2nd

0

0

67

0

1

0

0

-

-

0

0

0

0

0

0

8th

1

9

0

7

-

-

5

8th

4th

0

0

85

9

9

0

4th

-

-

0

3rd

5

5

0

0

0

0

4th

0

0

-

-

0

0

2nd

2nd

0

57

8th

8th

2nd

6

9

9

2nd

8th

-

2nd

5

5

5

9

9

2nd

5

8th

9

9

9

-

2nd

8th

58

7

8th

2nd

4th

8th

8th

3rd

7

6

0

0

0

0

0

0

0

0

0

3rd

0

0

0

0

0

59

3rd

7

1

2nd

7

8th

3rd

8th

2nd

0

0

0

0

0

5

0

0

0

2nd

0

5

2nd

0

2nd

58

0

8th

2nd

6

3rd

9

1

8th

0

6

0

0

0

0

0

0

0

0

2nd

0

0

0

7

0

63

2nd

8th

0

0

9

9

0

7

0

9

0

0

7

3rd

8th

1

1

7

9

6

9

9

0

9

60

8th

9

3rd

8th

9

9

5

9

8th

4th

0

9

9

8th

9

5

7

9

9

8th

9

9

0

4th

64

2nd

8th

0

3rd

0

9

2nd

6

9

3rd

0

8th

9

9

9

5

7

9

9

9

9

8th

4th

7

61

2nd

8th

0

0

9

9

3rd

5

0

0

2nd

9

9

9

9

8th

9

9

9

9

9

6

5

8th

62

8th

9

0

0

9

9

6

7

0

0

0

9

9

9

9

8th

9

9

9

9

9

3rd

0

8th

65

2nd

4th

0

0

0

2nd

2nd

2nd

0

0

2nd

8th

9

8th

9

2nd

8th

9

9

8th

9

7

2nd

2nd

43

3rd

6

0

0

3rd

8th

3rd

7

0

0

0

7

9

8th

9

3rd

6

8th

9

9

9

2nd

0

8th

44

3rd

9

3rd

7

4th

9

0

9

0

5

0

0

2nd

0

9

0

0

4th

8th

0

9

1

0

6

45 9 2 9 6 0 9 S 9 9

9799100 6979920 8

46 8598 56568

9899 720 8989924 0

637 917 18

Table I (continued)

Before emergence (bottom)

After emergence (leaves)

G.K.

f.T.

W.S.

Sbl.

Soya

Wz.

Bw.

F.K.

G.F.

f.T.

w.S.

Sbl.

Soya

Wz.

Bw.

example

I.

II

I.

II

I.

II

I.

II

II

II

II

I.

II

I.

II

I.

II

I.

II

I.

