CA2012499A1 - Nematicidal and fungicidal compositions - Google Patents
Nematicidal and fungicidal compositionsInfo
- Publication number
- CA2012499A1 CA2012499A1 CA002012499A CA2012499A CA2012499A1 CA 2012499 A1 CA2012499 A1 CA 2012499A1 CA 002012499 A CA002012499 A CA 002012499A CA 2012499 A CA2012499 A CA 2012499A CA 2012499 A1 CA2012499 A1 CA 2012499A1
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- Prior art keywords
- unsubstituted
- substituted
- formula
- thiazol
- halo
- Prior art date
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
- A01N43/82—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 three ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Nematicidal and fungicidal compositions Abstract of the Disclosure 2-Mercapto-5-thiazol-(2-, 4- or 5-yl)-1,3,4-oxa- and -thia-diazoles and 2-mercapto-5-oxa-zol-(2-, 4- or 5-yl)-1,3,4-oxa- and -thia-diazoles of formula I
(I) wherein X1 and X2 independently of one another are oxygen or sulfur, R1 is unsubstituted C1-C5alkyl or C1-C5alkyl substituted by halogen, C1-C3alkoxy or by cyano; unsubstituted or halo-substituted C3-C7alkenyl; or unsubstituted or halo-substituted C3-C7alkynyl, R2 and R3 independently of one another are hydrogen, C1-C5alkyl, unsubstituted or halo-sub-stituted C3-C7alkenyl, unsubstituted phenyl or phenyl substituted by identical or different substituents selected from C1-C3alkyl, C1-C3alkoxy and halogen, or the radical -NR4R5 wherein R4 and R5 independently of one another are hydrogen, C1-C5alkyl or unsubsti-tuted or halo-substituted C3-C7alkenyl, or one of the two substituents R2 and R3 may be one of the unsubstituted or substituted heterocycles pyridyl, thienyl, furyl and thiazolyl, a process for the preparation of the compounds of formula I, and novel intermediates of the preparation process are described.
The compounds of formula I possess nematicidal and fungicidal properties. Nematicidal and fungicidal compositions that contain at least one compound of formula I as active ingredient, and also methods of using the active ingredients and the compositions in the control of nematodes and fungi, are described.
(I) wherein X1 and X2 independently of one another are oxygen or sulfur, R1 is unsubstituted C1-C5alkyl or C1-C5alkyl substituted by halogen, C1-C3alkoxy or by cyano; unsubstituted or halo-substituted C3-C7alkenyl; or unsubstituted or halo-substituted C3-C7alkynyl, R2 and R3 independently of one another are hydrogen, C1-C5alkyl, unsubstituted or halo-sub-stituted C3-C7alkenyl, unsubstituted phenyl or phenyl substituted by identical or different substituents selected from C1-C3alkyl, C1-C3alkoxy and halogen, or the radical -NR4R5 wherein R4 and R5 independently of one another are hydrogen, C1-C5alkyl or unsubsti-tuted or halo-substituted C3-C7alkenyl, or one of the two substituents R2 and R3 may be one of the unsubstituted or substituted heterocycles pyridyl, thienyl, furyl and thiazolyl, a process for the preparation of the compounds of formula I, and novel intermediates of the preparation process are described.
The compounds of formula I possess nematicidal and fungicidal properties. Nematicidal and fungicidal compositions that contain at least one compound of formula I as active ingredient, and also methods of using the active ingredients and the compositions in the control of nematodes and fungi, are described.
Description
2012499 ~ ~
PS/5-17507/~-3/=
Nematicidal and fungicidal compositions ~ ~ ~
The present invention relates to novel substituted oxa- and thia-diazoles, to their prepara- ~ ;
tion and to nematicidal compositions that contain at least one of those compounds as active ingredient. The invention also relates to novel intermediates of the process for the preparation of the active ingredients, to their use and to compositions for controlling nematodes and fungi, especially plant-destructive nematodes and fungi.
The invention relates to 2-mercapto-5-thiazol-(2-, 4- or 5- yl)-1,3,4-oxa- and -thia-diazoles and 2-mercapto-5-oxazol-(2-, 4- or 5-yl)-1,3,4-oxa- and -thia-diazoles of formula I -N N--N
R3~X ~--SR~
~:' . ':
wherein Xl and X2 independently of one another are oxygen or sulfur, Rl is unsubstituted ; ~ ~ -Cl-Csalkyl or Cl-C5alkyl substituted by halogen, Cl-C3alkoxy or by cyano; unsubstituted ~;
or halo-substituted C3-C7aLIcenyl; or unsubstituted or halo-substituted C3-C7aLlcynyl, R2 ~ ;
and R3 independently of one another are hydrogen, Cl-Csalkyl, unsubstituted or halo-substituted C3-C7aL~cenyl, unsubstituted phenyl or phenyl substituted by identical or different substituents selected from Cl-C3aLl~yl, Cl-C3aL~oxy and halogen, or the radical `
-NR4Rs wherein R4 and Rs independently of one another are hydrogen, Cl-CsaLtcyl or unsubstituted or halo-substituted C3-C7allcenyl, or one of the two substituents R2 and R
may be one of the heterocyclic radicals pyridyl, thienyl, furyl and thiazolyl, which may be unsubstituted or monO- or poly-substituted by identical or different substituents selected from Cl-C3alkyl, Cl-C3alkoxy and halogen; and salts of those compounds.
:,: . - ~ ;- :~:.
Alkyl as an independent radical and as part of another group, such as aL~coxy, shall be understood as being straight-chain and branched-chain alkyl groups. Such groups include methyl, ethyl and norrnal and isomeric propyl, butyl and pentyl groups. Halo-substituted alkyl is a mono- to per-halogenated alkyl radical, for example CHCl2, CH2F, CCl3, ;
CH2Cl, CHFCH3, CH2CH2Br, CF2CF3, C2Cls, CH2Br, CHBrCl etc., preferably CHF2.
Z0~2499 ALtcenyl is, for example, propenyl-(l), allyl, butenyl-(l), butenyl-(2) or butenyl-(3) and chains having several double bonds. Alkynyl is, for example, propynyl-(2), butynyl-(l), ~ -butynyl-(2), pentynyl-(4), etc.. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
The pyridyl radical mentioned as substituent may be bonded to the oxazole or thiazole ring by the carbon atom in the 2-, 3- or 4-position, the furyl or thienyl radicals by the carbon atom in the 2- or 3-position, and the thiazolyl radical by the carbon atom in the 2-, 4- or 5-position.
Examples of sal,-forrning acids are, of the inorganic acids: hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid and also sulfuric acid, phosphoric acid, phosphorous acid, nitric acid, and of the organic acids: acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid or 2-acetoxybenzoic acid.
Oxadiazole and thiadiazole derivatives that are described as being nematicidally active are already known. For example, US Patent Specification 3 770 754 discloses suchcompounds in which the hetero atoms are in the 1,2,4-position, while US Patent Specifi-cation 4 454 147 describes 1,3,4-thiadiazole derivatives in which, as compared with the compounds according to the invention, the heterocycle is substituted by a chlorine atom ;~
instead of by mercapto groups. As nematicides, these known compounds have hitherto been unable fully to satisfy the demands made of them in practice. In addition, oxa-diazole derivatives having fungicidal activity are described in DE-OS 2 361 613 but none of the compounds mentioned expressis verbis therein falls within the scope of formula I
according to the invention.
With the provision of the compounds of formula I according to the invention, it is now possible to make a valuable contribution to controlling plant nematodes and fungi which cause considerable agricultural damage to plants. In this manner, harvest losses of cultivated plants, for example potatoes, cereals, beet crops, rape, cabbage, tobacco, soybeans, cotton, maize, rice and vegetables, and also damage caused in tree nurseries and to ornamentals can be inhibited over a prolonged period. The compounds according to the invention are distinguished especially by the feature that they effectively control soil ::: :, ', .. , ':., ., , , :, . '~ :,: . ,., . ",, ',: . ~ , .: . ' ,' . .:`:, . ..
2012499 : ~
PS/5-17507/~-3/=
Nematicidal and fungicidal compositions ~ ~ ~
The present invention relates to novel substituted oxa- and thia-diazoles, to their prepara- ~ ;
tion and to nematicidal compositions that contain at least one of those compounds as active ingredient. The invention also relates to novel intermediates of the process for the preparation of the active ingredients, to their use and to compositions for controlling nematodes and fungi, especially plant-destructive nematodes and fungi.
The invention relates to 2-mercapto-5-thiazol-(2-, 4- or 5- yl)-1,3,4-oxa- and -thia-diazoles and 2-mercapto-5-oxazol-(2-, 4- or 5-yl)-1,3,4-oxa- and -thia-diazoles of formula I -N N--N
R3~X ~--SR~
~:' . ':
wherein Xl and X2 independently of one another are oxygen or sulfur, Rl is unsubstituted ; ~ ~ -Cl-Csalkyl or Cl-C5alkyl substituted by halogen, Cl-C3alkoxy or by cyano; unsubstituted ~;
or halo-substituted C3-C7aLIcenyl; or unsubstituted or halo-substituted C3-C7aLlcynyl, R2 ~ ;
and R3 independently of one another are hydrogen, Cl-Csalkyl, unsubstituted or halo-substituted C3-C7aL~cenyl, unsubstituted phenyl or phenyl substituted by identical or different substituents selected from Cl-C3aLl~yl, Cl-C3aL~oxy and halogen, or the radical `
-NR4Rs wherein R4 and Rs independently of one another are hydrogen, Cl-CsaLtcyl or unsubstituted or halo-substituted C3-C7allcenyl, or one of the two substituents R2 and R
may be one of the heterocyclic radicals pyridyl, thienyl, furyl and thiazolyl, which may be unsubstituted or monO- or poly-substituted by identical or different substituents selected from Cl-C3alkyl, Cl-C3alkoxy and halogen; and salts of those compounds.
:,: . - ~ ;- :~:.
Alkyl as an independent radical and as part of another group, such as aL~coxy, shall be understood as being straight-chain and branched-chain alkyl groups. Such groups include methyl, ethyl and norrnal and isomeric propyl, butyl and pentyl groups. Halo-substituted alkyl is a mono- to per-halogenated alkyl radical, for example CHCl2, CH2F, CCl3, ;
CH2Cl, CHFCH3, CH2CH2Br, CF2CF3, C2Cls, CH2Br, CHBrCl etc., preferably CHF2.
Z0~2499 ALtcenyl is, for example, propenyl-(l), allyl, butenyl-(l), butenyl-(2) or butenyl-(3) and chains having several double bonds. Alkynyl is, for example, propynyl-(2), butynyl-(l), ~ -butynyl-(2), pentynyl-(4), etc.. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
The pyridyl radical mentioned as substituent may be bonded to the oxazole or thiazole ring by the carbon atom in the 2-, 3- or 4-position, the furyl or thienyl radicals by the carbon atom in the 2- or 3-position, and the thiazolyl radical by the carbon atom in the 2-, 4- or 5-position.
Examples of sal,-forrning acids are, of the inorganic acids: hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid and also sulfuric acid, phosphoric acid, phosphorous acid, nitric acid, and of the organic acids: acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid or 2-acetoxybenzoic acid.
