CA2039779A1 - Nitroenamine derivatives - Google Patents
Nitroenamine derivativesInfo
- Publication number
- CA2039779A1 CA2039779A1 CA002039779A CA2039779A CA2039779A1 CA 2039779 A1 CA2039779 A1 CA 2039779A1 CA 002039779 A CA002039779 A CA 002039779A CA 2039779 A CA2039779 A CA 2039779A CA 2039779 A1 CA2039779 A1 CA 2039779A1
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- CA
- Canada
- Prior art keywords
- compound
- formula
- spp
- hydrogen
- halogen
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
-
- 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
- C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- 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
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
-
- 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
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- 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
- C07D213/60—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 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
- C07D213/61—Halogen atoms or nitro radicals
-
- 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
- C07D213/89—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 with hetero atoms directly attached to the ring nitrogen atom
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Health & Medical Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pyridine Compounds (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Pyrrole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Nitroenamine derivatives Abstract Novel nitroenamine derivatives of the formula I
(I) in which R1 is hydrogen, C1-C6alkyl or C3-C6cycloalkyl, R2 is hydrogen or C1-C6alkyl, R3 is hydrogen, C1-C6alkyl or C3-C6cycloalkyl, R4 is hydrogen, C1-C6alkyl, C3-C6cycloalkyl or a radical -CH2-B, or R3 and R4 together are -(CH2)4- or -(CH2)5-;
X is halogen or C1-C6haloalkyl;
Y and Z are halogen;
A is an unsubstituted or monosubstituted to tetrasubstituted aromatic or non-aromatic, monocyclic or bicyclic, heterocyclic radical in which one or two substituents belong to the group comprising C1-C3haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl, C2-C3haloalkynyl, C1-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro and one to four substituents belong to the group comprising C1-C3alkyl, C1-C3alkoxy and halogen;
B is phenyl, cyanophenyl, nitrophenyl, halophenyl having 1 to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, or 5-thiazolyl which is substituted by one to two substituents from the group comprising C1-C3alkyl, C1-C3haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C1-C3alkoxy, C2-C3haloalkenyl, C2-C3haloalkynyl, C1-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro; or 3-pyridyl which is substituted by one to two radicals from the group comprising C1-C3haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl, C2-C3haloalkynyl,C1-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro or by one to four radicals from the group comprising C1-C3alkyl, C1-C3alkoxy or halogen, and their salts with inorganic acids; it only being possible for one of the radicals R1, R3 and R4 to be hydrogen, and their salts can be used as pesticides.
Insects and arachnids can preferably be controlled.
(I) in which R1 is hydrogen, C1-C6alkyl or C3-C6cycloalkyl, R2 is hydrogen or C1-C6alkyl, R3 is hydrogen, C1-C6alkyl or C3-C6cycloalkyl, R4 is hydrogen, C1-C6alkyl, C3-C6cycloalkyl or a radical -CH2-B, or R3 and R4 together are -(CH2)4- or -(CH2)5-;
X is halogen or C1-C6haloalkyl;
Y and Z are halogen;
A is an unsubstituted or monosubstituted to tetrasubstituted aromatic or non-aromatic, monocyclic or bicyclic, heterocyclic radical in which one or two substituents belong to the group comprising C1-C3haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl, C2-C3haloalkynyl, C1-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro and one to four substituents belong to the group comprising C1-C3alkyl, C1-C3alkoxy and halogen;
B is phenyl, cyanophenyl, nitrophenyl, halophenyl having 1 to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, or 5-thiazolyl which is substituted by one to two substituents from the group comprising C1-C3alkyl, C1-C3haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C1-C3alkoxy, C2-C3haloalkenyl, C2-C3haloalkynyl, C1-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro; or 3-pyridyl which is substituted by one to two radicals from the group comprising C1-C3haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl, C2-C3haloalkynyl,C1-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro or by one to four radicals from the group comprising C1-C3alkyl, C1-C3alkoxy or halogen, and their salts with inorganic acids; it only being possible for one of the radicals R1, R3 and R4 to be hydrogen, and their salts can be used as pesticides.
Insects and arachnids can preferably be controlled.
Description
3 .
PS/S- I 8()26/A
Nitroenamine derivatives The present invention relates to novel nitroenamine derivatives, i.e. novel 1,1-diamino-2-nitro-3-hydroxybut-1-ene derivatives, to processes for their preparation, tO
pesticides comprising these compounds, and to their use in pest control.
The nitroenamine derivatives aceording to the invention are those of the formula I
1 1 l2 X~4 3 2 I N - CH A
Y C~H(OH)-C(NO2)=C~N_R3 (I) in which Rl is hydrogen, Cl-C6alkyl or C3-C6cycloalkyl, R2 is hydrogen or Cl-C6alkyl, R3 is hydrogen, Cl-C6alkyl or C3-C6eyeloalkyl, R4 is hydrogen, Cl-C6alkyl7 C3-C6eyeloalkyl or a ntclieal -Cl-12-B, or R3 and R4 together are -(Cl~ or -(CI-I2)s-;
X is halogen or Cl-C6haloalkyl;
Y allLI Z ;lre l1al0g~n;
A is .ln unsubstituted or rnonosubstituted to tetrasubstituted arornatic or nall-aromatic, monoeyelie or bieyelie, heterocyelic radieal in whieh one or two substituents belong to the group comprising Cl-C3haloalkyl, eyclopropyl, halocyelopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl, C2-(:3haloalkynyl, Cl-C3haloalkoxy, Cl-C3aLkylthio, Cl-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro and one to four substituents belong to the group comprising C1-C3alkyl, Cl-C3alkoxy and halogen;
B is phenyl, cyanophenyl, nitrophenyl, halophenyl having I to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, or 5-thi~zolyl which is substituted by one to two substituents from the group comprising Cl-C3alkyl, Cl-C3haloalkyl, cyclopropyl, halocyelopropyl, C2-C3alkenyl, , , 3 7 ~ ~
C2-C3alkynyl, Cl-C3alkoxy, C2-C3haloalkenyl, C2-C3haloalkynyl, Cl-C3h~1ualkoxy, Cl-C3alkylthio, C'l-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro; or 3-pyridyl which is substitutecl by one tO two radicals from the group comprising Cl-C3haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloal1kenyl, C2-C3haloalkynyl, Cl-C3haloalkoxy, Cl-C3alkylthio, Cl-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro or by one to four radicals from the group comprising Cl-C3alkyl, Cl-C3alkoxy or halogen, and their salts with inorganic acids; it only heing possible for one of the radicals Rl, R3 and R4 to be hydrogen.
Preferred compounds of the forrnula I according to the invention are those in which the heterocyclic radical A is unsaturated and bonded to the radical of the compound of the formula I via one of its ring carbon atoms; those in which the heterocyclic radical A
contains at least one nitrogen atom; and those in which the heterocyclic radical A contains one to three hetero atoms from ~he series comprising oxygen, sulfur and nitrogen, of which not more than one is an oxygen or sulfur atom.
The ring systems which come under the definition of the heterocyclic radical A therefore contain, as a ring member, at least one hetero atom, i.e. at least one of the atoms which form the basic ring-shaped skeleton is other than carbon. In principle, all atoms of the periodic system of the elements are capable of acting as ring members if they can form at least two covalent bonds. In this context, the heterocyclic radicall is pre~era~ly unsalturllted and bonded to the skeleton of the nitroenamine of the formulal [ via al callbotl atolll rh1g member. IJnsaturated ring systems of the ~lefinitiotl A therefore contairl ona or more double bon~ls. RinL~ ~ysterns of this type alrc profcr.lbly polyunsatllr.lte(î alnd gcnerallly have alromaltic chalracter. Preferred rin~ systems which come uncler the definition of A are those in which the heterocyclic radical A contains one to three hetero atoms from theseries comprising oxygcn, sulfur and nitrogen, of which one hetero atom is always nitrogen and not more than one oxygen atom or sulfur atom is present. Examples of heterocyclic radicals according to the invention, of the definition A, can be found in the group of skeletons of the following structures:
p~ ~
N~ N~
0/~/ N~ N~ ~ N~N
O~N~J ~S 3 O~N~ s~oJI S~S } S~N~
E E
N~~N~ N~ N N~~N~.
o~ss~oJI s~s O~N
E
N~NN~ ~N~ N~NN~
o~ssd~sJI o~N 0~0S~N~I S
e E E
N~N N~ 3, ~ ~N ~ ~I N~; 3 s~oJ o~o o ~o o o~ o~ls ~N ' ~N3 O~NJ o~N
E E E
N~ 3 ~/ N ~, N N~ 3 ~ ~-- ~N
S O S oJ S 0~ S~S S sJ
3^~ 3 S ~ S ~ S S~ N } S ~N ~I S ~N ~ ~;3 E E E
N ~ N
Y
~3 r~3 r~3 r~
Y y N N N N N
~ " ~ 11~ -11 N~o/ ' N~S ~ N~N/ ~ ~ ~N ~ ~ "N
I
Y
N ~ T~ ~ ~N . I I r ~N~'N ~o~ N~S~N ~N~ ~1`1J
Y Y Y
~1 N--N N l ~1l ~
N~N ~ N ~N ~N~ ~N ~ N~N .
O O O Y S
N--N N ~ O--_ 3 ~ 5 1~3 N ~
N N N N IN/~
S S Y
PS/S- I 8()26/A
Nitroenamine derivatives The present invention relates to novel nitroenamine derivatives, i.e. novel 1,1-diamino-2-nitro-3-hydroxybut-1-ene derivatives, to processes for their preparation, tO
pesticides comprising these compounds, and to their use in pest control.
The nitroenamine derivatives aceording to the invention are those of the formula I
1 1 l2 X~4 3 2 I N - CH A
Y C~H(OH)-C(NO2)=C~N_R3 (I) in which Rl is hydrogen, Cl-C6alkyl or C3-C6cycloalkyl, R2 is hydrogen or Cl-C6alkyl, R3 is hydrogen, Cl-C6alkyl or C3-C6eyeloalkyl, R4 is hydrogen, Cl-C6alkyl7 C3-C6eyeloalkyl or a ntclieal -Cl-12-B, or R3 and R4 together are -(Cl~ or -(CI-I2)s-;
X is halogen or Cl-C6haloalkyl;
Y allLI Z ;lre l1al0g~n;
A is .ln unsubstituted or rnonosubstituted to tetrasubstituted arornatic or nall-aromatic, monoeyelie or bieyelie, heterocyelic radieal in whieh one or two substituents belong to the group comprising Cl-C3haloalkyl, eyclopropyl, halocyelopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl, C2-(:3haloalkynyl, Cl-C3haloalkoxy, Cl-C3aLkylthio, Cl-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro and one to four substituents belong to the group comprising C1-C3alkyl, Cl-C3alkoxy and halogen;
B is phenyl, cyanophenyl, nitrophenyl, halophenyl having I to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, or 5-thi~zolyl which is substituted by one to two substituents from the group comprising Cl-C3alkyl, Cl-C3haloalkyl, cyclopropyl, halocyelopropyl, C2-C3alkenyl, , , 3 7 ~ ~
C2-C3alkynyl, Cl-C3alkoxy, C2-C3haloalkenyl, C2-C3haloalkynyl, Cl-C3h~1ualkoxy, Cl-C3alkylthio, C'l-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro; or 3-pyridyl which is substitutecl by one tO two radicals from the group comprising Cl-C3haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloal1kenyl, C2-C3haloalkynyl, Cl-C3haloalkoxy, Cl-C3alkylthio, Cl-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro or by one to four radicals from the group comprising Cl-C3alkyl, Cl-C3alkoxy or halogen, and their salts with inorganic acids; it only heing possible for one of the radicals Rl, R3 and R4 to be hydrogen.
Preferred compounds of the forrnula I according to the invention are those in which the heterocyclic radical A is unsaturated and bonded to the radical of the compound of the formula I via one of its ring carbon atoms; those in which the heterocyclic radical A
contains at least one nitrogen atom; and those in which the heterocyclic radical A contains one to three hetero atoms from ~he series comprising oxygen, sulfur and nitrogen, of which not more than one is an oxygen or sulfur atom.