II

II

II

II

68

8th

8th

4th

5

8th

8th

5

6

0

5

0

8th

8th

8th

8th

3rd

3rd

9

9

9

9

5

0

3rd

69

0

9

0

0

0

0

0

0

0

0

0

8th

9

6

9

5

8th

7

9

2nd

9

1

0

6

70

5

5

0

0

-

-

0

0

0

3rd

0

2nd

3rd

2nd

5

0

0

-

-

4th

4th

2nd

0

0

49

0

0

-

-

-

-

-

-

0

-

3rd

7

8th

8th

8th

-

-

-

-

-

-

5

-

8th

48

6

6

-

-

-

-

-

-

0

-

0

7

9

8th

9

-

-

-

-

-

-

6

-

9

52

9

9

-

-

-

-

-

-

7

-

7

0

7

4th

5

-

-

-

-

-

-

6

-

8th

50

0

0

-

-

-

-

-

-

0

-

0

6

8th

8th

9

-

-

-

-

-

-

7

-

8th

51

0

0

-

-

-

-

-

-

0

-

0

7

7

6

9

-

-

-

-

-

-

5

-

7

47

7

8th

0

0

6

8th

0

0

0

0

0

7

7

4th

8th

7

7

8th

9

6

9

4th

9

7

54

8th

8th

4th

8th

-

-

7

9

7

4th

9

2nd

3rd

1

7

0

4th

-

-

5

8th

7

0

6

55

8th

9

0

4th

-

-

3rd

8th

0

1

0

3rd

9

9

9

7

8th

-

-

9

9

7

0

7

71

2nd

4th

0

0

-

-

0

0

3rd

0

0

0

3rd

6

7

0

0

-

-

5

5

2nd

0

0

76

0

0

0

0

-

-

0

0

0

0

0

0

5

4th

6

0

7

-

-

1

5

0

0

0

77

2nd

9

0

0

-

-

0

0

0

0

0

3rd

8th

8th

9

2nd

5

-

-

5

7

1

0

2nd

78

0

2nd

0

0

-

-

0

0

0

0

9

3rd

8th

6

8th

0

7

-

-

4th

9

2nd

0

0

83

3rd

6

0

0

-

-

0

0

0

4th

0

0

6

0

7

0

4th

-

-

0

7

1

0

0

79

1

5

0

0

-

-

0

0

0

0

0

1

4th

3rd

9

0

4th

-

-

6

8th

2nd

0

7

80

6

7

0

0

-

-

0

0

0

0

0

5

7

4th

9

5

7

-

-

3rd

8th

2nd

0

0

81 70-0 220-3

9 0 - 7000 7 8 7 - 940 2

53-000 50287

0 0 00-0 6 2 7 8 86 - 8

19th

637917

Table II

Evaluation of the experiments after emergence (spraying the leaves) Gl Dm

Example yellow autumn millet cinquefoil goose foot wild mustard velvet leaf fluffy chicken millet

Foxtail trespe

10th

0.32

1.0

0.7

0.4

0.4

> 2.0

-

-

11

<0.2

0.84

0.52

<0.2

<0.2

0.24

-

-

1

<0.2

0.52

<0.2

<0.2

<0.2

<0.2

-

-

2nd

2.0

> 2.0

> 2.0

<0.2

<0.2

> 2.0

-

-

3rd

<0.2

1.0

0.3

0.3

<0.2

0.48

-

-

13

1.0

1.64

1.5

1.34

0.52

2.0

> 2.0

2.0

15

2.0

1.34

> 2.0

2.0

0.22

0.44

> 2.0

> 2.0

14

0.84

1.34

1.0

0.92

0.22

0.3

2.0

1.6

16

> 2.0

> 2.0

> 2.0

1.34

<0.22

1.0

> 2.0

> 2.0

34

1.0

> 2.0

0.52

0.24

<0.22

2.0

> 2.0

1.34

35

> 2.0

> 2.0

1.0

<0.22

0.22

> 2.0

> 2.0

1.5

33

1.36

1.0

1.36

0.26

<0.22

0.3

> 2.0

> 2.0

25th

1.36

> 2.0

1.34

0.22

0.22

1.0

> 2.0

1.36

30th

> 2.0

> 2.0

1.5

0.22

<0.22

0.7

> 2.0

> 2.0

26

0.7

0.7

1.34

0.4

0.22

<0.22

> 2.0

0.7

27th

0.84

1.36

0.70

0.64

<0.22

<0.22

1.34

0.26

48

> 2.0

1.36

> 2.0

<0.2

<0.2

> 2.0

-

-

50

> 2.0

> 2.0

> 2.0

<0.2

<0.2

> 2.0

-

-

51

> 2.0

> 2.0

> 2.0

> 0.2

1.0

2.0

-

-

52

> 2.0

> 2.0

> 2.0

> 2.0

2.0

1.0

-

-

47

1.36

1.64

0.84

0.7

0.26

1.0

> 2.0

0.52

57

<0.22

0.58

0.22

<0.22

<0.22

<0.22

<1.8

<0.22

4th

1.64

1.34

2.0

> 2.0

1.0

1.0

> 2.0

> 2.0

6

> 2.0

> 2.0

> 2.0

1.12

1.64

1.64

> 2.0

> 2.0

9

<0.22

0.52

0.26

<0.22

<0.22

0.3

1.12

0.22

18th

0.7

0.92

0.64

<0.22

1.36

0.92

> 2.0

0.84

19th

<0.22

0.7

2.0

<0.22

<0.22

<0.22

2.0

0.22

20th

0.76

0.76

2.0

0.58

0.76

0.48

> 2.0

0.7

21st

0.76

0.4

1.34

<0.22

0.36

<0.22

2.0

0.52

Table III

Evaluation of the tests before emergence (spraying the soil) Gl Dio

Example type of earth yellow autumn millet cinquefoil goose foot wild mustard velvet leaf fluffy chicken millet

Foxtail trespe

4th

Webster

> 2.0

> 2.0

> 0.20

1.34

> 2.0

> 2.0

> 2.0

> 2.0

Hanford

> 1.0

> 1.0

> 1.0

0.58

0.7

> 1.0

> 1.0

> 1.0

6

Webster

> 2.0

> 2.0

> 2.0

1.5

> 2.0

> 2.0

> 2.0

> 2.0

Hanford

> 1.0

> 1.0

> 1.0

0.92

0.7

> 1.0

> 1.0

> 1.0

9

Webster

> 2.0

<1.0

> 2.0

<1.0

<1.0

> 2.0

> 2.0

> 2.0

Hanford

> 1.0

0.44

> 1.0

<0.22

0.36

> 1.0

> 1.0

1.0

7

Webster

> 2.0

<1.0

> 2.0

<1.0

<1.0

1.36

> 2.0

1.8

Hanford

0.84

0.32

> 1.0

0.22

0.24

0.64

0.3

0.52

8th

Webster

> 2.0

1.34

> 2.0

<1.0

<1.0

1.8

> 2.0

> 2.0

Hanford

0.92

1.0

> 1.0

0.22

<0.22

0.52

0.58

0.92

20th

Webster

> 2.0

1.12

> 2.0

<1.0

<1.0

1.36

> 2.0

> 2.0

Hanford

> 1.0

1.0

> 1.0

0.7

0.3

0.76

> 1.0

> 1.0

21st

Webster

> 2.0

<1.0

> 2.0

<1.0

<1.0

1.64

> 2.0

> 2.0

Hanford

> 1.0

0.52

> 1.0

0.26

0.7

0.76

> 1.0

> 1.0

637917

In many cases, the compounds according to the invention develop a selective action against weeds in crops of useful plants. For example, the occurrence of grasses and broad-leaf plants in cereals, e.g. Combat wheat fields with the help of the following compounds according to the invention:

4 '- (sec-butoxy) -3' - (trifluoromethyl) -1-methylcyclopropanecarboxanilide;

4 '- (isobutoxy) -3' - (trifluoromethyl) -1-methylcyclopropanecarboxanilide;

4 '- (isobutylsulfonyl) -3' - (trifluoromethyl) -1 -methylcyclopropanecarboxanilide; or

4 '- (ethylthio) -3' - (trifluoromethyl) -1 -methylcyclopropanecarboxanilide.

Weed control in soybean fields is an example of the selective herbicidal activity of 4 '- (isopropyla-mino) -3' - (trifluoromethyl) -1-methylcyclopropane carboxanilide or 4 '- (isopropylthio) -3' - (trifluoromethyl) -1 - methylcyclopropanecarboxanilide.

The above compounds, as well as other compounds according to the invention, also have a selective effect in crops of peanuts, millet (sorghum), cotton, rice, corn, alfalfa and the like after emergence and in some cases before emergence.

B

Claims (19)

