CA1087186A - Cycloalkane-carboxanilides - Google Patents
Cycloalkane-carboxanilidesInfo
- Publication number
- CA1087186A CA1087186A CA294,281A CA294281A CA1087186A CA 1087186 A CA1087186 A CA 1087186A CA 294281 A CA294281 A CA 294281A CA 1087186 A CA1087186 A CA 1087186A
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- Canada
- Prior art keywords
- group
- methyl
- carbon atoms
- compound according
- trifluoromethyl
- Prior art date
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- Expired
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/06—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals
- C07D295/073—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals with the ring nitrogen atoms and the substituents separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/04—Sulfonic acids; Derivatives thereof
- A01N41/06—Sulfonic acid amides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/10—Sulfones; Sulfoxides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D211/26—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
- C07D295/135—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
- G01D2205/00—Indexing scheme relating to details of means for transferring or converting the output of a sensing member
- G01D2205/40—Position sensors comprising arrangements for concentrating or redirecting magnetic flux
Abstract
ABSTRACT OF THE DISCLOSURE
Compounds of the general formula:
Compounds of the general formula:
Description
---` 1(1 !37~86 q'he present ;nv~n~ion re~ates to novel cyclo-alkanecarboxanilide derivatives which possess useful herbicidal activity. The invention relates also to herbicidal compositions comprising as active ingredient at least one of the cycloalkanecarboxanilide derivatives according to the present invention. The present invention also relates to a method of controlling plant growth by applying a cycloalkanecarboxanilide derivative according ~
to the present invention or a ~omp~ition comprising at ;
least one cycloalkanecarboxanilide derivative according to the present invention to a locus containing plants to be controlled.
The novel cycloalkanecar~xanilide derivatives according to the present invention can be represented by the general formula:
R1-X- ~ N- ~ C~2)n (I) wherein X represents an 0, S, S0, S02 or -NR3 moiety;
Y represents a ~luorine, chlorine or bromine atom, a cyano, nitro, C(R3)=NoR3 or C(o)R3 group, or the group -Zp-alkyl in which the alkyl portion contains from 1 to 6 carbon atoms and can be substituted by one or more fluorine, chlorine or bromine atoms and Z represents an 0, S, S0 or S02 group;
R1 represents an alkyl group of from 1 to 6 carbon atoms, an alkenyl group of from 2 to 6 carbon atoms or an aryl group of from 6 to 10 carbon atoms, each optionally substituted by one or more fluorine, chlorine or bromine , , ~ .: . , ~ :
atoms or represents an alkynyl group of from 3 to 4 carbon atoms, an alkoxyalkyl group in which each alkyl group contains from 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 7 carbon atoms in the ring, an aralkyl group of from 7 to 9 carbon atoms optionally ring-substituted by one or two fluorine, chlorine or bromine atoms or by an alkyl group of from 1 to 4 carbon atoms, a group of the formula:
' " 4 ' " 4 ~
-CHCR or -CHCNR RJ, or, when X represents the group NR3- then R1 can represent the group -CR6, -S02R6, or, when X represents the group S02 then R1 can also represent the group -NR4R5, -NR4-CR6, or -NR4So2R6; R2 represents an alkyl group of from 1 to 6 carbon atoms, a fluorine, chlorine or bromine atom, an alkoxy or alkylthio group, in which the alkyl portion contains from 1 to 6 carbon atoms;
with the proviso that when Y represents a N02 group, and X represents an 0-moiety, then R1 does not represent a methyl group; R3, R4 and R5 each independently represents a hydrogen atom or an alkyl or cycloalkyl group of up to 6 carbon atoms and R5 can also represent an alkoxy group of up to 6 carbon atoms; when X represents the group -NR3-then R1 and R3 together can form a part of a heterocyclic ring, such as -CH2-(CH2)mCH2-, -CH3(CH ) CH3 ' or -CH2CH20CH2CH2-; when R1 represents the group -NR4R5 then R4 and R5 together can form a part o~ a heterocyclic :
~ ~087~86 ring as is shown above lor It1 arld I~S w~len taken together;
R6 represents an alkyl group of Irom 1 to 6 car-bon atoms or an aryl or aralkyl group Or from 6 to lO carbon atoms optionally substituted by one or more fluorine, chlorine or bromine atoms; m is 2 or 3; n is l or 2; and p is 0 or l.
The compounds shown in formula I above are derivatives of substituted cyclopropane or substituted cyclobutane carboxylic acids, such that n in the formula I is l or 2. Examples where R2 in the formula represents an alkyl group include methyl, ethyl, propyl and n-butyl; R2 can also represent a methoxy- or methyl-thio group or their lower alkyl homologues.
As a general rule, the compounds preferred because of their herbicidal properties are those compounds of formula I, wherein n is l and R2 represents a methyl group. The compounds wherein R2 represents a chlorine atom are also very active. Compounds wherein R2 represents a methoxy group are also desirable.
The group Y can represent a chlorine, bromine or fluorine atom, a cyano, nitro, unsubstituted amino, methyl-amino, carboxy, methoxycarbonyl, aminocarbonyl, methyl-aminocarbonyl, formyl, hydrox,~minomethyl, trifluoromethyl, trifluoromethoxy, methyl, ethyl, methylsulphonyl or tri-fluoromethylsulphonyl group.
Preferred because of their herbicidal properties are compounds of formula I, wherein Y represents a tri-fluoromethyl group. Compounds wherein Y represents a :
10~37186 chlorine atom or a methyl or nitro group, are also very active.
R can represent a straight- or, preferably, branched-chPin alkyl group, such as methyl, ethyl, iso-propyl, isobutyl, secondary butyl, tertiary butyl, iso-amyl, 2-chlorethyl, trifluoromethyl, allyl, phenyl, p-chlorophenyl, naphthyl or propargyl group. Where R
represents a cycloalkyl group it can be alkylated or linked to X by an alkylene group, for example, a cyclo-propyl, cyclohexyl, methylcyclopropyl or cyclopropyl-methyl group. Additionally, Rl can represent such groups as methoxyethyl, benzyl, phenethyl, p-chlorobenzyl or o-methylbenzyl, or, when X represents the group -NR3 then Rl can also represent an acetyl, propionyl, caproyl, benzoyl, methylsulphonyl, trifluoroacetyl or dimethylamino group or, when X represents the group S02 then Rl can also represent an unsubstituted amino, monomethylamino, di-methylamino, acetamido or methylsulphonylamino group.
Compounds wherein R represents an alkyl group of 1 to 4 carbon atoms or a cycloalkyl group are generally preferred. Especially active are those compounds wherein Rl represents a branched-chain alkyl, such as an iso-propyl- or tert.-butyl group. Ethyl, methyl and cyclopropyl-methyl derivatives and ring alkylated forms appear also to be highly active. Variations in activity, of course, depend on the individual combinations of R , R , R3, X
and Y.
` 1~87~t36 R3, R4 and R5 each represents independently a ~;
hydrogen atom, an alkyl group, such as a methyl or ethyl group or a cycloalkyl group, such as a methylcyclopropyl group, or R5 can also represent an alkoxy group, such as a methoxy or ethoxy group. Although, when X represents the group -NR3, then R3 represents preferably an iso-propyl-, n-propy~ or tert.-butyl group.
R6 can represent an alkyl group, such as a methyl, ethyl, isopropyl, isobutyl, secondary-butyl, tertiary-butyl, isoamyl or hexyl group or an aryl or aralkyl group,such as a phenyl, p-chlorophenyl, 2-bromophenyl, naphthyl, phenethyl or benzyl group.
Species contemplated within the scope of the present invention include those compounds with reference to formula I, wherein R1, X, Y and R2 have the following meanings:
i-C3H7, 0, CF3, n-C4H9 - isoamyl, 0, N02, n-C4Hg -CH3C0, 0, N02, C2H5 - t.butyl, NH, CF3, OCH3 - sulphamoyl, (R1 ~ X~, Et, SCH3 - i-C3H7, 0, Me, F and i-C4Hg~ S02, CF3, F.
Species contemplated wherein X represents the 0 moiety and Y the trifluoromethyl group are those wherein R1 and R2 have the following meanings:
isobutyl, methyl - isoamyl, propyl - 2-fluorobenzyl, methyl -
to the present invention or a ~omp~ition comprising at ;
least one cycloalkanecarboxanilide derivative according to the present invention to a locus containing plants to be controlled.
The novel cycloalkanecar~xanilide derivatives according to the present invention can be represented by the general formula:
R1-X- ~ N- ~ C~2)n (I) wherein X represents an 0, S, S0, S02 or -NR3 moiety;
Y represents a ~luorine, chlorine or bromine atom, a cyano, nitro, C(R3)=NoR3 or C(o)R3 group, or the group -Zp-alkyl in which the alkyl portion contains from 1 to 6 carbon atoms and can be substituted by one or more fluorine, chlorine or bromine atoms and Z represents an 0, S, S0 or S02 group;
R1 represents an alkyl group of from 1 to 6 carbon atoms, an alkenyl group of from 2 to 6 carbon atoms or an aryl group of from 6 to 10 carbon atoms, each optionally substituted by one or more fluorine, chlorine or bromine , , ~ .: . , ~ :
atoms or represents an alkynyl group of from 3 to 4 carbon atoms, an alkoxyalkyl group in which each alkyl group contains from 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 7 carbon atoms in the ring, an aralkyl group of from 7 to 9 carbon atoms optionally ring-substituted by one or two fluorine, chlorine or bromine atoms or by an alkyl group of from 1 to 4 carbon atoms, a group of the formula:
' " 4 ' " 4 ~
-CHCR or -CHCNR RJ, or, when X represents the group NR3- then R1 can represent the group -CR6, -S02R6, or, when X represents the group S02 then R1 can also represent the group -NR4R5, -NR4-CR6, or -NR4So2R6; R2 represents an alkyl group of from 1 to 6 carbon atoms, a fluorine, chlorine or bromine atom, an alkoxy or alkylthio group, in which the alkyl portion contains from 1 to 6 carbon atoms;
with the proviso that when Y represents a N02 group, and X represents an 0-moiety, then R1 does not represent a methyl group; R3, R4 and R5 each independently represents a hydrogen atom or an alkyl or cycloalkyl group of up to 6 carbon atoms and R5 can also represent an alkoxy group of up to 6 carbon atoms; when X represents the group -NR3-then R1 and R3 together can form a part of a heterocyclic ring, such as -CH2-(CH2)mCH2-, -CH3(CH ) CH3 ' or -CH2CH20CH2CH2-; when R1 represents the group -NR4R5 then R4 and R5 together can form a part o~ a heterocyclic :
~ ~087~86 ring as is shown above lor It1 arld I~S w~len taken together;
R6 represents an alkyl group of Irom 1 to 6 car-bon atoms or an aryl or aralkyl group Or from 6 to lO carbon atoms optionally substituted by one or more fluorine, chlorine or bromine atoms; m is 2 or 3; n is l or 2; and p is 0 or l.
The compounds shown in formula I above are derivatives of substituted cyclopropane or substituted cyclobutane carboxylic acids, such that n in the formula I is l or 2. Examples where R2 in the formula represents an alkyl group include methyl, ethyl, propyl and n-butyl; R2 can also represent a methoxy- or methyl-thio group or their lower alkyl homologues.
As a general rule, the compounds preferred because of their herbicidal properties are those compounds of formula I, wherein n is l and R2 represents a methyl group. The compounds wherein R2 represents a chlorine atom are also very active. Compounds wherein R2 represents a methoxy group are also desirable.
The group Y can represent a chlorine, bromine or fluorine atom, a cyano, nitro, unsubstituted amino, methyl-amino, carboxy, methoxycarbonyl, aminocarbonyl, methyl-aminocarbonyl, formyl, hydrox,~minomethyl, trifluoromethyl, trifluoromethoxy, methyl, ethyl, methylsulphonyl or tri-fluoromethylsulphonyl group.
Preferred because of their herbicidal properties are compounds of formula I, wherein Y represents a tri-fluoromethyl group. Compounds wherein Y represents a :
10~37186 chlorine atom or a methyl or nitro group, are also very active.
R can represent a straight- or, preferably, branched-chPin alkyl group, such as methyl, ethyl, iso-propyl, isobutyl, secondary butyl, tertiary butyl, iso-amyl, 2-chlorethyl, trifluoromethyl, allyl, phenyl, p-chlorophenyl, naphthyl or propargyl group. Where R
represents a cycloalkyl group it can be alkylated or linked to X by an alkylene group, for example, a cyclo-propyl, cyclohexyl, methylcyclopropyl or cyclopropyl-methyl group. Additionally, Rl can represent such groups as methoxyethyl, benzyl, phenethyl, p-chlorobenzyl or o-methylbenzyl, or, when X represents the group -NR3 then Rl can also represent an acetyl, propionyl, caproyl, benzoyl, methylsulphonyl, trifluoroacetyl or dimethylamino group or, when X represents the group S02 then Rl can also represent an unsubstituted amino, monomethylamino, di-methylamino, acetamido or methylsulphonylamino group.
Compounds wherein R represents an alkyl group of 1 to 4 carbon atoms or a cycloalkyl group are generally preferred. Especially active are those compounds wherein Rl represents a branched-chain alkyl, such as an iso-propyl- or tert.-butyl group. Ethyl, methyl and cyclopropyl-methyl derivatives and ring alkylated forms appear also to be highly active. Variations in activity, of course, depend on the individual combinations of R , R , R3, X
and Y.
` 1~87~t36 R3, R4 and R5 each represents independently a ~;
hydrogen atom, an alkyl group, such as a methyl or ethyl group or a cycloalkyl group, such as a methylcyclopropyl group, or R5 can also represent an alkoxy group, such as a methoxy or ethoxy group. Although, when X represents the group -NR3, then R3 represents preferably an iso-propyl-, n-propy~ or tert.-butyl group.
R6 can represent an alkyl group, such as a methyl, ethyl, isopropyl, isobutyl, secondary-butyl, tertiary-butyl, isoamyl or hexyl group or an aryl or aralkyl group,such as a phenyl, p-chlorophenyl, 2-bromophenyl, naphthyl, phenethyl or benzyl group.
Species contemplated within the scope of the present invention include those compounds with reference to formula I, wherein R1, X, Y and R2 have the following meanings:
i-C3H7, 0, CF3, n-C4H9 - isoamyl, 0, N02, n-C4Hg -CH3C0, 0, N02, C2H5 - t.butyl, NH, CF3, OCH3 - sulphamoyl, (R1 ~ X~, Et, SCH3 - i-C3H7, 0, Me, F and i-C4Hg~ S02, CF3, F.
Species contemplated wherein X represents the 0 moiety and Y the trifluoromethyl group are those wherein R1 and R2 have the following meanings:
isobutyl, methyl - isoamyl, propyl - 2-fluorobenzyl, methyl -
2-chlorobenzyl, n-butyl - 4-chlorobenzyl, methyl - 2,6-dichlorobenzyl, ethyl - propargyl, methyl and sec.-butyl, propyl.
Preferred because of their herbicidal properties are those compounds according to formula I, wherein X
. ' ' 108~ 36 represents the 0 moiety, R2 represents a methyl group and R represents an alkyl group of f`rom 1 to 4 carbon atoms, a cyclopropylmethyl or a 1-methylcyclopropyl group. The alkyl group is preferably a sec.-butyl or isopropyl group.