The ring systems which come under the definition of the heterocyclic radical A therefore contain, as a ring member, at least one hetero atom, i.e. at least one of the atoms which form the basic ring-shaped skeleton is other than carbon. In principle, all atoms of the periodic system of the elements are capable of acting as ring members if they can form at least two covalent bonds. In this context, the heterocyclic radicall is pre~era~ly unsalturllted and bonded to the skeleton of the nitroenamine of the formulal [ via al callbotl atolll rh1g member. IJnsaturated ring systems of the ~lefinitiotl A therefore contairl ona or more double bon~ls. RinL~ ~ysterns of this type alrc profcr.lbly polyunsatllr.lte(î alnd gcnerallly have alromaltic chalracter. Preferred rin~ systems which come uncler the definition of A are those in which the heterocyclic radical A contains one to three hetero atoms from theseries comprising oxygcn, sulfur and nitrogen, of which one hetero atom is always nitrogen and not more than one oxygen atom or sulfur atom is present. Examples of heterocyclic radicals according to the invention, of the definition A, can be found in the group of skeletons of the following structures:
p~ ~
N~ N~
0/~/ N~ N~ ~ N~N
O~N~J ~S 3 O~N~ s~oJI S~S } S~N~
E E
N~~N~ N~ N N~~N~.
o~ss~oJI s~s O~N
E
N~NN~ ~N~ N~NN~
o~ssd~sJI o~N 0~0S~N~I S
e E E
N~N N~ 3, ~ ~N ~ ~I N~; 3 s~oJ o~o o ~o o o~ o~ls ~N ' ~N3 O~NJ o~N
E E E
N~ 3 ~/ N ~, N N~ 3 ~ ~-- ~N
S O S oJ S 0~ S~S S sJ
3^~ 3 S ~ S ~ S S~ N } S ~N ~I S ~N ~ ~;3 E E E
N ~ N
Y
~3 r~3 r~3 r~
Y y N N N N N
~ " ~ 11~ -11 N~o/ ' N~S ~ N~N/ ~ ~ ~N ~ ~ "N
I
Y
N ~ T~ ~ ~N . I I r ~N~'N ~o~ N~S~N ~N~ ~1`1J
Y Y Y
~1 N--N N l ~1l ~
N~N ~ N ~N ~N~ ~N ~ N~N .
O O O Y S
N--N N ~ O--_ 3 ~ 5 1~3 N ~
N N N N IN/~
S S Y
2. ~ 3 ~
N~ N ~ N~ ~N~
~NJ~N~OJ~NJI SJ~N~I NJ~N
--N ~3~ N ~3 ~r ~--~
N~\NN~\N N~N N~`N
o~\N1~3 O~N~1~3 O~N/1~3 5 N~NN~N
5~N~l~3 and ~ ,1~3 ~ where a r~dical according to the above y forrnulae is unsubstituted or can carry Up to four subs~ituents from those defined under forrnula I, depencling on the scope of the ring system in questioll for xubstitutioll, and E is Cl-C3.alkyl ancl Y is hydrogen, Cl-C3alkyl or cyclopropyl. Pref~r.lbly, these h~t~roeycles A are unsubstitllted or ealry one to three substituGIlts trom the gl'Ollp COlllpl'iSin~ halogen, C~-CInlkyl, (~ 3h;~ l1kyl, C'l-C3h~l10.llkoxy or Cl-C3alkoxy. Very parti~ lrly preferrc(l hutcro~:ycl~ A arc pyridyl r.~di~llls or thi.azolyl radic;lls, for cx~atllple 3-pyriclyl, 2-halopyrkl~S-yl, 2,3-dih~lopylid-5-yl, 2-halothiazol-4-yl, 1-oxopyrid-3-yl, 1-oxo-2-halopyrid-5-yl or 1-oxo-2,3-dihalopyrid-5-yl.
Other compounds of the formula I according to the invention which must be emphasi~ed are those in which the radical B is a phenyl, pyridyl or thiazolyl radical, each of which is unsubstituted or subslituted by one to two radicals from the group comprising halogen, Cl-C3alkyl, Cl-C3haloalkyl, Cl-C3haloalkoxy or Cl-C3alkoxy.
Compounds of the formula I which are prefer~d because of their biological action are those in which Rl and R3 are hydrogen, methyl, ethyl or cyclopropyl; in which R2 is hydrogen; in which R4 is hydrogen or methyl; in which Rl and R3 independently of one ~.
, . ~ .
r~ r~
arlother are hydrogen, methyl, ethyl or cyclopropyl~ R2 iS hydrogen, R4 is hydrogen or methyl, A is pyridyl, 1-oxopyridyl, thiazolyl, or is pyridyl, 1-oxopyridyl or thiazolyl, eacl of which is substituted by one to three substituents from the group comprising halogen, C~-C3alkyl, Cl-C3haloalkyl, C~-C3haloalkoxy or C1-C3alkoxy; in which X is fluorine, chlorine, bromine or Cl-C3haloalkyl having I to 7 fluorine atoms, and Y and Z
inclependently of one another are fluorine, chlorine or bromine in which, in particular, X, Y and Z independently of one another are fluorine, chlorine or bromine, and, especially, X, Y and Z are chlorine; in which Rl and R3 are methyl, R2 and R" are hydrogen; and X, Y and Z independently of one another are fluorine, chlorine or bromine; in which A is pyridyl or pyridyl which is substituted by one or two chlorine atoms; or in which A is thiazolyl or thiazolyl which is substituted by a chlorine atom, preferably 1,3-thiazol-5-yl.
Compounds of the formula I according tO the invention which are of special interest because of their good pesticidal properties are those in which X is fluorine or bromine, preferably fluorine, and Y and Z are halogen, preferably fluorine or chlorine; those in which X is C1-C6haloalkyl having 4 to 13, preferably 2 to 13, halogen atoms; and those in which X is trifluoromethyl or one of the radicals -C2Fs or -C3F7.
The individual generic terrns in the definition of the formula I according to the invention are to be understood as meaning the following:
The halogen atoms which are suitable as substituents are fluorine ancl chlorine as well as bromine alld iodine, fluor~ne, chlorine and brorninc beiIlg preferlecl. In this ~olltext, hnlogen is to be unclerstoo(l as meaning ~ subs~itllent in its own right or part o~ a sllbstituent, sllch as in halo.llkyl, haloalkylthio, halo.llkoxy, h~llo~ycloalkyl, h.lloalkenyl, hal(ralkyllyl, h;lloallyloxy or haloallylthio. 'I'he alkyl, alkylthio1 alkenyl, alkynyl ancl alkoxy radicals which are suitable as substituents can be straight-chain or branchecl.
Examples of such alkyls which may be mentioned are methyl, ethyl, propyl, isopropyl, butyl, i-butyl, sec-butyl or tert-butyl. Suitable alkoxy radicals which may be mentioned are, inter alia: methoxy, ethoxy, propoxy, isopropoxy or butoxy and their isomers.
Alkylthio is, for example, methylthio, ethylthio, isopropylthio, propylthio or the butylthio isomers. If the alkyl, alkoxy, alkenyl, alkynyl or cycloalkyl groups which are suitable as substituents are substituted by halogen, they can be only partially halogenated, or, alternatively, perhalogenated. In this context, the definitions of halogen, alkyl and alkoxy are those given above. Examples of the alkyl elements of these groups are methyl which is monosubstituted to trisubstituted by fluorine, chlorine and/or bromine, for example CHF2 2~3¢3~77~
or CF3; ethyl which is monosubstituted to pentasubstituted by flllorine, chlorine and/or bromine, for example CH2CF3, CF2CF3, CF2CCI3, CF2CE~C12, CF2CHF2, CF2CFCI2, CF2CHBr2, CF2CHClF, CF2CHE3rF or CCIFCHCIF; propyl or isopropyl, each of which is monosubstituted to heptasubstituted by fluorine, chlorine and/or bromine, for example CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3 or CH(CF3)2; butyl or one of its isomers, each of which is monosubstituted to nonasubstituted by fluorine, chlorine and/or bromine, for example CF(CF3)CHFCF3 or CH2(CF~)2CF3; 2-chlorocyclopropyl or 2,2-difluorocyclopropyl; 2,2-difluorovinyl, 2,2-dichlorovinyl, 2-chloroallyl, 2,3-dichlorovinyl or 2,3-dibromovinyl.
If the alkyl, alkoxy or cycloalkyl groups which have been de~med are subs~ituted by other substituents, they can be monosubstituted or polysubstituted by an identical substituent or by different substituents of those mentioned. The substituted groups preferably contain one or two further substituents. The cycloalkyl radicals which are suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Alkenyl and alkynyl groups contain an unsaturated carbon-carbon bond. Typical representatives are allyl, methallyl or propargyl, but also vinyl and ethynyl. The double or triple bonds in allyloxy, propargyloxy, allylthio or propargylthio are preferably separated from the site at which these are linked to the hetero atom (O or S) by a saturated carbon atom.
Heterocyclic compounds containing a nitroenarnine structure have already been disclosed as insecticides in EP-A-192 06(), EP-A-302 389 and EP-A-302 833; however, the biological properties of these compounds are not entiraly satisfactory when used in pest control. In terrns of structure, the compounds of the fo mula I accorclin~g to th~ invelltion are distinL~uished from the abovementioned, known nitroenamines in particular by the presence of tha spccific 3,4-substitucnts in the n-but-l-one chain, The compoun(ls of the formula I accorcling to the invention also encompass salts with inorg,lnic acids which are agriculturally acceptable. Examples of such acids arehydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid and nitric acid and acids which have the same central atom and higher or lower levels of oxidation, such as perchloric acid, nitrous acid or phosphorous acid.
The compounds of the formula I according to the invention can exist as double-bond isomers, for example cis and trans isomers, or as stereoisomers at the carbon atom 3. The compounds of the forrnula I are understood as meaning such isomeric fo rns and mixtures ;
of these.
The compounds of the forrnula I according to the invention can be prepared analogously to known processes. For example, the compound of the forrnula I is obtained by reacting a 1,1-diamino-2-nitroethyl derivative of the forrnula II
N ~ CH--A
CH(N02)= C~ , R3 with a compound of the forrnula III
x\ ~o Y ~c~c\ (III), Z H
in which Rl to R4, A, X, Y and Z are as de~lned above.
The above process according to the invention is advantageously can~ed out in an inert solvent at temperatures between 0C and ~120C, in particular between -~2(:)C and -~80C. The following are particularly suitable as solvents: example~ of suitable solventx are aromatic hyclrocarbons such ns benzene, toluene and xylene; ethr,rs such a~
tetrahydrofllran, clioxane and diethyl ether; halogenatecl hy(lrocarbolls sllch a~ methylene chlorkle, chloroform, c.lrbon tctrachloride ancl chlorobcnzene; alcohols such as metharlol, ethanol un~l propanol; esters of aliphatic acids, such as ethyl acetate; aliphatic amides, such as dimethylformamide and dimethylacetamide; acetonitrile, and other solvents which do not interfere with the reaction These solvents can also be used as rnixtures. The reaction can be carried out with the addition of a dehydrating agent, for example molecular sieves, or by azeotropic removal of the reaction water forrned, in particular when the aldehyde starting cornpound of the fonnula III is present in the hydrate forrn.
Basic conditions, i.e. pH values of > 8, and high ternperatures above approx. 100C should advantageously be avoided when carrying out the reaction, since the desired products of the forrnula I are unstable under these reaction conditions.
The interrnediates of the forrnulae II (1,1-diamino-2-nitroethylene derivatives) and III
N~ N ~ N~ ~N~
~NJ~N~OJ~NJI SJ~N~I NJ~N
--N ~3~ N ~3 ~r ~--~
N~\NN~\N N~N N~`N
o~\N1~3 O~N~1~3 O~N/1~3 5 N~NN~N
5~N~l~3 and ~ ,1~3 ~ where a r~dical according to the above y forrnulae is unsubstituted or can carry Up to four subs~ituents from those defined under forrnula I, depencling on the scope of the ring system in questioll for xubstitutioll, and E is Cl-C3.alkyl ancl Y is hydrogen, Cl-C3alkyl or cyclopropyl. Pref~r.lbly, these h~t~roeycles A are unsubstitllted or ealry one to three substituGIlts trom the gl'Ollp COlllpl'iSin~ halogen, C~-CInlkyl, (~ 3h;~ l1kyl, C'l-C3h~l10.llkoxy or Cl-C3alkoxy. Very parti~ lrly preferrc(l hutcro~:ycl~ A arc pyridyl r.~di~llls or thi.azolyl radic;lls, for cx~atllple 3-pyriclyl, 2-halopyrkl~S-yl, 2,3-dih~lopylid-5-yl, 2-halothiazol-4-yl, 1-oxopyrid-3-yl, 1-oxo-2-halopyrid-5-yl or 1-oxo-2,3-dihalopyrid-5-yl.
Other compounds of the formula I according to the invention which must be emphasi~ed are those in which the radical B is a phenyl, pyridyl or thiazolyl radical, each of which is unsubstituted or subslituted by one to two radicals from the group comprising halogen, Cl-C3alkyl, Cl-C3haloalkyl, Cl-C3haloalkoxy or Cl-C3alkoxy.
Compounds of the formula I which are prefer~d because of their biological action are those in which Rl and R3 are hydrogen, methyl, ethyl or cyclopropyl; in which R2 is hydrogen; in which R4 is hydrogen or methyl; in which Rl and R3 independently of one ~.
, . ~ .
r~ r~
arlother are hydrogen, methyl, ethyl or cyclopropyl~ R2 iS hydrogen, R4 is hydrogen or methyl, A is pyridyl, 1-oxopyridyl, thiazolyl, or is pyridyl, 1-oxopyridyl or thiazolyl, eacl of which is substituted by one to three substituents from the group comprising halogen, C~-C3alkyl, Cl-C3haloalkyl, C~-C3haloalkoxy or C1-C3alkoxy; in which X is fluorine, chlorine, bromine or Cl-C3haloalkyl having I to 7 fluorine atoms, and Y and Z
inclependently of one another are fluorine, chlorine or bromine in which, in particular, X, Y and Z independently of one another are fluorine, chlorine or bromine, and, especially, X, Y and Z are chlorine; in which Rl and R3 are methyl, R2 and R" are hydrogen; and X, Y and Z independently of one another are fluorine, chlorine or bromine; in which A is pyridyl or pyridyl which is substituted by one or two chlorine atoms; or in which A is thiazolyl or thiazolyl which is substituted by a chlorine atom, preferably 1,3-thiazol-5-yl.
Compounds of the formula I according tO the invention which are of special interest because of their good pesticidal properties are those in which X is fluorine or bromine, preferably fluorine, and Y and Z are halogen, preferably fluorine or chlorine; those in which X is C1-C6haloalkyl having 4 to 13, preferably 2 to 13, halogen atoms; and those in which X is trifluoromethyl or one of the radicals -C2Fs or -C3F7.
The individual generic terrns in the definition of the formula I according to the invention are to be understood as meaning the following:
The halogen atoms which are suitable as substituents are fluorine ancl chlorine as well as bromine alld iodine, fluor~ne, chlorine and brorninc beiIlg preferlecl. In this ~olltext, hnlogen is to be unclerstoo(l as meaning ~ subs~itllent in its own right or part o~ a sllbstituent, sllch as in halo.llkyl, haloalkylthio, halo.llkoxy, h~llo~ycloalkyl, h.lloalkenyl, hal(ralkyllyl, h;lloallyloxy or haloallylthio. 'I'he alkyl, alkylthio1 alkenyl, alkynyl ancl alkoxy radicals which are suitable as substituents can be straight-chain or branchecl.
Examples of such alkyls which may be mentioned are methyl, ethyl, propyl, isopropyl, butyl, i-butyl, sec-butyl or tert-butyl. Suitable alkoxy radicals which may be mentioned are, inter alia: methoxy, ethoxy, propoxy, isopropoxy or butoxy and their isomers.
Alkylthio is, for example, methylthio, ethylthio, isopropylthio, propylthio or the butylthio isomers. If the alkyl, alkoxy, alkenyl, alkynyl or cycloalkyl groups which are suitable as substituents are substituted by halogen, they can be only partially halogenated, or, alternatively, perhalogenated. In this context, the definitions of halogen, alkyl and alkoxy are those given above. Examples of the alkyl elements of these groups are methyl which is monosubstituted to trisubstituted by fluorine, chlorine and/or bromine, for example CHF2 2~3¢3~77~
or CF3; ethyl which is monosubstituted to pentasubstituted by flllorine, chlorine and/or bromine, for example CH2CF3, CF2CF3, CF2CCI3, CF2CE~C12, CF2CHF2, CF2CFCI2, CF2CHBr2, CF2CHClF, CF2CHE3rF or CCIFCHCIF; propyl or isopropyl, each of which is monosubstituted to heptasubstituted by fluorine, chlorine and/or bromine, for example CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3 or CH(CF3)2; butyl or one of its isomers, each of which is monosubstituted to nonasubstituted by fluorine, chlorine and/or bromine, for example CF(CF3)CHFCF3 or CH2(CF~)2CF3; 2-chlorocyclopropyl or 2,2-difluorocyclopropyl; 2,2-difluorovinyl, 2,2-dichlorovinyl, 2-chloroallyl, 2,3-dichlorovinyl or 2,3-dibromovinyl.
If the alkyl, alkoxy or cycloalkyl groups which have been de~med are subs~ituted by other substituents, they can be monosubstituted or polysubstituted by an identical substituent or by different substituents of those mentioned. The substituted groups preferably contain one or two further substituents. The cycloalkyl radicals which are suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Alkenyl and alkynyl groups contain an unsaturated carbon-carbon bond. Typical representatives are allyl, methallyl or propargyl, but also vinyl and ethynyl. The double or triple bonds in allyloxy, propargyloxy, allylthio or propargylthio are preferably separated from the site at which these are linked to the hetero atom (O or S) by a saturated carbon atom.
Heterocyclic compounds containing a nitroenarnine structure have already been disclosed as insecticides in EP-A-192 06(), EP-A-302 389 and EP-A-302 833; however, the biological properties of these compounds are not entiraly satisfactory when used in pest control. In terrns of structure, the compounds of the fo mula I accorclin~g to th~ invelltion are distinL~uished from the abovementioned, known nitroenamines in particular by the presence of tha spccific 3,4-substitucnts in the n-but-l-one chain, The compoun(ls of the formula I accorcling to the invention also encompass salts with inorg,lnic acids which are agriculturally acceptable. Examples of such acids arehydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid and nitric acid and acids which have the same central atom and higher or lower levels of oxidation, such as perchloric acid, nitrous acid or phosphorous acid.
The compounds of the formula I according to the invention can exist as double-bond isomers, for example cis and trans isomers, or as stereoisomers at the carbon atom 3. The compounds of the forrnula I are understood as meaning such isomeric fo rns and mixtures ;
of these.
The compounds of the forrnula I according to the invention can be prepared analogously to known processes. For example, the compound of the forrnula I is obtained by reacting a 1,1-diamino-2-nitroethyl derivative of the forrnula II
N ~ CH--A
CH(N02)= C~ , R3 with a compound of the forrnula III
x\ ~o Y ~c~c\ (III), Z H
in which Rl to R4, A, X, Y and Z are as de~lned above.
The above process according to the invention is advantageously can~ed out in an inert solvent at temperatures between 0C and ~120C, in particular between -~2(:)C and -~80C. The following are particularly suitable as solvents: example~ of suitable solventx are aromatic hyclrocarbons such ns benzene, toluene and xylene; ethr,rs such a~
tetrahydrofllran, clioxane and diethyl ether; halogenatecl hy(lrocarbolls sllch a~ methylene chlorkle, chloroform, c.lrbon tctrachloride ancl chlorobcnzene; alcohols such as metharlol, ethanol un~l propanol; esters of aliphatic acids, such as ethyl acetate; aliphatic amides, such as dimethylformamide and dimethylacetamide; acetonitrile, and other solvents which do not interfere with the reaction These solvents can also be used as rnixtures. The reaction can be carried out with the addition of a dehydrating agent, for example molecular sieves, or by azeotropic removal of the reaction water forrned, in particular when the aldehyde starting cornpound of the fonnula III is present in the hydrate forrn.
Basic conditions, i.e. pH values of > 8, and high ternperatures above approx. 100C should advantageously be avoided when carrying out the reaction, since the desired products of the forrnula I are unstable under these reaction conditions.
The interrnediates of the forrnulae II (1,1-diamino-2-nitroethylene derivatives) and III
3 ~ ~7 ~ ~
() (haloacetal(lehydes) are known or can be prepared in analogy to known pracesses (cf.
European Patent Application Nos. 302 389 and 302 833).
It has now been found that the compounds of the forrnula I according to the invention are valuable active substances in pest control while their toxicity properties as regards warm-blooded species, fish and plants are favourable. In par~icular, the use of the active substances according to the invention relates to insects and arachnids which occur in usefu} plants and ornamentals in agriculture, in particular in cotton plantations, vegetable plantations and fruit plantations, in forests, in the protection of stored products and materials, and in the hygiene field, in particular on domestic animals and productive livestock. The compounds of the forrnula I are also suitable for seed treatment (compositions for seed-dressing) for controlling, in particular, aphids, Ihe fact that the compounds have a low toxicity to birds being highly important. They are effecùve ag~inst all or individual development stages of nonnally sensitive, but also of resistant, species. In this context, their action can become apparent by immediate destruction of the pests or only after some time, for example during moulting, or by reduced oviposition and/or hatching rate. The abovementioned pests include:
from the order of the Lepidoptera, for example Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa syp., Busseol.
fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocr~cis spp., Cnephasia spp., Cochylis spp., (:oleophol;l spp,t Crociclolomia binotalis, Cryptophlebia leucotreta, Cyclia spp., Diatrae;l spp., Diparopsis cast.lllea, Earias spp., E~phesti.a spp., Ellcosma spp., Lllpoecilia ambigllella, E~uproctis spp., I~ XO;l xpp., Grapholita spp., ~le(lya nubi~cran.l, ~leliothis spp., llellula un~lalis, ~lyphnntria cune;l, Keiferia Iycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrarla, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.;
from the order of the Coleoptera, for example Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., ~?J ~
Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.; from the order of the Orthoptera, for example Blatta spp" Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.;
from the order of the Isoptera, for example Reticulitermes spp.; from the order of the Psocoptera, for éxample Liposcelis spp.; from the order of the Anoplura, for example Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp; from the order of the Mallophaga, for example Damalinea spp. and Trichodectes spp.;
from the order of the Thysanoptera, for example Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and Scirtothrips aurantii;
from the order of the Heteroptera, for example Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.;
from the order of the Homoptera, for example Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidurll, Empo,lsca spp., Eriosoma lariL~erurrl, Elythronellra spp, Cascardka spp, L,ao(lelph/lx spp" Lecanillnl corni, LepillosLIp}l~ spp, Maclosiphus spp" Myz~s spp, Nephotetti,Y spp" Nih~ lvatll sl~p, Par.ltorkl spp, PCll~ pp. ~ ()C~CCll~ s~ Px~ c;l.~pis s~ Ps~ cocclls spp., Psyll~l ~;pp., I'ulvinarkl actlliopica, Qua~lraspicliotlls spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Troiz~
erytreae and Unaspis citri;
frorn the order of the Hymenoptera, for example Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplo~ampa spp., Lasius spp., Monomoliurn pharaonis, Neodiprion spp., Solenopsis spp.
and ~/espa spp.;
from the order of the Diptera, for exarnple Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp, Gastrophilus spp., Glossina spp.~ Hypoderrna spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., (:~rseolia spp., Oscinella frit, Pegomyi,l hyoscy,lmi, Phorbi.l spp, Rhagoletis pomonella, Sci.ua spp., Stoms~xys spp., Tabanus spp., T.lnnia spp. and Tipula spp.;
from the order of the Siphonaptera, for example Ceratophyllus spp., Xenopsylla cheopis, from the order of the Acarina, for example Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp.,Boophilus spp., Brevipalpus spp., Bryobia praetiosLI, Calipitrimerus spp., Chorioptes spp., Vermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonyehus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sareoptes spp., Tarsonemus spp., and Tetranyehus spp.; and from the order of the Thysanura, for example Lepisma saccharina.
The good pesticidal action of the compounds of tlle formula I according to lhe invention corresponds to a destmction rate ~mortality) of at least 50-60 % of the pests mentioned.
The action of the compounds according to the invention and of the compositions which comprise them ean be broadened substantially by adding other insecticides and/oracaricides and can be adapted to suit prevailing cireumstanees. E~xamples of suitable additives are representatives of the following elasses of aetive substances:
organophosphorus eompour1ds, nitrophenols and derivatives, formamidines, ureas, carbam.ltes, pyre~hroi(ls, chlorin;lte(l hydlocarbons arlcl F~acilllls thuringiell~is prepa~ iorls.
'I`he colllpollll(ls of the formulLl I are ellll)loyed in ul~altere(l form")r prefer~lbly to~e~her with the allxiliaries eonverltionally used hl formul.ltioll teehnology, and they can therefore be processed in a known manner to give, for exa,Tlple, emulsion coneentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in polymerie substanees. The application methods, such as spraying, atomising, dusting, scattering or pouring, as well as the compositions are selected to suit the intended aims and the prevailing cireumstances.
The formulation, i.e. the compositions, preparations or combinations comprising the active substance of the formula I, or blends of these active substanees with other insecticides or acaricides, and, if desired, a solid or liquid additive, are prepared in a known manner, for example by intimately mixing andlor glinding the aetive substanees with extenders, for example with solvents, solid carners and, if desired, surface-ac~ve compounds (surfactants).
The following are possible as solvents: aromatic hydrocarbons, preferably the fractions C8 to Cl2, such as xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, sueh as cyclohexane, paraffins, alcohols and glycols as well as their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformarnide, and also epoxiclized or unepoxidized vegetable oils, such as epoxidized coconut oil or soya oil, or water.