637917 2. Compounds according to claim 1, characterized in that in formula IR2 represents a chlorine or bromine atom or a methyl or methoxy group and n is 1. 2nd PATENT CLAIMS 1. Substituted cycloalkane carboxanilides of the general formula: where the substituents X, Y, R1 and R2 have the following meaning: X represents O, S, SO, SO2 or the -NR3 group; Y represents a fluorine, chlorine or bromine atom or a cyano, a nitro, a C (R3) = NOR3 or a C (0) R3 group or the group -Zp-alkyl-, in which the alkyl part 1 to Contains 6 carbon atoms and can be substituted by one or more fluorine, chlorine or bromine atoms, while Z represents O, S, SO or SO2; R1 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, each of these groups optionally being substituted by one or more fluorine, chlorine or bromine atoms; or R1 represents an alkynyl group with 3 to 4 carbon atoms, an alkoxyalkyl group in which each alkyl group contains 1 to 6 carbon atoms, a cycloalkyl or cycloalkylalkyl group with 3 to 7 carbon atoms in the ring, an aralkyl group with 7 to 9 carbon atoms, which optionally is ring-substituted by one or two fluorine, chlorine or bromine atoms or by an alkyl group having 1 to 4 carbon atoms, or a group of the formula: R3 O R3 O I H "I II -CHCR4 or -CHCNR4R5; or, if X represents group NR3-, R1 can be for the group O II -CR6, or -SO2R6 or, if X represents group SO2, R1 can also stand for -NR4R5, -NR4-CR6 or-NR4S02R6 II O stand; R2 represents an alkyl group with 1 to 6 carbon atoms, a fluorine, chlorine or bromine atom or an alkoxy or alkylthio group, in which the alkyl part contains 1 to 6 carbon atoms; however, if Y is a NOî group and X is an O atom, R 'is not a methyl group; R3, R4 and R5 each independently represent a hydrogen atom or an alkyl or cycloalkyl group with up to 6 carbon atoms and R5 can also represent an alkoxy group with up to 6 carbon atoms; X represents the group -NR3, then R1 and R3 can together form part of a heterocyclic ring; R1 represents the group -NR4R5, then R4 and R5 can together form part of a heterocyclic ring; R6 represents an alkyl group with 1 to 6 carbon atoms or an aryl or aralkyl group with 6 to 10 carbon atoms, which may be substituted by one or more fluorine, chlorine or bromine atoms; and wherein n can be 1 or 2 and p can be 0 or 1. 3rd 637917 in the presence of a base with a cycloalkane carboxylic acid chloride of the general formula: Cl-C where X, Y, R1, R2 and n have the meaning given above. 3. Compounds according to claim 2, characterized in that R2 represents a methyl group. 4. Compounds according to claim 1, characterized in that in formula IY represents a chlorine atom or a methyl, a trifluoromethyl or a nitro group and n is 1. 5 5. Compounds according to claim 4, characterized in that Y represents a trifluoromethyl group. 6. Compounds according to claim 1, characterized in that in formula IR1 represents an alkyl group with 1 to 4 carbon atoms or a cycloalkyl group and n is 1. 7. Compounds according to claim 6, characterized in that R1 represents a methyl, ethyl, isopropyl, tert-butyl, cyclopropylmethyl group or a ring alkylated group. 8. Compounds according to claim 7, characterized in that R1 represents an isopropyl or a tert-butyl group. 9. Compounds according to claim 1, characterized in that the substituents R3, R4 and R5 each represent a hydrogen atom or a methyl, ethyl or methylcyclopropyl group, where R5 can also represent a methoxy or ethoxy group, and that n is 1 is. 10th 10. Compounds according to claim 1, characterized in that if X represents the group -NR3, R3 represents an isopropyl, n-propyl or tert-butyl group and n is 1. 11. Compounds according to claim 1, characterized in that X represents an O atom, R2 represents a methyl group, Y represents a trifluoromethyl group and R1 represents an alkyl group with 1 to 4 carbon atoms, a cyclopropylmethyl group or a 1-methylcyclopropyl group and n is 1. 12. Compounds according to claim 1, characterized in that X represents an S atom or an SO or SOa group, Y represents a trifluoromethyl group, R2 represents a methyl group and R1 represents an alkyl group with up to 4 carbon atoms and n is 1. 13. Compounds according to claim 1, characterized in that Y represents a nitro group, R1 an alkyl group having 2 to 4 carbon atoms and X represents an O or S atom or an SO or SOî group. 14. Compounds according to claim 13, characterized in that R1 represents an isopropyl group. 15 20th 25th 30th 35 40 45 50 55 60 65 15.4 '- (Isopropylamino) -3' -trifluoromethyl-1-methylcyclo-propanecarboxanilide as a compound according to claim 1. 16.4 '- (Isopropoxy) -3' -trifluoromethyl-1-methylcyclopro-pancarboxanilide as a compound according to claim 1. 17. 4 '- (Isopropylthio) -3' -trifluoromethyl-1-methylcyclo-propanecarboxanilide as a compound according to claim 1. 18. Process for the preparation of the compounds of the formula I, characterized in that an aniline of the general formula disubstituted in the 3,4-position is: r1 "*" / o) -nh? Y 19. Use of the compounds of formula I as an active ingredient in herbicides.