CN1189763A - Herbicides with 4-iodo-2-[3-(4-methoxy-6-methyl-1, 3, 5-triazin-2-yl) ureidosulfonyl]-benzoic acid esters - Google Patents

Abstract

Herbicidal compositions comprising A) at least one compound from the group of the substituted phenylsulfonylureas of the formula I and their agriculturally acceptable salts in which R1 is (C1-C8)alkyl, (C3-C4)alkenyl, (C3-C4)alkynyl or (C1-C4)alkyl which is mono- to tetrasubstituted by radicals selected from the group consisting of halogen and (C1-C2)alkoxy, and B) at least one herbicidally active compound from the group of compounds composed of Ba) herbicides which act selectively against grasses in cereals and/or maize, Bb) herbicides which act selectively against dicots in cereals and/or maize, Bc) herbicides which act selectively against grasses and dicots in cereals and/or maize and Bd) herbicides which act non-selectively against grass weeds and broad-leaved weeds in non-crop areas and/or selectively against grass weeds and broad-leaved weeds in transgenic crops.

Description

Include the Herbicidal combinations of the iodo- 2- of 4- [3- (4- methoxyl groups -6- methyl -1,3,5-triazines -2- bases) ureido sulfuryl] benzoic ether

The invention belongs to crop protection products field, specifically, the present invention relates to the Herbicidal combinations for including the iodo- 2- of 4- [3- (4- methoxyl group -6- methyl isophthalic acids, 3,5- triazine -2- bases) ureido sulfuryl] benzoic ethers and/or its salt.

WO 92/13845 (PCT/EP92/00304) discloses the iodo aryl sulfonyl urea and its salt of formula 1

Due to group Q, W, Y, Z, R, R¹、R²And R³Extensive definition, formula 1 includes a large amount of possible single compounds.

In WO 92/13845 Chemical Example 9; 2- [[[(4 is synthesized; 6- dimethoxy -2- pyrimidine radicals) amino] carbonyl] amino] sulfonyl] -4- iodo-benzoic acid methyl esters; and Chemical Example 10 is related to the iodo- 3- of 2- [[[[4- methoxyl group -6- methyl isophthalic acids; 3,5- triazine -2- bases] amino] carbonyl] amino] sulfonyl] ethyl benzoate.The Chemical Example of the iodo- 2- of 4- [3- (4- methoxyl group -6- methyl isophthalic acids, 3,5- triazine -2- bases) ureido sulfuryl] benzoic ether is not described.

WO 92/13845 table 3 lists the compound of formula 2

Embodiment 7,44,81,118,155,192,229,237,245,253,261,269,277,298,299 and 300 is related to such compound of formula 2, and wherein Y and Z are nitrogen, and Q and W are oxygen, R¹It is hydrogen, R²It is OCH₃And R³It is CH₃.However, only neutralizing embodiment 298 to 300 (sodium, lithium, sylvite in embodiment 7 (R=methyl) and 44 (R=ethyls)；R is respectively methyl) in give fusing point.

The biological Examples of independent listed compound are not above mentioned in WO 92/13845.Moreover, formula 1 also only makees general description with the possibility that other weedings are used together.Ensuing enumerated more than about 250 various the exemplary of standard activity material, there is acifluorfen in these compounds individually mentioned, alachlor, amidosulfuron, atrazine, bentazone, bifenox, Brominal, chlortoluron, chlorsulfuron, Mediben, diclofop-methyl methyl esters, difenzoquat, Diflufenican, fenoxaprop-P ethyl ester, flamprop methyl ester, second carboxylic nitrofen ethyl ester, fluroxypramide, Fomesafen, glufosinate-ammonium, glyphosate, miaow grass ester methyl ester, ioxynil, isoproturon, lactofen, the chlorine of 2 first 4, Vi par, methabenzthiazuron, isopropyl methoxalamine, metribuzin, metsul-furon methyl, Pendimethalin, primisulfuron methyl, Garagard, thifensulfuron-methyl, tralkoxydim, triasulfuron and tribenuron methyl.In WO 92/13845, the purpose together applied being related to beyond only enumerating outside material is had not seen, or some active materials are made with the information of the motivation of specific selection and combination.

Although; the most of iodo aryl sulfonyl ureas provided with formula 1 disclosed in WO 92/13845 have good activity to the economically important unifacial leaf and broadleaf weed of wide spectrum; and by means of the active material of formula 1; the weeds occurred under the specified conditions in seed rice plant can even be prevented and treated such as arrowhead, rhizoma alismatis, water chestnut, rush, nutgrass flatsedge; it is insufficient on the wide spectrum unifacial leaf and broadleaf weed particularly occurred in Cereal or corn and other crops but these single active materials are generally under the conditions of preventing and treating comes across actual agricultural.

In view of prior art providing and in this discussion made, an object of the present invention is to provide the activity of weeding mixture of novelty, the mixture allows applied once of the grower by herbicide, or seldom apply several times, it is possible to the single weeds species tackled is composed or be difficult to weeds of the preventing and treating in Cereal, corn and other crop species.In addition, the mixture of commonly known herbicidal active compoundses should contribute to make so-called " active gap " up, and reduce the consumption of single active material as much as possible simultaneously.

These and other does not describe purpose and obtained by carrying out the Herbicidal combinations of feature description in claim 1 in detail.Therefore, the present invention relates to Herbicidal combinations, the Herbicidal combinations are included：A) the herbicidal active compoundses of the group of at least one substituted phenyl sulfonyl base urea and its salt that agriculturally can tolerate and (be subjected to) from Formulas I

Wherein R¹It is (C₁-C₈) alkyl, (C₃-C₄) alkenyl, (C₃-C₄) alkynyl or by selected from halogen and (C₁-C₂) alkoxy composition group group list to quaternary (C₁-C₄) alkyl, and B) at least one weeding active compound Ba from following this group of compound) herbicide of dogstail that is selectively applied in Cereal and/or corn, Bb the herbicide for the dicotyledon) being selectively applied in Cereal and/or corn, Bc the dogstail) being selectively applied in Cereal and/or corn and the herbicide of dicotyledon, Bd) non-selectively act on non-crop area and/or the dogstail being selectively applied in genetically modified crops and the herbicide of broad leaved weed.

Especially advantageous control of weeds spectrum according to required for the combination of the A and B class herbicidal active compoundses of the present invention can obtain grower, is even difficult to the individual species tackled.In addition, the amount of the active material of the single component of combination is may be such that according to the combination of the present invention to be reduced, this can be more economical for user.Finally, it is surprising, the increased activity more than expected level is obtained, therefore Herbicidal combinations of the present invention show large-scale synergistic activity.

Although the Formulas I phenyl sulfonyl urea with iodine substituent is in principle for example included by the formula 1 in WO 92/13845 on 4 of phenyl ring, and prior art does not show them as the protrusion adaptability with the component in the Synergistic blend of other herbicides.Specifically; prior art literature does not mention strict limitation and the clearly defined optional iodo- 2- of the 4- [3- (4- methoxyl group -6- methyl isophthalic acids existed with its salt form; 3,5- triazine -2- bases) urea groups-sulfonyl] this group of compound of benzoic ether special status.

As the A class components of the present composition it is meaningfully especially such compound of formula I or its salt, wherein R¹It is methyl, ethyl, just or isopropyl, n-, tert-, 2- butyl or isobutyl group, n-pentyl, isopentyl, n-hexyl, isohesyl, 1,3- dimethylbutyls, n-heptyl, 1- methylhexyls or Isosorbide-5-Nitrae-dimethyl amyl group.

In particularly preferred embodiments, Herbicidal combinations of the present invention include wherein R¹It is the Formulas I of methyl or the A class compounds of its salt.

A classes compound (formula 1) can be with forming salt, wherein-SO₂The cation that hydrogen in-NH- groups can be agriculturally adapted to is substituted.The example of these salt is metal salt, particularly alkali metal salt (such as sodium or sylvite) or alkali salt, or ammonium salt or the salt with organic amine formation.Equally, salt, which is formed, to be implemented by the addition reaction of strong acid and the heterocyclic moiety of compound of formula I.The example for being suitable for this purpose is hydrochloric acid, nitric acid, trichloroacetic acid, acetic acid or palmitic acid.

Especially advantageous A class compounds are such compounds, and the salt of wherein formula (I) herbicide is the preferably sodium ion by this group of cation from alkali metal, alkaline-earth metal and ammonium, to substitute-SO₂Formed by hydrogen in-NH- groups.

If compound of formula I contains one or more asymmetric carbon atoms do not specifically noted in formula or double bond, they are according to just belonging to A class compounds.Formulas I includes all possible stereoisomer determined by its specific space form, such as enantiomer, diastereomer and Z- and E- isomers, and they by stereoisomer mixture acquisition or can be applied in combination by the pure initiation material of stereoselective reaction and spatial chemistry and obtained according to a conventional method.Therefore, stereoisomer above-mentioned can be used with pure isomer form and in the form of its mixture according to the present invention.

In general, B class components are the herbicides of standard, but these herbicides are selected with certain standard.Therefore, except two kinds are exception (Bd) subgroups) in addition to, B classes herbicide is the herbicide for the green bristlegrass grass being selectively applied in Cereal and/or corn.It is intended to the noxious plant especially dogstail and/or dicotyledon of preventing and treating.Consider the activity of B class standard herbicides, it can equally be screened according to the targeted preventing and treating plant of these B class materials.Therefore, some B class herbicides almost act only on dogstail, and another part but mainly acts on dicotyledon, and from Bc) the B classes herbicide of subgroup is using preventing and treating dogstail and dicotyledon.However, in either case, combination of the invention produces the best use of and composed by supplementing and strengthening A class compound herbicidal performances.This point is also particularly suitable to come from Bd) the B class compounds of group, Bd) group compound comprising active to grassy weed and broadleaf weed and be to be non-selective in non-crop area and/or be selective herbicide in genetically modified crops.

In preferred scheme, the present composition is characterised by, it includes one or more herbicides as B class herbicides, the dogstail acted in Cereal and/or corn described herbicide selective and its come from comprising following group：2- (4- aryloxy group-phenoxy group) propionic acid and its esters, ureas, sulfonylurea, cyclohexanedione oximes, aryl alanine class, 2,6- dinitroanilines, imidazolone type and difenzoquat.In addition to single material above-mentioned, described chemical substance species includes a series of dogstail herbicides, and these herbicides are adapted as the component combined with A class compounds.

It is preferred that the present composition include one or more herbicides as B class herbicides, the dogstail acted in Cereal described herbicide selective, and they are selected from consisting of the following group of B1) fenoxaprop-P, fenoxaprop-p-ethyl

(±) -2- [4- (chloro- 1, the 3- benzoxazoles -2- bases epoxides of 6-) phenoxy group] propionic acid, it includes particularly its type of service fenoxaprop-P-ethyl ester,

(R) -2- [4- (chloro- 1, the 3- benzoxazoles -2- bases epoxides of 6-) phenoxy group] propionic acid, it includes particularly most frequent type of service fenoxaprop-p-ethyl-ethyl ester, above-claimed cpd B1) by《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 439-441 pages and 441-442 pages known.B2) isoproturon3- (4- isopropyl phenyls) -1,1- dimethyl ureas,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 611-612 pages, B3) diclofop-methyl

(RS) -2- [4- (2,4- dichlorophenoxy) phenoxy group] propionic acid, it includes the methyl ester especially as most important type of service, i.e. diclofop-methyl methyl esters,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 315-317 pages, B4) clodinafop

(R) -2- [4- (the fluoro- 2- pyridines epoxides of the chloro- 3- of 5-) phenoxy group] propionic acid, it also includes particularly its type of service clodinafop- alkynes propyl ester,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 216-217 pages, B5) B4) with cloquintocet mixture(5- chloroquinoline -8- bases epoxide) acetic acid, it is also used in cloquintocet-mexyl forms, and particularly preferable as B4) safener,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 226-227 pages, B6) green wheat spirit

3- (the chloro- p-methylphenyls of 3-) -1,1- dimethyl ureas,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 195-196 pages, B7) methabenzthiazuron

1- (1,3- benzothiazole -2- bases) -1,3- dimethyl ureas,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 670-671 pages, B8) the careless ester of miaowReaction product includes (+) -6- (4- isopropyl-4-methyl -4- oxo -2- imidazoline -2- bases)-meta-toluic acids and (±) -6- (4- isopropyl-4-methyl -4- oxo -2- imidazoline -2- bases)-paratolunitrile, it can also be its methyl esters respectively, they are referred to as the careless ester methyl ester of miaow《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 582-584 pages, B9) tralkoxydim

2- [1- (ethoxy imino) propyl group] -3- hydroxyl -5- basic ring hex- 2- ketenes,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 995-996 pages, B10) difenzoquat

1,2- dimethyl -3,5- diphenylpypazole, such as the metilsulfate salt of difenzoquat,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 330-331 pages, B11) wheat straw is lied prostrate, wheat straw lies prostrate M

N- benzoyl-Ns-(the chloro- 4- fluorophenyls of 3-)-DL-Alanine N- benzoyl-Ns-(the chloro- 4- fluorophenyls of 3-)-D-alanine also lies prostrate M isopropyl esters comprising particularly flamprop methyl ester, wheat straw volt M methyl esters and wheat straw,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994,464-465 and 466-468 pages, B12) PendimethalinN- (1- ethyl propyls) -2,6- dinitro -3,4- xylidine,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 779-780 pages.

Compound B-11) to B12) be herbicide, they as to the document specified by each compound, it is known that and they are selectively applied to the dogstail in Cereal.That mentions does not only have basic material, the chemical formulas of these base substances be purpose illustrate also make it is general indicate, and mention the version of the conventional base substance used.Such as B4) (coldinafop) is typically to be used in the form of propargyl ester, and diclofop-methyl (B3)) then used as the form of methyl esters etc..If the optical active forms of B class compounds are conventional, it is also contemplated that these forms (such as Te other Shi oxazole diclofop-methyl ethyl esters and fenoxaprop-p-ethyl ethyl ester).

Compound B-11), B3) and B4) belong to 2- (4- aryloxyphenoxies) propionic acid or its ester derivant chemical substance class.B2), B6) and B7) be ureas, and B8) be imidazolone type representative, B9) be a kind of cyclohexanedione oxime, B11) be a kind of aryl alanine and B12) be one kind 2,6- dinitroanilines.Although for chemical constitution, the representative of this group of material has sizable difference, but according to its action spectrum, and because the fact that they represent the synergist of compound of formula I, they form a common subgroup.

In another preferred embodiment of the present invention, activity of weeding combination comprising as B class herbicides one or more be mainly be selectively applied to dogstail in corn and be selected from consisting of the following group of herbicide B13) nicosulfuron

1- (4,6- dimethoxypyridin -2- bases) -3- (3- formyl-dimethylamino -2- pyridyl sulfonyls) urea《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 734-735 pages, B14) rimsulfuron

1- (4,6- dimethoxypyridin -2- bases) -3- (3- ethylsulfonyl -2- pyridyl sulfonyls) urea《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 904-905 pages, and B15) Fluoropyrimidinesulfuron

2- (4,6- double (difluoro-methoxy) pyrimidine -2 --amino formoxyl sulfamoyls) benzoic acid, it mainly uses primisulfuron methyl,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 829-830 pages,

Above-claimed cpd B13) to B15) belonging to sulfonyl urea compound group, they are structurally different from the sulfonylureas of Formulas I.

Combined when according to the present invention comprising mixture (the registration mark Topik as the diclofop-methyl methyl esters of B class compounds, fenoxaprop-p-ethyl ethyl ester, isoproturon, clodinafop- alkynes propyl ester and cloquintocet-mexyl^), the careless ester methyl ester of miaow, nicosulfuron and/or during rimsulfuron, produce particularly advantageous mixture within the scope of the present invention.

For the present invention a part other compositions be those include come from Bb) subgroup B class herbicides composition.The herbicide of the particularly advantageous dicotyledon being selectively applied in Cereal and/or corn is that one or more are selected from the group included herbicide：Aryloxy alkyl carboxylic acids, hydroxy phenyl nitrile, diphenyl ether, azole and pyrazoles, Diflufenican and bentazone.

And the preferred herbicide in possible aryloxy group alkyl yl carboxylic acid is those herbicides in consisting of the following group：B16) Vi par, mecopropP

(RS) -2- (the chloro- o-tolyl epoxides of 4-) propionic acid, (R) -2- (the chloro- o-tolyl epoxides of 4-) propionic acid,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994,646-647 and 647-648 pages, B17) 2 first, 4 chlorine

(4- chloro-2-methyls phenoxy group) acetic acid, the form mainly used is the chlorine of (being particularly) 2 first 4 (2- fourth oxygen ethyl) (butotyl) ester, the chlorine dimethylammonium of 2 first 4, the different monooctyl ester of the chlorine of 2 first 4, the chlorine sylvite of 2 first 4 and the chlorine sodium salt of 2 first 4《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 638-640 pages, B18) 2,4- drops propionic acid, high 2,4- drops propionic acid

(RS) -2- (2,4- dichlorophenoxies) propionic acid, (R) -2- (2,4- dichlorophenoxies) propionic acid, the form mainly used is (being particularly) 2,4- drops propionic acid (2- fourth oxygen ethyl) ester, 2,4- drop propionic acid second ammonium, 2, the different monooctyl ester of 4- drop propionic acid and 2,4- drop propionic acid sylvite《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994,309-311 and 311-312 pages, B19) 2,4- drops(2,4- dichlorophenoxy) acetic acid, the form generally used：2,4- drops (2- fourth oxygen ethyl) ester, 2,4- d butyl esters, 2,4- drops dimethylammonium, 2,4- drops-diolamin, the different monooctyl ester of 2,4- drops, 2,4- drops isopropyl ester and 2,4- drop-trolamin,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 271-273 pages, B20) Mediben3,6- dichloro-o-anisicaacids are particularly used in the form of Mediben dimethylammonium, Mediben sylvite, dicamba sodium salt and Mediben-trolamin,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 298-300 pages, and B21) fluroxypramide

The fluoro- other types of service of 2- pyridines ethoxyacetic acid of the chloro- 6- of 4- amino -3,5- bis-：Fluroxypramide-meptyl,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 505-507 pages.

The Herbicidal combinations of the particularly interesting hydroxy phenyl nitrile also comprising the dicotyledon being selectively applied in Cereal and/or corn.These herbicides include B22) ioxynil

4- hydroxyl -3,5- diiodo- benzonitriles

Common type of service：Octanoate and ioxynil sodium,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 598-600 pages, B23) Brominal

3,5- bis- bromo- 4- hydroxy-phenies nitriles

Common type of service：Bromoxynil octanoate and Brominal potassium,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 121-123 pages.

It is distinguished by according to other advantageous compositions of the present invention, they are included is selectively applied to the dicotyledon in Cereal and/or corn and the diphenyl ether B24 selected from following herbicide as one or more of B class herbicides) bifenox

5- (2,4- dichlorophenoxy) -2- nitrobenzene methyls,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 94-96 pages, B25) second carboxylic nitrofen

O- [5- (the fluoro- p-methylphenyl epoxides of 2- chloro- α, α, α-three) -2- nitro benzoyls] glycolic, also using the form of second carboxylic nitrofen ethyl ester,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 492-494 pages, B26) acifluorfen5- (the fluoro- p-methylphenyl epoxides of 2- chloro- α, α, α-three) -2- nitrobenzoic acids, also using the form of acifluorfen sodium,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 12-13 pages, B27) lactofen

O- [5- (the fluoro- p-methylphenyl epoxides of 2- chloro- α, α, α-three) -2- nitro benzoyls]-DL-LACTIC ACID ethyl ester《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition page 1994,623, B28) Fomesafen5- (the fluoro- p-methylphenyl epoxides of 2- chloro- α, α, α-three)-N- methyl sulphonyl -2- nitrobenzamides, equally also use the form of Fomesafen sodium salt,《Agricultural chemicals handbook》[Pesticide Manual] the 10th edition 1994, the 520-521 pages, and B29) Oxyfluorfen

Fluoro- p-methylphenyl -3- ethyoxyls -4- nitrobenzophenone the ethers of 2- chloro- α, α, α-three,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 764-765 pages.

It is same it is particularly interesting also have such Herbicidal combinations, they are included is selectively applied to dicotyledon and in the group being made up of following herbicide azole and pyrazoles B30 in Cereal and/corn as one or more of B class compounds) ET-751The chloro- 5- of 2- (the chloro- 5- difluoro-methoxies -1- methylpyrazoles -3- bases of 4-) -4- fluorophenoxyacetate ethyl esters,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition page 1994,400, and B31) Formula II azole

Wherein R¹It is (C₁-C₄) alkyl, R²It is (C₁-C₄) alkyl, (C₁-C₄) alkylthio group or (C₁-C₄) alkoxy, these groups are each to be replaced by one or more halogen atoms, or R¹And R²Group (CH is formed together₂)_m, wherein m=3 or 4, R³It is hydrogen or halogen, R⁴It is hydrogen or (C₁-C₄) alkyl, R⁵It is one of hydrogen, nitro, cyano group or following groups：-COOR⁷,-C (=X) NR⁷R⁸Or-C (=X) R¹⁰, R⁶It is hydrogen, halogen, cyano group, (C₁-C₄) alkyl, (C₁-C₄) alkylthio group or-NR¹¹R¹², R⁷And R⁸It is identical or different and be hydrogen or (C₁-C₄) alkyl, or R⁷And R⁸The nitrogen-atoms being bonded therewith forms 5- the or 6- member carbocyclic rings of saturation, R together¹⁰It is hydrogen or (C₁-C₄) alkyl, the latter optionally can be replaced by one or more halogen atoms, and R¹¹And R¹²It is identical or different and be hydrogen, (C₁-C₄) alkyl or (C₁-C₄) alkoxy carbonyl or R¹¹And R¹²The nitrogen-atoms being bonded therewith forms 3-, 5- or 6- member carbocyclic ring or aromatic ring together, and one of carbon atom can be substituted optionally by oxygen atom；

The azole of Formula II is disclosed in particularly WO 94/08999.

Also preferred as B classes compound also has B32) Diflufenican

2 ', 4 '-two fluoro- 2- (fluoro- tolyl epoxide of α, α, α-three) nicotinanilides,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 335-336 pages.

Other Favourable implementations of the present invention are characterised by that Herbicidal combinations include the B33 as B class herbicides) bentazone

3- isopropyls -1H-2,1,3- benzothiadiazine -4 (3H) -one 2,2- dioxide,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 90-91 pages.

The component that is particularly suitable as very much in Herbicidal combinations of the present invention is, belong to Cereal and/or corn selectively and to dicotyledonous active B classes compound (Bb) subgroup includes herbicidal active compoundses B16)-B33) and its conventional derivatives), the chlorine of 2 first 4, Vi par, Mediben, fluroxypramide, Diflufenican, ioxynil and/or second carboxylic nitrofen.

The 3rd subgroup compound that being mixed with A class compounds can make Herbicidal combinations have outstanding feature is optionally to prevent and treat Cereal and/or the dogstail in corn and the herbicide Bc of dicotyledon) subgroup.B class materials with this feature are mainly seen in pyrrolotriazine derivatives, chloracetophenone amine and sulfonylurea, and they are different from the sulfonylurea given in Formulas I.

If it is preferred that representative be particularly those can mainly use come optionally prevent and treat Cereal neutralize suitably preventing and treating corn in dogstail and dicotyledon herbicide.Above-mentioned herbicide includes the activity of weeding triazine derivative and chloroacetanilide B34 being especially selected from the group that is made up of following active material) isopropyl methoxalamineThe chloro- 6 '-ethyl-N- of 2- (2- methoxyl group -1- Methylethyls) acetyl ortho-aminotoluene,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 693-694 pages, B35) metribuzin

4- amino -6- tert-butyl group -4,5- dihydro -3- methyl mercaptos -1,2,4- triazine -5- ketone,《Agricultural chemicals handbook》[Pesticide Manual] the 10th edition 1994, the 699-700 pages, B36) atrazine

The chloro- N of 6-²- ethyl-N⁴- isopropyl -1,3,5-triazines -2,4- diamines,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 51-52 pages, B37) Garagard

N²The chloro- N of-tert-butyl group -6-⁴- ethyl -1,3,5-triazines -2,4- diamines,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 960-961 pages, B38) alachlor

Chloro- 2 ', the 6 '-diethyl-N- methoxies antifebrins of 2-,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 21-22 pages, B39) Acetochlor

(- 6 '-ethyl of the chloro- N- ethoxyl methyls of 2-) acetyl ortho-aminotoluene,《Agricultural chemicals handbook》[Pcsticide Manual], the 10th edition 1994, the 10-11 pages, B40) dimethenamid

(RS) -2- ammonia-N- (2,4- dimethyl -3- thienyls)-N- (2- methoxyl group -1- Methylethyls) acetamide,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 345-346 pages.

In favourable embodiment, Herbicidal combinations of the present invention include optionally preventing and treating dogstail and dicotyledon, different from the A class compounds sulfonylurea of dogstail in Cereal and dicots and (optional) optionally in preventing and treating corn as one or more of B class components.Particularly preferred this kind of sulfonylurea particularly B41) amidosulfuron1- (4,6- dimethoxypyridin -2- bases) -3- mesyls (methyl) sulfamine urea,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 34-35 pages, B42) metsulfuron-methyl2- (4- methoxyl group -6- methyl isophthalic acids, 3,5- triazine -2- base carbamoyls sulfonamides) benzoic acid, routinely uses metsul-furon methyl form,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 701-702 pages, B43) tribenuron-methyl2- [4- methoxyl group -6- methyl isophthalic acids, 3,5- triazine -2- base (methyl) carbamoyls sulfamoyls] benzoic acid, it is conventional to use tribenuron methyl form,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 1010-1011 pages, B44) thiophene methyl3- (4- methoxyl group -6- methyl isophthalic acids, 3,5- triazine -2- base carbamoyls sulfamoyls) thiophene-2-carboxylic acid, usually using thifensulfuron-methyl form,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 976-978 pages, B45) cinosulfuron1- [2- (2- chloroethoxies) phenyl sulfonyl] -3- (4- methoxyl group -6- methyl isophthalic acids, 3,5- triazine -2- bases) urea,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 1005-1006 pages, B46) chlorsulfuron

1- (2- Chlorophenylsulfonyls) -3- (4- methoxyl group -6- methyl isophthalic acids, 3,5- triazine -2- bases) urea,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 203-205 pages, B47) prosulfuron or CGA-152005

1- (4- methoxyl group -6- methyl isophthalic acids, 3,5- triazine -2- bases) -3- [2- (3,3,3- trifluoro propyl) phenyl sulfonyl] urea,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 865-866 pages, B48) formula III sulfonylurea

Wherein R¹It is (C₁-C₄) alkyl, (C₂-C₄) alkenyl or (C₂-C₄) alkynyl, preferably (C₁-C₄) alkyl, pi-allyl or propargyl, R²It is CO-R⁵、COOR⁶、CO-NR⁸R⁹、CS-NR¹⁰R¹¹、SO₂R¹⁴Or SO₂NR¹⁵R¹⁶, R³It is COR¹⁷、COOR¹⁸、CONR¹⁹R²⁰Or CO-ON=CR²²R²³, preferably COOR¹⁸, R⁴It is hydrogen or (C₁-C₄) alkyl, preferably hydrogen or methyl, R⁵It is hydrogen, (C₁-C₆) alkyl, the alkyl is unsubstituted or by one or more selected from following substituent group：Halogen, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio group or NR³¹R³², or (C₃-C₆) cycloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl or unsubstituted or substituted heteroaryl, preferably H, (C₁-C₆) alkyl, (C₁-C₄) haloalkyl, cyclopropyl, cyclopenta, cyclohexyl, phenyl or heteroaryl, last-mentioned two groups are unsubstituted or by one or more selected from following substituent group：(C₁-C₄) alkyl, (C₁-C₄) alkoxy and halogen, R⁶It is (C₁-C₆) alkyl, (C₂-C₆) alkenyl, (C₂-C₆) alkynyl, (C₁-C₆) haloalkyl or (C₃-C₆) cycloalkyl, preferably (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, pi-allyl, propargyl or (C₃-C₆) cyclopropyl, R⁷It is (C₁-C₄) alkyl, R⁸It is hydrogen, (C₁-C₆) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) alkoxy or (C₁-C₄- alkoxy) carbonyl, R⁹It is hydrogen, (C₁-C₆) alkyl, the alkyl is unsubstituted or by one or more selected from halogen, (C₁-C₄) alkoxy or NR³¹R³²Substituent group, or CO-R³³、CO-OR³⁴Or CONR³⁵R³⁶, or R⁸And R⁹It is following divalent group together：-(CH₂)₄- or-(CH₂)₅- or-CH₂CH₂-O-CH₂CH₂-R¹⁰Similar to R⁸, R¹¹Similar to R⁹, R¹²Similar to R⁶, R¹³Similar to R⁶, R¹⁴It is (C₁-C₆) alkyl, (C₁-C₆) haloalkyl, preferably (C₁-C₄) alkyl or (C₁-C₄) haloalkyl, R¹⁵、R¹⁶It is separate and identical or different, it is hydrogen or (C₁-C₄) alkyl, R¹⁷It is hydrogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₃-C₆) cycloalkyl, phenyl or heteroaryl, last-mentioned two groups are unsubstituted or substituted, R¹⁸It is hydrogen, (C₁-C₄) alkyl, (C₂-C₆) alkenyl or (C₂-C₆) alkynyl, last-mentioned three groups are unsubstituted or by one or more selected from following substituent group：Halogen, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio group and NR³¹R³², or (C₃-C₆) cycloalkyl or (C₃-C₆) cycloalkyl-C₁-C₃- alkyl, R¹⁹Similar to R⁸, R²⁰Similar to R⁹, R²²And R²³It is separate and identical or different, it is hydrogen or (C₁-C₂) alkyl, R²⁹It is hydrogen, hydroxyl, amino, methylamino, dimethylamino, (C₁-C₄) alkyl or (C₁-C₄) alkoxy, R³⁰It is hydrogen or (C₁-C₄) alkyl, R³¹、R³²It is separate and identical or different, it is hydrogen or (C₁-C₄) alkyl, R³³It is hydrogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₃-C₆) cycloalkyl or phenyl, the phenyl is unsubstituted or is selected from following substituent group by one or more：Halogen, (C₁-C₄) alkyl or (C₁-C₄) alkoxy, R³⁴It is (C₁-C₄) alkyl, pi-allyl, propargyl or cycloalkyl, R³⁵And R³⁶It is separate and identical or different, it is hydrogen or (C₁-C₄) alkyl, W is oxygen or sulphur, and X is (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkyl, (C₁-C₄) alkylthio group, halogen or single-or two (C₁-C₂- alkyl) amino, preferably methyl, ethyl, methoxyl group, ethyoxyl, methyl mercapto, ethylmercapto group, chlorine, chlorine, methylamino or dimethylamino, Y is (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkyl or (C₁-C₄) alkylthio group, preferably methyl, ethyl, methoxyl group, ethyoxyl, and Z is CH or N, this formula III sulfonylurea is disclosed in WO 94/10154.  

It is especially meaningful be used as combination pairing B) compound be such formula III compound, wherein R¹It is methyl, ethyl, n-propyl, isopropyl or pi-allyl, R²It is CO-R⁵、COOR⁶、CO-NR⁸R⁹、CS-NR¹⁰R¹¹、SO₂R¹⁴Or SO₂NR¹⁵R¹⁶, R³It is COR¹⁷、COOR¹⁸、CONR¹⁹R²⁰Or CO-ON=CR²²R²³, R⁴It is hydrogen or (C₁-C₄) alkyl, R⁵It is hydrogen, (C₁-C₄) alkyl, (C₁-C₂) haloalkyl, cyclopropyl, phenyl, benzyl or the heteroaryl with 5 or 6 annular atoms, last-mentioned three groups are unsubstituted or are replaced by one or more halogen atoms, R⁶It is (C₁-C₄) alkyl, pi-allyl, propargyl or cyclopropyl, R⁸It is hydrogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl or (C₁-C₄- alkoxy) carbonyl, R⁹-R¹¹It is separate and identical or different, it is hydrogen or (C₁-C₄) alkyl, R¹⁴It is (C₁-C₄) alkyl, R¹⁵、R¹⁶It is separate and identical or different, it is hydrogen or (C₁-C₄) alkyl, R¹⁷It is hydrogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₃-C₆) cycloalkyl, phenyl or heteroaryl, last-mentioned two groups are unsubstituted or substituted, R¹⁸It is hydrogen, (C₁-C₄) alkyl, (C₂-C₆) alkenyl or (C₂-C₆) alkynyl, last-mentioned three groups are unsubstituted or by one or more selected from following substituent group：Halogen, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio group and NR³¹R³², or (C₃-C₆) cycloalkyl or (C₃-C₆) cycloalkyl-C₁-C₃- alkyl, R¹⁹Similar to R⁸, R²⁰Similar to R⁹, R²²And R²³It is separate and identical or different, it is hydrogen or (C₁-C₂) alkyl, R³¹And R³²It is separate and identical or different, it is hydrogen or (C₁-C₄) alkyl, W is oxygen or sulphur, and X is (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkyl, (C₁-C₄) alkylthio group, halogen or single-or two (C₁-C₂- alkyl) amino, Y is (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkyl or (C₁-C₄) alkylthio group, and Z is CH or N.

It is very especially meaningful be used as combination pairing B) compound be such formula III compound, wherein R¹It is methyl, ethyl, n-propyl, isopropyl or pi-allyl, R²It is CO-R⁵、COOR⁶、CO-NR⁸R⁹、CS-NR¹⁰R¹¹、SO₂R¹⁴Or SO₂NR¹⁵R¹⁶, R⁵It is hydrogen, (C₁-C₄) alkyl, (C₁-C₂) haloalkyl, cyclopropyl, phenyl, benzyl or the heteroaryl with 5 or 6 annular atoms, last-mentioned three groups are unsubstituted or are replaced by one or more halogen atoms, R⁶It is (C₁-C₄) alkyl, pi-allyl, propargyl or cyclopropyl, R⁸It is hydrogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl or (C₁-C₄- alkoxy) carbonyl, R⁹-R¹¹It is separate and identical or different, it is hydrogen or (C₁-C₄) alkyl, R¹⁴It is (C₁-C₄) alkyl, and R¹⁵And R¹⁶It is separate and identical or different, it is hydrogen or (C₁-C₄) alkyl.

Exception be suitable for as combination match B) compound be such formula III compound, wherein R⁵It is H, CH₃、C₂H₅, n or i-C₃H₇, n-, i-, t- or 2- butyl, n-pentyl, CF₃、CH₂Cl、CCl₃、CH₂Br、CH₂CCl₃, cyclopropyl, phenyl, thienyl, furyl or pyridine radicals, last-mentioned four groups can replace by 1 to 3 halogen atom, B49) flupyrsulfuron (DPX-KE459)It is preferred that its sodium salt, is introduced in Brighton Crop Protection Conferenee Weeds 1995, and/or B50) sulfosulfuron (MON37500)

It is introduced in Brighton Crop Protection Conference Weeds 1995.

In another preferred embodiment of the present, Herbicidal combinations of the present invention further comprise as the B51 of B class components) KIH-20232,6- double [(4,6- dimethoxypyridin -2- bases) epoxide] sodium benzoates《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition page 1994,620.

It is selective to Cereal and/or corn and act on dogstail and dicotyledon B classes compound Bc) subgroup includes herbicidal active compoundses B34)-B51) and its conventional derivative in be particularly suitable as very much the components of Herbicidal combinations of the present invention be atrazine, metsul-furon methyl, tribenuron methyl and/or amidosulfuron.

The 4th subgroup compound that Herbicidal combinations can be made and have super-additive activity by being mixed with A class compounds is active to dogstail and broad leaved weed and is non-selective in non-crop area and/or is selective Bd in genetically modified crops) subgroup.B classes material particularly B52 with this feature) glufosinate-ammonium, high glufosinate-ammonium

4- [hydroxyl (methyl) phosphinyl]-DL- high lactamines, 4- [hydroxyl (methyl) phosphinyl]-L- high lactamines, they respectively preferably use glufosinate-ammonium ammonium salt or high glufosinate-ammonium ammonium salts,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 541-542 pages, B53) glyphosate

N- ((phosphonomethyl)) glycine, it preferably uses glyphosate-isopropylammonium, glyphosate-sesquinatrium, glyphosate-trimesium forms,《Agricultural chemicals handbook》[Pesticide Manual], the 10th edition 1994, the 542-544 pages.

Active material A+B combination shows that super-additive is acted on, i.e. Herbicidal combinations of the present invention cause amount of application to reduce and/or the margin of safety increase particularly in Cereal and/or corn crop, and concurrently still retain the good preventive effect equivalent to noxious plant.This is all meaningful economically and environmentally.It is intended to the selection of the component A+B used amount, component A：The time sequencing that component B ratio and component is applied depends on various factor, is such as intended to the preparation chosen.It is not unessential in content in this section to be particularly in mixture type, broad leaved weed or the growth period of dogstail of component, the weeds spectrum, environmental factor, weather conditions, the edaphic condition that are intended to preventing and treating etc..

In embodiment of the present invention very particularly preferably, Herbicidal combinations of the invention are characterized in that they include the combination of compound of formula I or its salt (A classes compound) and the compound from B groups of synergistic activity content.It must be emphasized that, particularly, some amounts of application or A: B weight than combination, its synergistic effect is difficult to be detected-for example typically combine with very different amount of application because of single compound, or because preventing and treating of the single compound to noxious plant has had a very good effect-even in such combination, synergistic effect be typically still Herbicidal combinations of the present invention inherently.

As it has been mentioned, the weight of composite weedicide is than A: B, and its amount of application, it can change in wide limitation.Preferred composition in the scope of the invention is that those include the compound of formula I or its salt (A classes compound) and the compound from B groups that weight ratio is 1: 2500 to 20: 1.

It is preferred to use following weight ratio：

B class compounds	A: B mixing ratio standard is preferred
			Ba dogstail herbicide { such as B1)-B12) }) in Cereal	1: 500 to 1: 1	1: 200 to 1: 2
Ba dogstail herbicide { such as B13)-B15) }) in Cereal	1: 30 to 8: 1	1: 10 to 1: 1
			Bb dicotyledon herbicide { such as B16)-B21) }) in Cereal and corn	1: 1500 to 1: 1	1: 500 to 1: 10
Bb dicotyledon herbicide { such as B22)-B23) }) in Cereal and corn	1: 500 to 1: 1	1: 200 to 1: 3
			Bb dicotyledon herbicide { such as B24)-B29) }) in Cereal and corn	1: 500 to 8: 1	1: 300 to 2: 1
Bb dicotyledon herbicide { such as B30) and B31) }) in Cereal and corn	1: 20 to 20: 1	1: 10 to 10: 1
			Bb dicotyledon herbicide { such as B32) }) in Cereal and corn	1: 250 to 1: 1	1: 100 to 1: 3

B class compounds	A: B mixing ratio standard is preferred
			Bb dicotyledon herbicide { such as B33) }) in Cereal and corn	1: 2500 to 1: 5	1: 2000 to 1: 10
Bc) Cereal and/or dogstail in corn and dicotyledon herbicide { such as B34)-B40) }	1: 2500 to 1: 2	1: 2000 to 1: 4
			Bc) Cereal and/or dogstail in corn and dicotyledon herbicide { such as B41)-B51) }	1: 40 to 20: 1	1: 20 to 10: 1
Bd) the non-selective or only selective broad-spectrum herbicide { such as B52)-B53) } in genetically modified crops	1: 1500 to 1: 2	1: 1000 to 1: 10

The amount of application of herbicide A in active substance combination of the present invention is 0.1 to 100 gram of a.i./ha (a.i.=active components, i.e., the amount of application on the basis of active material), preferably in 2 to 40 grams of a.i./ha.

In general, the amount of application of the B class compounds in inventive mixture is：

B class compounds	Amount of application, standard is preferred in terms of gram a.i./ha
			Ba dogstail herbicide { such as B1)-B12) }) in Cereal	10 to 4000	50 to 1000
Ba dogstail herbicide { such as B13)-B15) }) in corn	5 to 60	5 to 30
			Bb dicotyledon herbicide { such as B16)-B21) }) in Cereal and corn	50 to 3000	100 to 2000
Bb dicotyledon herbicide { such as B22)-B23) }) in Cereal and corn	50 to 1000	100 to 500
			Bb dicotyledon herbicide { such as B24)-B29) }) in Cereal and corn	5 to 1000	10 to 500
Bb dicotyledon herbicide { such as B30) and B31) }) in Cereal and corn	3 to 25	5 to 20
			Bb dicotyledon herbicide { such as B32) }) in Cereal and corn	50 to 500	100 to 250
Bb dicotyledon herbicide { such as B33) }) in Cereal and corn	500 to 2500	750 to 2000
			Bc) Cereal and/or dogstail in corn and dicotyledon herbicide { such as B34)-B40) }	100 to 5000	250 to 2500
Bc) Cereal and/or dogstail in corn and dicotyledon herbicide { such as B41)-B51) }	2 to 80	5 to 50
			Bd) the non-selective or only selective broad-spectrum herbicide { such as B52)-B53) } in genetically modified crops	100 to 3000	100 to 1000

Active substance combination of the present invention can exist with the mix preparation of two kinds of components, the conventional mode of described mix preparation is applied in the form of being diluted with water, either exist with so-called tank mix, and tank mix together dilutes the component processed respectively by using water and prepared.

A and B classes active material can be with processed in various ways, depending on given biology and/or physico-chemical parameter.Possible suitable preparation is for example：Wettable powder (WP), missible oil (EC), water solube powder (SP), dense dose (SL) of water solubility, emulsifiable concentrate (BW) such as oil-in-water and water-in-oil emulsion, sprayable solution or emulsion, capsule suspension (CS), oil-or water-based dispersant (SC), suspension emulsion, suspending agent, pulvis (DP), the miscible liquid (OL) of oil, seed dressing product, particulate, spraying granule, coating particle and the granule of adsorption particle form (GR), soil application spreads fertilizer over the fields and uses granule, water-soluble granular formulation (SG), water dispersible granule (WG), ultra-low volume (ULV) preparation, microcapsules and cerate.

The single type of these formulations is essentially known, and is described in such as following documents：Winnacker-Kuchler,《Chemical technology》[Chemische Technologie], volume 7, C.Hauser Verlag Munich, the 4th edition 1986；Wade van Valkenburg,《The formulations of pesticide》[Pesticide Formulation], Marcel Dekker, New York, 1973；K.Martens,《Spray Drying Handbook》[Spray Drying Handbook], the 3rd edition 1979, G.Goodwin Ltd. London.

Required processing aids such as inert material, surfactant, solvent or other additives are also known or are described in such as following documents：Watkins,《The agent of insecticide dust dilution agent and carrier handbook》[Handbook of Inseeticide Dust Diluents andCarriers], second edition, Darland Books, Caldwell N.J.；H.v.Olphen《Clay colloid chemistry is got started》[Introduction to Clay ColloidChemistry], second edition, J.Wiley ＆ Sons, New York；Marsden《Solvent guide》[Solvent Guide], the second edition, Interscience, New York 1963；McCutcheon’s《Detergent and emulsifying agent yearbook》[Detergents and Emulsifiers Annual], MC Publ.Corp., Ridgewood, N.J.；Sisley and Wood,《Surfactant macropaedia》[Encyclopedia of Surface Active Agents], Chem.Publ.Co.Inc., New York, 1964；Schonfeldt,《Surface-active ethylene oxide adduct》[Grenzflachenaktive Athylenoxidaddukts], Wiss.Verlagsgesell-schaft, Stuttgart, 1976；Winnacker-Kuchler,《Chemical technology》[Chemische Technologie], volume 7, C.Hauser Verlag Munich, the 4th edition 1986.

According to these formulations, the combination with other pesticidal active substances, herbicide, insecticide, bactericide and antidote, safener, chemical fertilizer and/or growth regulator can also be prepared, such as in the form of it can directly mix thing or tank mix.

Combinations of herbicides of the present invention is particularly advantageous that by the way that by compound of formula I or its salt (A classes compound), with being prepared by way of protecting formulation by the following conventional crop of processing as one or more B class compounds, described formulation, which is selected from, includes following group：Water-soluble wettable powder (WP), water dispersible granule (WDG), the emulsifiable granule of water (WEG), suspension emulsion (SE) and oil-suspending agent (SC).

Wettable powder is can homogeneous scattered preparation in water; it is in addition to active component; also comprising ionically and/or non-ionically surfactant (wetting agent, dispersant); such as polyoxyethylated alkyl phenols, polyoxyethylenated alcohol and fatty amine, fatty alcohol polyglycol ether sulfate, alkylsulfonate or alkylaryl sulfonates, sodium lignosulfonate, 2; 2 '-dinaphthylmethane -6; 6 '-sodium disulfonate, nekal or oleoyl N-methyltaurine sodium, in addition also diluent or inert substance.

Missible oil is by the way that one or more active materials are dissolved in added with preparation in one or more the ionically and/or non-ionically organic solvent (such as butanol, cyclohexanone, dimethylformamide, dimethylbenzene or high boiling aromatic compounds or hydrocarbon) of surfactant (emulsifying agent).The example for the emulsifying agent that can be used is：Alkyl aryl sulphonic acid calcium, such as calcium dodecyl benzene sulfonate, or nonionic emulsifier such as fatty acid polyethylene glycol ester, alkylaryl polyglycol ether, fatty alcohol polyglycol ether, expoxy propane/ethylene oxide condensate (such as block copolymer), alkyl, polyether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester or other polyoxyethylene sorbitan esters.

Pulvis is prepared by the way that one or more active materials are ground together with finely divided material such as talcum, natural clay such as kaolin, montmorillonite and pyrophyllite or diatomite.

Granule can be by the way that one or more active materials be sprayed on absorbability particle inert material, or by means of adhesive such as polyvinyl alcohol, Sodium Polyacrylate or mineral oil, active material concentrate is coated to carrier surface, carrier such as sand, kaolinite or granular inert material and prepared.Water dispersible granule is prepared generally by conventional method.Described conventional method if any spray drying, fluidized bed prilling, disc granulation, using high-speed mixer mix and without solid inert material extrude.Suitable active material can also be granulated with washing conventionally used for preparing the mode of chemical fertilizer granule, can be the form with fertilizer mixtures if desired.

In general, in addition to conventional processing aids, agrochemical formulations of the invention include by weight 0.1 to 99%, are especially by weight 2 to 95% A and B class active materials.

In different formulations, active material A+B concentration can change.In wettable powder, active material concentration is such as about by weight 10 to 95%, and surplus is conventional machining component.In the case of missible oil, the concentration of active material can be about by weight 1 to 85%, and preferably by weight 5 to 80%.In the formulation of pulvis, comprising by weight about 1 to 25%, the in most cases active material for by weight 5 to 20%, sprayable solution is by weight about 0.2 to 25%, preferably 2 to 20% active material.In granule, in such as dispersible granule, it is liquid or solid form that the content of active material, which depends in part on active material, and depending on granulation adjuvant and filler used.In general, the content in water dispersible granule is between by weight 10 to 90%.

In addition, above-mentioned active component formulation includes (if suitable) adhesive, wetting agent, dispersant, emulsifying agent, bleeding agent, preservative, antifreeze, solvent, filler, colouring agent, carrier, defoamer, evaporation suppressor and pH and viscosity modifier common in each formulation.

Due to the low amount of application that A+B of the present invention is combined, it is general they had good tolerance.With herbicidal active compoundses individually compared with, combination of the invention is in particular so that absolute dosage is reduced.However, if it is desired to further increase the tolerance and/or selectivity of Herbicidal combinations of the present invention, then advantageously by them together with safener or antidote, together or at different time points use in the mixture.The compound for being adapted as the safener of the invention combined or antidote is e.g., as disclosed in EP-A-333 131 (ZA-89/1960), EP-A-269806 (US-A-4,891,057), it can be prepared in EP-A-346 620 (AU-A-89/34951) and International Patent Application PCT/EP 90/01966 (WO-91/08202) and PCT/EP 90/02020 (WO-91/078474) and document recited in them or by the method being described in these open source literatures.Other suitable safeners are the known in the literatures quoted from EP-A-94 349 (US-A-4,902,304), EP-A-191 736 (US-A-4,881,966) and EP-A-0 492 366 and these open source literatures.

The Herbicidal mixture or combination application of the present invention is favorably characterised by, also contains C) one or more formulas C1 or C2 compound or its salts

Wherein X is hydrogen, halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, nitro or (C₁-C₄) haloalkyl, Z is OR¹、SR¹、NR¹R, wherein R are hydrogen, (C₁-C₆) alkyl, (C₁-C₆) alkoxy or unsubstituted or substituted phenyl or saturation or unsaturation 3- be to 7- circle heterocycles bases, described heterocyclic radical contains at least one nitrogen-atoms and at most 3 hetero atoms, and is connected to carbonyl through this nitrogen-atoms and is unsubstituted or by selected from following substituent group：(C₁-C₄) alkyl, (C₁-C₄) alkoxy or unsubstituted or substituted phenyl, preferably following formula group：OR¹、NHR¹Or N (CH₃)₂, particularly OR¹, R^*It is (C₁-C₂) alkylidene chain (=(C₁-C₂) alkane diyl), it can also be by one or two (C₁-C₄) alkyl or by [(C₁-C₃) alkoxy] carbonyl substitution, preferably-CH₂-, R¹It is hydrogen, (C₁-C₁₈) alkyl, (C₃-C₁₂) cycloalkyl, (C₂-C₈) alkenyl or (C₂-C₈) alkynyl, above-mentioned carbon containing group can be unsubstituted or single or multiple substitution, preferably be replaced by identical or different selected from following group at most three：Halogen, hydroxyl, (C₁-C₈) alkoxy, (C₁-C₈) alkylthio group, (C₂-C₈) alkenyl thio, (C₂-C₈) alkynes sulfenyl, (C₂-C₈) alkenyloxy, (C₂-C₈) alkynyloxy group, (C₃-C₇) cycloalkyl, (C₃-C₇) cycloalkyloxy, cyano group, list-and two (C₁-C₈) alkyl amino, carboxyl, (C₁-C₈) alkoxy carbonyl, (C₂-C₈) alkenyloxycarbonyl groups, (C₁-C₈) alkylthiocarbonyl, (C₂-C₈) alkynyloxycar bonyl, (C₁-C₈) alkyl-carbonyl, (C₂-C₈) alkenyl carbonyl, (C₂-C₈) alkynylcarbonyl groups, 1- (oxyimino)-(C₁-C₆) alkyl, 1- [(C₁-C₄) alkyl imino]-(C₁-C₄) alkyl, 1- [(C₁-C₄) Alkoximino]-(C₁-C₆) alkyl, (C₁-C₈) alkyl-carbonyl-amino, (C₂-C₈) alkenyl carbonyl amino, (C₂-C₈) alkynylcarbonylamino, amino carbonyl, (C₁-C₈) alkyl amino-carbonyl, two-(C₁-C₆) alkyl amino-carbonyl, (C₂-C₆) alkenylaminocarbonyl, (C₂-C₆) alkynylaminocarbonyl, (C₁-C₈) alkoxycarbonyl amino, (C₁-C₈) alkyl amino-carbonyl-amino, unsubstituted or by halogen, nitro, (C₁-C₄) alkoxy or unsubstituted or substituted phenyl substitution (C₁-C₆) alkyl carbonyl epoxide, (C₂-C₆) alkenyl carbonyl epoxide, (C₂-C₆) alkynylcarbonyl groups epoxide, (C₁-C₈) alkyl sulphonyl, phenyl, phenyl (C₁-C₆) alkoxy, phenyl (C₁-C₆) alkoxy carbonyl, phenoxy group, phenoxy group (C₁-C₆) alkoxy, phenoxy group-(C₁-C₆) alkoxy carbonyl, phenylcarbonyl group epoxide, benzylcarbonylamino, phenyl-(C₁-C₆)-alkyl-carbonyl-amino, it is unsubstituted on phenyl ring or by identical or different single or multiple substituted, preferably up to three substitutions selected from following group finally to mention nine groups：Halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkyl, (C₁-C₄) halogenated alkoxy and nitro, and following formula group：SiR’₃、-O-SiR’₃、R’₃Si(C₁-C₈) alkoxy ,-CO-O-NR '₂,-O-N=CR '₂,-N=CR '₂、-O-NR’₂、CH(OR’)₂With-O- (CH₂)_m-CH(OR’₂)₂, R ' therein is hydrogen, (C independently of each other₁-C₄) alkyl, phenyl, described phenyl is unsubstituted or is selected from the single or multiple substitution of following group by identical or different, and preferably up to three replace：Halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkyl, (C₁-C₄) halogenated alkoxy and nitro, or, when paired, (C₂-C₆) alkylidene chain and m are 0 to 6, and formula R " O-CHR ' " (OR ")-(C₁-C₆) alkoxy base, group R " is independently of one another (C₁-C₄) alkyl or be (C together₁-C₆) alkylidene group and R ' " it is hydrogen or (C₁-C₄) alkyl, R is hydrogen, (C₁-C₆) alkyl, (C₁-C₆) alkoxy or unsubstituted or substituted phenyl, n is integer 1 to 5, and preferably 1 to 3, W is the divalent heterocyclic group of the formula W1 to W4 with 5 annular atoms：Wherein R²It is hydrogen, (C₁-C₈) alkyl, (C₁-C₈) haloalkyl, (C₃-C₁₂) cycloalkyl or unsubstituted or substituted phenyl, and R³It is hydrogen, (C₁-C₈) alkyl, (C₁-C₈) haloalkyl, (C₁-C₄) alkoxy-(C₁-C₄) alkyl, (C₁-C₆) hydroxy alkyl, (C₃-C₁₂) cycloalkyl or three ((C₁-C₄) alkyl) silicyl.

Unless otherwise special restriction, following definition is suitable for the group in formula：

Alkyl, alkenyl and alkynyl are straight or branched and have at most 8, preferably up to 4 carbon atoms；This point is similarly adapted for alkyl, alkenyl or the alkynyl group or the aliphatic part by its derivative group (such as haloalkyl, hydroxy alkyl, alkoxy carbonyl, alkoxy, alkanoyl, halogenated alkoxy) of substitution.

Alkyl is such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group and 2- butyl, amyl group (particularly n-pentyl and neopentyl), hexyl (such as n-hexyl and isohesyl and 1,3- dimethylbutyls), heptyl (such as n-heptyl, 1- methylhexyls and Isosorbide-5-Nitrae-dimethyl amyl group)；Alkenyl is for example (to be particularly) pi-allyl, 1- methyl propyl- 2- alkene -1- bases, but-2-ene -1- bases, butyl- 3- alkene -1- bases, 1- methyl butyl- 3- alkene and 1- methyl but-2-enes；Alkynyl is (being particularly) propargyl, butyl- 2- alkynes -1- bases, butyl- 3- alkynes -1- bases, 1- methyl butyl- 3- alkynes；

Cycloalkyl preferably has 3 to 8 carbon atoms, and is such as cyclobutyl, cyclopenta, cyclohexyl and suberyl.If suitable, cycloalkyl can be carried to too many by two (C₁-C₄) alkyl group is used as substituent.

Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, particularly fluorine or chlorine；Haloalkyl, halogenated alkenyl and halo alkynyl are alkyl, alkenyl and alkynyl, and each of which is single-, two- or polysubstituted by halogen, e.g. CF₃、CHF₂、CH₂F、CF₃CF₂、CH₂FCHCl、CCl₃、CHCl₂、CH₂CH₂Cl；Halogenated alkoxy is for example (to be particularly) OCF₃、OCHF₂、OCH₂F、CF₃CF₂O、CF₃CH₂O；

Aryl preferably has 6 to 12 carbon atoms, and is such as phenyl, naphthyl or xenyl, preferably phenyl.This point be similarly adapted for by derivative group, such as aryloxy group, aroyl or aroylalkyl；

Unsubstituted or substituted phenyl is for example such phenyl, and the phenyl is unsubstituted or by the identical or different following group list-or polysubstituted that is selected from, preferably single-, two- or three substitutions：Halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkyl, (C₁-C₄) halogenated alkoxy, (C₁-C₄) alkylthio group, (C₂-C₅) alkoxy carbonyl, (C₂-C₅) alkyl carbonyl epoxide, carbamoyl (carbonamid), (C₂-C₅) alkyl-carbonyl-amino, two [(C₁-C₄) alkyl] amino carbonyl and nitro, such as o-, m- and p-methylphenyl, 3,5-dimethylphenyl, 2-, 3- and 4- chlorphenyl, 2-, 3- and 4- tri- be fluoro- and-trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3- dichlorophenyl or o-, m- and p- methoxyphenyl.This point is similarly adapted for optionally substituted aryl.

Especially interesting Herbicidal combinations of the present invention are such Herbicidal combinations, wherein the R in formula C1 and C2 compound¹It is hydrogen, (C₁-C₈) alkyl, (C₃-C₇) cycloalkyl, (C₂-C₈) alkenyl or (C₂-C₈) alkynyl, above-mentioned carbon containing group is unsubstituted or by halogen list-or polysubstituted, or by selected from following group list-or disubstituted, it is preferably monosubstituted：Hydroxyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio group, (C₂-C₄) alkenyloxy, (C₂-C₆) alkynyloxy group, list-or two-((C₁-C₂) alkyl) amino, (C₁-C₄) alkoxy carbonyl, (C₂-C₄) alkenyloxycarbonyl groups, (C₂-C₄) alkynyloxycar bonyl, (C₁-C₄) alkyl-carbonyl, (C₂-C₄) alkenyl carbonyl, (C₂-C₄) alkynylcarbonyl groups, (C₁-C₄) alkyl sulphonyl, phenyl, phenyl-(C₁-C₄) alkoxy carbonyl, phenoxy group, phenoxy group-(C₁-C₄) alkoxy, phenoxy group-(C₁-C₄) alkoxy carbonyl, wherein last-mentioned six groups are unsubstituted on phenyl ring or by selected from following group list-or polysubstituted：Halogen, (C₁-C₂) alkyl, (C₁-C₂) alkoxy, (C₁-C₂) haloalkyl, (C₁-C₂) halogenated alkoxy and nitro, and following formula group：SiR’₃,-O-N=CR '₂,-N=CR '₂With-O-NR '₂-CH(OR’)₂, the R ' in above-mentioned formula is hydrogen, (C independently of each other₁-C₂) alkyl, phenyl, described phenyl is unsubstituted or is selected from the single or multiple substitution of following group by identical or different：Halogen, (C₁-C₂) alkyl, (C₁-C₂) alkoxy, (C₁-C₂) haloalkyl, (C₁-C₂) halogenated alkoxy and nitro, or, it is (C when paired₄-C₅) alkane diyl chain, R²It is hydrogen, (C₁-C₈) alkyl, (C₁-C₆) haloalkyl, (C₃-C₇) cycloalkyl or phenyl, and R³It is hydrogen, (C₁-C₈) alkyl, (C₁-C₈) haloalkyl, ((C₁-C₄) alkoxy)-(C₁-C₄) alkyl, (C₁-C₆) hydroxy alkyl, (C₃-C₇) cycloalkyl or three ((C₁-C₄) alkyl) silicyl.

Other especially interesting Herbicidal combinations of the present invention are such Herbicidal combinations, wherein X is hydrogen, halogen, methyl, ethyl, methoxyl group, ethyoxyl, (C in formula C1 and C2 compound₁-C₂) haloalkyl, preferably hydrogen, halogen or (C₁-C₂) haloalkyl.

It is preferred that Herbicidal combinations of the present invention be such Herbicidal combinations, wherein X is hydrogen, halogen, nitro or (C in formula C1₁-C₄) haloalkyl, Z is formula OR¹Group, n is integer 1 to 3, R¹It is hydrogen, (C₁-C₈) alkyl, (C₃-C₇) cycloalkyl, above-mentioned carbon containing group is unsubstituted or by halogen list-or polysubstituted, or by replacing selected from following group list or two, it is preferably unsubstituted or monosubstituted：Hydroxyl, (C₁-C₄) alkoxy, ((C₁-C₄) alkoxy) carbonyl, (C₂-C₆) alkenyloxycarbonyl groups, ((C₂-C₆) alkynyloxy group) carbonyl, and following formula group：  SiR’₃,-O-N=CR '₂,-N=CR '₂、-O-NR’₂, the group R ' in above-mentioned formula is hydrogen or (C independently of each other₁-C₄) alkyl, or, when paired, (C₄-C₅) alkylidene chain, and R²It is hydrogen, (C₁-C₈) alkyl, (C₁-C₆) haloalkyl, (C₃-C₇) cycloalkyl or phenyl, R³It is hydrogen, (C₁-C₈) alkyl, (C₁-C₈) haloalkyl, ((C₁-C₄) alkoxy)-(C₁-C₄) alkyl, (C₁-C₆) hydroxy alkyl, (C₃-C₇) cycloalkyl or three ((C₁-C₄) alkyl) silicyl.

Other preferred Herbicidal combinations of the present invention are such Herbicidal combinations, wherein in C2, X is hydrogen, halogen or (C₁-C₄) haloalkyl and n be 1 to 3 integer, preferably (X)_n=5-Cl, Z are formula OR¹Group, R^*It is CH₂, and R¹It is hydrogen, (C₁-C₈) alkyl, (C₁-C₈) haloalkyl, (C₁-C₄) alkoxy-(C₁-C₄) alkyl or (C₁-C₄) alkenyloxy-(C₁-C₄) alkyl, preferably (C₁-C₈) alkyl.

Particularly preferred Herbicidal combinations of the present invention are that W is W1 in the compound for including formula C1, formula C1, and X is hydrogen, halogen or (C₁-C₂) haloalkyl and n=1-3, particularly (X)_n=2,4-Cl₂, Z is formula OR¹Group, R¹It is hydrogen, (C₁-C₈) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) hydroxy alkyl, (C₃-C₇) cycloalkyl, (C₁-C₄) alkoxy-(C₁-C₄) alkyl, three ((C₁-C₂) alkyl)-silicyl, preferably (C₁-C₄) alkyl, R²It is hydrogen, (C₁-C₈) alkyl, (C₁-C₄) haloalkyl or (C₃-C₇) cycloalkyl, preferably hydrogen or (C₁-C₄) alkyl, R³It is hydrogen, (C₁-C₈) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) hydroxy alkyl, (C₃-C₇) cycloalkyl, (C₁-C₄) alkoxy-(C₁-C₄) alkyl or three ((C₁-C₂) alkyl)-silicyl, preferably H or (C₁-C₄) alkyl.

Other particularly preferred Herbicidal combinations of the present invention are that W is W2 in the Herbicidal combinations that those include formula C1 compounds, formula C1, and X is hydrogen, halogen or (C₁-C₂) haloalkyl and n=1-3, particularly (X)_n=2,4-Cl₂, Z is formula OR¹Group, R¹It is hydrogen, (C₁-C₈) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) hydroxy alkyl, (C₃-C₇) cycloalkyl, (C₁-C₄) alkoxy-(C₁-C₄) alkyl, three ((C₁-C₂) alkyl)-silicyl, preferably (C₁-C₄) alkyl, R²It is hydrogen, (C₁-C₈) alkyl, (C₁-C₄) haloalkyl or (C₃-C₇) cycloalkyl or phenyl, preferably hydrogen or (C₁-C₄) alkyl.

Same particularly preferred Herbicidal combinations of the present invention are that W is W3 in the Herbicidal combinations that those include formula C1 compounds, formula C1, and X is hydrogen, halogen or (C₁-C₂) haloalkyl and n=1-3, particularly (X)_n=2,4-Cl₂, Z is formula OR¹Group, R¹It is hydrogen, (C₁-C₈) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) hydroxy alkyl, (C₃-C₇) cycloalkyl, (C₁-C₄) alkoxy-(C₁-C₄) alkyl, three ((C₁-C₂) alkyl)-silicyl, preferably (C₁-C₄) alkyl, R²It is (C₁-C₈) alkyl or (C₁-C₄) haloalkyl, preferably C₁- haloalkyl.

Other particularly preferred Herbicidal combinations of the present invention are that W is W4 in the Herbicidal combinations that those include formula C1 compounds, formula C1, and X is hydrogen, halogen, nitro, (C₁-C₄) alkyl, (C₁-C₄) alkoxy or (C₁-C₂) haloalkyl and n=1-3, preferably CF₃Or (C₁-C₄) alkoxy, Z is formula OR¹Group, and R¹It is hydrogen, (C₁-C₄) alkyl or (C₁-C₄) alkoxy-carbonyl-(C₁-C₄) alkyl, preferably (C₁-C₄) alkoxy -C O-CH₂-、(C₁-C₄) alkoxy -C O-C (CH₃)H-、HO-CO-CH₂- or HO-CO-C (CH₃)H-。

Formula C1 compounds are disclosed in EP-A-0 333 131, EP-A 0 269 806, EP-A-0346 620, International Patent Application PCT/EP 90/01966 and International Patent Application PCT/EP90/02020 and the document of citation therein, or they can be by preparing similar to the method described in it.Formula C2 compound is disclosed in EP-A-0 086 750, EP-A-0 094 349 and EP-A-0 191 736 and its recited document, or can be by being prepared similar to the method described in it.They are also mentioned in DE-A-40 41 121.4.

Particularly preferred antidote or safener or it has been proven that its be suitably the said goods of the present invention combination safener or antidote particularly：A) dichlorophenyl pyrazoline -3- carboxylic acid compounds (i.e. formula C1 compounds, wherein W=W1 and (X)_n=2,4-Cl₂), preferred compound such as 1- (2,4- dichlorophenyls) -5- (ethoxy carbonyl) -5- antazoline -3- carboxylic acid, ethyl esters (compound C1-1) and related compound, they are described in international patent application WO 91/07874 (PCT/EP 90/02020)；B) dichlorophenyl pyrazole carboxylic acid type derivative (that is, formula C1 compounds, wherein W=W2 and (X)_n=2,4-Cl₂), preferred compound 1- (2,4- dichlorophenyls) -5- methylpyrazole-3-carboxyl acid ethyl esters (compound C1-2), 1- (2,4- dichlorophenyls) -5- isopropylpyrazol -3- carboxylic acid, ethyl esters (compound C1-3), 1- (2,4- dichlorophenyls) -5- (1,1- dimethyl ethyls)-pyrazoles -3- carboxylic acid, ethyl esters (compound C1-4), 1- (2,4- dichlorophenyls) -5- Phenylpyrazole -3- carboxylic acid, ethyl esters (compound C1- 5) and its related compound, they are described in EP-A-0 333 131 and EP-A-0 269 806；C) triazolylcarboxylic acid's type compound (that is, formula C1 compounds, wherein W=W3 and (X)_n=2,4-Cl₂), preferred compound 1- (2,4- dichlorophenyl) -5- trichloromethyls-(1H) -1,2,4- triazole -3- carboxylic acid, ethyl esters (compound C1-6, fenchlorazole) and its related compound (referring to EP-A-0 174 562 and EP-A-0 346 620)；D) dichloro benzyl -2- isoxazolines -3- carboxylic acid compounds (that is, formula C1 compounds, wherein W=W4 and (X)_n=2,4-Cl₂), 5- benzyls-or 5- phenyl -2- isoxazoline -3- carboxylic acid compounds, preferred compound such as 5- (2,4- dichloro benzyls) -2- isoxazoline -3- carboxylic acid, ethyl esters (compound C1-7) or 5- phenyl -2- isoxazoline -3- carboxylic acid, ethyl esters (compound C1-8) and its related compound, they are described in international patent application WO 91/08202 (PCT/EP 90/01966)；

E) 8- quinoline oxies acetic acid type compound (i.e. formula C2 compounds, wherein (X)_n=5-Cl, hydrogen, Z=OR¹, R^*=CH₂), preferred compound such as (the chloro- 8- quinoline oxies of 5-) acetic acid (1- methyl hex- 1- yls) ester (C2-1), (the chloro- 8- quinoline oxies of 5-) acetic acid (1, 3- dimethyl butyrate -1- bases) ester (C2-2), (the chloro- 8- quinoline oxies of 5-) acetic acid (4- allyloxys butyl) ester (C2-3), (the chloro- 8- quinoline oxies of 5-) acetic acid (1- allyloxy propyl- 2- yls) ester (C2-4), (the chloro- 8- quinoline oxies of 5-) ethyl acetate (C2-5), (the chloro- 8- quinoline oxies of 5-) methyl acetate (C2-6), (the chloro- 8- quinoline oxies of 5-) allyl acetate (C2-7), (the chloro- 8- quinoline oxies of 5-) acetic acid [2- (2- propylene iminos epoxide) -1- ethyls] ester (C2-8), (the chloro- 8- quinoline oxies of 5-) acetic acid (2- oxo propyl- 1- yls) ester (C2-9), and its related compound, they are described in EP-A-0 086 750, in EP-A-0 094 349 and EP-A-0 191 736 or EP-A-0 492 366；F) (the chloro- 8- quinoline oxies of 5-) malonic acid type compound, i.e. formula C2 compounds, wherein (X)_n=5- Cl, hydrogen, Z=OR¹, R^*=-CH (COO- alkyl)-, preferred compound such as (the chloro- 8- quinoline oxies of 5-) diethyl malonate, (the chloro- 8- quinoline oxies of 5-) diallyl malonate, (the chloro- 8- quinoline oxies of 5-) malonic acid Methylethyl ester and related compound, they are described and advised in German patent application P 40 41 121.4 already, g) with phenoxyacetic acid or phenoxy propionic acid derivatives or aromatic carboxylic acid's type active material, such as 2, 4- dichlorophenoxyacetic acids (ester) (2, 4- drops), 4- chloro-2-methyls phenoxypropionic acid ester (Vi par), the chlorine of 2 first 4 or 3, the chloro- O-Anisic Acids (ester) (Mediben) of 6- bis-.In addition, above-claimed cpd, at least some of which, are described in EP-A-0 640 587, this article is mentioned herein is used for disclosed purpose.

In addition to the safener and antidote that are described as compound of formula I, the mixture with standard herbicide is also arrived in disclosed above.But, on the one hand, lack the single of necessary compound of formula I and enumerate, because they are included in the very wide chemical formula of connotations in EP-A-0 640 587, on the other hand, not mentioning combination in the displosure document has any surprising super-additive activity increase.

Above-mentioned a)-g) group safener (antidote) (especially formula C1 and C2 compounds) can reduce or suppress the product mix of the present invention phytotoxic effect that occurs in industrial crops are applied, without influenceing the activity of weeding to noxious plant.Thus the application field of Herbicidal mixture of the present invention can be expanded significantly, and allowed to by using safener using such combination, their current uses are only limited or do not obtain enough achievements, i.e., produce the combination of unsatisfactory preventing and treating to the evil grass of narrower action spectrum with low dosage without safener.

Herbicidal combinations of the present invention and above-mentioned safener can be applied (as the method that can directly mix thing or be mixed by bucket) together or be applied one by one with any required order.Safener：The weight of herbicide (A groups, i.e. compound of formula I) in comparatively wide scope than can change, and preferably in the range of 1: 10 to 10: 1, and particularly 1: 10 to 5: 1.The amount of optimal herbicide (A classes and B classes compound) and safener is depending on Herbicidal mixtures used and/or safener used and the property for the plant for being intended to processing at each occurrence, and can by appropriate advance experiment, determine each it is single in the case of amount.

Depending on their property, C) the class safener seed (seed dressing) that can use to anticipate crop or prior to seeding in incorporation seed Gong's ditch, or applied before or after plant germination together with Herbicidal mixture.Before seedling processing not only includes the preceding cultivation area of processing sowing, and including handling the cultivation area sowed already, but the region is also without plant growth.Preferably together applied together with Herbicidal mixture.Tank mix can be used for this purpose or can directly mix thing.

The amount of application of required safener can change in comparatively wide scope, depending on purpose and herbicide used, and they are general in 0.001 to 1 kilogram of per hectare, preferably 0.005 to 0.2 kilogram of active material.

In use, the formulation (if suitable) of viable commercial form is diluted with usual manner, such as in the case of wettable powder, missible oil, dispersant and water dispersible granule, make to be diluted with water.Pulvis, soil particle agent, spread fertilizer over the fields granule and sprayable solution form preparation be routinely not required to using preceding with the dilution of other inert substances.

The invention further relates to prevent and treat the method for noxious plant, described method is included the active material A+B of the present invention of herbicidally effective amount combined administration in these plants or cultural area.Active material can be applied to the seed or cultural area of plant, plant part, plant.In preferred the inventive method scheme, formula (I) compound or its salt (A classes compound) is applied with 0.1 to 100 gram/ha of amount, preferably 2 to 40 grams/ha, and B class compounds are 1 to 5000 gram/ha.The administration of A and B class active materials is preferably to be applied simultaneously or with different time points with 1: 2500 to 20: 1 weight ratio.The together administration of the active material of tank mix form is it is also especially preferred to, the concentrate formulation of the optimal preparation of single active material is common to be mixed in bucket with water, and applies the spraying mixture of gained.    

Because crop is extremely good to the tolerance that combines of the present invention, and simultaneously to noxious plant to prevent and treat degree very high, therefore present invention combination is considered as selective.Therefore, in preferred embodiments, the Herbicidal combinations comprising active component of the present invention are used for optionally preventing and treating noxious plant.When Herbicidal combinations of the present invention are used for crop such as in Cereal, corn, rice, sugarcane, plantation, meadow or grassplot, using from Ba) to Bc) B) to prevent and treat the method for noxious plant be particularly advantageous for the selectivity of class component.

A classes component in itself in Cereal and corn, annual and perennial broadleaf weed, grassy weed and the Cyperaceae of coming before seedling or the unusual wide spectrum of after seedling preventing and treating is used in non-crop area and plantation crops.

The action spectrum of A class components is also improved by the way that it is combined with the B class components mentioned in the present invention.

Therefore, compound B-11) to B12) supplement and strengthen and (be particularly) effect of the grassy weed in before seedling or after seedling preventing and treating Cereal, it is and in some cases, also such during broad leaved weed in preventing and treating Cereal.

From Ba) sulfonylurea (compound B-11 3) of subgroup is to B15)) be mainly used in more effectively preventing and treating grassy weed and broad leaved weed, the after seedling preventing and treating mainly in corn.

Bb) the component B16 of subgroup) to B21) it is growth regulating herbicide as a rule, these herbicides improve effect of the A classes compound in many agricultural crops (preferably Cereal and corn), especially when preventing and treating broad leaved weed and Cyperaceae.Their preferred after seedlings are used.

Compound B22) and B23) be herbicidal active compoundses, they mainly improve the control of weeds effect in corn and Cereal.In most cases, they are that after seedling is used.Nitro diphenyl ether B24) to B29) used in before seedling or after seedling.They are not only used to improve the effect in Cereal, corn, and for improving the effect in rice or soybean.

From Bb) azole of subgroup (such as B30) and pyrazoles can be particularly advantageously under at a fairly low amount of application, the broadleaf weed in after seedling preventing and treating Cereal.When preventing and treating weeds in Cereal and other crop species, B33) improve before seedling and after seedling action spectrum that the present invention is combined, and B33) it is the herbicidal active compoundses that the weeds in many agricultural crops are prevented and treated for after seedling.

From Bc) triazine of subgroup and chloroacetanilide (such as B34) be to B40)) it is widely used active material, they can be with before seedling and after seedling using improving effect of the A classes compound in preventing and treating particularly corn in terms of grassy weed and broad leaved weed, in some cases, Cereal, non-crop area or with it is also such in plantation crops.

Finally, in the present invention, compound B41) to B51) (Bc) subgroup) be preferably used for preventing and treating Cereal and neutralize in some cases in corn and in potato, meadow or the broad leaved weed in non-crop area, grassy weed is also prevented and treated in some cases, prevented and treated using after seedling, but can also be before seedling preventing and treating in some cases.

Depending on component B property, it is even the noxious plant in non-crop area and/or genetically modified crops such as corn, rice, soybean, Cereal and other crops that Herbicidal combinations of the present invention, which can be advantageously used to preventing and treating,.It is to come from Bd to be particularly suitable for this purpose) component (compound B52) and B53)).

In this context, the non-crop area of term is not only included in road, square, industrial area and railway line (these regions must frequently keep no weeds), and this generic term for being also included in the scope of the present invention of plantation.Therefore, the component of present invention combination (particularly those, which are included, comes from Bd) subgroup), annual and perennial weeds such as wheatgrass, ditch millet, Bermuda grass, cogongrass, Chinese pennisetum, japanese bearbind and the Ji of these combination preventing and treating wide spectrums are to garden sorrel and other weeds, they can be for optionally preventing and treating plantation crops such as oil palm, coco, rubberplant (Heveabrasiliensis), tangerine, pineapple, cotton, coffee, cocoa etc., and can be used in planting fruit trees and vinegrowing.Equally, present invention combination is used in the farming crop of non-cultivated or no-tillage method.However, as it has been mentioned, they can also be used in proper non-crop area, i.e. non-selectively for road, square etc., for keeping these regions without noxious plant.However, from Bd) component of subgroup, themselves it is non-selective, when the tolerance of crop is suitable, these components not only become selective, and also when for so-called genetically modified plants, combination of the invention also becomes selective.Genetically modified plants are to have carried out genetic engineering regulation and turned into the plant to itself being non-selective herbicide resistance.The crop of this change such as corn, Cereal or soybean allow containing B52) and/or B53) selectivity of combination is used.

In summary; it may be said that; when the iodo- 2- of 4- [3- (4- methoxyl group -6- methyl isophthalic acids; 3; 5- triazine -2- bases) ureido sulfuryl] benzoic ether and/or its salt and one or more active materials from B groups; optionally and particularly preferably also when one or more safeners from C groups are used together, it was observed that super-additive (=synergy) is acted on.The activity of combination exceedes the activity that single product is administered alone.These effects allow to | reduction amount of application, | preventing and treating wide spectrum broad leaved weed and dogstail, | rapider and more reliable effect, | the effect of longer-term, | only with once or seldom administration just can prevent and treat noxious plant completely several times, | the active material in combination is extended using the phase.

Above-mentioned performance is needed in actual control of weeds, to keep agricultural zone without unwanted competitor, and therefore ensures or increase the quality and quantity of harvest.Present invention combination significantly exceeds prior art in the feature.

The following examples are intended to illustrate invention：1. Formulation Example a) pulvis, it by that will be mixed according to the active substance combination of 10 parts by weight of the present invention with the talcum as inert substance of 90 parts by weight, and in sledge mill crushed mixture and obtain.B) wettable powder; it is readily dispersed in water; it is by the way that the active material A+B of 25 parts by weight, 64 parts by weight are mixed as oleoyl methyl sodium taurocholate as wetting agent and dispersant of the inert substance containing kaolinic quartz, the lignin sulfonic acid potassium of 10 parts by weight and 1 parts by weight, and mixture to be ground in rod mill and obtained.C) dispersion concentration thing, it is readily dispersed in water, it be by by the active material A+B of 20 parts by weight and the alkyl phenol polyethylene glycol ethers of 6 parts by weight (^Triton X 207), paraffin sample mineral oil (boiling range is such as about 255 to the 277 DEG C) mixing of the isotrideyl alcohol polyglycol ether (8EO) of 3 parts by weight and 71 parts by weight, and mixture is ground to what fineness was obtained less than 5 microns in ball milling.D) missible oil, it by 15 parts by weight as solvent cyclohexanone and 10 parts by weight the ethoxylation as emulsifying agent nonyl phenol obtain.E) water dispersible granule, it is obtained as below：By the active material A+B for mixing 75 parts by weight, the Lignosite of 10 parts by weight, the lauryl sodium sulfate of 5 parts by weight, the polyvinyl alcohol of 3 parts by weight and the kaolin of 7 parts by weight grind mixture in rod mill, and granulate powder in fluid bed as granulation liquid by using water.F) water dispersible granule can also be obtained as below, by being homogenized and the following material of precomminution in colloid mill：The active material A+B of 25 parts by weight; the 2 of 5 parts by weight; 2 '-two tea methylmethanes -6; 6 '-sodium disulfonate; the polyvinyl alcohol of the parts by weight of oleoyl methyl sodium taurocholate 1 of 2 parts by weight; the water of the calcium carbonate of 17 parts by weight and 50 parts by weight, then grinds mixture in bead mill, and the suspension of gained is atomized and dried by single substance nozzle in spray tower.G) extrusion type granule, it is soaked by the way that by the kaolin mixing of 20 parts by weight of activated substance A+B, the sodium lignosulfonate of 3 parts by weight, the carboxymethyl cellulose of 1 parts by weight and 76 parts by weight, mixture is ground, and will be used water.This mixture is extruded, then dried in the air stream.2. biological Examples

Example given below is carried out in greenhouse, in some cases, is carried out in big Tanaka.Field experiment

Using cell sprayer, after weeds germinate naturally, by herbicide or its be administered in combination in Cereal Tanaka.After, by way of visual score, evaluation result, such as injury to crop and the effect to broad leaved weed/dogstail.Compared by untreated with processing cell, with the effect and minus green of plant growth and the situation of necrosis until weeds are killed completely (0-100%) for standard, and quantitative assessment qualitative to herbicide effect.It is administered when crop plant and weeds are in the 2-4 leaf phases.Experiment is estimated after applying 4 weeks.Greenhouse experiments

In greenhouse experiments, allow crop plant and broad leaved weed/dogstail to be grown in No. 13 basins, and handled in the 2-4 leaf phases.Then basin is placed in the greenhouse under excellent growing conditions and (provides temperature, air humidity, water).

Evaluated similar to field experiment, i.e. compared with untreated fish group, the plant visual score to processing.These evaluate test preparation or its be administered in combination 3 weeks after carry out.Experiment sets secondary repetition.The evaluation of combined effect in embodiment

When evaluating combined effect, the activity of single component is added, and compared with the activity of the mixture of same dose.It has been generally observed that the effect of combination exceedes single active summation.

Effect less clearly in the case of, it is contemplated that value is calculated by Colby formula, and compared with actually determined result.The calculating effect of combination is theoretical expected value, is calculated by S.R.Colby formula：" synergy of Herbicidal combination and the calculating of Antagonistic reaction ",《Weeds》[Weeds] (1967), page 20 to 22.

In the case of binary combination, Colby formula are： $E=X+Y-\frac{X\·Y}{100}$ In the case of three kinds of herbicidal active compoundses combinations, this formula is correspondingly： $E=X+Y+Z+\frac{X\·Y\·Z}{10000}-\frac{\mathrm{XY}+\mathrm{XZ}+\mathrm{YZ}}{100}$ The infringement %E=desired values that the infringement %Z=that the infringement %Y=that wherein X=is caused by herbicide A under x kilograms of a.i./hectare of dosage is caused by herbicide B under y kilograms of a.i./hectare of dosage is caused by herbicide C under z kilograms of a.i./hectare of dosage, that is, the speculative damage % caused by herbicide A+B (or A+B+C) under dosage x+y (or x+y+z) kilograms of a.i./hectare.

When actual value exceedes desired value, just think there is synergistic effect.In the case of the combination of the single component with identical active material, it is also possible to compare through total formula.

However, as a rule, synergistic activity increase is so significantly, so that Colby standards can be omitted；In this case, the activity of combination is substantially beyond formula activity (pressing numerical value) sum of single material.

Such a fact must be mentioned, when evaluating the synergistic effect of used active material, it is necessary to consider to differ greatly from single active material application dosage.Therefore, it is nonsensical in the activity of each identical amount of application to compare active substance combination with single active material.Only compared with single active material, herbicide effect super-additive increase when using unitized dose, or the amount of application of two kinds of single active materials is reduced during combination, and identical effect is concurrently obtained, then saving of the present invention in the amount of active material just becomes apparent.

Table 1

Active material	g ai/ha	PHACA APESV % are prevented and treated		TRZAW% is damaged
					A)	3    5    10    20	0    15    35    53	85    93    97    98	0    0    0    0
B3)	225    450    900	0    0    0	0    0    8	0    0    0
					A)+B3)	3+450    5+450	90(0+0) 90(15+0)	97(85+0)97(93+0)	0    0

PHACA=Phalaris canariensisAPESV=wind grass (Apera spica venti) TRZAW=wheat A) the iodo- 2- of=4- [3- (4- methoxyl group -6- methyl isophthalic acids; 3,5- triazine -2- bases) ureido sulfuryl] methyl benzoate sodium salt B3) and=diclofop-methyl methyl esters ()=single active material effect %

Table 2

Active material	g ai/ha	LOLMU PHACA % are prevented and treated		TRZAW% is damaged
					A)	3    5    10    20	0    5    10    48	0    15    35    53	0    0    0    0
B1)	18    37    75	0    0    8	0    0    60	0    0    0
					A)+B1)	3+37    5+37    10+37	58(0+0)83(5+0)85(10+0)	88(0+0)97(15+0)99(35+0)	0    0    0
B5)	10    20    40	0    0    5	0    0    5	0    0    0
					A)+B5)	3+20    5+20    10+10	75(0+0)85(5+0)81(10+0)	70(0+0)80(15+0)78(35+0)	0    0    0

LOLMU=spends more black oat (Lolium multiflorum) PHACA=Phalaris canariensisTRZAW=wheat A) the iodo- 2- of=4- [3- (4- methoxyl group -6- methyl isophthalic acids; 3,5- triazine -2- bases) ureido sulfuryl] methyl benzoate sodium salt B1)=Puma S^=fenoxaprop-p-ethyl ethyl ester and safener fenchlorazole ethyl ester=1- (2,4- dichlorophenyl) -5- (trichloromethyl) -1H-1, the ratio of 2,4- triazole -3- carboxylic acid, ethyl esters are 2: 1 mixture B5)=Topik^The ratio of=clodinafop- propynyl esters and safener cloquintocet methyl esters is the effect % of 4: 1 mixture ()=single active material

Table 3

Active material	g ai/ha	LOLMU PHACA % are prevented and treated		TRZAW% is damaged
					A)	3    5    10    20	0    5    10    48	0    15    35    53	0    0    0    0
B2)	375    750    1500	0    0    0	0    0    50	0    0    0
					A)+B2)	3+1500    5+1500    10+1500	20(0+0) 43(5+0) 55(10+0)	80(0+50)85(15+50)83(35+50)	0    0    0
B8)	375    750    1500	0    0    20	0    0    13	0    0    5
					A)+B8)	3+750    10+375	93(0+0) 93(10+0)	99(0+0)99(35+0)	5    5

LOLMU=spends more black oat PHACA=Phalaris canariensisTRZAW=wheat A) the iodo- 2- of=4- [3- (4- methoxyl group -6- methyl isophthalic acids; 3,5- triazine -2- bases) ureido sulfuryl] methyl benzoate sodium salt B2)=isoproturon (Arelon^) B8) the careless ester methyl ester (Assert of=miaow^) ()=single active material effect %

Table 4

Active material	g ai/ha	ECHCR % are prevented and treated	ZEAMA% is damaged
				A)	10    20    40    80	65    75    80    88	0    0    0    0
B13)	15    30    60	0    73    75	0    0    2
				A)+B13)	10+15	97(65+0)	3
B14)	5    10    20	15    60    85	0    2    3
				A)+B14)	10+5  10+10	80(65+15)      {70}    92(65+60)      {86}	0    0

ECHCR=barnyard grasses (Echinochloa crus galli) ZEAMA=corn A) the iodo- 2- of=4- [3- (4- methoxyl group -6- methyl isophthalic acids; 3,5- triazine -2- bases) ureido sulfuryl] methyl benzoate sodium salt B13)=nicosulfuron B14)=rimsulfuron ()=single active material the desired value that calculates of effect % { }=use Colby formula

Table 5

Active material	g ai/ha	LOLMU FALCO % are prevented and treated			TRZAW% is damaged
						A)	2,5 10 20 40 80 160	68    75    83	73    85    88    97    98    99    99		0    0    0    10    15    18    28
B17)	150    500    1000		0    68    75		0    3    0
						A)+B17)	10+250    5+500		94(88+0) 98(85+68)    {95}		0    0
B16)	125    250    500    1000		0    15    55    68		0    0    0    0
						A)+B16)	10+125		91(88+0)		0
B20)	50    100    200    400	5    10    18    40			0    0    0    10
						A)+B20)	5+50   10+100	78(75+5)    {76}94(93+10)    {86}			0    0
B21)	50    100    200		73    80    95		0    0    0
						A)+B21)	5+100    10+50    10+100		99{97} 98{97} 100{98}		0    0    0

LOLMU=spends more black oat FALCO=Fallopia convolvulusTRZAW=wheat A) the iodo- 2- of=4- [3- (4- methoxyl group -6- methyl-l; 3,5- triazine -2- bases) ureido sulfuryl] methyl benzoate sodium salt B17) 4 chlorine sodium salt B16 of=2 first)=mecopropP B20)=Mediben B21)=fluroxypramide (Starane^) ()=single active material the desired value that calculates of effect % { }=use Colby formula

Table 6

Active material	g ai/ha	CENCY % are prevented and treated	SECCW% is damaged
				A)	5    10    15	0    30    60	0    0    5
B16)	600    2500	30    70	0    0
				A)+B16)	10+600	100(30+30)	0

CENCY=corn flowers (Centaurea cyanus) SECCW=ryes (Secale cereale) A) the iodo- 2- of=4- [3- (4- methoxyl group -6- methyl isophthalic acids; 3,5- triazine -2- bases) ureido sulfuryl] methyl benzoate sodium salt B16) and=mecopropP ()=single active material effect %

Table 7

Active material	g ai/ha	GALAP VIOAR % are prevented and treated		TRZAW% is damaged
					A)	2,55 10 20	35    58    60    99	58    75    95    98	0    0    2    10
B22)	62,5 125 250 500	0    3    10    18		0    0    0    0
					A)+B22)	10+125    10+250	68(60+3)   85(60+10)		0    0
B25)	4    8    15    30		3    18    38    62	0    0    0    0
					A)+B25)	5+15		93(75+38)    {85}	0
B32)	13    25    50    100	0    0    5    5		0    0    0    0
					A)+B32)	10+13	98(60+0)		0

LOLMU=spends more black oat VIOAR=field violas (Viola arvensis) TRZAW=wheat A) the iodo- 2- of=4- [3- (4- methoxyl group -6- methyl isophthalic acids; 3,5- triazine -2- bases) ureido sulfuryl] methyl benzoate sodium salt B22)=ioxynil B25)=second carboxylic nitrofen ethyl ester (Compete^) B32) and=Diflufenican ()=single active material the desired value that calculates of effect % { }=use Colby formula

Table 8

Active material	g ai/ha	ECHCR % are prevented and treated	ZEAMA% is damaged
				A)	10    20    40    80	65    73    80    88	0    0    0    0
B36)	375    750    1500    3000	0    0    3    3	0    0    0    0
				A)+B36)	10+375    10+750	88(65+0)    93(65+0)	0    0

ECHCR=barnyard grass ZEAMA=corn A) the iodo- 2- of=4- [3- (4- methoxyl group -6- methyl isophthalic acids; 3,5- triazine -2- bases) ureido sulfuryl] methyl benzoate sodium salt B36) and=atrazine ()=single active material effect %

Table 9

Active material	g ai/ha	FALCO CENCY % are prevented and treated		TRZAW% is damaged
					A)	2,55 10 20 40	73    85    88    97    98	30    43    58    78	0    0    2    10    15
B42)	1    3    5    10		0    0    0    0	0    0    0    0
					A)+B42)	2,5+3 5+3 10+3		50(30+0)    75(43+0)    78(58+0)	0    0    0
B43)	5    10    20    40	88    93    95    97		0    0    0    0
					A)+B43)	5+5	100(85+88)    {98}		0

CENCY=corn flower FALCO=Fallopia convolvulusTRZAW=wheat A) the iodo- 2- of=4- [3- (4- methoxyl group -6- methyl isophthalic acids; 3,5- triazine -2- bases) ureido sulfuryl] methyl benzoate sodium salt B42)=metsul-furon methyl (Gropper^) B43)=tribenuron methyl (Pointer^) ()=single active material the desired value that calculates of effect % { }=use Colby formula

Table 10

Active material	g ai/ha	CENCY % are prevented and treated	SECCW% is damaged
				A)	5    10    15	0    30    60	0    0    5
B41)	20	25	0
				A)+B41)	10+20	95(30+25)	0

CENCY=corn flower SECCW=rye A) the iodo- 2- of=4- [3- (4- methoxyl group -6- methyl isophthalic acids; 3,5- triazine -2- bases) ureido sulfuryl] methyl benzoate sodium salt B41) and=amidosulfuron ()=single active material effect %

Table 11

Active material	g ai/ha	GALAP AVEFA MERAN % are prevented and treated
					A)	5    10	75    98	60    80	70    94
B52)	150    300    450	55    73    85	60    70    80	65    78    90
					A)+B52)	5+150	99(75+55)    {89}	90(60+60)    {84}	98(70+65)   {98}

GALAP=clearvers (Gallium aparine) AVEFA=wild oats (Avena fatua) MERAN=annual mercury (Mercurialis annua) A) the iodo- 2- of=4- [3- (4- methoxyl group -6- methyl isophthalic acids; 3,5- triazine -2- bases) ureido sulfuryl] methyl benzoate sodium salt B52) and=glufosinate-ammonium ammonium salt ()=single active material the desired value that calculates of effect % { }=use Colby formula

These embodiments confirm that some weeds can only be prevented and treated completely under the single active material of high dose.When applying low dosage, it is poor that the effect of these components is in general, and is differed greatly with the requirement under physical condition.Good prevention effect to the weeds of all experiment species is simply obtained in the case where active material is together applied.The addition effect of single component is significantly exceeded, i.e. required level of preventing and treating is obtained by the amount of application substantially reduced.These effects have significantly widened action spectrum.    

Adverse effect is not affected by with the compatibility of crop, i.e. combination may be considered completely selectively.Above-mentioned compatibility is evaluated with the form damaged to crop.

The further advantage and type of service of the present invention is found in following claims.

Claims (35)

1. a kind of Herbicidal combinations, it includes A) material of the group of at least one substituted phenyl sulfonyl base urea and its salt that agriculturally can tolerate and (be subjected to) from Formulas IWherein R¹It is (C₁-C₈) alkyl, (C₃-C₄) alkenyl, (C₃-C₄) alkynyl or by selected from halogen and (C₁-C₂) alkoxy composition group group list to quaternary (C₁-C₄) alkyl, and B) at least one weeding active compound Ba from following this group of compound) herbicide of dogstail that is selectively applied in Cereal and/or corn, Bb the herbicide for the dicotyledon) being selectively applied in Cereal and/or corn, Bc the dogstail) being selectively applied in Cereal and/or corn and the herbicide of dicotyledon, Bd) non-selectively act on non-crop area and/or the dogstail being selectively applied in genetically modified crops and the herbicide of broad leaved weed.    

2. according to composition required in claim 1, wherein, in formula (I) herbicide or its salt, R¹It is methyl, ethyl, just or isopropyl, n-, tert-, 2- butyl or isobutyl group, n-pentyl, isopentyl, n-hexyl, isohesyl, 1,3- dimethylbutyls, n-heptyl, 1- methylhexyls or Isosorbide-5-Nitrae-dimethyl amyl group.

3. according to composition required in claim 1 or 2, wherein, in formula (I) herbicide or its salt, R¹It is methyl.

4. the composition according to required by one or more of preceding claims, the salt of wherein formula (I) herbicide is that the preferably cation of sodium substitutes wherein-SO by using from alkali metal, alkaline-earth metal and ammonium₂Formed by hydrogen in-NH- groups.

5. the composition according to required by one or more of preceding claims, it includes one or more herbicides as B class herbicides, the dogstail acted in Cereal and/or corn and it comes from the group for including following herbicide composition described herbicide selective：2- (4- aryloxy group-phenoxy group) propionic acid, preferably its esters, ureas, sulfonylurea, cyclohexanedione oximes, aryl alanine class, 2,6- dinitroanilines, imidazolone type and difenzoquat.

6. the composition according to required by one or more of preceding claims, it includes one or more herbicides as B class herbicides, the dogstail acted in Cereal, and they carry out the group B1 of freely following herbicides composition described herbicide selective) fenoxaprop-P, fenoxaprop-p-ethyl

B2) isoproturon

B3) diclofop-methylB4)clodinafopB5) B4) with cloquintocet mixture

B6) green wheat spiritB7) methabenzthiazuron

B8) the careless ester of miaowB9) tralkoxydimB10) difenzoquat

B11) wheat straw volt, wheat straw volt M

B12) Pendimethalin

7. the composition according to required by one or more of claim 1-5, it includes one or more herbicides as B class herbicides, the group B13 that is dogstail and carrying out freely following herbicide composition acted in corn described herbicide selective) nicosulfuronB14)rimsulfuron

And B15) Fluoropyrimidinesulfuron

8. according to the composition of one of claim 6 or 7, it includes the careless ester methyl ester of mixture, miaow, nicosulfuron and/or the rimsulfuron as the diclofop-methyl methyl esters of B class herbicides, fenoxaprop-p-ethyl ethyl ester, isoproturon, clodinafop- alkynes propyl ester and cloquintocet-mexyl.

9. according to composition required in one or more of Claims 1-4, it includes one or more herbicides as B classes, the dicotyledon acted in Cereal and/or corn and the group for carrying out freely following herbicide composition described herbicide selective：Aryloxy alkyl carboxylic acids, hydroxy phenyl nitrile, diphenyl ether, azole and pyrazoles, Diflufenican and bentazone.

10. according to composition required in one or more of Claims 1-4, it includes one or more herbicides as B classes, the dicotyledon acted in Cereal and/or corn and the group for carrying out freely following herbicide composition described herbicide selective：B16) Vi par, mecopropP

B17) the chlorine of 2 first 4

B18) 2,4- drops propionic acid, high 2,4- drops propionic acid

B19) 2,4- drops

B20) MedibenAnd B21) fluroxypramide

11. according to Claims 1-4 or 9 one or more in required composition, it is selectively applied to the herbicide B22 that are dicotyledon and carrying out freely groups of following herbicides composition in Cereal and/or corn comprising one or more) ioxynil

B23) Brominal

12. according to composition required in Claims 1-4 or one or more of 9, it includes one or more herbicides as B class herbicides, the group B24 that is dicotyledon and carrying out freely following herbicide composition acted in Cereal and/or corn described herbicide selective) bifenox 5- (2,4- dichlorophenoxy) -2- nitrobenzene methyls

B25) second carboxylic nitrofenB26) acifluorfen

B27) lactofen

B28) FomesafenAnd B29) Oxyfluorfen

13. according to Claims 1-4 or 9 one or more in required by composition, it includes one or more herbicides as B classes, acts on dicotyledon in Cereal and/corn and selected from the group B30 being made up of following herbicide described herbicide selective) ET-751And B31) Formula II azoleWherein R¹It is (C₁-C₄) alkyl, R²It is (C₁-C₄) alkyl, (C₁-C₄) alkylthio group or (C₁-C₄) alkoxy, these groups are each to be replaced by one or more halogen atoms, or R¹And R²Group (CH is formed together₂)_m, wherein m=3 or 4, R³It is hydrogen or halogen, R⁴It is hydrogen or (C₁-C₄) alkyl, R⁵It is one of hydrogen, nitro, cyano group or following groups：-COOR⁷,-C (=X) NR⁷R⁸Or-C (=X) R¹⁰, R⁶It is hydrogen, halogen, cyano group, (C₁-C₄) alkyl, (C₁-C₄) alkylthio group or-NR¹¹R¹², R⁷And R⁸With or it is different and be hydrogen or (C₁-C₄) alkyl, or R⁷And R⁸The nitrogen-atoms being bonded therewith forms 5- the or 6- member carbocyclic rings of saturation, R together¹⁰It is hydrogen or (C₁-C₄) alkyl, the latter optionally can be replaced by one or more halogen atoms, and R¹¹And R¹²It is identical or different and be hydrogen, (C₁-C₄) alkyl or (C₁-C₄) alkoxy carbonyl or R¹¹And R¹²The nitrogen-atoms being bonded therewith forms 3-, 5- or 6- member carbocyclic ring or aromatic ring together, and one of carbon atom can be substituted optionally by oxygen atom.

14. according to tertiary profit require 1 to 4 or 9 one or more in required composition, the B class herbicides that wherein it is included are B32) DiflufenicanThe dicotyledon acted in Cereal and/or corn the herbicide selective.

15. according to Claims 1-4 or 9 one or more in required composition, the B class herbicides that wherein it is included are B33) bentazoneThe dicotyledon acted in Cereal and/or corn the herbicide selective.

16. the composition according to required by one or more of claim 10 to 15, it includes the chlorine of 2 first 4, Vi par, Mediben, fluroxypramide, Diflufenican, ioxynil and/or the fluoroglycofen-ethyl as B class herbicides.

17. the composition according to required by one or more of Claims 1-4, it includes one or more herbicides as B class herbicides, and Cereal is prevented and treated described herbicide selective and neutralizes dogstail and dicotyledon and the group for carrying out self-contained following herbicide in optionally selectively preventing and treating corn：Pyrrolotriazine derivatives, chloracetophenone amine, KIH-2023 and the sulfonylurea different from the sulfonylurea given in Formulas I.

18. according to Claims 1-4 or 17 one or more in required composition, it include as B class herbicides one or more come self-contained following herbicides group herbicide：B34) isopropyl methoxalamineB35) metribuzin

B36) atrazine

B37) Garagard

B38) alachlor

B39) Acetochlor

And B40) dimethenamid

19. according to Claims 1-4 or 17 one or more in required composition, it include as B class herbicides one or more come self-contained following herbicides group herbicide B41) amidosulfuron

B42) metsulfuron-methyl

B43) tribenuron-methylB44) thiophene methyl

B45) cinosulfuron

B46) chlorsulfuronB47) prosulfuron or CGA-152005

B48) the sulfonylurea of formula III

Wherein R¹It is methyl, ethyl, n-propyl, isopropyl or pi-allyl, R²It is CO-R⁵、COOR⁶、CO-NR⁸R⁹、CS-NR¹⁰R¹¹、SO₂R¹⁴Or SO₂NR¹⁵R¹⁶, R³It is COR¹⁷、COOR¹⁸、CONR¹⁹R²⁰Or COON=CR²²R²³, R⁴It is hydrogen or (C₁-C₄) alkyl, R⁵It is hydrogen, (C₁-C₄) alkyl, (C₁-C₂) haloalkyl, cyclopropyl, phenyl, benzyl or the heteroaryl with 5 or 6 annular atoms, wherein 3 groups finally referred to are unsubstituted or replaced by 1 or multiple halogen atom, R⁶It is (C₁-C₄) alkyl, pi-allyl, propargyl or cyclopropyl, R⁸It is hydrogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl or (C₁-C₄- alkoxy) carbonyl, R⁹-R¹¹It is identical or different independently of each other, it is H or (C₁-C₄) alkyl, R¹⁴It is (C₁-C₄) alkyl, R¹⁵And R¹⁶It is identical or different independently of each other, it is H or (C₁-C₄) alkyl, R¹⁷It is hydrogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₃-C₆) cycloalkyl, phenyl or heteroaryl, last-mentioned two groups are unsubstituted or substituted, R¹⁸It is hydrogen, (C₁-C₄) alkyl, (C₂-C₆) alkenyl or (C₂-C₆) alkynyl, last-mentioned three groups are unsubstituted or by one or more selected from following substituent group：Halogen, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio group and NR³¹R³², or (C₃-C₆) cycloalkyl or (C₃-C₆) cycloalkyl-C₁-C₃- alkyl, R¹⁹Similar to R⁸, R²⁰Similar to R⁹, R²²And R²³It is separate and identical or different, it is hydrogen or (C₁-C₂) alkyl, R³¹、R³²It is separate and identical or different, it is hydrogen or (C₁-C₄) alkyl, W is oxygen or sulphur, and X is (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkyl, (C₁-C₄) alkylthio group, halogen or single-or two (C₁-C₂- alkyl) amino, Y is (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkyl or (C₁-C₄) alkylthio group, and Z is CH or N, B49) flupyrsulfuron (DPX-KE459)And/or B50) sulfosulfuron (MON37500)

20. according to Claims 1-4 or 17 one or more in required composition, wherein the herbicide for being included as B classes is B51) KIH-2023

21. the composition according to required by one of claim 18 or 19, the B class herbicides that wherein it is included are atrazine, metsul-furon methyl, tribenuron methyl and/or amidosulfuron.

22. the composition according to required by one of claim 1 or 4, wherein it includes one or more herbicides as B class herbicides, described herbicide non-selectively acts in non-crop area and/or is selectively applied to dogstail and broad leaved weed in genetically modified crops, and carrys out self-contained following group B52) glufosinate-ammonium, high glufosinate-ammonium

B53) glyphosate

23. according to composition required in claim 22, the B class herbicides that wherein it is included are glufosinate-ammonium ammonium salts.

24. the composition according to required by one or more of preceding claims, its compound of formula I comprising synergistic activity amount or its salt (A classes compound) and the combination of the compound from B groups.

25. the composition according to required by one or more of preceding claims, it includes the compound of formula I or its salt (A classes compound) and the compound from B groups that weight ratio is 1: 2500 to 20: 1.

26. the composition according to required by one or more of preceding claims, it includes by weight 0.1 to 99% active material A and B, and surplus is conventional machining adjuvant.

27. a kind of method for preparing the composition required in one or more according to preceding claims; it include compound of formula I or its salt (A classes compound) and one or more B classes compounds and optionally with one or more C class compounds, similarly prepared in the way of processing following conventional crop and protecting formulation：Wettable powder, missible oil, aqueous solution, emulsion, sprayable solution (tank mix), water-or oil-base dispersant, suspension emulsion, pulvis, seed dressing product, soil treatment are spread fertilizer over the fields with granule, water dispersible granule, ultra-low volume (ULV) preparation, microcapsules and cerate.

28. a kind of method for preventing and treating noxious plant, it includes one of active material A+B combination defined in one or more of the claim 1 to 23 of herbicidally effective amount being applied to above-mentioned plant or cultural area.

29. according to method required in claim 28, wherein the amount of application of formula (I) compound or its salt (A classes herbicide) is 0.1 to 100 gram of a.i./ha, it is preferred that 2 to 40 grams of a.i./ha, and the amount of application of B class compounds is 1 to 5000 gram of a.i./ha.

30. according to method required in claim 28 or 29, it using weight ratio is to apply at 1: 2500 to 20: 1 that wherein A and B classes active material, which is, using can be simultaneously or in different time point progress.

31. according to method required in one of claim 28 to 30 item, wherein the combination is to be used to optionally prevent and treat noxious plant.

32. according to method required in claim 31, wherein the combination is used in genetically modified plants.

33. according to method required in claim 31, wherein described combination is used in Cereal, corn, rice, sugarcane, plantation crops, meadow or pasture.

34. according to method required in one of claim 28 to 30 item, wherein described combination is used in crop.

35. according to method required in one of claim 28 to 30 item, wherein described combination is to be used for non-crop area.