Haloalkyl groups, such as 2-chloroethyl groups, are also desirable.
Species contemplated wherein X represents the S, S0 or S02 moiety and Y the trifluoromethyl group are those wherein R1, X and R2 have the following meanings:
CH30C2H4, S, methyl - allyl, S, pentyl - isoamyl, S0, ethyl -i-C4Hg, S02, n-C4H9 - cyclopropyl, S0, methyl - 2-fluorobenzyl, S02, n-C3H7 - 2-chlorobenzyl, S, methyl - sec.-C4Hg, S02, methyl - 4-chlorobenzyl, S0, n-C4H9 - 2,6-dichlorobenzyl, S02, methyl - propargyl, S, ethyl and sec.-C4Hg, S02, n-C3H7.
Preferred because of their herbicidal properties are those compounds wherein X represents the S, S0 or S02 moiety, R2 represents a methyl group and R1 represents an alkyl group of 1 to 4 carbon atoms, such as a methyl, isopropyl or isobutyl group. Especially useful compounds appear to be those wherein R1 represents an isopropyl or an ethyl group.
Species contemplated wherein X represents the group NR3 and Y the trifluoromethyl group are those wherein R1, R3 and R2 have the following meanings:
t.-butyl, H, methyl - phenyl, H, methoxy - propargyl, H, methylthio - benzyl, H, F - methoxy, methyl, methyl -methylsulphonyl, H, methyl - trifluoromethylsulphonyl, H, methyl - acetyl, H, methyl and trifluoroacetyl, H, methyl.
108~186 _~
A preferred subclass because of their herbicidal properties are those compounds of formula I, wherein X
represents the group NR3, wherein R3 represents a hydrogen atom or an alkyl group of from 1 to 4 carbon atoms, such as a methyl, ethyl or propyl group, and R represents an alkyl group of from 1 to 4 carbon atoms, especially an isopropyl, t.-butyl or n-propyl group.
Species contemplated wherein R1 represents a group -NR4R5, -NR4so2R6 or -NR4C(o~R6, X represents the S02 moiety and Y a trifluoromethyl group are those wherein 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 - acetyl, H, methyl - trifluoro- -acetyl, H, methyl - (H, methyl), methyl and (H, trifluoro-methyl), methyl.
Similarly, compounds of the above subclasses, wherei n Y represents a halogen atom, especially a bromine or chlorine atom, or a methyl group in place of a trifluoromethyl group are also highly useful subclasses of herbicides.
Compounds according to formula I, wherein Y
represents a nitro group are a useful subclass due to their relatively easy and low cost of preparation as well as to their herbicidal properties.
Species contemplated wherein Y represents a nitro group are those wherein R1X and R2 have the fol-lowing meanings:
:, ~
, 1~87186 propyloxyethylsulphonyl, ethyl - isobutylthio, n-C4H9 -ethylsulphinyl, propyl - allyloxy, ethyl and 2,6-dichloro-benzylsulphonyl, propyl.
Preferred because of their herbicidal properties are those compounds wherein Y represents a nitro group and R represents an alkyl group of 2 to 4 carbon atoms.
Especially useful compounds appear to be those wherein R represents an isopropyl group and X represents an 0, S, S0 or S02 moiety as these compounds show useful crop selectivities. The compounds wherein-X represents a NR3 group are also highly active.
Species contemplated wherein Y represents an alkyl group are those wherein R1X, 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 - ethylsulphonyl, methyl, methyl - methylthio, methyl, methyl - methylsulphonyl, methyl, methyl - isopropylthio, methyl, methyl - isopropylsulphonyl, methyl, methyl - methyl-thio, isopropyl, methyl - isopropylamino, methyl, methyl -t.-butylamino, methyl, methyl - (1-methylcyclopropyl)amino, methyl, methyl - sulphamoy~,methyl, methyl - methoxy, sec.-butyl, methyl - (N-methoxy-N-methyl)amino, methyl, methyl -N-(methylsulphonyl)amino, methyl~ methyl - N-(trifluoro-methylsulphonyl)amino, methyl, methyl - acetamido, methyl, methyl and trifluoroacetamido, methyl, methyl.
--` 10871 !36 Species contemplated wherein Y represents a bromine atom are those wherein R1X and R2 have the following meanings:
ethoxy, methyl - methoxy, methyl - 2-methylpropoxy, methyl -1-cyclopropylethoxy, methyl - ethylthio, methyl - methyl-thio, methyl - isopropylthio, methyl - ethylsulphonyl, methyl - dimethylamino, methyl - diethylamino, methyl -isopropylamino, methyl and t.-butylamino, methyl. ` :
The corresponding chloro derivatives are also contemplated:
sulphamoyl, methyl - dimethylsulphamoyl, methyl - t.butyl- .
sulphamoyl, methyl - N-(acetyl)sulphamoyl, methyl -N-(methylsulphonyl)sulphamoyl, methyl - (N-methoxy-N-methyl)amino, methyl - N-(methylsulphonyl)amino, methyl -N-(tri~luoromethylsulphonyl)amino, methyl - acetamide, methyl and trifluoroacetamido, methyl, as are the following fluoro derivatives:
isopropoxy, methyl - isopropylamino, methyl - ethylthio, methyl - isobutylsulphonyl, methyl and sec.-butoxy, methyl.
Of course,the corresponding bromo derivatives can ~so be used.
The cycloalkane carboxanilides according to formula I can be prepared according to the ~ollowing æquenceo~ reactions:
` r~ 36 Rl-XNa + Cl ~ N02 ~ R -X ~ No2 (la) Y Y
R -X- ~ N02 redUctio~ Rl X ~ ~H2 (2a) 10Rl-X- ~ NH2 + C18 ~ (CH2)n ~ Rl-X ~ l ~ 2)n (3a) The appropriate sodium alkoxide or mercaptide compound (or the appropriate amine) is allowed to react with a 3- substituted - 4 - chloronitrobenzene in step (la) to give a 3, 4 - disubstituted nitrobenzene, which is reduced in step (2a) to give the corresponding aniline. In step (3a) the aniline and a cycloalkane carboxylic chloride are allowed to react to give the desired cycloalkanecarboxanilide according to formula I.
Reaction (la) is readily conducted by mixing the reactants in a solvent such an an alcohol, dimethyl sulphoxide or dimethylformamide at room temperature or at a moderately elevated temperature, for example up to 150 C.
10~7186 -~2-The reduction ol` the 3,~l-disubstituted nitro-benzenes, step (2a) is readily carried out in boiling water containing iron filings and up to 5% of acetic or hydro-chloric acid. However, any of numerous reduction techniques ;
that reduce an aromatic nitro group to the corresponding amino group are applicable here (see, for instance, R. Schr8ter and F. M811er in 1'Methoden der Organischen Chemie", (Houben-Weyl), Vol. 11, 1, part IV, pages 341-731, Georg Thieme Verlag, Stuttgart (1957)).
The corresponding 4'-hydrocarbylsulphinyl- or sulphonyl derivatives are prepared by treating the appropriate 4'-hydrocarbylthio derivative with 85% meta-chloroperoxybenzoic acid.
The acylation reaction ~a) is conducted by treating the 3,4-disubstituted aniline with a cycloalkanecarboxylic acid chloride in a suitable solvent, such as ether, tetra-hydrofuran, benzene, toluene or hexane in the presence of one molar equivalent of an organic or inorganic base that can serve as acceptor for the hydrogen chloride formed in the reaction. Organic bases, such as tertiary amines (pyridine, triethylamine, collidine, N,N-dimethylaniline, diethylisopropylamine) or inorganic bases (Na2C03, NaHC03, K2C03, CaC03) may be used to trap the hydrogen chloride formed during the acylation reaction.
The cycloalkanecarboxylic acid chlorides used in the reaction or simple esters from which they can be generated are generally known in the art (e.g., U.S.
patents 3,277,171, 3S211,544 and South African patent 1~7186 application 64~1283). The l-fluorocycloalkanecarboxylic acid chlorides can be readily prepared by treating l-chlorocycloalkanecarboxylic acid ethyl ester with potassium fluoride at elevated temperatures option~lly in the presence of solvents and /or phase transfer catalysts and converting the ester to acid chloride in a known manner. The l-bromocycloalkanecarboxylic acid chlorides can be prepared by bromination of cycloalkane-carboxylic acid chlorides under refluxing conditions in a nitrogen atmosphere.
~he l-ethoxycyclobutanecarboxylic acid chloride used in the preparation of the above anilides can be prepared by alkali treatment of ethyl l-bromocyclobutane carboxylate, a known compound, to liberate a mixture of l-bromocyclobutanecarboxylic acid and l-ethoxycyclobutane-carboxylic acid and conversion to the corresponding acid chlorides in a known manner, e.g., by treatment with thionyl chloride.
~he compounds according to the present invention, for example, 4'-(isopropylamino)-3`-(trifluoromethyl)-l-methylcyclopropanecarboxanilide, 4 -(isopropoxy)-3~-(trifluoromethyl)-l-methylcyclopropanecarboxanilide and 4 -(isopropylthio)-3'-(trifluoromethyl)-l-methylcyclo-propanecarboxanilide have been found to be useful for controlling undesirable plant growth. ~hat is, certain members of the class have been found to be herbicidally effective against a wide range of plant species. Others of the class are effective only against a limited .
10871~6 number of plant species and are considered to be selective herbicides. Some of the compounds exhibit a high degree ~ - --of herbicidal activity in the control of a variety of economically important species of grasses and broad-leaved weeds. Some of the compounds are particularly useful as selective herbicides for use in certain im-portant crops.
The invention therefore also includes plant growth regulating compositions comprising a carrier or a surface-active agent, or both a carrier and a surface-active agent, and, as active ingredient, at least one cycloalkane carboxanilide derivative according to formula I. Likewise the invention also includes a method of controlling plant growth which comprises applying to the locus an effective amount of a cycloalkane carboxanilide according to formula I.
The term "carrier" as used herein means a solid or fluid material, which may be inorganic or organic and of synthetic or natural origin, with which the active compound is mixed or formulated to facilitate its application to the plant, seed, soil or other object to be treated, or its storage, transport or handling.
Suitable solid carriers are natural and syn-thetic clays and silicates, for example, natural silicas, such as diatomaceous earths; magnesium silicates, for example, talcs; magnesium aluminium silicates, for example, attapulgites and vermiculites; aluminium silicates, for example, kaolinites, montmorillinites 10~37186 and micas; calcium carbonates, calcium sulphate;
synthetic hydrated silicon oxides and synthetic calcium or aluminium silicates, elements, such as carbon and sulphurj natural and synthetic resins, for example, coumarone resins, polyvinyl chloride and styrene polymers and copolymers, solid polychlorophenols;
bitumen, waxes, such as beeswax, paraffin wax, and chlorinated mineral waxes; and solid fertilizers, for example superphosphates.
Examples of suitable fluid carriers are water, alcohols, for example, isopropanol, glycols; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers; aromatic hydrocarbons, such as benzene, toluene and xylene, petroleum fractions, for example, kerosene, light mineral oils; chlorinated hydrocarbons, such as carbon tetrachloride; perchloro-ethylene, trichloroethane, including liquefied normally vaporous gaseous compounds. Mixtures of different liquids are often suitable.
~he surface-active agent may be an emulsifying agent or a dispersing agent or a wetting agent; it may be non-ionic or ionic. Any of the surface-active agents usually applied in formulating herbicides or insecticides may be used. Examples of suitable surface-active agents are the sodium or calcium salts of polyacrylic acids and lignin sulphonic acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide - ,. : , .
.
1()87186 and/or propylene oxide; fatty acid esters of glycerol, - -sorbitan, sucrose or pentaerythritol; condensates of these with ethylene oxide and/or propylene oxide;
condensation products of fatty alcohols or alkyl phenols, for example, p-octylphenol or p-octylcresol, with ethylene oxide and/or propylene oxide; sulphates or sulphonates of these condensation products, alkali or alkaline earth metal salts, preferably sodium salts ~ , of sulphuric or sulphonic acid esters containing at least 10 carbon atoms in the molecule, for example, sodium lauryl sulphate, sodium secondary alkyl sulphates, sodium salts of sulphonated castor oil, and sodium alkyl~
aryl sulphonates, such as sodium dodecylbenzene sulphonate;
and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.
The compositions of the invention may be formulated ~: :
as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Wettable powders are usually compounded to ~.
contain 25, 50 or 75% by weight of toxicant and usually contain in addition to solid carrier, 3-10% by weight of a dispersing agent, 1-5~ by weight of a surface-active agent and where necessary, 0-10% by weight of stabilizer(s) and/or other additives, such as penetrants or stickers.
Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant or surface-active agent, and are diluted in the field with further solid carrier to give .
~ 7186 1 ~/
a composition usually containing 0.5-10% by weight of toxicant. Granules are usually prepared to have a size between 10 and 100 BS mesh (1.676 - 0.152 mm), and may be manufactured by agglomeration or impregnation techniques.
Generally,granules will contain 0.5-25% by weight of toxicant and 0-10% by weight of additives, such as stabilizers, slow-release modifiers and binding agents.
Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, co-solvent, 10-50%
by weight per volume of toxicant, 2-20% by weight per volume of emulsifiers and 0-20% by weight per volume of appropriate additives, such as stabilizers, penetrants and corrosion inhibitors. Suspension concentrates are compounded so as to obtain a stable, non-sedimenting, flowable product and usually contain 10-75% by weight of toxicant, 0.5-5% by weight of dispersing agents, 1-5% by weight of surface-active agent, 0.1-10% by weight of suspending agents, such as protective colloids and thixotropic agents, 0-10% by weight of appropriate additives, such as de-foamers, corrosion inhibitors, stabilizers, penetrantsand stickers, and as carrier, water or an organic liquid in which the toxicant is substantially insoluble; certain organic solids or inorganic salts may be dissolved in the carrier to assist in preventing sedimentation or as anti-freeze agents for water.
Aqueous dispersions and emulsions, for example, compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also .:
.
1()~7186 lie within the scope of the present invention. The said emulsions may be of the water-in-oil or Or the oil-in-water type, and may have a thick mayonnaise-like consistency.
The compositions of the invention may also contain other ingredients, for example,other compounds possessing pesticidal, especially insecticidal, acaricidal, herbicidal or fungicidal properties.
The method of applying the compounds according to the present invention comprises applying a compound according to formula I, ordinarily in a composition of one of the afore-mentioned types, to a locus or area to be protected from un-desirable plant growth. The active compound, of course, is applied in amounts sufficient to exert the desired action. ~-The amount of compound to be used in controlling un-desirable vegetation will naturally depend on the condition of the vegetation, the degree of activity desired, the form-ulation used, the mode of application, the climate, the season of the year, and other variables. Recommendations as to precise amounts are, therefore, not possible. In general, however, application to the locus to be protected of from 0.1 to 10.0 pounds per acre of the compound used in this invention will be satisfactory.
EXAMPLES
The manner in which the compounds according to the present invention can be prepared is illustrated in the fol-lowing examples, which demonstrate the preparation of typical species of the invention. In these examples, the identities of all compounds, intermediates and final, were confirmed by elemental analysis, and infrared and nuclear magnetic spectral analyses. The examples are for the purpose of illustration only and should not be regarded as limiting the invention in any way.