Oxadiazole and thiadiazole derivatives that are described as being nematicidally active are already known. For example, US Patent Specification 3 770 754 discloses suchcompounds in which the hetero atoms are in the 1,2,4-position, while US Patent Specifi-cation 4 454 147 describes 1,3,4-thiadiazole derivatives in which, as compared with the compounds according to the invention, the heterocycle is substituted by a chlorine atom ;~
instead of by mercapto groups. As nematicides, these known compounds have hitherto been unable fully to satisfy the demands made of them in practice. In addition, oxa-diazole derivatives having fungicidal activity are described in DE-OS 2 361 613 but none of the compounds mentioned expressis verbis therein falls within the scope of formula I
according to the invention.
With the provision of the compounds of formula I according to the invention, it is now possible to make a valuable contribution to controlling plant nematodes and fungi which cause considerable agricultural damage to plants. In this manner, harvest losses of cultivated plants, for example potatoes, cereals, beet crops, rape, cabbage, tobacco, soybeans, cotton, maize, rice and vegetables, and also damage caused in tree nurseries and to ornamentals can be inhibited over a prolonged period. The compounds according to the invention are distinguished especially by the feature that they effectively control soil ::: :, ', .. , ':., ., , , :, . '~ :,: . ,., . ",, ',: . ~ , .: . ' ,' . .:`:, . ..
2012499 : ~
-3- ~ ~
., .
nematodes that parasitise roots, for example those nematodes of the genera Heterodera and Globodera (cystogenic nematodes), Meloidogyne (root-knot nematodes) and also of the genera Radopholus, Pratylenchus, Tylenchulus, Longidorus, Trichodorus and Xiphinema. The nematodegeneraDitylenchus(stemparasites),Aphelenchoides (leaf nematodes) and Anguina (blossom nematodes) can also be effectively controlled with the activeingredients according totheinvention.
:
Preferably, the compounds of formula I are used for successfully controlling especially harmful nematode species of the genus Meloidogyne, for example Meloidogyne incognita, of the genus Heterodera, for example Heterodera glycines (soybean cyst nematode), and of the genus Globodera, for example Globodera rostochiensis (potato cyst nematode), as well as representatives of migrating endoparasites, for example Pratylenchus penetrans or Radopholus similis, and representatives of ectoparasites, for -example Trichodorus spp. and Xiphinema spp..
Preferably, the compounds of formula I are likewise used for successfully controlling - - -especially harmful soil fungi of the genus Pythium, for example Pythium ultimum, and of ~ `
the genus Rhizoctonia, for example Rhizoctonia solani.
:
To control plant nematodes and soil fungi and for the preservation of plant health, the -novel active ingredients may be used curatively, preventively or systemically. They have ~ -a broad spectrum of activity against the various nematode and soil fungus species and therefore meet the requirements made of them in practice. The nematicidal and `~
fungicidal mode of action of the compounds of the invention is coupled in advantageous manner with their low phytotoxicity, whereby the generally desirable reduction of harm `
to the environment is especially accommodated.
:, :.:. :, : . :
A preferred sub-group comprises compounds of formula I wherein X1 and X2 indepen-dently of one another are O or S, and Rl is halo-substituted C~-CsaLkyl; unsubstituted or halo-substituted C3-C7aLkenyl; or unsubstituted or halo-substituted C3-C7alkynyl; R2 is hydrogen or Cl-C3alkyl; R3 is hydrogen, Cl-C3alkyl, unsubstituted phenyl or phenyl substituted by identical or different substituents selected from Cl-C3alkyl, Cl-C3alkoxy and halogen, or is the radical - NR4Rs, or one of the two substituents R2 and R3 may be - `
one of the heterocycles pyridyl, thienyl, furyl and thiazolyl, which may be unsubstituted or mono- or di-substituted by identical or different substituents selected from C1-C3alkyl, C1-C3aLkoxy and halogen. - -. . . -::.,: .
. ~" : ,....
,~ :,. .
: .'. ..:
., .
nematodes that parasitise roots, for example those nematodes of the genera Heterodera and Globodera (cystogenic nematodes), Meloidogyne (root-knot nematodes) and also of the genera Radopholus, Pratylenchus, Tylenchulus, Longidorus, Trichodorus and Xiphinema. The nematodegeneraDitylenchus(stemparasites),Aphelenchoides (leaf nematodes) and Anguina (blossom nematodes) can also be effectively controlled with the activeingredients according totheinvention.
:
Preferably, the compounds of formula I are used for successfully controlling especially harmful nematode species of the genus Meloidogyne, for example Meloidogyne incognita, of the genus Heterodera, for example Heterodera glycines (soybean cyst nematode), and of the genus Globodera, for example Globodera rostochiensis (potato cyst nematode), as well as representatives of migrating endoparasites, for example Pratylenchus penetrans or Radopholus similis, and representatives of ectoparasites, for -example Trichodorus spp. and Xiphinema spp..
Preferably, the compounds of formula I are likewise used for successfully controlling - - -especially harmful soil fungi of the genus Pythium, for example Pythium ultimum, and of ~ `
the genus Rhizoctonia, for example Rhizoctonia solani.
:
To control plant nematodes and soil fungi and for the preservation of plant health, the -novel active ingredients may be used curatively, preventively or systemically. They have ~ -a broad spectrum of activity against the various nematode and soil fungus species and therefore meet the requirements made of them in practice. The nematicidal and `~
fungicidal mode of action of the compounds of the invention is coupled in advantageous manner with their low phytotoxicity, whereby the generally desirable reduction of harm `
to the environment is especially accommodated.
:, :.:. :, : . :
A preferred sub-group comprises compounds of formula I wherein X1 and X2 indepen-dently of one another are O or S, and Rl is halo-substituted C~-CsaLkyl; unsubstituted or halo-substituted C3-C7aLkenyl; or unsubstituted or halo-substituted C3-C7alkynyl; R2 is hydrogen or Cl-C3alkyl; R3 is hydrogen, Cl-C3alkyl, unsubstituted phenyl or phenyl substituted by identical or different substituents selected from Cl-C3alkyl, Cl-C3alkoxy and halogen, or is the radical - NR4Rs, or one of the two substituents R2 and R3 may be - `
one of the heterocycles pyridyl, thienyl, furyl and thiazolyl, which may be unsubstituted or mono- or di-substituted by identical or different substituents selected from C1-C3alkyl, C1-C3aLkoxy and halogen. - -. . . -::.,: .
. ~" : ,....
,~ :,. .
: .'. ..:
Of this group, significant compounds are those wherein Xl and X2 independently of one another are oxygen or sulfur and Rl is Cl-Cshaloalkyl; unsubstituted or halo-substituted C3-C7alkenyl; or unsubstituted or halo-substituted C3-C7aikynyl; R2 is hydrogen or Cl-C3-alkyl; R3 is hydrogen, Cl-Csalkyl, unsubstituted phenyl or phenyl substituted by identical or different substituents selected from Cl-C3alkyl, Cl-C3alkoxy and halogen, or one of the two substituents R2 and R3 may be one of the heterocycles pyridyl, thienyl, furyl and thiazolyl, which may be unsubstituted or rnono- or di-substituted by identical or different substituents selected from Cl-C3alkyl, Cl-C3alkoxy and halogen.
Also preferred are compounds of formula I wherein Xl and X2 independently of oneanother are oxygen or sulfur, Rlis unsubstituted Cl-Csalkyl or Cl-Csalkyl substituted by -halogen, Cl-C3alkoxy or by cyano; unsubstituted or halo- substituted C3-C7aL~cenyl; or ~ -unsubstituted or halo-substituted C3-C7alkynyl; R2 and R3 independently of one another are hydrogen, Cl-C3alkyl, unsubstituted phenyl or phenyl substituted by Cl-C3aLtcyl, Cl-C3alkoxy or by halogen, or pyridyl, thienyl, furyl or thiazolyl.
Also preferred within the scope of the present invention are those 2-mercapto-5-thiazol- ~ :
(2-, 4- or 5-yl)-1,3,4-oxadiazoles of formula Ia N N--N
3~o~--SR1 (Ia) X1 :'' wherein Rl is difluoromethyl, 3,4,4-trifluoro-3-butene, cyanomethyl, difluoromethyl-difluoromethyl or propargyl, and R2 and R3 independently of one another are hydrogen or methyl.
Of those compounds, the following individual compounds are especially preferred:2-difluoromethylthio-S-(thiazol-2-yl)-1,3,4-oxadiazole, 2-(3,4,4-trifluoro-3-butenylthio)-(thiazol-2-yl)-1,3,4-oxadiazole, 2-difluoromethylthio-5-(2-methylthiazol-4-yl)-1,3,4-oxadiazole, 2-(3,4,4-trifluoro-3-butenylthio)-5-(2-methylthiazol-4-yl)- 1 ,3,4-oxadiazole, 2-(3,4,4-trifluoro-3-butenylthio)-5-2-(pyrid-3-yl)-thiazol-4-yl- 1 ,3,4-oxadiazole, 2-difluoromethylthio-5-(thiazol-5-yl)-1,3,4-oxazole, 2-(3,4,4-trifluoro-3-butenylthio)-5-(thiazol-5-yl)-1,3,4-oxadiazole.
.
zn~2499 ~ ~
Also preferred are those 2-mercapto-5-oxazol-(2-, 4- or 5-yl)-1,3,4-thiadiazoles of : :
formula Ib N N--N
~X ~S~--SR1 (Ib) wherein Rl is difluoromethyl,3,4,4-trifluoro-3-butene, tetrafluoroethyl,cyanomethyl, allyl, propargyl or 2-bromoalkyl, and R2 and R3 independently of one another are ~ :
hydrogen or methyl. ~ ~:
Of this group, the following individual compounds are especially preferred~
2-difluoromethylthio-5-(thiazol-2-yl)-1,3,4-oxadiazole, 2-(3,4,4-trifluoro-3-butenylthio)-(thiazol-2-yl)-1,3,4-thiadiazole, 2-difluoromethylthio-5-(2-methylthiazol-4-yl)-1,3,4-thiadiazole, ~ `:
2-(3,4,4-trifluoro-3-butenylthio)-5-(2-methylthiazol-4-yl)-1,3,4-thiadiazole, 2-difluoromethylthio-5-(thiazol-5-yl)-1,3,4-thiadiazole, 2-(3,4,4-trifluoro-3-butenylthio)-5-(thiazol-5-yl)-1,3,4-thiadiazole. -:. : ~. .
C~ompounds of formula I are prepared according to the invention by ;
a) in a condensation reaction, reacting a compound of formula II
N N--N ... . .
3~X ~--SH (lI) or a compound of formula III
R~X ~--SM
' ''' ''' '' '~
with a compound of formula IV . ;
". : . :', . ::
;,' , ~ ~
,~ .
Hal-Rl (IV) in an inert solvent or solvent mixture at room temperature or at elevated temperature optionally in the presence of a catalyst and optionally at elevated pressure, the reaction of a compound of formula II proceeding in the presence of a base, or ~ : .
b) in an addition reaction, reacting a compound of formula II
R 1rN N--N
~x JJ~x2 SH (II) with a compound of formula V
F F
C = C (V) ~'' F R' in an inert solvent or solvent mixture at elevated temperature, optionally in the presence of a catalyst and optionally at elevated pressure, this reaction resulting in a compound of formula Ic . -N N--N F H . ~ . :
R3 ~ ~ S--C--C--R' (Ic) Xl 2 F F :
or a compound of formula Id ~ ::
- R2~Jk ~ s 1 = c R~ !
X 2 F . ~ ~-in the above-mentioned formulae II, III, Ic, Id, IV and V, M is an alkali metal or ammonium, Hial is halogen, preferably chlorine, bromine or iodine, and R' is fluorine or trifluoromethyl, while Rl, R2, R3, Xl and X2 are as defined under formola I.
,~',' '.
'.'' , .... ' ' . i . ~ i -7- ~ .
Suitable alkali metals for the radical M are, for example, potassium and sodium; the -ammonium radical may also signify organic radicals, for example the t~ialkylammonium radical.
Solvents or diluents suitable for the preparation of the active ingredients according to the invention are, for example, ethers and ethereal compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert.-butyl methyl ether etc.), anisole, dioxane, tetrahydrofuran;
aliphatic and aromatic hydrocarbons, such as benzene, toluene, petroleum ether;
halogenated hydrocarbons, such as chlorobenzene, methylene chloride, chloroform,ethylene chloride, carbon tetrachloride, tetrachloroethylene; nitriles, such as acetonitrile, propionitrile; N,N-dialkylated amides, such as dimethylformarnide; dimethyl sulfoxide;
ketones, such as acetone, diethyl ketone, methyl ethyl ketone, as well as water and alcohols, for example methanol, ethanol, isopropanol or butanol; and, very generally, mixtures of such solvents with one another. ~ ~-Suitable bases are organic and inorganic bases; for example preferably tertiary amines, ~- -;
such as trialkylamines (trimethylamine, triethylamine, tripropylamine, etc.) as well as oxides, hydroxides, carbonates and hydrogen carbonates of aLkali and alkaline earth metals (for example CaO, BaO, NaOH, KOH, Ca(OH)2, KHCO3, NaHCO3, Ca(HCO3)2, K2CO3, Na2CO3, etc.), and also acetates, for example CH3COONa or CH3COOK.
Furthermore, suitable bases ale also alkali metal alcoholates, for example sodium ; -ethanolate, sodium propanolate, potassium tert.-butanolate or sodium ethanolate. ~ - -In the preparation processes, the addition of catalytic arnounts of a crown ether, for example 18-crown-6 or 15-crown-5, has a favourable effect on the course of the reaction.
Furthermore, the catalytic use of tetraalkylarnine salts, for exarnple tetraaLIcylammonium chlorides or bromides, preferably tetra-n-butylammonium bromide or tetramethyl-ammonium chloride, has proved advantageous for the same purpose. AL~cali metal iodides, - ;-preferably potassium iodide, can also be used advantageously as catalysts. ! ', . ,'' ", The reaction temperatures in the preparation processes are from 10 to 90C, preferably from 30 to 80C. The pressure conditions in the course of the reaction are to be from ;~
1 to 20 bar, preferably from 6 to 14 bar.
Some of the starting compounds of formula II are known and they can be prepared by known methods [G.B. 845 715, Egypt J. Chem. 29, 259-263 (1986) C.A. 109 (19) : , Z0~2499 170319u,C.A.186358s]; they have no nematicidal properties.
The invention also relates to compositions, for controlling plant-destructive nematodes and fungi and for protecting plants from attack by nematodes and fungi, that contain the compounds of formula I.
In addition, the present invention also includes the preparation of nematicidal and fungicidal compositions, which comprises homogeneously mixing compounds of formula I with one or more of the carriers and adjuvants described herein. Also included is a method of treating plants, which comprises applying thereto the compounds of formula I or the novel compositions.
A preferred method of applying a compound of formula I or a nematicidal and fungicidal composition containing at least one of those compounds, is incorporation into the soil, which comprises treating the locus of the plants with a liquid or solid formulation.
The compounds of formula I can, however, also be applied to seeds (dressing/coating~
either by impregnating the seeds with a liquid formulation of the active ingredient or by coating them with a solid formulation. In special cases, other methods of application are also possible, for example selective treatment of the plant stems, buds or leaves.
The compounds of formula I are normally applied in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds These further compounds can also include other substances applied in agriculture which are used to increase production by promoting growth of useful plants, such as fertilisers, herbicides, insecticides, fungicides, molluscicides etc., or may be mixtures of several of these preparations, if desired together with further carriers, su~factants or other application-promodng adjuvants customarily employed in the art of formulation.
:, .
Suitable carriers and adjuvants can be solid or liquid and correspond to the substances ordinarily employed in formu1ation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers. -~
The compounds of formula I are used in unmodi~led form or, preferably, together with the ' :~'~ .'".;
' .:: ': , adjuvants conventionally employed in the art of formulation. They are formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solu-tions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. Advantageous rates of application are normally from 500 g to 6 kg of active ingredient (a.i.) per hectare, pref~rably from 1 to 4 kg a.i./ha. ~ ~
":,:.' ,' ~ ,,:, The formulations, i.e. the compositions, preparations or mixtures containing the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant, are ~ ~
prepared in known manner, e.g. by homogeneously mixing andlor grinding the active ~ - -ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, - ~ ~ -surface-activecompounds (surfactants).
,: ~ . . .
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing , 8 to 12 carbon atoms, e.g. xylene rnixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or ;
paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as ~ ~ -epoxidised eoeonut oil or soybean oil; or water.
. ' The solid earriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers sueh as ealeite, taleum, kaolin, montmorillonite or attapulgite. In order to ~ ;
improve the physieal properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite, and suitable nonsorbent ; ~ ;
earriers are, for example, ealcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues. - ~ -~
Depending on the nature of the compound of formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be , ,~, , ' ." ' understood as comprising mixtures of surfactants.
Both so-called water-soluble soaps and also water-soluble synthetic surface-active com-pounds are suitable anionic surfactants.
Suitable soaps are the aL~ali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g.
from coconut oil or tallow oil. Mention may also be made of fatty acid methyllaurin salts and modified and unmodified phospholipids.
More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylsulfonates.
The fatty alcohol sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a Cg-C22alkyl radical which also includes the allcyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohoUethylene oxide adducts. The sulfonated benz-imidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium,calcillm or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalene-sulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.
Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.
, .
Non-iohic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said -derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide withpolypropylene glycol,ethylenediaminopolypropyleneglycoland alkylpoly-r~
- 11 - 201Z499 ~
,.. ..
propylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 2~0 ethylene glycol ether groups and 10 tO 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene ~ ~ -glycol unit. ~
. ,~ - ... .
Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy-polyethyleneethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
. ~ -, .:
- . . ~
Cationic surfactants are preferably quaternary ammonium salts which contain, as - ~ ~
N-substituent, at least one C8-C22alkyl radical and, as further substituents, unsubstituted -or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are -preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethyl-ammonium chloride or benzyldi(2- chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of formulation are described, inter alia, in the following publications:
~, .: -"Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Kidgewood, - -New Jersey, 1979; Dr. Helmut Stache "Tensid-Taschenbuch", Carl Hanser Verlag Munich/Vienna.
-~ , The agrochemical compositions usually contain 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a compound of formula I, 99.9 to 1 % by weight, preferably 99.8 to 5 % by weight, of a solid or liquid adjuvant, and 0 to 25 % by weight, preferably -0.1 to 25 % by weight, of a surfactant.
Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
::; ~.:' .' The compositions may also contain further auxiliaries such as stabilisers, antifoarns, ;
viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for obtaining special effects.
.
The present invention relates also to such agrochemical compositions.
The following Examples serve to illustrate the invention in more detail and do not constitute a limitation thereof.
1. Preparation Examples 2-Difluoromethylthio-5-(2-methvlthiazol-4-yl)-1,3~4-oxadiazole (Comp. 2.6) 2.4 g (0.0369 mol) of 85 % potassium hydroxide are dissolved in 12 ml of water, and 4.9 g (0.0246 mol) of 2-mercapto-5-(2-methylthiazol-4-yl)-1,3,4-oxadiazole, 2.5 g of tetramethylammonium chloride and 120 ml of 1,4-dioxane are added. While the reaction mixture is stirred vigorously, 3.2 g (0.037 mol) of Freon 22 are introduced at room temperature over a period of 8 hours. A further 1.2 g (0.018 mol) of 85 % potassium hydroxide and 1.2 g of tetramethylammonium chloride are then added, and 1.6 g (0.018 mol) of Freon 22 are introduced at 25C over a further period of 8 hours. The solvent is distilled off under reduced pressure, and the residue is dissolved in 100 ml of ethyl acetate and extracted, in succession, with 3 x S0 ml of lN sodium hydroxide solution and 3 x 50 ml of water. The ethyl acetate solution is dried with sodium sulfate, filtered and concentrated under reduced pressure to give 0.6 g of product having a -melting point of 82-85C.
2-(3~4,4-Trifluoro-3-butenylthio)-5-(2-methylthiazol-4-vl)-1~3~4-thiadiazole (ComP.2.10) ~ ~ ~
3 g (0.014 mol) of 2-mercapto-5-(2-methylthiazol-4-yl)-1,3,4-thiadiazole are dissolved in ~ ; -a mixture of 100 ml of 1,4-dioxane and 10 ml of dimethylformamide, and 1.7 g (0.0154 mol) of potassium tert.-butanolate are added. 4 g (0.021 mol) of 4-bromo-1,1,2-t~ifluorobutene aTe then added dropwise at 25C and the reaction mixture is stirred at 25C
for 16 hours. The solvent is then distilled off under reduced pressure, and the residue is dissolved in approximately 100 ml of ethyl acetate and extracted, in succession, with 3 x S0 ml of lN sodium hydroxide solution and 3 x 50 ml of water. The ethyl acetate ;
solution is dried with sodium sulfate, filtered and concentrated under reduced pressure to ;
give 2.9 g of product having a melting point of 65-68C.
.: .,: : .: . --13- 20124~39 - ~
Table 1: Oxa- and thiazol-2-yl derivatives -R2 :::
\~N N--N ~ .
Comp. Rl R2 R3 Xl X2 Physical data .
1.1 H H H S O m.p.192-195C -1.2 H H H S S from 125C decomp.
1.3 -CH3 H H S O
1.4 -CF3 H H S O : :
1.5 -CF2CHF2 H H S O m.p.98-102C
1.6 -CHF2 H H S O m.p. 91-93C -1.7 -CHF2 CH3 H S S ~ ;~ :~
1.8 -CHF2 CH3 H S O
1.9 -CHF2 H H S S :
1.10 -CHF2 H CH3 S O
1.11 -CHF2 CH3 CH3 S S -~
1.12 -CHF2 CH3 CH3 S O -- :: -1.13 -CHF2 H CH3 S S :-1.14 -CHF2 H H O O : - :
1.15 -CHF2 H H O S
1.16 -CHF2 CH3 H O O ~.
1.17 -CHF2 CH3 H O S
1.18 H H H O O :~
1.19 H H H O S -1.20 H CH3 H O O : ~
1.21 H CH3 H O S :
1.22 -CH2CH2CF=CF2 H H S O nD: 1.5683 1.23 -CH2CH2CF=CF2 H H S S nD: 1.6088 1.24 -CH2CH2CF=CF2 CH3 H S O
1.25 -CH2CH2CF=CF2 CH3 H S S .
1.26 -CH2CH2CF=cF2 CH3 H O O - :
1.27 -CH2CH2CF=cF2 CH3 H O S
1.28 -CH2CH2CF=CF2 H CH3 S O
1.29 -CH2CH2CF=CF2 CH3 CH3 S O ~ ~.
1.30 -CH2CH2CF=cF2 CH3 CH3 1.31' -CH2CH=CH2 H H S O
1.32 -CH2CH=CH2 : H H O O
1.33 -CH2CH=CH2 H H S S . . .
1.34 -CH2CH=CH2 H H O S
1.35 -CH2CH=CH H H S O
1.36 -CH2CH=CH H H S S : ~:
1.37 -CH2CH=CH H H O S ..
1.38 -CH2CH_CH H H O O ::
1.39 -CH2CN H H S O
1.40 -CH2CN H H O O ~:
__ : ,:
' ~,,:' Table 2: Oxa- and thiazol-4-y~ derivatives N N
N ~X2lSR1 R2 X~ , .
Comp. Rl R2 Xl ~2 Physical data . .
2.1 H CH3 S O m.p. 198-202C
2.2 H CH3 O O
2.3 H CH3 S m.p. (decomp.) from 143C . :
2.4 H CH3 S S .
2.5 -CHF2 CH3 O . O . :
2.6 -CHF2 CH3 S O m.p. 82-85C ~ .
2.7 -CHF2 CH3 S
2.8 -CHF2 CH3 S S m.p. 98-100C . -:
2.9 -CH2CH2CF=CF2 CH3 1:) O
2.10 -CH2CH2CF=CF2 CH3 S S m.p. 65-68C ::
2.11 -CH2CH2CF=CF2 CH3 S
2.12 -CH2CH2CF=CF2 CH3 S O nS0 1.5482 2.13 - CH2CH2CF=CF2 H S O
2.14 -CH2CH2CF=CF2 H S S . ~ :
2.15 -CH2CH2CF=CF2 C2Hs S O ~ :
2.16 -CH2CH2CF=CF2 C2Hs S S
2.17 -CH2CH2CF=CF2 C3H7(n) S S
2.18 -CH2CH2CF=CF2 C3H7(n) S O
2.19 -CH2CH2CF=CF2 C3H7(i) S S . ; ~ .
2.20 -CH2CH2CF=CF2 C3H7(i) S O
2.21 -CHF2 H S O .
2.22 -CHF2 H S S -2.23 -CHF2 C2Hs S O
2.24 -CHF2 C2H5 S S ~ ~
2.25 -CHF2 C3H7(n). S O ~: :
2.26 -CHF2 C3H7(n) S S
2.27 -CHF2 C3H7(i) S O ~ : .
2.28 -CHF2 C3H7(i) S S :
2.29 H C6Hs S O : --. ~:
2.30 H C6Hs S S ;:
2.31 -CHF2 C6Hs S O :~
2.32 1 -CHF2 C6Hs S S
2.33 -CH2CH2CF=CF2 C6Hs S O
2.34 -CH2CH2CF=CF2 C6Hs S S
~\ / .~
2.36 H ., I . S O m.p.>270C : ~ ;: ;:
~N~ : ~
_ _ ,,~ .:~'~'.'.
;~
'-: '~.: ~: :-ZOlZ49~ ~
Table 2 (Continuation) .;
Comp. Rl ----~ Xl X2 Physicaldata 2.36 ~-- S S m.p. > 260C
N
¦ 2.3 ¦ -CHF2 ¦ ~'1 S ¦ O ¦ ¦
2.38 ¦-CHF2 ¦~ ¦ S ¦ S Im.p. 22-124C ¦ ;
2.39 ¦ -CH2C 12CF=CF2 ¦ ~ ¦ 5 ¦ Im.p. 06-103C
2.40 -CH2CH2CF=CF2 ~/ S S m.p. 125-130C ~ ;
2.41 H ~L S O
2.42 H ~L S S
2.43 -CHF2 ~3L S O
2.44 -CHF2 ~3L S S
2.45 -CH2CH2CF=CF2 ~3L S O
2.46 -CH2CH2CF=CF2 ~L S S ;
2 n H S O
, Table 2 (Connnuation) .
Comp. R1 R2 Xl _ Physical data 2.48 H ~L S S ~ ~ ;
2.4g ,-CHF2 ~ S O . '~
2.50 -CHF2 ~3L S S ~ `
2.51 -CH2OEI2CF=CF2 ~lL S O
2.52 -CH2CH2CF=CF2 ~L S S . ;
2.53 H CH3~ S S m.p. > 221C decomp.
2.54 H CH3~ S O m.p. ~ 250C ;
2.55 -CHF2 CH3~ S S m.p. 156-158C ; ~
2.56 -CHF2 CH3~ S O m.p. 191-193C
. 2.57 -CH2CH2CF=cF2 CH3~ S S m.p. 136-138C .~
~CH2CH2CP=C k ICHS~JI S I OlmP 150 ~
.., ~
. ~i,. . .
. ........ .
... ~. ~;. .. ..
.,..;. ;~...1~. .
.... ....... .. ;
. ~ . , ~. ~ ..
;.. ,..i ~ .
. . . ~ ~. . .
- 17- ZOlZ499 Table 3: Oxa- and thiazol-5-YI derivatives N N--N
Il 11 11 ~1 :
R2--X----X SR~ ~
Comp. Rl R2 Xl X2 Physical data -No.
3.1 H H S O m.p. 208-211C
3.2 H H S S m.p. 186-188c 3.3 H CH3 S O
3.4 H CH3 S S
3.5 H CH3 - O O
3.6 H CH3 O S
3.7 -CHF2 CH3 S O
3.8 -CHF2 CH3 S S
3.9 -CH2CH2CF=cF2 CH3 S O ~ -3.10 -CH2CH2CF=CF2 CH3 S S
3.11 H -NH2 S O
3.12 H -NH2 S S
3.13 -CHF2 -NH2 S O -3.14 -CHF~ -NH2 S S
3.15 -CH2CH2CF=cF2 CF2=CFCH2CH2NH- S O
3.16 -CH2CH2CF=cF2 CF2=CFCH2CH2NH- S S
3.17 -CHF2 H S O oil 3.18 -CHF2 H S S m.p. 107-109C
3.19 -CH2CH2CF=CF2 H S O oil 3.20 -CH2CH2CF=CF2 H S S m.p. 72-74C ~ ;
2. Formulation Examples for liquid active in~iredients of forrnula I (throuPhout.
percenta~es are bv wei ht) , 2.1 Emulsifiable concentrates a) b) c) acompoundofTables l to3 25 %40%50 %
calcium dodecyl benzenesulfonate 5 % 8 % 6 %
castor oil polyethylene glycol ether (36 moles of ethylene oxide) S %
tributylphenol polyethylene glycol - ~ ;
ether (30 moles of ethylene oxide) - 12 % 4 %
cyclohexanone -15 % 20 %
xylenemixture 65 %25 %20 % ~
: ~ .,, , .- ~. .
20124~9 Emulsions of any desired concentration can be produced from such concentrates bydilution with water.
2.2 Solutions a) b) c) d) a compound of Tables 1 to 3 80 % 10 % 5 % 95 %
ethylene glycol monomethyl ether20 ~io polyethylene glycol (mol. wt. 400) - 70 %
N-methyl-2-pyrrolidone - 20 % - -epoxidised coconut oil - - 1 % 5 %
petroleumfraction (boiling range 160-190C) - ~ 94 %
These solutions are suitable for application in the form of microdrops.
, ~ ~
2.3 Granulates a) b) a compound of Tables 1 to 3 5 % 10 %
.
kaolin 94 %
highly dispersed silicic acid 1%
attapulgite - 90 %
The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the ~ ~ ;
carrier, and the solvent is subsequently evaporated off in vacuo. -2.4 Dusts a) b) a compound of Tables 1 to 3 2 % 5 %
highlydispersedsilicicacid 1% 5%
talcum 97 %
kaolin - 90 % `
Ready-for-use dusts are obtained by intit,nately rnixing the ca~iers with the active ingredient. -- :
Formulation Examples for solid active in~redients of formula I (throu~hout. percenta~es are bv wei~ht) 2.5 Wettablepowders a) b) c) a compound of Tables 1 to 3 25 % 50 % 75 %
~ ' ': -20~2499 - 19- , .
sodium lignosulfonate 5 % 5 %
sodiumlauryl sulfate 3 % - 5 %
sodium diisobutyl naphthalenesulfonate - 6 % 10 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 %
highly dispersed silicic acid 5 % 10 % 10 %
kaolin 62 %27 %
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
, . ~, 2.6 Emulsifiableconcentrate a compound of Tables 1 to 3 10 % ~ :
sctylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3 %
calcium dodecyl benzenesulfonate 3 %
castor oil polyglycol ether (35 moles of ethylene oxide) 4 %
cyclohexanone 30 %
xylene mixture 50 %
Emulsions of any required concentration can be obtained from this concentrate by dilution with water.
....
2.7 Dusts a) b) a compound of Tables 1 to 3 5 % 8 %
talcum 95 % -kaolin ' - 92 %
,: ~ ,- ':
Ready-for-use dusts are obtained by mixing the active ingredient with the carriers, and grinding the mixture in a suitable mill.
-: ~; :.' 2.8 Extruder~ranulate ~ -a compound of Tables 1 to 3 10 %
sodium lignosulfonate 2 %
ZOlZ499 ~ ~:
carboxymethylcellulose 1 %
kaolin 87 %
.
The active ingredient is mixed and ground with the adjuvants, and the mixture ismoistened with water. The m~xture is ex~uded and then dried in a stream of air.
2.9 Coated ~ranulate acompoundofTables 1 to3 3 %
polyethylene glycol (mol. wt. 200 3 %
kaolin 94 %
The finely ground active ingredient is uniforrnly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
2.10 Suspension concentrate a compound of Tables 1 to 3 40 %
ethylene glycol 10 %
nonylphenol polyethylene glycol ether (lS moles of ethylene oxide) 6 % ;
sodium lignosulfonate 10 %
carboxymethylcellulose 1 %
37 % aqueous forrnaldehyde solution 0.2 % --silicone oil in the form of a 75 %
aqueous emulsion 0.8 % ;
water 32 %
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
::... . :-Biological ExamPles : : ~ - , . ~, 3.1 Actiona ainstMeloido~YneincoienitaontomatoPlants Eggs of Meloidogyne incognita are mixed into sand. This mixture is then put into 200 ml clay pots (5000 eggs per pot). On the same day a three-week-old tomato plant is planted ~ -,' ' `'. ' '.
., ,. ::-, .: , in each pot and the folmulated test compound is introduced into the pots by drench appli-cation (0.0006 % of active ingredient, based on the volume of the soil). The potted plants are then placed in a greenhouse at a temperature of 26ilC and a relative humidity of 60 %. After 4 weeks, evaluation is made by examining the plants for root-knotformation in accordance with the so-called Root-Knot Index.
.
Compounds of Tables 1-3 exhibit good activity against Meloidogyne incognita by substantial reduction of root-knot formation. On the other hand, untreated and infected control plants exhibit severe root-knot formation (= 100 %). In this test, for example compounds nos. 2.6, 2.8, 2.10, 2.12, 2.38 and 2.39 inhibit root-knot formation almost completely (0-10 % residual attack).
3.2 PYthium ultimum on Beta vuli~aris (sugar beet~ cv. Kleinwanzleben Mono~erm~ and Pvthium ultimum on Zea mays (maize~ cv. Sweet Corn) Test principle: soil fungus: protective local soil application Test method: mycelium of Pvthium ultimum is mixed with soil (500 ml of mycelium suspension to 10 litres of soil) and the fungus-soil mixture is placed in 250 ml plastic dishes~ After 4 days' inculQation at 10C, 10 seeds of the test plant (maize or sugar beet) are sown in each dish. The following day, the dishes so prepared are watered with 50 ml in each case of spray solutions prepared from 25 % wettable powder and water with 20;
6; 2; 0.6; 0.2; 0.0~ and 0.02 ppm a.i.. After a 7-day incubation phase at 10C and a subsequent 4-day incubation phase at 22C, the action of the test compounds is evaluated by counting the number of test plants emerging in accordance with the following scale of ratings: -microbicidal activity rating . : -0-50 9 (= no action) Compounds of Tables 1-3, for example 2.6, exhibit good activity against Pvthium ultimum.
-ZOlZ499 3.3 Action a iainst Rhizoctonia solani (soil fun~us on rice Plants) Protective local soil application A spray mixture (0.002 % active ingredient) prepared from a formulation of the active ingredient is used to water 12-day-old rice plants without contaminating the parts of the plants above the soil. In order to infect the treated plants, a suspension of mycelium and sclerotia of R. solani is applied to the surface of the soil. The fungus attack on the foliar sheath, leaves and stems is evaluated after 6 days' incubation at 27C (day) and 23C
(night) and 100 % relative humidity (humidity chamber) in a climatic chamber.
There was no attaclc following treatment with the active ingredient.
:~ . . -'~ '" ~;' , . ', -
Also preferred are compounds of formula I wherein Xl and X2 independently of oneanother are oxygen or sulfur, Rlis unsubstituted Cl-Csalkyl or Cl-Csalkyl substituted by -halogen, Cl-C3alkoxy or by cyano; unsubstituted or halo- substituted C3-C7aL~cenyl; or ~ -unsubstituted or halo-substituted C3-C7alkynyl; R2 and R3 independently of one another are hydrogen, Cl-C3alkyl, unsubstituted phenyl or phenyl substituted by Cl-C3aLtcyl, Cl-C3alkoxy or by halogen, or pyridyl, thienyl, furyl or thiazolyl.
Also preferred within the scope of the present invention are those 2-mercapto-5-thiazol- ~ :
(2-, 4- or 5-yl)-1,3,4-oxadiazoles of formula Ia N N--N
3~o~--SR1 (Ia) X1 :'' wherein Rl is difluoromethyl, 3,4,4-trifluoro-3-butene, cyanomethyl, difluoromethyl-difluoromethyl or propargyl, and R2 and R3 independently of one another are hydrogen or methyl.
Of those compounds, the following individual compounds are especially preferred:2-difluoromethylthio-S-(thiazol-2-yl)-1,3,4-oxadiazole, 2-(3,4,4-trifluoro-3-butenylthio)-(thiazol-2-yl)-1,3,4-oxadiazole, 2-difluoromethylthio-5-(2-methylthiazol-4-yl)-1,3,4-oxadiazole, 2-(3,4,4-trifluoro-3-butenylthio)-5-(2-methylthiazol-4-yl)- 1 ,3,4-oxadiazole, 2-(3,4,4-trifluoro-3-butenylthio)-5-2-(pyrid-3-yl)-thiazol-4-yl- 1 ,3,4-oxadiazole, 2-difluoromethylthio-5-(thiazol-5-yl)-1,3,4-oxazole, 2-(3,4,4-trifluoro-3-butenylthio)-5-(thiazol-5-yl)-1,3,4-oxadiazole.
.
zn~2499 ~ ~
Also preferred are those 2-mercapto-5-oxazol-(2-, 4- or 5-yl)-1,3,4-thiadiazoles of : :
formula Ib N N--N
~X ~S~--SR1 (Ib) wherein Rl is difluoromethyl,3,4,4-trifluoro-3-butene, tetrafluoroethyl,cyanomethyl, allyl, propargyl or 2-bromoalkyl, and R2 and R3 independently of one another are ~ :
hydrogen or methyl. ~ ~:
Of this group, the following individual compounds are especially preferred~
2-difluoromethylthio-5-(thiazol-2-yl)-1,3,4-oxadiazole, 2-(3,4,4-trifluoro-3-butenylthio)-(thiazol-2-yl)-1,3,4-thiadiazole, 2-difluoromethylthio-5-(2-methylthiazol-4-yl)-1,3,4-thiadiazole, ~ `:
2-(3,4,4-trifluoro-3-butenylthio)-5-(2-methylthiazol-4-yl)-1,3,4-thiadiazole, 2-difluoromethylthio-5-(thiazol-5-yl)-1,3,4-thiadiazole, 2-(3,4,4-trifluoro-3-butenylthio)-5-(thiazol-5-yl)-1,3,4-thiadiazole. -:. : ~. .
C~ompounds of formula I are prepared according to the invention by ;
a) in a condensation reaction, reacting a compound of formula II
N N--N ... . .
3~X ~--SH (lI) or a compound of formula III
R~X ~--SM
' ''' ''' '' '~
with a compound of formula IV . ;
". : . :', . ::
;,' , ~ ~
,~ .
Hal-Rl (IV) in an inert solvent or solvent mixture at room temperature or at elevated temperature optionally in the presence of a catalyst and optionally at elevated pressure, the reaction of a compound of formula II proceeding in the presence of a base, or ~ : .
b) in an addition reaction, reacting a compound of formula II
R 1rN N--N
~x JJ~x2 SH (II) with a compound of formula V
F F
C = C (V) ~'' F R' in an inert solvent or solvent mixture at elevated temperature, optionally in the presence of a catalyst and optionally at elevated pressure, this reaction resulting in a compound of formula Ic . -N N--N F H . ~ . :
R3 ~ ~ S--C--C--R' (Ic) Xl 2 F F :
or a compound of formula Id ~ ::
- R2~Jk ~ s 1 = c R~ !
X 2 F . ~ ~-in the above-mentioned formulae II, III, Ic, Id, IV and V, M is an alkali metal or ammonium, Hial is halogen, preferably chlorine, bromine or iodine, and R' is fluorine or trifluoromethyl, while Rl, R2, R3, Xl and X2 are as defined under formola I.
,~',' '.
'.'' , .... ' ' . i . ~ i -7- ~ .
Suitable alkali metals for the radical M are, for example, potassium and sodium; the -ammonium radical may also signify organic radicals, for example the t~ialkylammonium radical.
Solvents or diluents suitable for the preparation of the active ingredients according to the invention are, for example, ethers and ethereal compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert.-butyl methyl ether etc.), anisole, dioxane, tetrahydrofuran;
aliphatic and aromatic hydrocarbons, such as benzene, toluene, petroleum ether;
halogenated hydrocarbons, such as chlorobenzene, methylene chloride, chloroform,ethylene chloride, carbon tetrachloride, tetrachloroethylene; nitriles, such as acetonitrile, propionitrile; N,N-dialkylated amides, such as dimethylformarnide; dimethyl sulfoxide;
ketones, such as acetone, diethyl ketone, methyl ethyl ketone, as well as water and alcohols, for example methanol, ethanol, isopropanol or butanol; and, very generally, mixtures of such solvents with one another. ~ ~-Suitable bases are organic and inorganic bases; for example preferably tertiary amines, ~- -;
such as trialkylamines (trimethylamine, triethylamine, tripropylamine, etc.) as well as oxides, hydroxides, carbonates and hydrogen carbonates of aLkali and alkaline earth metals (for example CaO, BaO, NaOH, KOH, Ca(OH)2, KHCO3, NaHCO3, Ca(HCO3)2, K2CO3, Na2CO3, etc.), and also acetates, for example CH3COONa or CH3COOK.
Furthermore, suitable bases ale also alkali metal alcoholates, for example sodium ; -ethanolate, sodium propanolate, potassium tert.-butanolate or sodium ethanolate. ~ - -In the preparation processes, the addition of catalytic arnounts of a crown ether, for example 18-crown-6 or 15-crown-5, has a favourable effect on the course of the reaction.
Furthermore, the catalytic use of tetraalkylarnine salts, for exarnple tetraaLIcylammonium chlorides or bromides, preferably tetra-n-butylammonium bromide or tetramethyl-ammonium chloride, has proved advantageous for the same purpose. AL~cali metal iodides, - ;-preferably potassium iodide, can also be used advantageously as catalysts. ! ', . ,'' ", The reaction temperatures in the preparation processes are from 10 to 90C, preferably from 30 to 80C. The pressure conditions in the course of the reaction are to be from ;~
1 to 20 bar, preferably from 6 to 14 bar.
Some of the starting compounds of formula II are known and they can be prepared by known methods [G.B. 845 715, Egypt J. Chem. 29, 259-263 (1986) C.A. 109 (19) : , Z0~2499 170319u,C.A.186358s]; they have no nematicidal properties.
The invention also relates to compositions, for controlling plant-destructive nematodes and fungi and for protecting plants from attack by nematodes and fungi, that contain the compounds of formula I.
In addition, the present invention also includes the preparation of nematicidal and fungicidal compositions, which comprises homogeneously mixing compounds of formula I with one or more of the carriers and adjuvants described herein. Also included is a method of treating plants, which comprises applying thereto the compounds of formula I or the novel compositions.
A preferred method of applying a compound of formula I or a nematicidal and fungicidal composition containing at least one of those compounds, is incorporation into the soil, which comprises treating the locus of the plants with a liquid or solid formulation.
The compounds of formula I can, however, also be applied to seeds (dressing/coating~
either by impregnating the seeds with a liquid formulation of the active ingredient or by coating them with a solid formulation. In special cases, other methods of application are also possible, for example selective treatment of the plant stems, buds or leaves.
The compounds of formula I are normally applied in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds These further compounds can also include other substances applied in agriculture which are used to increase production by promoting growth of useful plants, such as fertilisers, herbicides, insecticides, fungicides, molluscicides etc., or may be mixtures of several of these preparations, if desired together with further carriers, su~factants or other application-promodng adjuvants customarily employed in the art of formulation.
:, .
Suitable carriers and adjuvants can be solid or liquid and correspond to the substances ordinarily employed in formu1ation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers. -~
The compounds of formula I are used in unmodi~led form or, preferably, together with the ' :~'~ .'".;
' .:: ': , adjuvants conventionally employed in the art of formulation. They are formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solu-tions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. Advantageous rates of application are normally from 500 g to 6 kg of active ingredient (a.i.) per hectare, pref~rably from 1 to 4 kg a.i./ha. ~ ~
":,:.' ,' ~ ,,:, The formulations, i.e. the compositions, preparations or mixtures containing the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant, are ~ ~
prepared in known manner, e.g. by homogeneously mixing andlor grinding the active ~ - -ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, - ~ ~ -surface-activecompounds (surfactants).
,: ~ . . .
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing , 8 to 12 carbon atoms, e.g. xylene rnixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or ;
paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as ~ ~ -epoxidised eoeonut oil or soybean oil; or water.
. ' The solid earriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers sueh as ealeite, taleum, kaolin, montmorillonite or attapulgite. In order to ~ ;
improve the physieal properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite, and suitable nonsorbent ; ~ ;
earriers are, for example, ealcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues. - ~ -~
Depending on the nature of the compound of formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be , ,~, , ' ." ' understood as comprising mixtures of surfactants.
Both so-called water-soluble soaps and also water-soluble synthetic surface-active com-pounds are suitable anionic surfactants.
Suitable soaps are the aL~ali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g.
from coconut oil or tallow oil. Mention may also be made of fatty acid methyllaurin salts and modified and unmodified phospholipids.
More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylsulfonates.
The fatty alcohol sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a Cg-C22alkyl radical which also includes the allcyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohoUethylene oxide adducts. The sulfonated benz-imidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium,calcillm or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalene-sulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.
Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.
, .
Non-iohic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said -derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide withpolypropylene glycol,ethylenediaminopolypropyleneglycoland alkylpoly-r~
- 11 - 201Z499 ~
,.. ..
propylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 2~0 ethylene glycol ether groups and 10 tO 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene ~ ~ -glycol unit. ~
. ,~ - ... .
Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy-polyethyleneethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
. ~ -, .:
- . . ~
Cationic surfactants are preferably quaternary ammonium salts which contain, as - ~ ~
N-substituent, at least one C8-C22alkyl radical and, as further substituents, unsubstituted -or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are -preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethyl-ammonium chloride or benzyldi(2- chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of formulation are described, inter alia, in the following publications:
~, .: -"Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Kidgewood, - -New Jersey, 1979; Dr. Helmut Stache "Tensid-Taschenbuch", Carl Hanser Verlag Munich/Vienna.
-~ , The agrochemical compositions usually contain 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a compound of formula I, 99.9 to 1 % by weight, preferably 99.8 to 5 % by weight, of a solid or liquid adjuvant, and 0 to 25 % by weight, preferably -0.1 to 25 % by weight, of a surfactant.
Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
::; ~.:' .' The compositions may also contain further auxiliaries such as stabilisers, antifoarns, ;
viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for obtaining special effects.
.
The present invention relates also to such agrochemical compositions.
The following Examples serve to illustrate the invention in more detail and do not constitute a limitation thereof.
1. Preparation Examples 2-Difluoromethylthio-5-(2-methvlthiazol-4-yl)-1,3~4-oxadiazole (Comp. 2.6) 2.4 g (0.0369 mol) of 85 % potassium hydroxide are dissolved in 12 ml of water, and 4.9 g (0.0246 mol) of 2-mercapto-5-(2-methylthiazol-4-yl)-1,3,4-oxadiazole, 2.5 g of tetramethylammonium chloride and 120 ml of 1,4-dioxane are added. While the reaction mixture is stirred vigorously, 3.2 g (0.037 mol) of Freon 22 are introduced at room temperature over a period of 8 hours. A further 1.2 g (0.018 mol) of 85 % potassium hydroxide and 1.2 g of tetramethylammonium chloride are then added, and 1.6 g (0.018 mol) of Freon 22 are introduced at 25C over a further period of 8 hours. The solvent is distilled off under reduced pressure, and the residue is dissolved in 100 ml of ethyl acetate and extracted, in succession, with 3 x S0 ml of lN sodium hydroxide solution and 3 x 50 ml of water. The ethyl acetate solution is dried with sodium sulfate, filtered and concentrated under reduced pressure to give 0.6 g of product having a -melting point of 82-85C.
2-(3~4,4-Trifluoro-3-butenylthio)-5-(2-methylthiazol-4-vl)-1~3~4-thiadiazole (ComP.2.10) ~ ~ ~
3 g (0.014 mol) of 2-mercapto-5-(2-methylthiazol-4-yl)-1,3,4-thiadiazole are dissolved in ~ ; -a mixture of 100 ml of 1,4-dioxane and 10 ml of dimethylformamide, and 1.7 g (0.0154 mol) of potassium tert.-butanolate are added. 4 g (0.021 mol) of 4-bromo-1,1,2-t~ifluorobutene aTe then added dropwise at 25C and the reaction mixture is stirred at 25C
for 16 hours. The solvent is then distilled off under reduced pressure, and the residue is dissolved in approximately 100 ml of ethyl acetate and extracted, in succession, with 3 x S0 ml of lN sodium hydroxide solution and 3 x 50 ml of water. The ethyl acetate ;
solution is dried with sodium sulfate, filtered and concentrated under reduced pressure to ;
give 2.9 g of product having a melting point of 65-68C.
.: .,: : .: . --13- 20124~39 - ~
Table 1: Oxa- and thiazol-2-yl derivatives -R2 :::
\~N N--N ~ .
Comp. Rl R2 R3 Xl X2 Physical data .
1.1 H H H S O m.p.192-195C -1.2 H H H S S from 125C decomp.
1.3 -CH3 H H S O
1.4 -CF3 H H S O : :
1.5 -CF2CHF2 H H S O m.p.98-102C
1.6 -CHF2 H H S O m.p. 91-93C -1.7 -CHF2 CH3 H S S ~ ;~ :~
1.8 -CHF2 CH3 H S O
1.9 -CHF2 H H S S :
1.10 -CHF2 H CH3 S O
1.11 -CHF2 CH3 CH3 S S -~
1.12 -CHF2 CH3 CH3 S O -- :: -1.13 -CHF2 H CH3 S S :-1.14 -CHF2 H H O O : - :
1.15 -CHF2 H H O S
1.16 -CHF2 CH3 H O O ~.
1.17 -CHF2 CH3 H O S
1.18 H H H O O :~
1.19 H H H O S -1.20 H CH3 H O O : ~
1.21 H CH3 H O S :
1.22 -CH2CH2CF=CF2 H H S O nD: 1.5683 1.23 -CH2CH2CF=CF2 H H S S nD: 1.6088 1.24 -CH2CH2CF=CF2 CH3 H S O
1.25 -CH2CH2CF=CF2 CH3 H S S .
1.26 -CH2CH2CF=cF2 CH3 H O O - :
1.27 -CH2CH2CF=cF2 CH3 H O S
1.28 -CH2CH2CF=CF2 H CH3 S O
1.29 -CH2CH2CF=CF2 CH3 CH3 S O ~ ~.
1.30 -CH2CH2CF=cF2 CH3 CH3 1.31' -CH2CH=CH2 H H S O
1.32 -CH2CH=CH2 : H H O O
1.33 -CH2CH=CH2 H H S S . . .
1.34 -CH2CH=CH2 H H O S
1.35 -CH2CH=CH H H S O
1.36 -CH2CH=CH H H S S : ~:
1.37 -CH2CH=CH H H O S ..
1.38 -CH2CH_CH H H O O ::
1.39 -CH2CN H H S O
1.40 -CH2CN H H O O ~:
__ : ,:
' ~,,:' Table 2: Oxa- and thiazol-4-y~ derivatives N N
N ~X2lSR1 R2 X~ , .
Comp. Rl R2 Xl ~2 Physical data . .
2.1 H CH3 S O m.p. 198-202C
2.2 H CH3 O O
2.3 H CH3 S m.p. (decomp.) from 143C . :
2.4 H CH3 S S .
2.5 -CHF2 CH3 O . O . :
2.6 -CHF2 CH3 S O m.p. 82-85C ~ .
2.7 -CHF2 CH3 S
2.8 -CHF2 CH3 S S m.p. 98-100C . -:
2.9 -CH2CH2CF=CF2 CH3 1:) O
2.10 -CH2CH2CF=CF2 CH3 S S m.p. 65-68C ::
2.11 -CH2CH2CF=CF2 CH3 S
2.12 -CH2CH2CF=CF2 CH3 S O nS0 1.5482 2.13 - CH2CH2CF=CF2 H S O
2.14 -CH2CH2CF=CF2 H S S . ~ :
2.15 -CH2CH2CF=CF2 C2Hs S O ~ :
2.16 -CH2CH2CF=CF2 C2Hs S S
2.17 -CH2CH2CF=CF2 C3H7(n) S S
2.18 -CH2CH2CF=CF2 C3H7(n) S O
2.19 -CH2CH2CF=CF2 C3H7(i) S S . ; ~ .
2.20 -CH2CH2CF=CF2 C3H7(i) S O
2.21 -CHF2 H S O .
2.22 -CHF2 H S S -2.23 -CHF2 C2Hs S O
2.24 -CHF2 C2H5 S S ~ ~
2.25 -CHF2 C3H7(n). S O ~: :
2.26 -CHF2 C3H7(n) S S
2.27 -CHF2 C3H7(i) S O ~ : .
2.28 -CHF2 C3H7(i) S S :
2.29 H C6Hs S O : --. ~:
2.30 H C6Hs S S ;:
2.31 -CHF2 C6Hs S O :~
2.32 1 -CHF2 C6Hs S S
2.33 -CH2CH2CF=CF2 C6Hs S O
2.34 -CH2CH2CF=CF2 C6Hs S S
~\ / .~
2.36 H ., I . S O m.p.>270C : ~ ;: ;:
~N~ : ~
_ _ ,,~ .:~'~'.'.
;~
'-: '~.: ~: :-ZOlZ49~ ~
Table 2 (Continuation) .;
Comp. Rl ----~ Xl X2 Physicaldata 2.36 ~-- S S m.p. > 260C
N
¦ 2.3 ¦ -CHF2 ¦ ~'1 S ¦ O ¦ ¦
2.38 ¦-CHF2 ¦~ ¦ S ¦ S Im.p. 22-124C ¦ ;
2.39 ¦ -CH2C 12CF=CF2 ¦ ~ ¦ 5 ¦ Im.p. 06-103C
2.40 -CH2CH2CF=CF2 ~/ S S m.p. 125-130C ~ ;
2.41 H ~L S O
2.42 H ~L S S
2.43 -CHF2 ~3L S O
2.44 -CHF2 ~3L S S
2.45 -CH2CH2CF=CF2 ~3L S O
2.46 -CH2CH2CF=CF2 ~L S S ;
2 n H S O
, Table 2 (Connnuation) .
Comp. R1 R2 Xl _ Physical data 2.48 H ~L S S ~ ~ ;
2.4g ,-CHF2 ~ S O . '~
2.50 -CHF2 ~3L S S ~ `
2.51 -CH2OEI2CF=CF2 ~lL S O
2.52 -CH2CH2CF=CF2 ~L S S . ;
2.53 H CH3~ S S m.p. > 221C decomp.
2.54 H CH3~ S O m.p. ~ 250C ;
2.55 -CHF2 CH3~ S S m.p. 156-158C ; ~
2.56 -CHF2 CH3~ S O m.p. 191-193C
. 2.57 -CH2CH2CF=cF2 CH3~ S S m.p. 136-138C .~
~CH2CH2CP=C k ICHS~JI S I OlmP 150 ~
.., ~
. ~i,. . .
. ........ .
... ~. ~;. .. ..
.,..;. ;~...1~. .
.... ....... .. ;
. ~ . , ~. ~ ..
;.. ,..i ~ .
. . . ~ ~. . .
- 17- ZOlZ499 Table 3: Oxa- and thiazol-5-YI derivatives N N--N
Il 11 11 ~1 :
R2--X----X SR~ ~
Comp. Rl R2 Xl X2 Physical data -No.
3.1 H H S O m.p. 208-211C
3.2 H H S S m.p. 186-188c 3.3 H CH3 S O
3.4 H CH3 S S
3.5 H CH3 - O O
3.6 H CH3 O S
3.7 -CHF2 CH3 S O
3.8 -CHF2 CH3 S S
3.9 -CH2CH2CF=cF2 CH3 S O ~ -3.10 -CH2CH2CF=CF2 CH3 S S
3.11 H -NH2 S O
3.12 H -NH2 S S
3.13 -CHF2 -NH2 S O -3.14 -CHF~ -NH2 S S
3.15 -CH2CH2CF=cF2 CF2=CFCH2CH2NH- S O
3.16 -CH2CH2CF=cF2 CF2=CFCH2CH2NH- S S
3.17 -CHF2 H S O oil 3.18 -CHF2 H S S m.p. 107-109C
3.19 -CH2CH2CF=CF2 H S O oil 3.20 -CH2CH2CF=CF2 H S S m.p. 72-74C ~ ;
2. Formulation Examples for liquid active in~iredients of forrnula I (throuPhout.
percenta~es are bv wei ht) , 2.1 Emulsifiable concentrates a) b) c) acompoundofTables l to3 25 %40%50 %
calcium dodecyl benzenesulfonate 5 % 8 % 6 %
castor oil polyethylene glycol ether (36 moles of ethylene oxide) S %
tributylphenol polyethylene glycol - ~ ;
ether (30 moles of ethylene oxide) - 12 % 4 %
cyclohexanone -15 % 20 %
xylenemixture 65 %25 %20 % ~
: ~ .,, , .- ~. .
20124~9 Emulsions of any desired concentration can be produced from such concentrates bydilution with water.
2.2 Solutions a) b) c) d) a compound of Tables 1 to 3 80 % 10 % 5 % 95 %
ethylene glycol monomethyl ether20 ~io polyethylene glycol (mol. wt. 400) - 70 %
N-methyl-2-pyrrolidone - 20 % - -epoxidised coconut oil - - 1 % 5 %
petroleumfraction (boiling range 160-190C) - ~ 94 %
These solutions are suitable for application in the form of microdrops.
, ~ ~
2.3 Granulates a) b) a compound of Tables 1 to 3 5 % 10 %
.
kaolin 94 %
highly dispersed silicic acid 1%
attapulgite - 90 %
The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the ~ ~ ;
carrier, and the solvent is subsequently evaporated off in vacuo. -2.4 Dusts a) b) a compound of Tables 1 to 3 2 % 5 %
highlydispersedsilicicacid 1% 5%
talcum 97 %
kaolin - 90 % `
Ready-for-use dusts are obtained by intit,nately rnixing the ca~iers with the active ingredient. -- :
Formulation Examples for solid active in~redients of formula I (throu~hout. percenta~es are bv wei~ht) 2.5 Wettablepowders a) b) c) a compound of Tables 1 to 3 25 % 50 % 75 %
~ ' ': -20~2499 - 19- , .
sodium lignosulfonate 5 % 5 %
sodiumlauryl sulfate 3 % - 5 %
sodium diisobutyl naphthalenesulfonate - 6 % 10 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 %
highly dispersed silicic acid 5 % 10 % 10 %
kaolin 62 %27 %
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
, . ~, 2.6 Emulsifiableconcentrate a compound of Tables 1 to 3 10 % ~ :
sctylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3 %
calcium dodecyl benzenesulfonate 3 %
castor oil polyglycol ether (35 moles of ethylene oxide) 4 %
cyclohexanone 30 %
xylene mixture 50 %
Emulsions of any required concentration can be obtained from this concentrate by dilution with water.
....
2.7 Dusts a) b) a compound of Tables 1 to 3 5 % 8 %
talcum 95 % -kaolin ' - 92 %
,: ~ ,- ':
Ready-for-use dusts are obtained by mixing the active ingredient with the carriers, and grinding the mixture in a suitable mill.
-: ~; :.' 2.8 Extruder~ranulate ~ -a compound of Tables 1 to 3 10 %
sodium lignosulfonate 2 %
ZOlZ499 ~ ~:
carboxymethylcellulose 1 %
kaolin 87 %
.
The active ingredient is mixed and ground with the adjuvants, and the mixture ismoistened with water. The m~xture is ex~uded and then dried in a stream of air.
2.9 Coated ~ranulate acompoundofTables 1 to3 3 %
polyethylene glycol (mol. wt. 200 3 %
kaolin 94 %
The finely ground active ingredient is uniforrnly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
2.10 Suspension concentrate a compound of Tables 1 to 3 40 %
ethylene glycol 10 %
nonylphenol polyethylene glycol ether (lS moles of ethylene oxide) 6 % ;
sodium lignosulfonate 10 %
carboxymethylcellulose 1 %
37 % aqueous forrnaldehyde solution 0.2 % --silicone oil in the form of a 75 %
aqueous emulsion 0.8 % ;
water 32 %
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
::... . :-Biological ExamPles : : ~ - , . ~, 3.1 Actiona ainstMeloido~YneincoienitaontomatoPlants Eggs of Meloidogyne incognita are mixed into sand. This mixture is then put into 200 ml clay pots (5000 eggs per pot). On the same day a three-week-old tomato plant is planted ~ -,' ' `'. ' '.
., ,. ::-, .: , in each pot and the folmulated test compound is introduced into the pots by drench appli-cation (0.0006 % of active ingredient, based on the volume of the soil). The potted plants are then placed in a greenhouse at a temperature of 26ilC and a relative humidity of 60 %. After 4 weeks, evaluation is made by examining the plants for root-knotformation in accordance with the so-called Root-Knot Index.
.
Compounds of Tables 1-3 exhibit good activity against Meloidogyne incognita by substantial reduction of root-knot formation. On the other hand, untreated and infected control plants exhibit severe root-knot formation (= 100 %). In this test, for example compounds nos. 2.6, 2.8, 2.10, 2.12, 2.38 and 2.39 inhibit root-knot formation almost completely (0-10 % residual attack).
3.2 PYthium ultimum on Beta vuli~aris (sugar beet~ cv. Kleinwanzleben Mono~erm~ and Pvthium ultimum on Zea mays (maize~ cv. Sweet Corn) Test principle: soil fungus: protective local soil application Test method: mycelium of Pvthium ultimum is mixed with soil (500 ml of mycelium suspension to 10 litres of soil) and the fungus-soil mixture is placed in 250 ml plastic dishes~ After 4 days' inculQation at 10C, 10 seeds of the test plant (maize or sugar beet) are sown in each dish. The following day, the dishes so prepared are watered with 50 ml in each case of spray solutions prepared from 25 % wettable powder and water with 20;
6; 2; 0.6; 0.2; 0.0~ and 0.02 ppm a.i.. After a 7-day incubation phase at 10C and a subsequent 4-day incubation phase at 22C, the action of the test compounds is evaluated by counting the number of test plants emerging in accordance with the following scale of ratings: -microbicidal activity rating . : -0-50 9 (= no action) Compounds of Tables 1-3, for example 2.6, exhibit good activity against Pvthium ultimum.
-ZOlZ499 3.3 Action a iainst Rhizoctonia solani (soil fun~us on rice Plants) Protective local soil application A spray mixture (0.002 % active ingredient) prepared from a formulation of the active ingredient is used to water 12-day-old rice plants without contaminating the parts of the plants above the soil. In order to infect the treated plants, a suspension of mycelium and sclerotia of R. solani is applied to the surface of the soil. The fungus attack on the foliar sheath, leaves and stems is evaluated after 6 days' incubation at 27C (day) and 23C
(night) and 100 % relative humidity (humidity chamber) in a climatic chamber.
There was no attaclc following treatment with the active ingredient.
:~ . . -'~ '" ~;' , . ', -
Claims (17)
1. 2-Mercapto-5-thiazol-(2-, 4- or 5-yl)-1,3,4-oxa- and -thia-diazoles and 2-mercapto-5-oxazol-(2-, 4- or 5-yl)-1,3,4-oxa- and -thia-diazoles of formula I
(I) wherein X1 and X2 independently of one another are oxygen or sulfur, R1 is unsubstituted C1-C5alkyl or C1-C5alkyl substituted by halogen, C1-C3alkoxy or by cyano; unsubstituted or halo-substituted C3-C7alkenyl; or unsubstituted or halo-substituted C3-C7alkynyl, R2 and R3 independently of one another are hydrogen, C1-C5alkyl, unsubstituted or halo-substituted C3-C7alkenyl, unsubstituted phenyl or phenyl substituted by identical or different substituents selected from C1-C3alkyl, C1-C3alkoxy and halogen, or the radical -NR4R5 wherein R4 and R5 independently of one another are hydrogen, C1-C5alkyl or unsubstituted or halo-substituted C3-C7alkenyl, or one of the two substituents R2 and R3 may be one of the heterocycles pyridyl, thienyl, furyl and thiazolyl, which may be unsubstituted or mono- or poly-substituted by identical or different substituents selected from C1-C3alkyl, C1-C3alkoxy and halogen; and salts of those compounds.
(I) wherein X1 and X2 independently of one another are oxygen or sulfur, R1 is unsubstituted C1-C5alkyl or C1-C5alkyl substituted by halogen, C1-C3alkoxy or by cyano; unsubstituted or halo-substituted C3-C7alkenyl; or unsubstituted or halo-substituted C3-C7alkynyl, R2 and R3 independently of one another are hydrogen, C1-C5alkyl, unsubstituted or halo-substituted C3-C7alkenyl, unsubstituted phenyl or phenyl substituted by identical or different substituents selected from C1-C3alkyl, C1-C3alkoxy and halogen, or the radical -NR4R5 wherein R4 and R5 independently of one another are hydrogen, C1-C5alkyl or unsubstituted or halo-substituted C3-C7alkenyl, or one of the two substituents R2 and R3 may be one of the heterocycles pyridyl, thienyl, furyl and thiazolyl, which may be unsubstituted or mono- or poly-substituted by identical or different substituents selected from C1-C3alkyl, C1-C3alkoxy and halogen; and salts of those compounds.
2. Compounds of formula I according to claim 1, wherein X1 and X2 independently of one another are O or S, and R1 is halo-substituted C1-C5alkyl; unsubstituted or halo-substi-tuted C3-C7alkenyl; or unsubstituted or halo-substituted C3-C7alkynyl; R2 is hydrogen or C1-C3alkyl; R3 is hydrogen, C1-C3alkyl, unsubstituted phenyl or phenyl substituted by identical or different substituents selected from C1-C3alkyl, C1-C3alkoxy and halogen, or is the radical - NR4R5, or one of the two substituents R2 and R3 may be one of the hetero-cycles pyridyl, thienyl, furyl and thiazolyl, which may be unsubstituted or mono- or di-substituted by identical or different substituents selected from C1-C3alkyl, C1-C3alkoxy and halogen.
3. Compounds of formula I according to claim 2, wherein X1 and X2 independently of one another are oxygen or sulfur, R1 is unsubstituted C1-C5alkyl or C1-C5alkyl substituted by halogen, C1-C3alkoxy or by cyano; unsubstituted or halo-substituted C3-C7alkenyl; or unsubstituted or halo-substituted C3-C7alkynyl; R2 and R3 independently of one aanother are hydrogen, C1-C5alkyl, unsubstituted or halo-substituted C3-C7alkenyl, unsubstituted phenyl or phenyl substituted by identical or different substituents selected from C1-C3-alkyl, C1-C3alkoxy and halogen, or one of the two substituents R2 and R3 may be one of the heterocycles pyridyl, thienyl, furyl and thiazolyl, which may be unsubstituted or mono- or poly-substituted by identical or different substituents selected from C1-C3alkyl, C1-C3alkoxy and halogen.
4. Compounds according to claim 3, wherein X1 and X2 independently of one another are oxygen or sulfur, R1 is unsubstituted C1-C5alkyl or C1-C5alkyl substituted by halogen, C1-C3alkoxy or by cyano; unsubstituted or halo-substituted C3-C7alkenyl; or unsubstituted or halo-substituted C3-C7alkynyl; R2 and R3 independently of one another are hydrogen, C1-C3alkyl, unsubstituted phenyl or phenyl substituted by C1-C3alkyl, C1-C3alkoxy or by halogen, or pyridyl, thienyl, furyl or thiazolyl, and salts of those compounds.
5. 2-mercapto-5-thiazol-(2-, 4- or 5-yl)-1,3,4-oxadiazoles of formula Ia (Ia) according to claim 4, wherein R1 is difluoromethyl, 3,4,4-trifluoro-3-butene, cyanomethyl, 1,1,2,2-tetrafluoroethyl or propargyl, and R2 and R3 independently of one another are hydrogen or methyl.
6. A 2-mercapto-5-thiazol-(2-, 4- or 5-yl)-1,3,4-oxadiazole according to claim 1, selected from the group consisting of 2-difluoromethylthio-5-(thiazol-2-yl)-1,3,4-oxadiazole, 2-(3,4,4-trifluoro-3-butenylthio)-5-(thiazol-2-yl)-1,3,4-oxadiazole, 2-difluoromethylthio-5-(2-methylthiazol-4-yl)-1,3,4-oxadiazole, 2-(3,4,4-trifluoro-3-butenylthio)-5-(2-methyl-thiazol-4-yl)-1,3,4-oxadiazole, 2-difluoromethylthio-5-(thiazol-5-yl)-1,3,4-oxazole, and 2-(3,4,4-trifluoro-3-butenylthio)-5-(thiazol-5-yl)-1,3,4-oxadiazole.
7. 2-(3,4,4-Trifluoro-3-butenylthio)-5-2-(pyrid-3-yl)-thiazol-4-yl-1,3,4-oxadiazole according to claim 1.
8. 2-Mercapto-5-oxazol-(2-, 4- or 5-yl)-1,3,4-thiadiazoles of formula Ib (Ib) according to claim 4, wherein R1 is difluoromethyl, 3,4,4-trifluoro-3-butene, 1,1,2,2-tetra-fluoroethyl, cyanomethyl, allyl, propargyl or 2-bromoalkyl, and R2 and R3 independently of one another are hydrogen or methyl.
9. A 2-mercapto-5-oxazol-(2-, 4- or 5-yl)-1,3,4-thiadiazole according to claim 1, selected from a group consisting of 2-difluoromethylthio-5-(thiazol-2-yl)-1,3,4-thiadiazole, 2-(3,4,4-trifluoro-3-butenylthio)-5-(thiazol-2-yl)-1,3,4-thiadiazole, 2-difluoromethylthio-5-(2-methylthiazol-4-yl)-1,3,4-thiadiazole, 2-(3,4,4-trifluoro-3-butenylthio)-5-(2-methyl-thiazol-4-yl)-1,3,4-thiadiazole, 2-difluoromethylthio-5-(thiazol-5-yl)-1,3,4-thiadiazole, and 2-(3,4,4-trifluoro-3-butenylthio)-5-(thiazol-5-yl)-1,3,4-thiadiazole.
10. A process for the preparation of the compounds of formula I according to claim 1, which comprises a) in a condensation reaction, reacting a compound of formula II
(II) or a compound of formula III
(III) with a compound of formula IV
Hal-RI (IV) in an inert solvent or solvent mixture at room temperature or at elevated temperature optionally in the presence of a catalyst and optionally at elevated pressure, the reaction of a compound of formula II proceeding in the presence of a base, or b) in an addition reaction, reacting a compound of formula II
(II) with a compound of formula V
(V) in an inert solvent or solvent mixture at elevated temperature, optionally in the presence of a catalyst and optionally at elevated pressure, this reaction resulting in a compound of formula Ic (Ic) or a compound of formula Id (Id), in the above-mentioned formulae II, III, Ic, Id, IV and V, M being an alkali metal or ammonium, Hal being halogen, preferably chlorine, bromine or iodine, and R' being fluorine or trifluoromethyl, while R1, R2, R3, X1 and X2 are as defined under formula I.
(II) or a compound of formula III
(III) with a compound of formula IV
Hal-RI (IV) in an inert solvent or solvent mixture at room temperature or at elevated temperature optionally in the presence of a catalyst and optionally at elevated pressure, the reaction of a compound of formula II proceeding in the presence of a base, or b) in an addition reaction, reacting a compound of formula II
(II) with a compound of formula V
(V) in an inert solvent or solvent mixture at elevated temperature, optionally in the presence of a catalyst and optionally at elevated pressure, this reaction resulting in a compound of formula Ic (Ic) or a compound of formula Id (Id), in the above-mentioned formulae II, III, Ic, Id, IV and V, M being an alkali metal or ammonium, Hal being halogen, preferably chlorine, bromine or iodine, and R' being fluorine or trifluoromethyl, while R1, R2, R3, X1 and X2 are as defined under formula I.
11. A pesticidal composition for controlling or preventing attacks on plants by nematodes and fungi, which contains as active ingredient at least one compound of formula I
according to claim 1.
according to claim 1.
12. A composition according to claim 11, which contains as active ingredient at least one compound of formula I according to claims 2 to 8.
13. A composition according to claim 11, which contains as active ingredient a compound selected from a group consisting of 2-mercapto-5-thiazol-(2-, 4- or 5-yl)-1,3,4-oxadiazole.
14. A composition according to claim 11, which contains as active ingredient a compound selected from a group consisting of 2-difluoromethylthio-5-(thiazol-2-yl)-1,3,4-thiadia-zole, 2-(3,4,4-trifluoro-3-butenylthio)-5-(thiazol-2-yl)-1,3,4-thiadiazole, 2-difluoromethyl-thio-5-(2-methylthiazol-4-yl)-1,3,4-thiadiazole, 2-(3,4,4-trifluoro-3-butenylthio)-5-(2-methylthiazol-4-yl)-1,3,4-thiadiazole, 2-difluoromethylthio-5-(thiazol-5-yl)-1,3,4-thiadia-zole, and 2-(3,4,4-trifluoro-3-butenylthio)-5-(thiazol-5-yl)-1,3,4-thiadiazole.
15. A process for the preparation of an agrochemical composition, which comprises homogeneously mixing at least one compound of formula I according to claim 1 with suitable solid or liquid adjuvants and surfactants.
16. A method of controlling or preventing attacks on cultivated plants by nematodes and fungi, which comprises applying a compound of formula I according to any one of claims 1 to 9 to the plant or the locus thereof.
17. The use of compounds of formula I according to claim 1 for controlling and/or preventing attacks on plants by nematodes and fungi.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH103889 | 1989-03-21 | ||
| CH1038/89-0 | 1989-03-21 | ||
| CH195/90-4 | 1990-01-23 | ||
| CH19590 | 1990-01-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2012499A1 true CA2012499A1 (en) | 1990-09-21 |
Family
ID=25683842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002012499A Abandoned CA2012499A1 (en) | 1989-03-21 | 1990-03-19 | Nematicidal and fungicidal compositions |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0389426A1 (en) |
| JP (1) | JPH02286678A (en) |
| KR (1) | KR900014373A (en) |
| AR (1) | AR245867A1 (en) |
| AU (1) | AU5201690A (en) |
| BR (1) | BR9001313A (en) |
| CA (1) | CA2012499A1 (en) |
| IL (1) | IL93789A0 (en) |
| NZ (1) | NZ232981A (en) |
| PT (1) | PT93495A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995012977A1 (en) * | 1993-11-09 | 1995-05-18 | Monsanto Company | Improved compositions for nematode control |
| ITUB20153829A1 (en) * | 2015-09-23 | 2017-03-23 | Isagro Spa | Trifluoroalchenyl heterocyclic compounds with nematocidal activity, their agronomic compositions and their use |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE757577A (en) * | 1969-10-18 | 1971-04-15 | Fisons Ltd | NEW BLOCKED DIAZOLES AND PLANT GROWTH REGULATORS |
| FR2211008A5 (en) * | 1972-12-18 | 1974-07-12 | Pepro | |
| US4454147A (en) * | 1982-05-27 | 1984-06-12 | Fmc Corporation | Nematicidal 2-chloro-5-aryl-1,3,4-thiadiazoles |
| DD258814A1 (en) * | 1987-03-19 | 1988-08-03 | Bitterfeld Chemie | PROCESS FOR THE PREPARATION OF NEW 2-HETEROARYL-5-AMINOTHIAZOLENE |
-
1990
- 1990-03-13 EP EP90810194A patent/EP0389426A1/en not_active Withdrawn
- 1990-03-19 AR AR90316410A patent/AR245867A1/en active
- 1990-03-19 NZ NZ232981A patent/NZ232981A/en unknown
- 1990-03-19 PT PT93495A patent/PT93495A/en not_active Application Discontinuation
- 1990-03-19 CA CA002012499A patent/CA2012499A1/en not_active Abandoned
- 1990-03-19 IL IL93789A patent/IL93789A0/en unknown
- 1990-03-20 AU AU52016/90A patent/AU5201690A/en not_active Abandoned
- 1990-03-20 JP JP2071748A patent/JPH02286678A/en active Pending
- 1990-03-21 KR KR1019900003887A patent/KR900014373A/en not_active Application Discontinuation
- 1990-03-21 BR BR909001313A patent/BR9001313A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NZ232981A (en) | 1991-02-26 |
| KR900014373A (en) | 1990-10-23 |
| AR245867A1 (en) | 1994-03-30 |
| JPH02286678A (en) | 1990-11-26 |
| IL93789A0 (en) | 1990-12-23 |
| PT93495A (en) | 1990-11-07 |
| BR9001313A (en) | 1991-04-02 |
| AU5201690A (en) | 1990-09-27 |
| EP0389426A1 (en) | 1990-09-26 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued |