CA2230100A1 - Fluorobutene acid amides - Google Patents
Fluorobutene acid amides Download PDFInfo
- Publication number
- CA2230100A1 CA2230100A1 CA002230100A CA2230100A CA2230100A1 CA 2230100 A1 CA2230100 A1 CA 2230100A1 CA 002230100 A CA002230100 A CA 002230100A CA 2230100 A CA2230100 A CA 2230100A CA 2230100 A1 CA2230100 A1 CA 2230100A1
- Authority
- CA
- Canada
- Prior art keywords
- spp
- alkyl
- formula
- halogen
- compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C233/09—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to carbon atoms of an acyclic unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/40—Acylated substituent nitrogen atom
-
- 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
-
- 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
-
- 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
- A01N37/24—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 containing at least one oxygen or sulfur atom being directly attached to the same aromatic ring system
-
- 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
-
- 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
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/12—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
- C07C233/15—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
- C07C233/24—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
- C07C233/27—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/30—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by doubly-bound oxygen atoms
- C07C233/33—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by doubly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/42—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
- C07C233/44—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a carbon atom of an unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
- C07C233/53—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
- C07C233/55—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a carbon atom of an unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
- C07C255/60—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton at least one of the singly-bound nitrogen atoms being acylated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
- C07C317/38—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atom of at least one amino group being part of any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylaminosulfones
- C07C317/40—Y being a hydrogen or a carbon atom
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/14—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/36—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
- C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to new fluorobutene acid amides of formula (I), in which R1 is hydrogen or halogen; R2 is hydrogen, alkyl or phenyl optionally substituted by halogen or alkyl; R3 is one of the residues specified under a);
b); c), wherein a methylene group is optionally replaced by SO2, or one or two not directly adjacent methylene groups are replaced by oxygen, sulphur or nitrogen (which is optionally substituted by alkyl, phenyl or benzyl); or d) 5 or 6-membered hetarylalkyl optionally substituted by alkyl or by phenyl optionally substituted by halogen, alkyl, alkyl halide, alkoxy or alkoxy halide, and one to three heteroatoms from the series of oxygen, sulphur and nitrogen; or e) is benzthiazolyl or pyridyl in each case optionally substituted by halogen, alkyl or alkyl halide, wherein X, Y, Z, R4, W, n, l and m have the meaning given in the description. It also relates to a method for the preparation thereof, and the use thereof for the control of animal pests.
b); c), wherein a methylene group is optionally replaced by SO2, or one or two not directly adjacent methylene groups are replaced by oxygen, sulphur or nitrogen (which is optionally substituted by alkyl, phenyl or benzyl); or d) 5 or 6-membered hetarylalkyl optionally substituted by alkyl or by phenyl optionally substituted by halogen, alkyl, alkyl halide, alkoxy or alkoxy halide, and one to three heteroatoms from the series of oxygen, sulphur and nitrogen; or e) is benzthiazolyl or pyridyl in each case optionally substituted by halogen, alkyl or alkyl halide, wherein X, Y, Z, R4, W, n, l and m have the meaning given in the description. It also relates to a method for the preparation thereof, and the use thereof for the control of animal pests.
Description
.
It Le A 31 182-Forei~n countries / Ba/bo/S-P
i:~L~ L~3 E~ ;e J ~
- 1 - 'fE~ ~'P~Ah~l ~fl3N
orolJ.~ ..;des The present invention relates to novel fluorobutenamides, to processes for theirpreparation and to their use for controlling animal pests, in particular insects, arachnids and nematodes, encountered in agriculture, in forests, in the protection of stored 5 products and of materials, and in the hygiene sector.
WO 92/15 555 discloses that the compounds N-phenyl-3,4,4-trifluorobut-3-enamide and N-(3-carboxyphenyl)-3,4,4-trifluorobut-3-enamide have insecticidal, acaricidal and nematicidal properties. Fluorovinylcarboxamide derivatives having insecticidal and acaricidal properties are known from EP-A-O 661 289.
10 However, the efficacy and the activity spectrum of these compounds, in particular at low application rates and concentrations, are not always entirely satisfactory.
This invention, accordingly, provides novel fluorobutenamides of the formula (I) CF2=f--CH2--CoNR2R3 (I) R
in which 15 R' represents hydrogen or halogen, R2 represents hydrogen, alkyl or optionally halogen- or alkyl-substituted phenyl, R3 represents a) ~ o r ~ X
Le A 31 182-Foreign countries in which X represents amino, hydroxyl, mercapto, nitro, cyano, halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, alkylsulphonyl, halogenoalkylsulphonyl, . 5 .alkylcarbonyl, alkoxycarbonyl, alkylamino, dialkylamino, aminocarbonyl, alkylaminocarbonyl, dialkylarninocarbonyl or halogenoalkenylcarbonylamino, ~ Y and Z independently of one another each represent hydrogen, amino, hydroxyl, mercapto, cyano, carboxyl, halogen, alkyl, halogenoalkyl, - alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, alkylcarbonyl, alkoxycarbonyl, alkylamino, dialkylamino, alkylaminocarbonyl or dialkylaminocarbonyl or b) ~ I H (CH2)n~ or - I H (CH2)n'~ ~X
in which 15X and Y are each as defined above, R4 represents hydrogen or alkyl and n represents 0, 1, 2, 3 or 4 or W
c) -(C H2), ¦ ¦
(CH2)m . CA 02230100 1998-02-20 I ~- A 31 182-Foreign countries in which optionally one methylene group is replaced by SO2 or one or two non-adjacent methylene groups in the ring are replaced by oxygen, sulphur or nitrogen (which is optionally substituted by alkyl, phenyl or benzyl), 1 represents 0, 1 or 2, m represents 0, 1, 2, 3, 4 or 5 and .
W represents halogen, alkyl or optionally halogen-, alkyl-, halogenoalkyl-, alkoxy- or halogenoalkoxy-substituted phenyl or d) 5- or 6-membered hetarylalkyl having one to three hetero atoms from the group oxygen, sulphur and nitrogen and optionally substituted by halogen, alkyl or by optionally halogen-, alkyl-, halogenoalkyl-, alkoxy-or halogenoalkoxy-substituted phenyl or e) respectively optionally halogen-, alkyl- or halogenoalkyl-substituted pyridyl or benzothiazolyl.
15 The compounds of formula (I) can be present as geometrical and/or optical isomers or isomer mixtures of varying compositions, depending on the nature of the substituents.
The invention provides both the pure isomers and the isomer mixtures.
Furthermore, it has been found that the fluorobutenamides of the formula (I) areobtained when 20 amines of the formula (II) HNR2R3 (II) ~ , Le A 31 182-Foreign countries in which R2 and R3 are each as defined above, are reacted with acyl chlorides of the formula (m) CF2= C--CH2--COCI
I 1 (m) 5 in which .
R' is as defined above, if appropriate in the presence of a diluent and if appropriate in the presence of a base.
Finally, it has been found that the novel fluorobutenamides of the formula (I) have pronounced biological properties and are suitable especially for controlling animal 10 pests, in particular insects, arachnids and nematodes, encountered in agriculture, in forests, in the protection of stored products and of materials, and in the hygiene sector.
The formula (I) provides a general definition of the fluorobuten~mi~les according to the mventlon.
Preferred substituents or ranges of the radicals listed in the formulae mentioned lS hereinabove and hereinbelow are illustrated below:
R' preferably represents hydrogen, fluorine, chlorine or bromine R2 preferably represents hydrogen, C,-C~alkyl or optionally fluorine-, chlorine-, bromine- or C,-C4-alkyl-substituted phenyl.
R3 preferably represents one of the radicals mentioned under a), b), c), d) or e).
Le A 31 1~2-Foreign countries X
a) ~ or ~X
in which X represents amino, hydroxyl, mercapto, nitro, cyano, fluorine, chlorine, bromine, Cl-C6-alkyl, Cl-C4-halogenoalkyl, Cl-C6-alkoxy, Cl-C4-halogenoalkoxy, Cl-C6-alkylthio, Cl-C4-halogenoalkylthio, C,-C6-alkylsulphonyl, Cl-C4-halogenoalkylsulphonyl, Cl-C6-alkylcarbonyl, Cl-C6-alkoxycarbonyl, Cl-C6-alkylamino, di-(CI-C6-alkyl)amino, aminocarbonyl, C~-C6-alkylaminocarbonyl, di-(CI-C6-alkyl)aminocarbonyl or C2-C6-halogenoalkenylcarbonylamino and Y and Z independently of one another each represent hydrogen, amino, hydroxyl, mercapto, cyano, carboxyl, fluorine, chlorine, bromine, C,-C6-alkyl, Cl-C4-halogenoalkyl, C,-C6-alkoxy, C,-C4-halogenoalkoxy, C,-C6-alkylthio, Cl-C4-halogenoalkylthio, Cl-C6-alkylcarbonyl, Cl-C6-alkoxycarbonyl, Cl-C6-alkylamino, di-(CI-C6-alkyl)amino, Cl-C6-alkylaminocarbonyl or di-(CI-C6-alkyl)aminocarbonyl.
b) ~ I H (CH2)n~ or -CH (CH ) ~X
in which X and Y each have the meanings given above under a) as preferred in each case for these substituents, R4 represents hydrogen or Cl-C4-alkyl and i Le A 31 182-Forei~n countries n represents 0, 1 or 2.
W
-(CH2j, c (CH2)m in which optionally one methylene group is replaced by SO2 or one or two non-adjacent methylene groups are replaced by oxygen, sulphur or nitrogen (which is optionally substituted by Cl-C4-alkyl, phenyl or benzyl), represents O or 1, m represents 0, 1, 2, 3, 4 or 5 and W represents fluorine, chlorine, Cl-C6-alkyl or optionally fluorine-, chlorine-, bromine-, Cl-C4-alkyl-, Cl-C4-halogenoalkyl-, C,-C4-alkoxy- or Cl-C4-halogenoalkoxy-substituted phenyl.
d) Pyridyl-CI-C2-alkyl, furanyl-CI-C2-alkyl or thienyl-CI-Cz-alkyl, each of which is optionally substituted by fluorine, chlorine, bromine, Cl-C4-alkyl or by optionally fluorine-, chlorine-, Cl-C4-alkyl-, Cl-C4-halogenoalkyl-, Cl-C4-alkoxy-or Cl-C4-halogenoalkoxy-substituted phenyl.