Solid carriers used as a rule, for example for dusts and dispersible powders, are ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly-disperse silicas or highly-disperse absorptive polymers. Possible particulate, adsorptive carriers for granules a~e either porous types, for example pumice, brick grit, sepiolite or bentonite, or non-sorptive carner materials, such as calcite or sand. Moreover, a large number of ~ranulated materials of inorganic or organic nature can be used, such as, in particular, dolornite or comminuted plant residues.
Suitable surface~clctive compollrlds arc non-ionic, cationic an(l/or anionic surfclct.lnts h(lvin6 good emulsifyinL~, dispersillg and wottin~ propertie/., deperlding on the nature of the active xubst.lrlce of the formula ~ to b~ formlllatecl or ot' the blcn~ls of thcse active subst,lllces with other insectici-les or acaricicles. Surfactants are also to be understoocl as meaning mixtures of surfactants Anionic surfactants which are suitable can be either so-called ~ater-soluble soaps or water-soluble synthetic surface-active compounds.
Suitable soaps which may be mentioned are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids (C1O-C22), such as the sodium salts or potassium salts of oleic or ste~ric acid, or of natural mixtures of ~fatty acids which can be obtained, for exarnple, from coconut or tall oil. Mention must also be made of the fatty acid methyltaurinates aml of modified and unmoclified phospholipids as surfactants.
r~ r~ 3 However, so-called synthetic surf.lctants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole deriYatives or alkylarylsulfonates.
The fatty sulfonates or fatty sulfates are, as a rule, in the form of alkali metal salts, alkaline earth met~l salts or substituted or unsubstituted ammonium salts, an~l generally have an alkyl radical having 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals, for example the sodium or calcium salt of ligninsul~onic acid, of the dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and one fatty acid radical having 8 to 22 C atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid/forrnaldehyde condensation product. Other suitable compounds are the corresponding phosphates, such as the salts of the phosphoric ester of ap-nonylphenol-(~-14)-ethylene oxide adduct, or phospholipids.
Suitable non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to ~0 carbon atoms in the (aliphatic) hyclrocarbon radical and 6 to 18 carbon atoms in the alkyl rallical of the alkylptlenols.
Other non-ionic surfact~lnts which are suitable are the water-soluble polyethylene oxi~le ad(lllcts with polypropylf~l1e ~Iycol, ethylet1edi.~ opolypropylene L~lycol and ;Itlcylpolypropylene glycol WtliCtl h.tve I to 1() calborl atoms irl the alkyl chain alld which contain 20 to 250 ethylene glycol ether groups an(l 10 to 100 propylene glycol ether groups. Ttle abovementioned compounds customarily contain 1 to 5 ethylene glycol units per propylene glycol unit.
Examples of non-ionic surfactants which may be mentioned are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, castor oil thioxilate, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Other suitable substances are fatty acid esters of polyoxyethylenesorbitan, such as polyoxyethylenesorbitan trioleate.
The cationic surfactants are mainly quaternary ammonium salts, which contain at least one .
alkyl radical having 8 to 22 C atoms as N-substituents and which have lower halogenated or free alkyl, benzyl or lower hydroxyalkyl radicals as further substituents. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, for example stear,vltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customary in forrnulation technology are described, inter alia, in the following publications:
"1885 International McCutcheon's Emulsifiers & Detergents", Glen Rock NJ USA, 1985", H. Stache, "Tensid-Taschenbuch [Surfactant Guide]", 2nd edition, C. Hanser Verlag, Munich, Vienna, 1981;
M. and J. Ash. "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981.
As a rule, the pesticidal preparations contain 0.1 to 99 %, in particular 0.1 to 95 %, of the active subs~ance of the formula I or of blends of this active substance with other insecticides or acaricides, 1 to 99.9 % of a solid or liquid additive and 0 to 25 %, in particular 0.1 to 20 %, of a surfactant. While concentrated compositions are more preferred as commercial goods, the end user uses, as a rule, dilute preparations which have substantially lower concentrations of active substance. Typical use concentrations are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The application rates per hectare are generally 1 to 1000 g of active substance per hectare, preferably 25 to 500 g/l~
In p.lrtic~ prcfcrrc~l formul~ltiolls c()nsist of thc followin~ (C/o ~ perc~nt by w~ ht)~ thc active sLlbstance comprise(l being a compourld of the formula I, for example thecompoundsNos. 1.0()1, 1.008, 1.009, 1.011, 1.012, 1.015, 1.028, 1.081, 1.084, 1.085, 1.101, 1.102, 1.157, 1.105, 1.1()9, 1.010, 1.028, 1.022:
Emulsi~lable concentrates:
Active substance: 1 to 20 %, 5 to 10 % being preferred Surfactant: S to 30 %, preferably 10 to 20 %
Liquid carrier: 50 to 94 %, preferably 70 to 85 %
Dusts:
Active substance: 0.1 to 10 %, preferably 0.1 to 1 %
Solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
- 15- , Suspension concentrates:
Active substance: 5 to 75 %, preferably 10 to 50 %
Water. 94 to 24 %, preferably 88 to 30 %
Surfactant: 1 to 40 %, preferably 2 to 30 %
Wettable powders:
Active substance: 0.5 to 90 %, preferably 1 to 80 %
Surfactant: 0.5 to 20 %, preferably l to 15 %
Solid carrier: 5 to 95 %, preferably 15 to 90 %.
Granules:
Active substance: 0.5 to 30 %, preferably 3 to 15 %
Solid carrier: 99.5 to 70 %, preferably 97 to 85 5to.
The compositions can also contain other additives such as stabilisers, antifoams, preservatives, viscosity regulators, binders, adhesives and fertilisers or other active substances for achieving specific effects.
The examples which follow are intended to illustrate the invention. They do not impose any restriction on the invention.
_x m~Preparltis1n oP l m t.byl~ ~(6-chloropyrld-3 ylme~ ne~
2-ni~o~ . xy-4 4,4-trichlorobllt- I-ene.
L~
'I'o a mixture of 2.56 g (10 mmol) of 1-methylamino-1-[N-(6-cllloropyrid-3-ylmethyl)-N-methyll-amino-2-nitroethylene in 30 ml of methylene chloride there are added 1.06 ml (10.8 mmol) of chloral. After the reaction mixture has been stirred at room temperature for 2 1/2 hours~ it is filtered, and the crystals obtained are washed with a large amount of methylene chloride. 3.81 g (94 %) of the title compound of the formula C~13 CC13-CH(OH)-C(N02)=C~ ~L Cl of melting point 1 30C ~re obtained (Cornpound No 1.0()8).
Example 2: Preparation of l-methvlamino-l-~N-(6-chloropYrid-3-YlmethYl)-N-meth~-2-nitro-3-hYdroxy-4,4-difluoro-4-chlorobut- 1 -ene.
To a mixture of 14.4 g of 1-methylamino-1-[N-(6-chloropyrid-3-ylmethyl)-N-methyl]-amino-2-nitroethylene in 150 ml of methylene chloride there are adcled 7.42 g ofchlorodifluoroacetaldehyde H20. After the reaction mixture has been sti-rred at room temperature for 2 days, it is filtered, and the crystals obtained are washed with methylene chloride. The title compound of the forrnula below ~N--CH2~
CF2CI-CH(OH)-C(N02)= \NH--CH3 ~NJI--Cl is obtained in an arnount of 17.2 g, melting point 142-143C (Compound No. 1.011).
Example 3: Preparation of 1-methylamino-1-fN~(6-chloropyrid-3-~lmethyl)-N_e ~-2-nitro-3-hydroxY-4.4,5~5 ,6~6 6 heptafluorohex- 1 -ene.
To a Inixture of 2.56 ~ o~ 1-methylamino-1-[N-(6-chloropyrid-3-ylmettlyl)-N-lllethylJ-amino-2-nitroethylene an~l 3.24 g of hopt.lflllorobutyr~Lldehyde hydr.lte in 5() ml of mcthylcne chlori(lt~ therc slre s~ le~i S L~ Of molecLllslr siove 4 A. ~ftcr tlle reactioll mixtLIre hLIS bccn stirrc~l at room ternperature for 2 ~lays, it is filterc(l an(l the filtratc is evaporate(l 'rhe resulting cr~stals are washed with hexsme/isopropsmol (1:1) 4.02 g of the title compound of the formula CF3cF2cF2-cH(vH)-c(No2)= C~ l~L Cl of melting point 93-98C are obtained (Compoun~l No. 1.012).
ç.;,~
The compounds of the formula Ia which are listed in Table I below can be prcpared in an analogous manner to the above procedure.
Table 1 R~
~N--CH2---A
R5-CH(OH)-C(Nt)2)= C ~N ~ R3 (Ia) V~ ~ V~ ~ ~
D~
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_ ~ C~ C~ V ~ V V
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Z
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t-y o C~
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X
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~ ~Z~ Z ~Z~_~Z~Z~Z
Z ~ .. ~
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r J ~
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:
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C) ~ ~ ~ ~
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, ~ ~ ~ ~ ~Z_O~z-PO~
~ ~Z~O ~Z~O \~ ~
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~ ~_o~ ~ ~Z_O~Z-~o ,, Z
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~ Z-_O~ c~O
9 ~
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a ~ _ _ ~
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() (haloacetal(lehydes) are known or can be prepared in analogy to known pracesses (cf.
European Patent Application Nos. 302 389 and 302 833).
It has now been found that the compounds of the forrnula I according to the invention are valuable active substances in pest control while their toxicity properties as regards warm-blooded species, fish and plants are favourable. In par~icular, the use of the active substances according to the invention relates to insects and arachnids which occur in usefu} plants and ornamentals in agriculture, in particular in cotton plantations, vegetable plantations and fruit plantations, in forests, in the protection of stored products and materials, and in the hygiene field, in particular on domestic animals and productive livestock. The compounds of the forrnula I are also suitable for seed treatment (compositions for seed-dressing) for controlling, in particular, aphids, Ihe fact that the compounds have a low toxicity to birds being highly important. They are effecùve ag~inst all or individual development stages of nonnally sensitive, but also of resistant, species. In this context, their action can become apparent by immediate destruction of the pests or only after some time, for example during moulting, or by reduced oviposition and/or hatching rate. The abovementioned pests include:
from the order of the Lepidoptera, for example Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa syp., Busseol.
fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocr~cis spp., Cnephasia spp., Cochylis spp., (:oleophol;l spp,t Crociclolomia binotalis, Cryptophlebia leucotreta, Cyclia spp., Diatrae;l spp., Diparopsis cast.lllea, Earias spp., E~phesti.a spp., Ellcosma spp., Lllpoecilia ambigllella, E~uproctis spp., I~ XO;l xpp., Grapholita spp., ~le(lya nubi~cran.l, ~leliothis spp., llellula un~lalis, ~lyphnntria cune;l, Keiferia Iycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrarla, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.;
from the order of the Coleoptera, for example Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., ~?J ~
Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.; from the order of the Orthoptera, for example Blatta spp" Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.;
from the order of the Isoptera, for example Reticulitermes spp.; from the order of the Psocoptera, for éxample Liposcelis spp.; from the order of the Anoplura, for example Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp; from the order of the Mallophaga, for example Damalinea spp. and Trichodectes spp.;
from the order of the Thysanoptera, for example Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and Scirtothrips aurantii;
from the order of the Heteroptera, for example Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.;
from the order of the Homoptera, for example Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidurll, Empo,lsca spp., Eriosoma lariL~erurrl, Elythronellra spp, Cascardka spp, L,ao(lelph/lx spp" Lecanillnl corni, LepillosLIp}l~ spp, Maclosiphus spp" Myz~s spp, Nephotetti,Y spp" Nih~ lvatll sl~p, Par.ltorkl spp, PCll~ pp. ~ ()C~CCll~ s~ Px~ c;l.~pis s~ Ps~ cocclls spp., Psyll~l ~;pp., I'ulvinarkl actlliopica, Qua~lraspicliotlls spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Troiz~
erytreae and Unaspis citri;
frorn the order of the Hymenoptera, for example Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplo~ampa spp., Lasius spp., Monomoliurn pharaonis, Neodiprion spp., Solenopsis spp.
and ~/espa spp.;
from the order of the Diptera, for exarnple Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp, Gastrophilus spp., Glossina spp.~ Hypoderrna spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., (:~rseolia spp., Oscinella frit, Pegomyi,l hyoscy,lmi, Phorbi.l spp, Rhagoletis pomonella, Sci.ua spp., Stoms~xys spp., Tabanus spp., T.lnnia spp. and Tipula spp.;
from the order of the Siphonaptera, for example Ceratophyllus spp., Xenopsylla cheopis, from the order of the Acarina, for example Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp.,Boophilus spp., Brevipalpus spp., Bryobia praetiosLI, Calipitrimerus spp., Chorioptes spp., Vermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonyehus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sareoptes spp., Tarsonemus spp., and Tetranyehus spp.; and from the order of the Thysanura, for example Lepisma saccharina.