1~8~186 -1'3-Example 1 4'-Isopropoxy-3'-(trifluor~methyl)-1-methyl-cyclopropanecarboxanilide a) Preparation of 3-(tr~fluoromethyl) -4-isopropoxy-nitrobenzen~
To a chilled (5C) solution of 118g (0.5 mole) of
Preferred because of their herbicidal properties are those compounds according to formula I, wherein X
. ' ' 108~ 36 represents the 0 moiety, R2 represents a methyl group and R represents an alkyl group of f`rom 1 to 4 carbon atoms, a cyclopropylmethyl or a 1-methylcyclopropyl group. The alkyl group is preferably a sec.-butyl or isopropyl group.
Haloalkyl groups, such as 2-chloroethyl groups, are also desirable.
Species contemplated wherein X represents the S, S0 or S02 moiety and Y the trifluoromethyl group are those wherein R1, X and R2 have the following meanings:
CH30C2H4, S, methyl - allyl, S, pentyl - isoamyl, S0, ethyl -i-C4Hg, S02, n-C4H9 - cyclopropyl, S0, methyl - 2-fluorobenzyl, S02, n-C3H7 - 2-chlorobenzyl, S, methyl - sec.-C4Hg, S02, methyl - 4-chlorobenzyl, S0, n-C4H9 - 2,6-dichlorobenzyl, S02, methyl - propargyl, S, ethyl and sec.-C4Hg, S02, n-C3H7.
Preferred because of their herbicidal properties are those compounds wherein X represents the S, S0 or S02 moiety, R2 represents a methyl group and R1 represents an alkyl group of 1 to 4 carbon atoms, such as a methyl, isopropyl or isobutyl group. Especially useful compounds appear to be those wherein R1 represents an isopropyl or an ethyl group.
Species contemplated wherein X represents the group NR3 and Y the trifluoromethyl group are those wherein R1, R3 and R2 have the following meanings:
t.-butyl, H, methyl - phenyl, H, methoxy - propargyl, H, methylthio - benzyl, H, F - methoxy, methyl, methyl -methylsulphonyl, H, methyl - trifluoromethylsulphonyl, H, methyl - acetyl, H, methyl and trifluoroacetyl, H, methyl.
108~186 _~
A preferred subclass because of their herbicidal properties are those compounds of formula I, wherein X
represents the group NR3, wherein R3 represents a hydrogen atom or an alkyl group of from 1 to 4 carbon atoms, such as a methyl, ethyl or propyl group, and R represents an alkyl group of from 1 to 4 carbon atoms, especially an isopropyl, t.-butyl or n-propyl group.
Species contemplated wherein R1 represents a group -NR4R5, -NR4so2R6 or -NR4C(o~R6, X represents the S02 moiety and Y a trifluoromethyl group are those wherein 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 - acetyl, H, methyl - trifluoro- -acetyl, H, methyl - (H, methyl), methyl and (H, trifluoro-methyl), methyl.
Similarly, compounds of the above subclasses, wherei n Y represents a halogen atom, especially a bromine or chlorine atom, or a methyl group in place of a trifluoromethyl group are also highly useful subclasses of herbicides.
Compounds according to formula I, wherein Y
represents a nitro group are a useful subclass due to their relatively easy and low cost of preparation as well as to their herbicidal properties.
Species contemplated wherein Y represents a nitro group are those wherein R1X and R2 have the fol-lowing meanings:
:, ~
, 1~87186 propyloxyethylsulphonyl, ethyl - isobutylthio, n-C4H9 -ethylsulphinyl, propyl - allyloxy, ethyl and 2,6-dichloro-benzylsulphonyl, propyl.
Preferred because of their herbicidal properties are those compounds wherein Y represents a nitro group and R represents an alkyl group of 2 to 4 carbon atoms.
Especially useful compounds appear to be those wherein R represents an isopropyl group and X represents an 0, S, S0 or S02 moiety as these compounds show useful crop selectivities. The compounds wherein-X represents a NR3 group are also highly active.
Species contemplated wherein Y represents an alkyl group are those wherein R1X, 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 - ethylsulphonyl, methyl, methyl - methylthio, methyl, methyl - methylsulphonyl, methyl, methyl - isopropylthio, methyl, methyl - isopropylsulphonyl, methyl, methyl - methyl-thio, isopropyl, methyl - isopropylamino, methyl, methyl -t.-butylamino, methyl, methyl - (1-methylcyclopropyl)amino, methyl, methyl - sulphamoy~,methyl, methyl - methoxy, sec.-butyl, methyl - (N-methoxy-N-methyl)amino, methyl, methyl -N-(methylsulphonyl)amino, methyl~ methyl - N-(trifluoro-methylsulphonyl)amino, methyl, methyl - acetamido, methyl, methyl and trifluoroacetamido, methyl, methyl.
--` 10871 !36 Species contemplated wherein Y represents a bromine atom are those wherein R1X and R2 have the following meanings:
ethoxy, methyl - methoxy, methyl - 2-methylpropoxy, methyl -1-cyclopropylethoxy, methyl - ethylthio, methyl - methyl-thio, methyl - isopropylthio, methyl - ethylsulphonyl, methyl - dimethylamino, methyl - diethylamino, methyl -isopropylamino, methyl and t.-butylamino, methyl. ` :
The corresponding chloro derivatives are also contemplated:
sulphamoyl, methyl - dimethylsulphamoyl, methyl - t.butyl- .
sulphamoyl, methyl - N-(acetyl)sulphamoyl, methyl -N-(methylsulphonyl)sulphamoyl, methyl - (N-methoxy-N-methyl)amino, methyl - N-(methylsulphonyl)amino, methyl -N-(tri~luoromethylsulphonyl)amino, methyl - acetamide, methyl and trifluoroacetamido, methyl, as are the following fluoro derivatives:
isopropoxy, methyl - isopropylamino, methyl - ethylthio, methyl - isobutylsulphonyl, methyl and sec.-butoxy, methyl.
Of course,the corresponding bromo derivatives can ~so be used.
The cycloalkane carboxanilides according to formula I can be prepared according to the ~ollowing æquenceo~ reactions:
` r~ 36 Rl-XNa + Cl ~ N02 ~ R -X ~ No2 (la) Y Y
R -X- ~ N02 redUctio~ Rl X ~ ~H2 (2a) 10Rl-X- ~ NH2 + C18 ~ (CH2)n ~ Rl-X ~ l ~ 2)n (3a) The appropriate sodium alkoxide or mercaptide compound (or the appropriate amine) is allowed to react with a 3- substituted - 4 - chloronitrobenzene in step (la) to give a 3, 4 - disubstituted nitrobenzene, which is reduced in step (2a) to give the corresponding aniline. In step (3a) the aniline and a cycloalkane carboxylic chloride are allowed to react to give the desired cycloalkanecarboxanilide according to formula I.
Reaction (la) is readily conducted by mixing the reactants in a solvent such an an alcohol, dimethyl sulphoxide or dimethylformamide at room temperature or at a moderately elevated temperature, for example up to 150 C.
10~7186 -~2-The reduction ol` the 3,~l-disubstituted nitro-benzenes, step (2a) is readily carried out in boiling water containing iron filings and up to 5% of acetic or hydro-chloric acid. However, any of numerous reduction techniques ;
that reduce an aromatic nitro group to the corresponding amino group are applicable here (see, for instance, R. Schr8ter and F. M811er in 1'Methoden der Organischen Chemie", (Houben-Weyl), Vol. 11, 1, part IV, pages 341-731, Georg Thieme Verlag, Stuttgart (1957)).
The corresponding 4'-hydrocarbylsulphinyl- or sulphonyl derivatives are prepared by treating the appropriate 4'-hydrocarbylthio derivative with 85% meta-chloroperoxybenzoic acid.
The acylation reaction ~a) is conducted by treating the 3,4-disubstituted aniline with a cycloalkanecarboxylic acid chloride in a suitable solvent, such as ether, tetra-hydrofuran, benzene, toluene or hexane in the presence of one molar equivalent of an organic or inorganic base that can serve as acceptor for the hydrogen chloride formed in the reaction. Organic bases, such as tertiary amines (pyridine, triethylamine, collidine, N,N-dimethylaniline, diethylisopropylamine) or inorganic bases (Na2C03, NaHC03, K2C03, CaC03) may be used to trap the hydrogen chloride formed during the acylation reaction.
The cycloalkanecarboxylic acid chlorides used in the reaction or simple esters from which they can be generated are generally known in the art (e.g., U.S.
patents 3,277,171, 3S211,544 and South African patent 1~7186 application 64~1283). The l-fluorocycloalkanecarboxylic acid chlorides can be readily prepared by treating l-chlorocycloalkanecarboxylic acid ethyl ester with potassium fluoride at elevated temperatures option~lly in the presence of solvents and /or phase transfer catalysts and converting the ester to acid chloride in a known manner. The l-bromocycloalkanecarboxylic acid chlorides can be prepared by bromination of cycloalkane-carboxylic acid chlorides under refluxing conditions in a nitrogen atmosphere.
~he l-ethoxycyclobutanecarboxylic acid chloride used in the preparation of the above anilides can be prepared by alkali treatment of ethyl l-bromocyclobutane carboxylate, a known compound, to liberate a mixture of l-bromocyclobutanecarboxylic acid and l-ethoxycyclobutane-carboxylic acid and conversion to the corresponding acid chlorides in a known manner, e.g., by treatment with thionyl chloride.
~he compounds according to the present invention, for example, 4'-(isopropylamino)-3`-(trifluoromethyl)-l-methylcyclopropanecarboxanilide, 4 -(isopropoxy)-3~-(trifluoromethyl)-l-methylcyclopropanecarboxanilide and 4 -(isopropylthio)-3'-(trifluoromethyl)-l-methylcyclo-propanecarboxanilide have been found to be useful for controlling undesirable plant growth. ~hat is, certain members of the class have been found to be herbicidally effective against a wide range of plant species. Others of the class are effective only against a limited .
10871~6 number of plant species and are considered to be selective herbicides. Some of the compounds exhibit a high degree ~ - --of herbicidal activity in the control of a variety of economically important species of grasses and broad-leaved weeds. Some of the compounds are particularly useful as selective herbicides for use in certain im-portant crops.
The invention therefore also includes plant growth regulating compositions comprising a carrier or a surface-active agent, or both a carrier and a surface-active agent, and, as active ingredient, at least one cycloalkane carboxanilide derivative according to formula I. Likewise the invention also includes a method of controlling plant growth which comprises applying to the locus an effective amount of a cycloalkane carboxanilide according to formula I.
The term "carrier" as used herein means a solid or fluid material, which may be inorganic or organic and of synthetic or natural origin, with which the active compound is mixed or formulated to facilitate its application to the plant, seed, soil or other object to be treated, or its storage, transport or handling.
Suitable solid carriers are natural and syn-thetic clays and silicates, for example, natural silicas, such as diatomaceous earths; magnesium silicates, for example, talcs; magnesium aluminium silicates, for example, attapulgites and vermiculites; aluminium silicates, for example, kaolinites, montmorillinites 10~37186 and micas; calcium carbonates, calcium sulphate;
synthetic hydrated silicon oxides and synthetic calcium or aluminium silicates, elements, such as carbon and sulphurj natural and synthetic resins, for example, coumarone resins, polyvinyl chloride and styrene polymers and copolymers, solid polychlorophenols;
bitumen, waxes, such as beeswax, paraffin wax, and chlorinated mineral waxes; and solid fertilizers, for example superphosphates.
Examples of suitable fluid carriers are water, alcohols, for example, isopropanol, glycols; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers; aromatic hydrocarbons, such as benzene, toluene and xylene, petroleum fractions, for example, kerosene, light mineral oils; chlorinated hydrocarbons, such as carbon tetrachloride; perchloro-ethylene, trichloroethane, including liquefied normally vaporous gaseous compounds. Mixtures of different liquids are often suitable.
~he surface-active agent may be an emulsifying agent or a dispersing agent or a wetting agent; it may be non-ionic or ionic. Any of the surface-active agents usually applied in formulating herbicides or insecticides may be used. Examples of suitable surface-active agents are the sodium or calcium salts of polyacrylic acids and lignin sulphonic acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide - ,. : , .
.
1()87186 and/or propylene oxide; fatty acid esters of glycerol, - -sorbitan, sucrose or pentaerythritol; condensates of these with ethylene oxide and/or propylene oxide;
condensation products of fatty alcohols or alkyl phenols, for example, p-octylphenol or p-octylcresol, with ethylene oxide and/or propylene oxide; sulphates or sulphonates of these condensation products, alkali or alkaline earth metal salts, preferably sodium salts ~ , of sulphuric or sulphonic acid esters containing at least 10 carbon atoms in the molecule, for example, sodium lauryl sulphate, sodium secondary alkyl sulphates, sodium salts of sulphonated castor oil, and sodium alkyl~
aryl sulphonates, such as sodium dodecylbenzene sulphonate;
and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.
The compositions of the invention may be formulated ~: :
as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Wettable powders are usually compounded to ~.
contain 25, 50 or 75% by weight of toxicant and usually contain in addition to solid carrier, 3-10% by weight of a dispersing agent, 1-5~ by weight of a surface-active agent and where necessary, 0-10% by weight of stabilizer(s) and/or other additives, such as penetrants or stickers.
Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant or surface-active agent, and are diluted in the field with further solid carrier to give .
~ 7186 1 ~/
a composition usually containing 0.5-10% by weight of toxicant. Granules are usually prepared to have a size between 10 and 100 BS mesh (1.676 - 0.152 mm), and may be manufactured by agglomeration or impregnation techniques.
Generally,granules will contain 0.5-25% by weight of toxicant and 0-10% by weight of additives, such as stabilizers, slow-release modifiers and binding agents.
Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, co-solvent, 10-50%
by weight per volume of toxicant, 2-20% by weight per volume of emulsifiers and 0-20% by weight per volume of appropriate additives, such as stabilizers, penetrants and corrosion inhibitors. Suspension concentrates are compounded so as to obtain a stable, non-sedimenting, flowable product and usually contain 10-75% by weight of toxicant, 0.5-5% by weight of dispersing agents, 1-5% by weight of surface-active agent, 0.1-10% by weight of suspending agents, such as protective colloids and thixotropic agents, 0-10% by weight of appropriate additives, such as de-foamers, corrosion inhibitors, stabilizers, penetrantsand stickers, and as carrier, water or an organic liquid in which the toxicant is substantially insoluble; certain organic solids or inorganic salts may be dissolved in the carrier to assist in preventing sedimentation or as anti-freeze agents for water.
Aqueous dispersions and emulsions, for example, compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also .:
.
1()~7186 lie within the scope of the present invention. The said emulsions may be of the water-in-oil or Or the oil-in-water type, and may have a thick mayonnaise-like consistency.
The compositions of the invention may also contain other ingredients, for example,other compounds possessing pesticidal, especially insecticidal, acaricidal, herbicidal or fungicidal properties.
The method of applying the compounds according to the present invention comprises applying a compound according to formula I, ordinarily in a composition of one of the afore-mentioned types, to a locus or area to be protected from un-desirable plant growth. The active compound, of course, is applied in amounts sufficient to exert the desired action. ~-The amount of compound to be used in controlling un-desirable vegetation will naturally depend on the condition of the vegetation, the degree of activity desired, the form-ulation used, the mode of application, the climate, the season of the year, and other variables. Recommendations as to precise amounts are, therefore, not possible. In general, however, application to the locus to be protected of from 0.1 to 10.0 pounds per acre of the compound used in this invention will be satisfactory.