IS e) Respectively optionally fluorine-, chlorine-, bromine-, Cl-C4-alkyl- or C,-C4-halogenoalkyl-substituted pyridyl or benzothiazolyl.
R' particularly preferably represents hydrogen or fluorine.
R2 particularly preferably represents hydrogen or C,-C4-alkyl.
R3 particularly preferably represents one of the radicals mentioned under a), b), c), Le A 31 182-Foreign countries d) or e).
a) ~ or ~X
in which X represents mercapto, nitro, cyano, fluorine, chlorine, bromine, Cl-C4-alkoxy, S Cl-C4-halogenoalkoxy, Cl-C4-alkylthio, Cl-C4-alkylsulphonyl, C,-C2-halogenoalkylsulphonyl, Cl-C4-alkylcarbonyl, C,-C4-alkylamino, di-(CI-C4-alkyl)amino, aminocarbonyl or C3-Cs-halogenoalkenylcarbonylamino and Y and Z independently of one another each represent hydrogen, fluorine, chlorine, carboxyl, Cl-C4-alkyl, Cl-C4-halogenoalkyl, Cl-C2-alkylcarbonyl or C~-C4-1 0 alkoxycarbonyl.
b) -CH ~X
in which X' represents fluorine, chlorine or C,-C4-alkyl and R4 represents hydrogen, methyl or ethyl.
-(CH2), 15 c) (CH2)m Le A 31 182-Foreign countries in which for m ~ O optionally one methylene group is replaced by SO2, oxygen, sulphur or nitrogen (which is optionally substituted by Cl-C4-alkyl or benzyl), represents O or 1 and m represents 0, 2 or 3.
S d) Furanylmethyl or pyridylmethyl, each of which is optionally substituted by fluorine, chlorine, methyl, ethyl or by optionally fluorine-, chlorine- or methyl-substituted phenyl.
e) Respectively optionally fluorine-, chlorine-, methyl-, ethyl- or trifluoromethyl-substituted pyridyl or benzothiazolyl.
10 Rl very particularly preferably represents fluorine.
R2 very particularly preferably represents hydrogen or methyl.
R3 very particularly preferably represents one of the radicals mentioned under a), b), c), d) or e).
a) ~ or = X
15 in which X represents nitro, cyano, fluorine, chlorine, bromine, methoxy, trifluoromethoxy, methylthio, methylsulphonyl, ethylsulphonyl, trifluoromethylsulphonyl, methylcarbonyl, aminocarbonyl or 3,4,4-trifluorobut-3-en-1-yl-carbonylamino, Le A 31 182-Foreign countries g Y and Z independently of one another each represent hydrogen, fluorine, chlorine, carboxyl, methyl, ethyl, n-propyl, isopropyl or trifluoromethyl.
f ~x1 in which S Xl represents chlorine and R4 represents hydrogen or methyl.
c~ 2 d) -CH2~3 or -CH2-~CI -~, ~N ~CI or ~/ ~
10 A most particularly preferred group of compounds are those compounds of the formula (I) in which R3 represents one of the radicals listed under a).
A further most particularly preferred group of compounds are those compounds of the formula (I) in which R3 represents one of the radicals listed under b).
Le ~ 31 182-Foreign countries Also most particularly pl~relL~d are compounds of the formula (I) in which R3 represents one of the radicals listed under c).
The abovementioned general or preferred radical definitions or illustrations apply to the end products and, correspondingly, to the starting m~t~ and intermediates. These5 radical definitions can be combined with one another as desired, that is to say combinations between the respective plefe~led ranges are also possible.
Preference according to the invention is given to those compounds of the formula (I) which contain a combination of the definitions listed above as being preferred (preferable).
10 Particular preference according to the invention is given to those compounds of the formula (I) which contain a combination of the definitions listed above as beingparticularly preferred.
Very particular preference according to the invention is given to those compounds of the formula (I) which contain a combination of the definitions listed above as being 15 very particularly preferred.
In the radical definitions mentioned hereinabove and hereinbelow, hydrocarbon radicals such as alkyl or alkenyl are - including in combination with hetero atoms such as alkoxy or alkylthio - straight-chain or branched as far as this is possible.
Using, for example, 3,4,4-trifluorobut-3-enoyl chloride and 4-bromoaniline as starting 20 materials for preparing compounds of the formula (I), the course of the reaction can be illustrated by the following scheme:
Le A 31 182-Foreign countries CF2=CF-CH2-COCI + H2N~Br CF2=CF-CH2-CO-NH ~Br The process for preparing compounds of the formula (I) described above is characterized in that amines of the formula (II) are reacted with acyl chlorides of the formula (m), if appl~pliate in the presence of a diluent and if a~pr~,pl;ate in the 5 presence of a base.
The process according to the invention is preferably carried out in the presence of a diluent.
Suitable diluents are in particular organic solvents, for example optionally chlorinated aliphatic or aromatic hydrocarbons such as cyclohexane, toluene, xylene, 10 dichloromethane, dichloroethane, chloroform or chlorobenzene, ethers such as diethyl ether, dioxane or tetrahydrofuran or nitriles such as acetonitrile.
Suitable diluents are also two-phase systems consisting of water and an organic solvent, for example water/methylene chloride or water/toluene.
It is also possible to employ an excess of the amine of the formula (II) as diluent.
15 In principle, suitable bases are all organic or inorganic bases suitable for such acylation reactions.
Preference is given to using amines, in particular tertiary amines such as triethylamine, diazabicycloundecene (DBU), diazabicyclononene (DBN), diazabicyclooctane (DABCO) or pyridine or alkali metal or alkaline earth metal carbonates, bicarbonates 20 or oxides. Examples include sodium carbonate, potassium carbonate, sodium bicarbonate and calcium oxide.
Le A 31 182-Foreign countries The reaction l~n~eldLul~ may be varied over a relatively wide range. In general,temperatures between -20~C and 140~C, preferably between 0~C and 60~C, are employed.
The molar ratio of the compound of the formula (II) to the compound of the formula 5 (III) is generally 2:1 to 1:2.
The reaction is generally carried out at a pressure from 0.5 to 6 bar, but preferably under atmospheric pressure.
.
For work-up, the reaction mixture is, for example, hydrolysed, the product is extracted with an organic solvent such as ethyl acetate, dichloromethane or toluene and the 10 organic phase is then concentrated.
The amines of the formula (II) required as starting materials are known and/or can be prepared in a simple manner by known methods.
The acyl chlorides of the formula (m) required as starting materials are known (see for example US-5 389 680 and EP-432 861).
15 The compounds of the forrnula (I) can also be prepared by reacting amines of the formula (II) with carboxylic acids of the forrnula (IV) CF2=C-CH2-COOH
1 1 (IV) in which Rl is as defined above, 20 in the presence of a reactive auxiliary such as dicyclohexylcarbodiimide or carbonylbisimidazole in the presence of a diluent such as tetrahydrofuran, methylene Ee A 31 182-Foreign countries chloride or acetonitrile (cf. Houben-Weyl, Methoden der Organischen Chemie, Volume E5, p. 941 ff (1985)).
The active compounds are suitable for controlling animal pests, in particular insects, arachnids and nematodes, encountered in agriculture, in forests, in the protection of 5 stored products and of materials, and in the hygiene sector. They can preferably be employed as crop protection agents. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:
From the order of the Isopoda, for example, Oniscus asellus, Armadillidium vulgare 10 and Porcellio scaber.
From the order of the Diplopoda, for example, Blaniulus guttulatus.
From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec.
From the order of the Symphyla, for example, Scutigerella immaculata.
15 From the order of the Thysanura, for example, Lepisma saccharina.
From the order of the Collembola, for example, Onychiurus armatus.
From the order of the Orthoptera, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria.
20 From the order of the Dermaptera, for example, Forficula auricularia.
From the order of the Isoptera, for example, Reticulitermes spp.
I,e A 31 182-Foreign countries From the order of the Anoplura, for example, Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.
From the order of the Mallophaga, for example, Trichodectes spp. and D~m~line~ spp.
From the order of the Thysanoptera, for example, Hercinothrips femoralis and Thrips 5 tabaci.
From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.
From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, 10 Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arlln~lini.~, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.
15 From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella,Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis 20 flammea, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona m~gn~nim~
and Tortrix viridana.
25 From the order of the Coleoptera, for example, Anobium punct~t-lm, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica y ~ .
Le A 31 182-Foreign countries alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., 5 Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp.,Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica.
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., 10 Lasius spp., Monomorium pharaonis and Vespa spp.
From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus,15 Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa.
From the order of the Siphonaptera, for example, Xenopsylla cheopis, Ceratophyllus spp. and Ctenocephalides felis.
From the order of the Arachnida, for example, Scorpio maurus and Latrodectus 20 mactans.
From the order of the Acarina, for example, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp.
25 and Tetranychus spp.
The phytoparasitic nematodes include, for example, Pratylenchus spp., Radopholus T~. A 31 182-Foreign countries similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp. andTrichodorus spp.
The compounds of the formula (I) according to the invention in particular have 5 outstanding nematicidal activity, for example against Meloidogyne incognita, and very good acaricidal activity, for example against the common spider mite (Tetranychus urticae).
They act systemically and can be applied via the leaves.
.
In addition, they have foliar insecticidal activity and activity against Pyricularia oryzae 10 in rice.
The active compounds can be converted to the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound and very fine capsules in polymeric substances.
lS These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, if applup,iate with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. Essentially, the following are suitable liquid solvents:
20 aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl 25 isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and water.
Le A 31 182-Foreign countries Suitable solid carriers are:
for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for 5 granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, 10 polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and 15 polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo 20 dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
The active compound according to the invention can be present in its commercially 25 available formulations and in the use forms, prepared from these formulations, as a mixture with other active compounds, such as insecticides, attractants, sterilizing agents, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphates, carbamates, Le A 31 182-Foreign countries carboxylates, chlorinated hydrocarbons, phenylureas and substances produced by microorg~ni~m~, inter alia.
Examples of particularly advantageous mixing components are the following:
Fungicides:
It Le A 31 182-Forei~n countries / Ba/bo/S-P
i:~L~ L~3 E~ ;e J ~
- 1 - 'fE~ ~'P~Ah~l ~fl3N
orolJ.~ ..;des The present invention relates to novel fluorobutenamides, to processes for theirpreparation and to their use for controlling animal pests, in particular insects, arachnids and nematodes, encountered in agriculture, in forests, in the protection of stored 5 products and of materials, and in the hygiene sector.
WO 92/15 555 discloses that the compounds N-phenyl-3,4,4-trifluorobut-3-enamide and N-(3-carboxyphenyl)-3,4,4-trifluorobut-3-enamide have insecticidal, acaricidal and nematicidal properties. Fluorovinylcarboxamide derivatives having insecticidal and acaricidal properties are known from EP-A-O 661 289.
10 However, the efficacy and the activity spectrum of these compounds, in particular at low application rates and concentrations, are not always entirely satisfactory.
This invention, accordingly, provides novel fluorobutenamides of the formula (I) CF2=f--CH2--CoNR2R3 (I) R
in which 15 R' represents hydrogen or halogen, R2 represents hydrogen, alkyl or optionally halogen- or alkyl-substituted phenyl, R3 represents a) ~ o r ~ X
Le A 31 182-Foreign countries in which X represents amino, hydroxyl, mercapto, nitro, cyano, halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, alkylsulphonyl, halogenoalkylsulphonyl, . 5 .alkylcarbonyl, alkoxycarbonyl, alkylamino, dialkylamino, aminocarbonyl, alkylaminocarbonyl, dialkylarninocarbonyl or halogenoalkenylcarbonylamino, ~ Y and Z independently of one another each represent hydrogen, amino, hydroxyl, mercapto, cyano, carboxyl, halogen, alkyl, halogenoalkyl, - alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, alkylcarbonyl, alkoxycarbonyl, alkylamino, dialkylamino, alkylaminocarbonyl or dialkylaminocarbonyl or b) ~ I H (CH2)n~ or - I H (CH2)n'~ ~X
in which 15X and Y are each as defined above, R4 represents hydrogen or alkyl and n represents 0, 1, 2, 3 or 4 or W
c) -(C H2), ¦ ¦
(CH2)m . CA 02230100 1998-02-20 I ~- A 31 182-Foreign countries in which optionally one methylene group is replaced by SO2 or one or two non-adjacent methylene groups in the ring are replaced by oxygen, sulphur or nitrogen (which is optionally substituted by alkyl, phenyl or benzyl), 1 represents 0, 1 or 2, m represents 0, 1, 2, 3, 4 or 5 and .
W represents halogen, alkyl or optionally halogen-, alkyl-, halogenoalkyl-, alkoxy- or halogenoalkoxy-substituted phenyl or d) 5- or 6-membered hetarylalkyl having one to three hetero atoms from the group oxygen, sulphur and nitrogen and optionally substituted by halogen, alkyl or by optionally halogen-, alkyl-, halogenoalkyl-, alkoxy-or halogenoalkoxy-substituted phenyl or e) respectively optionally halogen-, alkyl- or halogenoalkyl-substituted pyridyl or benzothiazolyl.
15 The compounds of formula (I) can be present as geometrical and/or optical isomers or isomer mixtures of varying compositions, depending on the nature of the substituents.
The invention provides both the pure isomers and the isomer mixtures.
Furthermore, it has been found that the fluorobutenamides of the formula (I) areobtained when 20 amines of the formula (II) HNR2R3 (II) ~ , Le A 31 182-Foreign countries in which R2 and R3 are each as defined above, are reacted with acyl chlorides of the formula (m) CF2= C--CH2--COCI
I 1 (m) 5 in which .
R' is as defined above, if appropriate in the presence of a diluent and if appropriate in the presence of a base.
Finally, it has been found that the novel fluorobutenamides of the formula (I) have pronounced biological properties and are suitable especially for controlling animal 10 pests, in particular insects, arachnids and nematodes, encountered in agriculture, in forests, in the protection of stored products and of materials, and in the hygiene sector.
The formula (I) provides a general definition of the fluorobuten~mi~les according to the mventlon.
Preferred substituents or ranges of the radicals listed in the formulae mentioned lS hereinabove and hereinbelow are illustrated below:
R' preferably represents hydrogen, fluorine, chlorine or bromine R2 preferably represents hydrogen, C,-C~alkyl or optionally fluorine-, chlorine-, bromine- or C,-C4-alkyl-substituted phenyl.
R3 preferably represents one of the radicals mentioned under a), b), c), d) or e).
Le A 31 1~2-Foreign countries X
a) ~ or ~X
in which X represents amino, hydroxyl, mercapto, nitro, cyano, fluorine, chlorine, bromine, Cl-C6-alkyl, Cl-C4-halogenoalkyl, Cl-C6-alkoxy, Cl-C4-halogenoalkoxy, Cl-C6-alkylthio, Cl-C4-halogenoalkylthio, C,-C6-alkylsulphonyl, Cl-C4-halogenoalkylsulphonyl, Cl-C6-alkylcarbonyl, Cl-C6-alkoxycarbonyl, Cl-C6-alkylamino, di-(CI-C6-alkyl)amino, aminocarbonyl, C~-C6-alkylaminocarbonyl, di-(CI-C6-alkyl)aminocarbonyl or C2-C6-halogenoalkenylcarbonylamino and Y and Z independently of one another each represent hydrogen, amino, hydroxyl, mercapto, cyano, carboxyl, fluorine, chlorine, bromine, C,-C6-alkyl, Cl-C4-halogenoalkyl, C,-C6-alkoxy, C,-C4-halogenoalkoxy, C,-C6-alkylthio, Cl-C4-halogenoalkylthio, Cl-C6-alkylcarbonyl, Cl-C6-alkoxycarbonyl, Cl-C6-alkylamino, di-(CI-C6-alkyl)amino, Cl-C6-alkylaminocarbonyl or di-(CI-C6-alkyl)aminocarbonyl.
b) ~ I H (CH2)n~ or -CH (CH ) ~X
in which X and Y each have the meanings given above under a) as preferred in each case for these substituents, R4 represents hydrogen or Cl-C4-alkyl and i Le A 31 182-Forei~n countries n represents 0, 1 or 2.
W
-(CH2j, c (CH2)m in which optionally one methylene group is replaced by SO2 or one or two non-adjacent methylene groups are replaced by oxygen, sulphur or nitrogen (which is optionally substituted by Cl-C4-alkyl, phenyl or benzyl), represents O or 1, m represents 0, 1, 2, 3, 4 or 5 and W represents fluorine, chlorine, Cl-C6-alkyl or optionally fluorine-, chlorine-, bromine-, Cl-C4-alkyl-, Cl-C4-halogenoalkyl-, C,-C4-alkoxy- or Cl-C4-halogenoalkoxy-substituted phenyl.
d) Pyridyl-CI-C2-alkyl, furanyl-CI-C2-alkyl or thienyl-CI-Cz-alkyl, each of which is optionally substituted by fluorine, chlorine, bromine, Cl-C4-alkyl or by optionally fluorine-, chlorine-, Cl-C4-alkyl-, Cl-C4-halogenoalkyl-, Cl-C4-alkoxy-or Cl-C4-halogenoalkoxy-substituted phenyl.
IS e) Respectively optionally fluorine-, chlorine-, bromine-, Cl-C4-alkyl- or C,-C4-halogenoalkyl-substituted pyridyl or benzothiazolyl.
R' particularly preferably represents hydrogen or fluorine.
R2 particularly preferably represents hydrogen or C,-C4-alkyl.
R3 particularly preferably represents one of the radicals mentioned under a), b), c), Le A 31 182-Foreign countries d) or e).
a) ~ or ~X
in which X represents mercapto, nitro, cyano, fluorine, chlorine, bromine, Cl-C4-alkoxy, S Cl-C4-halogenoalkoxy, Cl-C4-alkylthio, Cl-C4-alkylsulphonyl, C,-C2-halogenoalkylsulphonyl, Cl-C4-alkylcarbonyl, C,-C4-alkylamino, di-(CI-C4-alkyl)amino, aminocarbonyl or C3-Cs-halogenoalkenylcarbonylamino and Y and Z independently of one another each represent hydrogen, fluorine, chlorine, carboxyl, Cl-C4-alkyl, Cl-C4-halogenoalkyl, Cl-C2-alkylcarbonyl or C~-C4-1 0 alkoxycarbonyl.
b) -CH ~X
in which X' represents fluorine, chlorine or C,-C4-alkyl and R4 represents hydrogen, methyl or ethyl.
-(CH2), 15 c) (CH2)m Le A 31 182-Foreign countries in which for m ~ O optionally one methylene group is replaced by SO2, oxygen, sulphur or nitrogen (which is optionally substituted by Cl-C4-alkyl or benzyl), represents O or 1 and m represents 0, 2 or 3.
S d) Furanylmethyl or pyridylmethyl, each of which is optionally substituted by fluorine, chlorine, methyl, ethyl or by optionally fluorine-, chlorine- or methyl-substituted phenyl.
e) Respectively optionally fluorine-, chlorine-, methyl-, ethyl- or trifluoromethyl-substituted pyridyl or benzothiazolyl.
10 Rl very particularly preferably represents fluorine.
R2 very particularly preferably represents hydrogen or methyl.
R3 very particularly preferably represents one of the radicals mentioned under a), b), c), d) or e).
a) ~ or = X
15 in which X represents nitro, cyano, fluorine, chlorine, bromine, methoxy, trifluoromethoxy, methylthio, methylsulphonyl, ethylsulphonyl, trifluoromethylsulphonyl, methylcarbonyl, aminocarbonyl or 3,4,4-trifluorobut-3-en-1-yl-carbonylamino, Le A 31 182-Foreign countries g Y and Z independently of one another each represent hydrogen, fluorine, chlorine, carboxyl, methyl, ethyl, n-propyl, isopropyl or trifluoromethyl.
f ~x1 in which S Xl represents chlorine and R4 represents hydrogen or methyl.
c~ 2 d) -CH2~3 or -CH2-~CI -~, ~N ~CI or ~/ ~
10 A most particularly preferred group of compounds are those compounds of the formula (I) in which R3 represents one of the radicals listed under a).
A further most particularly preferred group of compounds are those compounds of the formula (I) in which R3 represents one of the radicals listed under b).
Le ~ 31 182-Foreign countries Also most particularly pl~relL~d are compounds of the formula (I) in which R3 represents one of the radicals listed under c).
The abovementioned general or preferred radical definitions or illustrations apply to the end products and, correspondingly, to the starting m~t~ and intermediates. These5 radical definitions can be combined with one another as desired, that is to say combinations between the respective plefe~led ranges are also possible.
Preference according to the invention is given to those compounds of the formula (I) which contain a combination of the definitions listed above as being preferred (preferable).
10 Particular preference according to the invention is given to those compounds of the formula (I) which contain a combination of the definitions listed above as beingparticularly preferred.
Very particular preference according to the invention is given to those compounds of the formula (I) which contain a combination of the definitions listed above as being 15 very particularly preferred.
In the radical definitions mentioned hereinabove and hereinbelow, hydrocarbon radicals such as alkyl or alkenyl are - including in combination with hetero atoms such as alkoxy or alkylthio - straight-chain or branched as far as this is possible.
Using, for example, 3,4,4-trifluorobut-3-enoyl chloride and 4-bromoaniline as starting 20 materials for preparing compounds of the formula (I), the course of the reaction can be illustrated by the following scheme:
Le A 31 182-Foreign countries CF2=CF-CH2-COCI + H2N~Br CF2=CF-CH2-CO-NH ~Br The process for preparing compounds of the formula (I) described above is characterized in that amines of the formula (II) are reacted with acyl chlorides of the formula (m), if appl~pliate in the presence of a diluent and if a~pr~,pl;ate in the 5 presence of a base.
The process according to the invention is preferably carried out in the presence of a diluent.
Suitable diluents are in particular organic solvents, for example optionally chlorinated aliphatic or aromatic hydrocarbons such as cyclohexane, toluene, xylene, 10 dichloromethane, dichloroethane, chloroform or chlorobenzene, ethers such as diethyl ether, dioxane or tetrahydrofuran or nitriles such as acetonitrile.
Suitable diluents are also two-phase systems consisting of water and an organic solvent, for example water/methylene chloride or water/toluene.
It is also possible to employ an excess of the amine of the formula (II) as diluent.
15 In principle, suitable bases are all organic or inorganic bases suitable for such acylation reactions.
Preference is given to using amines, in particular tertiary amines such as triethylamine, diazabicycloundecene (DBU), diazabicyclononene (DBN), diazabicyclooctane (DABCO) or pyridine or alkali metal or alkaline earth metal carbonates, bicarbonates 20 or oxides. Examples include sodium carbonate, potassium carbonate, sodium bicarbonate and calcium oxide.
Le A 31 182-Foreign countries The reaction l~n~eldLul~ may be varied over a relatively wide range. In general,temperatures between -20~C and 140~C, preferably between 0~C and 60~C, are employed.
The molar ratio of the compound of the formula (II) to the compound of the formula 5 (III) is generally 2:1 to 1:2.
The reaction is generally carried out at a pressure from 0.5 to 6 bar, but preferably under atmospheric pressure.
.
For work-up, the reaction mixture is, for example, hydrolysed, the product is extracted with an organic solvent such as ethyl acetate, dichloromethane or toluene and the 10 organic phase is then concentrated.
The amines of the formula (II) required as starting materials are known and/or can be prepared in a simple manner by known methods.
The acyl chlorides of the formula (m) required as starting materials are known (see for example US-5 389 680 and EP-432 861).
15 The compounds of the forrnula (I) can also be prepared by reacting amines of the formula (II) with carboxylic acids of the forrnula (IV) CF2=C-CH2-COOH
1 1 (IV) in which Rl is as defined above, 20 in the presence of a reactive auxiliary such as dicyclohexylcarbodiimide or carbonylbisimidazole in the presence of a diluent such as tetrahydrofuran, methylene Ee A 31 182-Foreign countries chloride or acetonitrile (cf. Houben-Weyl, Methoden der Organischen Chemie, Volume E5, p. 941 ff (1985)).
The active compounds are suitable for controlling animal pests, in particular insects, arachnids and nematodes, encountered in agriculture, in forests, in the protection of 5 stored products and of materials, and in the hygiene sector. They can preferably be employed as crop protection agents. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:
From the order of the Isopoda, for example, Oniscus asellus, Armadillidium vulgare 10 and Porcellio scaber.
From the order of the Diplopoda, for example, Blaniulus guttulatus.
From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec.
From the order of the Symphyla, for example, Scutigerella immaculata.
15 From the order of the Thysanura, for example, Lepisma saccharina.
From the order of the Collembola, for example, Onychiurus armatus.
From the order of the Orthoptera, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria.
20 From the order of the Dermaptera, for example, Forficula auricularia.
From the order of the Isoptera, for example, Reticulitermes spp.
I,e A 31 182-Foreign countries From the order of the Anoplura, for example, Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.
From the order of the Mallophaga, for example, Trichodectes spp. and D~m~line~ spp.
From the order of the Thysanoptera, for example, Hercinothrips femoralis and Thrips 5 tabaci.
From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.
From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, 10 Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arlln~lini.~, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.
15 From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella,Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis 20 flammea, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona m~gn~nim~
and Tortrix viridana.
25 From the order of the Coleoptera, for example, Anobium punct~t-lm, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica y ~ .
Le A 31 182-Foreign countries alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., 5 Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp.,Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica.
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., 10 Lasius spp., Monomorium pharaonis and Vespa spp.
From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus,15 Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa.
From the order of the Siphonaptera, for example, Xenopsylla cheopis, Ceratophyllus spp. and Ctenocephalides felis.
From the order of the Arachnida, for example, Scorpio maurus and Latrodectus 20 mactans.
From the order of the Acarina, for example, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp.
25 and Tetranychus spp.
The phytoparasitic nematodes include, for example, Pratylenchus spp., Radopholus T~. A 31 182-Foreign countries similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp. andTrichodorus spp.
The compounds of the formula (I) according to the invention in particular have 5 outstanding nematicidal activity, for example against Meloidogyne incognita, and very good acaricidal activity, for example against the common spider mite (Tetranychus urticae).
They act systemically and can be applied via the leaves.
.
In addition, they have foliar insecticidal activity and activity against Pyricularia oryzae 10 in rice.
The active compounds can be converted to the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound and very fine capsules in polymeric substances.
lS These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, if applup,iate with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. Essentially, the following are suitable liquid solvents:
20 aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl 25 isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and water.
Le A 31 182-Foreign countries Suitable solid carriers are:
for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for 5 granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, 10 polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and 15 polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo 20 dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
The active compound according to the invention can be present in its commercially 25 available formulations and in the use forms, prepared from these formulations, as a mixture with other active compounds, such as insecticides, attractants, sterilizing agents, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphates, carbamates, Le A 31 182-Foreign countries carboxylates, chlorinated hydrocarbons, phenylureas and substances produced by microorg~ni~m~, inter alia.
Examples of particularly advantageous mixing components are the following:
Fungicides:
2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazole-5-carboxanilide; 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide; (E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide; 8-hydroxyquinoline sulphate; methyl (E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl } -3-methoxyacrylate; methyl (E)-methoximino[alpha-(o-10 tolyloxy)-o-tolyl]acetate; 2-phenylphenol (OPP), aldimorph, alllplupylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate, calcium polysulphide, captafol, captan, carbendazim, carboxin, quinomethionate, 15 chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cypro-conazole, cyprofuram, dichlorophen, diclobutrazol, diclofluanid, diclomezine, dicloran, diethofencarb,difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolon, 20 edifenphos, epoxyconazole, ethirimol, etridiazole, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, flu:~7.in~m,fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox, 25 guazatine, hexachlorobenzene, hexaconazole, hymexazol, im~7.~1il, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione, isoprothiolane, kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture, 30 mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, Le A 31 182-Foreign countries methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazole, pencycuron, phosdiphen, phth~ le, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrim~th~nil, pyroquilon, quintozene (PCNB), sulphur and sulphur preparations, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thicyofen, 10 thiophanate-methyl, thiram, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, validamycin A, vinclozolin, zineb, ziram.
Bactericides: .
15 bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
Insecticides/Acaricides/Nematicides:
abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin,20 amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin, Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarboxim, butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, CGA 157419, 25 CGA 184699, chloethocarb, chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton M, demeton S, demeton-~-methyl, diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubell~ul~ll, dimethoate, 30 dimethylvinphos, dioxathion, disulfoton, Le A 31 182-Foreign countries edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox, ethoprophos, etrimfos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, S flll~7.in~n, flucycloxuron, flucythrin~t~--, flufenoxuron, flufenprox, fluvalinate, fonofos, formothion, fosthi~7~t~7 fubfenprox, furathiocarb, HCH, heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos, isazofos, isofenphos, isoprocarb, isoxathion, ivermectin, lambda-cyhalothrin, lufenuron, malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled, NC 184, NI 25, nitenpyram, omethoate, oxamyl, oxydemeton M, oxydeprofos, parathion A, parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozine, pyrachlofos,pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxyfen, quinalphos, RH 5992, salithion, sebufos, silafluofen, sulfotep, sulprofos, tebufenozide, tebufenpyrad, tebupirimifos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin, triarathene, triazophos, triazuron, trichlorfon, triflumuron, trimethacarb, vamidothion, XMC, xylylcarb, YI 5301 / 5302, zetamethrin.
A mixture with other known active compounds, such as herbicides, or with fertilizers and growth-regulators is also possible.
The active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these Le A 31 182-Foreign countries formulations, as a mixture with synergists. Synergists are compounds which increase the action of the active compounds, without it being necessary for the synergist added to be active itself.
The active compound content of the use forms prepared from the commercially 5 available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.
The compounds are employed in a customary manner appropriate for the use forms.
When used against hygiene and stored-product pests, the active compound has excellent 10 residual action on wood and clay and good stability to alkali on limed substrates.
The active compounds according to the inven~ion are not only active against plant, hygiene and stored-product pests, but also, in the veterinary medicine sector, against animal parasites (ectoparasites), such as ixodid ticks, argasid ticks, scab mites, trombiculid mites, flies (stinging and sucking), parasitic fly larvae, lice, hair lice, bird 15 lice and fleas. These parasites include:
From the order of the Anoplurida, for example, ~f mzltopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.
From the order of the Mallophagida and the sub-orders Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., 20 Werneckiella spp., Lepikentron spp., D~m~lin~ spp., Trichodectes spp. and Felicola spp.
From the order of the Diptera and the sub-orders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp.,Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca 25 spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Le A 31 182-Forei~n countries Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.
From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., 5 Xenopsylla spp. and Ceratophyllus spp.
From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp.
10 From the sub-class of the Acaria (Acarida) and the orders of the Meta- and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.
15 From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), forexample, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp.,Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., 20 Cytodites spp. and Laminosioptes spp.
For example, they have an outstanding activity against Boophilus microplus and Lucilia cuprina.
The active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which attack agricultural livestock, such as, for example, 25 cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, Lç A 31 182-Foreign countries ducks, geese, honey bees, other domestic ~nim~l.s, such as, for example, dogs, cats, caged birds, aquarium fish, and so-called experimental ~nim~ls, such as, for example, hamsters, guinea-pigs, rats and mice. By controlling these arthropods, it is intended to reduce mortality and decreased performances (in meat, milk, wool, hides, eggs, honey 5 and the like), so that more economical and simpler animal keeping is possible by using the active compounds according to the invention.
In the veterinary sector, the active compounds according to the invention are used in a known manner by enteral ~-lmini.stration, for example in the form of tablets, capsules, drinks, drenches, granules, pastes, boluses, the feed-through method, suppositories, by 10 parenteral ~-lministration, such as, for example, by means of injections (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal ~clministration, by dermal a~ministration, for example in the form of dipping orbathing, spraying, pouring-on and spotting-on, washing, dusting, and with the aid of shaped articles which comprise active compound, such as collars, ear tags, tail marks, 15 limb bands, halters, marking devices and the like.
When ~lmini.stered to livestock, poultry, domestic animals and the like, the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowables) which comprise the active compounds in an amount of 1 to 80%
by weight, directly or after dilution by a factor of 100 to 10 000, or they may be used 20 in the form of a chemical bath.
The preparation and the use of the active compounds according to the invention are illustrated by the examples below.
L~ A 31 1~2-Foreign countries ~dtiOn ~,Y~rnrles ~,Y~ ple 1 CF2=CF-CH2-CONH~CI
With ice-cooling and stirring, 23.8 g (0.15 mol) of 3,4,4-trifluorobut-3-enoyl chloride 5 dissolved in 40~ml of dichloromethane are added dropwise to a solution of 19.1 g (0.15 mol) of 4-chloroaniline in 200 ml of dichloromethane and 15.2 g (0.15 mol) of triethylamine. The mixture is stirred at 20~C for 3 hours, water is then added and the organic phase is separated off, washed with dilute hydrochloric acid and then with water. The organic phase is concentrated under reduced pressure and the residue is 10 stirred with petroleum ether, filtered off with suction and dried. 29.5 g of N-(4-chlorophenyl)-3,4,4-trifluorobutene-3-carboxamide of m.p.: 124~C are obtained.
Similarly and/or according to the general preparation procedures, the following compounds of the formula (I) are obtained:
CF2=C--CH2--CoNR2R3 R1 (I) Ex. R' R2 R3 physic. constant No.
2 F H ~\~ m.p.: 179~C
Lc A 31 182-Foreign countries Ex. Rl R2 R3 physic. constant No.
Cl 3 F H ~CF3 log p* (pH 2) = 3.04 Cl 4 F H ~ m.p.: 135~C
HNCOCH2CF=CF2 F H ~ m.p.: 200-202~C
HO
6 F H ~ m.p.: 118-120~C
~ .
Cl 7 F H ~--Cl m.p.: 78-80~C
8 F H ~CH3 m.p.: 140-142~C
Le A 31 182-Foreign countries Ex. Rl R2 R3 physic. constant No.
9 F H ~-CI m.p.: 119-122~C
F H ~C(CH3)3 m p. 105-107~C
11 F H --~CF3 m.p.: 118-120~C
12 F H ~ m.p.: 104-106~C
13 F H ~cl m.p.: 118~C
14 F H ~cl m.p.: 142-144~C
. CA 02230100 1998-02-20 Le A 31 182-~oreign countries . - 27 -Ex. Rl R2 R3 physic. constant No.
F H ~ Cl m.p.: 110-112~C
16 F H ~ OCH3 m.p.: 117-119~C
17 F H ~ ~ F m-p: 71-74~C
18 F H ~ m.p.: 115-117~C
19 F H ~ Br m.p.:137-139~C
F H ~ OCH3 m.p.: 88-90~C
21 F H ~ COCH3 m p.: 142-144~C
Le A 31 182-Foreign countries - 28 -Ex. Rl R2 R3 physic. constant No. Cl 22 F CH3 ~CI m.p.: 46-48~C
23 F CH3 ~CH3 log p* (pH 2) = 2.69 24 F H -CH2~ Cl m.p.: 125- 127~C
F H -CH(CH3)~ m.p.: 80~C
26 F H {~> m.p.: 102-104~C
27 F H ~ m.p.: 60-62~C
28 F H 'h m.p.: 132-134~C
29 F H ~ m.p.: 65-66~C
Le A 31 182-Foreign countries Ex. Rl R2 R3 physic. constant No.
HOOC
F H >~\ m.p.: 189-190~C
31 F H ~NO2 m.p.: 184-186~C
32 F H ~ m.p.: 138-139~C
~.
33 F H ~ m.p.: 73-75~C
34 F H ~\ m.p.: 122-124~C
CH(CH3)2 F H ~\ m.p.: 230-232~C
~Y
CH(CH3)2 . CA 02230100 1998-02-20 . ~
Le A 31 182-Foreign countnes Ex. Rl R2 . R3 physic. constant No.
HOOC
36 F H ~ m.p.: 208-209~C
Cl 37 F H ~ m.p.: 162-163~C
~Y
Cl HOOC
38 F H ~ m.p.: 176-178~C
39 F H ~ m.p.: 127-128~C
(cH3)3c F H ~ m.p.: 120-122~C
~ Cl T~ A 31 182-Foreign countries - 31 -Ex. Rl R2 R3 physic. constant No.
(CH3)3c 41 F H ~ m.p.: 209-210~C
NC
42 F H _~ m.p.: 118-120~C
43 F H ~COOC2Hs m p 129-132~C
44 F H -CH2--~ m.p.: 63-65~C
F H -CH2--~ m.p.: 50~C
46 F H ~OCF3 m.p.: 120~C
47 F ~--OH m.p.: 120-122~C
, ~
Le ~ 31 182-Foreign countries - 32 -Ex. Rl R~ R3 physic. constant No.
Cl Cl 48 F H ~OH m.p.: 146~C
HO
49 F H ~ m.p.: 176~C
~y F H ~SCH3 m.p.: 124~C
~=N
51 F H -CH2~CI m.p.: 100~C
52 F H ~OH m.p.: 174~C
Cl 53 F H ~SO2CH3 m p.: 180~C
54 F H _ CN--CH2~ m.p.: 128-130~C
Le ~ 31 182-Foreign countries Ex. Rl R2 R3 physic. constant No.
56 F H ~CI m.p.: 104~C
57 F H N ~ m.p.: 220-222~C
~/~ .
58 F H -~OCH3 m.p.: 120~C
*log p: Logarithm to base ten of the n-octanollwater partition coefficient, determined by reversed phase HPLC analysis using H2O/CH3CN.
Le A 31 182-Foreign countries Use F,Y~mrles Fx~Tnrle A
Critical concentration test / nematodes Test nematode: Meloidogyne incognita Solvent: 4 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of activecompound is mixed with the stated amount of solvent, the stated amount of emulsifler is added and the concentrate is diluted with water to the desired concentration.
The active compound preparation is intim~tf Iy mixed with soil which is heavily infested with the test nematodes. The active compound concentration in the preparation is immaterial, only the amount of active compound per unit volume of soil, which is given in ppm (= mgA), matters. The treated soil is transferred into pots, lettuce is sown in, and the pots are kept at a greenhouse temperature of 25~C.
After four weeks, the lettuce roots are checked for infestation with nematodes (root galls) and the efficacy of the active compound in % is determined. The efficacy is 100% when infestation is avoided completely and 0% when the infestation level is just as high as in the control plants in untreated, but equally infested, soil.
In this test, an efficacy of 100% was shown, for example, by the compounds of Preparation Examples 1, 5, 15, 16, 17, 18, 19, 20, 21, 24, 25, 26, 27, 28 and 44 at an exemplary active compound concentration of 20 ppm.
. ~
Le ~ 31 182-Foreign countries ~,Y~lnple B
Tetranychus test (OP-resistant/dip treatment) ~olvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether 5 To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
Bean plants (Phaseolus vulgaris) which are heavily infested with all development stages of the common spider mite Tetranychus urticae are dipped into an active compound10 preparation of the desired concentration.
After the desired period of time, the kill in % is determined. 100% means that all the spider mites have been killed; 0% means that none of the spider mites have been killed.
In this test, an activity of at least 95% was shown, for example, by the compounds of Preparation Examples 1, 13 and 19 after 13 days at an exemplary active compound concentration of 0.01%.
Tr A 31 182-Foreign countries ~Y~rn~ple C
Test with flies (Musca domestica) Test anim~ls: adult Musca domestica, Reichswald strain (OP, SP, carbamate-resistant) Solvent: 35 parts by weight of ethylene glycol monomethyl ether 35 parts by weight of nonylphenol polyglycol ether To produce a suitable formulation, three parts by weight of active compound are mixed with seven parts of the abovementioned solvent-emulsifier mixture, and the resulting emulsion concentrate is diluted with water to the respectively desired concentration.
2 ml of this active compound preparation are pipetted onto filterpaper discs (0 9.5 cm) 10 situated in Petri dishes of corresponding size. After the filter discs have dried, 25 test ~nim~ are transferred into the Petri dishes and covered.
The activity of the active compound preparation is determined after 1, 3, 5 and 24 hours. 100% means that all the flies have been killed; 0% means that none of the flies have been killed.
15 In this test, an activity of 100% was shown, for example, by the compound of Preparation Example 12 at an exemplary concentration of 1000 ppm.
, ~ TR A 31 182-Foreign countries ~,~a~nple D
Test with fly larvae / development-inhibitory action Test ~nim~l.s: All larval stages of Lucilia cuprina (OP-resistant) tpupae and adults (without contact with the active compound)]
5 Solvent: 35 parts by weight of ethylene glycol monomethyl ether Emulsifier: 35 parts by weight of nonylphenol polyglycol ether To produce a suitable formulation, three parts by weight of active compound are mixed with seven parts of the abovementioned-solvent-emulsifier mixture, and the resulting emulsion concentrate is diluted with water to the desired concentration.
10 For each concentration, 30 to 50 larvae are introduced into a test tube which contains 1 cm3 of horsemeat. 500 1ll of the dilution to be tested are pipetted onto this horsemeat.
The test tubes are placed in plastic beakers whose bottom is covered with seasand, and kept in an air-conditioned room (26~C + 1.5~C, 70% + 10% relative humidity). Theactivity is examined (larvicidal action) after 24 hours and 48 hours. After emergence 15 of the larvae (about 72 h), the test tubes are removed and perforated plastic lids are fitted onto the beakers. After 1.5 times the development time (hatching of control flies), the hatched flies and the pupae/cocoons are counted.
The activity criterion is the incidence of death in the treated larvae after 48 h (larvicidal effect), or the inhibition of hatching of adults from pupae or the inhibition 20 of pupae formation. The criterion for the in vitro activity of a substance is the inhibition of the development of the flies, or a development standstill before the adult stage. 100% larvicidal action means that all the larvae have been killed after 48 hours.
100% development-inhibitory action means that no adult flies have hatched.
. ~
Ie A 31 182-Foreign countries In this test, an activity of in each case 100% was shown, for example, by the compounds of Preparation Examples 6, 7, 8, 9, 10, 12, 13, 14, 15, 22, 29, 32, 33, 34, 44 and 55 at an exemplary active compound concentration of 1000 ppm.
. CA 02230100 1998-02-20 Le A 31 182-Foreign countries FY~mrle E
Test with Boophilus microplus resistant / SP-resistant Parkhurst strain Test ~nim~l~ adult females which have sucked themselves full Solvent: dimethyl sulphoxide 5 20 mg of active compound are dissolved in 1 ml of dimethyl sulphoxide, and lower concentrations are prepared by (lillltin~; in the same solvent.
The test is carried out in 5 replications. 1 ~1 of the solutions is injected into the abdomen, and the animals are transferred into dishes and kept in an air-conditioned room. The activity is determined via the inhibition of oviposition. 100% means that no 10 tick has deposited eggs.
In this test, an activity of in each case 100% was shown, for example, by the compounds of Preparation Examples 3, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 25, 32, 33, 34, 36, 39, 40, 42 and 44 at an exemplary concentration of 20 llg/animal.
Le A 31 182-Foreign countries F~rnrle F
Cockroach test Test ~nim~ Periplaneta americana Solvent: 35 parts by weight of ethylene glycol monomethyl ether S Emulsifier: 35 parts by weight of nonylphenol polyglycol ether To produce a suitable formulation, three parts by weight of active compound are mixed with seven parts of the abovementioned solvent-emulsifier mixture, and the resulting emulsion concentrate is diluted with water to the respectively desired concentration.
2 ml of this active compound preparation are pipetted onto filterpaper discs (0 9.5 cm) 10 situated in Petri dishes of corresponding size. After the filter discs have dried, S test ~nimzll~ P. americana are transferred and covered.
The activity of the active compound p,t;pa,dlion is determined after 3 days. Theactivity is expressed in %. 100% means that all the cockroaches have been killed; 0%
means that none of the cockroaches have been killed.
15 In this test, an activity of in each case 100% was shown, for example, by thecompounds of Preparation Examples 12 and 55 at an exemplary active compound concentration of 1000 ppm.
Bactericides: .
15 bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
Insecticides/Acaricides/Nematicides:
abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin,20 amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin, Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarboxim, butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, CGA 157419, 25 CGA 184699, chloethocarb, chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton M, demeton S, demeton-~-methyl, diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubell~ul~ll, dimethoate, 30 dimethylvinphos, dioxathion, disulfoton, Le A 31 182-Foreign countries edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox, ethoprophos, etrimfos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, S flll~7.in~n, flucycloxuron, flucythrin~t~--, flufenoxuron, flufenprox, fluvalinate, fonofos, formothion, fosthi~7~t~7 fubfenprox, furathiocarb, HCH, heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos, isazofos, isofenphos, isoprocarb, isoxathion, ivermectin, lambda-cyhalothrin, lufenuron, malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled, NC 184, NI 25, nitenpyram, omethoate, oxamyl, oxydemeton M, oxydeprofos, parathion A, parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozine, pyrachlofos,pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxyfen, quinalphos, RH 5992, salithion, sebufos, silafluofen, sulfotep, sulprofos, tebufenozide, tebufenpyrad, tebupirimifos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin, triarathene, triazophos, triazuron, trichlorfon, triflumuron, trimethacarb, vamidothion, XMC, xylylcarb, YI 5301 / 5302, zetamethrin.
A mixture with other known active compounds, such as herbicides, or with fertilizers and growth-regulators is also possible.
The active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these Le A 31 182-Foreign countries formulations, as a mixture with synergists. Synergists are compounds which increase the action of the active compounds, without it being necessary for the synergist added to be active itself.
The active compound content of the use forms prepared from the commercially 5 available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.
The compounds are employed in a customary manner appropriate for the use forms.
When used against hygiene and stored-product pests, the active compound has excellent 10 residual action on wood and clay and good stability to alkali on limed substrates.
The active compounds according to the inven~ion are not only active against plant, hygiene and stored-product pests, but also, in the veterinary medicine sector, against animal parasites (ectoparasites), such as ixodid ticks, argasid ticks, scab mites, trombiculid mites, flies (stinging and sucking), parasitic fly larvae, lice, hair lice, bird 15 lice and fleas. These parasites include:
From the order of the Anoplurida, for example, ~f mzltopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.
From the order of the Mallophagida and the sub-orders Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., 20 Werneckiella spp., Lepikentron spp., D~m~lin~ spp., Trichodectes spp. and Felicola spp.
From the order of the Diptera and the sub-orders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp.,Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca 25 spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Le A 31 182-Forei~n countries Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.
From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., 5 Xenopsylla spp. and Ceratophyllus spp.
From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp.
10 From the sub-class of the Acaria (Acarida) and the orders of the Meta- and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.
15 From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), forexample, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp.,Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., 20 Cytodites spp. and Laminosioptes spp.
For example, they have an outstanding activity against Boophilus microplus and Lucilia cuprina.
The active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which attack agricultural livestock, such as, for example, 25 cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, Lç A 31 182-Foreign countries ducks, geese, honey bees, other domestic ~nim~l.s, such as, for example, dogs, cats, caged birds, aquarium fish, and so-called experimental ~nim~ls, such as, for example, hamsters, guinea-pigs, rats and mice. By controlling these arthropods, it is intended to reduce mortality and decreased performances (in meat, milk, wool, hides, eggs, honey 5 and the like), so that more economical and simpler animal keeping is possible by using the active compounds according to the invention.
In the veterinary sector, the active compounds according to the invention are used in a known manner by enteral ~-lmini.stration, for example in the form of tablets, capsules, drinks, drenches, granules, pastes, boluses, the feed-through method, suppositories, by 10 parenteral ~-lministration, such as, for example, by means of injections (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal ~clministration, by dermal a~ministration, for example in the form of dipping orbathing, spraying, pouring-on and spotting-on, washing, dusting, and with the aid of shaped articles which comprise active compound, such as collars, ear tags, tail marks, 15 limb bands, halters, marking devices and the like.
When ~lmini.stered to livestock, poultry, domestic animals and the like, the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowables) which comprise the active compounds in an amount of 1 to 80%
by weight, directly or after dilution by a factor of 100 to 10 000, or they may be used 20 in the form of a chemical bath.
The preparation and the use of the active compounds according to the invention are illustrated by the examples below.
L~ A 31 1~2-Foreign countries ~dtiOn ~,Y~rnrles ~,Y~ ple 1 CF2=CF-CH2-CONH~CI
With ice-cooling and stirring, 23.8 g (0.15 mol) of 3,4,4-trifluorobut-3-enoyl chloride 5 dissolved in 40~ml of dichloromethane are added dropwise to a solution of 19.1 g (0.15 mol) of 4-chloroaniline in 200 ml of dichloromethane and 15.2 g (0.15 mol) of triethylamine. The mixture is stirred at 20~C for 3 hours, water is then added and the organic phase is separated off, washed with dilute hydrochloric acid and then with water. The organic phase is concentrated under reduced pressure and the residue is 10 stirred with petroleum ether, filtered off with suction and dried. 29.5 g of N-(4-chlorophenyl)-3,4,4-trifluorobutene-3-carboxamide of m.p.: 124~C are obtained.
Similarly and/or according to the general preparation procedures, the following compounds of the formula (I) are obtained:
CF2=C--CH2--CoNR2R3 R1 (I) Ex. R' R2 R3 physic. constant No.
2 F H ~\~ m.p.: 179~C
Lc A 31 182-Foreign countries Ex. Rl R2 R3 physic. constant No.
Cl 3 F H ~CF3 log p* (pH 2) = 3.04 Cl 4 F H ~ m.p.: 135~C
HNCOCH2CF=CF2 F H ~ m.p.: 200-202~C
HO
6 F H ~ m.p.: 118-120~C
~ .
Cl 7 F H ~--Cl m.p.: 78-80~C
8 F H ~CH3 m.p.: 140-142~C
Le A 31 182-Foreign countries Ex. Rl R2 R3 physic. constant No.
9 F H ~-CI m.p.: 119-122~C
F H ~C(CH3)3 m p. 105-107~C
11 F H --~CF3 m.p.: 118-120~C
12 F H ~ m.p.: 104-106~C
13 F H ~cl m.p.: 118~C
14 F H ~cl m.p.: 142-144~C
. CA 02230100 1998-02-20 Le A 31 182-~oreign countries . - 27 -Ex. Rl R2 R3 physic. constant No.
F H ~ Cl m.p.: 110-112~C
16 F H ~ OCH3 m.p.: 117-119~C
17 F H ~ ~ F m-p: 71-74~C
18 F H ~ m.p.: 115-117~C
19 F H ~ Br m.p.:137-139~C
F H ~ OCH3 m.p.: 88-90~C
21 F H ~ COCH3 m p.: 142-144~C
Le A 31 182-Foreign countries - 28 -Ex. Rl R2 R3 physic. constant No. Cl 22 F CH3 ~CI m.p.: 46-48~C
23 F CH3 ~CH3 log p* (pH 2) = 2.69 24 F H -CH2~ Cl m.p.: 125- 127~C
F H -CH(CH3)~ m.p.: 80~C
26 F H {~> m.p.: 102-104~C
27 F H ~ m.p.: 60-62~C
28 F H 'h m.p.: 132-134~C
29 F H ~ m.p.: 65-66~C
Le A 31 182-Foreign countries Ex. Rl R2 R3 physic. constant No.
HOOC
F H >~\ m.p.: 189-190~C
31 F H ~NO2 m.p.: 184-186~C
32 F H ~ m.p.: 138-139~C
~.
33 F H ~ m.p.: 73-75~C
34 F H ~\ m.p.: 122-124~C
CH(CH3)2 F H ~\ m.p.: 230-232~C
~Y
CH(CH3)2 . CA 02230100 1998-02-20 . ~
Le A 31 182-Foreign countnes Ex. Rl R2 . R3 physic. constant No.
HOOC
36 F H ~ m.p.: 208-209~C
Cl 37 F H ~ m.p.: 162-163~C
~Y
Cl HOOC
38 F H ~ m.p.: 176-178~C
39 F H ~ m.p.: 127-128~C
(cH3)3c F H ~ m.p.: 120-122~C
~ Cl T~ A 31 182-Foreign countries - 31 -Ex. Rl R2 R3 physic. constant No.
(CH3)3c 41 F H ~ m.p.: 209-210~C
NC
42 F H _~ m.p.: 118-120~C
43 F H ~COOC2Hs m p 129-132~C
44 F H -CH2--~ m.p.: 63-65~C
F H -CH2--~ m.p.: 50~C
46 F H ~OCF3 m.p.: 120~C
47 F ~--OH m.p.: 120-122~C
, ~
Le ~ 31 182-Foreign countries - 32 -Ex. Rl R~ R3 physic. constant No.
Cl Cl 48 F H ~OH m.p.: 146~C
HO
49 F H ~ m.p.: 176~C
~y F H ~SCH3 m.p.: 124~C
~=N
51 F H -CH2~CI m.p.: 100~C
52 F H ~OH m.p.: 174~C
Cl 53 F H ~SO2CH3 m p.: 180~C
54 F H _ CN--CH2~ m.p.: 128-130~C
Le ~ 31 182-Foreign countries Ex. Rl R2 R3 physic. constant No.
56 F H ~CI m.p.: 104~C
57 F H N ~ m.p.: 220-222~C
~/~ .
58 F H -~OCH3 m.p.: 120~C
*log p: Logarithm to base ten of the n-octanollwater partition coefficient, determined by reversed phase HPLC analysis using H2O/CH3CN.
Le A 31 182-Foreign countries Use F,Y~mrles Fx~Tnrle A
Critical concentration test / nematodes Test nematode: Meloidogyne incognita Solvent: 4 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of activecompound is mixed with the stated amount of solvent, the stated amount of emulsifler is added and the concentrate is diluted with water to the desired concentration.
The active compound preparation is intim~tf Iy mixed with soil which is heavily infested with the test nematodes. The active compound concentration in the preparation is immaterial, only the amount of active compound per unit volume of soil, which is given in ppm (= mgA), matters. The treated soil is transferred into pots, lettuce is sown in, and the pots are kept at a greenhouse temperature of 25~C.
After four weeks, the lettuce roots are checked for infestation with nematodes (root galls) and the efficacy of the active compound in % is determined. The efficacy is 100% when infestation is avoided completely and 0% when the infestation level is just as high as in the control plants in untreated, but equally infested, soil.
In this test, an efficacy of 100% was shown, for example, by the compounds of Preparation Examples 1, 5, 15, 16, 17, 18, 19, 20, 21, 24, 25, 26, 27, 28 and 44 at an exemplary active compound concentration of 20 ppm.
. ~
Le ~ 31 182-Foreign countries ~,Y~lnple B
Tetranychus test (OP-resistant/dip treatment) ~olvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether 5 To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
Bean plants (Phaseolus vulgaris) which are heavily infested with all development stages of the common spider mite Tetranychus urticae are dipped into an active compound10 preparation of the desired concentration.
After the desired period of time, the kill in % is determined. 100% means that all the spider mites have been killed; 0% means that none of the spider mites have been killed.
In this test, an activity of at least 95% was shown, for example, by the compounds of Preparation Examples 1, 13 and 19 after 13 days at an exemplary active compound concentration of 0.01%.
Tr A 31 182-Foreign countries ~Y~rn~ple C
Test with flies (Musca domestica) Test anim~ls: adult Musca domestica, Reichswald strain (OP, SP, carbamate-resistant) Solvent: 35 parts by weight of ethylene glycol monomethyl ether 35 parts by weight of nonylphenol polyglycol ether To produce a suitable formulation, three parts by weight of active compound are mixed with seven parts of the abovementioned solvent-emulsifier mixture, and the resulting emulsion concentrate is diluted with water to the respectively desired concentration.
2 ml of this active compound preparation are pipetted onto filterpaper discs (0 9.5 cm) 10 situated in Petri dishes of corresponding size. After the filter discs have dried, 25 test ~nim~ are transferred into the Petri dishes and covered.
The activity of the active compound preparation is determined after 1, 3, 5 and 24 hours. 100% means that all the flies have been killed; 0% means that none of the flies have been killed.
15 In this test, an activity of 100% was shown, for example, by the compound of Preparation Example 12 at an exemplary concentration of 1000 ppm.
, ~ TR A 31 182-Foreign countries ~,~a~nple D
Test with fly larvae / development-inhibitory action Test ~nim~l.s: All larval stages of Lucilia cuprina (OP-resistant) tpupae and adults (without contact with the active compound)]
5 Solvent: 35 parts by weight of ethylene glycol monomethyl ether Emulsifier: 35 parts by weight of nonylphenol polyglycol ether To produce a suitable formulation, three parts by weight of active compound are mixed with seven parts of the abovementioned-solvent-emulsifier mixture, and the resulting emulsion concentrate is diluted with water to the desired concentration.
10 For each concentration, 30 to 50 larvae are introduced into a test tube which contains 1 cm3 of horsemeat. 500 1ll of the dilution to be tested are pipetted onto this horsemeat.
The test tubes are placed in plastic beakers whose bottom is covered with seasand, and kept in an air-conditioned room (26~C + 1.5~C, 70% + 10% relative humidity). Theactivity is examined (larvicidal action) after 24 hours and 48 hours. After emergence 15 of the larvae (about 72 h), the test tubes are removed and perforated plastic lids are fitted onto the beakers. After 1.5 times the development time (hatching of control flies), the hatched flies and the pupae/cocoons are counted.
The activity criterion is the incidence of death in the treated larvae after 48 h (larvicidal effect), or the inhibition of hatching of adults from pupae or the inhibition 20 of pupae formation. The criterion for the in vitro activity of a substance is the inhibition of the development of the flies, or a development standstill before the adult stage. 100% larvicidal action means that all the larvae have been killed after 48 hours.
100% development-inhibitory action means that no adult flies have hatched.
. ~
Ie A 31 182-Foreign countries In this test, an activity of in each case 100% was shown, for example, by the compounds of Preparation Examples 6, 7, 8, 9, 10, 12, 13, 14, 15, 22, 29, 32, 33, 34, 44 and 55 at an exemplary active compound concentration of 1000 ppm.
. CA 02230100 1998-02-20 Le A 31 182-Foreign countries FY~mrle E
Test with Boophilus microplus resistant / SP-resistant Parkhurst strain Test ~nim~l~ adult females which have sucked themselves full Solvent: dimethyl sulphoxide 5 20 mg of active compound are dissolved in 1 ml of dimethyl sulphoxide, and lower concentrations are prepared by (lillltin~; in the same solvent.
The test is carried out in 5 replications. 1 ~1 of the solutions is injected into the abdomen, and the animals are transferred into dishes and kept in an air-conditioned room. The activity is determined via the inhibition of oviposition. 100% means that no 10 tick has deposited eggs.
In this test, an activity of in each case 100% was shown, for example, by the compounds of Preparation Examples 3, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 25, 32, 33, 34, 36, 39, 40, 42 and 44 at an exemplary concentration of 20 llg/animal.
Le A 31 182-Foreign countries F~rnrle F
Cockroach test Test ~nim~ Periplaneta americana Solvent: 35 parts by weight of ethylene glycol monomethyl ether S Emulsifier: 35 parts by weight of nonylphenol polyglycol ether To produce a suitable formulation, three parts by weight of active compound are mixed with seven parts of the abovementioned solvent-emulsifier mixture, and the resulting emulsion concentrate is diluted with water to the respectively desired concentration.
2 ml of this active compound preparation are pipetted onto filterpaper discs (0 9.5 cm) 10 situated in Petri dishes of corresponding size. After the filter discs have dried, S test ~nimzll~ P. americana are transferred and covered.
The activity of the active compound p,t;pa,dlion is determined after 3 days. Theactivity is expressed in %. 100% means that all the cockroaches have been killed; 0%
means that none of the cockroaches have been killed.
15 In this test, an activity of in each case 100% was shown, for example, by thecompounds of Preparation Examples 12 and 55 at an exemplary active compound concentration of 1000 ppm.
Claims (7)
1. Compounds of the formula (I) in which R1 represents hydrogen or halogen, R2 represents hydrogen, alkyl or optionally halogen- or alkyl-substituted phenyl, R3 represents or in which X represents amino, hydroxyl, mercapto, nitro, cyano, halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, alkylsulphonyl, halogenoalkylsulphonyl, alkylcarbonyl, alkoxycarbonyl, alkylamino, dialkylamino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl or halogenoalkenylcarbonylamino, Y and Z independently of one another each represent hydrogen, amino, hydroxyl, mercapto, cyano, carboxyl, halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, alkylcarbonyl, alkoxycarbonyl, alkylamino, dialkylamino, alkylaminocarbonyl or dialkylaminocarbonyl or b) or in which X and Y are each as defined above, R4 represents hydrogen or alkyl and n represents 0, 1, 2, 3 or 4 or C) in which optionally one methylene group is replaced by SO2 or one or two non-adjacent methylene groups in the ring are replaced by oxygen, sulphur or nitrogen (which is optionally substituted by alkyl, phenyl or benzyl), l represents 0, 1 or 2, m represents 0, 1, 2, 3, 4 or 5 and W represents halogen, alkyl or optionally halogen-, alkyl-, halogenoalkyl-, alkoxy- or halogenoalkoxy-substituted phenyl, d) 5- or 6-membered hetarylalkyl having one to three hetero atoms from the group oxygen, sulphur and nitrogen and optionally substituted by halogen, alkyl or by optionally halogen-, alkyl-, halogenoalkyl-, alkoxy-or halogenoalkoxy-substituted phenyl or e) respectively optionally halogen-, alkyl- or halogenoalkyl-substituted pyridyl or benzothiazolyl.
2. Process for preparing compounds of the formula (I) according to Claim 1, characterized in that amines of the formula (II) HNR2R3 (II) in which R2 and R3 are each as defined above, are reacted with acyl chlorides of the formula (III) (see fig. III) (III) in which Rl is as defined above, if appropriate in the presence of a diluent and if appropriate in the presence of a base.
3. Pesticides, characterized in that they comprise at least one compound of the formula (I) according to Claim 1.
4. Use of compounds of the formula (I) according to Claim 1 for controlling pests.
5. Method for controlling pests, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on pests and/or their habitat.
6. Process for preparing pesticides, characterized in that compounds of the formula (I) according to Claim 1 are mixed with extenders and/or surfactants.
7. Use of compounds of the formula (I) according to Claim 1 for preparing pesticides.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19531300.3 | 1995-08-25 | ||
| DE19531300A DE19531300A1 (en) | 1995-08-25 | 1995-08-25 | Fluorobutenic acid amides |
| PCT/EP1996/003570 WO1997008132A1 (en) | 1995-08-25 | 1996-08-13 | Fluorobutene acid amides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2230100A1 true CA2230100A1 (en) | 1997-03-06 |
Family
ID=7770372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002230100A Abandoned CA2230100A1 (en) | 1995-08-25 | 1996-08-13 | Fluorobutene acid amides |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0848698A1 (en) |
| JP (1) | JPH11511438A (en) |
| KR (1) | KR19990044034A (en) |
| CN (1) | CN1200109A (en) |
| AU (1) | AU6872996A (en) |
| BR (1) | BR9610023A (en) |
| CA (1) | CA2230100A1 (en) |
| DE (1) | DE19531300A1 (en) |
| TR (1) | TR199800297T1 (en) |
| WO (1) | WO1997008132A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE271030T1 (en) * | 1998-06-02 | 2004-07-15 | Syngenta Participations Ag | DIFLUOROALKENE CARBOXANILIDES AND PESTICIDES |
| PE20040711A1 (en) * | 2002-12-11 | 2004-10-16 | Ishihara Sangyo Kaisha | HALOALKENE COMPOUNDS, PROCESS FOR THEIR PRODUCTION AND PESTICIDES THAT CONTAIN THEM |
| WO2007089455A1 (en) * | 2006-01-27 | 2007-08-09 | E. I. Du Pont De Nemours And Company | Fluoroalkenyl derivatives as insecticides and nematicides |
| AR090545A1 (en) * | 2012-03-28 | 2014-11-19 | Intervet Int Bv | HETEROARILO COMPOUND WITH AN ACICLIC BRIDGE UNIT |
| CN106554334B (en) * | 2015-09-30 | 2017-09-22 | 山东省联合农药工业有限公司 | A kind of nematicide containing lactonic ring and its production and use |
| CN106554335B (en) * | 2015-09-30 | 2017-09-19 | 山东省联合农药工业有限公司 | A kind of nematicide containing lactonic ring of transconfiguration and its production and use |
| CN108484538B (en) * | 2018-06-08 | 2020-06-12 | 山东省联合农药工业有限公司 | Synthesis method of nematicide containing lactone ring |
| WO2020144695A1 (en) * | 2019-01-09 | 2020-07-16 | Yeda Research And Development Co. Ltd. | Modulators of pin1 activity and uses thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69227527T2 (en) * | 1991-03-01 | 1999-06-24 | Monsanto Co., St. Louis, Mo. | FLUOROALKENYL COMPOUNDS AND THEIR USE AS A PEST CONTROL |
| SG44489A1 (en) * | 1993-12-29 | 1997-12-19 | Ciba Geigy Ag | Vinylcarboxylic acid derivatives |
-
1995
- 1995-08-25 DE DE19531300A patent/DE19531300A1/en not_active Withdrawn
-
1996
- 1996-08-13 CN CN96197624A patent/CN1200109A/en active Pending
- 1996-08-13 CA CA002230100A patent/CA2230100A1/en not_active Abandoned
- 1996-08-13 TR TR1998/00297T patent/TR199800297T1/en unknown
- 1996-08-13 WO PCT/EP1996/003570 patent/WO1997008132A1/en not_active Application Discontinuation
- 1996-08-13 BR BR9610023A patent/BR9610023A/en not_active Application Discontinuation
- 1996-08-13 AU AU68729/96A patent/AU6872996A/en not_active Abandoned
- 1996-08-13 JP JP9509775A patent/JPH11511438A/en active Pending
- 1996-08-13 EP EP96929247A patent/EP0848698A1/en not_active Withdrawn
- 1996-08-13 KR KR1019980701266A patent/KR19990044034A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| KR19990044034A (en) | 1999-06-25 |
| CN1200109A (en) | 1998-11-25 |
| JPH11511438A (en) | 1999-10-05 |
| EP0848698A1 (en) | 1998-06-24 |
| BR9610023A (en) | 1999-07-06 |
| WO1997008132A1 (en) | 1997-03-06 |
| MX9801493A (en) | 1998-08-30 |
| DE19531300A1 (en) | 1997-02-27 |
| AU6872996A (en) | 1997-03-19 |
| TR199800297T1 (en) | 1998-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU702938B2 (en) | Fluorobutenyl(thio)ethers used as pesticides | |
| AU711483B2 (en) | Biphenyl etheroxazolines and their use as pest control agents | |
| CA2230100A1 (en) | Fluorobutene acid amides | |
| CA2230031A1 (en) | 4,4-difluoro-3-butenylester derivatives or 4,4-difluoro-3-halogen-3-butenylester derivatives and the use thereof as pesticides | |
| US6001829A (en) | Fluoropropenyl oxadiazoles and the use thereof as pest control agents | |
| US5929118A (en) | Fluorobutenic acid hydrazides | |
| US6004992A (en) | Aminocarboxylic acid fluorobutenyl esters | |
| WO1996014295A1 (en) | Dithiocarbazonic acid butenyl esters and their use as pesticides | |
| WO1997002238A1 (en) | Fluorobutenoic acid hydrazones | |
| US5648316A (en) | Substituted (1,4) Dioxino (2,3-F) Benzoimidazole derivative and their use in pest control | |
| EP0861227A1 (en) | Fluorobutenoyloxyacetamides | |
| DE19638047A1 (en) | Biphenyl ether oxazolines | |
| WO1997002237A1 (en) | Fluorobutenic acid oxime esters | |
| MXPA98001248A (en) | Hydrazides of fluorbuten acid | |
| MXPA98001493A (en) | Amidas of fluorbutine acid | |
| JP2001523665A (en) | Acylated 4-aminopyridines as pesticides and fungicides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |