Microbiocidal quinoline (thio)carboxamide derivatives
11185073 · 2021-11-30
Assignee
Inventors
Cpc classification
International classification
Abstract
Compounds of the formula (I) wherein the substituents are as defined in claim 1. Furthermore, the present invention relates to agrochemical compositions which comprise compounds of formula (I), to preparation of these compositions, and to the use of the compounds or compositions in agriculture or horticulture for combating, preventing or controlling infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi. ##STR00001##
Claims
1. A compound of formula (I) ##STR00053## wherein X is O or S; R.sub.1 is hydrogen, halogen, methyl or cyano; R.sub.2 is hydrogen, methyl or halogen; R.sub.3 and R.sub.4 are each independently selected from hydrogen, halogen and methyl; R.sub.5 is C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.2 haloakyl, C.sub.2-C.sub.4 alkenyl or C.sub.3-C.sub.6 cycloalkyl, wherein the alkyl, alkenyl and cycloalkyl may be optionally substituted with 1 to 3 substituents independently selected from halogen, cyano, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 alkoxy and C.sub.1-C.sub.3 alkylthio; R.sub.6 is hydrogen, cyano or C.sub.1-C.sub.4 alkyl; R.sub.7 is C.sub.1-C.sub.5 alkyl, C.sub.3-C.sub.7 cycloalkyl, C.sub.3-C.sub.5 alkenyl, C.sub.3-C.sub.6 cycloalkenyl, C.sub.3-C.sub.5 alkynyl, a C.sub.5-C.sub.10 saturated or partially unsaturated bicyclic carbocycle, aryl, aryl(C.sub.1-C.sub.4)alkyl, a saturated or partially unsaturated heterocycle or heteroaryl, wherein the alkyl, cycloalkyl, alkenyl, cycloalkenyl, carbocycle, alkynyl, may be optionally substituted with one or more substituents independently selected from halogen, cyano, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 alkylthio; C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 haloalkylthio, C.sub.3-C.sub.5 cycloalkyl or phenyl, and wherein the aryl, heterocycle or heteroaryl may be optionally substituted with one or more substituents independently selected from halogen, cyano, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 alkylthio; C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 haloalkylthio or C.sub.3-C.sub.5 cycloalkyl; or a salt or N-oxide thereof.
2. The compound according to claim 1 wherein R.sub.1 is hydrogen, fluoro, chloro, bromo or methyl.
3. The compound according to claim 1 wherein R.sub.2 is hydrogen, methyl, chloro or fluoro.
4. The compound according to claim 1 wherein R.sub.3 and R.sub.4 are each independently selected from hydrogen, chloro and methyl.
5. The compound according to claim 1 wherein R.sub.5 is C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.2 haloakyl, C.sub.2-C.sub.4 alkenyl or C.sub.3-C.sub.6 cycloalkyl, wherein the alkyl, alkenyl and cycloalkyl may be optionally substituted with 1 to 3 substituents independently selected from fluoro, cyano, methyl, methoxy and methylthio.
6. The compound according to claim 1 wherein R.sub.6 is hydrogen or C.sub.1-C.sub.3 alkyl.
7. The compound according to claim 1 wherein R.sub.7 is C.sub.1-C.sub.5 alkyl, C.sub.3-C.sub.7 cycloalkyl, C.sub.3-C.sub.5 alkenyl, C.sub.3-C.sub.6 cycloalkenyl, C.sub.3-C.sub.5 alkynyl, a C.sub.5-C.sub.10 saturated bicyclic carbocycle, a C.sub.5-C.sub.10 partially unsaturated bicyclic carbocycle, phenyl, phenyl(C.sub.1-C.sub.3)alkyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, pyridinyl, thiophenyl, thiazolyl, oxazolyl or pyrazolyl, wherein the alkyl, cycloalkyl, alkenyl, cycloalkenyl, carbocycle and alkynyl may be optionally substituted with one or more substituents independently selected from fluoro, chloro, cyano, methyl, methoxy, methylthio; C.sub.1-C.sub.2 fluoroalkoxy, C.sub.1-C.sub.2 fluoroalkylthio, cyclopropyl and cyclobutyl, and wherein the phenyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, pyridinyl, thiophenyl, thiazolyl, oxazolyl and pyrazolyl may be optionally substituted with one or more substituents independently selected from fluoro, chloro, cyano, methyl, methoxy, methylthio; C.sub.1-C.sub.2 fluoroalkoxy, C.sub.1-C.sub.2 fluoroalkylthio, cyclopropyl and cyclobutyl.
8. The compound according to claim 1 wherein R.sub.1 is fluoro, chloro or methyl; R.sub.2 is hydrogen or fluoro; R.sub.3 and R.sub.4 are each independently selected from hydrogen and methyl; R.sub.5 is C.sub.1-C.sub.4 alkyl, C.sub.1-haloakyl, C.sub.2-C.sub.4 alkenyl or C.sub.3-C.sub.4 cycloalkyl, wherein the alkyl, alkenyl and cycloalkyl may be optionally substituted with 1 to 3 substituents independently selected from fluoro, cyano and methyl; and R.sub.6 is hydrogen, methyl or ethyl.
9. The compound according to claim 1 wherein R.sub.7 is C.sub.1-C.sub.8 alkyl, C.sub.3-C.sub.7 cycloalkyl, C.sub.3-C.sub.4 alkenyl, C.sub.3-C.sub.6 cycloalkenyl, a C.sub.6-C.sub.8 saturated bicyclic carbocycle, a C.sub.6-C.sub.8 partially unsaturated bicyclic carbocycle, phenyl, phenyl(C.sub.1-C.sub.3)alkyl, pyridinyl, thiophenyl, thiazolyl, oxazolyl and pyrazolyl wherein the alkyl, cycloalkyl, alkenyl, cycloalkenyl and carbocycle may be optionally substituted with 1 to 3 substituents independently selected from fluoro, chloro, cyano, methyl, methoxy, methylthio, cyclopropyl and cyclobutyl, and wherein the phenyl, pyridinyl, thiophenyl, thiazolyl, oxazolyl and pyrazolyl may be optionally substituted with 1 to 3 of substituents independently selected from fluoro, chloro, cyano, methyl and cyclopropyl.
10. The compound according to claim 1 wherein X is O or S; R.sub.1 is fluoro, chloro or methyl; R.sub.2 is hydrogen or fluoro; R.sub.3 and R.sub.4 are each independently selected from hydrogen and methyl; R.sub.5 is C.sub.1-C.sub.4 alkyl, C.sub.1-haloakyl, C.sub.2-C.sub.4 alkenyl or C.sub.3-C.sub.4 cycloalkyl, wherein the alkyl, alkenyl and cycloalkyl may be optionally substituted with 1 to 3 substituents independently selected from fluoro, cyano and methyl; R.sub.6 is hydrogen, methyl or ethyl; R.sub.7 is C.sub.1-C.sub.5 alkyl, C.sub.3-C.sub.7 cycloalkyl, C.sub.3-C.sub.4 alkenyl, C.sub.3-C.sub.6 cycloalkenyl, a C.sub.6-C.sub.8 saturated bicyclic carbocycle, a C.sub.6-C.sub.8 partially unsaturated bicyclic carbocycle, phenyl, phenyl(C.sub.1-C.sub.3)alkyl, pyridinyl, thiophenyl, thiazolyl, oxazolyl and pyrazolyl wherein the alkyl, cycloalkyl, alkenyl, cycloalkenyl and carbocycle may be optionally substituted with 1 to 3 substituents independently selected from fluoro, chloro, cyano, methyl, methoxy, methylthio, cyclopropyl and cyclobutyl, and wherein the phenyl, pyridinyl, thiophenyl, thiazolyl, oxazolyl and pyrazolyl may be optionally substituted with 1 to 3 of substituents independently selected from fluoro, chloro, cyano, methyl and cyclopropyl; or a salt or N-oxide thereof.
11. The compound according to claim 1 wherein X is O or S; R.sub.1 is fluoro or methyl; R.sub.2 is hydrogen; R.sub.3 is methyl and R.sub.4 is hydrogen; or R.sub.3 is hydrogen and R.sub.4 is methyl; or R.sub.3 is hydrogen and R.sub.4 is hydrogen; R.sub.5 is C.sub.1-C.sub.4 alkyl, trifluoromethyl, C.sub.2-C.sub.4 alkenyl or C.sub.3-C.sub.4 cycloalkyl, wherein the alkyl, alkenyl and cycloalkyl may be optionally substituted with 1 to 3 fluorine atoms or a methyl; R.sub.6 is methyl; R.sub.7 is C.sub.3-C.sub.5 alkyl, C.sub.3-C.sub.7 cycloalkyl, C.sub.3-C.sub.4 alkenyl, a C.sub.6-C.sub.8 saturated bicyclic carbocycle, phenyl, phenyl(C.sub.1-C.sub.2)alkyl or pyridyl, wherein the alkyl, cycloalkyl, alkenyl and carbocycle may be optionally substituted with 1 to 3 substituents independently selected from fluoro and methyl or 1 or 2 substituents independently selected from cyclopropyl and cyclobutyl, and wherein the phenyl and pyridyl may be optionally substituted with 1 to 2 substituents independently selected from fluoro, chloro and methyl; or a salt or N-oxide thereof.
12. The compound according to claim 1 wherein X is O.
13. A composition comprising a fungicidally effective amount of a compound of formula (I) as defined in claim 1.
14. The composition according to claim 13, wherein the composition further comprises at least one additional active ingredient and/or a diluent.
15. A method of combating, preventing or controlling phytopathogenic fungi which comprises applying to phytopathogenic fungi, to the locus of phytopathogenic fungi, or to a plant susceptible to attack by phytopathogenic fungi, or to propagation material thereof, a fungicidally effective amount of a compound of formula (I) as defined in claim 1.
16. A compound selected from the group consisting of: N-[1-(2,2-dimethylpropoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; 8-chloro-N-[1-[(3,3-dimethylcyclobutoxy)methyl]-3,3,3-trifluoro-1-methyl-propyl]quinoline-3-carboxamide; N-[1-[(4,4-difluorocyclohexoxy)methyl]-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[1-[(3,3-dimethylcyclobutoxy)methyl]-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[1-[(4-chlorophenoxy)methyl]-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(cyclopropylmethoxymethyl)-1,3,3-trimethyl-butyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(cyclobutoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-4-methyl-quinoline-3-carboxamide; N-[1-(cyclobutoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-7,8-difluoro-quinoline-3-carboxamide; N-[1-(cyclobutoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-2-methyl-quinoline-3-carboxamide; 8-fluoro-N-[3,3,3-trifluoro-1-methyl-1-[(1-methylcyclopentoxy)methyl]propyl]quinoline-3-carboxamide; N-[1-(cyclobutoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-methyl-quinoline-3-carboxamide; 8-chloro-N-[1-(cyclobutoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]quinoline-3-carboxamide; N-[(1S)-1-(cyclobutoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[(1S)-1-(cyclobutoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; 8-fluoro-N-[3,3,3-trifluoro-1-methyl-1-[(1-methylcyclohexoxy)methyl]propyl]quinoline-3-carboxamide; N-[(1R)-1-(cyclohexoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[(1S)-1-(cyclohexoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(benzyloxymethyl)-1-methyl-2-(1-methylcyclopropyl)ethyl]-8-fluoro-quinoline-3-carboxamide; 8-fluoro-N-[3,3,3-trifluoro-1-methyl-1-(phenoxymethyl)propyl]quinoline-3-carboxamide; N-[1,3-dimethyl-1-(2-methylallyloxymethyl)butyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(cyclobutoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(1-ethylpropoxymethyl)-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(cyclobutoxymethyl)-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide; 8-fluoro-N-[1-(isopropoxymethyl)-1,3-dimethyl-butyl]quinoline-3-carboxamide; 8-fluoro-N-[1-(isobutoxymethyl)-1,3-dimethyl-butyl]quinoline-3-carboxamide; N-[1-(cycloheptoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(cyclohexoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[1,3-dimethyl-1-(phenoxymethyl)butyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(cyclohexoxymethyl)-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(benzyloxymethyl)-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(cyclopentoxymethyl)-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide; 8-fluoro-N-[1-(methoxymethyl)-1,3-dimethyl-butyl]quinoline-3-carboxamide; and 8-fluoro-N-[1-(methoxymethyl)-1-methyl-nonyl]quinoline-3-carboxamide.
17. The compound of claim 16, wherein the compound is selected from the group consisting of: 8-fluoro-N-[1-(isopropoxymethyl)-1,3-dimethyl-butyl]quinoline-3-carboxamide; 8-fluoro-N-[1-(isobutoxymethyl)-1,3-dimethyl-butyl]quinoline-3-carboxamide; N-[1-(cycloheptoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(cyclohexoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[1,3-dimethyl-1-(phenoxymethyl)butyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(cyclohexoxymethyl)-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(benzyloxymethyl)-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(cyclopentoxymethyl)-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide; 8-fluoro-N-[1-(methoxymethyl)-1,3-dimethyl-butyl]quinoline-3-carboxamide; and 8-fluoro-N-[1-(methoxymethyl)-1-methyl-nonyl]quinoline-3-carboxamide.
18. The compound of claim 16, wherein the compound is selected from the group consisting of: 8-chloro-N-[1-(cyclobutoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]quinoline-3-carboxamide; N-[(1S)-1-(cyclobutoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[(1S)-1-(cyclobutoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; 8-fluoro-N-[3,3,3-trifluoro-1-methyl-1-[(1-methylcyclohexoxy)methyl]propyl]quinoline-3-carboxamide; N-[(1R)-1-(cyclohexoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[(1S)-1-(cyclohexoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(benzyloxymethyl)-1-methyl-2-(1-methylcyclopropyl)ethyl]-8-fluoro-quinoline-3-carboxamide; 8-fluoro-N-[3,3,3-trifluoro-1-methyl-1-(phenoxymethyl)propyl]quinoline-3-carboxamide; N-[1,3-dimethyl-1-(2-methylallyloxymethyl)butyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(cyclobutoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(1-ethylpropoxymethyl)-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide; and N-[1-(cyclobutoxymethyl)-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide.
19. The compound of claim 16, wherein the compound is selected from the group consisting of: N-[1-(2,2-dimethylpropoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; 8-chloro-N-[1-[(3,3-dimethylcyclobutoxy)methyl]-3,3,3-trifluoro-1-methyl-propyl]quinoline-3-carboxamide; N-[1-[(4,4-difluorocyclohexoxy)methyl]-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[1-[(3,3-dimethylcyclobutoxy)methyl]-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[1-[(4-chlorophenoxy)methyl]-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(cyclopropylmethoxymethyl)-1,3,3-trimethyl-butyl]-8-fluoro-quinoline-3-carboxamide; N-[1-(cyclobutoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-4-methyl-quinoline-3-carboxamide; N-[1-(cyclobutoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-7,8-difluoro-quinoline-3-carboxamide; N-[1-(cyclobutoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-2-methyl-quinoline-3-carboxamide; 8-fluoro-N-[3,3,3-trifluoro-1-methyl-1-[(1-methylcyclopentoxy)methyl]propyl]quinoline-3-carboxamide; and N-[1-(cyclobutoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-methyl-quinoline-3-carboxamide.
Description
EXAMPLES
(1) The Examples which follow serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.
(2) Throughout this description, temperatures are given in degrees Celsius and “m.p.” means melting point. LC/MS means Liquid Chromatography Mass Spectroscopy and the description of the apparatus and the methods are:
(3) Method G:
(4) Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 3.00 kV, Cone range: 30 V, Extractor: 2.00 V, Source Temperature: 150° C., Desolvation Temperature: 350° C., Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650 l/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment, diode-array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C., DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5% MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 1.2 min; Flow (ml/min) 0.85
(5) Method H:
(6) Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 3.00 kV, Cone range: 30V, Extractor: 2.00 V, Source Temperature: 150° C., Desolvation Temperature: 350° C., Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650 l/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment, diode-array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C., DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5% MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 2.7 min; Flow (ml/min) 0.85
(7) Method W:
(8) Spectra were recorded on a Mass Spectrometer (ACQUITY UPLC) from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150° C., Desolvation Temperature: 400° C., Cone Gas Flow: 60 L/Hr, Desolvation Gas Flow: 700 L/Hr, Mass range: 140 to 800 Da), DAD Wavelength range (nm): 210 to 400, and an Acquity UPLC from Waters: Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 m, 30×2.1 mm, Temp: 60° C., DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=Water/Methanol 9:1, 0.1% formic acid, B=Acetonitrile+0.1% formic acid, gradient: 0-100% B in 2.5 min; Flow (ml/min) 0.75
Formulation Examples
(9) TABLE-US-00002 Wettable powders a) b) c) active ingredient [compound of formula (I)] 25% 50% 75% sodium lignosulfonate 5% 5% — sodium lauryl sulfate 3% — 5% sodium diisobutylnaphthalenesulfonate — 6% 10% phenol polyethylene glycol ether — 2% — (7-8 mol of ethylene oxide) highly dispersed silicic acid 5% 10% 10% Kaolin 62% 27% —
(10) The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
(11) TABLE-US-00003 Powders for dry seed treatment a) b) c) active ingredient [compound of formula (I)] 25% 50% 75% light mineral oil 5% 5% 5% highly dispersed silicic acid 5% 5% — Kaolin 65% 40% — Talcum — 20
(12) The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
(13) Emulsifiable Concentrate
(14) TABLE-US-00004 active ingredient [compound of formula(I)] 10% octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether (35 mol of ethylene oxide) 4% Cyclohexanone 30% xylene mixture 50%
(15) Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
(16) TABLE-US-00005 Dusts a) b) c) Active ingredient 5% 6% 4% [compound of formula (I)] talcum 95% — — Kaolin — 94% — mineral filler — — 96%
(17) Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
(18) Extruder Granules
(19) TABLE-US-00006 Active ingredient [compound of formula (I)] 15% sodium lignosulfonate 2% carboxymethylcellulose 1% Kaolin 82%
(20) The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
(21) Coated Granules
(22) TABLE-US-00007 Active ingredient [compound of formula (I)] 8% polyethylene glycol (mol. wt. 200) 3% Kaolin 89%
(23) The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
(24) Suspension Concentrate
(25) TABLE-US-00008 active ingredient [compound of formula (I)] 40% propylene glycol 10% nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6% Sodium lignosulfonate 10% carboxymethylcellulose 1% silicone oil (in the form of a 75% emulsion in water) 1% Water 32%
(26) The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
(27) Flowable Concentrate for Seed Treatment
(28) TABLE-US-00009 active ingredient [compound of formula (I)] 40% propylene glycol 5% copolymer butanol PO/EO 2% tristyrenephenole with 10-20 moles EO 2% 1,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5% monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water 45.3%
(29) The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
(30) Slow Release Capsule Suspension
(31) 28 parts of a combination of the compound of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
(32) The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns.
(33) The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
Preparation Examples
Example 1: Preparation of N-[1-(cyclohexoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide
Step 1, preparation of 2-methylallyloxycyclohexane
(34) ##STR00016##
(35) To a suspension of sodium hydride (60%, 1.75 g, 43.9 mmol) in tetrahydrofuran (40 mL)/dimethyl formamide (4 mL) was added cyclohexanol (4.0 g, 39.9 mmol) at 5-10° C. The resulting mixture was warmed to room temperature and stirred for 30 minutes. 3-bromo-2-methyl-prop-1-ene (5.7 g, 41.9 mmol) was added slowly and the reaction aged for 24 h at 20° C. Water was then added carefully and the mixture was extracted with methyl tertbutyl ether. The organic layer was washed with water, brine, dried over MgSO4, filtrated and concentrated in vacuo. The residual oil was filtrated through a short silica plug (rinsed with cyclohexane/ethyl acetate) to give the title compound as colorless liquid.
(36) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 4.97-4.99 (m, 1H), 4.85-4.87 (m, 1H), 3.91 (s, 2H), 3.22-3.30 (m, 1H), 1.84-1.98 (m, 2H), 1.67-1.82 (m, 5H), 1.13-1.39 (m, 6H).
Step 2, preparation of [1-(cyclohexoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-phenyl-diazene
(37) ##STR00017##
(38) 2-methylallyloxycyclohexane (0.8 g, 5.0 mmol) was added to a solution of sodium trifluoromethylsulfinate (2.0 g 10 mmol) in acetonitrile (20 mL). To this was added sequentially benzenediazonium fluoroborate (1 M in acetonitrile, 10 mL, 10 mmol), CuBF.sub.4-(MeCN).sub.4 (0.08 g, 0.3 mmol) and H.sub.2O.sub.2 (aq. 30%, 0.06 g) at RT. The resulting mixture was stirred for 18 h at room temperature after which time no further gas evolution was observed. The brown-red suspension was diluted with water and extracted with cyclohexane. The organic layer was washed with water, brine, dried over MgSO4, filtrated and concentrated in vacuo. The residue was purified by medium pressure chromatography through silica gel (cyclohexane/ethyl acetate) to afford the title compound as yellow, viscous oil.
(39) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.59-7.73 (m, 2H), 7.33-7.54 (m, 3H), 3.80 (d, 1H), 3.60 (d, 1H), 3.20-3.25 (m, 1H), 2.74-2.99 (m, 2H), 1.62-1.89 (m, 4H), 1.45 (s, 3H), 1.13-1.38 (m, 6H).
(40) .sup.19F NMR (376 MHz, CDCl.sub.3) δ −59.4.
Step 3, preparation of 1-(cyclohexoxy)-4,4,4-trifluoro-2-methyl-butan-2-amine
(41) ##STR00018##
(42) To a solution of [1-(cyclohexoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-phenyl-diazene (0.32 g, 0.97 mmol) in ethanol (15 mL) was added Raney nickel (aq. slurry, ca. 0.8 g) and the resulting mixture was stirred for 1 h at 65° C. under hydrogen atmosphere (1 bar). The resulting colorless emulsion was cooled to 20° C., filtrated through Celite and the filtrate was concentrated in vacuo. The residue was taken up in aq. HCl (1 M) and washed with cyclohexane. The aqueous layer was basified to pH 12 with aq. NaOH and extracted with methyl tertbutylether. The organic layer was washed with brine, dried over MgSO4, filtrated and concentrated in vacuo to afford a mixture of the title compound and aniline which was used as such for the next step. An analytically pure sample was obtained by medium pressure chromatography (silica gel, cyclohexane/EtOAc).
(43) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 3.23-3.34 (m, 2H), 3.21 (d, 1H), 2.31 (dq, 2H), 1.65-1.92 (m, 4H), 1.22-1.61 (m, 6H), 1.20 (s, 3H)
(44) .sup.19F NMR (376 MHz, CDCl.sub.3) δ −59.9
Step 4, preparation of N-[1-(cyclohexoxymethyl)-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide
(45) ##STR00019##
(46) A suspension of 8-fluoroquinoline-3-carboxylic acid (0.17 g, 0.87 mmol) in acetonitrile (1.5 mL) was treated with triethylamine (0.28 mL, 2 mmol) and propylphosphonic anhydride (50% in ethyl acetate, 0.8 mL, 1.3 mmol) at 20° C. The resulting solution was aged for 5 min before a solution of 1-(cyclohexoxy)-4,4,4-trifluoro-2-methyl-butan-2-amine (0.16 g, 0.67 mmol) in acetonitrile (1.5 mL) was added. The reaction was stirred for 1 h at 20° C., diluted with water and extracted with ethyl acetate. The organic layer was washed with aq. NaHCO.sub.3, NH.sub.4Cl and brine, dried over MgSO.sub.4, filtrated and concentrated in vacuo. The residue was purified by medium pressure chromatography (silica gel, cyclohexane/EtOAc) to afford the title compound as white solid.
(47) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 9.23 (d, 1H), 8.59 (t, 1H), 7.41-7.82 (m, 3H), 6.74 (s, 1H), 3.74 (d, 1H), 3.61 (d, 1H), 3.34-3.44 (m, 1H), 3.03-3.16 (m, 1H), 2.74-2.95 (m, 1H), 1.69-1.99 (m, 4H), 1.68 (s, 3H), 1.19-1.40 (m, 6H)
(48) .sup.19F NMR (376 MHz, CDCl.sub.3) δ −60.2, −124.6
(49) TABLE-US-00010 TABLE E Physical data of compounds of formula (I) RT [M + H] MP Entry IUPAC Name Structure (min) (measured) Method ° C. E.001 N-[1-(2,2-dimethyl- propoxymethyl)- 3,3,3-trifluoro-1- methyl-propyl]-8- fluoro-quinoline-3- carboxamide
Biological Examples
(50) Botryotinia fuckeliana (Botrytis cinerea)/Liquid Culture (Gray Mould)
(51) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically 3-4 days after application.
(52) The following compounds gave at least 80% control of Botryotinia fuckeliana at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
(53) E.001, E.002, E.003, E.004, E.005, E.006, E.007, E.008, E.009, E.010, E.011, E.012, E.013, E.0014, E.015, E.016, E.017, E.018, E.019, E.020, E.021, E.022, E.023, E.024, E.025, E.026, E.027, E.028, E.029, E.030, E.031, E.032, E.033
(54) Glomerella lagenarium (Colletotrichum lagenarium)/Liquid Culture (Anthracnose)
(55) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is measured photometrically 3-4 days after application.
(56) The following compounds gave at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
(57) E.001, E.002, E.003, E.004, E.005, E.006, E.007, E.008, E.009, E.010, E.011, E.012, E.013, E.014, E.015, E.016, E.017, E.019, E.020, E.021, E.022, E.023, E.024, E.025, E.026, E.027, E.0028, E.029, E.030, E.031, E.033
(58) Fusarium culmorum/Liquid Culture (Head Blight)
(59) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically 3-4 days after application.
(60) The following compounds gave at least 80% control of Fusarium culmorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
(61) E.001, E.002, E.003, E.004, E.005, E.006, E.007, E.008, E.009, E.010, E.011, E.012, E.013, E.014, E.015, E.016, E.017, E.018, E.019, E.020, E.021, E.022, E.023, E.024, E.025, E.026, E.027, E.028, E.029, E.030, E.031, E.032, E.033
(62) Fusarium culmorum/Wheat/Spikelet Preventative (Head Blight)
(63) Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The spikelets are inoculated with a spore suspension of the fungus 1 day after application. The inoculated spikelets are incubated at 20° C. and 60% rh under a light regime of 72 h semi darkness followed by 12 h light/12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check spikelets (6-8 days after application).
(64) The following compounds gave at least 80% control of Fusarium culmorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
(65) E.001, E.002, E.003, E.004, E.005, E.006, E.007, E.008, E.010, E.011, E.012, E.013, E.014, E.016, E.017, E.019, E.020, E.022, E.023, E.024, E.025, E.026, E.027, E.028, E.029, E.031
(66) Gibberella zeae (Fusarium graminearum)/Wheat/Spikelet Preventative (Head Blight)
(67) Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. One day after application, the spikelets are inoculated with a spore suspension of the fungus. The inoculated test leaf disks are incubated at 20° C. and 60% rh under a light regime of 72 h semi darkness followed by 12 h light/12 h darkness in a climate chamber, the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check spikelets (6-8 days after application).
(68) The following compounds gave at least 80% control of Gibberella zeae at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: E.001, E.003, E.007, E.008, E.010, E.012, E.014, E.017, E.019, E.020, E.023, E.024, E.025, E.027, E.033
(69) Monographella nivalis (Microdochium nivale)/Liquid Culture (Foot Rot Cereals)
(70) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically 4-5 days after application.
(71) The following compounds gave at least 80% control of Monographella nivalis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
(72) E.001, E.002, E.003, E.004, E.005, E.006, E.007, E.008, E.010, E.011, E.012, E.013, E.016, E.018, E.019, E.020, E.022, E.023, E.025, E.026, E.027, E.028, E.029, E.030, E.031, E.033
(73) Magnaporthe grisea (Pyricularia oryzae)/Liquid Culture (Rice Blast)
(74) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically 3-4 days after application.
(75) The following compounds gave at least 80% control of Magnaporthe grisea at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development:
(76) E.001, E.002, E.003, E.004, E.005, E.006, E.007, E.008, E.009, E.011, E.012, E.015, E.016, E.017, E.018, E.019, E.020, E.021, E.022, E.023, E.024, E.025, E.026, E.027, E.029, E.030, E.031