CN1658758A - Herbicidal composition - Google Patents

Herbicidal composition Download PDF

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Publication number
CN1658758A
CN1658758A CN 03812931 CN03812931A CN1658758A CN 1658758 A CN1658758 A CN 1658758A CN 03812931 CN03812931 CN 03812931 CN 03812931 A CN03812931 A CN 03812931A CN 1658758 A CN1658758 A CN 1658758A
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little less
formula
compound
variant
medium
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E·劳尔斯
C·L·邓恩
M·D·约翰逊
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Syngenta Participations AG
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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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Selectively herbicidal composition for controlling grasses and weeds in crops of useful plants, comprising a) a herbicidally effective amount of a compound of formula (I), wherein M is an alkali metal or alkaline earth metal; n is 1 or 2; r and s are each independently of the other 0, [1/2], 1, 1[1/2], 2, 2[1/2] or 3; and L is ethyl acetate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, Nmethyl-2-pyrrolidone, acetone, butanone, methylene chloride, trichloromethane, trichloroethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, chlorobenzene, toluene or xylene, and b) a herbicide-antagonistically effective amount of a compound of formula (II), wherein R1 is chlorine, methoxy or methylthio, R2 is ethyl or isopropyl and R3 is ethyl, isopropyl, -C(CN)(CH3)-CH3 or tert-butyl.

Description

Herbicidal composition
The present invention relates to the new selective herbicidal composition and use weeds in this composition for preventing and controlling crop; said composition is used for preventing and treating crop particularly cotton, sugarcane and paddy rice gramineous plants and weeds; it comprises weed killer herbicide and safener (counteragent; antipoison), and cover crop avoid the vegetable poison effect of weed killer herbicide but do not protect weeds.
Use weed killer herbicide to produce very major injury to weeds, but under certain conditions for example according to concentration, the using method of weed killer herbicide, cultivate crop, soil property and weather conditions such as light application time, temperature and deposition, such injury is also to the farming crop.In order to eliminate these and similar problem; advised using all cpds as safener antagonism weed killer herbicide to cultivating the injury effect of crop; that is to say to protect and cultivate the injury effect that crop avoids weed killer herbicide, but weed killer herbicide is not to being affected basically by the injury effect of controlling weeds.The safener that has been found that suggestion all has very single-minded effect to cultivating crop and weed killer herbicide, certainly application method is also depended in so single-minded effect sometimes, and a kind of in other words safener mostly just is applicable to a kind of specific crop and specific weed killer herbicide or a kind of specific weed killer herbicide of a class of cultivating.
Have been found that known some compound in triazine class at present now, under low formulation rate, be specially adapted to protect some sulfonylurea herbicide cultivating the phytotoxicity effect of crop with good herbicidal effect.
Obtain from US-A-6 180 563, such triaizine compounds and sulfonylureas mix weed killer herbicide are produced synergistic effect, that is to say add sulfonylureas behind the triazine herbicide to the herbicidal effects of weeds obtain super add and increase.
Therefore, very surprisingly such triaizine compounds can be used as the safener of some sulfonylurea herbicide under no herbicide effect dosage.
According to the present invention, a kind of selectivity herbicide composition is provided, it also comprises the following mixture as active component except containing the conventional inert formulation assistant agent such as carrier, solvent and wetting agent that uses
A) the formula I weed killer herbicide of weeding effect amount,
Figure A0381293100041
Wherein
M is alkali metal or alkaline earth metal;
N is 1 or 2;
R and s are 0 independently of one another, 1/ 2, 1,1 1/ 2, 2,2 1/ 2Perhaps 3; With
L is ethyl acetate, acetonitrile, methyl-sulfoxide, dimethyl formamide, dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-, acetone, butanone, carrene, chloroform, trichloroethanes, oxolane, ether, 1,2-dimethoxy-ethane, dioxane, methyl tertiary butyl ether(MTBE), chlorobenzene, toluene or dimethylbenzene and
B) the formula II compound of weed killer herbicide antagonism effective dose
R wherein 1Be chlorine, methoxyl group or methyl mercapto, R 2Be ethyl or isopropyl and R 3For ethyl, isopropyl ,-C (CN) (CH 3)-CH 3The perhaps tert-butyl group.
M represents alkali metal or alkaline earth metal in the context of the present invention, is preferably sodium, potassium, magnesium or calcium.The present invention includes the crystal modification that all can be formed by formula I compound.
For the present composition, preferred formula I compound be those wherein L be the composition of dioxane, oxolane or water.Also preferably wherein n be 1, M especially is the formula I compound of sodium.
Formula I compound preferably also, wherein M be that sodium, n are 1, r be 0 and s be 0.
The method according to this invention, also pay special attention to be wherein M be that sodium, n are 1, r be 0 and s be 0 the compound amorphous shape solid of formula I, this amorphous solid can be used to prepare other crystal modification, as the C variant.
For the individualized compound in the formula I scope, especially be preferred for compound in the present composition and can mention and be selected from these following compounds:
A) wherein M is a sodium, n is 1, r be 0 and s be 1 formula I compd B variant, X ray powder figure be characterized as d ()/intensity: 10.0/ is medium; 9.2/ it is strong; 8.6/ very; 8.1/ a little less than; 7.2/ it is strong; 6.9/ it is strong; 6.4/ it is medium; 5.82/ it is strong; 5.75/ it is strong; 5.64/ it is very strong; 5.53/ very; 5.13/ it is medium; 4.97/ it is very strong; 4.65/ it is medium; 4.30/ it is very strong; 4.22/ a little less than; 4.15/ very; 4.02/ a little less than; 3.94/ a little less than; 3.79/ it is medium; 3.73/ a little less than; 3.68/ it is medium; 3.61/ a little less than; 3.58/ a little less than; 3.52/ it is very strong; 3.42/ very; 3.37/ a little less than; 3.31/ very; 3.27/ very; 3.23/ a little less than; 3.18/ it is medium; 3.08/ very; 3.03/ very; 2.95/ very; 2.87/ it is strong; 2.82/ very; 2.79/ very; 2.73/ very; 2.68/ very; 2.65/ very; 2.63/ very; 2.60/ a little less than; 2.57/ a little less than.
B) wherein M be that sodium, n are 1, L be oxolane, r be 1/2 and s be 0 formula I compound J variant, X ray powder figure be characterized as d ()/intensity: a little less than in the of 15.7/; 10.2/ it is very strong; 8.2/ a little less than; 7.8/ a little less than; 7.3/ a little less than; 6.7/ a little less than; 6.5/ very; 6.2/ it is medium; 5.64/ very; 5.53/ a little less than; 5.42/ a little less than; 5.09/ a little less than; 4.96/ it is medium; 4.86/ very; 4.60/ it is medium; 4.37/ it is medium; 4.24/ a little less than; 4.1/ it is very strong; 3.95/ very; 3.90/ a little less than; 3.81/ very; 3.71/ it is medium; 3.62/ a little less than; 3.52/ very; 3.43/ it is strong; 3.37/ a little less than; 3.32/ very; 3.27/ a little less than; 2.94/ very; 2.82/ it is medium;
C) wherein M be that sodium, n are 1, r be 0 and s be 0 formula I compound K variant, X ray powder figure be characterized as d ()/intensity: a little less than in the of 13.4/; 10.1/ very; 9.3/ it is very strong; 7.8/ a little less than; 6.9/ very; 6.7/ very; 5.63/ very; 5.35/ it is medium; 4.66/ a little less than; 4.44/ very; 4.35/ a little less than; 4.12/ it is strong; 3.94/ it is strong; 3.87/ very; 3.76/ a little less than; 3.61/ it is medium; 3.49/ very; 3.40/ very;
D) wherein M be that sodium, n are 1, r be 0 and s be 1 formula I Compound C variant, X ray powder figure be characterized as d ()/intensity: 13.1/ is medium; 11.0/ it is very strong; 8.8/ a little less than; 7.7/ it is very strong; 7.2/ it is very strong; 7.0/ a little less than; 6.4/ a little less than; 6.2/ it is strong; 5.96/ a little less than; 5.90/ a little less than; 5.64/ it is strong; 5.47/ a little less than; 5.34/ it is medium; 5.19/ a little less than; 4.79/ a little less than; 4.74/ it is medium; 4.64/ very; 4.55/ it is strong; 4.47/ a little less than; 4.35/ it is strong; 4.26/ it is medium; 4.13/ a little less than; 4.06/ very; 3.92/ it is very strong; 3.87/ a little less than; 3.79/ it is very strong; 3.67/ a little less than; 3.61/ it is medium; 3.58/ it is strong; 3.47/ a little less than; 3.32/ very; 3.24/ it is medium; 3.14/ a little less than; 3.12/ a little less than; 3.07/ a little less than; 3.04/ it is strong; 2.97/ very; 2.92/ very; 2.88/ a little less than; 2.82/ a little less than; 2.77/ very; 2.74/ very; 2.69/ a little less than; 2.66/ very; With
E) wherein M be that sodium, n are 1, L be oxolane, r be 1 and s be 1 formula I Compound I variant, X ray powder figure be characterized as d ()/intensity: a little less than in the of 11.6/; 9.8/ very; 8.0/ it is very strong; 7.6/ it is medium; 6.7/ it is strong; 6.4/ very; 6.3/ a little less than; 6.1/ very; 5.80/ it is medium; 5.66/ very; 5.47/ it is strong; 5.12/ very; 5.08/ very; 4.84/ very; 4.76/ a little less than; 4.47/ it is strong; 4.40/ a little less than; 4.21/ it is medium; 4.19/ it is medium; 4.15/ very; 4.00/ very; 3.93/ very; 3.84/ it is medium; 3.72/ it is very strong; 3.58/ it is medium; 3.52/ it is medium; 3.32/ very; 3.28/ very; 3.25/ very; 3.11/ very; 3.07/ very; 2.95/ very; 2.86/ a little less than; 2.82/ very; 2.75/ very; 2.57/ a little less than; 2.49/ very.
Preferred compound is as follows in addition:
A) wherein M be that sodium, n are 1, r be 0 and s be 0 formula K Compound I variant, it by dry wherein M in 35 ℃ of-65 ℃ of vacuum be that sodium, n are 1, L be oxolane, r be 1/2 and s be that 0 formula I compound (J variant) makes;
B) wherein M be that sodium, n are 1, r be 0 and s be 1 formula I Compound C variant, by following method preparation:
I) be that 98% air contacts with essentially amorphous compound (A variant) and relative moisture, perhaps
Ii) to M wherein be that sodium, n are 1, r be 0 and s add water in 0 the formula I compound K variant, the ratio of water and K variant is 0.1: 1 to 0.4: 1, separates and is 30-90 ℃ in temperature, pressure is 0.01 to the 0.1 crust product of dry gained down;
C) wherein M is a sodium, n is 1, r be 0 and s be 1 formula I compd B variant, it is sodium by adding water to M wherein, n is 1 and L, prepare in r and s the formula I compound suc as formula the I definition, the ratio of water and compound is 0.5: 1 to 20: 1, after filtration, being 30-90 ℃ in temperature is dry filter residue under 0.01 to 0.1 crust with pressure, be sodium to M wherein preferably perhaps by adding water, n is 1, L is an oxolane, r be 1/2 and s be preparation in 0 the formula I compound (K variant), perhaps adding water is sodium to M wherein, n is 1, L is an oxolane, r be 1/2 and s be preparation in 0 the formula I compound (J variant), perhaps adding water is sodium to M wherein, n is 1, L is an oxolane, r be 1 and s be preparation in 1 the formula I compound (I variant), perhaps adding water is sodium to M wherein, n is 1, r be 0 and s be preparation in 1 the formula I compound (C variant), water and K, J, the ratio of I or C variant is 0.5: 1 to 20: 1, after filtration, being 30-90 ℃ in temperature is dry filter residue under 0.01 to 0.1 crust with pressure.
The formula II compound that is particularly preferred for the present composition is atrazine, Garagard, Simanex, prometryn, terbutryn, cyanazine and ametryn, and particularly preferred is prometryn.Each can combine these formulas II compound with the crystal modification of the preferred formula I compound of the top conduct of mentioning especially, obtains particularly advantageous weeding selectivity composition.According to the present invention, particularly preferred composition is that those wherein M that comprise as formula I compound are that sodium, n are 1, r be 0 and s be 0 formula I compound, the perhaps J of formula I compound or K crystal modification and as the composition of the prometryn of formula II compound.
According to conventional methods, but formula I compound passing type II compound
At ethyl acetate, acetonitrile, methyl-sulfoxide, dimethyl formamide, dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-, acetone, butanone, carrene, chloroform, trichloroethanes, oxolane, ether, 1, in 2-dimethoxy-ethane, dioxane, methyl tertiary butyl ether(MTBE), chlorobenzene, toluene or the dimethylbenzene, with formula V compound prepared in reaction
Figure A0381293100072
Wherein M is suc as formula defining among the I.
The reaction temperature of formula IIa compound and formula III compound is-20 ℃ to 180 ℃, is preferably 30 ℃ to 80 ℃; Formula IIa uses with identical equivalent with the formula III compound, but excessive slightly isocyanates may be favourable.
The preparation of formula IIa initial compounds is existing to be described, for example 067,29 page of EP-A-0232.The formula III compound can be prepared as follows, and for example passes through the water chlorination with formula IV compound
R wherein 1For-CH 2-phenyl or isopropyl,
Be converted into formula V compound
This compound ammonia treatment, gained sulfonamide compounds then with the reaction of 30% sodium methoxide.Such reaction is known, by those skilled in the art is known.
Being prepared as follows of the preferred crystal modification of formula I compound:
For example, wherein M be that sodium, n are 1, L be oxolane, r be 1/2 and s be 0 formula I compound J variant can by under 35-65 ℃ with 4 of 5-25% weight, the solution in 6-dimethoxy-pyrimidine-2-isocyanates anhydrous tetrahydro furan joins in 15-35% weight 3-(the 2-trifluoro ethoxy)-pyridine-solution of sulfonamide sodium salt in anhydrous tetrahydro furan and prepares.
Add 4, behind 6-dimethoxy-pyrimidine-2-isocyanates, stirred reaction mixture is finished up to conversion.This method is preferably carried out under 40-50 ℃ temperature, and gained J variant is separated from reactant mixture by filtering.
Wherein M be that sodium, n are 1, r be 0 and s be being prepared as follows of 0 formula I compound K variant: 35-65 ℃ down will be in anhydrous tetrahydro furan 5-25% weight 4,6-dimethoxy-pyrimidine-2-isocyanate solution joins in 3-(the 2-trifluoro ethoxy)-pyridine-sulfonamide sodium salt suspension of 15-35% weight in anhydrous tetrahydro furan, through filtering, filtration residue (J variant) is drying under 30-90 ℃ and 0.01 to 0.1 bar pressure then.
Add 4, behind 6-dimethoxy-pyrimidine-2-isocyanates, stirred reaction mixture is finished up to conversion.For drying, preferred temperature is that 40-60 ℃ and pressure are the 0.02-0.06 crust in this method.
Wherein M be that sodium, n are 1, r be 0 and s be that the preparation method of 1 formula I Compound C variant is as follows: it is in 98% the air that essentially amorphous compound (A variant) is exposed to relative moisture, perhaps add water to the K variant, the ratio of water and K variant is 0.1: 1 to 0.4: 1, through filtering, filtration residue is drying under 30-90 ℃ and 0.01 to 0.1 bar pressure then.
For the preparation of C variant, the ratio of water and K variant can change in 0.1: 1 to 0.4: 1, ratio be 0.1: 1 to 0.3: 1 for preferred especially.Temperature when adding water is 0-60 ℃, is in particular 5-40 ℃.The drying of C variant is preferably carried out under 40-60 ℃ and 0.02 to 0.06 bar pressure.
The method that makes things convenient for for preparing the C variant in addition; with N-((4; 6-dimethoxy-2-pyrimidine radicals) carbamoyl)-3-(2; 2,2-trifluoro ethoxy)-pyridine-2-sulfuryl amine joins in the sodium hydrate aqueous solution, evaporation and concentration in 50 ℃ of vacuum then; stir the residue of gained with ether; through filtering, ℃ dry down in temperature 〉=120, then the essentially amorphous salt of gained (A variant) is exposed to relative moisture and is in 98% the air.
Wherein M be that sodium, n are 1, L be oxolane, r be 1 and s be that the preparation method of 1 formula I Compound I variant is as follows: 0-30 ℃ down will be in anhydrous tetrahydro furan 5-25% weight 4,6-dimethoxy-pyrimidine-2-isocyanate solution joins in 3-(2-the trifluoro ethoxy)-pyridine sulfonamide sodium salt suspension of 10-35% weight in anhydrous tetrahydro furan, adds the water with respect to 3-(2-trifluoro ethoxy)-pyridine sulfonamide sodium salt 1-20 molar equivalent then.In suc scheme, add the water of 2-5 molar equivalent for especially preferred.
Wherein M be that sodium, n are 1, r be 0 and s be that the preparation method of 1 formula I compd B variant is as follows: with water be added to wherein M be sodium, n be 1 and L, r and s suc as formula in the defined formula I compound of I, the ratio of water and this compound is 0.5: 1 to 20: 1, filter dry filter residue under 30-90 ℃ temperature and 0.01 to 0.1 bar pressure.
Preferred B variant preparation method is as follows: being added to water wherein, M is a sodium, n is 1, r be 0 and s be in 0 the formula I compound (K variant), be sodium perhaps to M wherein, n is 1, L is an oxolane, r be 1/2 and s be in 0 the formula I compound (J variant), be sodium perhaps to M wherein, n is 1, L is an oxolane, r be 1 and s be in 1 the formula I compound (I variant), be sodium perhaps to M wherein, n is 1, r be 0 and s be in 1 the formula I compound (C variant), water and K, J, the ratio of I or C variant is 0.5: 1 to 20: 1, filter, then dry filter residue under 30-90 ℃ and 0.01 to 0.1 bar pressure.
The temperature that adds water can be 0-80 ℃, is preferably 5-40 ℃ especially.The dry filter residue can carry out under 30-90 ℃ and 0.01 to 0.1 bar pressure, and preferred temperature is that 40-60 ℃ and pressure are the 0.02-0.06 crust.Especially advantageously the crystal seed with the B variant joins in the suspension, so that quicken the growth of crystallization.
Formula I compound and their preparation are existing to be described, for example at WO 00/52006.The preparation of formula II compound also has description, for example in " agricultural chemicals handbook the 11st edition, Britain crop protection association, 1997, entry number 34,692,651,693,168 and 20.
The invention still further relates to method for weed in the selectivity control useful plant, this method comprises with the formula II safener while of the formula I compound of herbicidally effective amount and weed killer herbicide antagonism effective dose or the zone of handling useful plant or seed or cutting or farming respectively.
Composition according to the present invention is specially adapted to prevent and treat weeds and non-selective controlling weeds in the useful plant crop, wherein crop such as cereal class, rape, sugar beet, sugarcane, plantation crops, rice, cotton, corn and soybean especially are cotton, sugarcane and rice.
Crop also comprises those by the conventional method breeding or by the gene engineering improvement, to the crop of a kind of weed killer herbicide or class weed killer herbicide generation resistance, as the crop that glyphosate, HPPD inhibitor or ALS-inhibitor are had resistance.
The weeds that prevented and treated can be unifacial leaf and broadleaf weed, as Stellaria, bean cotyledon Lepidium, Agrostis, knotgrass, Avena, setaria, sinapsis alba genus, Lolium, Solanum, Echinochloa, swallow grass genus, Monochoria, arrowhead genus, Brome, amur foxtail genus, stone thatch Chinese sorghum, Rottboellia exaltata L. F genus, Cyperus, abutilon, chrysanthemum harvest spp, Xanthium, Amaranthus, Chenopodium, sweet potato genus, crowndaisy chrysanthemum genus, Bedstraw, Viola and Veronica class weeds.
The zone of farming is understood to include to grow soil that the seed material of the soil of crop or these kinds plant sowed and soil that will these kinds of farming plant.
According to application target, can or be administered in the soil prior to seeding or after planting with the seed material (capsuled seed or cutting) of formula II safener preliminary treatment kind plant, also can emerge the back separately or simultaneously with the weed killer herbicide dispenser crop with formula II safener.Therefore with safener plant or seed material dispenser are independent of the spraying time of weed killer herbicide in principle.But for the processing of plant, weed killer herbicide and safener dispenser simultaneously (mixing method) as bucket.With respect to weed killer herbicide, the formulation rate of safener depends on method of application to a great extent.
Field rotating medicine can adopt the dark compound of bucket that contains safener and weed killer herbicide to carry out, perhaps adopt safener and the weed killer herbicide method of dispenser respectively, the ratio of safener and weed killer herbicide was generally 10: 1 to 1: 100, was in particular 1: 1 to 1: 10, was more particularly 1: 4 to 1: 9.
For the weed killer herbicide of known use, the amount of application of formula II compound be 0.8 to 2.5kg (according to " agricultural chemicals handbook, the 11st edition, the amount of application of prometryn 1997, is recommended by Britain crop protection association).
But, be to use with low many, weeding ineffective dose at composition Chinese style II compound according to the present invention.In general, the amount of field rotating medicine is 0.0005 to 0.01kg/ha according to the present invention, is in particular formula II compound/ha of 0.0005 to 0.007kg, is preferably formula II compound/ha of 0.0005 to 0.005kg.
The formulation rate of weed killer herbicide is generally 0.0005 to 0.05kg/ha, is in particular 0.001 to 0.01kg/ha.
In especially preferred herbicidal composition of the present invention, the dispenser total amount of the compound of formula I and formula II is 0.003 to 0.008kg/ha, especially is 0.004 to 0.0075kg/ha.
Composition according to the present invention is applicable to that all agriculturals go up conventional application methods, as the preceding use of emerging, the back of emerging are used and seed pelleting.Under the situation of seed pelleting, the formulation rate of safener is generally 0.001 to 10g safener/kg seed, especially is 0.05 to 2g safener/kg seed.If safener uses by soaking seed with liquid before being about to sowing, the concentration that contains the dispenser solution of active component safener is 1 to 10000ppm, especially is 100 to 1000ppm.
In the use, the safener of formula II or such safener and the combination of formula I weed killer herbicide, assistant agent advantageously is processed into preparation in conventional formulation technology, for example is processed into missible oil, but the dressing paste, can directly spray or dilute solution, dilute emulsion, wetting powder, soluble powder, pulvis, granule or microcapsule formulations.Such preparation is existing to be described, and for example, is described in the 9-13 page or leaf of WO97/34485.Preparation can be with the preparation of known method, and for example active component and liquid or solid pharmaceutical preparation assistant agent such as solvent or solid carrier fully mix or grind.In addition can also be with surface active cpd (surfactant) in formulation preparation.The solvent and the solid carrier that are suitable for this purpose comprise, for example, and the material that those are mentioned in the 6th page of WO 97/34485.
According to the character of the formula I compound of desiring to be processed into preparation, suitable surfactant is nonionic, cation and/or anion surfactant and the surfactant mixture with well emulsify, dispersiveness and wettability.The example of anion, nonionic and the cationic surfactant that is suitable for is listed in the 7th, 8 pages of WO 97/34485.In addition, the surfactant that uses in the conventional formulation technology particularly is described in " McCutcheon ' s Detergents and EmulsifiersAnnual " MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., " Tensid-Taschenbuch ", Carl Hanser Verlag, Munich/Vienna1981 and M.and J.Ash, " Encyclopedia of Surfactants ", Vol.I-III, Chemical Publishing Co., New York, the surfactant among the 1980-81 also is applicable to the preparation of herbicidal composition of the present invention.
Herbicide formulations generally contains 0.1-99% weight, be in particular the mixture of active principles of 0.1-95% weight, comprise formula II compound and formula I compound, the solid of 1-99.9% weight or liquid preparation assistant agent and 0-25% weight, the particularly surfactant of 0.1-25% weight.Yet the commodity preparation is preferably made concentrate formulation, and terminal user need dilute preparation usually.
Composition can further include other composition, and as vegetable oil or epoxidised vegetable oil (epoxidised cocoa butter, rapeseed oil or soya-bean oil), defoamer is as silicone oil as stabilizing agent, preservative, viscosity modifier, adhesive, tackifier and fertilizer or other active component.Exempt from the injury effect of formula I weed killer herbicide for protection farming crop, can adopt multiple technologies and method to use formula II safener or contain their composition, for example following method:
I) Seed pelleting
A) with the wetting powder capsuled seed of formula II compound, seed and preparation are evenly distributed in the surface (dried dressing) of seed in the vibration container up to preparation.
B) but with the emulsion concentrate capsuled seed of formula II compound, its method such as a) (wet dressing).
C) dressing of dipping seed material, seed soaking is sub-material 1-72 hour in the liquid that contains 100-1000ppm formula II compound, then dry seed (dipping dressing) selectively.
Ii) The mixed dispenser of bucket
(ratio of respective amount is 10: 1-1: the 100) liquid preparation of mixture, the formulation rate of weed killer herbicide are the 0.0005-0.5Kg/ hectare to use antipoison and weed killer herbicide.Bucket like this is mixed in before the sowing or the back dispenser.
Iii) Dispenser in kind of ditch
But the form with emulsion concentrate, wetting powder or granule was sowed formula II dispenser in the sub ditch to opening up wasteland.Cover if plant cunette, use weed killer herbicide with the method for dispenser before the conventional seedling.
Iv) The sustained release of active component
The solution of formula II compound is administered on particulate mineral carrier or the aggregated particles (urea/formaldehyde), drying.If desired, use coating agent (bag is by particle), active component is quantitatively discharged in special time.
Preferred formulation especially has following composition (%=percentage by weight; " mixture of active principles " represents the mixture of formula I compound and formula II compound):
Pulvis:
Mixture of active principles: 0.1-10%, preferred 0.1-5%
Solid carrier: 99.9-90%, preferred 99.9-99%
Suspending 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 carrier: 5-95%, preferred 15-90%
Granule:
Mixture of active principles: 0.1-30%, preferred 0.1-15%
Solid carrier: 99.5-70%, preferred 97-85%
Following embodiment further explains, does not still limit the present invention.
The example of formulations (%=percentage by weight) of formula I weed killer herbicide and formula II safener mixture
F1. emulsifiable concentrateA) d c b)))
Mixture of active principles 5% 10% 25% 50%
Calcium dodecyl benzene sulfonate 6% 8% 6% 8%
Castor oil polyglycol ether 4%-4% 4%
(36 moles of ethylene oxide)
Octyl phenol polyglycol ether-4%-2%
(7-8 moles of ethylene oxide)
Cyclohexanone--10% 20%
Aromatic hydrocarbons mixture 85% 78% 55% 16%
C 9-C 12
The emulsion of any desired concn can obtain by the such concentrate of thin up.
F2. solutionA) d c b)))
Mixture of active principles 5% 10% 50% 90%
1-methoxyl group-3--20% 20%-
(the 3-methoxyl group-
Propoxyl group)-propane
Polyethylene glycol MW 400 20% 10%--
N-N-methyl-2-2-pyrrolidone N---30% 10%
Aromatic hydrocarbons mixture 75% 60%--
C 9-C 12
Described solution is applicable to the form of droplet and uses.
F3. wetting powderA) d c b)))
Mixture of active principles 5% 25% 50% 80%
Sodium lignosulfonate 4%-3%-
Lauryl sodium sulfate 2% 3%-4%
Diisobutyl sodium naphthalene sulfonate-6% 5% 6%
Octyl phenol polyglycol ether-1% 2%-
(7-8 moles of ethylene oxide)
High dispersive silicic acid 1% 3% 5% 10%
Kaolin 88% 62% 35%-
Active component fully mixes with assistant agent, and mixture fully grinds on suitable mill, and the wetting powder dilute with water of formation obtains the suspension of any desired concn.
F4. wrap by granuleA) c b))
Mixture of active principles 0.1% 5% 15%
Polymolecularity silicic acid 0.9% 2% 2%
Inorganic carrier 99.0% 93% 83%
(diameter 0.1-1mm)
As calcium carbonate or silica
Active component is dissolved in the carrene, and this solution is sprayed on the carrier, then solvent is evaporated in a vacuum.
F.5 wrap by granuleA) c b))
Mixture of active principles 0.1% 5% 15%
Polyethylene glycol MW 200 1.0% 2% 3%
Polymolecularity silicic acid 0.9% 1% 2%
Inorganic carrier 98.0% 92% 80%
(diameter 0.1-1mm)
As calcium carbonate or silica
In blender, the active component of fine gtinding is applied to equably with on the moistening carrier of polyethylene glycol.Obtain not having the dust bag in this way by granule.
F.6 extrude granuleA) d c b)))
Mixture of active principles 0.1% 3% 5% 15%
Sodium lignosulfonate 1.5% 2% 3% 4%
Carboxymethyl cellulose 1.4% 2% 2% 2%
Kaolin 97.0% 93% 90% 79%
Active component mixes with assistant agent and grinds, and the mixture water is moistening.The mixture that obtains is through extruding, and is dry in air flow then.
F.7 pulvisA) c b))
Mixture of active principles 0.1% 1% 5%
Talcum powder 39.9% 49% 35%
Kaolin 60.0% 50% 60%
Active component mixes with carrier, and milled mixtures is promptly used pulvis in suitable mill.
F.8 concentrating agents suspendsA) d c b)))
Mixture of active principles 3% 10% 25% 50%
1,2 ethylene glycol 5% 5% 5% 5%
Nonyl phenol polyglycol ether-1% 2%-
(15 moles of ethylene oxide)
Sodium lignosulfonate 3% 3% 4% 5%
Carboxymethyl cellulose 1% 1% 1% 1%
37% formalin 0.2% 0.2% 0.2% 0.2%
Silicone oil emulsion 0.8% 0.8% 0.8% 0.8%
Water 87% 79% 62% 38%
The active component of fine gtinding fully mixes with assistant agent, forms suspending concentrate, obtains the suspension of any desired concn through dilute with water.
Practical operation often is that formula I compound and formula II are made preparation respectively, before being about to dispenser, with the form of " the mixed thing of bucket " both is mixed with needed ratio in giver then.
Embodiment F 9: the preparation of the granular water-dispersible agent of formula I compound:
Following material is mixed together, and grinds with getting mill on the market then:
75% formula I compound crystal modification A
4% nekal salt
8% sodium lignosulfonate
0.5% silicone defoamer
Add silica to 100%
Add 22-26% weight water then in mixture, carry out granulating.Be used in be dried to residual moisture content＜4.5% in the continuous drier that can get on the market after, it is 0.4-1.6mm that the particle of formation is sieved to (vibration and travelling sieve) particle size with sieve, obtains containing the granule of the formula I compound of crystal modification C form.
Embodiment F 10: the preparation of the granular water-dispersible agent of formula I compound:
Following material is mixed together, and grinds with obtaining mill on the market then:
75% formula I compound crystal variant B
4% nekal salt
8% sodium lignosulfonate
0.5% silicone defoamer
Add silica to 100%
Add 18-20% weight water then in mixture, carry out granulating.After being used in the continuous drier that can get on the market and being dried to residual moisture content＜4.5%, it is 0.4-1.6mm that the particle of formation is sieved to (vibration and travelling sieve) particle size with sieve, obtains containing the granule of the crystal modification B of formula I compound.
Embodiment F 11: the preparation of the granular water-dispersible agent of formula I compound:
Following material is mixed together, and grinds with obtaining mill on the market then:
75% formula I compound crystal variant K
4% nekal salt
8% sodium lignosulfonate
0.5% silicone defoamer
Add silica to 100%
Add 43-48% weight water then in mixture, carry out granulating.Be used in the continuous drier that can get on the market and be dried to residual moisture content＜4.5%, it is 0.4-1.6mm that the particle of formation is sieved to (vibration and travelling sieve) particle size with sieve, obtains containing the granule of the mixture of the crystal modification B of formula I compound and variant C.
The preparation embodiment of preparation I compound:
Embodiment P1: prepare wherein M and be sodium, n and be 1, L is that oxolane, r are1/2 And s Be 0 formula I compound (J variant):
Will be under 40-45 ℃ at the 40g 4 in the 300g oxolane (anhydrous), 6-dimethoxy-pyrimidine-2-isocyanate solution is added in 59g 3-(the 2-trifluoro ethoxy)-pyridine-suspension of sulfonamide sodium salt in the 210g anhydrous tetrahydro furan.Reactant mixture stirs down at 40 ℃ then and finishes up to conversion.Obtain the J variant through filtration and anhydrous tetrahydro furan washing at last.
Table R1: the X ray powder figure of variant J:
2 θ (degree) D () Intensity
5.6 a little less than in the of 15.7
8.6 10.2 is very strong
10.7 a little less than in the of 8.2
11.3 a little less than in the of 7.8
12.1 a little less than in the of 7.3
13.1 a little less than in the of 6.7
13.6 6.5 very a little less than
14.4 6.2 is medium
15.7 5.64 very a little less than
16.0 a little less than in the of 5.53
16.3 a little less than in the of 5.42
17.4 a little less than in the of 5.09
17.9 4.96 is medium
18.2 4.86 very a little less than
19.3 4.60 is medium
20.3 4.37 is medium
21.0 a little less than in the of 4.24
21.6 4.24 is very strong
22.5 3.95 very a little less than
22.8 a little less than in the of 3.90
23.3 3.81 very a little less than
24.0 3.71 is medium
24.5 a little less than in the of 3.62
25.3 3.52 very a little less than
26.0 the last 3.43
26.4 a little less than in the of 3.37
26.8 3.32 very a little less than
27.3 a little less than in the of 3.27
30.4 2.94 very a little less than
31.7 2.82 is medium
Embodiment P2: prepare M wherein and be sodium, n and be 1, r be 0 and s be 0 formula I chemical combination Thing (K variant):
Under 60 ℃ and 0.04 bar pressure, the dry J variant that obtains from embodiment P1 forms the K variant.This crystalline solid is anhydrous and solvent-free: thermogravimetric analysis shows that working as temperature reaches 175 ℃ of losses in weight less than 0.1% weight.
Table R2: the X ray powder figure of variant K:
2 θ (degree) D () Intensity
6.6 a little less than in the of 13.4
8.8 10.1 very a little less than
9.5 9.3 is very strong
11.4 a little less than in the of 7.8
12.9 6.9 very a little less than
13.3 6.7 very a little less than
15.7 5.63 very a little less than
16.6 5.35 is medium
19.0 a little less than in the of 4.66
20.0 4.44 very a little less than
20.4 a little less than in the of 4.35
21.5 the last 4.12
22.6 the last 3.94
22.9 3.87 very a little less than
23.7 a little less than in the of 3.76
24.6 3.61 is medium
25.5 3.49 very a little less than
26.2 3.40 very a little less than
Embodiment P3: prepare wherein M and be sodium, n and be 1, L be oxolane, r be 1 and s be 1 Formula I compound (I variant):
Under 25 ℃, will be at the 19.9g 4 in the 350g oxolane (anhydrous), 6-dimethoxy-pyrimidine-2-isocyanate solution is added in 34.2g 3-(the 2-trifluoro ethoxy)-pyridine-suspension of sulfonamide sodium salt in the 200ml anhydrous tetrahydro furan.Reactant mixture stirs down at 25 ℃ then and finishes up to conversion.Add 10g water then, stirred the mixture 18 hours.Obtain the I variant through filtration and anhydrous tetrahydro furan washing at last.
Table R3: the X ray powder figure of variant I:
2 θ (degree) D () Intensity
7.6 a little less than in the of 11.6
9.0 9.8 very a little less than
11.0 8.0 is very strong
11.6 7.6 is medium
13.3 the last 6.7
13.7 6.4 very a little less than
14.0 a little less than in the of 6.3
14.4 6.1 very a little less than
15.3 5.80 is medium
15.6 5.66 very a little less than
16.2 the last 5.47
17.3 5.12 very a little less than
17.4 5.08 very a little less than
18.3 a little less than in the of 4.84
18.6 a little less than in the of 4.76
19.8 the last 4.47
20.1 a little less than in the of 4.40
21.1 4.21 is medium
21.2 4.19 is medium
21.4 4.15 very a little less than
22.2 4.00 very a little less than
22.6 3.93 very a little less than
23.2 3.84 is medium
23.9 3.72 is very strong
24.8 3.58 is medium
25.3 3.52 is medium
26.9 3.32 very a little less than
27.2 3.28 very a little less than
27.5 3.25 very a little less than
28.7 3.11 very a little less than
29.0 3.07 very a little less than
30.2 2.95 very a little less than
31.2 a little less than in the of 2.86
31.7 2.82 very a little less than
32.6 2.75 very a little less than
34.9 a little less than in the of 2.57
36.0 2.49 very a little less than
Embodiment P4: prepare M wherein and be sodium, n and be 1, r be 0 and s be 1 formula I compound (B Variant):
Be suspended in the 230g water 15 minutes according to the 100g K variant of embodiment P2 preparation, preferably inoculate the crystal seed of 1-3g B variant then, finish up to conversion, optionally obtain the B variant at 20-25 ℃ of following stirred suspension.Suspension after filtration, the dry filter residue is to weight under 60 ℃ and 0.04 bar pressure.
Table R4: the X ray powder figure of variant B:
2 θ (degree) D () Intensity
8.9 10.0 is medium
9.6 the last 9.2
10.3 8.6 very a little less than
11.0 a little less than in the of 8.1
12.2 the last 7.2
12.9 the last 6.9
13.8 6.4 is medium
15.2 the last 5.82
15.4 the last 5.75
15.7 5.64 is very strong
16.0 5.53 very a little less than
17.3 5.13 is medium
17.8 4.97 is very strong
19.1 4.65 is medium
20.6 4.30 is very strong
21.0 a little less than in the of 4.22
21.4 4.15 very a little less than
22.1 a little less than in the of 4.02
22.5 a little less than in the of 3.94
23.4 3.79 is medium
23.8 a little less than in the of 3.73
24.2 3.68 is medium
24.6 a little less than in the of 3.61
24.8 a little less than in the of 3.58
25.3 3.52 is very strong
26.0 3.42 very a little less than
26.4 a little less than in the of 3.37
26.9 3.31 very a little less than
27.3 3.27 very a little less than
27.6 a little less than in the of 3.23
28.0 3.18 is medium
28.9 3.08 very a little less than
29.4 3.03 very a little less than
30.3 2.95 very a little less than
31.2 the last 2.87
31.7 2.82 very a little less than
32.1 2.79 very a little less than
32.7 2.73 very a little less than
33.4 2.68 very a little less than
33.8 2.65 very a little less than
34.0 2.63 very a little less than
34.5 a little less than in the of 2.60
34.9 a little less than in the of 2.57
Crystal form A, C, F, I and J can also be converted into the B variant with similar method, these crystal formations can be still wetting by solvent institute.The content of water may some increase in this case.
Embodiment P5: prepare M wherein and be sodium, n and be 1, r be 0 and s be 0 formula I compound (C Variant):
100g K variant according to embodiment P2 preparation mixed 3 hours with 20g water, then drying under 60 ℃ and 0.04 bar pressure.
Table R5: the X ray powder figure of variant C:
2 θ (degree) D () Intensity
6.7 13.1 is medium
8.1 11.0 is very strong
10.1 a little less than in the of 8.8
11.4 7.7 is very strong
12.2 7.2 is very strong
12.7 a little less than in the of 7.0
13.9 a little less than in the of 6.4
14.3 the last 6.2
14.9 a little less than in the of 5.96
15.0 a little less than in the of 5.90
15.7 the last 5.64
16.2 a little less than in the of 5.47
16.6 5.34 is medium
17.1 a little less than in the of 5.19
18.5 a little less than in the of 4.79
18.7 4.74 is medium
19.1 4.64 very a little less than
19.5 the last 4.55
19.9 a little less than in the of 4.47
20.4 the last 4.35
20.8 4.26 is medium
21.5 a little less than in the of 4.13
21.9 4.06 very a little less than
22.7 3.92 is very strong
23.0 a little less than in the of 3.87
23.5 3.79 is very strong
24.2 a little less than in the of 3.67
24.6 3.61 is medium
24.9 the last 3.58
25.7 a little less than in the of 3.47
26.9 3.32 very a little less than
27.5 3.24 is medium
28.4 a little less than in the of 3.14
28.6 a little less than in the of 3.12
29.1 a little less than in the of 3.07
29.3 the last 3.04
30.1 2.97 very a little less than
30.6 2.92 very a little less than
31.0 a little less than in the of 2.88
31.7 a little less than in the of 2.82
32.3 2.77 very a little less than
32.7 2.74 very a little less than
33.3 a little less than in the of 2.69
33.7 2.66 very a little less than
Embodiment P6: prepare M wherein and be sodium, n and be 1, r be 0 and s be 0 unformed substantially formula I compound (A variant):
Under 20 ℃, N-((4,6-dimethoxy-2-pyrimidine radicals) carbamoyl)-3-(2,2, the 2-trifluoro ethoxy)-pyridine-2-sulfuryl amine of 1.56g is added in the sodium hydrate aqueous solution of 40ml 0.1N.Reaction mixture stirred 18 hours down at 20 ℃.After evaporation and concentration in 50 ℃ of vacuum, the residue of gained stirs and filters with ether.Dried filtrate obtains the A variant under rising temperature (＞120 ℃).
Embodiment P7: from the A variant, prepare M wherein and be sodium, n and be 1, r be 0 and s be 0 formula I Compound (C variant):
Under 20 ℃, it is in 98% the air 4 hours that the crystallization of A variant is exposed to relative moisture, obtains the C variant, and the crystallography data are shown in embodiment P5.
Embodiment P8: prepare wherein M and be sodium, n and be 1, r is 2, L is that dioxane and s are 0 formula I compound (G variant):
The for example A variant 15g according to embodiment P6 preparation is being stirred 2 under 20 ℃ in the 85g dioxane 1/ 2My god, filtering mixt then.Through filtering, the filtration residue of gained is the G variant, and the X-ray crystallography data are given as table R8:
Table R8: the X ray powder figure of variant G:
2 θ (degree) D () Intensity
5.8 the last 15.3
7.0 12.7 very a little less than
8.4 a little less than in the of 10.5
11.1 7.9 is medium
12.8 6.9 is medium
13.4 6.6 very a little less than
14.3 6.2 is very strong
14.9 5.96 is medium
17.4 5.08 is medium
17.8 a little less than in the of 4.98
18.3 4.84 is medium
19.3 4.60 is medium
19.7 4.51 is medium
19.8 4.47 very a little less than
20.8 a little less than in the of 4.27
21.0 4.23 is medium
22.3 3.98 is medium
22.7 3.91 is medium
23.3 a little less than in the of 3.81
23.9 the last 3.71
24.4 3.65 is medium
24.9 a little less than in the of 3.57
25.4 3.50 is medium
26.2 3.39 very a little less than
26.7 a little less than in the of 3.33
28.9 3.08 very a little less than
29.5 3.02 very a little less than
30.5 a little less than in the of 2.93
Embodiment P9: prepare wherein M and be sodium, n and be 1, r is 1, L is that dioxane and s are 0 formula I compound (F variant):
Being exposed to relative moisture according to the G variant of embodiment P8 preparation under 20-25 ℃ is in 50% air 8 days, obtains the F variant.
Table R9: the X ray powder figure of variant G:
2 θ (degree) D () Intensity
6.0 14.7 very a little less than
7.0 12.6 very a little less than
8.1 10.9 is medium
11.4 7.8 is medium
12.0 7.4 very a little less than
12.7 a little less than in the of 7.0
13.4 a little less than in the of 6.6
14.3 a little less than in the of 6.2
16.2 the last 5.45
18.0 4.91 is medium
18.4 a little less than in the of 4.83
18.6 4.76 very a little less than
20.8 4.28 very a little less than
21.7 a little less than in the of 4.10
22.2 4.00 very a little less than
23.7 3.75 is very strong
24.7 3.60 very a little less than
X ray powder figure has provided d value (interplanar distance), the X ray reflection of associated described crystal modification and diffraction 2 θ angles (instrument is specific).The mensuration of X ray powder figure is that the Guinier camera FR552 with CuKalphal ray and Enraf-Nonius carries out.The coatings that are recorded on the X-ray film are estimated with Line-Scanner LS-18 and the Scanpi-Software software of Johansson.
The protection I weed killer herbicide of formula II compound acts on following to the phytotoxicity of farming crop
Explain among the embodiment.
Biology embodiment
Embodiment B 1: test behind the seedling:
Under greenhouse experiment, test plants grows into early stage dispenser after-stage (1 to 2 leaf) in basin, and standard soil is as medium.In the seedling later stage, weed killer herbicide is mixed together dispenser on test plants separately or as mixed method of bucket and safener.The optium concentration decision that formulation rate is measured by field or greenhouse.(100% is that plant is all dead to 1 or 2 all post-evaluation result of the tests; 0% is the plant-less toxicity effect).The mixture that uses in this test shows good result.
Prometryn is shown in the following table 1 embodiment of the good protective action of formula Ia compound (N-of J variant form (3-(2-trifluoro ethoxy)-pyridine radicals-2-sulfonyl)-N '-(4,6-dimethoxy-pyrimidine radicals-2-yl)-urea sodium salt):
Crop: cotton
Weeds: IPOHE (pharbitis nilChoisy)
Table 1: prometryn is to the protective action of formula Ia compound
Plant/compound/dosage Cotton ??IPOHE
Formula Ia compound/2.5g/ha ????23 ????-
Prometryn 0.56g/ha ????0 ????-
Formula Ia compound/2.5g/ha+ prometryn 0.56g/ha ????17 ????-
Formula Ia compound/5g/ha ????27 ????85
Formula Ia compound/5g/ha+ prometryn 0.56g/ha ????17 ????83
Table 1 result shows known weed killer herbicide prometryn when formulation rate is 0.56g/ha, and two kinds of test formulation rates of formula Ia compound can both be reduced significantly to the vegetable lamb toxic action.Simultaneously, formula Ia compound only slightly reduces the herbicide effect of test weeds when formulation rate is 5g/ha.This does not have the injury effect of demonstration to cotton down in the test formulation rate prometryn.

Claims (3)

1. the composition of a selective herbicide except comprising conventional inert formulation adjuvant, contains the following mixture as active component
A) the formula I weed killer herbicide of herbicidally effective amount
Figure A038129310002C1
Wherein
M is alkali metal or alkaline earth metal;
N is 1 or 2;
R and s are 0 independently of one another, , 1,1 , 2,2  or 3; With
L is ethyl acetate, acetonitrile, methyl-sulfoxide, dimethyl formamide, dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-, acetone, butanone, carrene, chloroform, trichloroethanes, oxolane, ether, 1,2-dimethoxy-ethane, dioxane, methyl tertiary butyl ether(MTBE), chlorobenzene, toluene or dimethylbenzene and
B) the formula II compound of weed killer herbicide antagonism effective dose
Figure A038129310002C2
R wherein 1Be chlorine, methoxyl group or methyl mercapto, R 2Be ethyl or isopropyl and R 3For ethyl, isopropyl ,-C (CN) (CH 3)-CH 3The perhaps tert-butyl group.
2. the method for weeds and gramineous plants in the selectivity control useful plant crop, this method comprise to be used according to the formula I weed killer herbicide of the herbicidally effective amount of claim 1 with according to formula II compound treatment useful plant or seed or the cutting or the cultivation area of the weed killer herbicide antagonism effective dose of claim 1.
3. according to the method for claim 2, wherein the useful plant crop is cotton, sugarcane and rice.
CN 03812931 2002-06-05 2003-06-04 Herbicidal composition Pending CN1658758A (en)

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AU708918B2 (en) * 1997-01-28 1999-08-19 Syngenta Participations Ag Herbicidal synergistic composition and method of weed control
AU2915700A (en) * 1999-03-01 2000-09-21 Syngenta Participations Ag Sulfonylurea salts as herbicides

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