CN1257490A - Substituted pyridylpyrazoles as herbicides, insecticides and acaricides - Google Patents

Substituted pyridylpyrazoles as herbicides, insecticides and acaricides Download PDF

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CN1257490A
CN1257490A CN 98805248 CN98805248A CN1257490A CN 1257490 A CN1257490 A CN 1257490A CN 98805248 CN98805248 CN 98805248 CN 98805248 A CN98805248 A CN 98805248A CN 1257490 A CN1257490 A CN 1257490A
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replacement
alkyl
halogen
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O·沙尔纳
K·-H·林克
M·多林格
C·埃尔德伦
U·瓦亨多夫-纽曼
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
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Abstract

The invention relates to novel substituted pyridylpyrazoles of general formula (I), wherein m = 0 or 1; n = 1, 2 or 3; R<1> = hydrogen, optionally cyano, halogen or C1-C4-alkoxy substituted alkyl with 1-6 C atoms, or optionally cyano or halogen substituted alkenyl or alkinyl with 2-6 C atoms; R<2> = hydrogen, nitro, hydroxy, mercapto, carboxy, cyano, thiocarbamoyl, halogen, or cyano, halogen or C1-C4-alkoxy substituted alkyl or cyano, halogen or C1-C4-alkoxy substituted alkoxy, alkoxycarbonyl, alkythio, alkylsulfinyl or alkylsulfonyl with 1-6 C atoms; R<3> = hydrogen, cyano, halogen or optionally cyano, halogen or C1-C4-alkoxy substituted alkyl with 1-6 C atoms and R<4> = nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, hydroxy, mercapto, amino, hydroxyamino, halogen or for one of the following groups: -Q-R<5>, -NH-R<5>, -NH-O-R<5>, -NH-SO2-R<5>, -N(SO2-R<5>)2, -CQ<1>-R<5>, -CQ<1>-Q<2>-R<5>, -CQ<1>-NH-R<5>, -Q<2>-CQ<1>-R<5>, -NH-CQ<1>-R<5>, -N(SO2-R<5>) (CQ<1>-R<5>), -Q<2>-CQ<1>-Q<2>-R<5>, -NH-CQ<1>-Q<2>-R<5> or -Q<2>-CQ<1>-NH-R<5>, wherein Q = O, S, SO or SO2, Q<1> and Q<2> = oxygen or sulfur, and R5 has the meaning cited in the description. The invention also relates to a method for the production and use of novel pyridylpyrazoles as phytosanitary agents, specially as herbicides, insecticides and acaricides.

Description

Pyridylpyrazole compound as weedicide, sterilant and acaricidal replacement
The present invention relates to the pyridylpyrazole of novel substituted, relate to its preparation method and relate to it, especially as weedicide, sterilant and acaricidal application as crop treatment agent.
Reported in (patent) document a large amount of replacements pyridyl pyrazoles (referring to, " journal of medicinal chemistry " [J.Med.Chem.] 38 (1995), 3524-3535; DE 2623302; DE 19530606, and WO 93/07138; JP 08193067-quotes from chemical abstracts 125:247808).Known wherein some are suitable as crop treatment agent, as mycocide, weedicide, sterilant or miticide.Yet these compounds do not obtain any special importance as yet.
Therefore, the invention provides the pyridyl pyrazoles of the novel substituted of general formula (I)
Figure A9880524800061
Wherein
M represents numeral 0 or 1,
N represents numeral 1,2 or 3,
R 1Represent hydrogen, represent each optional by cyano group-, halogen-or C 1-C 4The alkyl with 1 to 6 carbon atom of-alkoxyl group-replacement, or represent each optional by cyano group-or the alkenyl or the alkynyl that respectively have 2 to 6 carbon atoms of halogen-replacement,
R 2Represent hydrogen, nitro, hydroxyl, sulfydryl, carboxyl, cyano group, thiocarbamoyl, halogen, representative by cyano group-, halogen-or C 1-C 4The alkyl with 1 to 6 carbon atom of-alkoxyl group-replacement, or represent each optional by cyano group-, halogen-or C 1-C 4The alkoxyl group, alkoxy carbonyl, alkylthio, alkyl sulphinyl or the alkyl sulphonyl that respectively have 1 to 6 carbon atom of-alkoxyl group-replacement,
R 3Represent hydrogen, cyano group, halogen, or representative optional by cyano group-, halogen-or C 1-C 4The alkyl with 1 to 6 carbon atom of-alkoxyl group-replacement and
R 4Represent nitro, cyano group, carboxyl, formamyl, thiocarbamoyl, hydroxyl, sulfydryl, amino, hydroxyl amino, halogen, or represent one of following groups :-Q-R 5,-NH-R 5,-NH-O-R 5,-NH-SO 2-R 5,-N (SO 2-R 5) 2,-CQ 1-R 5,-CQ 1-Q 2-R 5,-CQ 1-NH-R 5,-Q 2-CQ 1-R 5,-NH-CQ 1-R 5,-N (SO 2-R 5) (CQ 1-R 5) ,-Q 2-CQ 1-Q 2-R 5,-NH-CQ 1-Q 2-R 5Or-Q 2-CQ 1-NH-R 5, wherein Q represents O, S, SO or SO 2, Q 1And Q 2Each represents oxygen or sulphur, and
R 5Representative optional by cyano group-, halogen-, C 1-C 4-alkoxyl group-, C 1-C 4-alkylthio-, C 1-C 4-alkyl-carbonyl-, C 1-C 4-alkoxyl group-carbonyl-or C 1-C 4The alkyl with 1 to 6 carbon atom of-alkylamino-carbonyl-replacement,
R 5Also represent each optional by cyano group-, carboxyl-, halogen-, C 1-C 4-alkyl-carbonyl-, C 1-C 4-alkoxyl group-carbonyl-or C 1-C 4The alkenyl or the alkynyl that respectively have 2 to 6 carbon atoms of-alkylamino-carbonyl substituted,
R 5Also represent each optional by cyano group-, carboxyl-, halogen-, C 1-C 4-alkyl-carbonyl-or C 1-C 4Each of-alkoxyl group-carbonyl-replacement has 3 to 6 carbon atoms and chooses cycloalkyl or the cycloalkylalkyl that has 1 to 4 carbon atom at moieties wantonly in group of naphthene base,
R 5Also represent each optional by hydroxyl-, sulfydryl-, amino-, cyano group-, carboxyl-, formamyl-, thiocarbamoyl-, C 1-C 4-alkyl-, C 1-C 4-haloalkyl-, C 1-C 4-alkoxyl group-, C 1-C 4-halogenated alkoxy-, C 1-C 4-alkylthio-, C 1-C 4-halogenated alkylthio-, C 1-C 4-alkyl sulphinyl-, C 1-C 4-alkyl sulphonyl-, C 1-C 4-alkylamino-or each of dimethylamino-replacement in aromatic yl group, have 6 or 10 carbon atoms and choose the aryl or aralkyl that has 1 to 4 carbon atom at moieties wantonly, or
R 5Also represent each optional by hydroxyl-, sulfydryl-, amino-, cyano group-, carboxyl-, formamyl-, thiocarbamoyl-, C 1-C 4-alkyl-, C 1-C 4-haloalkyl-, C 1-C 4-alkoxyl group-, C 1-C 4-halogenated alkoxy-, C 1-C 4-alkylthio-, C 1-C 4-halogenated alkylthio-, C 1-C 4-alkyl sulphinyl-, C 1-C 4-alkyl sulphonyl-, C 1-C 4-alkylamino-or dimethylamino-replacement have 2 to 6 carbon atoms and 1 to 3 nitrogen-atoms and/or 1 or 2 Sauerstoffatom and/or a sulphur atom and choose heterocyclic radical or the heterocyclic radical alkyl that has 1 to 4 carbon atom at moieties wantonly in the heterocyclic radical group.
The following acquisition of pyridyl pyrazoles of the novel substituted of general formula (I):
Make the hydrazine or derivatives thereof of general formula (II)
H 2N-NH-R 1(II) R wherein 1As defined above, with the pyridyl-1 of the replacement of general formula (III), the reaction of 3-dicarbonyl compound
Figure A9880524800081
Wherein m, n, R 2, R 3And R 4As defined above, or with pyridyl-carbonyl compound reaction of the replacement of general formula (IV)
Figure A9880524800082
Wherein m, n, R 3And R 4As defined above,
Q 3Represent oxygen or sulphur and
R represents hydrogen or alkyl,
-and/or, if suitable, with the tautomerism precursor reactant of general formula (IV) compound,
If react in the thinner existence with suiting at the reaction auxiliary if suit,
And formula (I) compound with gained further transforms in substituent above-mentioned definition according to conventional methods if desired.
General formula (I) compound can change into other general formula (I) compound of substituting group according to above-mentioned definition according to conventional methods, for example by conventional alkylation, acylations or sulphonyl glycosylation reaction (R for example 1: H → CH 3, CHF 2, C 2H 5, CH 2CH=CH 2R 4: OH → OCH 3, OC 2H 5, OCHF 2, OCH 2CH=CH 2, OCOCH 3SH → SCH 3, SC 2H 5NH 2→ NHC 3H 7, NHCOCH 3, NHSO 2CH 3); Or by close electricity or nucleophilic substitution reaction (R for example 3: H → Cl, Br; R 4: F → OH, SH, NH 2)-also is referring to preparation embodiment.
The pyridyl pyrazoles of the novel substituted of general formula (I) has valuable biological property, this make can use as crop treatment agent.They have strong weeding, kill insect and kill the acarid activity, and have excellence and selectively herbicide effect especially.
In definition, saturated or undersaturated alkyl, as alkyl, alkenyl or alkynyl, equal straight or brancheds.
Halogen is represented fluorine, chlorine, bromine or iodine usually, preferably fluorine, chlorine or bromine, particularly fluorine or chlorine.
The present invention preferably provides the compound of general formula (I), wherein
M represents numeral 0 or 1,
N represents numeral 1,2 or 3,
R 1Represent hydrogen, represent each optional by cyano group-, fluoro-, chloro-, methoxyl group-or the methyl of oxyethyl group-replacements, ethyl, just-or sec.-propyl, just-, different-, the second month in a season-or the tertiary butyl, or represent each optional by cyano group-, fluoro-, chloro-or the bromo-propenyl, butenyl, proyl or the butynyl that replace
R 2Represent hydrogen; nitro; hydroxyl; sulfydryl; carboxyl; cyano group; thiocarbamoyl; fluorine; chlorine; bromine; the representative each by cyano group-; fluoro-; chloro-; methoxyl group-or the methyl of oxyethyl group-replacement; ethyl; just-or sec.-propyl; just-; different-; secondary-or the tertiary butyl; or represent each optional by cyano group-; fluoro-; chloro-; methoxyl group-or the methoxyl group of oxyethyl group-replacement; oxyethyl group; just-or isopropoxy; just-; different-; secondary-or tert.-butoxy; methoxycarbonyl; ethoxy carbonyl; methylthio group; ethylmercapto group; just-or the iprotiazem base; just-; different-; secondary-or uncle's butylthio; methylsulfinyl; the ethyl sulfinyl; just-or different-propyl group sulfinyl; just-; different-; secondary-or tertiary butyl sulfinyl; methyl sulphonyl; ethylsulfonyl; just-or the sec.-propyl alkylsulfonyl; just-; different-; secondary-or tertiary butyl alkylsulfonyl
R 3Represent hydrogen, fluorine, chlorine, bromine, or representative optional by cyano group-, fluoro-, chloro-, methoxyl group-or the methyl of oxyethyl group-replacements, ethyl, just-or sec.-propyl, just-, different-, the second month in a season-or the tertiary butyl, and
R 4Represent nitro, cyano group, carboxyl, formamyl, thiocarbamoyl, hydroxyl, sulfydryl, amino, hydroxyl amino, fluorine, chlorine, bromine, or represent one of following groups :-Q-R 5,-NH-R 5,-NH-O-R 5,-NH-SO 2-R 5,-N (SO 2-R 5) 2,-CQ 1-R 5,-CQ 1-Q 2-R 5,-CQ 1-NH-R 5,-Q 2-CQ 1-R 5,-NH-CQ 1-R 5,-N (SO 2-R 5) (CQ 1-R 5) ,-Q 2-CQ 1-Q 2-R 5,-NH-CQ 1-Q 2-R 5Or-Q 2-CQ 1-NH-R 5, wherein Q represents O, S, SO or SO 2, Q 1And Q 2Each represents oxygen or sulphur, and
R 5Represent each optional by cyano group-, fluoro-, chloro-, methoxyl group-, oxyethyl group-, methylthio group-, ethylmercapto group-, ethanoyl-, propionyl-, methoxycarbonyl-, ethoxy carbonyl-, the methylamino carbonyl-or the methyl of ethylamino carbonyl-replacements, ethyl, just-or sec.-propyl, just-, different-, the second month in a season-or the tertiary butyl
R 5Also represent each optional by cyano group-, carboxyl-, fluoro-, chloro-, bromo-, ethanoyl-, propionyl-, methoxycarbonyl-, ethoxy carbonyl-, methylamino carbonyl-or propenyl, butenyl, proyl or the butynyl of ethylamino carbonyl-replacement,
R 5Also represent each optional by cyano group-, carboxyl-, fluoro-, chloro-, bromo-, ethanoyl-, propionyl-, methoxycarbonyl-or cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyl methyl, cyclobutylmethyl, cyclopentyl-methyl or the cyclohexyl methyl of ethoxy carbonyl-replacement
R 5Also represent each optional by hydroxyl-; sulfydryl-; amino-; cyano group-; carboxyl-; formamyl-; thiocarbamoyl-; methyl-; ethyl-; just-or different-propyl group-; just-; different-; secondary-or the tertiary butyl-; difluoromethyl-; trifluoromethyl-; methoxyl group-; oxyethyl group-; just-or isopropoxy-; difluoro-methoxy-; trifluoromethoxy-; methylthio group-; ethylmercapto group-; the difluoro methylthio group-; trifluoromethylthio-; methylsulfinyl-; the ethyl sulfinyl; methyl sulphonyl-; ethylsulfonyl-; methylamino-; ethylamino-or the phenyl of dimethylamino-replacement; benzyl or styroyl, or
R 5Also represent each optional by hydroxyl-; sulfydryl-; amino-; cyano group-; carboxyl-; formamyl-; thiocarbamoyl-; methyl-; ethyl-; just-or sec.-propyl-; just-; different-; secondary-or the tertiary butyl; dichloromethyl-; trichloromethyl-; difluoromethyl-; trifluoromethyl-; one chlorodifluoramethyl--; one fluorine dichloromethyl-; methoxyl group-; oxyethyl group-; just-or isopropoxy-; difluoro-methoxy-; trifluoromethoxy-; methylthio group-; ethylmercapto group-; just-or the iprotiazem base-; the difluoro methylthio group-; trifluoromethylthio-; one chlorine difluoro methylthio group-; one fluorine dichloromethane sulfenyl-; methylsulfinyl-; the ethyl sulfinyl-; methyl sulphonyl-; ethylsulfonyl-; methylamino-; ethylamino-; just-or sec.-propyl amino-or dimethylamino-replacement be selected from Oxyranyle; oxetanyl; furyl; tetrahydrofuran base; dioxolanyl; thienyl; tetrahydro-thienyl; pyrryl; pyrazolyl; imidazolyl; triazolyl oxazolyl isoxazolyl; thiazolyl; isothiazolyl oxadiazole base; thiadiazolyl group; pyridyl; pyrimidyl; triazinyl; the pyrazolyl methyl; furyl methyl; thienyl methyl oxazolyl methyl isoxazolyl methyl; the thiazolyl methyl; pyridylmethyl; the heterocyclic radical of Pyrimidylmethyl or heterocyclic radical alkyl.
In particular, the present invention relates to formula (I) compound, wherein
M represents numeral 0 or 1,
N represents numeral 1,2 or 3,
R 1Represent each optional by cyano group-, fluoro-, chloro-, methoxyl group-or the methyl or the ethyl of oxyethyl group-replacement,
R 2Representation hydroxy, sulfydryl, fluorine, chlorine, bromine; or representative each by cyano group-, fluoro-, chloro-, methoxyl group-or methyl, ethyl, methoxyl group, oxyethyl group, methylthio group, ethylmercapto group, methylsulfinyl, ethyl sulfinyl, methyl sulphonyl or the ethylsulfonyl of oxyethyl group-replacement
R 3Represent fluorine, chlorine, bromine or optional by cyano group-, fluoro-, chloro-, methoxyl group-or the methyl of oxyethyl group-replacement or ethyl and
R 4Represent nitro, cyano group, carboxyl, formamyl, thiocarbamoyl, hydroxyl, sulfydryl, amino, hydroxyl amino, halogen or represent one of following groups :-Q-R 5,-NH-R 5,-NH-O-R 5,-NH-SO 2-R 5,-N (SO 2-R 5) 2,-CQ 1-R 5,-CQ 1-Q 2-R 5,-CQ 1-NH-R 5,-Q 2-CQ 1-R 5,-NH-CQ 1-R 5,-N (SO 2-R 5) (CQ 1-R 5) ,-Q 2-CQ 1-Q 2-R 5,-NH-CQ 1-Q 2-R 5Or-Q 2-CQ 1-NH-R 5, wherein Q represents O, S, SO or SO 2, Q 1And Q 2Each represents oxygen or sulphur, and
R 5Represent each optional by cyano group-, fluoro-, chloro-, methoxyl group-, oxyethyl group-, methylthio group-, ethylmercapto group-, ethanoyl-, propionyl-, methoxycarbonyl-, ethoxy carbonyl-, the methylamino carbonyl-or the methyl of ethylamino carbonyl-replacements, ethyl, just-or sec.-propyl, just-, different-, the second month in a season-or the tertiary butyl
R 5Also represent each optional by cyano group-, carboxyl-, fluoro-, chloro-, bromo-, ethanoyl-, propionyl-, methoxycarbonyl-, ethoxy carbonyl-, methylamino carbonyl-or propenyl, butenyl, proyl or the butynyl of ethylamino carbonyl-replacement,
R 5Also represent each optional by cyano group-, carboxyl-, fluoro-, chloro-, bromo-, ethanoyl-, propionyl-, methoxycarbonyl-or cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyl methyl, cyclobutylmethyl, cyclopentyl-methyl or the cyclohexyl methyl of ethoxy carbonyl-replacement
R 5Also represent each optional by hydroxyl-; sulfydryl-; amino-; cyano group-; carboxyl-; formamyl-; thiocarbamoyl-; methyl-; ethyl-; just-or different-propyl group-; just-; different-; secondary-or the tertiary butyl-; difluoromethyl-; trifluoromethyl-; methoxyl group-; oxyethyl group-; just-or isopropoxy-; difluoro-methoxy-; trifluoromethoxy-; methylthio group-; ethylmercapto group-; the difluoro methylthio group-; trifluoromethylthio-; methylsulfinyl-; the ethyl sulfinyl-; methyl sulphonyl-; ethylsulfonyl-; methylamino-; ethylamino-or the phenyl of dimethylamino-replacement; benzyl or styroyl, or
R 5Also represent each optional by hydroxyl-; sulfydryl-; amino-; cyano group-; carboxyl-; formamyl-; thiocarbamoyl-; methyl-; ethyl-; just-or sec.-propyl-; just-; different-; secondary-or the tertiary butyl; dichloromethyl-; trichloromethyl-; difluoromethyl-; trifluoromethyl-; one chlorodifluoramethyl--; one fluorine dichloromethyl-; methoxyl group-; oxyethyl group-; just-or isopropoxy-; difluoro-methoxy-; trifluoromethoxy-; methylthio group-; ethylmercapto group-; just-or the iprotiazem base-; the difluoro methylthio group-; trifluoromethylthio-; one chlorine difluoro methylthio group-; one fluorine dichloromethane sulfenyl-; methylsulfinyl-; the ethyl sulfinyl-; methyl sulphonyl-; ethylsulfonyl-; methylamino-; ethylamino-; just-or sec.-propyl amino-or dimethylamino-replacement be selected from Oxyranyle; oxetanyl; furyl; tetrahydrofuran base; dioxolanyl; thienyl; tetrahydro-thienyl; pyrryl; pyrazolyl; imidazolyl; triazolyl oxazolyl isoxazolyl; thiazolyl; isothiazolyl oxadiazole base; thiadiazolyl group; pyridyl; pyrimidyl; triazinyl; the pyrazolyl methyl; furyl methyl; thienyl methyl oxazolyl methyl isoxazolyl methyl; the thiazolyl methyl; pyridylmethyl; the heterocyclic radical of Pyrimidylmethyl or heterocyclic radical alkyl.
Particularly preferred one group of general formula (I) compound is formula (Ia) compound
Figure A9880524800131
Wherein n, R 1, R 2, R 3And R 4Respectively has aforesaid particularly preferred implication.
Another organizes particularly preferred general formula (I) compound is formula (Ib) compound
Figure A9880524800132
Wherein n, R 1, R 2, R 3And R 4Respectively has aforesaid particularly preferred implication.
Another organizes particularly preferred general formula (I) compound is formula (Ic) compound
Figure A9880524800141
Wherein
N, R 1, R 2, R 3And R 4Respectively has aforesaid particularly preferred implication.
The definition general or preferred group that above provides is suitable for the end product of formula (I), equally also is suitable for starting raw material and intermediate required under each preparation situation.The definition of these groups can be made up as required mutually,, comprises the combination between the preferable range that provides that is.
Use for example methyl hydrazine and 2-chloro-1-(4-cyano group-3-methoxyl group-pyridine-2-yl)-4,4-two fluoro-butane-1,3-diketone are as starting raw material, and the reaction path in the inventive method can illustrate with the following formula reaction scheme:
Figure A9880524800142
Formula (II) is provided at the General Definition that is used as the hydrazine derivative of starting raw material in the inventive method of preparation formula (I) compound.In formula (II), R 1Preferably or particularly has the R that those had been mentioned already in the description of relevant formula of the present invention (I) compound 1Preferred or special preferred meaning.Produce
Formula (II) starting raw material is the known synthetic chemical that is used for.
Formula (III) is provided at the pyridyl-1 that is used as the replacement of another kind of starting raw material in the inventive method of preparation formula (I) compound, the General Definition of 3-dicarbonyl compound.In formula (III), n, R 2, R 3And R 4Preferably or particularly have n, R that those had been mentioned already in the description of relevant formula of the present invention (I) compound 2, R 3And R 4Preferred or special preferred meaning.
Formula (IV) is provided at the General Definition that is used as the pyridyl-carbonyl compound of another kind of starting raw material in the inventive method of preparation formula (I) compound.In formula (IV), n, R 3And R 4Preferably or particularly have n, R that those had been mentioned already in the description of relevant formula of the present invention (I) compound 3And R 4Preferred or special preferred meaning; Q 3Preferably represent oxygen or sulphur, and R preferably represents hydrogen or C 1-C 4-alkyl, particularly hydrogen, methyl or ethyl.
Formula (III) and (IV) initial compounds be known and/or can prepare with currently known methods (referring to, for example, Chemical Society's magazine, C 1969,2738-2747; Ditto, C 1970,796-800; J.Chem.Soc., Perkin Trans.I 1988,2785-2789; The heterocyclic chemistry magazine, 30 (1993), 855-859; Journal of medicinal chemistry, 33 (1990), 1859-1865; The organic chemistry magazine, 47 (1982), 3027-3038; Ditto, 49 (1984), 3733-3742; Pharmazie 23 (1968), 557-560; Synthetic, 1993,290-292; DE 2458808; DE 4031798; DE 4425650; EP 206294; EP 306251; US 4026900; US 4980357; Preparation embodiment).
The thinner that is suitable for the inventive method of the formula that is prepared (I) compound is all organic solvents.These solvents are the optional halogenated hydrocarbon of aliphatics, alicyclic or aromatics particularly, such as gasoline, benzene,toluene,xylene, chlorobenzene, dichlorobenzene, sherwood oil, hexane, hexanaphthene, methylene dichloride, chloroform, tetracol phenixin; Ethers is as ether, isopropyl ether, diox, tetrahydrofuran (THF) or glycol dimethyl ether or ethylene glycol diethyl ether; Ketone is as acetone, butanone or mibk; Carboxylic-acid is as acetate or propionic acid; Nitrile is as acetonitrile, propionitrile or butyronitrile; Amides, as, N, dinethylformamide, N,N-dimethylacetamide, N-methyl-formylaniline, N-Methyl pyrrolidone or HMPA; The ester class, as methyl acetate or ethyl acetate, the sulfoxide class is as dimethyl sulfoxide (DMSO); Alcohols, as methyl alcohol, ethanol, just or different-propyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether.
The reaction auxiliary that is suitable for the inventive method is general conventional inorganic or organic bases or acid acceptor.They preferably include acetate, amide, carbonate, the supercarbonate of basic metal or alkaline-earth metal, hydride, oxyhydroxide or alkoxide, as sodium acetate, potassium acetate or lime acetate, lithamide, ammonification sodium, ammonification potassium or ammonification calcium, yellow soda ash, salt of wormwood or lime carbonate, sodium bicarbonate, saleratus or Calcium hydrogen carbonate, lithium hydride, sodium hydride, potassium hydride KH or hydrolith, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methylate, sodium ethylate, just or sodium isopropylate, just-, different-, secondary-or sodium tert-butoxide; Or potassium methylate, potassium ethylate, just-or potassium isopropoxide, just-, different-, secondary-or potassium tert.-butoxide; Also has alkaline organic nitrogen compound in addition, as, Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, ethyl diisopropyl amine, N, N-dimethyl-cyclo-hexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, accelerine, N, N-dimethyl-benzyl amine, pyridine, the 2-methyl-, the 3-methyl-, the 4-methyl-, 2, the 4-dimethyl-, 2, the 6-dimethyl-, 3, the 4-dimethyl-and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidines, 1,4-diazabicyclo [2.2.2]-octane (DABCO), 1,5-diazabicyclo [4.3.0]-ninth of the ten Heavenly Stems-5-alkene (DBN) or 1,8-diazabicyclo [5.4.0]-11 carbon-7-alkene (DBU).
When carrying out the inventive method, temperature of reaction can change in wide relatively scope.Usually, this method is at 0 ℃ to 150 ℃, preferably carries out under the temperature between 20 ℃ to 120 ℃.
The inventive method is normally carried out under normal pressure.Yet, under also can or reducing pressure in pressurization-to 10 crust, carry out the inventive method at 0.1 crust usually.
When carrying out the inventive method, adopt starting raw material with about equimolar amount usually.Yet, also can be relatively excessively to use one of these reactive components.Reaction is normally carried out in the presence of the reaction auxiliary in the thinner that is fit to, and reaction mixture stirred several hours under required temperature usually.Aftertreatment be carry out according to conventional methods (referring to, the preparation embodiment).
Active compound of the present invention can be used as defoliating agent, siccative, kill the cane agent, in particular as the agent of cutting weeds.So-called weeds with regard to it the most in the broadest sense, are interpreted as being grown in all plants in the place that should not grow.Material of the present invention is as steriland herbicide or selective herbicide depends on used amount basically.
The compounds of this invention can relevant use with following plants:
The broadleaf weed of following dependent of dead military hero: mustard belongs to, the grass of walking alone belongs to, Bedstraw, Stellaria, Matricaria, Anthemis, Achyranthes, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, japanese bearbind belongs to, sweet potato genus, Polygonum, Daubentonia, Ambrosia, Cirsium, bristlethistle, sonchus L, Solanum Han Lepidium, Herba Clinopodii Polycephali belongs to, Vandellia, lamium, Veronica, abutilon, the thorn Rumex, Datura, Viola, the weasel hemp nettle belongs to, papaver, bachelor's-button, Trifolium, Ranunculus and Dandelion
The dicotyledonous crops of following dependent of dead military hero: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, linum, sweet potato genus, Vetch, Nicotiana, tomato genus, Arachis, Btassica, Lactuca, Cucumis and Cucurbita,
The monocotyledon weed of following dependent of dead military hero: Echinochloa, setaria, Panicum, lady's-grass, ladder forage spp, annual bluegrass genus, festuca, yard grass genus, Brachiaria, lolium, Brome, Avena, Cyperus, jowar genus, Agropyron, Cynodon, Monochoria, genus fimbristylis, arrowhead genus, Eleocharis, Fischer grass genus, Paspalum, ischaemum, cusp Pittosporum, talon eria, Agrostis, amur foxtail genus and wind grass belong to
The monocot crops of following dependent of dead military hero: Oryza, Zea, Triticum, Hordeum, Avena, Secale, jowar genus, Panicum, saccharum, Ananas, Asparagus and allium.
Yet the application of The compounds of this invention never is limited to these genus, and also can extend to other plant in an identical manner.
Depend on compound concentrations, the compound natural disposition controlling weeds that is suitable for going out, for example industrial region and railway line, and the road and the square that have or do not have the plantation woods.Equally, compound can be used for preventing and treating the weeds of perennial crop, for example forest, decorate the weeds in the woods, orchard, vineyard, citrus woods, nut garden, any of several broadleaf plants plantation, cafetal, tea place, rubber plantation, oil palm plantation, cocoa plantation, mushy fruit woods and hops field, grassland, turf and the pasture and optionally prevent and treat weeds in the annual crop.
Formula of the present invention (I) compound is particularly suitable for optionally preventing and treating unifacial leaf and broadleaf weed in unifacial leaf and the dicotyledonous crops in two kinds of modes before the bud and behind the bud.
Active compound of the present invention is fit to the control animal pest, particularly appears at insect, acarian and nematode on agricultural, forest, storage product and material protection and the health aspect.They have activity to normal sensitivity and resistance kind with to all or some growth and development stages.Above-mentioned insect comprises:
Isopoda, for example, damp worm (Oniscus asellus), pillworm (Armadillidiumvulgare) and spot pillworm (Porcellio scaber).
Doubly sufficient order, for example, tool zebra land (Blaniulus guttulatus).
Lip foot order, for example, food fruit DIWUGONG (Geophilus carpophagus) and common house centipede (Scutigera spec).
Comprehensive order, for example, clean symphilid (Scutigerella immaculata).
Thysanura, for example, silverfiss (Lepisma saccharina).
Collembola, for example, Onychiurus arcticus (Onychiurus armatus).
Orthoptera, for example, oriental cockroach (Blatta orientalis), periplaneta americana (Periplaneta americana), leucophaea maderae (Leucophaea maderae), Groton bug (Blattella germanica), acheta domestica (Achetadomesticus), Gryllotalpa spp (Gryllotalpa spp.), tropical migratory locusts (Locustamigratoria migratorioids), very plant grasshopper (Melanoplusdifferentialis) and desert locust (Schistocerca gregaria).
Dermaptera, for example, European earwig (Forficula auricularia).
Isoptera, for example, Reticulitermes (Reticulitermes spp.).
Anoplura, for example, body louse (Pediculus humanus corporis), Haematopinus (Haematopinus spp.) and jaw lice belong to (Linognathus spp.).
Mallophaga, for example, Trichodectes (Trichodectes spp.) and poultry belong to lice (Damalinea spp.).
Thysanoptera, for example, greenhouse Hercinothrips spp (Hercinothrips femoralis) and cotton thrips (Thrips tabaci).
Hemiptera, for example, Eurygasterspp belongs to (Eurygaster spp.), middle red cotton bug (Dysdercus intermedius), beet is intended lace bug (Piesma quadrata), the smelly stinkbug in temperate zone (Cimex lectularius), phodnius prolixus (Rhodnius prolixus) and Triatoma (Triatoma spp.).
Homoptera, for example, wild cabbage aleyrodid (Aleurodes brassicae), sweet potato whitefly (Bemisia tabaci), greenhouse whitefly (Trialeurodes vaporariorum), cotten aphid (Aphis gossypii), brevicoryne brassicae (Brevicoryne brassicae), the tea Fischer conceals knurl aphid (Cryptomyzus ribis), aphis fabae (Aphis fabae), apple aphid (Aphispomi), eriosoma lanigerum (Eriosoma lanigerum), mealy plum aphid (Hyalopterusarundinis), grain aphid (Macrosiphum avenae), knurl volume Aphis (Myzusspp.), Pemphigus spp., phorodon aphid (Phorodon humili), Phylloxeravastatrix, rhopalosiphum padi (Rhopalosiphum padi), Empoasca spp belongs to (Empoasca spp.), blunt nose leaf cicada (Euscelis bilobatus), rice green leafhopper (Nephotettix cincticeps), the hard a red-spotted lizard (Lecanium corni) of water and soil, oil lam black helmet kuwana (Saissetia oleae), small brown-back rice plant-hopper (Laodelphax striatellus), Nilaparvata lugen (brown planthopper) (Nilaparvata lugens), red kidney garden armored scale (Aoni diellaaurantii), Folium seu Cortex Nerii garden a red-spotted lizard (Aspidiotus hederae), mealybug belongs to (Pseudococcus spp.) and Psylla spp (Psylla spp.).
Lepidopteran, for example, cotton red sandfly insect (Pectinophora gossypiella), pine sphinx moth (Bupalus piniarius), winter geometrid moth (Cheimatobia brumata), the thin moth of apple (Lithocolletis blancardella), apple ermine moth (Hyponomeutapadella), small cabbage moth (Plutella maculipennis), tent caterpillar (Malacosoma neustris), pornography and drug moth (Euproctis chrysorrhoea), Euproctis (Lymantria spp.), cotton lyonetid (Bucculatrix thurberiella), tangerine leaf miner (Phyllocnistis citrella), Agrotis (Agrotis spp.), cutworm belongs to (Euxoa spp.), Noctua (Feltia spp.), the real moth (Eariasinsulana) of cotton spot, genus heliothis (Heliothis spp.), beet armyworm (Spodopteraexigua), lopper worm (Mamestra brassicae), small noctuid (Panolisflammea), prodenia litura (Prodenia litura), Spodoptera (Spodopteraspp.), cabbage looper (Trichoplusia ni), the moth-eaten moth (Carpocapsapomonella) of apple, Pier (Pieris spp.), straw borer spp (Chilo spp.), Pyrausta nubilalis (Hubern). (Pyrausta nubilalis), Anagasta kuehniella (Ephestiakuehniella), greater wax moth (Galleria mellonella), curtain casemaking clothes moth (Tineolabisselliella), bag casemaking clothes moth (Tinea pellionella), brownly knit moth (Hofmannophila pseudospretella), the yellow volume of flax moth (Cacoeciapodana), Capua reticulana, spruce bunworm (Choristoneurafumiferana), grape codling moth (Clysia ambiguella) (Clysia ambiguella), tea long paper moth (Homonamagnanima) and the green volume of oak moth (Tortrix viridana).
Coleoptera, for example, tool spot death watch beetle (Anobium punctatum), lesser grain borer (Rhizopertha dominica), bean weevil (Bruchidius obtectus), bean weevil (Acanthoscelides obtectus), house longhorn beetle (Hylotrupes bajulus), the purple flea beetle (Agelasrtica alni) of alder, colorado potato bug (Leptinotarsadecemlineata), horseradish ape chrysomelid (Phaedon cochleariae), the chrysomelid genus of bar (Diabrotica spp.), rape blue flea beetle (Psylliodes chrysocephala), Mexico's beans first (Epilachna varivestis), latent wing first belongs to (Atomariaspp.), saw-toothed grain beetle (Oryzaephilus surinamensis), Anthonomus spp belongs to (Anthonomus spp.), Sitophilus (Sitophilus spp.), vine black ear beak resembles (Otiorrhynchus sulcatus), banana root weevil (Cosmopolitessordidus), wild cabbage pod weevil (Ceuthorrhynchus assimilis), alfalfa weevil (Hypera postica), khapra beetle belongs to (Dermestes spp.), the spot khapra beetle belongs to (Trogoderma spp.), Anthrenus (Anthrenus spp.), moth-eaten belong to (the Attagenus spp.) of hair, moth-eaten belong to (the Lyctus spp.) of powder, pollen beetle (Meligethes aeneus), Ptinus (Ptinus spp.), golden yellow ptinid (Niptushololeucus), globose spider beetle (Gibbium psylloides), Tribolium (Triboliumspp.), tenebrio molitor (Tenebrio molitor), Agriotes spp (Agriotes spp.), wide chest Agriotes spp (Conoderus spp.), the west melolonthid in May (Melolonthamelolontha), the potato melolonthid (Amphimallon sostitialis) and the brown New Zealand rib wing melolonthid (Costelytra zealandica).
Hymenoptera, for example, Neodiprion spp belongs to (Diprion spp.), tenthredinidae (Hoplocampaspp.), the field ant belongs to (Lasius spp.), MonomoriumMayr (Monomorium pharaonis) and wasp (Vespa spp.).
Diptera, for example, Aedes (Aedes spp.), Anopheles (Anophelesspp.), Culex (Culex spp.), drosophila yellow gorilla (Drosophilamelanogaster), fly belongs to (Musca spp.), Fannia (Fannia spp.), calliphora erythrocephala (Callophora erythrocephala), Lucilia (Lucilia spp.), Carysomyia (Chrysomyia spp.), cuterbrid belongs to (Cuterebra spp.), Gasterophilus (Gastrophilus spp.), Hippobosca (Hyppobosca spp.), Genus Stomoxys (Stomoxys spp.), Oestrus (Oestrus spp.), Hypoderma (Hypodermaspp.), Gadfly (Tabanus spp.), a smaller kind of cicada cicada belongs to (Tannia spp.), garden march fly (Bibio hortulanus), Sweden's wheat stem chloropid fly (Oscinella frit), grass Hylemyia (Phorbia spp.), spinach leaf mining flowerfly (Pegomyia hyoscyami), Mediterranean fruitfly (Ceratitis capitata), oil olive trypetid (Dacus oleae) and marsh daddy-longlegs (Tipula paludosa).
Siphonaptera, for example, Xanthopsyllacheopis (Xenopsylla cheopis) and hair row flea belong to (Ceratophyllus spp.).
Spider shape order, for example, scorpion (Scorpio maurus) and black widow (Latrodectusmactans).
Acarina, for example, Acarus siro (Acarus siro), latent beak tick belongs to (Argasspp.), blunt beak tick belongs to (Ornithodoros spp.), Dermanyssus gallinae (Dermanyssusgallinae), acaphylla theae (Eriophyes ribis), citrus rust mite (Phyllocoptruta oleivora), Boophilus (Boophilus spp.), Rh (Rhipicephalus spp.), Amblyomma (Amblyomma spp.), glass eye tick belongs to (Hyalomma spp.), hard tick belongs to (Ixodes spp.), the scabies mite belongs to (Psoroptesspp.), Chorioptes (Chorioptes spp.), itch mite belongs to (Sarcoptes spp.), tarsonemid mite belongs to (Tarsonemus spp.), Bryobia praetiosa (Bryobia praetiosa), Panonychus citri belongs to (Panonychus spp.) and Tetranychus (Tetranychus spp.).
Plant nematode comprises that for example short body belongs to (Pratylenchus spp.), similar similes thorne (Radopholus similis), play knitting wool Ditylenchus dipsaci (Ditylenchusdipsaci), the nematode (Tylenchulus semipenetrana) of partly puncturing, Heterodera (Heterodera spp.), ball Heterodera (Globodera spp.), root knot belongs to (Meloidogyne spp.), sliding sword belongs to (Aphelechoides spp.), minute hand belongs to (Longidorus spp.), Xiphinema (Xiphinema spp.), burr belongs to (Trichodorus spp.), the pad sword belongs to (Tylenchus spp.), spiral-line Eimeria (Helicotylenchus spp.), Turbatrix (Rotylenchus spp.) and pad sword genus (Tylenchulus spp.) spiral.
Active compound can change into conventional formulation, as solution, emulsion, wettable powder, suspension agent, pulvis, the agent of dusting, paste, water solube powder, granule, suspension emulsion, with the natural or synthetic materials of active compound dipping, and wrap in micro-fine capsule in the polymkeric substance.
These type agent can be produced in a known manner, for example, with active compound and weighting agent, i.e. liquid and/or mix, and optional tensio-active agent, i.e. emulsifying agent and/or dispersion agent and/or the pore forming material of using with solid carrier.
Using water as under the situation of weighting agent, also can make solubility promoter with organic solvent.As liquid solvent, suitable mainly contains: aromatic substance, as dimethylbenzene, toluene or alkylnaphthalene, chloro aromatic substance or chlorinated aliphatic hydrocarbon are as chlorinated benzene class, polyvinyl chloride-base or methylene dichloride, aliphatic hydrocrbon, as hexanaphthene or paraffin, for example mineral oil fraction, mineral and vegetables oil, alcohols, as butanols or ethylene glycol with and ether and ester, ketone, as acetone, methylethylketone, methyl iso-butyl ketone (MIBK) or pimelinketone, intensive polar solvent, as dimethyl formamide or dimethyl sulfoxide (DMSO), and water.
The solid carrier that is fit to is: for example ammonium salt and ground natural mineral matter such as kaolin, clay, talcum, chalk, quartz, attapulgite, montmorillonite or diatomite and ground synthetic mineral matter, as high dispersive silicon-dioxide, alumina and silicate; Be used for suitable the having of solid carrier of granule: for example crush and fractionated natural mineral matter such as calcite, marble, float stone, sepiolite and rhombspar, and the synthetic particle of organic and inorganic powder and following organic particle: wood sawdust, coconut husk, corn cob and tobacco stem; The emulsifying agent and/or the pore forming material that are fit to are: for example nonionic and anionic emulsifier, as polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether, for example, alkylaryl polyglycol ether, alkylsulfonate, alkyl-sulphate, arylsulphonate and albumin hydrolysate; The dispersion agent that is fit to is: for example, and lignin sulfite waste liquor and methylcellulose gum.
Can use the natural and synthetic polymer of tackiness agent such as carboxymethyl cellulose and powdery, particle or latex form in the preparation, as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipid, as kephalin and Yelkin TTS, and synthetic phospholipid.Other tackiness agent can be mineral oil and vegetables oil.
Also may use dyestuff, as mineral dye, for example ferric oxide, titanium oxide and Prussian blue, and organic dye are as alizarine dyestuff, azoic dyestuff and metal phthalocyanine dyestuff and micro-nutrients such as iron, manganese, boron, copper, cobalt, molybdenum and zinc salt.
Usually contain 0.1 to 95% active compound by weight in the preparation, preferred 0.5 to 90%.
When being used for controlling weeds, active compound of the present invention itself or its dosage form can be the forms of direct available preparation or the mixed thing of bucket to use with the form of mixtures of known weedicide also.
Possible common component in mixture is known weedicide, for example
Acetochlor, acifluorfen (sodium salt), aclonifen, alachlor, alloxydim (sodium salt), ametryn, amidochlor, amidosulfuron, the spirit of sulphur grass, atrazine, azimsulfuron, benazolin, benfuresate, benzyl ethyl methyl (methyl esters), bentazone, benzofenap, benzoylpropethyl (ethyl ester), two alanyl phosphorus, bifenox, bromobutide, bromofenoxim, bromoxynil, Butachlor technical 92, the fourth grass is special, cafenstrole, block careless amine, chlomethoxyfen, weed eradication is flat, pyrazon, chlorimuron (ethyl ester), chlornitrofen, chlorsulfuron, chlorotoluron, cinmethylin, ether is yellow grand, clethodim, clodinafop (propargyl) clomazone, difluoro pyridine acid, clopyrasulfuron, cloransulam (methyl), cumyluron, cyanazine, the weed eradication spy, cyclosulfamuron, cycloxydim, cyhalofop (butyl), 2,4-drips, 2, the 4-Embutox, 2,4-drips propionic acid, desmedipham, di_allate, dicamba 98, diclofop-methyl (methyl esters), two benzene azoles are fast, diflufenican Ding Evil is grand, dimepiperate, dimethachlor, diformazan third second is clean, dimethenamid, the spirit of amino second fluorine, diphenamide, diquat, dithiopyr, Diuron Tech, daimuron, EPTC, esprocarb, ethalfluralin, Ethanetsulfuron (methyl esters), ethofumesate, ethoxyfen, etobenzanid oxazole diclofop-methyl ethyl ester, wheat straw volt (isopropyl ester), the wheat straw volt (isopropyl ester-L), wheat straw volt (methyl esters), the pyridine ethyl methyl, fluazifop (butyl ester), flumetsulam, flumiclorac (pentyl), flumioxazin, flumipropyn, fluometuron, the fluorine cisanilide, fluoroglycofenethyl (ethyl ester), amine grass azoles, flupropacil, the fluorenes butyric acid, the fluorine butanone, fluroxypyr, flurprimidol, flurtamone, Fomesafen, Glufosinate (ammonium salt), glyphosate (isopropyl ammonium salt), halosafen, pyrrole fluorine chlorine standing grain spirit (ethoxy ethyl ester), hexazinone, miaow grass ester (methyl esters), imazamethapyr, imazamox, the weed eradication cigarette, the weed eradication quinoline, Imazethapyr, imidazoles is yellow grand, ioxynil, isopropalin, isoproturon, isoxaben, isoxaflutole Evil grass ether, lactofen, lenacil, methoxydiuron, 2 first, 4 chlorine, Vi par, mefenacet, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metsulfuron-methyl (methyl esters), the piperazine humulone, Hydram, monolinuron, naproanilide, napropamide, neburon, nicoculsfuron, norflurazon, orbencarb, oryzalin Evil humulone, oxyfluorfen, Paraquat, pendimethalin, phenmedipham, piperophos, the third careless amine, Fluoropyrimidinesulfuron (methyl esters), prometryn, propachlor, Stam F-34, propaquizafop, pentyne grass amine, prosulfocarb, prosulfuron, pyrazolate, pyrazosulfuron (ethyl ester), pyrazoxyfen, pyributicarb, pyridate, pyrithiobac (sodium), quinclorac, quinmerac, quizalofop (ethyl ester), quizalofop (tetrahydrochysene chaff ester), rimsulfuron, sethoxydim, simazine, simetryn, sulcitrione, sulfentrazone, ethyl methyl (methyl esters), grass sulphur phosphorus, tebutam, terbufos benzthiazuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thiophene methyl (methyl esters), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron-methyl (methyl esters), TRICLOPYR ACID, tridiphane, trifluralin and fluorine amine yellow grand (triflusulfuron).
It also can be mixture with other known activity compound such as mycocide, sterilant, miticide, nematocides, bird repellent, plant food and soil conditioner.
Active compound can with itself, with its preparation or by further dilution and the type of service of preparation uses of warp, as direct available solution, suspension, emulsion, pulvis, paste and granule.They use with ordinary method, for example pour, spraying, atomizing or spread fertilizer over the fields or the like.
Active compound of the present invention can be used before or after plant germination.They also can mix in the soil prior to seeding.
The amount of used active compound can change in quite wide scope.Consumption depends on required effect basically.Usually, usage quantity is between per hectare soil surface restrains to 10 kilograms with 1, and preferred per hectare 5 grams are to 5 kilograms.
The preparation of active compound of the present invention and application are found in embodiment hereinafter.
Preparation embodiment
Embodiment 1
Figure A9880524800241
Earlier 20.2g (89mmol) 3-(6-chloro-pyridin-3-yl)-3-oxo-ethyl propionate is added in the 40ml acetate, and is under about 40 ℃, be added dropwise to 5.8g (126mmol) methyl hydrazine and mix in interior temperature.Subsequently mixture was heated about 90 minutes down at 90-100 ℃, and be settled out the brown solid thing.Cold mixing is poured in the 300ml water, and leach the solids that is settled out, wash with water, and at 50 ℃ of following drying under reduced pressure.
Provide 5-(6-chloro-pyridin-3-yl)-2-methyl-2H-pyrazoles-3-alcohol of 13.6g (theoretical value 73%) thus, 220 ℃ of fusing points.
Embodiment 2
Figure A9880524800251
8.0g (160mmol) hydrazine hydrate and 16.3g (160mmol) diacetyl oxide are added 33.5g (133mmol) 1-(6-chloro-pyridin-3-yl)-4,4 successively, and 4-trifluoro fourth-1 is in the 160ml acetic acid solution of 3-diketone.Reaction mixture heated one hour down at 90-100 ℃, and cold mixture is poured in the 800ml ice-water.Leach the solid that is settled out, wash with water and at 50 ℃ of following drying under reduced pressure.
Provide 29.8g (theoretical value 90%) 2-chloro-5-(5-Trifluoromethyl-1 H-pyrazole-3-yl)-pyridine thus, 183 ℃ of fusing points.
Embodiment 3
Figure A9880524800252
With 12.6g (60mmol) 5-(6-chloro-pyridin-3-yl)-pure and mild 100ml N of 2-methyl-2H-pyrazoles-3-, the mixture of the mixture of N-dimethyl-methane amide and 16.5g salt of wormwood heated about 60 minutes down at 50 ℃.Under 60-70 ℃, with importing about 30g (0.35mol) monochlorodifluoromethane in one hour.The reaction mixture cool to room temperature is poured in 1.3 premium on currency, and uses the 2N hcl acidifying.Suction leaches the solid that is settled out, and is dissolved in the methylene dichloride, with saturated sodium bicarbonate aqueous solution and saturated sodium-chloride water solution washing, uses dried over mgso, and filters successively.Filtrate concentrates under pump vacuum, and residue is used toluene/ethyl acetate (Vol1: 1) carry out column chromatography and separate.
In main fraction, obtain 6.5g (theoretical value 42%) 2-chloro-5-(5-difluoro-methoxy-1-methyl isophthalic acid H-pyrazole-3-yl)-pyridine, 102 ℃ of fusing points.
Embodiment 4
Figure A9880524800261
Under room temperature (about 20 ℃), add 2.2g (1.63mmol) SULPHURYL CHLORIDE while stirring in the 15ml dichloromethane solution of 3.6g (13.9mmol) 2-chloro-5-(5-difluoro-methoxy-1-methyl isophthalic acid H-pyrazole-3-yl)-pyridine.This mixture stirred three hours down at about 20 ℃, with the dilution of 20ml methylene dichloride, with saturated sodium bicarbonate aqueous solution and saturated sodium-chloride water solution washing, used dried over mgso, and filtered successively.Under pump vacuum, distill solvent carefully.
Provide 4.05g (theoretical value 99%) 2-chloro-5-(4-chloro-5-dichloromethane Oxy-1-methyl isophthalic acid H-pyrazole-3-yl)-pyridine thus, 42 ℃ of fusing points.
Use the corresponding solution of bromine in methylene dichloride to replace SULPHURYL CHLORIDE, obtain 2-chloro-5-(4-bromo-5-difluoro-methoxy-1-methyl isophthalic acid H-pyrazole-3-yl)-pyridine (embodiment 11), 60 ℃ of fusing points with similar yield.Embodiment 5
Figure A9880524800262
Under about 20 ℃, in the solution with the 150ml acetonitrile that 18.3g (129mmol) methyl iodide was joined in about 2 minutes 10.1g (40mmol) 2-chloro-5-(5-Trifluoromethyl-1 H-pyrazole-3-yl)-pyridine and 8.4g (60mmol) salt of wormwood.Reaction mixture stirred 3 hours down at 40 ℃, after cooling, concentrated under pump vacuum.Residue digests with 100ml methylene dichloride and 200ml water, and isolates organic phase, washes with water, with dried over mgso and filtration.Filtrate concentrates under pump vacuum, and residue uses n-hexane/ethyl acetate (Vol 2: 1) to separate by column chromatography.
Provide 2-chloro-5-(1-methyl-5-Trifluoromethyl-1 H-pyrazole-3-yl)-pyridine of 6.6g (theoretical value 50.5%) thus, 95 ℃ of fusing points.
Embodiment 6
Figure A9880524800271
Under 75 to 85 ℃, while stirring 10g (141mmol) chlorine was imported in the 40ml acetic acid solution of 2.0g (7.6mmol) 2-chloro-5-(1-methyl-5-Trifluoromethyl-1 H-pyrazole-3-yl)-pyridine with 2 hours.With the reaction mixture cooling, and pour in the 100ml ice-water, and use ethyl acetate extraction.Isolate organic phase, successively with saturated sodium bicarbonate aqueous solution and saturated sodium-chloride water solution washing, with dried over mgso and filtration.Filtrate is concentrated under pump vacuum.
Provide 2.05g (theoretical value 91%) 2-chloro-5-(4-chloro-1-methyl-5-Trifluoromethyl-1 H-pyrazole-3-yl)-pyridine thus, 55 ℃ of fusing points.
Embodiment 7
Under about 20 ℃, 10.3g (224mmol) methyl hydrazine is added to 23.0g (88.6mmol) 1-(6-chloro-pyridin-3-yl)-3, in the 145ml acetonitrile solution of the two methylthio groups of 3--2-propylene-1-ketone.Reaction mixture reflux 120 minutes is poured in ice-water afterwards.Suction leaches the solid that is settled out, washes with water, and drying under reduced pressure.
Provide 17.9g (theoretical value 84%) 3-(6-chloro-pyridin-3-yl)-1-methyl-5-methylthio group-1H-pyrazoles thus, 93 ℃ of fusing points.
Embodiment 8
Figure A9880524800282
Under 0 ℃, successively with acetate and 1.8g (9mmol) 1,3-two chloro-5,5-dimethyl beta-lactam join in the 30ml diethyl ether solution of 3.8g (16mmol) 3-(6-chloro-pyridin-3-yl)-1-methyl-5-methylthio group-1H-pyrazoles.Reaction mixture stirred 18 hours in room temperature (under about 20 ℃), and added 20ml water and the mixing of 20ml ethyl acetate successively.Isolate organic phase, successively with saturated sodium bicarbonate aqueous solution and saturated sodium-chloride water solution washing, with dried over mgso and filtration.Filtrate concentrates under pump vacuum.
Provide 3.8g (theoretical value 87%) 4-chloro-3-(6-chloro-pyridin-3-yl)-1-methyl-5-methylthio group-1H-pyrazoles thus, be the amorphism residue.
Embodiment 9
Under 0 ℃, while stirring 7.5g (30mmol) 3-chlorine peroxybenzoic acid is joined in the 30ml dichloromethane solution of 1.9g (7.7mmol) 4-chloro-3-(6-chloro-pyridin-3-yl)-1-methyl-5-methylthio group-1H-pyrazoles.Reaction mixture stirred 18 hours in room temperature (under about 20 ℃), leached throw out, and filtrate is washed with saturated sodium bicarbonate aqueous solution and saturated sodium-chloride water solution successively, with dried over mgso and filtration.Filtrate concentrates under pump vacuum.
Provide 2.0g (theoretical value 81%) 4-chloro-3-(6-chloro-1-oxygen base-pyridin-3-yl)-1-methyl-5-methyl sulphonyl-1H-pyrazoles thus, be the amorphism residue.
By preparing the method for embodiment 1 to 9, and the general description of method produced according to the present invention, can prepare equally, for example, list in the hereinafter formula of table 1 (I) compound
Figure A9880524800292
Table 1: formula (I) examples for compounds
Figure A9880524800301
Table 1:(is continuous)
Figure A9880524800311
Table 1:(is continuous)
Figure A9880524800321
Table 1:(is continuous)
Figure A9880524800331
Table 1:(is continuous)
Figure A9880524800341
Table 1:(is continuous)
Figure A9880524800351
Formula (III) starting raw material embodiment (III-1)
Figure A9880524800361
Under 10 to 15 ℃, successively 50.5g (0.5mol) triethylamine and 58.8g (0.617mol) Magnesium Chloride Anhydrous are joined in the mixture of 89.3g (0.525mol) propanedioic acid list ethyl ester sylvite in the 500ml acetonitrile.And with mixture under about 20 ℃, stirred about 150 minutes, be cooled to-10 ℃ to-5 ℃, and under this temperature, use 88.0g (0.50mol) 2-chloro-pyridine-5-carbonyl chloride and 5.05g (0.05mol) triethylamine to mix successively.Reaction mixture stirred 18 hours down at about 20 ℃, concentrated afterwards.Residue stirs with 500ml toluene, and mixes with the salt slow acid of 240ml concentration 33%.Mixture at room temperature stirred 3 hours, leached the solid that is settled out, and organic phase is separated from filtrate.Organic phase use dried over mgso with dilute hydrochloric acid and washing with water, and filtration.Filtrate concentrates under pump vacuum, and residue uses methylene chloride (vol 9: 1) to separate by column chromatography.
As the main branch, obtain 82.9g (theoretical value 73%) 3-(6-chloro-pyridin-3-yl)-3-oxo-propionic acid acetate, 48 ℃ of fusing points.
Embodiment (III-2)
Figure A9880524800371
Step 1
The 60ml acetic acid solution of 40g (0.176mol) 3-(6-chloro-pyridin-3-yl)-3-oxo-ethyl propionate is mixed with the 40ml water and the 7.5ml vitriol oil successively, heated 90 minutes down at about 80 ℃ afterwards.Allow reaction mixture be cooled to room temperature, and pour in the 600ml ice-water.The suspension of gained neutralizes with dilute sodium hydroxide aqueous solution, and uses dichloromethane extraction.Organic phase is washed with saturated sodium-chloride water solution, with dried over mgso and filtration.Under pump vacuum, carefully solvent is distilled from filtrate.
Provide 21.4g (theoretical value 78%) 5-ethanoyl-2-chloro-pyridine thus, 98 ℃ of fusing points.
Step 2
Figure A9880524800381
At first; under about 20 ℃, with 20.7g (0.146mol) Trifluoroacetic Acid Ethyl Ester, afterwards; under-5 ℃, the methanol solution of sodium methylate of 30.2g (0.168mol) concentration 30% is joined in the 200ml diethyl ether solution of 17.4g (0.112mol) 5-ethanoyl-2-chloropyridine successively.Reaction mixture stirred 2 hours down at 0 ℃, pour into afterwards in the 200ml ice-water, and use 1N hydrochloric acid, with its pH regulator to 2 between 3.Isolate organic phase afterwards, with the saturated sodium-chloride water solution washing, use dried over mgso, and filter.Under pump vacuum, carefully solvent is distilled from filtrate.
Provide 27.1g (theoretical value 96%) 1-(6-chloro-pyridin-3-yl)-4 thus, 4-trifluoro fourth-1,3-diketone, 54 ℃ of fusing points.
Embodiment (III-3)
Under-40 ℃,, the 50ml tetrahydrofuran solution of 23.3g (0.15mol) 5-ethanoyl-2-chloro-pyridine is added dropwise to 33.6g (0.3mol) potassium tert.-butoxide in the suspension of 210ml tetrahydrofuran (THF) with 15 minutes.Mixture stirred 30 minutes down at-40 ℃, mixed with 11.4g (0.15mol) dithiocarbonic anhydride afterwards.After 30 minutes, add 42.6g (0.3mol) methyl iodide, and with this reaction mixture with being warmed to room temperature in two hours.Reaction mixture is poured in the 1.5l ice-water, used 1N hydrochloric acid to be adjusted between the pH2 to 3, and with l.5 rising ethyl acetate extraction.Organic phase is washed with sodium chloride solution, through dried over mgso, and under reduced pressure removes.The raw product of gained stirs with about 100ml ether, leaches the solid that is settled out, and dry.
Provide 24.3g (theoretical value 62%) 1-(6-chloro-pyridin-3-yl)-3 thus, the two methylthio groups of 3--2-propylene-1-ketone are a kind of crystalline light yellow solid, 145 ℃ of fusing points.
Application Example
Embodiment A
Test before the bud
Solvent: 5 parts of weight acetones
Emulsifying agent: the alkylaryl polyglycol ether of 1 part of weight
When preparing the active agent preparations that is fit to, with the active compound of 1 part of weight and the solvent of described amount, with the emulsifying agent adding of described amount, and water is diluted to desired concn with this missible oil.
The seed of test plant is broadcast in the normal soil, after 24 hours, watered with active agent preparations.Preferably make the water yield of per unit area keep constant.The concentration of active compound is unessential in the preparation, and it is crucial having only the amount of the active compound that per unit uses.
After three weeks, the degree of damage of plant and the developmental phase of untreated control are compared, make infringement %.The implication of numerical value is as follows:
0%=do not have effect (be untreated identical)
100%=damages fully
In this test, for example, under the using dosage of 60 to 2000 gram/hectares, the compound for preparing embodiment 4,6 and 7 has very strong activity to weeds, for example, knotgrass (100%), sorghum (95%), Amaranthus (100%), Chenopodium (100%), Solanum (100%), wild avena sativa (80-100%), setaria (100%), abutilon (100%), Bedstraw (90-100%) and mustard belong to (80-100%), and crop then has for example cotton (0%) of extraordinary tolerance to it.
Embodiment B
Test behind the bud
Solvent: 5 parts of weight acetones
Emulsifying agent: the alkylaryl polyglycol ether of 1 part of weight
When preparing the active agent preparations that is fit to, with the active compound of 1 part of weight and the solvent of described amount, with the emulsifying agent adding of described amount, and water is diluted to desired concn with this missible oil.
Press a certain amount of required active agent preparations of unit surface spray application to plant height 5-15 centimetre test plant.Choose spraying concentration, make and use concrete required active compound amount with 1000 liters/hectare spray amount.
After three weeks, the degree of damage of plant and the developmental phase of untreated control are compared, make infringement %.
The implication of numerical value is as follows:
0%=does not have effect (identical with untreated control)
100%=damages fully
In this test, for example, under the using dosage of 15 to 2000 gram/hectares, for example, the compound for preparing embodiment 4,6 and 7 demonstrates very strong activity to weeds, belong to (100%), wild avena sativa (100%), setaria (100%), abutilon (100%), Amaranthus (100%), Bedstraw (100%), sweet potato genus (100%), Chenopodium (100%) and Solanum (100%) as amur foxtail, crop to the very tolerance of excellence, for example wheat (10%) then arranged.
Embodiment C
T.urticae Koch (Tetranvchus) test (OP-resistance/dip in processing)
Solvent: the dimethyl formamide of 3 parts of weight
Emulsifying agent: the alkylaryl polyglycol ether of 1 part of weight
During the appropriate formulation of preparation active compound,, and this missible oil is diluted with water to desired concn with the active compound of 1 part of weight and the solvent and the emulsifier mix of described amount.
The Kidney bean plant (Phaseolus vulgaris) that seriously grows the greenhouse T.urticae Koch (Tetranychusurticae) of all growth phases is immersed in the active agent preparations of desired concn.
Through after the regular hour, determine to kill %.100% is meant that all tetranychids all are killed; 0% is meant do not have tetranychid to be killed.In this test, for example, under 0.01% activity compound concentration, after 7 days, the acaricidal rate of the compound of preparation embodiment 1 is 95%.
Embodiment D
Spodoptera frugiperda test/synthetic foodstuff
Solvent: the acetone of 100 parts of weight
The methyl alcohol of 1900 parts of weight
During the appropriate formulation of preparation active compound,, and this missible oil is diluted to desired concn with methyl alcohol with the active compound of 1 part of weight and the solvent of described amount.
The active agent preparations of the described concentration of described amount is drawn onto on the synthetic foodstuff of normalized amount with suction pipe.After the methyl alcohol evaporation, in each case with the larva (L of mythimna separata (Spodopterafrugiperda) 2-L 3) place on the food, triplicate.
Through after the regular hour, determine % efficient.100% is meant that all insects all are killed; 0% is meant do not have insect to be killed.
In this test, for example, under 0.05% activity compound concentration, after 7 days, the kill ratio of the compound of preparation embodiment 2 is 100%.

Claims (7)

1. the pyridyl pyrazoles of the replacement of general formula (I)
Figure A9880524800021
Wherein
M represents numeral 0 or 1,
N represents numeral 1,2 or 3,
R 1Represent hydrogen, represent each optional by cyano group-, halogen-or C 1-C 4The alkyl with 1 to 6 carbon atom of-alkoxyl group-replacement, or represent each optional by cyano group-or the alkenyl or the alkynyl that respectively have 2 to 6 carbon atoms of halogen-replacement,
R 2Represent hydrogen, nitro, hydroxyl, sulfydryl, carboxyl, cyano group, thiocarbamoyl, halogen, representative by cyano group-, halogen-or C 1-C 4The alkyl with 1 to 6 carbon atom of-alkoxyl group-replacement, or represent each optional by cyano group-, halogen-or C 1-C 4The alkoxyl group, alkoxy carbonyl, alkylthio, alkyl sulphinyl or the alkyl sulphonyl that respectively have 1 to 6 carbon atom of-alkoxyl group-replacement,
R 3Represent hydrogen, cyano group, halogen, or representative optional by cyano group-, halogen-or C 1-C 4The alkyl with 1 to 6 carbon atom of-alkoxyl group-replacement and
R 4Represent nitro, cyano group, carboxyl, formamyl, thiocarbamoyl, hydroxyl, sulfydryl, amino, hydroxyl amino, halogen, or represent one of following groups :-Q-R 5,-NH-R 5,-NH-O-RO 5,-NH-SO 2-R 5,-N (SO 2-R 5) 2,-CQ 1-R 5,-CQ 1-Q 2-R 5,-CQ 1-NH-R 5,-Q 2-CQ 1-R 5,-NH-CQ 1-R 5,-N (SO 2-R 5) (CQ 1-R 5) ,-Q 2-CQ 1-Q 2-R 5,-NH-CQ 1-Q 2-R 5Or-Q 2-CQ 1-NH-R 5, wherein Q represents O, S, SO or SO 2, Q 1And Q 2Each represents oxygen or sulphur, and
R 5Representative optional by cyano group-, halogen-, C 1-C 4-alkoxyl group-, C 1-C 4-alkylthio-, C 1-C 4-alkyl-carbonyl-, C 1-C 4-alkoxyl group-carbonyl-or C 1-C 4The alkyl with 1 to 6 carbon atom of-alkylamino-carbonyl-replacement,
R 5Also represent each optional by cyano group-, carboxyl-, halogen-, C 1-C 4-alkyl-carbonyl-, C 1-C 4-alkoxyl group-carbonyl-or C 1-C 4The alkenyl or the alkynyl that respectively have 2 to 6 carbon atoms of-alkylamino-carbonyl substituted,
R 5Also represent each optional by cyano group-, carboxyl-, halogen-, C 1-C 4-alkyl-carbonyl-or C 1-C 4Each of-alkoxyl group-carbonyl-replacement has 3 to 6 carbon atoms and chooses cycloalkyl or the cycloalkylalkyl that has 1 to 4 carbon atom at moieties wantonly in group of naphthene base,
R 5Also represent each optional by hydroxyl-, sulfydryl-, amino-, cyano group-, carboxyl-, formamyl-, thiocarbamoyl-, C 1-C 4-alkyl-, C 1-C 4-haloalkyl-, C 1-C 4-alkoxyl group-, C 1-C 4-halogenated alkoxy-, C 1-C 4-alkylthio-, C 1-C 4-halogenated alkylthio-, C 1-C 4-alkyl sulphinyl-, C 1-C 4-alkyl sulphonyl-, C 1-C 4-alkylamino-or each of dimethylamino-replacement in aromatic yl group, have 6 or 10 carbon atoms and choose the aryl or aralkyl that has 1 to 4 carbon atom at moieties wantonly, or
R 5Also represent each optional by hydroxyl-, sulfydryl-, amino-, cyano group-, carboxyl-, formamyl-, thiocarbamoyl-, C 1-C 4-alkyl-, C 1-C 4-haloalkyl-, C 1-C 4-alkoxyl group-, C 1-C 4-halogenated alkoxy-, C 1-C 4-alkylthio-, C 1-C 4-halogenated alkylthio-, C 1-C 4-alkyl sulphinyl-, C 1-C 4-alkyl sulphonyl-, C 1-C 4-alkylamino-or dimethylamino-replacement have 2 to 6 carbon atoms and 1 to 3 nitrogen-atoms and/or 1 or 2 Sauerstoffatom and/or a sulphur atom and choose heterocyclic radical or the heterocyclic radical alkyl that has 1 to 4 carbon atom at moieties wantonly in the heterocyclic radical group.
2. the method for pyridyl pyrazoles of the replacement of preparation general formula (I) Wherein m, n, R 1, R 2, R 3And R 4Each is characterized in that as defined in claim 1, makes the hydrazine or derivatives thereof of general formula (II)
H 2N-NH-R 1(II) R wherein 1As defined above, with the pyridyl-1 of the replacement of general formula (III), the reaction of 3-dicarbonyl compound
Figure A9880524800041
Wherein m, n, R 2, R 3And R 4As defined above, or with pyridyl-carbonyl compound reaction of the replacement of general formula (IV) Wherein m, n, R 3And R 4As defined above,
Q 3Represent oxygen or sulphur and
R represents hydrogen or alkyl,
-and/or, if suitable, with the tautomerism precursor reactant of general formula (IV) compound.
3. weedicide, sterilant and miticide composition is characterized in that, they comprise the pyridyl pyrazoles of replacement of the formula (I) of at least a claim 1.
4. prevent and treat the method for undesired plant, it is characterized in that, make the pyridyl pyrazoles of replacement of the formula (I) of claim 1 act on undesired plant and/or its dried rhizome of rehmannia of dwelling.
5. the pyridyl pyrazoles formula of the replacement of the formula of claim 1 (I) is prevented and treated the application of undesired plant, insect or acarid.
6. prepare the method for weedicide, sterilant or miticide composition, it is characterized in that, the pyridyl pyrazoles of the replacement of the formula (I) of claim 1 is mixed with weighting agent and/or tensio-active agent.
7. the method for control animal pest is characterized in that, makes the pyridyl pyrazoles of replacement of the formula (I) of claim 1 act on animal pest and/or its dried rhizome of rehmannia of dwelling.
CN 98805248 1997-05-20 1998-05-07 Substituted pyridylpyrazoles as herbicides, insecticides and acaricides Pending CN1257490A (en)

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