CN1202800A - Herbicidal composition - Google Patents
Herbicidal composition Download PDFInfo
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- CN1202800A CN1202800A CN96198501A CN96198501A CN1202800A CN 1202800 A CN1202800 A CN 1202800A CN 96198501 A CN96198501 A CN 96198501A CN 96198501 A CN96198501 A CN 96198501A CN 1202800 A CN1202800 A CN 1202800A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
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- Pest Control & Pesticides (AREA)
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- Health & Medical Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
A selectively herbicidal composition which comprises, besides customary inert formulation auxiliaries, as active ingredient a mixture of: a) a herbicidally active amount of a herbicide selected from the group consisting of the compounds of formula (Ia), and/or (Ib), in which R is hydrogen or fluorine and/or (Ic) or of a salt of the compounds of formulae (Ia) and/or (Ib) and/or (Ic), and b) a herbicidally antagonistically active amount of a compound of formula (IIa), of a compound of formula (IIb1), of a compound of formula (IIb2), of a compound of formula (IIc), of a compound of formula (IIe), of a compound of formula (IIf), or of a compound of formula (IIg), in which the substituents have the meanings given in claim 1.
Description
The present invention relates to new selective herbicidal composition; be used for controlling gramineous plants and the weeds of useful crop; gramineous plants and weeds in cereal class and the rice crop particularly; said composition comprises a kind of weed killer herbicide and a kind of safener (antipoison) and protection useful plant rather than the weeds plant toxicity activity with the opposing weed killer herbicide, also relates to the purposes of said composition controlling weeds in useful crop.
When using weed killer herbicide, crop plant may also be subjected to the infringement of certain degree, and for example this depends on the dosage and the application type of weed killer herbicide, crop plant, soil structure and climatic factor such as photoperiod, temperature and rainfall.
In order to handle this problem and similar problem; many materials had been proposed already as resisting the detrimental effect of weed killer herbicide to crop plant; be the safener that the cover crop plant avoids the weed killer herbicide influence, the activity of weeding for the treatment of the weeds of control does not simultaneously affect adversely.Found that the safener that is proposed all works in very specific mode usually for crop plant and weed killer herbicide, and also change in some cases with application type, this means that specific safener only is suitable for the weeding material of specific crop and particular types usually, or specific weed killer herbicide.
Have now found that EP-A-492,366; Disclosed safener is suitable for the cover crop plant so that it avoids EP-A-679 among WO91/7874 and the WO94/987, and 646; EP-A-502,740; EP-A-0,477,808 and US-A-5, the phytotoxicity effect of sulfonylureas described in 009,699 and sulfamoyl urea herbicide.
According to the present invention, a kind of selective Herbicidal combinations has been proposed, said composition is except the inertia preparation auxiliary agent such as carrier, solvent and wetting agent of routine, and the mixture that contains following component is made active component: a) a kind of herbicide of activity of weeding amount is selected from formula Ia compoundAnd/or formula Ib compound
Wherein R is hydrogen or fluorine, and/or formula Ic compound
Or the salt of formula Ia and/or Ib and/or Ic compound, and b) a kind of formula IIa compound of weeding antagonistic activity amount
R wherein010For hydrogen, C1-C
8Alkyl or C1-C
6Alkoxyl or C3-C
6The C that alkenyloxy replaces1-C
8Alkyl and X2For hydrogen or chlorine, formula IIb1Compound
Wherein E is nitrogen or methine R11For-CCl3Or do not replace or phenyl that halogen replaces R12And R13Be hydrogen or halogen independently of one another, and R14For C1-C
4Alkyl, formula IIb2Compound
R wherein12And R13Have above connotation, and R66、R
67And R68Be C independently of one another1-C
4Alkyl, the compound of formula IIc
A wherein2For group
R
25And R26Be hydrogen independently of one another, C1-C
8Alkyl, C3-C
8Cycloalkyl, C3-C
6Alkenyl, C3-C
6Alkynyl,, or C1-C
4Alkoxyl orThe C that replaces1-C
4Alkyl; Or R25And R26Form together C4-C
6The alkylidene bridged bond, this bridged bond can be by oxygen, sulphur, SO, SO2, NH or-N (C1-C
4Alkyl)-interval, R27For hydrogen or C1-C
4Alkyl; RaaFor hydrogen, halogen, cyano group, trifluoromethyl, nitro, C1-C
4Alkyl, C1-C
4Alkoxyl, C1-C
4Alkylthio group, C1-C
4The alkyl sulfinyl, C1-C
4The alkyl sulfonyl base ,-COORj，-CONR
kR
m，-COR
n，-SO
2NR
kR
mOr-OSO2-C
1-C
4Alkyl; RgFor hydrogen, halogen, cyano group, nitro, C1-C
4Alkyl, C1-C
4Haloalkyl, C1-
C
4Alkylthio group, C1-C
4The alkyl sulfinyl, C1-C
4The alkyl sulfonyl base ,-COORj，
-CONR
kR
m，-COR
n，-SO
2NR
kR
m，-OSO
2-C
1-C
4Alkyl, C1-C
6Alkoxyl or by C1-C
4The C that alkoxy or halogen replaces1-C
6Alkoxyl, C3-C
6Alkenyloxy or the C that is replaced by halogen3-C
6Alkenyloxy, or C3-C
6Alkynyloxy group, or RaaAnd RbbForming together can be by halogen or C1-C
4The C that alkyl replaces3-C
4The alkylidene bridged bond, or formation can be by halogen or C1-C
4The C that alkyl replaces3-C
4The alkylidene bridged bond, or formation can be by halogen or C1-C
4The C that alkyl replaces4Inferior alkadienyl, RbbAnd RhBe hydrogen independently of one another, halogen, C1-C
4Alkyl, trifluoromethyl, C1-C
6Alkoxyl, C1-C
6Alkylthio group or-COORj；
R
cFor hydrogen, halogen, nitro, C1-C
4Alkyl or methoxyl group; RdFor hydrogen, halogen, nitro, C1-C
4Alkyl, C1-C
4Alkoxyl, C1-C
4Alkylthio group, C1-C
4The alkyl sulfinyl, C1-C
4The alkyl sulfonyl base ,-COORjOr-CONRkR
m；
R
eFor hydrogen, halogen, C1-C
4Alkyl ,-COORj, trifluoromethyl or methoxyl group, or RdAnd ReForm together C3-C
4The alkylidene bridged bond; RfFor hydrogen, halogen or C1-C
4Alkyl; RxAnd RyBe hydrogen independently of one another, halogen, C1-C
4Alkyl, C1-C
4Alkoxyl, C1
-C
4Alkylthio group ,-COOR28, trifluoromethyl, nitro or cyano group; Rj，R
kAnd RmBe hydrogen or C independently of one another1-C
4Alkyl; Or RkAnd RmForm together can by oxygen, NH or-N (C1-C
4The C at alkyl)-interval4-C
6The alkylidene bridged bond; RnFor C1-C
4Alkyl, phenyl or by halogen, C1-C
4Alkyl, methoxyl group, the phenyl that nitro or trifluoromethyl replace; R28For hydrogen, C1-C
10Alkyl, C1-C
4Alkoxy-C1-C
4Alkyl, C1-C
4Alkylthio group-C1-C
4Alkyl, two C1-C
4Alkylamino-C1-C
4Alkyl, halo-C1-
C
8Alkyl, C2-C
8Alkenyl, halo-C2-C
8Alkenyl, C3-C
8Alkynyl, C3
-C
7Cycloalkyl, halo-C3-C
7Cycloalkyl, C1-C
8The alkyl carbonyl, pi-allyl carbonyl, C3-C
7Naphthene base carbonyl, do not replace or by identical or different substituting group trisubstituted benzoyl at the most on phenyl ring, described substituting group is selected from halogen, C1-C
4Alkyl, halo-C1-C
4Alkyl, halo-C1-C
4Alkoxyl or C1-C
4Alkoxyl; Or furanylcarbonyl, thienyl; Or by phenyl, halogenophenyl, C1-C
4Alkyl phenyl, C1-C
4Alkoxyphenyl radical, halo-C1-
C
4Alkyl phenyl, halo-C1-C
4Alkoxyphenyl radical, C1-C
6Alkoxy carbonyl group, C1-C
4Alkoxy-C1-C
8Alkoxy carbonyl group, C3-C
8Alkenyloxy carbonyl, C3-C
8Alkynyloxy group carbonyl, C1-C
8Alkylthio group carbonyl, C3-C
8Alkenyl thio carbonyl, C3-C
8Alkynes sulfenyl carbonyl, carbamoyl, single C1-C
4Alkyl amino-carbonyl, two C1-C
4The C that alkyl amino-carbonyl replaces1-C
4Alkyl; Or do not replace or by identical or different substituting group trisubstituted phenylamino carbonyl at the most on phenyl, described substituting group is selected from halogen, C1-C
4Alkyl, halo-C1-C
4Alkyl, halo-C1-C
4Alkoxyl or C1-C
4Alkoxyl, or by cyano group or the mono-substituted phenyl of nitro, or do not replace or by one or two C1-C
4The dioxolanes that alkyl replaces-2-base, or do not replace or by one or two C1-C
4Alkyl replaces De diox-2-base, or by cyano group, nitro, carboxyl or C1-C
8Alkylthio group-C1-C
8The C that alkoxy carbonyl group replaces1-C
4Alkyl, formula IIe compound
R wherein33And R34Be C independently of one another1-C
6Alkyl or C2-C
6Alkenyl; Or R33And R34Be together
R
35And R36Be hydrogen or C independently of one another1-C
6Alkyl; Or R33And R34Be together
R
37And R38Be C independently of one another1-C
4Alkyl, or R37And R38Be together-(CH2)
5-；
R
39For hydrogen, C1-C
4Alkyl orOr R33And R34Be together
R
40、R
41、R
42、R
43、R
44、R
45、R
46、R
47、R
48、R
49、R
050、
R
51、R
52、R
53、R
54And R55Be hydrogen or C independently of one another1-C
4Alkyl; The compound of formula IIfR wherein63For hydrogen or chlorine, and R64For cyano group or trifluoromethyl, or the compound of formula IIg
R wherein65For hydrogen or methyl.
The present invention also comprises the salt that can tolerate on the agronomy that formula Ia, Ib and Ic compound for example can form with amine, alkali metal base and alkaline earth metal alkali or quaternary ammonium base.
Preferred salt precursor is the hydroxide of lithium, sodium, potassium, magnesium or calcium in alkali metal hydroxide and alkaline earth metal hydroxide, but the hydroxide of sodium or potassium particularly.
The amine example that is suitable for forming ammonium salt not only has ammonia, also has primary, the second month in a season and uncle C
1-C
18Alkylamine, C
1-C
4Hydroxyalkyl amine and C
2-C
4Alkoxyalkyl amine, as methylamine, ethamine, n-propylamine, isopropylamine, the butylamine of four kinds of isomeries, n-amylamine, iso-amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, pentadecyl amine, hexadecylamine, heptadecyl amine, octadecylamine, Methylethyl amine, isopropyl methyl amine, methyl hexyl amine, methyl nonyl amine, methyl pentadecyl amine, methyl octadecylamine, N-Ethylbutylamine, hexyl heptyl amine, the ethyl octyl amine, hexyl heptyl amine, hexyl octyl amine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, two n-amylamines, di-iso-amylamine, dihexylamine, two heptyl amices, dioctylamine, monoethanolamine, normal propyl alcohol amine, isopropanolamine, N, the N-diethanol amine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butene base-2-amine, positive pentenyl-2-amine, 2,3-dimethyl butyrate thiazolinyl-2-amine, two-cyclobutenyl-2-amine, n-hexylene base-2-amine, propane diamine, trimethylamine, triethylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, triisobutylamine, tri sec-butylamine, tri-n-amyl amine, methoxyethyl amine and ethoxy ethyl amine; Heterocyclic amine, as pyridine, quinoline, isoquinolin, morpholine, piperidines, pyrrolidines, indoline, quinoline rather encircle and azepines; Uncle's arylamine, as aniline, methyl oxyaniline, ethoxy aniline, o, m, p-toluidines, phenylenediamine, benzidine, naphthylamines and o, m, p-chloroaniline; But particularly triethylamine, isopropylamine and diisopropylamine.
Alkyl in the substituting group definition of formula IIa-IIg compound can be side chain and straight chain, for example is methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group and amyl group, hexyl, heptyl, octyl group, nonyl, decyl and branched isomer thereof.These alkyl can have other substituting groups, as halogen, and particularly fluorine, chlorine or bromine, alkoxyl, alkylthio group, cycloalkyl, phenyl, amino, acyl group is (as R
8CO-) or oxo (O=).Suitable alkoxyl, alkylthio group, haloalkyl and halogenated alkoxy are obtained by abovementioned alkyl.
The unsaturated group example is a vinyl in the substituting group, acrylic, cyclobutenyl, pentenyl, hexenyl, heptenyl, octenyl, acetenyl, propinyl, butynyl, pentynyl, hexin base, the heptyne base, octyne base and the diverse location of one or more unsaturated bond in molecule and the structure body, contain the isomer of branched chain and cis under the olefine situation and transisomer.
The example of alkenyloxy, alkynyloxy group, halogenated alkenyl and halo alkenyloxy can be obtained by abovementioned alkyl.
Cycloalkyl for example comprises cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl and ring octyl group.Corresponding cycloolefin can be for single or polyunsaturated.
Term " replacement " not only refers to single replacement, also refer to polysubstituted, if this is if possible in described group.
In the salt of formula Ia compound, formula Id compound is particularly suitable for the present composition:
The particularly preferred composition of the present invention comprises formula Ia or Id compound and makes weed killer herbicide and formula IIa compound (X wherein
2Be chlorine and R
010Be 1-methyl hexyl) make safener.
Preferred composition of the present invention comprises formula IIa, IIb
1, IIb
2Or the IIc compound is made safener.
Wherein preferred compositions is to comprise formula IIb
1Or IIb
2Compound is made the compound of safener.
Another group preferred composition comprises formula IIa compound and makes safener, particularly X wherein
2Be chlorine and R
010For-CH (CH
3) C
5H
11The formula IIa compound of-n.
During the safener that is particularly useful for the present composition is listed in the table below.Table 1: formula IIa compound:
Compound number X
2R
0104.01 Cl-CH (CH
3)-C
5H
11-n4.02 Cl-CH (CH
3)-CH
2OCH
2CH=CH
24.03 Cl H4.04 Cl C
4H
9-n table 2: formula IIb
1Compound
Compound number R
14R
11R
12R
13E5.01 CH
3Phenyl 2-Cl H CH5.02 CH
3Phenyl 2-Cl 4-Cl CH5.03 CH
3Phenyl 2-F H CH5.04 CH
32-chlorphenyl 2-F H CH5.05 C
2H
5CCl
32-Cl 4-Cl N5.06 CH
3Phenyl 2-Cl 4-CF
3N5.07 CH
3Phenyl 2-Cl 4-CF
3N5.08 CH
32-fluorophenyl 2-Cl H CH table 3: formula IIb
2Compound
Compound number R
68R
67R
66R
12R
136.01 CH
3CH
3CH
32-Cl 4-Cl6.02 CH
3C
2H
5CH
32-Cl 4-Cl6.03 CH
3C
2H
5C
2H
52-Cl 4-Cl table 4: formula IIc compound
Compound number A
2R
267.001
H7.002
H7.003
CH
37.004
CH
3Table 5: formula IIe compound
Compound number R
33R
34R
33+ R
348.001 CH
2=CHCH
2CH
2=CHCH
2-8.002--
8.003-
8.004-
8.005-
8.006-
8.007-
Table 6: formula IIf compound
Compound number R
63R
649.01 H CN9.02 Cl CF
3Table 7: formula IIg compound
Compound number R
6510.01 H10.02 CH
3
Table among the 1-7 safener and preparation example as being disclosed in EP-A-492,366, among WO91/7874 and the WO 94/987.
Very important Herbicidal combinations of the present invention is to comprise those of one of following active ingredients combination: Ia+4.01; Ia+4.02; Ia+4.03; Ia+4.04; Ib, wherein R is a hydrogen ,+4.01; Ib, wherein R is a hydrogen ,+4.02; Ib, wherein R is a hydrogen ,+4.03; Ib, wherein R is a hydrogen ,+4.04; Ib, wherein R is a fluorine ,+4.01; Ib, wherein R is a fluorine ,+4.02; Ib, wherein R is a fluorine ,+4.03; Ib, wherein R is a fluorine ,+4.04; Ia+5.01; Ia+5.02; Ia+5.03; Ia+5.04; Ia+5.05; Ia+5.06; Ia+5.07; Ia+5.08; Ib, wherein R is a hydrogen ,+5.01; Ib, wherein R is a hydrogen ,+5.02; Ib, wherein R is a hydrogen ,+5.03; Ib, wherein R is a hydrogen ,+5.04; Ib, wherein R is a hydrogen ,+5.05; Ib, wherein R is a hydrogen ,+5.06; Ib, wherein R is a hydrogen ,+5.07; Ib, wherein R is a hydrogen ,+5.08; Ib, wherein R is a fluorine ,+5.01; Ib, wherein R is a fluorine ,+5.02; Ib, wherein R is a fluorine ,+5.03; Ib, wherein R is a fluorine ,+5.04; Ib, wherein R is a fluorine ,+5.05; Ib, wherein R is a fluorine ,+5.06; Ib, wherein R is a fluorine ,+5.07; Ib, wherein R is a fluorine ,+5.08; Ia+6.03; Ib, wherein R is a hydrogen ,+6.03; Ib, wherein R is a fluorine ,+6.03; Ia+7.01; Ia+7.02; Ia+7.03; Ia+7.04; Ib, wherein R is a hydrogen ,+7.01; Ib, wherein R is a hydrogen ,+7.02; Ib, wherein R is a hydrogen ,+7.03; Ib, wherein R is a hydrogen ,+7.04; Ib, wherein R is a fluorine ,+7.01; Ib, wherein R is a fluorine ,+7.02; Ib, wherein R is a fluorine ,+7.03; And Ib, wherein R is a fluorine ,+7.04.
The invention still further relates to selectivity method of controlling weeds in useful crop, be the while or handle useful plant, the zone of its seed or plant propagation material or its growth with the formula Ia of activity of weeding amount and/or the formula II safener of Ib weed killer herbicide and weeding antagonistic activity amount separately.
Available formula II safener protection and avoid suitable crop particularly the cereal class and the paddy rice of the detrimental effect of above-mentioned weed killer herbicide.Crop also is interpreted as referring to making it have those of patience to weed killer herbicide or weed killer herbicide family by conventional breeding or gene engineering method.
Weeds to be controlled can be unifacial leaf or broadleaf weed, Stellaria for example, and watercress belongs to, and creeping bentgrass belongs to, knotgrass, Avena, setaria, mustard belongs to, and lolium temulentum belongs to, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, arrowhead belongs to, Brome, amur foxtail belongs to, johnson grass, Rottboellia exaltata L. F belongs to, Cyperus, abutilon, chrysanthemum harvest spp, Xanthium, Amaranthus, Chenopodium, sweet potato genus, Chrysanthemum, Bedstraw, Viola and Veronica.
" its growth district " is the soil region of having grown and crop having been arranged or broadcast the seed of these crops, the soil that is intended to plant these crops in addition.
Depend on the purpose that is intended to, the safener of formula II can be used for preliminary treatment crop seed (seed dressing or propagating materials are handled), or the back adds in the soil prior to seeding.Yet, also can when plant emerges, use separately or with weed killer herbicide.Therefore, can be independent of the time point of using weed killer herbicide in principle with safener processing plant or seed carries out.Yet, also can handle plant by using weed killer herbicide and safener (for example mixing thing) simultaneously with bucket.
Treat using with respect to the safener of herbicide application with to use type very relevant.Handle (wherein the mixed thing of use bucket is used safener and combinations of herbicides or used safener and weed killer herbicide separately) in the situation in the rice field, the ratio of weed killer herbicide and safener is generally 1: 100 to 1: 1, preferred 1: 50 to 5: 1.
Usually, use 0.001-5.0kg safener/ha, preferred 0.001-0.5kg safener/ha for the rice field processing.
Usually, the herbicide application rate is 0.001-2kg/ha, but is preferably 0.005-1kg/ha.
The present composition is suitable for application method commonly used in all agriculturals, the preceding dispenser of for example emerging, emerge back dispenser and seed dressing.
For seed dressing, use 0.001-10g safener/kg seed usually, preferred 0.05-2g safener/kg seed.If use safener by seed soaking with liquid form prior to seeding, be to use easily that to comprise concentration be 1-10000, the safener solution of the active component of preferred 100-1000ppm.
For dispenser, formula II safener or these safeners are processed with the adjuvant that is usually used in the preparaton field with the combined and instant ground of the weed killer herbicide of formula Ia and/or Ib and/or Ic, obtain preparation, for example missible oil can apply paste, but direct sprayable or dilute solution, dilute emulsion, wetting powder, soluble powder, pulvis, granule or microcapsule formulations.Preparaton prepares in a known way, for example by closely mixing and/or grinding active component and liquid or solid-state formulation aid, for example solvent or solid-state carrier.In addition, in the preparaton preparation, also can use surface active cpd (surfactant).
Following compound is suitable for use as solvent: aromatic hydrocarbons, preferred C
8-C
12Fraction, for example xylene mixture or replace naphthalene, phthalic acid ester such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbon such as cyclohexane or alkane, alcohols and glycols or its ether and ester, as ethanol, ethylene glycol, glycol monoethyl ether or ethylene glycol monoethyl ether, ketone such as cyclohexanone, intensive polar solvent such as N-N-methyl-2-2-pyrrolidone N-, methyl-sulfoxide or N, dinethylformamide, and epoxidation or not epoxidized vegetable oil such as epoxidation cocoa butter or soybean oil; Or water.
But the solid-state carrier that for example is used for pulvis and dispersion powder is generally natural minerals such as calcite, talcum, kaolin, imvite or the Attagel of porphyrize.For improving the physical property of preparaton, also can add polymolecularity silicic acid or polymolecularity adsorbability polymer.The suitable granular adsorptive support that is used for granule is a porous carriers, float stone for example, and the brick slag, sepiolite or bentonite, the example of non-adsorptive support material are calcite or sand.In addition, can use the inorganic or organic materials of a large amount of pre-granulations, as particularly dolomite or efflorescence plant residue.
Suitable surface active cpd depends on the surfactant mixture that is in the nature nonionic, cation and/or anion surfactant and has well emulsify, dispersion and wettability of formula I active component to be prepared.
Suitable anion surfactant can be so-called water-soluble soap, and water-soluble synthetic surface reactive compound.
The soap that can mention is higher fatty acid (C
10-C
22) alkali metal salt, alkali salt or replacement or unsubstituting ammonium salt, for example sodium or the sylvite of oleic acid or stearic acid or the natural acid mixture that can obtain by for example cocoa butter or fatty oil.Also can mention fatty acid methyl ethyl sulfonic acid (methyltauride) salt.
Yet, so-called synthetic surfactant, particularly fatty alcohol sulfonate, aliphatic alcohol sulfate, the more normal use of sulphonated benzimidazole derivative or alkylaryl sulfonates.
Usually; there are and have the alkyl of 8-22 carbon atom in fatty alcohol sulfonate or aliphatic alcohol sulfate with alkali metal salt, alkali salt or replacement or unsubstituting ammonium salt form; alkyl also comprises the moieties of acyl group; the for example sodium of lignosulphonic acid or calcium salt; the sodium of laurilsulfate or calcium salt, or by the sodium or the calcium salt of the fatty alcohol sulphuric acid salt mixture of natural acid preparation.This group also comprises the sulfuric ester of fatty alcohol/ethylene oxide adduct and the salt of sulfonic acid.Sulphonated benzimidazole derivative preferably has the fatty acid-based of two sulfonic groups and about 8-22 carbon atom.Alkylaryl sulfonates for example is sodium salt, calcium salt or the tri ethanol ammonium salt of DBSA, dibutyl naphthalene sulfonic acids or naphthalene sulfonic acids/formaldehyde condensation products.
Suitable phosphate is as also being suitable to nonyl phenol/(4-14) salt of the phosphate of ethylene oxide adduct, or phosphatide.
Suitable non-ionic surface active agent mainly is aliphatic series or cycloaliphatic alcohol, the polyglycol ether derivative of saturated or unsaturated fatty acid and alkyl phenol, these derivatives can have 3-30 ethylene glycol ether group and have 8-20 carbon atom in (aliphatic series) alkyl, have 6-18 carbon atom in the alkyl of alkyl phenol.
Other suitable non-ionic surface active agents are polyoxyethylene and polyoxypropylene, the water-soluble addition thing of ethylene amino-propanediol and alkyl polypropylene glycol, have 1-10 carbon atom in the alkyl chain, and have 20-250 ethylene glycol ether group and 10-100 propylene glycol group.Described compound has 1-5 ethylene glycol unit/propane diols unit usually.
The non-ionic surface active agent example that can mention is the nonyl phenol polyethoxy ethanol, castor oil polyglycol ether, poly(propylene oxide)/PEO adduct, tributyl phenoxy group polyethoxy ethanol, polyethylene glycol and octylphenoxy polyethoxy ethanol.
Other suitable materials are fatty acid esters of polyethenoxy sorbitan, as the polyethenoxy sorbitan trioleate.
Cationic surfactant mainly is a quaternary ammonium salt, has at least one C
8-C
22Alkyl is as the N substituting group, and lower halogenated or haloalkyl not, and benzyl or rudimentary hydroxyalkyl are made other substituting groups.This salt is preferably halide mode, methylsulfuric acid salt form or ethyl sulfuric acid salt form.Example is stearyl trimethyl ammonium chloride and benzyl two (2-chloroethyl) ethyl ammonium bromide.
Also can be used for formulation art surfactant commonly used in the present composition especially be disclosed in " Mc Cutcheon ' s washing agent and emulsifier yearbook " (MC Cutcheon ' s Detergentsand Emulsifiers Annual "; MC Publishing Corp.; Ridgewood New Jersey; 1981; Stache H.; " Tensid-Taschenbuch " (surfactant guide, CarlHanser Verlag, Munich/Vienna, 1981, and M. and J.Ash, " " surfactant complete works " (Encyclopedia of Surfactants) ", Vol I-III.Chemical Publishing Co., New York is among the 1980-81.
Usually, herbicide formulation comprises 0.1-99wt%, the mixture of active principles of the formula Ia of 0.1-95wt% and/or Ib and/or Ic compound and formula II compound particularly, the solid-state or liquid formulation aid of 1-99.9wt% and the surfactant of 0-25wt%, particularly 0.1-25wt%.
Although usually preferred concentrate composition is the commercially available prod, the consumer uses diluted composition usually.
Composition also can comprise other additives, as stabilizing agent such as epoxidation or epoxidized vegetable oil (epoxidation cocoa butter, rapeseed oil or soybean oil) not, and antifoaming agent, silicone oil for example, preservative, viscosity modifier, adhesive, thickener and fertilizer or other active components.
The composition that many methods and technology (for example following those) are suitable for using formula II safener or comprise them comes cover crop, to avoid the detrimental effect of formula Ia and/or Ib and/or Ic weed killer herbicide.I) seed dressing a) is evenly distributed on the surface of the seed dress seed (dry seeds processing) with the formula II active component that is made into wetting powder until active component by jolting in container.Every 100kg seed uses about 1-500g formula II active component (4g-2kg wetting powder).B) with the missible oil of formula II active component by method a) dress seed (wet seed treatment).C) by seed being immersed in the mixture comprise 100-1000ppm formula II active component 1-72 hour, dry seed and dress seed (impregnation process) then if desired.
Certainly, be preferred application process to beginning that seeds germinated benevolence dresses seed or handle, because on target crop, carry out fully with the processing of active component.Usually, every 100kg seed uses the 1-1000g antipoison, preferred 5-250g antipoison, according to diverse ways can on the giving concentration limits or under use, this also allows to add other active components or micronutrient element (reprocessing).Ii mixes thing with bucket and uses
Use the liquid preparation of the mixture (mutual weight ratio is 10: 1 to 1: 100) of antipoison and weed killer herbicide, the amount of application of weed killer herbicide is 0.005-5.0kg/ha.The mixed thing of this bucket used before or after sowing.Iii) impose in the ditch dug with a plow
Safener is imported the open seed ditch dug with a plow of having sowed with missible oil form, wetting powder form or granule form.The seed ditch dug with a plow is used weed killer herbicide before emerging in a usual manner after covering.The iv) sustained release of active component
With the solution form formula II active component is applied on the mineral carrier of granule or aggregated particles (urea/formaldehyde) is gone up and dry.If need, can apply the coating (coated granule) that allows active component in preset time, to discharge with the given dose rate.
Preferred preparaton has following composition especially: (%=percetage by weight) pulvis: mixture of active principles: 0.1-10%, preferred 0.1-5% solid-state carrier: 99.9-90%, preferred 99.9-95% suspension concentrate: mixture of active principles: 5-75%, preferred 10-50% water: 94-24%, preferred 88-30% surfactant: 1-40%, preferred 2-30% wetting powder: mixture of active principles: 0.5-90%, preferred 1-80% surfactant: 0.5-20%, preferred 1-15% solid-state carrier material: 5-95%, preferred 15-90% granule: mixture of active principles: 0.1-30%, preferred 0.1-15% solid-state carrier: 99.5-70%, preferred 97-85%
The following example is described in more detail the present invention, preparation embodiment (%=percetage by weight) the F1. solution of but does not limit the present invention. formula Ia and/or Ib and/or Ic herbicide and formula II safener mixture is b a)) c) d) mixture of active principles 5% 10% 50% 90%1-methoxyl group-3-(3-methoxy propoxy) propane-20% 20%-polyethylene glycol MW 400 20% 10%--METHYLPYRROLIDONEs--30% 10% aromatic hydrocarbons mixture C9-C
1275% 60%--
This solution is suitable for using with the droplet form.F2. wettable powder is b a)) c) d) mixture of active principles 5% 25% 50% 80% sodium lignosulfonate 4%-3%-NaLS 2% 3%-4% diisobutyl sodium naphthalene sulfonates-6% 5% 6% octyl phenyl polyglycol ether (7-8mol EO)-1% 2%-high dispersive silica 1 % 3% 5% 10% kaolin 88% 62% 35%-
Active component is thoroughly mixed with additive, thoroughly grind this mixture with suitable grinding machine.Obtain the wetting powder that dilutable water obtains the suspension of any desired concn.F3. mixture of active principles 0.1% 5% 15% high dispersive silica 0.9% 2% 2% inorganic carrier materials 99.0% 93% 83% (φ 0.1-1mm), for example CaCO c a) b of coated granule))
3Or SiO
2
Active component is dissolved in carrene, solution is sprayed on the carrier, subsequently vacuum evaporating solvent.F4. mixture of active principles 0.1% 5% 15% polyethylene glycol MW 200 1.0% 2% 3% high dispersive silica 0.9% 1% 2% inorganic carrier materials (φ 0.1-1mm) c a) b of coated granule)), 98.0% 92% 80% CaCO for example
3Or SiO
2
In mixer, the active component of porphyrize evenly imposed on and used on the wetting carrier material of polyethylene glycol.Obtain dustless coated granule.F5. extrude a) b of granule) c) d) mixture of active principles 0.1% 3% 5% 15% sodium lignosulfonates 1.5% 2% 3% 4% carboxymethyl celluloses 1.4% 2% 2% 2% kaolin 97.0% 93% 90% 79%
Active component is mixed with additive, and porphyrization mixture is also used water-wet.Extrusioning mixture is also dry in air flow subsequently.F6. c a) b of pulvis)) mixture of active principles 0.1% 1% 5% talcums 39.9% 49% 35% kaolin 60.0% 50% 60%
Heterocyclic aryl group of 2 - furyl group, 3 - furyl, 2 - thienyl group, a 3 - thienyl group, a 1 - pyrrolyl group, 2 - pyrrole,
3 - pyrrolyl group, 2 - oxazolyl group, 4 - oxazolyl, 5 - oxazolyl group, a 2 - thiazolyl group, a 4 - thiazolyl, 5 - thiazolyl group, a 3 - Clomazone
Yl group, a 4 - isoxazolyl, 5 - isoxazolyl group, a 3 - isothiazolyl group, a 4 - isothiazolyl, 5 - isothiazolyl group, a 3 - furazanyl,
1 - pyrazolyl group, a 3 - pyrazolyl group, a 4 - pyrazolyl group, a 3 - oxo-pyrazol-1 - yl, 3 - oxazol-2-oxo-pyrazol - yl, 3 - oxopyrazolo -
³ - 3 - oxo-pyrazol-4 - yl, 4 - oxo-pyrazol-3 - yl, 1 - imidazolyl, 2 - imidazolyl group, 4 - imidazolyl, 2 - oxo-
Imidazol-1 - yl, 2 - oxo-imidazol-4 - yl, 1,2,3 - triazol-1 - yl, 1,2,3 - triazol-2 - yl, 1,2,3 - triazol- -4 -
Yl, 1,2,4 - triazol-1 - yl, 1,2,4 - triazol-3 - yl, 1,2,4 - triazol-4 - yl, 1,2,4 (2H, 4H ) - triazole -
3 - one-2 - yl, 1,2,4 (2H, 4H) - triazol-3 - one-4 - yl, 1,2,4 (2H, 4H) - triazol-3 - one-5 - group 1,
2,4 (1H, 2H) - triazol-3 - one-1 - yl, 1,2,4 (1H, 2H) - triazol-3 - one-2 - yl, 1,2,4 (1H, 2H) -
Triazol-3 - one-5 - yl, 1 - tetrazolyl group, a 2 - tetrazolyl, 5 - tetrazolyl group, a 2 - pyran group, 3 - pyran group, 4 - pyranyl,
2 - pyridyl, 3 - pyridyl, 4 - pyridyl, 2 - pyridon-1 - yl, 2 - pyridin-one-3 - yl, 2 - pyridon-4-- group,
2 - pyridin-5 - yl, 2 - pyridin-keto-6 - yl, 4 - pyridin-on-1 - yl, 4 - pyridone-2 - yl, 4 - pyridin-one-3 - group,
3 - pyridazinyl group, 4 - pyridazinyl, 3 (2H) - pyridazin-on-2 - yl, 3 (2H) - pyridazin-one-4 - yl, 3 (2H) - pyridazinone -
5 - yl, 3 (2H) - pyridazin-keto-6 - yl, 4 (1H) - pyridazin-one-1 - yl, 4 (1H) - pyridazin-one-3 - yl, 4 (1H) - da
Triazin-5 - yl, 4 (1H) - pyridazin-keto-6 - group, a 2 - pyrimidinyl group, a 4 - pyrimidinyl group, a 5 - pyrimidinyl, 2 (1H) - pyrimidinone -
1 - yl, 2 (1H) - pyrimidin-one-4 - yl, 2 (1H) - pyrimidin-5 - yl, 2 (1H) - pyrimidin-on-6 - yl, 4 (3H) - ethyl
Piperidine one-2 - yl, 4 (3H) - pyrimidin-one-3 - yl, 4 (3H) - pyrimidin-5 - yl, 4 (3H) - pyrimidin-on-6 - yl, 4
(1H) - pyrimidin-one-1 - yl, 4 (1H) - pyrimidin-one-2 - yl, 4 (1H) - pyrimidin-5 - yl, 4 (1H) - pyrimidin-oxo-6 -
Group, a 2 - pyrazinyl, 2 (1H) - pyrazine--1 - yl, 2 (1H) - pyrazin-3 - yl, 2 (1H) - pyrazine -5 - yl, 2 (1H) 2 pyrazole
Triazin -6 - yl, 1,2,3 - triazin-4 - yl, 1,2,3 - triazin-5 - yl, 1,2,4 - triazin-3 - yl, 1,2,4 - triazin-5 -
Yl, 1,2,4 - triazin-6 - yl, 1,2,3,4 - tetrazine -5 - yl, 1,2,4,5 - Four-3 - yl, 1 - indolyl 2 - indole
Group, a 3 - indolyl group, a 4 - indolyl, 5 - indolyl, 6 - indolyl 7 - indolyl group, a 2 - quinolyl group, 3 - quinolyl group, 4 -
Quinolyl, 5 - quinolyl, 6 - quinolyl 7 - quinolyl 8 - quinolyl group, a 2 - quinolone one-1 - yl, 2 - quinolone one-3 -
Group, a 2 - quinolone one-4 - yl, 2 - quinolone-5 - yl, 2 - quinolone keto-6 - yl, 2 - quinolone one-7 - yl, 2 - quinolone keto-8 -
Yl, 4 - quinolone one-1 - yl, 4 - quinolone one-2 - yl, 4 - quinolone one-3 - yl, 4 - quinolone-5 - yl, 4 - quinolone one-6 -
Yl, 4 - quinolone one-7 - yl, 4 - quinolone keto-8 - yl, 2 - benzofuranyl group, 3 - benzofuranyl group, a 4 - benzofuranyl,
5 - benzofuranyl, 6 - benzofuranyl 7 - benzo-furyl, 2 - benzothienyl group, 3 - benzothienyl group, a 4 - phenyl
And thienyl group, a 5 - benzothienyl, 6 - benzothienyl 7 - benzothienyl, 1 - isoquinolyl group, 3 - isoquinoline
Group, a 4 - isoquinolyl 5 - isoquinolyl 6 - isoquinolyl 7 - isoquinolyl 8 - isoquinoline group, 1 - isoquinolone -
2 - group, 1 - iso-quinolone one-3 - yl, 1 - iso-quinolone one-4 - yl, 1 - iso-quinolone-5 - yl, 1 - iso-quinolone keto-6 - yl, 1 -
Iso quinolone one-7 - group, 1 - iso quinolone keto-8 - yl, 3 - isobutyl quinolone one-2 - yl, 3 - isobutyl quinolone one-4 - yl, 3 - isoquinoline Connaught
-5 - yl, 3 - iso-quinolone keto-6 - yl, 3 - iso-quinolone one-7 - yl, 3 - iso-quinolone keto-8 - yl, 2 - benzoxazolyl,
4 - benzoxazolyl, 5 - benzoxazolyl, 6 - benzoxazolyl 7 - benzoxazolyl group, a 2 - benzothiazolyl group, a 4 - phenyl
And thiazolyl, 5 - benzothiazolyl, 6 - benzothiazolyl 7 - benzothiazolyl, 1 - benzo-pyrazolyl group, a 2 - benzopyran
Yl group, a 3 - benzo-pyrazolyl group, 4 - benzo-pyrazolyl, 5 - benzo pyrazolyl, 6 - benzo-pyrazolyl 7 - benzo pyrazole
Group, a 1 - benzimidazolyl group, 2 - benzimidazolyl group, 4 - benzimidazolyl, 5 - benzimidazolyl, 1 - benzotriazolyl,
4 - benzotriazole group, a 5 - benzotriazole group, a 2 - benzopyran group, 3 - benzo pyran group, 4 - benzo-pyran group, a 5 - phenyl
And pyranyl, 6 - benzo-pyran-yl, 7 - benzopyranyl 8 - benzopyranyl, 1 - indolizinyl 2 - indolizine
Group, a 3 - indolizinyl, 5 - indolizinyl, 6 - indolizinyl 7 - indolizinyl 8 - indolizinyl 2 - purine group, a 6 -
Purine-yl, 7 - purinyl 8 - purinyl, 1 - phthalazinyl group, a 5 - phthalazinyl group, a 6 - phthalazine group, 1 - oxo-phthalazin-2 - yl, 1 -
Oxo-phthalazin-4 - yl, 1 - oxo-phthalazin -5 - yl, 1 - oxo-phthalazin -6 - yl, 1 - oxo-phthalazin -7 - group, 1 - oxo phthalocyanine
Triazin -8 - yl, 1,5 - naphthyridin-2 - yl, 1,5 - naphthyridine-3 - yl, 1,5 - diaza-naphthyridin-4 - yl, 2 - quinoxaline
Group, a 5 - quinoxalinyl, 6 - quinoxalinyl 2 - quinazolinyl group, 4 - quinazolinyl group, a 5 - quinazolinyl, 6 - quinazolinyl,
7 - quinazolinyl 8 - quinazolinyl, 1,2 - naphthyridine-3 - yl, 1,2 - diaza-naphthyridin-4 - yl, 1,2 - naphthyridine
-5 - Yl, 1,2 - naphthyridine -6 -, 1,2 - naphthyridin-7 - yl, 1,2 - naphthyridine -8 -, 1,4 - benzo two
Dioxan-2 - yl, 1,4 - benzo-dioxan-5 - yl, 1,4 - benzodioxan-6 - yl, 1,4 - oxo-2 - yl, 1,4- -
Oxo-naphthyl -5 - yl, 1,4 - naphthalene-oxo -6 - yl, 2,3 - dihydro-4 - benzofuranyl, 2,3 - dihydro-5 - benzofuran
Yl, 2,3 - dihydro-6 - benzofuranyl, 2,3 - dihydro-7 - benzofuranyl, 1,4 - triazin-2 benzothiazine - yl, 1,4 -
Benzothiazine-3 - yl, 1,4 - benzothiazine-4 - yl, 1,4 - benzothiazine -5 - yl, 1,4 - benzothiazine-6 - yl, 1,
4 - benzothiazin -7 -, 1,4 - benzothiazine -8 - yl, 2 - pteridinyl group, 4 - pteridine group, a 6 - pteridinyl 7 - pteridine group,
Pyrazolo [1,5-a] pyrimidine-2 - yl, pyrazolo [1,5-a] pyrimidine-3 - yl, pyrazolo [1,5-a] pyrimidin-5 - yl,
Pyrazolo [1,5-a] pyrimidin-6 - yl, pyrazolo [1,5-a]-pyrimidin-7 - yl, pyrazolo [5,1-c] [1,2,4]
-3 - yl, pyrazolo [5,1-c] [1,2,4] triazin-4 - yl, pyrazolo [5,1-c] [1,2,4] triazin - 7 - base,
Pyrazolo [5,1-c] [1,2,4] triazin -8 - yl, thiazolo [3,2-b] triazol-2 - yl, thiazolo [3,2-b] three
-5 - yl, thiazolo [3,2-b] triazol -6 - yl, benzo-pyrano [2,3-b] pyridin-2 - yl, benzopyran and
[2,3-b] pyridin-3 - yl, benzo-pyrano [2,3-b] pyridin-4 - yl, benzo-pyrano [2,3-b] pyridine-5 -
Group, benzo-pyrano [2,3-b] pyridine-6 - yl, benzo-pyrano [2,3-b] pyridin-7 - yl, benzopyran and
[2,3-b] pyridin-8 - yl, benzo-pyrano [2,3-b] pyridine -9 - yl, 5H-benzo-pyrano [2,3-b] pyridine -
5 - one-2 - yl, 5H-benzo-pyrano [2,3-b] pyridine-5 - one-3 - yl, 5H-benzo-pyrano [2,3-b] pyridine
-5 - One-4 - yl, 5H-benzo-pyrano [2,3-b] pyridine-5 - oxo-6 - yl, 5H-benzo-pyrano [2,3-b] pyridine
Piperidine -5 - one-7 - yl, 5H-benzo-pyrano [2,3-b] pyridine-5 - one-8 - yl, 1 - xanthene group, 2 - xanthene group, a 3 - xanthan
T group, a 4 - xanthenyl, 9 - xanthene group, 1 - thiophene oxathiazole group, 2 - thiophene oxathiazole group, 3 - thiophene oxathiazole group, a 4 - thiazolyl phenoxazinediyl group, 1 -
Carbazolyl group, a 2 - carbazolyl group, a 3 - carbazolyl group, 4 - carbazolyl, 9 - carbazolyl, 1 - acridine group, a 2 - acridine group, a 3 - acridine
Yl, 4 - acridine group, 9 - acridinyl, 1 - phenazine group, a 2 - phenazine group, a 3 - phenazine group, 4 - phenazine group, 1 - phenothiazine group,
2 - phenothiazine group, 3 - phenothiazine group, 4 - phenothiazine group, 10 - phenothiazine group, a 1 - phenoxazine group, a 2 - phenoxazine group, a 3 -
Phenoxazine group, 4 - phenoxazine group, a 10 - phenoxazine group, 1 - thiazolyl anthryl group, 2 - thiazolyl anthryl group, a 3 - thiazolyl anthryl group, a 4 - thiazolyl anthryl group,
6 - thianthrenyl 7 - thianthrenyl 8 - or 9-thianthrenyl - thianthrenyl, said C4-C6 aliphatic heterocyclic group is 1 - piperidinyl
Group, a 2 - piperidyl group, 3 - piperidyl group, 4 - piperidinyl, 1 - pyrrolidinyl, 2 - pyrrolidinyl, 3 - pyrrolidinyl, 1 - imidazolyl
Alkyl 2 - imidazolyl group, a 4 - imidazolyl group, a 1 - pyrazolyl group, 3 - pyrazolyl group, a 4 - pyrazolyl group 2 - morpholinyl,
3 - morpholinyl group, 4 - morpholinyl group, 2 - tetrahydrofuranyl, 3 - tetrahydrofuranyl;
...
The active component of porphyrize is closely mixed with additive, obtain suspending concentrate, can prepare the suspension of any desired concn by dilute with water.
Usually more convenient is prepares other components of the active component of formula Ia and/or Ib and/or Ic and formula II separately and they are mixed into " barrel mixed thing " with required mixing ratio in water using before in giver.Biological Examples Embodiment B 1: formula Ia and/or Ib and/or lc weed killer herbicide and formula IIa to IIg safener are used after the emerging of cereal crop
Wheat grew to for 2.5 leaf stages in plastic basin under greenhouse experiment.In this stage, with formula Ia and/or Ib and/or Ic weed killer herbicide separately and the mixture of these weed killer herbicides and formula IIa to IIg safener be applied on the test plant.Use by 500l water/ha and carry out with the aqueous suspension of substances (example of formulations F7).After using 28 days, use the evaluation test of percentage yardstick.The gained result shows that formula Ia and/or Ib and/or lc weed killer herbicide can significantly reduce by use formula IIa to IIg safener the infringement of wheat.
When formula Ia and/or Ib compound are prepared shown in embodiment F1-F6, to identical result.
Claims (12)
1. selective herbicidal composition comprises that except that conventional inertia formulation aid the mixture of following component makes active component:
A) a kind of herbicide of activity of weeding amount, be selected from formula Ia compoundAnd/or formula Ib compoundWherein R is hydrogen or fluorine, and/or formula Ic compoundOr the salt of formula Ia and/or Ib and/or Ic compound, and b) a kind of formula IIa compound of weeding antagonistic activity amount
R wherein010For hydrogen, C1-C
8Alkyl or C1-C
6Alkoxyl or C3-C
6The C that alkenyloxy replaces1-C
8Alkyl and X2For hydrogen or chlorine, formula IIb1Compound
Wherein E is nitrogen or methine R11For-CCl3Or do not replace or phenyl that halogen replaces R12And R13Be hydrogen or halogen independently of one another, and R14For C1-C
4Alkyl, formula IIb2CompoundR wherein12And R13Have above connotation, and R66、R
67And R68Be C independently of one another1-C
4Alkyl, the compound of formula IIc
A wherein2For group
Or
R
25And R26Be hydrogen independently of one another, C1-C
8Alkyl, C3-C
8Cycloalkyl, C3-C
6Alkenyl, C3-C
6Alkynyl,
, or C1-C
4Alkoxyl or
The C that replaces1-C
4Alkyl; Or R25And R26Form together C4-C
6The alkylidene bridged bond, this bridged bond can be by oxygen, sulphur, SO, SO2, NH or-N (C1-C
4Alkyl)-interval, R27For hydrogen or C1-C
4Alkyl; RaaFor hydrogen, halogen, cyano group, trifluoromethyl, nitro, C1-C
4Alkyl, C1-C
4Alkoxyl, C1-C
4Alkylthio group, C1-C
4The alkyl sulfinyl, C1-C
4The alkyl sulfonyl base ,-COORj，-CONR
kR
m，-COR
n，-SO
2NR
kR
mOr-OSO2-C
1-C
4Alkyl; RgFor hydrogen, halogen, cyano group, nitro, C1-C
4Alkyl, C1-C
4Haloalkyl, C1-
C
4Alkylthio group, C1-C
4The alkyl sulfinyl, C1-C
4The alkyl sulfonyl base ,-COORj，
-CONR
kR
m，-COR
n，-SO
2NR
kR
m，-OSO
2-C
1-C
4Alkyl, C1-C
6Alkoxyl or by C1-C
4The C that alkoxy or halogen replaces1-C
6Alkoxyl, C3-C
6Alkenyloxy or the C that is replaced by halogen3-C
6Alkenyloxy, or C3-C
6Alkynyloxy group, or RaaAnd RbbForming together can be by halogen or C1-C
4The C that alkyl replaces3-C
4The alkylidene bridged bond, or formation can be by halogen or C1-C
4The C that alkyl replaces3-C
4The alkylidene bridged bond, or formation can be by halogen or C1-C
4The C that alkyl replaces4Inferior alkadienyl, RbbAnd RhBe hydrogen independently of one another, halogen, C1-C
4Alkyl, trifluoromethyl, C1-C
6Alkoxyl, C1-C
6Alkylthio group or-COORj；
R
cFor hydrogen, halogen, nitro, C1-C
4Alkyl or methoxyl group; RdFor hydrogen, halogen, nitro, C1-C
4Alkyl, C1-C
4Alkoxyl, C1-C
4Alkylthio group, C1-C
4The alkyl sulfinyl, C1-C
4The alkyl sulfonyl base ,-COORjOr-CONRkR
m；
R
cFor hydrogen, halogen, C1-C
4Alkyl ,-COORj, trifluoromethyl or methoxyl group, or RdAnd ReForm together C3-C
4The alkylidene bridged bond; RfFor hydrogen, halogen or C1-C
4Alkyl; RxAnd RyBe hydrogen independently of one another, halogen, C1-C
4Alkyl, C1-C
4Alkoxyl, C1
-C
4Alkylthio group ,-COOR28, trifluoromethyl, nitro or cyano group; Rj，R
kAnd RmBe hydrogen or C independently of one another1-C
4Alkyl; Or RkAnd RmForm together can by oxygen, NH or-N (C1-C
4The C at alkyl)-interval4-C
6The alkylidene bridged bond; RnFor C1-C
4Alkyl, phenyl or by halogen, C1-C
4Alkyl, methoxyl group, the phenyl that nitro or trifluoromethyl replace; R28For hydrogen, C1-C
10Alkyl, C1-C
4Alkoxy-C1-C
4Alkyl, C1-C
4Alkylthio group-C1-C
4Alkyl, two C1-C
4Alkylamino-C1-C
4Alkyl, halo-C1-
C
8Alkyl, C2-C
8Alkenyl, halo-C2-C
8Alkenyl, C3-C
8Alkynyl, C3
-C
7Cycloalkyl, halo-C3-C
7Cycloalkyl, C1-C
8The alkyl carbonyl, pi-allyl carbonyl, C3-C
7Naphthene base carbonyl, do not replace or by identical or different substituting group trisubstituted benzoyl at the most on phenyl ring, described substituting group is selected from halogen, C1-C
4Alkyl, halo-C1-C
4Alkyl, halo-C1-C
4Alkoxyl or C1-C
4Alkoxyl; Or furanylcarbonyl, thienyl; Or by phenyl, halogenophenyl, C1-C
4Alkyl phenyl, C1-C
4Alkoxyphenyl radical, halo-C1-
C
4Alkyl phenyl, halo-C1-C
4Alkoxyphenyl radical, C1-C
6Alkoxy carbonyl group, C1-C
4Alkoxy-C1-C
8Alkoxy carbonyl group, C3-C
8Alkenyloxy carbonyl, C3-C
8Alkynyloxy group carbonyl, C1-C
8Alkylthio group carbonyl, C3-C
8Alkenyl thio carbonyl, C3-C
8Alkynes sulfenyl carbonyl, carbamoyl, single C1-C
4Alkyl amino-carbonyl, two C1-C
4The C that alkyl amino-carbonyl replaces1-C
4Alkyl; Or do not replace or by identical or different substituting group trisubstituted phenylamino carbonyl at the most on phenyl, described substituting group is selected from halogen, C1-C
4Alkyl, halo-C1-C
4Alkyl, halo-C1-C
4Alkoxyl or C1-C
4Alkoxyl, or by cyano group or the mono-substituted phenyl of nitro, or do not replace or by one or two C1-C
4The dioxolanes that alkyl replaces-2-base, or do not replace or by one or two C1-C
4Alkyl replaces De diox-2-base, or by cyano group, nitro, carboxyl or C1-C
8Alkylthio group-C1-C
8The C that alkoxy carbonyl group replaces1-C
4Alkyl, formula IIe compound
R wherein33And R34Be C independently of one another1-C
6Alkyl or C2-C
6Alkenyl; Or R33And R34Be together
R
35And R36Be hydrogen or C independently of one another1-C
6Alkyl; Or R33And R34Be together
R
37And R38Be C independently of one another1-C
4Alkyl, or R37And R38Be together-(CH2)
5-；
R
39For hydrogen, C1-C
4Alkyl orOr R33And R34Be together
R
40、R
41、R
42、R
43、R
44、R
45、R
46、R
47、R
48、R
49、R
050、
R
51、R
52、R
53、R
54And R55Be hydrogen or C independently of one another1-C
4Alkyl; The compound of formula IIfR wherein63For hydrogen or chlorine, and R64For cyano group or trifluoromethyl, or the compound of formula IIg wherein
R
65For hydrogen or methyl.
2. according to the composition of claim 1, comprise formula Id compound as formula Ia compound:
3. according to the composition of claim 1, comprise formula Ia or Id compound and make weed killer herbicide and X wherein
2Be chlorine and R
010For the formula IIa compound of 1-methyl hexyl is made safener.
4. according to the composition of claim 1, comprise the weed killer herbicide of the salt of the compound of the formula that the is selected from Ia of activity of weeding amount and/or Ib or formula Ia and/or Ib compound:
Wherein R is hydrogen or fluorine.
5. according to the composition of claim 1, comprise formula IIa, IIb
1, IIb
2Or the IIc compound is made safener.
6. according to the composition of claim 5, comprise formula IIb
1Or IIb
2Compound is made safener.
7. according to the composition of claim 5, comprise formula IIa compound and make safener.
8. according to the composition of claim 7, comprise wherein X
2Be chlorine and R
010For-CH (CH
3) C
5H
11-nFormula IIa compound make safener.
9. according to the composition of claim 5, comprise one of following active ingredients combination and make weed killer herbicide and safener: Ia+4.01; Ia+4.02; Ia+4.03; Ia+4.04; Ib, wherein R is a hydrogen ,+4.01; Ib, wherein R is a hydrogen ,+4.02; Ib, wherein R is a hydrogen ,+4.03; Ib, wherein R is a hydrogen ,+4.04; Ib, wherein R is a fluorine ,+4.01; Ib, wherein R is a fluorine ,+4.02; Ib, wherein R is a fluorine ,+4.03; Ib, wherein R is a fluorine ,+4.04; Ia+5.01; Ia+5.02; Ia+5.03; Ia+5.04; Ia+5.05; Ia+5.06; Ia+5.07; Ia+5.08; Ib, wherein R is a hydrogen ,+5.01; Ib, wherein R is a hydrogen ,+5.02; Ib, wherein R is a hydrogen ,+5.03; Ib, wherein R is a hydrogen ,+5.04; Ib, wherein R is a hydrogen ,+5.05; Ib, wherein R is a hydrogen ,+5.06; Ib, wherein R is a hydrogen ,+5.07; Ib, wherein R is a hydrogen ,+5.08; Ib, wherein R is a fluorine ,+5.01; Ib, wherein R is a fluorine ,+5.02; Ib, wherein R is a fluorine ,+5.03; Ib, wherein R is a fluorine ,+5.04; Ib, wherein R is a fluorine ,+5.05; Ib, wherein R is a fluorine ,+5.06; Ib, wherein R is a fluorine ,+5.07; Ib, wherein R is a fluorine ,+5.08; Ia+6.03; Ib, wherein R is a hydrogen ,+6.03; Ib, wherein R is a fluorine ,+6.03; Ia+7.01; Ia+7.02; Ia+7.03; Ia+7.04; Ib, wherein R is a hydrogen ,+7.01; Ib, wherein R is a hydrogen ,+7.02; Ib, wherein R is a hydrogen ,+7.03; Ib, wherein R is a hydrogen ,+7.04; Ib, wherein R is a fluorine ,+7.01; Ib, wherein R is a fluorine ,+7.02; Ib, wherein R is a fluorine ,+7.03; And Ib, wherein R is a fluorine ,+7.04.
10. the method for Selective Control weeds and gramineous plants in a useful crop comprises simultaneously or handles useful plant, its seed or plant propagation material or its growth district with the formula Ia of activity of weeding amount and/or the formula II safener of Ib and/or Ic weed killer herbicide and weeding antagonistic activity amount separately.
11. according to the method for claim 10, wherein useful crop or its growth district 0.001-2kg/ha formula Ia and/or Ib and/or Ic weed killer herbicide and the processing of 0.001-0.5kg/ha formula II safener.
12. according to the method for claim 10, wherein useful crop is cereal crop or paddy rice.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH3314/95 | 1995-11-23 | ||
| CH331495 | 1995-11-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1202800A true CN1202800A (en) | 1998-12-23 |
Family
ID=4253318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96198501A Pending CN1202800A (en) | 1995-11-23 | 1996-11-11 | Herbicidal composition |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0863708A1 (en) |
| CN (1) | CN1202800A (en) |
| AR (1) | AR004736A1 (en) |
| AU (1) | AU719770B2 (en) |
| EA (1) | EA001418B1 (en) |
| WO (1) | WO1997018712A1 (en) |
| ZA (1) | ZA969798B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103392721A (en) * | 2013-06-30 | 2013-11-20 | 广东中迅农科股份有限公司 | Weeding composition containing cyclosulfamuron and pyriminobac-methyl |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19638233A1 (en) * | 1996-09-19 | 1998-03-26 | Hoechst Schering Agrevo Gmbh | Combinations of sulfonylurea herbicides and safeners |
| US6376424B1 (en) | 1998-01-21 | 2002-04-23 | Syngenta Crop Protection, Inc. | Herbicidal composition |
| SG10201913603QA (en) | 2014-10-06 | 2020-02-27 | Vertex Pharma | Modulators of cystic fibrosis transmembrane conductance regulator |
| PL3436446T3 (en) | 2016-03-31 | 2023-09-11 | Vertex Pharmaceuticals Incorporated | Modulators of cystic fibrosis transmembrane conductance regulator |
| LT3519401T (en) | 2016-09-30 | 2021-11-25 | Vertex Pharmaceuticals Incorporated | Modulator of cystic fibrosis transmembrane conductance regulator, pharmaceutical compositions, methods of treatment, and process for making the modulator |
| US10793547B2 (en) | 2016-12-09 | 2020-10-06 | Vertex Pharmaceuticals Incorporated | Modulator of the cystic fibrosis transmembrane conductance regulator, pharmaceutical compositions, methods of treatment, and process for making the modulator |
| AU2018279646B2 (en) | 2017-06-08 | 2023-04-06 | Vertex Pharmaceuticals Incorporated | Methods of treatment for cystic fibrosis |
| CA3069226A1 (en) | 2017-07-17 | 2019-01-24 | Vertex Pharmaceuticals Incorporated | Methods of treatment for cystic fibrosis |
| CN111051280B (en) | 2017-08-02 | 2023-12-22 | 弗特克斯药品有限公司 | Process for preparing pyrrolidine compounds |
| CA3078893A1 (en) | 2017-10-19 | 2019-04-25 | Vertex Pharmaceuticals Incorporated | Crystalline forms and compositions of cftr modulators |
| JP7245834B2 (en) | 2017-12-08 | 2023-03-24 | バーテックス ファーマシューティカルズ インコーポレイテッド | A process for creating modulators of cystic fibrosis transmembrane conductance regulators |
| TWI810243B (en) | 2018-02-05 | 2023-08-01 | 美商維泰克斯製藥公司 | Pharmaceutical compositions for treating cystic fibrosis |
| US11414439B2 (en) | 2018-04-13 | 2022-08-16 | Vertex Pharmaceuticals Incorporated | Modulators of cystic fibrosis transmembrane conductance regulator, pharmaceutical compositions, methods of treatment, and process for making the modulator |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3600288A1 (en) * | 1986-01-08 | 1987-07-16 | Bayer Ag | USE OF AMIDES FOR IMPROVING THE CROP PLANT TOLERABILITY OF HERBICIDE-ACTIVE SULFONYL URINE DERIVATIVES |
| US5225570A (en) * | 1987-08-13 | 1993-07-06 | Monsanto Company | 5-heterocyclic-substituted oxazolidine dihaloacetamides |
| US5009699A (en) * | 1990-06-22 | 1991-04-23 | American Cyanamid Company | 1-{[O-(cyclopropylcarbonyl)phenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)urea herbicidal composition and use |
| ZA917435B (en) * | 1990-09-26 | 1992-05-27 | Takeda Chemical Industries Ltd | Herbicides |
| EP0492366B1 (en) * | 1990-12-21 | 1997-03-26 | Hoechst Schering AgrEvo GmbH | New 5-chloroquinolin-8-oxyalkanecarbonic acid derivatives, process for their preparation and their use as antidotes for herbicides |
| ES2194629T3 (en) * | 1990-12-21 | 2003-12-01 | Bayer Cropscience Gmbh | BLENDS OF HERBICIDES AND ANTIDOTES. |
| CZ284541B6 (en) * | 1991-03-07 | 1998-12-16 | E.I. Du Pont De Nemours And Company | Methyl-2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-amino]sulfonyl] -6-(trifluormethyl)-3-pyridinecarboxylate, agriculturally suitable preparation containing thereof and compound useful as intermediate |
| DE4123469A1 (en) * | 1991-07-16 | 1993-01-21 | Basf Ag | Herbicidal compsns. contg. safener - comprising N-di:chloro-acetyl-di:aza-cycloalkane deriv. |
| EP0558448A1 (en) * | 1992-02-26 | 1993-09-01 | Ciba-Geigy Ag | 1,5-diphenylpyrazole-3-carboxylic acid derivatives as antidotes for sulfonylurea herbicides |
| WO1994000987A2 (en) * | 1992-07-08 | 1994-01-20 | Ciba-Geigy Ag | Selective herbicidal composition |
| EP0597807A1 (en) * | 1992-11-12 | 1994-05-18 | Ciba-Geigy Ag | Selective herbicidal agent |
| ATE169179T1 (en) * | 1992-12-02 | 1998-08-15 | Ciba Geigy Ag | SELECTIVE HERBICIDES |
| DE4315153A1 (en) * | 1993-05-07 | 1994-11-10 | Hoechst Schering Agrevo Gmbh | Substituted quinoline compounds, processes for their preparation, compositions containing them and their use as safeners |
| DE4323122A1 (en) * | 1993-07-10 | 1995-01-12 | Hoechst Schering Agrevo Gmbh | Herbicide/antidote mixtures |
| US5492884A (en) * | 1994-04-29 | 1996-02-20 | American Cyanamid Company | 1-[2-(cyclopropylcarbonyl)-4-fluorophenyl]sulfamoyl)-3-(4,6-dimethoxy-2-pyrimidinyl) urea and its herbicidal method of use |
-
1996
- 1996-11-11 WO PCT/EP1996/004914 patent/WO1997018712A1/en not_active Application Discontinuation
- 1996-11-11 AU AU75691/96A patent/AU719770B2/en not_active Expired
- 1996-11-11 CN CN96198501A patent/CN1202800A/en active Pending
- 1996-11-11 EA EA199800469A patent/EA001418B1/en not_active IP Right Cessation
- 1996-11-11 EP EP96938166A patent/EP0863708A1/en not_active Withdrawn
- 1996-11-21 AR ARP960105283A patent/AR004736A1/en unknown
- 1996-11-22 ZA ZA969798A patent/ZA969798B/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103392721A (en) * | 2013-06-30 | 2013-11-20 | 广东中迅农科股份有限公司 | Weeding composition containing cyclosulfamuron and pyriminobac-methyl |
| CN103392721B (en) * | 2013-06-30 | 2016-12-28 | 广东中迅农科股份有限公司 | Containing AC322140 and the Herbicidal combinations of KIH 6127 |
Also Published As
| Publication number | Publication date |
|---|---|
| AR004736A1 (en) | 1999-03-10 |
| AU719770B2 (en) | 2000-05-18 |
| WO1997018712A1 (en) | 1997-05-29 |
| EP0863708A1 (en) | 1998-09-16 |
| EA001418B1 (en) | 2001-02-26 |
| EA199800469A1 (en) | 1998-12-24 |
| AU7569196A (en) | 1997-06-11 |
| ZA969798B (en) | 1997-07-21 |
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