SUBSTITUTED PYRAZOLYLPYRAZOLE DERIVATIVE AND USE OF SAME AS HERBICIDE
20170367334 · 2017-12-28
Assignee
Inventors
Cpc classification
A01N29/04
HUMAN NECESSITIES
A01N43/90
HUMAN NECESSITIES
A01N25/04
HUMAN NECESSITIES
A01N25/04
HUMAN NECESSITIES
A01N53/00
HUMAN NECESSITIES
A01N53/00
HUMAN NECESSITIES
A01N43/90
HUMAN NECESSITIES
International classification
Abstract
Provided is a compound capable of effectively control worst weeds of higher leaf stages that present practical problems. A specific pyrazolylpyrazole derivative of formula. (I) is disclosed that is able to solve the above-mentioned problems.
##STR00001##
Claims
1. A compound represented by the following formula (I): ##STR00006## wherein, R.sup.1 represents a chlorine atom or bromine atom, R.sup.2 represents a cyano group or nitro group, R.sup.3 represents a C.sub.3-C.sub.6 cycloalkyl group which may be substituted with one or more halogen atoms depending on the case, or may be substituted with a C.sub.1-C.sub.4 alkyl group which may be substituted with one or more halogen atoms depending on the case, or C.sub.3-C.sub.6 cycloalkenyl group which may be substituted with one or more halogen atoms depending on the case, or may be substituted with a C.sub.1-C.sub.4 alkyl group which may be substituted with one or more halogen atoms depending on the case, a represents 3 to 5, and b represents 0 to 2 (with the exception of compounds in which R.sup.1 represents a chlorine atom, R.sup.2 represents a cyano group, R.sup.3 represents a cyclopropyl group and b represents 0).
2. The compound according to claim 1, wherein R.sup.1 represents a chlorine atom, R.sup.3 represents a C.sub.3-C.sub.6 cycloalkyl group which may be substituted with one or more halogen atoms depending on the case, or may be substituted with a C.sub.1-C.sub.4 alkyl group which may be substituted with one or more halogen atoms depending on the case, a represents 4, and b represents 0 to 1.
3. A herbicide composition containing a herbicidally effective amount of at least one type of the compound according to claim 1.
4. The herbicide composition according to claim 3, further containing a formulation assistant.
5. A method for controlling undesirable plants, said method comprising the step of applying an effective amount of at least one compound according to claim 1 to an undesirable plant or the location of the undesirable plant.
6. (canceled)
7. (canceled)
8. A herbicide composition containing a herbicidally effective amount of at least one compound according to claim 2.
9. The herbicide composition according to claim 8, further containing a formulation assistant.
10. A method for controlling undesirable plants, said method comprising the step of applying an effective amount of at least one compound according to claim 2 to an undesirable plant or the location of the undesirable plant.
11. A method for controlling undesirable plants, said method comprising the step of applying an effective amount of the herbicide composition according to claim 3 to an undesirable plant or the location of the undesirable plant.
12. A method for controlling undesirable plants, said method comprising the step of applying an effective amount of the herbicide composition according to claim 8 to an undesirable plant or the location of the undesirable plant.
13. A method for controlling undesirable plants, said method comprising the step of applying an effective amount of the herbicide composition according to claim 4 to an undesirable plant or the location of the undesirable plant.
14. A method for controlling undesirable plants, said method comprising the step of applying an effective amount of the herbicide composition according to claim 9 to an undesirable plant or the location of the undesirable plant.
Description
EXAMPLES
Example 1
Method for the synthesis of Methyl N-(1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)4-cyanopy razol-5-yl)-2-cyclopropyl Acetoamide (Compound 1)
[0062] Acetonitrile (10 ml) was added to 5-amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)pyraz ole-4-carbonitrile (2.6 g) followed by slowly dropping in cyclopropylacetyl chloride (2.4 g) and heating to reflux for 1 day. Following completion of the reaction, water was added to the reaction solution followed by extraction with ethyl acetate. After washing with an aqueous sodium bicarbonate solution and drying with sodium sulfate, the solvent was distilled off under reduced pressure. The crude product was purified by silica gel column chromatography (hexane/ethyl acetate=1:1) to obtain the desired compound (3.2 g).
[0063] The starting material in the form of the compound of formula (II) was synthesized in accordance with WO 93/10100 and WO 94/08999.
[0064] The examples listed in the following tables can be synthesized by the same manner as the above-mentioned methods or obtained in the same manner as the above-mentioned methods.
TABLE-US-00001 TABLE 1
TABLE-US-00002 TABLE 2 Refractive Compound R.sup.1 R.sup.2 R.sup.3 a b mp index (° C.) 11 Cl CN 2,2-difluorocyclopropyl 4 0 12 Cl CN 2,2-dichlorocyclopropyl 4 1 13 Cl CN 2,2-difluorocyclopropyl 4 1 14 Cl NO.sub.2 2,2-dichlorocyclopropyl 4 1 15 Cl NO.sub.2 2,2-difluorocyclopropyl 4 1 16 Cl CN 3,3-difluorocyclobutyl 4 0 17 Cl CN 3-chlorocyclobutyl 4 0 18 Cl CN 1-trifluoromethylcyclobutyl 4 0 19 Cl CN 1-chlorocyclopentyl 4 0 20 Cl CN 3-chlorocyclopentyl 4 0 21 Cl CN 1-trifluoromethylcyclopentyl 4 0 22 Cl CN 1-methylcyclohexyl 4 0 23 Cl CN 2-methylcyclohexyl 4 0 24 Cl CN 3-methylcyclohexyl 4 0 25 Cl CN 4-methylcyclohexyl 4 0 26 Cl CN 4-tert-butylcyclohexyl 4 0 27 Cl CN 1-trifluoromethylcyclohexyl 4 0 28 Cl CN 4-trifluoromethylcyclohexyl 4 0 29 Cl CN cyclopentyl 4 1 97-99 30 Cl CN cyclopentyl 4 2 125-127 31 Cl CN 3-cyclohexenyl 4 2 194-199
PREPARATION EXAMPLES
[0065]
TABLE-US-00003 1. Dustable Powder Compound of formula (I) 10 parts by weight Talc 90 parts by weight
[0066] A dustable powder is obtained by mixing the above components and finely crushing with a hammer mill.
TABLE-US-00004 2. Wettable Powder Compound of formula (I) 10 parts by weight Polyoxyethylene alkyl aryl ether sulfate 22.5 parts by weight White carbon 67.5 parts by weight
[0067] A wettable powder is obtained by mixing the above components and finely crushing the mixture with a hammer mill.
TABLE-US-00005 3. Flowable Concentrate Compound of formula (I) 10 parts by weight Polyoxyethylene alkyl ether phosphate 10 parts by weight Bentonite 5 parts by weight Ethylene glycol 5 parts by weight Water 70 parts by weight
[0068] A flowable concentrate is obtained by mixing the above components and crushing using a wet pulverizer.
TABLE-US-00006 4. Emulsifiable Concentrate Compound of formula (I) 15 parts by weight Ethoxylated nonylphenol 10 parts by weight Cyclohexanone 75 parts by weight
[0069] An emulsifiable concentrate is obtained by mixing the above components.
TABLE-US-00007 5. Granules Compound of formula (I) 5 parts by weight Calcium lignin sulfonate 3 parts by weight Polycarboxylate 3 parts by weight Calcium carbonate 89 parts by weight
[0070] The above components are mixed followed by adding water, kneading, extruding and granulating. Subsequently, granules are obtained by drying followed by sizing.
BIOLOGICAL. TESTING EXAMPLES
[0071] 1. Paddy Herbicidal Activity Test
[0072] Rice paddy soil was filled into a 1/10000 are pot followed by the addition of suitable amounts of water and chemical fertilizer, kneading, seeding with Echinochloa crus-galli, Monochoria vaginalis and Scirpus juncoides and maintaining in an irrigated state at a water depth of 3 cm.
[0073] Wettable powders of Target Compound (1) shown in. Table 1 prepared in compliance with the preparation examples were diluted with a suitable amount of water, rice plants in the 2.0 leaf stage were transplanted during 3.5 leaf stage of Echinochloa crus-galli, and treated by dropping in chemical in the prescribed amount per 10 are using a pipette.
[0074] After treating for 30 days in a glass greenhouse at an average atmospheric temperature of 30° C., the herbicidal efficacy thereof was investigated.
[0075] Evaluation of herbicidal efficacy was carried out by comparing growth inhibition rate (%) with an untreated group, while evaluation of phytotoxicity was carried out by comparing growth inhibition rate (%) with the state of a complete eradication group, and were evaluated at 11 levels indicated below.
[0076] 0 (exponent): 0% to less than 10% (growth inhibition rate)
[0077] 1: 10% to less than 20%
[0078] 2: 20% to less than 30%
[0079] 3: 30% to less than 40%
[0080] 4: 40% to less than 50%
[0081] 5: 50% to less than 60%
[0082] 6: 60% to less than 70%
[0083] 7: 70% to less than 80%
[0084] 8: 80% to less than 90%
[0085] 9: 90% to less than 100%
[0086] 10: 100%
[0087] The results are shown in Table 2.
[0088] Control agent 4.190 (described in WO 94/08999)
##STR00005##
TABLE-US-00008 TABLE 2 5g.sup.a.i./10a 1g.sup.a.i./10a Echinochloa Scirpus Monochoria Oryza Echinochloa Scirpus Monochoria Oryza Compound crus-galli juncoides vaginalis sativa crus-galli juncoides vaginalis sativa 1 10 10 10 1 10 10 10 1 2 10 9 10 1 10 9 10 1 6 10 9 10 1 10 9 10 0 8 10 10 10 0 9 9 10 0 4.190 6 5 5 9 6 4 4 8
[0089] 2. Farming Soil Treatment Test
[0090] Field soil was filled into a 1/6000 are pot followed by seeding with Digitaria ciliaris, Chenopodium album and Amaranthus retroflexus and covering with soil.
[0091] Wettable powders of compounds of formula (I) shown in Table 1 prepared in compliance with the preparation examples were diluted with water to the prescribed amount of chemical and uniformly sprayed onto each soil surface layer using 100 liters of sprayed water per 10 are prior to weed growth following seeding.
[0092] After treating for 30 days in a glass greenhouse at an average atmospheric temperature of 30° C., the herbicidal efficacy thereof was investigated.
[0093] Evaluation of herbicidal efficacy was carried out in the same manner as the above-mentioned Test Example 1.
[0094] The results are shown in Table 3.
TABLE-US-00009 TABLE 3 10g.sup.a.i./10a 5g.sup.a.i./10a Digitaria Chenopodium Amaranthus Digitaria Chenopodium Amaranthus Compound ciliaris album retroflexus ciliaris album retroflexus 1 10 10 10 9 10 10 2 9 9 10 9 9 10 6 9 9 10 9 9 10 8 10 10 10 9 10 10 4.190 4 6 4 3 5 4
[0095] 3. Weed Foliar Treatment Test
[0096] Soil was filled into a 1/6000 are pot followed by seeding with Digitaria ciliaris, Chenopodium album and Amaranthus retroflexus, covering with soil, and cultivating in a glass greenhouse at an average atmospheric temperature of 25° C.
[0097] Wettable powders of Target Compound (I) shown in Table 1 prepared in compliance with the preparation examples were diluted with water to the prescribed amount of chemical and uniformly sprayed onto the weeds using 150 liters of sprayed water per 10 are when Digitaria ciliaris had grown to the 1.0 to 2.0 leaf stage.
[0098] After treating for 3 weeks in a glass greenhouse at an average atmospheric temperature of 25° C., the herbicidal efficacy thereof was investigated.
[0099] Evaluation of herbicidal efficacy was carried out in the same manner as the above-mentioned Test Example 1.
[0100] The results are shown in Table 4.
TABLE-US-00010 TABLE 4 10g.sup.a.i./10a 5g.sup.a.i./10a Digitaria Chenopodium Amaranthus Digitaria Chenopodium Amaranthus Compound ciliaris album retroflexus ciliaris album retroflexus 1 10 10 10 10 10 10 2 10 10 10 10 10 10 6 10 10 10 10 10 10 8 10 10 10 9 10 10 4.190 6 6 6 5 5 4
[0101] 4. Weed Foliar Treatment Test
[0102] Field soil was filled into a 1/4500 are pot followed by seeding with Digitaria ciliaris and Galinsoga parviflora, covering with soil and cultivating in a glass greenhouse at an average atmospheric temperature of 25° C.
[0103] Wettable powders of Target Compound (I) shown in Table 1 prepared in compliance with the preparation examples were diluted with water to the prescribed amount of chemical and uniformly sprayed onto the weeds using 100 liters of sprayed water per 10 are when Digitaria ciliaris had grown to the 4.0 to 5.0 leaf stage (plant height: 10 cm to 15 cm).
[0104] After treating for 20 days in a glass greenhouse at an average atmospheric temperature of 25° C., the herbicidal efficacy thereof was investigated.
[0105] Evaluation of herbicidal efficacy was carried out in the same manner as the above-mentioned Test Example 1.
[0106] The results are shown in Table 5.
TABLE-US-00011 TABLE 5 10g.sup.a.i./10a Compound Digitaria ciliaris Galinsoga parviflora 1 10 10 2 10 10 3 10 10 4 10 10 5 10 10 6 9 10 7 10 10 8 9 10 29 10 10 30 10 10 31 10 10 4.190 2 4
INDUSTRIAL APPLICABILITY
[0107] According to the present invention, the compound for formula (I) of the present invention is useful as a herbicide against harmful plants since it has superior herbicidal efficacy against undesirable plants.