EXAMPLES
The manner in which the compounds according to the present invention can be prepared is illustrated in the fol-lowing examples, which demonstrate the preparation of typical species of the invention. In these examples, the identities of all compounds, intermediates and final, were confirmed by elemental analysis, and infrared and nuclear magnetic spectral analyses. The examples are for the purpose of illustration only and should not be regarded as limiting the invention in any way.
1~8~186 -1'3-Example 1 4'-Isopropoxy-3'-(trifluor~methyl)-1-methyl-cyclopropanecarboxanilide a) Preparation of 3-(tr~fluoromethyl) -4-isopropoxy-nitrobenzen~
To a chilled (5C) solution of 118g (0.5 mole) of
3-(trifluoromethyl)-4-chloronitrobenzene in 100 ml of dimethyl sulfoxidetDMSO) was added dropwise a solution containing 41g (0.5 mole) of sodium isopropoxide in 300 ml of dimethyl sulpn-oxide. The dark reaction mixture was stirred at ambienttemperature for one hour, poured into water and extracted with ether. The ether extracts were washed with water, dried and concentrated. Recrystallization of the residual liquid from hexane gave 115.5g (92.7~)of~ white cry~talline solid;
m.p. 34-36C (la).
~j Preparation of 3-(*rifluoromethyl)-4--isopropoxyaniline To a refluxing mixture containing 113.3g (0.455 mole) of (la) in 1200 ml of 5% aqueous acetic acid and 50 ml of methanol was added portionwise with stirring 137.5g of iron filings. Th.e reaction mixture was refluxed for one hour, filtered while hot, cooled and extracted with ether. The ether extracts were dried and concentrated to give 72.3g (72.6~) of product as an amber oil (lb).
c) Preparation of 4'-isopropoxy-3'-(trifluoro-methyl)-l-methylcyclo~opanecarboxanilide To a stirred solution containing lO.9g (0.05 mole) of (lb) and 5.0g (0.05 mole) of triethylamine in 100 ml of tetrahydrofuran was added dropwise 5.9g (0.05 mole) of l-methylcyclopropanecarboxylic acid chloride. This addition was . .
exothermic to 55C. The reaction mixture was stirred and refluxed for 30 minutes, and concentrated under reduced pressure. ~he resulting solid was washed with water, dried and recrystallized from ether to give 14.5g (97%) of a white crystalline solid; m.p. 106-109C. -~
Example 2
m.p. 34-36C (la).
~j Preparation of 3-(*rifluoromethyl)-4--isopropoxyaniline To a refluxing mixture containing 113.3g (0.455 mole) of (la) in 1200 ml of 5% aqueous acetic acid and 50 ml of methanol was added portionwise with stirring 137.5g of iron filings. Th.e reaction mixture was refluxed for one hour, filtered while hot, cooled and extracted with ether. The ether extracts were dried and concentrated to give 72.3g (72.6~) of product as an amber oil (lb).
c) Preparation of 4'-isopropoxy-3'-(trifluoro-methyl)-l-methylcyclo~opanecarboxanilide To a stirred solution containing lO.9g (0.05 mole) of (lb) and 5.0g (0.05 mole) of triethylamine in 100 ml of tetrahydrofuran was added dropwise 5.9g (0.05 mole) of l-methylcyclopropanecarboxylic acid chloride. This addition was . .
exothermic to 55C. The reaction mixture was stirred and refluxed for 30 minutes, and concentrated under reduced pressure. ~he resulting solid was washed with water, dried and recrystallized from ether to give 14.5g (97%) of a white crystalline solid; m.p. 106-109C. -~
Example 2
4'-(Benzyloxy)-3~-trifluoromethyl-l-meth propanec-arboxanilide a) Preparation of 3-(trifluoromethyl)-4--(benzyloxy)nitrobenzene To a solution containing 45.1g (0.2 mole) of 3-(trifluoromethyl)-4-chloronitrobenzene in 100 ml of DMSO was added dropwise at ambient temperature a solution containing 26g tO.2 mole) of sodium benzyloxide in 75 ml of benzyl alcohol causing the temperature to rise ~o 40`~.After 48 hours at ambient temperature, the reaction mixture was poured into ice water and extracted with ether, and the extract was dried and concentrated to about 200 ml. To the concentrated solution was added 200ml of hexane and the resulting solution was cooled. Filtration gave 51.5g (87%) of colourlesscrystalline solid; m.p. 112-114C (2a).
b) Preparation of 3-(trifluoromethy1)-4- --~benzylox~ aniline ~o a refluxing mixture containing 64.5g (0.217 mole) of ~2a) in 700 ml of 5% aqueous acetic acid and 30 ml of methanol was added portionwise within 15 minutes 65.5g of iron filings. The mixture was stirred and refluxed for an additional 30 minutes, filtered while hot, cooled and extracted with ether. ~he ether extract was washed with water, dried and concentrated to give 56.0g (97%) of product as a light-amber oil that crystallized on standins (2b)~
'.
--` 1087~86 -,'1 -c) Pre~aration of 4'-(benzyloxy)-3'-(trifluoro-methyl?-l-methylcyclopro~anecarboxanilide To a solution of 2.7g (O.Ol~mole) of (2b) and 2.7 g,(0.01 mole) of triethylamine in 50 ml of tetra-hydrofuran was added with stirring at ambient temperature 1.2g (0.01 mole) of l-methylcyclopropanecarboxylic acid chloride.
After one hour, the reaction mixture was poured into ice water and extracted with 200 ml of ether. The ether extract was dried and concentrated. Recrystallization of the residual solid from ether gave 3.6 g of product, m.p. 120-122C.
Example 3 4'-(Cyclopropylmethoxy)-3'-(trifluoromethyl)--l-methylcyclopropanecarboxanilide a) Preparation of 3-(trifluoromethy1)-4--(cyclopropylmethoxy)nitrobenzene To a cooled (10C) solution containing 22.5g (0.1 mole) of 3-(trifluoromethyl)-4-chloronitrobenzene in 100 ml of DMSO
was added with stirring at ambient temperature a solution containing 0.11 mole of sodium cyclopropylmethoxide (prepared by dissolving 4.9g of 57~ sodium hydride in 7.9g of cyclo-propylmethanol and 50 ml of tetrahydrofuran) in 100 ml of DMSO.
The reaction mixture was heated at 50C for one hour, poured into ice water and filtered. Recrystallization of the filtrate from hexane gave ll.Og (42~) of product as a white crystalline solid, m.p. 41-44C (3a).
~) Preparation of 3-(trifluoromethyl)-4-(cyclo-propylmethoxy)aniline To a stirring and refluxing mixture containing ; ll.Og (0.042 mole) of (3a) in 150 ml of 5% aqueous acetic acid was added 28g of iron filings and 10 ml of methanol. The .
`" 10~3~186 mixture was refluxed and stirred vieorously for one hour, then extracted with ether after cooling. The ether extract was ~ :
washed with aqueous sodium bicarbonate, dried, and concentrated to give 9.5g (98%) of product as an amber oil (3b).
c) Preparation of 4!i-(cyclopropylmethoxy)-3'--(trifluoromethyl)-l-methylcyclopropane-carboxanilide To a solution of 4.6 g (0.02 mole) of (3b) and 2.0g (0.02 mole) of triethylamine in 30 ml of tetrahydrofuran was added 2.4g (0.02 mole) of l-methylcyclopropanecarboxylic acid chloride. The mixture was refluxed for one hour, poured into ice water, and extracted with ether. The extract was dried and concentrated, and the residue was recrystalli~ed from hexane to give 5.0g (79%) of white crystalline solid;m.p. 84-85 C.
Example 4 4'-(Methylthio)-3'-(trifluoromethyl)-1--methylcyclopropanecarboxanilide a) Preparation of 3-(trifluoromethyl)-4-(methyl-thio)-nitrobenzene To a stirred solution containing 45.1g (0.20 mole) of 3-(trifluoromethyl)-4-chloronitrobenzene and 15 g (0.30 mole) of methyl mercaptan in 150 ml of DMS0 was added dropwise at ambient a solution containing ô.Og (0.20 mole) of sodium hydroxide in 20 ml of water. This addition was exothermic to 60C. After one hour, the reaction mixture was poured into ice water. The product was filtered and dried to give 45.0g (95%) of yellow solid; m.p. 50C (4a).
b) Preparation of 3-(trifluoromethyl -(methylthio) aniline To a mixture containing 45.0g (0.19 mole) of (4a) in refluxing 5% aqueous acetic acid was added 61g .
1~87186 of iron powder. The reaction mixture was reflu~:ed for 3 hoursand filtered through Celite (filter aid) t~Jhile hot. The cooled filtrate was extracted with ether. The ether extract was washed with 10~ aqueous sodium bicarbonate, and then with water, dried over anhydrous MgSO~, and concentrated under reduced pressure to give 31.8g (81~) of product as a light yellow oil (4b).
c) Preparation of 4'-(methylthio)-3'-(trifluoro-methyl)-l-methylcyclopropanecarboxanilide To a stirred solution containing 31.8g ~0.154 mole) of (4~) and 15.6g (0.154 mole) of triethylamine in 200 ml of tetrahydrofuran was added dropwise over 10 minutes 18.2g (0.154 mole) of l-methylcyclopropanecarboxylic acid chloride. This addition was exothermic to 65C. The mixture was stirred and refluxed for one hour, poured into ice water and filtered.
The filter cake was washed with water and dried to give 43.5g (98~) of product as a yellow solid; m.p. 97-98C.
Example 5 4'-(Methylsu~hiny1)-3'-(trifluoro~ethyl)~
-methylcyclopropanecarboxanilide To a chilled (5C) solution containing 14.5g (0.05 mole) of 4'-(methylthio)-3'-(trifluoromethyl)-1-methylcyclopropane-carboxanilide (prepared in Example 4 above) in 150 ml of chloroform was added dropwise over 20 minutes with stirring a solution of 10.2g (0.05 mole) of 85% meta-chloroperoxy-benzoic acid in 150 ml of chloroform. The reaction solution was allowed to equilibrate gradually to 25C, and after 16 hours, washed well with lO~ sodium carbonate and ~ 1087186 - -2~!-water, dried, and concentrated. The residual solid was crystallized from methanol to give 13.0g (86%) of product as a light-cream colored solid; m.p. 181-184 C.
ExampIe 6 4'-(Methylsu~nyl)-3'-trifluoromethyl-1-methyl-cyclopropanecarboxanilide To a stirred solution containing 7.0g (0.024 mole) of 4'-(methylthio)-3'-(trifluoromethyl)-1-methylcyclopropane-carboxanilide (prepared in Example 4 above) in 200 ml of chloroform was added dropwise over a period of 10 minutes at ambient temperature 10.2g (0.05 mole) of 85% meta--chloroperoxybenzoic acid. The reaction was exothermic to 50C. The reaction mixture was stirred for 16 hours, washed with 10%-a~ueous sodium carbonate and then with water. The - chloroform layer was dried and concentrated to dryness. The - residue was crystallized from methanol to give 7.5g (97~) of product as a light-cream solid; m.p. 135-138C.
Example 7 -4'- lorophenoxy)-3'-(trifluoromethyl)-1-methyl-cyclopropanecarboxanilide a) Preparation of 4-(4-chlorophenoxy?-3-ttrifluoromethyl~nltrobenzene To a solution containing 64.2g (0.5 mole) of 4-chlorophenol and 112.7g tO.5 mole) of 2-chloro-5-nitro-benzotrifluoride in 400 ml of DMSO was added dropwise with stirring at 30-35C a solution containing 20g (0.5 mole) of sodium hydroxide in 20 ml of water. After ~- -1.5 hours, the reaction mixture was poured into cold water : ,.... . ~
.
--- 1087186 ~:
and extracted with 800 ml of ether. The ether solution was dried and concentrated under reduced pressure to give 158 g (99~) of product that crystallized on standing; melting point, 46-48C tfrom hexane) (7a).
b) Preparation of 4-(4-chlorophenoxy)-3-(trifluoromethyl)aniline To a refluxing mixture containing 156 g (0.492 mole) -~-~
of the nitro compound (7a) in 1180 ml of 5~ aqueous acetic acid was added portionwise 140g of powdered iron. After 2 hours, the reaction mixture was filtered through filter aid and the residue was washed with methanol. The combined filtrates were extracted with 7 X 300 ml of ether. The combined ether extracts were washed with aqueous sodium bic3rbonate, dried and concentrated to give 141.5g of product; melting point, 43-45C (from hexane) (7b) c) Preparation of 4'-(4-chlorophenoxy)-3'-(trifluorometh~l)-1-methylcyclopropane-.
carboxanilide To a stirred solution of 5.75g (0.02 mole) --of the aminQ ~7b) in 40 ml of tetrahydrofuran was added dropwise 2.4g (0.02 mole) of l-methylcyclopropylcarboxy]ic acid chloride. The mixture was stirred and heated at 60C for 0.5 hour, poured into ice water and filtered. The filter cake was recrystallized from ether-hexane (1:3) to give 6.5g (88~) of product, m.p. 115-117C.
. : , .
~ 1~87186 Example 8 4'-(4-Chlorophenoxy)-3'-(trifluoromethyl) -l-butylcyclopropanecarboxanilide To a solution containing 2.9g (0.01 mole) of the amine prepared according to Example 7b),an~1.0g(0.01 mole) of triethylamine in 50 ml of tetrahydrofuran was added dropwise 1.7g (0.01 mole) of l-butylcyclopropanecarboxylic acid chloride.
The mixture was stirred and heated at 60C for 0.5 hour, poured into ice water and extracted with ether. The ether extract was dried and concentrated under reduced pressure.
The residual yellow syrup was crystallized from hexane to give 3.3g (80~) of product as a tan solid, m.p. 104-106C.
Example 9 4'-(Isopropylthio)-3'-ltrifluoromethy~
-l-methylcyclopropanecarboxanilide a) Preparation of 4-(Isopropylthio)-3-(trifluoromethyl)nitrobenzene To a solution containing 112.8g tO.5 mole) of 2-chloro-5-nitrobenzotrifluoride and 46g (0.6 mole) of isopropyl mercaptan in 400 ml of DMS0 was added dropwise over 0.5 hour 40g of 50% aqueous sodium hydroxide.
This addition was exothermic to 50C. After 24 hours, the reaction mixture was poured into ice water and extracted with 3 X 200 ml of methylene chloride. The combined extracts were washed with water, dried and concentrated to give 132g (99%) of product as an orange liquid (9a).
~) Preparation of 4-(isopropylthio)-3--~trifluoromethyl)aniline A mixture containing 132.5g ~0.5 mole) of the nitro compound (~a) - in 800 ml of 5% aqueous 1~871~36 acetic acid was heated to reflux with stirring. The heat mantle was removed and 150g o~ powdered iron was added at such a rate as to maintain reflux. After com-. .
pletion of the addition, the mixture was stirred and refluxedfor one hour, and filtered while hot. The filtrate was extracted with ether (3 X 300 ml). The combined extracts were washed with 10% sodium carbonate, and then with water.
The dried solution was concentrated to dryness under reduced pressure to give 70.5~g (60~) of product as a yellow oil (9b).
c) Preparation of 4'-(isopropylthio)-3'-(trifluorometh~ l-methylcyclopropane-carboxanil de To a stirred solution containing 23.5g (O.1 mole).of the amine (9b) and lO.lg (0.1 mole) of triethylamine in lS0 ml of tetrahydrofuran was added dropwise over 5 minutes ll.9g (0.1 mole) of l-methylcyclopropyl- -carboxylic acid chloride. This addition was exothermic to 55C.
The mixture was refluxed for 1 hour, poured into ice water and filtered. The filter cake was recrystallized from hexane to give 25g (79~) of product as acoIourless crystalline solid, m.p. 103-105C.
Examples 10-41 In the manner described above, and illustrated in foregoing Examples, additional cyclopropanecarboxanilides listed in Table 1 were prepared.
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After three day~, the reaction mixture was poured into water and extracted with methylene chloride.~ The combined - extracts were washed with water, dried with anhydrous MgSO4, filtered and concentrated to give 41.1g (976)- of product as a red-brown syrup.(43a).
b) Preparation of 4'-(isopropy-lthio)-3l-nitr -methylcyclopropanecarboxanilide To a solution containing 16.0g (0.75 mole) of (4~) and 7.6g (0.75 mole) of triethylamine in 150 ml of 20 tetrahydrofuran was added dropwise with stirring 8.9g (0.075 mole) of l-methylcyclopropanecarboxylic aCi~t chloride.
This addition was exothermic to 60. The mixture was refluxed for one hour~ poured over ice water and extracted with ether.
The ether extract was dried and concentrated to give 20.7g of a dark red-brown oil. Purification by silica chromatography gave 10.5g (48~) of product as a light-yellow solid, melting point, 92-94C.
Examples 44-46 In the manner described in Example 43, additional 30 cyclopropanecarboxanilides listed in Table 2 were prepared.
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10~7~86 Example 47 4'-(Cyclopropylmethoxy)-3'-chloro-1-methyl_ cyclopropanecarboxanilide a) Preparation of 3-chloro-4-(cyclopropylmethoxy)- -nitrobenzene To a solution containing 38.4 g of 3,4-dichloronitro- ~ -benzene in 150 ml of DMS0 was added 17.3 g of cyclopropylmethanol.
This solution was stirred during the dropwise addition of 92 g -~
of sodium hydroxide dissolved in 10 ml of water. This addition was exothermic to 45C. The mixture was stirred and heated to 75-80C for 18 hours, then poured over ice water and filtered.
The filter cake was recrystallized from methanol to yield 27 g ~ ~-(59%) of light tan solid, melting point, 42-44C (47a).
b) PreParation of 3-chloro-4-(cyclopropylmethoxy)aniline To a heated mixture containing 26.7 g of (47a) in ~ -300 ml of 5% aqueous acetic acid was added 56 g of iron filings and 15 ml of methanol. The mixture was refluxed and stirred vigorously for one hour. The mixture was filtered while hot and the cooled filtrate was extracted with ether. The ether extract was washed with aqueous sodium bicarbonate, dried, and concentrated to give 22.8 g (99%) of product, melting point, 54-55C (47b).
c) Preparation of 4'-(cyclopropylmethoxy)-3'-chloro-1-methylcyclopropanecarboxanilide To a solution of 4.9 g of (47b) and 2.5 g of triethyl- -amine in 50 ml of tetrahydrofuran was added dropwise 3.0 g of 1-methylcyclopropanecarboxylic acid chloride. The mixture was refluxed for 30 minutes, poured into ice water, and filtered, and the filtrate was recrystallized from methanol/water (4:1) to give 6.5 g (93%) of white crystalline solid; m.p. 111-113C.
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1~7186 ~33-Examples 48-54 In the manner described in Example 47 :
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10~37~86 Example 5 4'-Piperidinyl-3'-(trifluoromethyl)-1-methyl-cyclopro~anecarboxanilide .. a) Preparation of 4-nitro-1-piperidinyl-2--(trifluoromethyl)benzene -To a solution of 4-nitro-2-(trifluoromethyl)-chlorobenzene in 150 ml DMSO was added dropwise 17g of piperidine. The mixture was stirred at ambient ..
temperature, while protected from air and moisture, for ~
several days, then poured over ice water and extracted with ~ -methylene chloride. The extract was washed with cold water, dried and concentrated to give 27.4g tlOO~) of yellow-brown oil(56a:
~) Preparation of 4-piperidinyL-3-(trifluor methyl)benzenamine To about 500 ml of 5% acetic acid heated to 95C
was added.26g of 56 a). 17g of iron powder was added portionwise at a rate to maintain reflux without an external source of heat. After the addition, the mixture was stirred and heated at reflux for 1.5 hours, then filtered while hot, and the cooled filtrate was extracted with ether. The ether extract was washed with 10% aqueous sodium bicarbonate and then with water, dried, and concentrated to 22g (96~) of yellow-brown oil (56b).
c) Preparation of 4'-piperidinyl-3'-(trifluoro-methyl?-l-methylcyclopropanecarboxanilide To llg of(56 b) in 75 ml of tetrahydrofuran ; and 4.6g of triethylamine was added dropwise 5.3g of l-methyl-cyclopropanecarboxylic acid chloride, the reaction temperature ~0!37186 going to 55C. The mixture was thel stlrred and heated at 64C for 1.5 hours, poured over ice water and extracted with ether. The ether extrac~ was washed with water, dried and concentrated to give 13g (88~) of a yellow syrup, which ~-was crystallized from hexane to give 12g (82~) of off-white solid; m.p. 109-11C.
Example 57 4~-(Isopropylamino)-3~-(trifluorom~th -methylcyclopropanecarboxanilide a) Preparation of N-isopropyl-4-nitro-2-(tri- -fluoromethyl)benzenamine To a solution of 45g of 3-(trifluoromethy1)-4--chloronitrobenzene in 150 ml of DMS0 was added 13g of isopropylamine. The mixture was heated at 80-90C for ' two hours, poured over ice water, acidified and filtered.
The filtra~e was dried to yield 49.6g of product; m.p.35~36Qc (57a)-~) Prepar'ation of 4-'(isopropYlamino')-3-(trifluoro- - ' methyl)_enzenamine About 565 ml of 5~ acetic acid was heated to 90C
and 49.6 g of 57 a) - was added. 123g of iron powder was ' -added portionwise. The resulting mixture was refluxed for 1 hour, then filtered while hot. The filtrate was cooled and extracted with ether. The ether extract was washed with 10% aqueous sodium bicarbonate and then with water, dried and concentrated to give 38.7g (89~) of product as a light amber oil (57b).
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c) Pre~aration of 4'-(isopropylamino)-3'--~trifluoromethyl)-l-methylcyclopropane-carboxanilide To a solution of about l9g of 57 b) in ~-150 ml of tetrahydrofuran and 8.8g of triethylamine was added 118.5g of l-methylcyclopropanecarboxylic acid chloride dropwise over 5 minutes at 25-64C. The reaction mixture was stirred, refluxed for 30 minutes, poured over ice water, and extracted with ether. The ether extract was dried and concentrated, and the residue was crystallized from ether/petroleum ether to give 22g (84~) of grey solid;
m.p. 100-102C.
Example 58-73 In the manner described in the E~amples 56 and 57 additional cyclopropanecarboxanilides listed in Table 4 were prepared.
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-- 10~71~6 Example 72 4'-(I opropoxy~-3'-(trifluoromethyl)-1-chlorocyclo-.
propanecarboxanilide To a solution of 10.95g(1 b) in 100 ml of tetrahydrofuran and 5.05 g of triethylamine was added dropwise at ambient temperature 6.95g of l-chlorocyclopropanecarboxylicacid chloride. The reaction mixture was allowed to stand for two days, then concentrated to dryness. The r~sulting solid was washed with water and recrystallized from 80~ aqueous methanol to give lOg (62~) of white solid; m.p. 106-108C.
ExamPle 73 -4'-Isopropoxy-3~-(trifluoromethy~ ethoxycyclobutane carboxanilide and 4'-isopropoxy-3'-(trifluoro-methyl)-l-bromoc~clobutanecarboxanilide - a) Preparation of l-ethoxycyclobutanecarboxylic acid chloride and l-bromocyclobutanecarboxylic acid .
chloride A solution containing 82.8 g of ethyl l-bromo-cyclobutanecarboxylate and 28 g of potassium hydroxide in -250 ml of 85% aqueous ethanol was refluxed for 15 minutes.
The reaction mixture was concentrated to dryness under reduced pressure, treated with cold hydrochloric acid, and extracted with ether. The ether extract was dried and concentrated to give 53 g of a viscous mixture of acids.
Treatment of this mixture with an excess of thionyl chloride under reflux conditions followed by distillation gave 18 g of a colourlessliquid, boiling at 70-75C ~16 mm). Gas--liquid chromatography indicated the presence, in the approximate ratio of 4:1, of l-bromocyclobutanecarboxylic acid chloride and l-ethoxycyclobutanecarboxylic acid chloride.
.
1C)87186 ~) Preparation_of 4'-isoproxy-3-(trifluoro-methyl)-l-ethoxycyclobutanecarboxanilide and 4'--isopropoxy-3'-(trifluoromethyl)-l-bromo-cyclobutanecarboxanilide To a solution containing 10.9 g of(l~) and 5.1 g of triethylamine in 175 ml of tetrahydrofuran was added dropwise at 10-20C 12.1 g of(73 a). After standing overnight, the reaction mixture was concentrated to dryness, washed with water, and extracted with ether. The ether extract was concen-trated and the product was purified by silica chromatography.The first fraction comprised 3.0 g (16~) of the l-ethoxycyclo-butane ester as a tan solid, m.p. 48-50C. The second fraction comprised 2.4 g (13~) of the l-bromocyclobutane ester as a white solid, m.p. 82-84C.
Example 74 4'-(IsopropoxY)-3l-methyl-l-methylcyclopropane carboxanilide a) Preparation of isopropyl ortho-tolyl ether To a solution of 54.1 g (0.5 mole) of ortho-cresol in 150 ml of DMSO was added portionwise and with stirring 12 g of 57% sodium hydroxide. This addition was exothermic to 45C. After 2 hours at ambient temperature, 61.5 g (0.5 mole) of isopropyl bromide in 50 ml of DMSO
was added dropwise with stirring. After another 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 product as a colorless liquid;
b.p. 94-96C (30 mm)~ (74a).
~) Preparation of 2-isopropoxy-5-nitrotoluene To a chilled (6C) solution containing 31.8 g (0.2 mole) of the ether ~74a) and 28.7 g of acetic anhydride in 200 ml of glacial acetic acid was added dropwise . . .. . , ~ . : '~, ., ~087186 a solution of 13.9 g (0.22 mole) of 90% nitric acid in 100 ml of glacial acetic acid. The reaction mixture was allowed to stand at ambient temperature for 12 hours, poured into water and extracted with methylene chloride. The extract was washed with 5% sodium carbonate, water, dried, and concentrated to give 21.8 g of product as an amber oil (74b).
c) Preparation of 4'-(isopropoxy)i-3'-methyl--l-methylcyclopropanecarboxanilide A Parr shaker was charged with 21.8 g tO.ll mole) -- -of (74b) and 2 g of 10% palladium-charcoal catalyst in 150 ml of tetrahydrofuran. The glass cylinder was pressurized with hydrogen (40 pounds) and shaken until hydrogen uptake ceased.
The catalyst was removed by filtration. To the resulting solution was added 11.2 g of triethylamine and 12.6 g of l-methylcyclopropanecarboxylic acid Gh~oride. T~is-additi~ was exotbermic to 35C. After 1 hour, the reaction mixture was concentrated to dryness and washed with water.
Purification by silica chromatography gave 0.8 g of a white crystalline solid; m.p. 99-101C.
Example 75 4'~tDimethylsu hamoy~3'-(trifluoromethyl)-l--methylcyclopropanecarboxanilide a) Preparation of 4-nitro-3-ttrifluoromethyl)-benzenesulphonyl chloride A mixture containing 57.5 g (0.28 mole) of 4-nitro-2-(trifluoromethyl)aniline in 200 ml of concentrated hydrochloric acid was heated to 90Cfor 15 minutes and left stirring at ambient temperature for 18 hours. The resulting mixture was chilled to 4 and diazotized with 21.4 g (0.31 mole) o~ sodium nitrite in 50 ml of water. After 1 hour, the diazonium salt solution was added dropwise over 20 minutes and .
.
,. . :
~ 1087186 with stirring to a cold (5-10C) solution containing 13 g of copper(II) chloride and 64 g of sulphur dioxide in 250 ml of glacial acetic acid. After 2 hours, the mixture was filtered.
The filter cake was washed well with water and dried to give 68 g (84%) of product as a light tan solid; m.p. 77-79C (75a).
b) Preparation of N,N-dimethyl-4-nitro-2-(trifluoromethyl)benzenesulphonamide To a stirred solution containing 14 g (0.05 mole) of the sulphonyl chloride (75a) in 100 ml of tetrahydrofuran was added through a gas-inlet tube an excess of anhydrous dimethyl-amine causing the internal temperature to rise to 60C. The mixture was stirred at ambient temperature for ~ hour, poured into 500 ml of ice water and filtered. The filter cake was washed with water and dried to give 14 g (94%) of product as a light tan solid; m.p. 95-97C (75b).
c) Preparation of 4-(dimethylsulphamoyl-3-(trifluoromethyl)aniline To a heated mixture containing 13.5 g (0.045 mole) of the amide (75b) in 250 ml of 5% acetic acid was added portionwise and with stirring 12 g of iron powder. The mixture was refluxed for ~ hour. The mixture was filtered while hot and the cooled filtrate was extracted with ether.
The ether extract was washed with aqueous sodium bicarbonate, dried, concentrated and recrystallized from ether-hexane (1:2) to give 10.1 g (83%) of product as a colourless solid; m.p.
140-142C (75c).
d) Preparation of 4'-(dimethylsulphamoyl)-3'-(trifluoro-.
methyl)-1-methylcyclopropanecarboxanilide To a solution of 6.7 g (0.025 mole) of the aniline (75c) and 2.5 g of triethylamine in 50 ml of tetra-hydrofuran was added dropwise 3.0 g (0.025 mole) of .. . . .
: . , 71~ -l-methylcyclopropanecarboxylic acid chloride. ~he mixture was refluxed for one hour, poured into ice water, filtered and recrystallized from methanol to give 7.5 g (86~) of product as a whi~e crystalline solid; m.p. 153-156C.
Example 76 4~-(Isopropoxy)-3'-chloro-l-methoXycyc-lopropane carboxanilide A mixture consisting of 5.6 g of 3-chloro-4-isopropoxy-aniline, 3.9 g of methyl l-methoxycyclopropanecarboxylate and 1.8 g of sodium methoxide in 50 ml of benzene was refluxed for 3 hours. The reaction mixture was concentrated to a volume of 25 ml, poured over ice water, acidified with - -hydrochloric acid and extracted with ether. The extract was dried, filtered and concentrated. Purification by silica ;~
chromatography gave 1.8 g of product as a white crystalline solid; m.p. 86-87C.
Examples 77-94 In the manner described for the above examples, additional cyclopropanecarboxanilides listed in Tables 5 and 6 were prepared.
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:, , 1087~86 ~xample 95 - Demonstration of herbicidal activity The pre-emergence herbicidal activity of the compounds according to the invention was evaluated by planting seeds of garden cress, downey brome, wild mustard, velvet leaf, soybean, wheat, and cotton in test tubes, nominally measuring 25 x 200 millimeters, containing soil treated with the test compound at the rates of 0.1 and 1 mg per tube designated in Table I at Rates I and II, respectively. The planted soil was held under controlled conditions of temperature, moisture, and light for 1~ to 14 days. The amount of germination and growth in each tube were evaluated on a 0 to 9 scale, 0 rating indicating no effect, 9 death of the seedlings or no germination.
The post-emergence activity of the compounds according to this invention was evaluated by spraying 7-day old crabgrass plants, 10-day old pigweed plants, 7-day old downey brome plants, 10-day old wild mustard, 10-day old velvet leaf, 14-day old soybean plants, 7-day old wheat and 14-day old cotton plants to run-off with a liquid formulation of the test compound at the rates of 0.62 milliliter of an 0.05% solution designated Rate I :~
in Table I, and o.56 milliliter of an 0.5% solution designated :~
Rate II in Table I. The sprayed plants were held under con-trolled conditions for 10 to 11 days and the effect of the test compound was then evaluated visually, the results being rated on the 0 to 9 scale described above.
The results of the pre- and post-emergence tests are summarized in Table I.
The herbicidal activity of the compounds according to the - present invention was further determined with respect to several common species of weeds, by spraying a formulation of the test compound on the soil in which the weed seeds had been planted --` 1087186 (pre-emergence test) or onto the foliage of the plants (post-emergence test). In each series of tests, the plants were grown in narrow trays and sprayed with the appropriate chemical. The solution of the test compound was sprayed over the tray, from one end to the other, the concentration of the test compound in the formulation varying logarithmically from a higher value at one end of the band to a lower value at the other end of the band. The effect of the test compound was evaluated visually and reported as the nominal rate of application, in pounds of test compound per acre (1.12 kg/ha) of the soil band, at which 90% inhibition of the growth of the weeds occurred, this being referred to as the 90% growth inhibition dosage (GIDgo)~ Results of the pre-emergence and post-emergence tests, as well as the weed species involved, are set out in Tables II and III.
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b) Preparation of 3-(trifluoromethy1)-4- --~benzylox~ aniline ~o a refluxing mixture containing 64.5g (0.217 mole) of ~2a) in 700 ml of 5% aqueous acetic acid and 30 ml of methanol was added portionwise within 15 minutes 65.5g of iron filings. The mixture was stirred and refluxed for an additional 30 minutes, filtered while hot, cooled and extracted with ether. ~he ether extract was washed with water, dried and concentrated to give 56.0g (97%) of product as a light-amber oil that crystallized on standins (2b)~
'.
--` 1087~86 -,'1 -c) Pre~aration of 4'-(benzyloxy)-3'-(trifluoro-methyl?-l-methylcyclopro~anecarboxanilide To a solution of 2.7g (O.Ol~mole) of (2b) and 2.7 g,(0.01 mole) of triethylamine in 50 ml of tetra-hydrofuran was added with stirring at ambient temperature 1.2g (0.01 mole) of l-methylcyclopropanecarboxylic acid chloride.
After one hour, the reaction mixture was poured into ice water and extracted with 200 ml of ether. The ether extract was dried and concentrated. Recrystallization of the residual solid from ether gave 3.6 g of product, m.p. 120-122C.
Example 3 4'-(Cyclopropylmethoxy)-3'-(trifluoromethyl)--l-methylcyclopropanecarboxanilide a) Preparation of 3-(trifluoromethy1)-4--(cyclopropylmethoxy)nitrobenzene To a cooled (10C) solution containing 22.5g (0.1 mole) of 3-(trifluoromethyl)-4-chloronitrobenzene in 100 ml of DMSO
was added with stirring at ambient temperature a solution containing 0.11 mole of sodium cyclopropylmethoxide (prepared by dissolving 4.9g of 57~ sodium hydride in 7.9g of cyclo-propylmethanol and 50 ml of tetrahydrofuran) in 100 ml of DMSO.
The reaction mixture was heated at 50C for one hour, poured into ice water and filtered. Recrystallization of the filtrate from hexane gave ll.Og (42~) of product as a white crystalline solid, m.p. 41-44C (3a).
~) Preparation of 3-(trifluoromethyl)-4-(cyclo-propylmethoxy)aniline To a stirring and refluxing mixture containing ; ll.Og (0.042 mole) of (3a) in 150 ml of 5% aqueous acetic acid was added 28g of iron filings and 10 ml of methanol. The .
`" 10~3~186 mixture was refluxed and stirred vieorously for one hour, then extracted with ether after cooling. The ether extract was ~ :
washed with aqueous sodium bicarbonate, dried, and concentrated to give 9.5g (98%) of product as an amber oil (3b).
c) Preparation of 4!i-(cyclopropylmethoxy)-3'--(trifluoromethyl)-l-methylcyclopropane-carboxanilide To a solution of 4.6 g (0.02 mole) of (3b) and 2.0g (0.02 mole) of triethylamine in 30 ml of tetrahydrofuran was added 2.4g (0.02 mole) of l-methylcyclopropanecarboxylic acid chloride. The mixture was refluxed for one hour, poured into ice water, and extracted with ether. The extract was dried and concentrated, and the residue was recrystalli~ed from hexane to give 5.0g (79%) of white crystalline solid;m.p. 84-85 C.
Example 4 4'-(Methylthio)-3'-(trifluoromethyl)-1--methylcyclopropanecarboxanilide a) Preparation of 3-(trifluoromethyl)-4-(methyl-thio)-nitrobenzene To a stirred solution containing 45.1g (0.20 mole) of 3-(trifluoromethyl)-4-chloronitrobenzene and 15 g (0.30 mole) of methyl mercaptan in 150 ml of DMS0 was added dropwise at ambient a solution containing ô.Og (0.20 mole) of sodium hydroxide in 20 ml of water. This addition was exothermic to 60C. After one hour, the reaction mixture was poured into ice water. The product was filtered and dried to give 45.0g (95%) of yellow solid; m.p. 50C (4a).
b) Preparation of 3-(trifluoromethyl -(methylthio) aniline To a mixture containing 45.0g (0.19 mole) of (4a) in refluxing 5% aqueous acetic acid was added 61g .
1~87186 of iron powder. The reaction mixture was reflu~:ed for 3 hoursand filtered through Celite (filter aid) t~Jhile hot. The cooled filtrate was extracted with ether. The ether extract was washed with 10~ aqueous sodium bicarbonate, and then with water, dried over anhydrous MgSO~, and concentrated under reduced pressure to give 31.8g (81~) of product as a light yellow oil (4b).
c) Preparation of 4'-(methylthio)-3'-(trifluoro-methyl)-l-methylcyclopropanecarboxanilide To a stirred solution containing 31.8g ~0.154 mole) of (4~) and 15.6g (0.154 mole) of triethylamine in 200 ml of tetrahydrofuran was added dropwise over 10 minutes 18.2g (0.154 mole) of l-methylcyclopropanecarboxylic acid chloride. This addition was exothermic to 65C. The mixture was stirred and refluxed for one hour, poured into ice water and filtered.
The filter cake was washed with water and dried to give 43.5g (98~) of product as a yellow solid; m.p. 97-98C.
Example 5 4'-(Methylsu~hiny1)-3'-(trifluoro~ethyl)~
-methylcyclopropanecarboxanilide To a chilled (5C) solution containing 14.5g (0.05 mole) of 4'-(methylthio)-3'-(trifluoromethyl)-1-methylcyclopropane-carboxanilide (prepared in Example 4 above) in 150 ml of chloroform was added dropwise over 20 minutes with stirring a solution of 10.2g (0.05 mole) of 85% meta-chloroperoxy-benzoic acid in 150 ml of chloroform. The reaction solution was allowed to equilibrate gradually to 25C, and after 16 hours, washed well with lO~ sodium carbonate and ~ 1087186 - -2~!-water, dried, and concentrated. The residual solid was crystallized from methanol to give 13.0g (86%) of product as a light-cream colored solid; m.p. 181-184 C.
ExampIe 6 4'-(Methylsu~nyl)-3'-trifluoromethyl-1-methyl-cyclopropanecarboxanilide To a stirred solution containing 7.0g (0.024 mole) of 4'-(methylthio)-3'-(trifluoromethyl)-1-methylcyclopropane-carboxanilide (prepared in Example 4 above) in 200 ml of chloroform was added dropwise over a period of 10 minutes at ambient temperature 10.2g (0.05 mole) of 85% meta--chloroperoxybenzoic acid. The reaction was exothermic to 50C. The reaction mixture was stirred for 16 hours, washed with 10%-a~ueous sodium carbonate and then with water. The - chloroform layer was dried and concentrated to dryness. The - residue was crystallized from methanol to give 7.5g (97~) of product as a light-cream solid; m.p. 135-138C.
Example 7 -4'- lorophenoxy)-3'-(trifluoromethyl)-1-methyl-cyclopropanecarboxanilide a) Preparation of 4-(4-chlorophenoxy?-3-ttrifluoromethyl~nltrobenzene To a solution containing 64.2g (0.5 mole) of 4-chlorophenol and 112.7g tO.5 mole) of 2-chloro-5-nitro-benzotrifluoride in 400 ml of DMSO was added dropwise with stirring at 30-35C a solution containing 20g (0.5 mole) of sodium hydroxide in 20 ml of water. After ~- -1.5 hours, the reaction mixture was poured into cold water : ,.... . ~
.
--- 1087186 ~:
and extracted with 800 ml of ether. The ether solution was dried and concentrated under reduced pressure to give 158 g (99~) of product that crystallized on standing; melting point, 46-48C tfrom hexane) (7a).
b) Preparation of 4-(4-chlorophenoxy)-3-(trifluoromethyl)aniline To a refluxing mixture containing 156 g (0.492 mole) -~-~
of the nitro compound (7a) in 1180 ml of 5~ aqueous acetic acid was added portionwise 140g of powdered iron. After 2 hours, the reaction mixture was filtered through filter aid and the residue was washed with methanol. The combined filtrates were extracted with 7 X 300 ml of ether. The combined ether extracts were washed with aqueous sodium bic3rbonate, dried and concentrated to give 141.5g of product; melting point, 43-45C (from hexane) (7b) c) Preparation of 4'-(4-chlorophenoxy)-3'-(trifluorometh~l)-1-methylcyclopropane-.
carboxanilide To a stirred solution of 5.75g (0.02 mole) --of the aminQ ~7b) in 40 ml of tetrahydrofuran was added dropwise 2.4g (0.02 mole) of l-methylcyclopropylcarboxy]ic acid chloride. The mixture was stirred and heated at 60C for 0.5 hour, poured into ice water and filtered. The filter cake was recrystallized from ether-hexane (1:3) to give 6.5g (88~) of product, m.p. 115-117C.
. : , .
~ 1~87186 Example 8 4'-(4-Chlorophenoxy)-3'-(trifluoromethyl) -l-butylcyclopropanecarboxanilide To a solution containing 2.9g (0.01 mole) of the amine prepared according to Example 7b),an~1.0g(0.01 mole) of triethylamine in 50 ml of tetrahydrofuran was added dropwise 1.7g (0.01 mole) of l-butylcyclopropanecarboxylic acid chloride.
The mixture was stirred and heated at 60C for 0.5 hour, poured into ice water and extracted with ether. The ether extract was dried and concentrated under reduced pressure.
The residual yellow syrup was crystallized from hexane to give 3.3g (80~) of product as a tan solid, m.p. 104-106C.
Example 9 4'-(Isopropylthio)-3'-ltrifluoromethy~
-l-methylcyclopropanecarboxanilide a) Preparation of 4-(Isopropylthio)-3-(trifluoromethyl)nitrobenzene To a solution containing 112.8g tO.5 mole) of 2-chloro-5-nitrobenzotrifluoride and 46g (0.6 mole) of isopropyl mercaptan in 400 ml of DMS0 was added dropwise over 0.5 hour 40g of 50% aqueous sodium hydroxide.
This addition was exothermic to 50C. After 24 hours, the reaction mixture was poured into ice water and extracted with 3 X 200 ml of methylene chloride. The combined extracts were washed with water, dried and concentrated to give 132g (99%) of product as an orange liquid (9a).
~) Preparation of 4-(isopropylthio)-3--~trifluoromethyl)aniline A mixture containing 132.5g ~0.5 mole) of the nitro compound (~a) - in 800 ml of 5% aqueous 1~871~36 acetic acid was heated to reflux with stirring. The heat mantle was removed and 150g o~ powdered iron was added at such a rate as to maintain reflux. After com-. .
pletion of the addition, the mixture was stirred and refluxedfor one hour, and filtered while hot. The filtrate was extracted with ether (3 X 300 ml). The combined extracts were washed with 10% sodium carbonate, and then with water.
The dried solution was concentrated to dryness under reduced pressure to give 70.5~g (60~) of product as a yellow oil (9b).
c) Preparation of 4'-(isopropylthio)-3'-(trifluorometh~ l-methylcyclopropane-carboxanil de To a stirred solution containing 23.5g (O.1 mole).of the amine (9b) and lO.lg (0.1 mole) of triethylamine in lS0 ml of tetrahydrofuran was added dropwise over 5 minutes ll.9g (0.1 mole) of l-methylcyclopropyl- -carboxylic acid chloride. This addition was exothermic to 55C.
The mixture was refluxed for 1 hour, poured into ice water and filtered. The filter cake was recrystallized from hexane to give 25g (79~) of product as acoIourless crystalline solid, m.p. 103-105C.
Examples 10-41 In the manner described above, and illustrated in foregoing Examples, additional cyclopropanecarboxanilides listed in Table 1 were prepared.
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~q u~ n o o _ _ ~ .' ~ U~ ~O tN CN ON~ ~ rf) ~(~ ~ _ - 1~87186 -3o-Example 43 4'-(Isopropylthio)-3~-nitro-l-methylcyclopr panecarboxanilide a) Preparation of 4-(isoE~ropylthio)-3-nitroaniline To a stirred solution containing 34.5g (0.20 mole) of 4-chloro-3-nitroaniline and 24g (0.30 mole) of isopropyl mercaptan in 200 ml of DMSO was added dropwise at ambient temperature a solution of 8.0g (0.20 mole) of sodium hydroxide in 10 ml of water. The addition was 10 exothennic to 60Cand the mixture became deep red in colour.
After three day~, the reaction mixture was poured into water and extracted with methylene chloride.~ The combined - extracts were washed with water, dried with anhydrous MgSO4, filtered and concentrated to give 41.1g (976)- of product as a red-brown syrup.(43a).
b) Preparation of 4'-(isopropy-lthio)-3l-nitr -methylcyclopropanecarboxanilide To a solution containing 16.0g (0.75 mole) of (4~) and 7.6g (0.75 mole) of triethylamine in 150 ml of 20 tetrahydrofuran was added dropwise with stirring 8.9g (0.075 mole) of l-methylcyclopropanecarboxylic aCi~t chloride.
This addition was exothermic to 60. The mixture was refluxed for one hour~ poured over ice water and extracted with ether.
The ether extract was dried and concentrated to give 20.7g of a dark red-brown oil. Purification by silica chromatography gave 10.5g (48~) of product as a light-yellow solid, melting point, 92-94C.
Examples 44-46 In the manner described in Example 43, additional 30 cyclopropanecarboxanilides listed in Table 2 were prepared.
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10~7~86 Example 47 4'-(Cyclopropylmethoxy)-3'-chloro-1-methyl_ cyclopropanecarboxanilide a) Preparation of 3-chloro-4-(cyclopropylmethoxy)- -nitrobenzene To a solution containing 38.4 g of 3,4-dichloronitro- ~ -benzene in 150 ml of DMS0 was added 17.3 g of cyclopropylmethanol.
This solution was stirred during the dropwise addition of 92 g -~
of sodium hydroxide dissolved in 10 ml of water. This addition was exothermic to 45C. The mixture was stirred and heated to 75-80C for 18 hours, then poured over ice water and filtered.
The filter cake was recrystallized from methanol to yield 27 g ~ ~-(59%) of light tan solid, melting point, 42-44C (47a).
b) PreParation of 3-chloro-4-(cyclopropylmethoxy)aniline To a heated mixture containing 26.7 g of (47a) in ~ -300 ml of 5% aqueous acetic acid was added 56 g of iron filings and 15 ml of methanol. The mixture was refluxed and stirred vigorously for one hour. The mixture was filtered while hot and the cooled filtrate was extracted with ether. The ether extract was washed with aqueous sodium bicarbonate, dried, and concentrated to give 22.8 g (99%) of product, melting point, 54-55C (47b).
c) Preparation of 4'-(cyclopropylmethoxy)-3'-chloro-1-methylcyclopropanecarboxanilide To a solution of 4.9 g of (47b) and 2.5 g of triethyl- -amine in 50 ml of tetrahydrofuran was added dropwise 3.0 g of 1-methylcyclopropanecarboxylic acid chloride. The mixture was refluxed for 30 minutes, poured into ice water, and filtered, and the filtrate was recrystallized from methanol/water (4:1) to give 6.5 g (93%) of white crystalline solid; m.p. 111-113C.
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1~7186 ~33-Examples 48-54 In the manner described in Example 47 :
additional cyclopropanecarboxanilides listed in Table 3 were prepared.
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10~37~86 Example 5 4'-Piperidinyl-3'-(trifluoromethyl)-1-methyl-cyclopro~anecarboxanilide .. a) Preparation of 4-nitro-1-piperidinyl-2--(trifluoromethyl)benzene -To a solution of 4-nitro-2-(trifluoromethyl)-chlorobenzene in 150 ml DMSO was added dropwise 17g of piperidine. The mixture was stirred at ambient ..
temperature, while protected from air and moisture, for ~
several days, then poured over ice water and extracted with ~ -methylene chloride. The extract was washed with cold water, dried and concentrated to give 27.4g tlOO~) of yellow-brown oil(56a:
~) Preparation of 4-piperidinyL-3-(trifluor methyl)benzenamine To about 500 ml of 5% acetic acid heated to 95C
was added.26g of 56 a). 17g of iron powder was added portionwise at a rate to maintain reflux without an external source of heat. After the addition, the mixture was stirred and heated at reflux for 1.5 hours, then filtered while hot, and the cooled filtrate was extracted with ether. The ether extract was washed with 10% aqueous sodium bicarbonate and then with water, dried, and concentrated to 22g (96~) of yellow-brown oil (56b).
c) Preparation of 4'-piperidinyl-3'-(trifluoro-methyl?-l-methylcyclopropanecarboxanilide To llg of(56 b) in 75 ml of tetrahydrofuran ; and 4.6g of triethylamine was added dropwise 5.3g of l-methyl-cyclopropanecarboxylic acid chloride, the reaction temperature ~0!37186 going to 55C. The mixture was thel stlrred and heated at 64C for 1.5 hours, poured over ice water and extracted with ether. The ether extrac~ was washed with water, dried and concentrated to give 13g (88~) of a yellow syrup, which ~-was crystallized from hexane to give 12g (82~) of off-white solid; m.p. 109-11C.
Example 57 4~-(Isopropylamino)-3~-(trifluorom~th -methylcyclopropanecarboxanilide a) Preparation of N-isopropyl-4-nitro-2-(tri- -fluoromethyl)benzenamine To a solution of 45g of 3-(trifluoromethy1)-4--chloronitrobenzene in 150 ml of DMS0 was added 13g of isopropylamine. The mixture was heated at 80-90C for ' two hours, poured over ice water, acidified and filtered.
The filtra~e was dried to yield 49.6g of product; m.p.35~36Qc (57a)-~) Prepar'ation of 4-'(isopropYlamino')-3-(trifluoro- - ' methyl)_enzenamine About 565 ml of 5~ acetic acid was heated to 90C
and 49.6 g of 57 a) - was added. 123g of iron powder was ' -added portionwise. The resulting mixture was refluxed for 1 hour, then filtered while hot. The filtrate was cooled and extracted with ether. The ether extract was washed with 10% aqueous sodium bicarbonate and then with water, dried and concentrated to give 38.7g (89~) of product as a light amber oil (57b).
.
.
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c) Pre~aration of 4'-(isopropylamino)-3'--~trifluoromethyl)-l-methylcyclopropane-carboxanilide To a solution of about l9g of 57 b) in ~-150 ml of tetrahydrofuran and 8.8g of triethylamine was added 118.5g of l-methylcyclopropanecarboxylic acid chloride dropwise over 5 minutes at 25-64C. The reaction mixture was stirred, refluxed for 30 minutes, poured over ice water, and extracted with ether. The ether extract was dried and concentrated, and the residue was crystallized from ether/petroleum ether to give 22g (84~) of grey solid;
m.p. 100-102C.
Example 58-73 In the manner described in the E~amples 56 and 57 additional cyclopropanecarboxanilides listed in Table 4 were prepared.
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-- 10~71~6 Example 72 4'-(I opropoxy~-3'-(trifluoromethyl)-1-chlorocyclo-.
propanecarboxanilide To a solution of 10.95g(1 b) in 100 ml of tetrahydrofuran and 5.05 g of triethylamine was added dropwise at ambient temperature 6.95g of l-chlorocyclopropanecarboxylicacid chloride. The reaction mixture was allowed to stand for two days, then concentrated to dryness. The r~sulting solid was washed with water and recrystallized from 80~ aqueous methanol to give lOg (62~) of white solid; m.p. 106-108C.
ExamPle 73 -4'-Isopropoxy-3~-(trifluoromethy~ ethoxycyclobutane carboxanilide and 4'-isopropoxy-3'-(trifluoro-methyl)-l-bromoc~clobutanecarboxanilide - a) Preparation of l-ethoxycyclobutanecarboxylic acid chloride and l-bromocyclobutanecarboxylic acid .
chloride A solution containing 82.8 g of ethyl l-bromo-cyclobutanecarboxylate and 28 g of potassium hydroxide in -250 ml of 85% aqueous ethanol was refluxed for 15 minutes.
The reaction mixture was concentrated to dryness under reduced pressure, treated with cold hydrochloric acid, and extracted with ether. The ether extract was dried and concentrated to give 53 g of a viscous mixture of acids.
Treatment of this mixture with an excess of thionyl chloride under reflux conditions followed by distillation gave 18 g of a colourlessliquid, boiling at 70-75C ~16 mm). Gas--liquid chromatography indicated the presence, in the approximate ratio of 4:1, of l-bromocyclobutanecarboxylic acid chloride and l-ethoxycyclobutanecarboxylic acid chloride.
.
1C)87186 ~) Preparation_of 4'-isoproxy-3-(trifluoro-methyl)-l-ethoxycyclobutanecarboxanilide and 4'--isopropoxy-3'-(trifluoromethyl)-l-bromo-cyclobutanecarboxanilide To a solution containing 10.9 g of(l~) and 5.1 g of triethylamine in 175 ml of tetrahydrofuran was added dropwise at 10-20C 12.1 g of(73 a). After standing overnight, the reaction mixture was concentrated to dryness, washed with water, and extracted with ether. The ether extract was concen-trated and the product was purified by silica chromatography.The first fraction comprised 3.0 g (16~) of the l-ethoxycyclo-butane ester as a tan solid, m.p. 48-50C. The second fraction comprised 2.4 g (13~) of the l-bromocyclobutane ester as a white solid, m.p. 82-84C.
Example 74 4'-(IsopropoxY)-3l-methyl-l-methylcyclopropane carboxanilide a) Preparation of isopropyl ortho-tolyl ether To a solution of 54.1 g (0.5 mole) of ortho-cresol in 150 ml of DMSO was added portionwise and with stirring 12 g of 57% sodium hydroxide. This addition was exothermic to 45C. After 2 hours at ambient temperature, 61.5 g (0.5 mole) of isopropyl bromide in 50 ml of DMSO
was added dropwise with stirring. After another 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 product as a colorless liquid;
b.p. 94-96C (30 mm)~ (74a).
~) Preparation of 2-isopropoxy-5-nitrotoluene To a chilled (6C) solution containing 31.8 g (0.2 mole) of the ether ~74a) and 28.7 g of acetic anhydride in 200 ml of glacial acetic acid was added dropwise . . .. . , ~ . : '~, ., ~087186 a solution of 13.9 g (0.22 mole) of 90% nitric acid in 100 ml of glacial acetic acid. The reaction mixture was allowed to stand at ambient temperature for 12 hours, poured into water and extracted with methylene chloride. The extract was washed with 5% sodium carbonate, water, dried, and concentrated to give 21.8 g of product as an amber oil (74b).
c) Preparation of 4'-(isopropoxy)i-3'-methyl--l-methylcyclopropanecarboxanilide A Parr shaker was charged with 21.8 g tO.ll mole) -- -of (74b) and 2 g of 10% palladium-charcoal catalyst in 150 ml of tetrahydrofuran. The glass cylinder was pressurized with hydrogen (40 pounds) and shaken until hydrogen uptake ceased.
The catalyst was removed by filtration. To the resulting solution was added 11.2 g of triethylamine and 12.6 g of l-methylcyclopropanecarboxylic acid Gh~oride. T~is-additi~ was exotbermic to 35C. After 1 hour, the reaction mixture was concentrated to dryness and washed with water.
Purification by silica chromatography gave 0.8 g of a white crystalline solid; m.p. 99-101C.
Example 75 4'~tDimethylsu hamoy~3'-(trifluoromethyl)-l--methylcyclopropanecarboxanilide a) Preparation of 4-nitro-3-ttrifluoromethyl)-benzenesulphonyl chloride A mixture containing 57.5 g (0.28 mole) of 4-nitro-2-(trifluoromethyl)aniline in 200 ml of concentrated hydrochloric acid was heated to 90Cfor 15 minutes and left stirring at ambient temperature for 18 hours. The resulting mixture was chilled to 4 and diazotized with 21.4 g (0.31 mole) o~ sodium nitrite in 50 ml of water. After 1 hour, the diazonium salt solution was added dropwise over 20 minutes and .
.
,. . :
~ 1087186 with stirring to a cold (5-10C) solution containing 13 g of copper(II) chloride and 64 g of sulphur dioxide in 250 ml of glacial acetic acid. After 2 hours, the mixture was filtered.
The filter cake was washed well with water and dried to give 68 g (84%) of product as a light tan solid; m.p. 77-79C (75a).
b) Preparation of N,N-dimethyl-4-nitro-2-(trifluoromethyl)benzenesulphonamide To a stirred solution containing 14 g (0.05 mole) of the sulphonyl chloride (75a) in 100 ml of tetrahydrofuran was added through a gas-inlet tube an excess of anhydrous dimethyl-amine causing the internal temperature to rise to 60C. The mixture was stirred at ambient temperature for ~ hour, poured into 500 ml of ice water and filtered. The filter cake was washed with water and dried to give 14 g (94%) of product as a light tan solid; m.p. 95-97C (75b).
c) Preparation of 4-(dimethylsulphamoyl-3-(trifluoromethyl)aniline To a heated mixture containing 13.5 g (0.045 mole) of the amide (75b) in 250 ml of 5% acetic acid was added portionwise and with stirring 12 g of iron powder. The mixture was refluxed for ~ hour. The mixture was filtered while hot and the cooled filtrate was extracted with ether.
The ether extract was washed with aqueous sodium bicarbonate, dried, concentrated and recrystallized from ether-hexane (1:2) to give 10.1 g (83%) of product as a colourless solid; m.p.
140-142C (75c).
d) Preparation of 4'-(dimethylsulphamoyl)-3'-(trifluoro-.
methyl)-1-methylcyclopropanecarboxanilide To a solution of 6.7 g (0.025 mole) of the aniline (75c) and 2.5 g of triethylamine in 50 ml of tetra-hydrofuran was added dropwise 3.0 g (0.025 mole) of .. . . .
: . , 71~ -l-methylcyclopropanecarboxylic acid chloride. ~he mixture was refluxed for one hour, poured into ice water, filtered and recrystallized from methanol to give 7.5 g (86~) of product as a whi~e crystalline solid; m.p. 153-156C.
Example 76 4~-(Isopropoxy)-3'-chloro-l-methoXycyc-lopropane carboxanilide A mixture consisting of 5.6 g of 3-chloro-4-isopropoxy-aniline, 3.9 g of methyl l-methoxycyclopropanecarboxylate and 1.8 g of sodium methoxide in 50 ml of benzene was refluxed for 3 hours. The reaction mixture was concentrated to a volume of 25 ml, poured over ice water, acidified with - -hydrochloric acid and extracted with ether. The extract was dried, filtered and concentrated. Purification by silica ;~
chromatography gave 1.8 g of product as a white crystalline solid; m.p. 86-87C.
Examples 77-94 In the manner described for the above examples, additional cyclopropanecarboxanilides listed in Tables 5 and 6 were prepared.
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:, , 1087~86 ~xample 95 - Demonstration of herbicidal activity The pre-emergence herbicidal activity of the compounds according to the invention was evaluated by planting seeds of garden cress, downey brome, wild mustard, velvet leaf, soybean, wheat, and cotton in test tubes, nominally measuring 25 x 200 millimeters, containing soil treated with the test compound at the rates of 0.1 and 1 mg per tube designated in Table I at Rates I and II, respectively. The planted soil was held under controlled conditions of temperature, moisture, and light for 1~ to 14 days. The amount of germination and growth in each tube were evaluated on a 0 to 9 scale, 0 rating indicating no effect, 9 death of the seedlings or no germination.
The post-emergence activity of the compounds according to this invention was evaluated by spraying 7-day old crabgrass plants, 10-day old pigweed plants, 7-day old downey brome plants, 10-day old wild mustard, 10-day old velvet leaf, 14-day old soybean plants, 7-day old wheat and 14-day old cotton plants to run-off with a liquid formulation of the test compound at the rates of 0.62 milliliter of an 0.05% solution designated Rate I :~
in Table I, and o.56 milliliter of an 0.5% solution designated :~
Rate II in Table I. The sprayed plants were held under con-trolled conditions for 10 to 11 days and the effect of the test compound was then evaluated visually, the results being rated on the 0 to 9 scale described above.
The results of the pre- and post-emergence tests are summarized in Table I.
The herbicidal activity of the compounds according to the - present invention was further determined with respect to several common species of weeds, by spraying a formulation of the test compound on the soil in which the weed seeds had been planted --` 1087186 (pre-emergence test) or onto the foliage of the plants (post-emergence test). In each series of tests, the plants were grown in narrow trays and sprayed with the appropriate chemical. The solution of the test compound was sprayed over the tray, from one end to the other, the concentration of the test compound in the formulation varying logarithmically from a higher value at one end of the band to a lower value at the other end of the band. The effect of the test compound was evaluated visually and reported as the nominal rate of application, in pounds of test compound per acre (1.12 kg/ha) of the soil band, at which 90% inhibition of the growth of the weeds occurred, this being referred to as the 90% growth inhibition dosage (GIDgo)~ Results of the pre-emergence and post-emergence tests, as well as the weed species involved, are set out in Tables II and III.
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~- 108~186 In many instances the compounds according to the invention possess a selective action against weeds in crop plant cultures. For example, control of grasses and broadleaf weeds in grain crops such as wheat can be achieved by post- :- -emergence application of such compounds according to the in-vention as:
4'-(sec-butoxy)-3'-(trifluoromethy~-1-methyl-cyclopropanecarboxanilide, 4'-(isobutoxy)-3'-(trifluoromethyl)-1-methyl-cyclopropanecarboxanilide, 4!-(isobutylsulphonyl)-3'-(trifluoromethyl)-1-methylcyclopropanecarboxanilide, or 4'-(ethylthio)-3'-(trifluoromethyl)-1-methyl-cyclopropanecarboxanilide.
Control of weeds in soybean crops is an example of the selective herbicidal activity of 4'-(isopropylamino)-3'-(trifluoromethyl)-l-methylcyclopropanecarboxanilide or 4'-(isopropylthio)-3'-(trifluoromethyl)-1-methylcyclopropane-carboxanilide~
The above species and/or other species of the in-vention have likewise shown post-emergence, and in some cases, pre-emergence selective activity for peanuts, grain sorghum, cotton, rice, corn, alfalfa or the like.
.
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~- 108~186 In many instances the compounds according to the invention possess a selective action against weeds in crop plant cultures. For example, control of grasses and broadleaf weeds in grain crops such as wheat can be achieved by post- :- -emergence application of such compounds according to the in-vention as:
4'-(sec-butoxy)-3'-(trifluoromethy~-1-methyl-cyclopropanecarboxanilide, 4'-(isobutoxy)-3'-(trifluoromethyl)-1-methyl-cyclopropanecarboxanilide, 4!-(isobutylsulphonyl)-3'-(trifluoromethyl)-1-methylcyclopropanecarboxanilide, or 4'-(ethylthio)-3'-(trifluoromethyl)-1-methyl-cyclopropanecarboxanilide.
Control of weeds in soybean crops is an example of the selective herbicidal activity of 4'-(isopropylamino)-3'-(trifluoromethyl)-l-methylcyclopropanecarboxanilide or 4'-(isopropylthio)-3'-(trifluoromethyl)-1-methylcyclopropane-carboxanilide~
The above species and/or other species of the in-vention have likewise shown post-emergence, and in some cases, pre-emergence selective activity for peanuts, grain sorghum, cotton, rice, corn, alfalfa or the like.
Claims (19)
1. A compound of the formula:
wherein X represents an O, S, SO, SO2 or -NR3 moiety;
Y represents a fluorine, chlorine or bromine atom, a cyano, nitro, C(R3)=NOR3 or C(O)R3 group, or the group -Zp-alkyl, in which the alkyl portion contains from 1 to 6 carbon atoms and can be substituted by one or more fluorine, chlorine or bromine atoms and Z represents an O, S, SO or SO2 group;
R1 represents an alkyl group of from 1 to 6 carbon atoms, an alkenyl group of from 2 to 6 carbon atoms or an aryl group of from 6 to 10 carbon atoms, each optionally substituted by one or more fluorine, chlorine or bromine atoms or represents an alkynyl group of from 3 to 4 carbon atoms, an alkoxyalkyl group in which each alkyl group contains from 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 7 carbon atoms in the ring, an aralkyl group of from 7 to 9 carbon atoms optionally ring-substituted by one or two fluorine, chlorine or bromine atoms, or by an alkyl group of from 1 to 4 carbon atoms, a group of the formula or , or when X represents the group NR3 then R1 can represent the group , -SO2R6, or, when X represents the group SO2 then R1 can also represent the group -NR4R5, , or -NR4SO2R6; R2 represents an alkyl group of from 1 to 6 carbon atoms, a fluorine, chlorine or bromine atom, an alkoxy or alkylthio group, in which the alkyl portion contains from 1 to 6 carbon atoms; with the proviso that when Y represents a NO2 group and X
represents an O-moiety then R1 does not represent a methyl group; R3, R4 and R5 each independently represents a hydrogen atom or an alkyl or cycloalkyl group of up to 6 carbon atoms and R5 can also represent an alkoxy group of up to 6 carbon atoms; when X represents the group NR3 then R1 and R3 together can form a part of a heterocyclic ring, such as -CH2-(CH2)mCH2-, , or -CH2CH2OCH2CH2-; when R1 represents the group NR4R5 then R4 and R5 together can form a part of a heterocyclic ring as is shown above for R1 and R3 when taken together; R6 represents an alkyl group of from 1 to 6 carbon atoms or an aryl or aralkyl group of from 6 to 10 carbon atoms optionally 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; provided that if X represents S, then R2 is other than an alkoxy group.
wherein X represents an O, S, SO, SO2 or -NR3 moiety;
Y represents a fluorine, chlorine or bromine atom, a cyano, nitro, C(R3)=NOR3 or C(O)R3 group, or the group -Zp-alkyl, in which the alkyl portion contains from 1 to 6 carbon atoms and can be substituted by one or more fluorine, chlorine or bromine atoms and Z represents an O, S, SO or SO2 group;
R1 represents an alkyl group of from 1 to 6 carbon atoms, an alkenyl group of from 2 to 6 carbon atoms or an aryl group of from 6 to 10 carbon atoms, each optionally substituted by one or more fluorine, chlorine or bromine atoms or represents an alkynyl group of from 3 to 4 carbon atoms, an alkoxyalkyl group in which each alkyl group contains from 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 7 carbon atoms in the ring, an aralkyl group of from 7 to 9 carbon atoms optionally ring-substituted by one or two fluorine, chlorine or bromine atoms, or by an alkyl group of from 1 to 4 carbon atoms, a group of the formula or , or when X represents the group NR3 then R1 can represent the group , -SO2R6, or, when X represents the group SO2 then R1 can also represent the group -NR4R5, , or -NR4SO2R6; R2 represents an alkyl group of from 1 to 6 carbon atoms, a fluorine, chlorine or bromine atom, an alkoxy or alkylthio group, in which the alkyl portion contains from 1 to 6 carbon atoms; with the proviso that when Y represents a NO2 group and X
represents an O-moiety then R1 does not represent a methyl group; R3, R4 and R5 each independently represents a hydrogen atom or an alkyl or cycloalkyl group of up to 6 carbon atoms and R5 can also represent an alkoxy group of up to 6 carbon atoms; when X represents the group NR3 then R1 and R3 together can form a part of a heterocyclic ring, such as -CH2-(CH2)mCH2-, , or -CH2CH2OCH2CH2-; when R1 represents the group NR4R5 then R4 and R5 together can form a part of a heterocyclic ring as is shown above for R1 and R3 when taken together; R6 represents an alkyl group of from 1 to 6 carbon atoms or an aryl or aralkyl group of from 6 to 10 carbon atoms optionally 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; provided that if X represents S, then R2 is other than an alkoxy group.
2. A compound according to claim 1, wherein R2 represents a chlorine or bromine atom or a methyl or methoxy group and n is 1.
3, A compound according to claim 2, wherein R2 represents a methyl group.
4. A compound according to claim 1, wherein Y represents a chlorine atom or a methyl, trifluoromethyl or nitro group, and n is 1.
5. A compound according to claim 4, wherein Y
represents a trifluoromethyl group.
represents a trifluoromethyl group.
6. A compound according to claim 1, wherein R1 represents an alkyl group of 1-4 carbon atoms or a cyclo-alkyl group, and n is 1.
7. A compound according to claim 6, wherein R1 represents a methyl, ethyl, isopropyl, tert.-butyl, cyclo-propylmethyl or ring-alkylated group.
8. A compound according to claim 7, wherein R1 represents an isopropyl or tert.-butyl group.
9. A compound according to claim 1, wherein R3, R4 or R5 each individually represents a hydrogen atom or a methyl, ethyl or methylcyclopropyl group and R5 may represent a methoxy or ethoxy group and n is 1.
10. A compound according to claim 1, wherein when X
represents the group NR3, R3 represents an isopropyl, n-propyl or tert.-butyl group and n is 1.
represents the group NR3, R3 represents an isopropyl, n-propyl or tert.-butyl group and n is 1.
11. A compound according to claim 1, wherein X
represents the O-moiety; R2 represents a methyl group;
Y represents a trifluoromethyl group and R1 represents an alkyl group of 1-4 carbon atoms, a cyclopropylmethyl or a 1-methylcyclopropyl group and n is 1.
represents the O-moiety; R2 represents a methyl group;
Y represents a trifluoromethyl group and R1 represents an alkyl group of 1-4 carbon atoms, a cyclopropylmethyl or a 1-methylcyclopropyl group and n is 1.
12. A compound according to claim 1, wherein X
represents an S, SO, SO2-moiety; Y represents a trifluoro-methyl group; R2 represents a methyl group and R1 represents an alkyl group of up to 4 carbon atoms and n is 1.
represents an S, SO, SO2-moiety; Y represents a trifluoro-methyl group; R2 represents a methyl group and R1 represents an alkyl group of up to 4 carbon atoms and n is 1.
13. A compound according to claim 1, wherein Y
represents a nitro group, R1 represents an alkyl group of 2-4 carbon atoms and X represents an O, S, SO or SO2 moiety.
represents a nitro group, R1 represents an alkyl group of 2-4 carbon atoms and X represents an O, S, SO or SO2 moiety.
14. A compound according to claim 13, wherein R1 represents an isopropyl group.
15. 4'-(Isopropylamino)-3'-trifluoromethyl-1-methylcyclopropane-carboxanilide.
16. 4'-(Isopropoxy)-3'-trifluoromethyl-1-methylcyclopropane-carboxanilide.
17. 4'-(Isopropylthio)-3'-trifluoromethyl-1-methylcyclopropane-carboxanilide.
18. A process for the preparation of compounds as claimed in claim 1; which comprises reacting a 3,4-disubstituted aniline of formula:
with a cycloalkanecarboxylic acid chloride of formula:
wherein X, Y, R1, R2 and n have the meanings defined hereinabove, in the presence of a base.
with a cycloalkanecarboxylic acid chloride of formula:
wherein X, Y, R1, R2 and n have the meanings defined hereinabove, in the presence of a base.
19. A method of controlling plant growth at a locus by applying thereto a herbicidally active amount of a cycloalkanecarboxanilide deriv-ative as claimed in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76151577A | 1977-01-21 | 1977-01-21 | |
| US761,515 | 1977-01-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1087186A true CA1087186A (en) | 1980-10-07 |
Family
ID=25062445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA294,281A Expired CA1087186A (en) | 1977-01-21 | 1978-01-04 | Cycloalkane-carboxanilides |
Country Status (16)
| Country | Link |
|---|---|
| JP (1) | JPS5392739A (en) |
| AT (1) | AT360799B (en) |
| AU (1) | AU523765B2 (en) |
| BE (1) | BE863074A (en) |
| BR (1) | BR7800354A (en) |
| CA (1) | CA1087186A (en) |
| CH (1) | CH637917A5 (en) |
| DE (1) | DE2802282A1 (en) |
| ES (1) | ES466142A1 (en) |
| FR (1) | FR2377999A1 (en) |
| GB (1) | GB1593932A (en) |
| IT (1) | IT7819434A0 (en) |
| LU (1) | LU78907A1 (en) |
| NL (1) | NL7800656A (en) |
| PT (1) | PT67546B (en) |
| SE (1) | SE7800692L (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5781449A (en) * | 1980-11-10 | 1982-05-21 | Sumitomo Chem Co Ltd | Cyclopropanecarboxamide derivative, its preparation and herbicide containinig said derivative as active component |
| US4749812A (en) * | 1985-05-27 | 1988-06-07 | Mitsui Toatsu Chemicals, Inc. | N-(3-chloro-4-isopropylphenyl) carboxamide derivative and selective herbicide |
| DE3814505A1 (en) * | 1988-04-29 | 1989-11-09 | Bayer Ag | SUBSTITUTED CYCLOALKYL OR HETEROCYCLYL-CARBONIC ACID ANILIDE |
| GB9016579D0 (en) * | 1990-07-27 | 1990-09-12 | Ici Plc | Fungicides |
| DE4302305A1 (en) * | 1993-01-28 | 1994-08-04 | Bayer Ag | Cycloalkylcarboxylic acid anilides |
| DE4402056A1 (en) * | 1994-01-25 | 1995-07-27 | Basf Ag | p-phenylenediamine derivatives and fungicidal compositions containing them |
| GB0813403D0 (en) | 2008-07-22 | 2008-08-27 | Lectus Therapeutics Ltd | Potassium ion channel modulators & uses thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH489198A (en) * | 1967-10-19 | 1970-04-30 | Ciba Geigy | Pesticides |
| US3753679A (en) * | 1968-05-03 | 1973-08-21 | Exxon Research Engineering Co | Herbicidal s-aryl arylamides as herbicides |
-
1978
- 1978-01-04 CA CA294,281A patent/CA1087186A/en not_active Expired
- 1978-01-19 DE DE19782802282 patent/DE2802282A1/en not_active Withdrawn
- 1978-01-19 PT PT67546A patent/PT67546B/en unknown
- 1978-01-19 BE BE184445A patent/BE863074A/en not_active IP Right Cessation
- 1978-01-19 BR BR7800354A patent/BR7800354A/en unknown
- 1978-01-19 CH CH56378A patent/CH637917A5/en not_active IP Right Cessation
- 1978-01-19 LU LU78907A patent/LU78907A1/en unknown
- 1978-01-19 FR FR7801493A patent/FR2377999A1/en active Granted
- 1978-01-19 IT IT7819434A patent/IT7819434A0/en unknown
- 1978-01-19 AT AT39578A patent/AT360799B/en not_active IP Right Cessation
- 1978-01-19 GB GB2214/78A patent/GB1593932A/en not_active Expired
- 1978-01-19 ES ES466142A patent/ES466142A1/en not_active Expired
- 1978-01-19 JP JP377878A patent/JPS5392739A/en active Pending
- 1978-01-19 AU AU32543/78A patent/AU523765B2/en not_active Expired
- 1978-01-19 SE SE7800692A patent/SE7800692L/en unknown
- 1978-01-19 NL NL7800656A patent/NL7800656A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| PT67546B (en) | 1979-06-18 |
| GB1593932A (en) | 1981-07-22 |
| BR7800354A (en) | 1978-10-10 |
| DE2802282A1 (en) | 1978-07-27 |
| AU523765B2 (en) | 1982-08-12 |
| IT7819434A0 (en) | 1978-01-19 |
| AT360799B (en) | 1981-01-26 |
| JPS5392739A (en) | 1978-08-15 |
| AU3254378A (en) | 1979-07-26 |
| FR2377999B1 (en) | 1981-03-27 |
| BE863074A (en) | 1978-07-19 |
| NL7800656A (en) | 1978-07-25 |
| LU78907A1 (en) | 1978-09-28 |
| CH637917A5 (en) | 1983-08-31 |
| FR2377999A1 (en) | 1978-08-18 |
| ATA39578A (en) | 1980-06-15 |
| SE7800692L (en) | 1978-07-22 |
| ES466142A1 (en) | 1979-06-01 |
| PT67546A (en) | 1978-02-01 |
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