The good pesticidal action of the compounds of tlle formula I according to lhe invention corresponds to a destmction rate ~mortality) of at least 50-60 % of the pests mentioned.
The action of the compounds according to the invention and of the compositions which comprise them ean be broadened substantially by adding other insecticides and/oracaricides and can be adapted to suit prevailing cireumstanees. E~xamples of suitable additives are representatives of the following elasses of aetive substances:
organophosphorus eompour1ds, nitrophenols and derivatives, formamidines, ureas, carbam.ltes, pyre~hroi(ls, chlorin;lte(l hydlocarbons arlcl F~acilllls thuringiell~is prepa~ iorls.
'I`he colllpollll(ls of the formulLl I are ellll)loyed in ul~altere(l form")r prefer~lbly to~e~her with the allxiliaries eonverltionally used hl formul.ltioll teehnology, and they can therefore be processed in a known manner to give, for exa,Tlple, emulsion coneentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in polymerie substanees. The application methods, such as spraying, atomising, dusting, scattering or pouring, as well as the compositions are selected to suit the intended aims and the prevailing cireumstances.
The formulation, i.e. the compositions, preparations or combinations comprising the active substance of the formula I, or blends of these active substanees with other insecticides or acaricides, and, if desired, a solid or liquid additive, are prepared in a known manner, for example by intimately mixing andlor glinding the aetive substanees with extenders, for example with solvents, solid carners and, if desired, surface-ac~ve compounds (surfactants).
The following are possible as solvents: aromatic hydrocarbons, preferably the fractions C8 to Cl2, such as xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, sueh as cyclohexane, paraffins, alcohols and glycols as well as their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformarnide, and also epoxiclized or unepoxidized vegetable oils, such as epoxidized coconut oil or soya oil, or water.
Solid carriers used as a rule, for example for dusts and dispersible powders, are ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly-disperse silicas or highly-disperse absorptive polymers. Possible particulate, adsorptive carriers for granules a~e either porous types, for example pumice, brick grit, sepiolite or bentonite, or non-sorptive carner materials, such as calcite or sand. Moreover, a large number of ~ranulated materials of inorganic or organic nature can be used, such as, in particular, dolornite or comminuted plant residues.
Suitable surface~clctive compollrlds arc non-ionic, cationic an(l/or anionic surfclct.lnts h(lvin6 good emulsifyinL~, dispersillg and wottin~ propertie/., deperlding on the nature of the active xubst.lrlce of the formula ~ to b~ formlllatecl or ot' the blcn~ls of thcse active subst,lllces with other insectici-les or acaricicles. Surfactants are also to be understoocl as meaning mixtures of surfactants Anionic surfactants which are suitable can be either so-called ~ater-soluble soaps or water-soluble synthetic surface-active compounds.
Suitable soaps which may be mentioned are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids (C1O-C22), such as the sodium salts or potassium salts of oleic or ste~ric acid, or of natural mixtures of ~fatty acids which can be obtained, for exarnple, from coconut or tall oil. Mention must also be made of the fatty acid methyltaurinates aml of modified and unmoclified phospholipids as surfactants.
r~ r~ 3 However, so-called synthetic surf.lctants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole deriYatives or alkylarylsulfonates.
The fatty sulfonates or fatty sulfates are, as a rule, in the form of alkali metal salts, alkaline earth met~l salts or substituted or unsubstituted ammonium salts, an~l generally have an alkyl radical having 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals, for example the sodium or calcium salt of ligninsul~onic acid, of the dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and one fatty acid radical having 8 to 22 C atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid/forrnaldehyde condensation product. Other suitable compounds are the corresponding phosphates, such as the salts of the phosphoric ester of ap-nonylphenol-(~-14)-ethylene oxide adduct, or phospholipids.
Suitable non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to ~0 carbon atoms in the (aliphatic) hyclrocarbon radical and 6 to 18 carbon atoms in the alkyl rallical of the alkylptlenols.
Other non-ionic surfact~lnts which are suitable are the water-soluble polyethylene oxi~le ad(lllcts with polypropylf~l1e ~Iycol, ethylet1edi.~ opolypropylene L~lycol and ;Itlcylpolypropylene glycol WtliCtl h.tve I to 1() calborl atoms irl the alkyl chain alld which contain 20 to 250 ethylene glycol ether groups an(l 10 to 100 propylene glycol ether groups. Ttle abovementioned compounds customarily contain 1 to 5 ethylene glycol units per propylene glycol unit.
Examples of non-ionic surfactants which may be mentioned are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, castor oil thioxilate, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Other suitable substances are fatty acid esters of polyoxyethylenesorbitan, such as polyoxyethylenesorbitan trioleate.
The cationic surfactants are mainly quaternary ammonium salts, which contain at least one .
alkyl radical having 8 to 22 C atoms as N-substituents and which have lower halogenated or free alkyl, benzyl or lower hydroxyalkyl radicals as further substituents. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, for example stear,vltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customary in forrnulation technology are described, inter alia, in the following publications:
"1885 International McCutcheon's Emulsifiers & Detergents", Glen Rock NJ USA, 1985", H. Stache, "Tensid-Taschenbuch [Surfactant Guide]", 2nd edition, C. Hanser Verlag, Munich, Vienna, 1981;
M. and J. Ash. "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981.
As a rule, the pesticidal preparations contain 0.1 to 99 %, in particular 0.1 to 95 %, of the active subs~ance of the formula I or of blends of this active substance with other insecticides or acaricides, 1 to 99.9 % of a solid or liquid additive and 0 to 25 %, in particular 0.1 to 20 %, of a surfactant. While concentrated compositions are more preferred as commercial goods, the end user uses, as a rule, dilute preparations which have substantially lower concentrations of active substance. Typical use concentrations are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The application rates per hectare are generally 1 to 1000 g of active substance per hectare, preferably 25 to 500 g/l~
In p.lrtic~ prcfcrrc~l formul~ltiolls c()nsist of thc followin~ (C/o ~ perc~nt by w~ ht)~ thc active sLlbstance comprise(l being a compourld of the formula I, for example thecompoundsNos. 1.0()1, 1.008, 1.009, 1.011, 1.012, 1.015, 1.028, 1.081, 1.084, 1.085, 1.101, 1.102, 1.157, 1.105, 1.1()9, 1.010, 1.028, 1.022:
Emulsi~lable concentrates:
Active substance: 1 to 20 %, 5 to 10 % being preferred Surfactant: S to 30 %, preferably 10 to 20 %
Liquid carrier: 50 to 94 %, preferably 70 to 85 %
Dusts:
Active substance: 0.1 to 10 %, preferably 0.1 to 1 %
Solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
- 15- , Suspension concentrates:
Active substance: 5 to 75 %, preferably 10 to 50 %
Water. 94 to 24 %, preferably 88 to 30 %
Surfactant: 1 to 40 %, preferably 2 to 30 %
Wettable powders:
Active substance: 0.5 to 90 %, preferably 1 to 80 %
Surfactant: 0.5 to 20 %, preferably l to 15 %
Solid carrier: 5 to 95 %, preferably 15 to 90 %.
Granules:
Active substance: 0.5 to 30 %, preferably 3 to 15 %
Solid carrier: 99.5 to 70 %, preferably 97 to 85 5to.
The compositions can also contain other additives such as stabilisers, antifoams, preservatives, viscosity regulators, binders, adhesives and fertilisers or other active substances for achieving specific effects.
The examples which follow are intended to illustrate the invention. They do not impose any restriction on the invention.
_x m~Preparltis1n oP l m t.byl~ ~(6-chloropyrld-3 ylme~ ne~
2-ni~o~ . xy-4 4,4-trichlorobllt- I-ene.
L~
'I'o a mixture of 2.56 g (10 mmol) of 1-methylamino-1-[N-(6-cllloropyrid-3-ylmethyl)-N-methyll-amino-2-nitroethylene in 30 ml of methylene chloride there are added 1.06 ml (10.8 mmol) of chloral. After the reaction mixture has been stirred at room temperature for 2 1/2 hours~ it is filtered, and the crystals obtained are washed with a large amount of methylene chloride. 3.81 g (94 %) of the title compound of the formula C~13 CC13-CH(OH)-C(N02)=C~ ~L Cl of melting point 1 30C ~re obtained (Cornpound No 1.0()8).
Example 2: Preparation of l-methvlamino-l-~N-(6-chloropYrid-3-YlmethYl)-N-meth~-2-nitro-3-hYdroxy-4,4-difluoro-4-chlorobut- 1 -ene.
To a mixture of 14.4 g of 1-methylamino-1-[N-(6-chloropyrid-3-ylmethyl)-N-methyl]-amino-2-nitroethylene in 150 ml of methylene chloride there are adcled 7.42 g ofchlorodifluoroacetaldehyde H20. After the reaction mixture has been sti-rred at room temperature for 2 days, it is filtered, and the crystals obtained are washed with methylene chloride. The title compound of the forrnula below ~N--CH2~
CF2CI-CH(OH)-C(N02)= \NH--CH3 ~NJI--Cl is obtained in an arnount of 17.2 g, melting point 142-143C (Compound No. 1.011).
Example 3: Preparation of 1-methylamino-1-fN~(6-chloropyrid-3-~lmethyl)-N_e ~-2-nitro-3-hydroxY-4.4,5~5 ,6~6 6 heptafluorohex- 1 -ene.
To a Inixture of 2.56 ~ o~ 1-methylamino-1-[N-(6-chloropyrid-3-ylmettlyl)-N-lllethylJ-amino-2-nitroethylene an~l 3.24 g of hopt.lflllorobutyr~Lldehyde hydr.lte in 5() ml of mcthylcne chlori(lt~ therc slre s~ le~i S L~ Of molecLllslr siove 4 A. ~ftcr tlle reactioll mixtLIre hLIS bccn stirrc~l at room ternperature for 2 ~lays, it is filterc(l an(l the filtratc is evaporate(l 'rhe resulting cr~stals are washed with hexsme/isopropsmol (1:1) 4.02 g of the title compound of the formula CF3cF2cF2-cH(vH)-c(No2)= C~ l~L Cl of melting point 93-98C are obtained (Compoun~l No. 1.012).
ç.;,~
The compounds of the formula Ia which are listed in Table I below can be prcpared in an analogous manner to the above procedure.
Table 1 R~
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Example 4: (Formulations - % = percent bY weigh~2 E:~ample4.1: Emulsion concen~ates a) b) c) Active substance of Table 1 25 % 40 % 50 %
Cadodecylbenzenesulfonate 5 % 8 %6 ~/~
Castor oil polyethylene glycol ether (36 mol of EO) 5 %
Tributylphenol polyethylene glycol ether (30 mol of EO) - 12 % 4 %
Cyclohexanone - 15 % 20 %
Xylenemixture 65 % 25 % 20 %
Emulsions of any desired concentration can be prepared from such concentrates bydilution with water.
Example4.2: Solutions a) b) c) d) Active substance of Table 180 %10 % 5 % 95 %
Ethylene glycol monomethyl ether 20 %
Polyethylene glycol MW 400 70 %
N-methyl 2-pyrroliclons~ -2() ~/o ~ -E~poxitlised eoconut oil - - I % 5 %
Petroleum ether (boiling range 160-19ûC) - - 94 %
The solutions are suitable for use in the form of microdrops.
Example 4.3: Granules a) b) Active substance of Table 15 % 10 %
Kaolin 94 %
Highly-clisperse silica 1 %
Attapulgite - 90 %
~3 ~ ~ ~ 7 ~ ~ ~
The active substance is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated in vacuo.
Example4.4: Dusts a) b) Active substance of Table 1 2 %5 %
I-lighly-disperse silica 1 %5 %
Talc 97 %
Kaolin - 9() %
Ready-for-use dusts are obtained by intimately mixing the carriers with the active substance~
Example 4.5: Wettable powders a)b) c) Active substance of Table 1 25 %sn %75 %
Naligninsulfonate 5 ~/O5 %
Na lauryl sulfate 3 % - S %
Na diisobutylnaphthalenesulfonate - 6 % 10 %
Octylphenol polyethylene glycol ether (7-8 mol of EO) - 2 %
Highly-disperse silica S %1()% 10 %
Kaolin 62 %27 ~/o 'ï he active subxtance or the active substance combination is mixed with the additives and thoroughly ground in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.
Example 4.6: Emulsion concentrate Active substance of Table 1 10 %
Octylphenol polyethylene glycol ether (4-5 molofEO) 3 %
Ca dodecylbenzenesulfonate 3 %
Castor oil polyglycol ether (36 mol of EO) 4 %
J,~j 3,~
., Cyclohexanone 30 %
Xylene mixture 50 %
Emulsions of any desired concentration can be prepared from this concentrate by dilution wilh water.
Example 4.7: Dusts a)b) Active substance of Table I 5 %8 %
Talc 95 %
Kaolin - 92 %
Ready-for-use dusts are obtained by mixing the active substance with the carrier and grinding the mixture on a suitable mill.
Example 4.8: Extruder ~ranules Active substance of Table 1 10 %
Na ligninsulfonate 2 %
Gurboxyrmethylcellulose 1 %
Kaolin 87 %
Tllc ,Ictive subst,lncc or the corllbitl.ltion of active xubst.lnce~ is mixed with the ad(litives7 and th~ mixture is groulld and moistcned with water. This mixture is extruded, gr"nul,lted alld subscquently dried in a stream of air.
Exarnple 4.9: Coated ~ranules Active substance of Table 1 3 %
Polyethylene glycol (MW 200) 3 %
Kaolin 94 %
In a mixer, the finely-ground active substance or combination of active substances is applied uniforrnly to the kaolin which has been moistened with polyethylene glycol. In this manner, dust-free coated granules are obtained.
t ~ r~
Example 4.10: _spension concentrate Active substance of Table 1 40 %
Ethyleneglycol 10 %
Nonylphenol polyethylene glycol ether .
(lSmolofEO) 6 %
Na ligninsulfonate 10 %
Carboxymethylcellulose 1 %
37 % aqueous formaldehyde solu~ion ().2%
Silicone oil in the folm of a 75 % aqueous emulsion 0.8%
Water 32 %
The finely-ground active substance or the combination of active substances is mixed intimately with the additives. In this manner, a suspension concentrate is obtainecl from which suspensions of any desired concen~ation can be prepared by dilution with water.
Example 5: Effectiveness agains~ Nilaparvata lu~ens Rice plants are treated with an aqucous ernulsion spray mixture which contains 400 ppm of the active substance. After the spray coating has clried on, the rice plants are pop~llated with cicada larvae of the ~nd .md 3rd stage. The test is evalu.lted after 21 (lays. 'l he percentage reduction of the populatiorl (% efÇectivcness) i9 determirled by cornparirl~ the nllmbor of .suIviving cica~ s on thl~ treated plants witll those Oll the untreated plants.
In this test, the compounc!s of Table I are very effective against Nilaparvata lugens. In particular, cvmpounds 1.001, 1.008, 1.~9, 1.010, 1.011, 1.012, 1.015, 1.022, 1.024, 1.025, 1.028, 1.039, 1.081, 1.0~5, 1.101, 1.102, 1.103, 1.149, 1.153, 1.157, 1.165, 1.169, 1.183 and 1.189 have an effectiveness of more than 80 %.
Example 6: Effectiveness aga-i-nst Nephotettix cincticeps Rice plants are treated with an aqueous emulsion spray mixture which contains 400 ppm of the active substance. After the spray coating has dried on, the rice plants are populated with cicada larvae of the 2nd and 3rd stage. The test is evaluated after 21 days. The percentage reduction of the popula~ion (% effectiveness) is determined by comparing the number of survivin~ cicadas on the treated plants with those Oll the untreated plants.
In this test, the compounds of Table 1 are very effective against Nephotettix cincticeps. In particular, compounds 1.001, 1.008, 1.009, 1.010, 1.011, 1.012, 1.015, 1.022, 1.024, 1.025, 1.028, 1.039, 1.081, 1.085, 1.101, 1.102, 1.103, 1.1~g, 1.153, 1.157, 1.165, 1.169, 1.183 and 1.184 have an effectiveness of more than 80 %.
Example 7: Effectiveness a~ainst Spodoptera littoralis caterpillars Young soya plants are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active substance. After the spray coating has dried on, the soya plants are populated with 10 Spodoptera littoralis caterpillars of the third stage and placed in a plastic container. The test is evaluated after 3 days. The percentage reduction of the population, or the percentage reduction of feeding darnage, (% effectiveness) isdetermined by comparing the number of dead caterpillars and the feeding damage on the treated plants with those on the untreated plants.
In this test, the compounds of Table 1 are very effective against Spodoptera littoralis. In particular, compound 1.015 has an effectiveness of more than 80 %.
Ex,l~e 8: Effectlveness a~ainst Aphis cracci a Pea seedlin~s are infec,ted with ~phis craecivor.l, then sprayed with a sprily mixtule wllich cont;lirls 4()0 pprn of the netiv~ ~ubstnrlee, an~l incub.ltc,cl at 2()C. 'l'he tost is ev.~ .lte(l .llt~r 3 iln(l 6 d;lys. Th~ percent.l~e redueti(ln of the population ~/o effectiv~lIes~) is cletc,Imined by comparing the number oP dead aphids on the treated plants with tl-ose on the untreated plants.
In this test, the compounds of Table 1 are very effective against Aphis craccivora. In particular,compounds 1.008,1.010,1.()11,1.012,1.015,1.022,1.028,1.081,1.084, 1.085, 1.101, 1.157, 1.165 and 1.169 have an effectiveness of more than 80%.
Example 9. Ef~ectiYeness a~ainst Nilaparvata lu~ens, sYstemic Pots containing rice plants are placed in m aqueous emulsion solution which contains 400 ppm of the active substance. The rice plants are then populatecl with larvae of the 2nd and - (17 3rd stage. The test is ev"luated .Ifter 6 days. The percentage recluction of the population (% effectiveness) is deterrnine:l by comparing the number of cicadas on the treated plants with those on the untreated plants.
In this test, the compounds of Table 1 ~ure very effective against Nilaparvata lugens. In particular, compounds 1.001, 1.008, l.010, 1.011, 1.012, 1.015, 1.022, 1.024, 1.025, 1.028, 1.039, 1.081, 1.084,1.085, l.101, 1.102, 1.103, 1.149, 1.153, 1.157, 1.165, 1.16~), 1.183 and 1.184 have an effectiveness of more than 80 %, even when the concentration is 12.5 ppm.
Example 10: Effectiveness a~ainst Nepho~ettix cincticeps, sYstemic Pots containing rice plants are placed in an aqueous emulsion solution which contains 400 ppm of the active substance. The rice plants are then populated with larvae of the 2nd and 3rd stage. The test is evaluated after 6 days. The percentage reduction of the population (% effectiveness) is determined by comparing the number of cicadas on the treated plants with those on the untreated plants.
In this test, the compounds of Table 1 are very effective against Nephotettix cincticeps. In particular, compounds 1.008, 1.010, 1.011, 1.012, 1.015, 1.022, 1.024, 1.025, 1.028, 1.039, 1.081, 1.084, 1 085,1.101, 1.102~ 1.10~, 1.1~9, 1.153, 1.157, l.l65, l.lt~, 1.183 I .184 have an effectiveness of more than 80 crto.
Exarl1~?le 11. E~f~ctiveness a~t MY~Ig ~ ;iCaC systerTlic Pe~a scc(llings are infectecl with Myxus persicae, then placed with their roots in a spray mixture which contains 400 ppm of the active substance, and incubated at 20C. The test is evaluated after 3 and 6 days. The percentage reduction of the population (% effectiveness) is deterrnined by comparing the number of dead aphids on the treated plants with those on the untreated plants.
In this test, the compounds of 'I'able 1 are very effective against Myzus persicae. In particular, compounds 1.008, 1.010, 1.011, 1.012, 1.015, 1.028, 1.081, 1.084, 1.085, 1.101, 1.149, 1.153, 1.157, 1.165 and 1.169 have an effectiveness of more than 80%.
~ ~3 ~
Example 12: Effectiveness a~ainst Anthonomus grandis adults Young cotton plants are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active substance. When the spray coating has dried on, the cotton plants are populated with 10 Anthonomus grandis adults and placed in a plastic container ~he test is evaluated after 3 days. The percentage reduction of the population, or the percentage reduction of the feeding damage ~% effectiveness), is determined by comparing the number of dead beetles and the feeding damage on the treated plants with those on the untreated plants.
In this test, the compounds of Table 1 are very effective against Anthonomus grandis. In particular, compounds 1.008, 1.010, 1.011, 1.012, 1.015, 1.022, 1.028, 1.101, 1.149 and 1.153 have an effectiveness of more than 80 %.
~xample 13: Effectiveness a~ainst Bemisia tabaci Dwarf bean plants are placed in gauze cages and populated with Bemisia tabaci adults (whitefly). When oviposition has taken place, all adults are removed, and, after 10 days, the plants together with the nymphs which live on them are treated with an aqueous emulsion spray mixture of the active substances to be tested (concentration 400 ppm). 14 days after the active substance has been applied, the h.ltching rate is evalu.ltecl as a percentage in cornparison with the untreated control batchex.
~n this test, the eompolln(ls in accor(l.lnce with l'able 1 are very efl~ective a~.lins~ Bemisia tabaci. In partieular, compouncls 1.011, 1.()12, 1.015, 1.081, 1.084, 1.085, 1.101 and 1.1~)2 have an effectiveness of more than 80 %.
Example 1~: Effectiveness against Diabrotica balteata larvae Maize seedlings are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active substance. When the spray coating has dried on, the rnaize seedlings are populated with 10 Diabrotica balteata larvae of the second stage and placed in a plastic container. The test is evaluated after 6 days. The percentage reduction of the population (/0 effectiveness) is determined by comparing the number of dead larvae on the treated plants with those on the untreated plants.
~J ~ ~, In this test, the compounds of Table 1 are very effective against Diabrotica balteata. In particular, compounds 1.010, 1.012 and 1.015 have an effectiveness of more than 80 %.
Exam~le 15: Effectiveness against Heliothis virescens caterpillars Young soya plants are sprayed with all aqueous emulsion spray mixture which contains 400 ppm of the active substance. After the spray coating has dried on, the soya plants are populated with 10 caterpillars of the first sta~e of Heliothis virescens and placed in a plastic container. The test is evaluated after 6 days. Ihe percentage reduction of the population, or the percentage reduction of the feeding damage, (% effectiveness) is determined by comparing the number of dead caterpillars and the feeding darnage on the treated plants with those on the untreated plants.
' In this test, the compounds of Table 1 are very effective against Heliothis virescens. In particular, compounds 1.010, 1.011 and 1.015 have an effectiveness of more than 80 %.
Example 16: Effectiveness a~ainst Crocidolomia binotalis caterpillars Young cabbage plants are sprayed with an aqueous esnulsion spray mixture which contains 400 ppm of the active substance. After the spray coating has dr~ed orl, the cabbage plants are populated with 10 caterpillars of the thircl ~tage of Crvci(:Lolvmia binotalis and placed in a plastic container. The test is evaluated aftcl 3 d;lys. The percenta~e reduction of the poplllation, or the pcrcenta~e redllctiorl of ~he fee(ling d;lmage, (% effectivencss) ix determined by comparin~ the numbcr of ~lea(l caterpillars and the Peeding darnage on the treated plants with those on the untreated plants.
In this test, the cornpounds of Table 1 are very effective against Crocidolomia binotalis. In particular, compound 1.015 has an effectiveness of more than 80 %.
Effectiveness a~ainst MYZUS persicae Pea seedlings are infected with Myzus persicae, th~n sprayed with a spray liquor which contains 400 ppm of the active substance, and incubated at 20C The test is evaluated after 3 and 6 days The percentage reduction of the popula~ion (% effectiveness) is deterrnined by comparing the number of dead aphids on the treated plants with those on the untreated plants.
r~ r~ ~3 - 7() -In this test, the compounds of Table I are very effec~ive against Myzus persicae. In particular, compounds 1.008, 1.010, 1.012, 1.015, 1.022 and 1.157 have an effectiveness of more than 80 %.
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Example 4: (Formulations - % = percent bY weigh~2 E:~ample4.1: Emulsion concen~ates a) b) c) Active substance of Table 1 25 % 40 % 50 %
Cadodecylbenzenesulfonate 5 % 8 %6 ~/~
Castor oil polyethylene glycol ether (36 mol of EO) 5 %
Tributylphenol polyethylene glycol ether (30 mol of EO) - 12 % 4 %
Cyclohexanone - 15 % 20 %
Xylenemixture 65 % 25 % 20 %
Emulsions of any desired concentration can be prepared from such concentrates bydilution with water.
Example4.2: Solutions a) b) c) d) Active substance of Table 180 %10 % 5 % 95 %
Ethylene glycol monomethyl ether 20 %
Polyethylene glycol MW 400 70 %
N-methyl 2-pyrroliclons~ -2() ~/o ~ -E~poxitlised eoconut oil - - I % 5 %
Petroleum ether (boiling range 160-19ûC) - - 94 %
The solutions are suitable for use in the form of microdrops.
Example 4.3: Granules a) b) Active substance of Table 15 % 10 %
Kaolin 94 %
Highly-clisperse silica 1 %
Attapulgite - 90 %
~3 ~ ~ ~ 7 ~ ~ ~
The active substance is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated in vacuo.
Example4.4: Dusts a) b) Active substance of Table 1 2 %5 %
I-lighly-disperse silica 1 %5 %
Talc 97 %
Kaolin - 9() %
Ready-for-use dusts are obtained by intimately mixing the carriers with the active substance~
Example 4.5: Wettable powders a)b) c) Active substance of Table 1 25 %sn %75 %
Naligninsulfonate 5 ~/O5 %
Na lauryl sulfate 3 % - S %
Na diisobutylnaphthalenesulfonate - 6 % 10 %
Octylphenol polyethylene glycol ether (7-8 mol of EO) - 2 %
Highly-disperse silica S %1()% 10 %
Kaolin 62 %27 ~/o 'ï he active subxtance or the active substance combination is mixed with the additives and thoroughly ground in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.
Example 4.6: Emulsion concentrate Active substance of Table 1 10 %
Octylphenol polyethylene glycol ether (4-5 molofEO) 3 %
Ca dodecylbenzenesulfonate 3 %
Castor oil polyglycol ether (36 mol of EO) 4 %
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., Cyclohexanone 30 %
Xylene mixture 50 %
Emulsions of any desired concentration can be prepared from this concentrate by dilution wilh water.
Example 4.7: Dusts a)b) Active substance of Table I 5 %8 %
Talc 95 %
Kaolin - 92 %
Ready-for-use dusts are obtained by mixing the active substance with the carrier and grinding the mixture on a suitable mill.
Example 4.8: Extruder ~ranules Active substance of Table 1 10 %
Na ligninsulfonate 2 %
Gurboxyrmethylcellulose 1 %
Kaolin 87 %
Tllc ,Ictive subst,lncc or the corllbitl.ltion of active xubst.lnce~ is mixed with the ad(litives7 and th~ mixture is groulld and moistcned with water. This mixture is extruded, gr"nul,lted alld subscquently dried in a stream of air.
Exarnple 4.9: Coated ~ranules Active substance of Table 1 3 %
Polyethylene glycol (MW 200) 3 %
Kaolin 94 %
In a mixer, the finely-ground active substance or combination of active substances is applied uniforrnly to the kaolin which has been moistened with polyethylene glycol. In this manner, dust-free coated granules are obtained.
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Example 4.10: _spension concentrate Active substance of Table 1 40 %
Ethyleneglycol 10 %
Nonylphenol polyethylene glycol ether .
(lSmolofEO) 6 %
Na ligninsulfonate 10 %
Carboxymethylcellulose 1 %
37 % aqueous formaldehyde solu~ion ().2%
Silicone oil in the folm of a 75 % aqueous emulsion 0.8%
Water 32 %
The finely-ground active substance or the combination of active substances is mixed intimately with the additives. In this manner, a suspension concentrate is obtainecl from which suspensions of any desired concen~ation can be prepared by dilution with water.
Example 5: Effectiveness agains~ Nilaparvata lu~ens Rice plants are treated with an aqucous ernulsion spray mixture which contains 400 ppm of the active substance. After the spray coating has clried on, the rice plants are pop~llated with cicada larvae of the ~nd .md 3rd stage. The test is evalu.lted after 21 (lays. 'l he percentage reduction of the populatiorl (% efÇectivcness) i9 determirled by cornparirl~ the nllmbor of .suIviving cica~ s on thl~ treated plants witll those Oll the untreated plants.
In this test, the compounc!s of Table I are very effective against Nilaparvata lugens. In particular, cvmpounds 1.001, 1.008, 1.~9, 1.010, 1.011, 1.012, 1.015, 1.022, 1.024, 1.025, 1.028, 1.039, 1.081, 1.0~5, 1.101, 1.102, 1.103, 1.149, 1.153, 1.157, 1.165, 1.169, 1.183 and 1.189 have an effectiveness of more than 80 %.
Example 6: Effectiveness aga-i-nst Nephotettix cincticeps Rice plants are treated with an aqueous emulsion spray mixture which contains 400 ppm of the active substance. After the spray coating has dried on, the rice plants are populated with cicada larvae of the 2nd and 3rd stage. The test is evaluated after 21 days. The percentage reduction of the popula~ion (% effectiveness) is determined by comparing the number of survivin~ cicadas on the treated plants with those Oll the untreated plants.
In this test, the compounds of Table 1 are very effective against Nephotettix cincticeps. In particular, compounds 1.001, 1.008, 1.009, 1.010, 1.011, 1.012, 1.015, 1.022, 1.024, 1.025, 1.028, 1.039, 1.081, 1.085, 1.101, 1.102, 1.103, 1.1~g, 1.153, 1.157, 1.165, 1.169, 1.183 and 1.184 have an effectiveness of more than 80 %.
Example 7: Effectiveness a~ainst Spodoptera littoralis caterpillars Young soya plants are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active substance. After the spray coating has dried on, the soya plants are populated with 10 Spodoptera littoralis caterpillars of the third stage and placed in a plastic container. The test is evaluated after 3 days. The percentage reduction of the population, or the percentage reduction of feeding darnage, (% effectiveness) isdetermined by comparing the number of dead caterpillars and the feeding damage on the treated plants with those on the untreated plants.
In this test, the compounds of Table 1 are very effective against Spodoptera littoralis. In particular, compound 1.015 has an effectiveness of more than 80 %.
Ex,l~e 8: Effectlveness a~ainst Aphis cracci a Pea seedlin~s are infec,ted with ~phis craecivor.l, then sprayed with a sprily mixtule wllich cont;lirls 4()0 pprn of the netiv~ ~ubstnrlee, an~l incub.ltc,cl at 2()C. 'l'he tost is ev.~ .lte(l .llt~r 3 iln(l 6 d;lys. Th~ percent.l~e redueti(ln of the population ~/o effectiv~lIes~) is cletc,Imined by comparing the number oP dead aphids on the treated plants with tl-ose on the untreated plants.
In this test, the compounds of Table 1 are very effective against Aphis craccivora. In particular,compounds 1.008,1.010,1.()11,1.012,1.015,1.022,1.028,1.081,1.084, 1.085, 1.101, 1.157, 1.165 and 1.169 have an effectiveness of more than 80%.
Example 9. Ef~ectiYeness a~ainst Nilaparvata lu~ens, sYstemic Pots containing rice plants are placed in m aqueous emulsion solution which contains 400 ppm of the active substance. The rice plants are then populatecl with larvae of the 2nd and - (17 3rd stage. The test is ev"luated .Ifter 6 days. The percentage recluction of the population (% effectiveness) is deterrnine:l by comparing the number of cicadas on the treated plants with those on the untreated plants.
In this test, the compounds of Table 1 ~ure very effective against Nilaparvata lugens. In particular, compounds 1.001, 1.008, l.010, 1.011, 1.012, 1.015, 1.022, 1.024, 1.025, 1.028, 1.039, 1.081, 1.084,1.085, l.101, 1.102, 1.103, 1.149, 1.153, 1.157, 1.165, 1.16~), 1.183 and 1.184 have an effectiveness of more than 80 %, even when the concentration is 12.5 ppm.
Example 10: Effectiveness a~ainst Nepho~ettix cincticeps, sYstemic Pots containing rice plants are placed in an aqueous emulsion solution which contains 400 ppm of the active substance. The rice plants are then populated with larvae of the 2nd and 3rd stage. The test is evaluated after 6 days. The percentage reduction of the population (% effectiveness) is determined by comparing the number of cicadas on the treated plants with those on the untreated plants.
In this test, the compounds of Table 1 are very effective against Nephotettix cincticeps. In particular, compounds 1.008, 1.010, 1.011, 1.012, 1.015, 1.022, 1.024, 1.025, 1.028, 1.039, 1.081, 1.084, 1 085,1.101, 1.102~ 1.10~, 1.1~9, 1.153, 1.157, l.l65, l.lt~, 1.183 I .184 have an effectiveness of more than 80 crto.
Exarl1~?le 11. E~f~ctiveness a~t MY~Ig ~ ;iCaC systerTlic Pe~a scc(llings are infectecl with Myxus persicae, then placed with their roots in a spray mixture which contains 400 ppm of the active substance, and incubated at 20C. The test is evaluated after 3 and 6 days. The percentage reduction of the population (% effectiveness) is deterrnined by comparing the number of dead aphids on the treated plants with those on the untreated plants.
In this test, the compounds of 'I'able 1 are very effective against Myzus persicae. In particular, compounds 1.008, 1.010, 1.011, 1.012, 1.015, 1.028, 1.081, 1.084, 1.085, 1.101, 1.149, 1.153, 1.157, 1.165 and 1.169 have an effectiveness of more than 80%.
~ ~3 ~
Example 12: Effectiveness a~ainst Anthonomus grandis adults Young cotton plants are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active substance. When the spray coating has dried on, the cotton plants are populated with 10 Anthonomus grandis adults and placed in a plastic container ~he test is evaluated after 3 days. The percentage reduction of the population, or the percentage reduction of the feeding damage ~% effectiveness), is determined by comparing the number of dead beetles and the feeding damage on the treated plants with those on the untreated plants.
In this test, the compounds of Table 1 are very effective against Anthonomus grandis. In particular, compounds 1.008, 1.010, 1.011, 1.012, 1.015, 1.022, 1.028, 1.101, 1.149 and 1.153 have an effectiveness of more than 80 %.
~xample 13: Effectiveness a~ainst Bemisia tabaci Dwarf bean plants are placed in gauze cages and populated with Bemisia tabaci adults (whitefly). When oviposition has taken place, all adults are removed, and, after 10 days, the plants together with the nymphs which live on them are treated with an aqueous emulsion spray mixture of the active substances to be tested (concentration 400 ppm). 14 days after the active substance has been applied, the h.ltching rate is evalu.ltecl as a percentage in cornparison with the untreated control batchex.
~n this test, the eompolln(ls in accor(l.lnce with l'able 1 are very efl~ective a~.lins~ Bemisia tabaci. In partieular, compouncls 1.011, 1.()12, 1.015, 1.081, 1.084, 1.085, 1.101 and 1.1~)2 have an effectiveness of more than 80 %.
Example 1~: Effectiveness against Diabrotica balteata larvae Maize seedlings are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active substance. When the spray coating has dried on, the rnaize seedlings are populated with 10 Diabrotica balteata larvae of the second stage and placed in a plastic container. The test is evaluated after 6 days. The percentage reduction of the population (/0 effectiveness) is determined by comparing the number of dead larvae on the treated plants with those on the untreated plants.
~J ~ ~, In this test, the compounds of Table 1 are very effective against Diabrotica balteata. In particular, compounds 1.010, 1.012 and 1.015 have an effectiveness of more than 80 %.
Exam~le 15: Effectiveness against Heliothis virescens caterpillars Young soya plants are sprayed with all aqueous emulsion spray mixture which contains 400 ppm of the active substance. After the spray coating has dried on, the soya plants are populated with 10 caterpillars of the first sta~e of Heliothis virescens and placed in a plastic container. The test is evaluated after 6 days. Ihe percentage reduction of the population, or the percentage reduction of the feeding damage, (% effectiveness) is determined by comparing the number of dead caterpillars and the feeding darnage on the treated plants with those on the untreated plants.
' In this test, the compounds of Table 1 are very effective against Heliothis virescens. In particular, compounds 1.010, 1.011 and 1.015 have an effectiveness of more than 80 %.
Example 16: Effectiveness a~ainst Crocidolomia binotalis caterpillars Young cabbage plants are sprayed with an aqueous esnulsion spray mixture which contains 400 ppm of the active substance. After the spray coating has dr~ed orl, the cabbage plants are populated with 10 caterpillars of the thircl ~tage of Crvci(:Lolvmia binotalis and placed in a plastic container. The test is evaluated aftcl 3 d;lys. The percenta~e reduction of the poplllation, or the pcrcenta~e redllctiorl of ~he fee(ling d;lmage, (% effectivencss) ix determined by comparin~ the numbcr of ~lea(l caterpillars and the Peeding darnage on the treated plants with those on the untreated plants.
In this test, the cornpounds of Table 1 are very effective against Crocidolomia binotalis. In particular, compound 1.015 has an effectiveness of more than 80 %.
Effectiveness a~ainst MYZUS persicae Pea seedlings are infected with Myzus persicae, th~n sprayed with a spray liquor which contains 400 ppm of the active substance, and incubated at 20C The test is evaluated after 3 and 6 days The percentage reduction of the popula~ion (% effectiveness) is deterrnined by comparing the number of dead aphids on the treated plants with those on the untreated plants.
r~ r~ ~3 - 7() -In this test, the compounds of Table I are very effec~ive against Myzus persicae. In particular, compounds 1.008, 1.010, 1.012, 1.015, 1.022 and 1.157 have an effectiveness of more than 80 %.
Claims (36)
1. A compound of the formula I
(I) in which R1 is hydrogen, C1-C6alkyl or C3-C6cycloalkyl, R2 is hydrogen or C1-C6alkyl, R3 is hydrogen, C1-C6alkyl or C3-C6cycloalkyl, R4 is hydrogen, C1-C6alkyl, C3-C6cycloalkyl or a radical -CH2-B, or R3 and R4 together are -(CH2)4- or -(CH2)5-;
X is halogen or C1-C6haloalkyl;
Y and Z are halogen;
A is an unsubstituted or monosubstituted to tetrasubstituted aromatic or non-aromatic, monocyclic or bicyclic, heterocyclic radical in which one or two substituents belong to the group comprising C1-C3haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl, C2-C3haloalkynyl, C1-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro and one to four substituents belong to the group comprising C1-C3alkyl, C1-C3alkoxy and halogen;
B is phenyl, cyanophenyl, nitrophenyl, halophenyl having 1 to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, or 5-thiazolyl which is substituted by one to two substituents from the group comprising C1-C3alkyl, C1-C3haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C1-C3alkoxy, C2-C3haloalkenyl, C2-C3haloalkynyl, C1-C3haloalkoxy, C1-C3alkylthio, Cl-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro; or 3-pyridyl which is substituted by one to two radicals from the group comprising C1-C3haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl, C2-C3haloalkynyl,C1-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro or by one to four radicals from the group comprising C1-C3alkyl, C1-C3alkoxy or halogen, and their salts with inorganic acids; it only being possible for one of the radicals R1, R3 and R4 to be hydrogen.
(I) in which R1 is hydrogen, C1-C6alkyl or C3-C6cycloalkyl, R2 is hydrogen or C1-C6alkyl, R3 is hydrogen, C1-C6alkyl or C3-C6cycloalkyl, R4 is hydrogen, C1-C6alkyl, C3-C6cycloalkyl or a radical -CH2-B, or R3 and R4 together are -(CH2)4- or -(CH2)5-;
X is halogen or C1-C6haloalkyl;
Y and Z are halogen;
A is an unsubstituted or monosubstituted to tetrasubstituted aromatic or non-aromatic, monocyclic or bicyclic, heterocyclic radical in which one or two substituents belong to the group comprising C1-C3haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl, C2-C3haloalkynyl, C1-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro and one to four substituents belong to the group comprising C1-C3alkyl, C1-C3alkoxy and halogen;
B is phenyl, cyanophenyl, nitrophenyl, halophenyl having 1 to 3 halogen atoms, 3-pyridyl, 5-thiazolyl, or 5-thiazolyl which is substituted by one to two substituents from the group comprising C1-C3alkyl, C1-C3haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C1-C3alkoxy, C2-C3haloalkenyl, C2-C3haloalkynyl, C1-C3haloalkoxy, C1-C3alkylthio, Cl-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro; or 3-pyridyl which is substituted by one to two radicals from the group comprising C1-C3haloalkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl, C2-C3haloalkynyl,C1-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro or by one to four radicals from the group comprising C1-C3alkyl, C1-C3alkoxy or halogen, and their salts with inorganic acids; it only being possible for one of the radicals R1, R3 and R4 to be hydrogen.
2. A compound of the formula I according to claim 1, in which the heterocyclic radical A
is unsaturated and bonded to the radical of the compound of the formula I via one of its ring carbon atoms.
is unsaturated and bonded to the radical of the compound of the formula I via one of its ring carbon atoms.
3. A compound of the formula I according to claim 2, in which the heterocyclic radical A
contains at least one nitrogen atom.
contains at least one nitrogen atom.
4. A compound of the formula I according to claim 2, in which the heterocyclic radical A
contains 1 to 3 hetero atoms from the series comprising oxygen, sulfur and nitrogen, of which not more than one is an oxygen or sulfur atom.
contains 1 to 3 hetero atoms from the series comprising oxygen, sulfur and nitrogen, of which not more than one is an oxygen or sulfur atom.
5. A compound of the formula I according to claim 2, in which the heterocyclic radical A
is one of the skeletons from the group comprising , , , , , , , , , , ' , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ' ' , , , , , , , and , each of which is unsubstituted or, depending on the scope of the ring system in question for substitution, carries up to four of the substituents defined in claim 1, E being C1-C3alkyl and Y being hydrogen, C1-C3alkyl or cyclopropyl.
is one of the skeletons from the group comprising , , , , , , , , , , ' , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ' ' , , , , , , , and , each of which is unsubstituted or, depending on the scope of the ring system in question for substitution, carries up to four of the substituents defined in claim 1, E being C1-C3alkyl and Y being hydrogen, C1-C3alkyl or cyclopropyl.
6. A compound of the formula I according to claim 1, in which the heterocyclic radicals A
are unsubstituted or carry one to three substituents from the group comprising halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3haloalkoxy or C1-C3alkoxy.
are unsubstituted or carry one to three substituents from the group comprising halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3haloalkoxy or C1-C3alkoxy.
7. A compound of the formula I according to claim 6, in which the heterocyclic radicals A
are pyridyl radicals or thiazolyl radicals.
are pyridyl radicals or thiazolyl radicals.
8. A compound of the formula I according to claim 7, in which A is 3-pyridyl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl or 2-halothiazol-4-yl, 1-oxopyrid-3-yl, 1-oxo-2-halopyrid-5-yl or 1-oxo-2,3-dihalopyrid-5-yl.
9. A compound of the formula I according to claim 1, in which the radical B is a phenyl, pyridyl or thiazolyl radical, each of which is unsubstituted or substituted by one to two radicals from the group comprising halogen, C1-C3alkyl, C1-C3haloalkyl, C1-C3haloalkoxy or C1-C3alkoxy.
10. A compound of the formula I according to claim 1, in which R1 and R3 are hydrogen, methyl, ethyl or cyclopropyl.
11. A compound of the formula I according to claim 1, in which R2 is hydrogen.
12. A compound of the formula I according to claim 1, in which R4 is hydrogen or methyl.
13. A compound of the formula I according to claim 1, in which R1 and R3 independently of one another are hydrogen, methyl, ethyl, or cyclopropyl, R2 is hydrogen, R4 is hydrogen or methyl, A is pyridyl, 1-oxopyridyl, thiazolyl, or pyridyl, 1-oxopyridyl or thiazolyl, each of which is substituted by one to three substituents from the group comprising halogen, C1-C3alkyl, C1-3haloalkyl, C1-C3haloalkoxy or C1-C3alkoxy.
14. A compound of the formula I according to claim 1, in which is fluorine, chlorine, bromine or C1-C3haloalkyl having 1 to 7 fluorine atoms, and Y and Z independently of one another are fluorine, chlorine or bromine.
15. A compound of the formula I according to claim 1, in which X, Y and Z independently of one another are fluorine, chlorine or bromine.
16. A compound of the formula I according to claim 15, in which X, Y and Z are chlorine.
17. A compound of the formula I according to claim 13, in which R1 and R3 are methyl;
R2 and R4 are hydrogen; and X, Y and Z independently of one another are fluorine, chlorine or bromine.
R2 and R4 are hydrogen; and X, Y and Z independently of one another are fluorine, chlorine or bromine.
18. A compound of the formula I according to claim 13, in which A is pyridyl or pyridyl which is substituted by one or two chlorine atoms.
19. A compound according to claim 15, in which X is fluorine or bromine, and Y and Z
are halogen.
are halogen.
20. A compound according to claim 19, in which X is fluorine, and Y and Z are fluorine or chlorine.
21. A compound according to claim 14, in which X is C1-C6haloalkyl having 4 to 13 halogen atoms.
22. A compound according to claim 21, in which X is C1-C6haloalkyl having 2 to 13 halogen atoms.
23. A compound according to claim 14, in which X is trifluoromethyl.
24. A compound according to claim 14, in which X is a radical -C2F5 or -C3F7.
25. A compound of the formula I according to claim 13, in which A is thiazolyl or thiazolyl which is substituted by one chlorine atom, preferably 1,3-thiazol-5-yl.
26. A compound according to claim 16, of the formula
27. A compound according to claim 16, of the formula
28. A compound according to claim 16, of the formula
29. A compound according to claim 16, of the formula
30. A compound according to claim 16, of the formula
31. A compound of the formula I according to claim 13, selected from the group comprising , , , , , , , , , , , , , , , , and .
32. A process for the preparation of a compound of the formula I according to claim 1 (I), which comprises reacting a compound of the formula II
(II) with a compound of the forrnula III
(III) under pH-neutral reaction conditions, R1 to R4, A, X, Y and Z being as defined in claim 1.
(II) with a compound of the forrnula III
(III) under pH-neutral reaction conditions, R1 to R4, A, X, Y and Z being as defined in claim 1.
33. A composition for controlling pests, which contains, besides inert additions and formulation auxiliaries, a pesticidally effective amount of a compound of the formula I
according to claim 1 as the active component.
according to claim 1 as the active component.
34. A method of controlling insects and representatives of the order of the Acarina, which comprises bringing in contact, or treating, pests or various development stages thereof, and/or their locus, with a pesticidally effective amount of a compound of the formula I
according to claim 1 or with a composition comprising, besides additives and carriers, a pesticidally effective amount of this compound.
according to claim 1 or with a composition comprising, besides additives and carriers, a pesticidally effective amount of this compound.
35. A method according to claim 34 for controlling plant-injurious insects.
36. A process according to claim 35 for controlling plant-injurious sucking insects.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1169/90-8 | 1990-04-06 | ||
| CH116990 | 1990-04-06 | ||
| CH3481/90-9 | 1990-11-02 | ||
| CH348190 | 1990-11-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2039779A1 true CA2039779A1 (en) | 1991-10-07 |
Family
ID=25686877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002039779A Abandoned CA2039779A1 (en) | 1990-04-06 | 1991-04-04 | Nitroenamine derivatives |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0453398A3 (en) |
| JP (1) | JPH04234848A (en) |
| KR (1) | KR910018356A (en) |
| CN (1) | CN1055356A (en) |
| AU (1) | AU640999B2 (en) |
| BR (1) | BR9101372A (en) |
| CA (1) | CA2039779A1 (en) |
| HU (1) | HUT56810A (en) |
| IE (1) | IE911142A1 (en) |
| IL (1) | IL97680A0 (en) |
| NZ (1) | NZ237681A (en) |
| PT (1) | PT97265A (en) |
| TR (1) | TR25776A (en) |
| YU (1) | YU60991A (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2061569T3 (en) * | 1987-08-01 | 1994-12-16 | Takeda Chemical Industries Ltd | ALPHA UNSATURATED AMINES, THEIR PRODUCTION AND USE. |
| US4918086A (en) * | 1987-08-07 | 1990-04-17 | Ciba-Geigy Corporation | 1-nitro-2,2-diaminoethylene derivatives |
| IL94027A (en) * | 1989-04-14 | 1995-03-15 | Takeda Chemical Industries Ltd | Diaminoethylene compounds, process for their preparation and insecticidal compositions containing them. |
-
1991
- 1991-03-26 IL IL97680A patent/IL97680A0/en unknown
- 1991-03-27 EP EP19910810225 patent/EP0453398A3/en not_active Withdrawn
- 1991-04-02 KR KR1019910005259A patent/KR910018356A/en not_active Application Discontinuation
- 1991-04-04 YU YU60991A patent/YU60991A/en unknown
- 1991-04-04 NZ NZ237681A patent/NZ237681A/en unknown
- 1991-04-04 CA CA002039779A patent/CA2039779A1/en not_active Abandoned
- 1991-04-04 AU AU74091/91A patent/AU640999B2/en not_active Ceased
- 1991-04-05 PT PT97265A patent/PT97265A/en not_active Application Discontinuation
- 1991-04-05 BR BR919101372A patent/BR9101372A/en not_active Application Discontinuation
- 1991-04-05 HU HU911125A patent/HUT56810A/en unknown
- 1991-04-05 TR TR91/0369A patent/TR25776A/en unknown
- 1991-04-05 JP JP3100470A patent/JPH04234848A/en active Pending
- 1991-04-05 CN CN91102178A patent/CN1055356A/en active Pending
- 1991-04-05 IE IE114291A patent/IE911142A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| TR25776A (en) | 1993-09-01 |
| AU7409191A (en) | 1991-10-24 |
| YU60991A (en) | 1994-05-10 |
| PT97265A (en) | 1992-01-31 |
| AU640999B2 (en) | 1993-09-09 |
| JPH04234848A (en) | 1992-08-24 |
| IE911142A1 (en) | 1991-10-09 |
| IL97680A0 (en) | 1992-06-21 |
| EP0453398A3 (en) | 1992-05-20 |
| NZ237681A (en) | 1994-08-26 |
| EP0453398A2 (en) | 1991-10-23 |
| KR910018356A (en) | 1991-11-30 |
| HUT56810A (en) | 1991-10-28 |
| BR9101372A (en) | 1991-11-26 |
| CN1055356A (en) | 1991-10-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |