CN100411515C - Difluoromethanesulfonyl anilide derivatives useful as herbicides - Google Patents

Difluoromethanesulfonyl anilide derivatives useful as herbicides Download PDF

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CN100411515C
CN100411515C CNB2005800099552A CN200580009955A CN100411515C CN 100411515 C CN100411515 C CN 100411515C CN B2005800099552 A CNB2005800099552 A CN B2005800099552A CN 200580009955 A CN200580009955 A CN 200580009955A CN 100411515 C CN100411515 C CN 100411515C
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compound
formula
herbicide
plant
weeds
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CN1937919A (en
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荒木恒一
工藤祐夫
佐藤善孝
远藤惠次
白仓伸一
中村新
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Bayer CropScience AG
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Abstract

Novel difluoromethanesulfonamide derivatives of the formula (I) Difluoromethanesulfonamide derivatives represented by the formula wherein X represents halogen, Y represents CH or N, R<1> represents hydrogen, and R<2> represents hydrogen or hydroxy, or R<1> and R<2> together may form C=O with the carbon atom to which they are bonded, and their use as herbicide for paddy field weeds.

Description

Difluoromethanesulfoanilide anilide derivatives as weed killer herbicide
The present invention relates to new difluoromethyl sulfamide derivative, its preparation method and as the purposes of weed killer herbicide.
Have now found that some sulfamide derivative has shown effect as weed killer herbicide (WO93/09099 for example, WO 96/41799, day disclosure unexamined patent application number 60562/1999 and day disclosure unexamined patent application number 44546/2000).
In the exploitation weed killer herbicide, have realized that in recent years weeds that control shows resistance to existing weed killer herbicide for example the problem of SU resistant weed (sulfonylureas resistant weed) be one of important theme.Need to develop and to control this class resistant weed and control other annual and weed killer herbicide perennial weed with single component simultaneously.
Therefore, the present invention has been found that the compound as shown in the formula (I)
Figure C20058000995500051
Wherein
X represents halogen,
Y represents CH or N,
R 1Expression hydrogen, and
R 2Expression hydrogen or hydroxyl, or
R 1And R 2Carbon atom with their bondings can form C=O.
Formula of the present invention (I) compound can obtain by the following method, wherein
With a) formula (II) compound
Figure C20058000995500061
Wherein
X, Y, R 1And R 2Have above-mentioned identical definition,
With the reaction of difluoromethyl sulfonic acid chloride, this is reflected under the atent solvent existence and carries out, and optionally has acid cement,
Or
B) at R 1And R 2Carbon atom with their bondings forms under the situation of C=O:
With formula (Ib) compound
Figure C20058000995500062
Wherein
X has above-mentioned identical definition with Y,
With oxidant reaction, this is reflected under the atent solvent existence and carries out, and optionally has acidic catalyst,
Or
C) at R 1Expression hydrogen, and R 2Under the situation of expression hydroxyl:
With formula (Ic) compound
Figure C20058000995500071
Wherein
X has above-mentioned identical definition with Y,
With alkali metal hydride complex compound or borane complex reaction, this is reflected under the atent solvent existence and carries out.
The difluoromethyl sulfamide derivative of formula of the present invention (I) has shown strong activity of weeding.
Be included in the WO 96/41799 described general formula compound although the difluoromethyl sulfamide derivative of formula (I) is conceptive, yet formula (I) compound is a noval chemical compound that it is not disclosed in the described list of references clearly.And compare with the known compound with analog structure in clearly being described in WO 96/41799, formula (I) compound has shown extremely strong herbicide effect unexpectedly.It has especially shown quite good herbicide effect to weeds in paddy field, and simultaneously the sulfonylureas resistant weed has been shown good herbicide effect, and this biological agent does not have record in WO 96/41799.
Therefore, to be used for the rice field as weed killer herbicide be especially favourable to the difluoromethyl sulfamide derivative of formula of the present invention (I).
In this manual, " halogen " expression fluorine, chlorine, bromine or iodine are preferably represented fluorine or chlorine.
In above-mentioned formula (I) compound, preferably,
X represents fluorine or chlorine,
Y represents CH or N,
R 1The expression hydrogen and
R 2Expression hydrogen or hydroxyl, or
R 1And R 2Carbon atom with their bondings can form C=O.
For example with 2-fluoro-6-[(4,6-dimethoxypyridin-2-yl)-hydroxymethyl] aniline and difluoromethyl sulfonic acid chloride are as under the situation of original material, above-mentioned preparation method (a) can be illustrated by following reaction icon.
Figure C20058000995500081
For example with 2-fluoro-6-[(4,6-dimethoxypyridin-2-yl)-methyl]-the N-Difluoromethanesulfoanilide anilide, be used as under the situation of oxidant as original material and with chromium oxide (VI), above-mentioned preparation method (b) can be illustrated by following reaction icon.
Figure C20058000995500082
For example with 2-fluoro-6-[(4,6-dimethoxypyridin-2-yl)-carbonyl]-the N-Difluoromethanesulfoanilide anilide as original material and with borohydride sodium as under the situation of alkali metal hydride complex compound, above-mentioned preparation method (c) can be illustrated by following reaction icon.
Figure C20058000995500083
In above-mentioned preparation method (a), be used as in formula (II) compound of original material this compound (R wherein 1And R 2Carbon atom with their bondings forms C=O) comprise the known compound described in the WO 96/41799, and can be easy to make according to for example method described in this list of references.
In addition, in above-mentioned formula (II) compound, this compound (R wherein 1Expression hydrogen and R 2The expression hydroxyl) comprise the known compound described in the Japanese laid-open publication number 60562/1999, and in above-mentioned formula (II), it can be according to the described method of this list of references by with compound (R wherein 1And R 2Carbon atom with their bondings forms C=O) be easy to make with metal hydride complex compound such as reactions such as borohydride sodium, lithium aluminium hydride reduction.
In above-mentioned formula (II) compound, this compound (R wherein 1And R 2All represent hydrogen) comprise the known compound described in the WO 96/41799, and can be, or react with Raney nickel (Raney nickel) and to be easy to make according to the method described in the document by with formula (III) compound and reductant such as borohydride sodium (in the presence of nickel chloride (II)).
Wherein X has above-mentioned identical definition with Y.
Above-mentioned formula (III) compound comprises the known compound described in the above-mentioned patent documentation, and can be easy to make according to the described method of for example document.
As the instantiation of formula (II) compound that in above-mentioned preparation method (a), is used as original material, can mention following compound:
2-fluoro-6-[(4,6-dimethoxypyridin-2-yl) methyl] aniline,
2-chloro-6-[(4,6-dimethoxypyridin-2-yl) methyl] aniline,
2-bromo-6-[(4,6-dimethoxypyridin-2-yl) methyl] aniline,
2-iodo-6-[(4,6-dimethoxypyridin-2-yl) methyl] aniline,
2-fluoro-6-[(4,6-dimethoxypyridin-2-yl) hydroxymethyl] aniline,
2-chloro-6-[(4,6-dimethoxypyridin-2-yl) hydroxymethyl] aniline,
2-bromo-6-[(4,6-dimethoxypyridin-2-yl) hydroxymethyl] aniline,
2-iodo-6-[(4,6-dimethoxypyridin-2-yl) hydroxymethyl] aniline,
2-fluoro-6-[(4,6-dimethoxypyridin-2-yl) carbonyl] aniline,
2-chloro-6-[(4,6-dimethoxypyridin-2-yl) carbonyl] aniline,
2-bromo-6-[(4,6-dimethoxypyridin-2-yl) carbonyl] aniline,
2-iodo-6-[(4,6-dimethoxypyridin-2-yl) carbonyl] aniline,
2-fluoro-6-[(4,6-dimethoxy-triazine-2-yl) methyl] aniline,
2-chloro-6-[(4,6-dimethoxy-triazine-2-yl) methyl] aniline,
2-bromo-6-[(4,6-dimethoxy-triazine-2-yl) methyl] aniline,
2-iodo-6-[(4,6-dimethoxy-triazine-2-yl) methyl] aniline,
2-fluoro-6-[(4,6-dimethoxy-triazine-2-yl) hydroxymethyl] aniline,
2-chloro-6-[(4,6-dimethoxy-triazine-2-yl) hydroxymethyl] aniline,
2-bromo-6-[(4,6-dimethoxy-triazine-2-yl) hydroxymethyl] aniline,
2-iodo-6-[(4,6-dimethoxy-triazine-2-yl) hydroxymethyl] aniline,
2-fluoro-6-[(4,6-dimethoxy-triazine-2-yl) carbonyl] aniline,
2-chloro-6-[(4,6-dimethoxy-triazine-2-yl) carbonyl] aniline,
2-bromo-6-[(4,6-dimethoxy-triazine-2-yl) carbonyl] aniline,
2-iodo-6-[(4,6-dimethoxy-triazine-2-yl) carbonyl] aniline, or the like.
Formula (Ib) compound that is used as original material in above-mentioned preparation method (b) can be mentioned its following particular instance corresponding to part formula of the present invention (I) compound that can make by said method (a):
2-fluoro-6-[(4,6-dimethoxypyridin-2-yl) methyl]-the N-Difluoromethanesulfoanilide anilide,
2-chloro-6-[(4,6-dimethoxypyridin-2-yl) methyl]-the N-Difluoromethanesulfoanilide anilide,
2-bromo-6-[(4,6-dimethoxypyridin-2-yl) methyl]-the N-Difluoromethanesulfoanilide anilide,
2-fluoro-6-[(4,6-dimethoxy-triazine-2-yl) methyl]-the N-Difluoromethanesulfoanilide anilide, or the like.
What be used in above-mentioned preparation method (b) that the oxidant of the above-mentioned formula of oxidation (Ib) compound can mention is for example chromium oxide (VI), manganese dioxide, selenium dioxide, selenium dioxide or the like.
Formula (Ic) compound that is used as original material in above-mentioned preparation method (c) is corresponding to can mentioning its following particular instance by said method (a) or the part that (b) makes formula of the present invention (I) compound:
2-fluoro-6-[(4,6-dimethoxypyridin-2-yl) carbonyl]-the N-Difluoromethanesulfoanilide anilide,
2-chloro-6-[(4,6-dimethoxypyridin-2-yl) carbonyl]-the N-Difluoromethanesulfoanilide anilide,
2-bromo-6-[(4,6-dimethoxypyridin-2-yl) carbonyl]-the N-Difluoromethanesulfoanilide anilide,
2-iodo-6-[(4,6-dimethoxypyridin-2-yl) carbonyl]-the N-Difluoromethanesulfoanilide anilide,
2-fluoro-6-[(4,6-dimethoxy-triazine-2-yl) carbonyl]-the N-Difluoromethanesulfoanilide anilide, or the like.
What be used in above-mentioned preparation method (c) that the alkali metal hydride complex compound of hydrogenation of formula (Ic) compound can mention is for example borohydride sodium, lithium aluminium hydride reduction etc., and can mention for example dimethyl sulfide borine, pyridine borine etc. as borane complex.
Above-mentioned preparation method's (a) reaction can be carried out in suitable thinner.What the example of the thinner that uses can be mentioned is aliphatic, alicyclic and aromatic hydrocarbon (can choose wantonly through chloro), for example pentane, hexane, cyclohexane, benzinum, volatile oil, benzene,toluene,xylene, carrene, chloroform, tetrahydro carbon, 1,2-carrene, chlorobenzene, dichloro-benzenes etc.; Ethers, for example ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxy-ethane (DME), oxolane (THF), diethylene glycol dimethyl ether (DGM) etc.; Ketone is acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methylisobutylketone (MIBK) etc. for example; Nitrile is acetonitrile, propionitrile etc. for example; The ester class is ethyl acetate, pentyl acetate etc. for example; Bases is pyridine etc. for example.
Preparation method (a) can carry out in the presence of sour cement.What can mention as described sour cement is inorganic base, hydride, hydroxide, carbonate, bicarbonate with alkali metal, alkaline earth metal etc., for example sodium hydride, lithium hydride, sodium bicarbonate, saleratus, sodium carbonate, potash, lithium hydroxide, sodium hydroxide, potassium hydroxide, slaked lime etc.; Inorganic alkali metal ammonia compound is lithium amide, sodium amide, amination potassium etc. for example; With tertiary amine, dialkyl amido aniline and the pyridines of organic base, for example triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N, accelerine, N, N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicylo [2,2,2] octane (DABCO), 1,8-diazabicylo [5,4,0] 11 carbon-7-alkene (DBU) etc.
Preparation method (a) can carry out under the temperature of suitable wide region.Yet, preferably to about 60 ℃ temperature range, carry out especially about-80 to about 40 ℃ in the pact-100 of routine.Carry out although described reaction is desirably under the normal pressure, it also can be chosen wantonly under pressurization or decompression and carry out.
In being prepared method (a), by with formula (II) compound of 1 to 5 mole difluoromethyl sulfonic acid chloride and 1 mole thinner for example in the carrene reaction can obtain target compound, this is reflected at 1 to 5 mole of pyridine and carries out under existing.
Above-mentioned preparation method's (b) reaction can be carried out in suitable thinner.What employed thinner example can be mentioned is water; Aliphatic, alicyclic and aromatic hydrocarbon (can choose wantonly) through chloro, for example hexane, cyclohexane, volatile oil, toluene, dimethylbenzene, carrene, chloroform, tetrahydro carbon, 1,2-carrene, chlorobenzene etc.; Ethers, for example ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxy-ethane (DME), oxolane (THF), diethylene glycol dimethyl ether (DGM) etc.; Ketone is acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methylisobutylketone (MIBK) etc. for example; Nitrile is acetonitrile, propionitrile, acrylonitrile etc. for example; The ester class is ethyl acetate, pentyl acetate etc. for example; Amide-type is dimethyl formamide (DMF), dimethyl acetamide (DMA), N-Methyl pyrrolidone, 1 for example, 3-dimethyl-2-imidazolinedione, HMPA (HMPA) etc.; Sulfone and sulfoxide class be methyl-sulfoxide (DMSO), sulfolane etc. for example; Bases is pyridine etc. for example; Acids is acetate etc. for example.
Preparation method (b) can carry out in the presence of acid catalyst, and what can mention as acid catalyst is for example nicotinic acid, sulfuric acid, nitric acid, hydrobromic acid, sodium hydrogensulfite etc. of inorganic acid herein; Organic acid is formic acid, acetate, trifluoroacetic acid, propionic acid, methanesulfonic acid, benzene sulfonic acid, right-toluenesulfinic acid etc. for example.
Preparation method (b) can carry out under the temperature of suitable wide region.Yet, preferably to about 150 ℃ temperature range, carry out especially about 20 to about 120 ℃ in the pact-100 of routine.Carry out although described reaction is desirably under the normal pressure, it also can be chosen wantonly under pressurization or decompression and carry out.
In being prepared method (b), by with 1 to 10 mole chromium oxide (VI) and 1 mole formula (Ib) compound thinner for example in the acetate reaction can obtain target compound.
Above-mentioned preparation method's (c) reaction can be carried out in suitable thinner.What employed thinner example can be mentioned is water; Aliphatic, alicyclic and aromatic hydrocarbon (can choose wantonly) through chloro, for example pentane, hexane, cyclohexane, benzinum, volatile oil, benzene,toluene,xylene, carrene, chloroform, tetrahydro carbon, 1,2-carrene, chlorobenzene, dichloro-benzenes etc.; Ethers, for example ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxy-ethane (DME), oxolane (THF), diethylene glycol dimethyl ether (DGM) etc.; Nitrile is acetonitrile, propionitrile etc. for example; Alcohols is methyl alcohol, ethanol, isopropyl alcohol, butanols, ethylene glycol etc. for example; The ester class is ethyl acetate, pentyl acetate etc. for example; Amide-type is dimethyl formamide (DMF), dimethyl acetamide (DMA), N-Methyl pyrrolidone, 1 for example, 3-dimethyl-2-imidazolinedione, HMPA (HMPA) etc.; Sulfone and sulfoxide class be methyl-sulfoxide (DMSO), sulfolane etc. for example; Bases is pyridine etc. for example.
Preparation method (c) can carry out under the temperature of suitable wide region.Yet, preferably to about 60 ℃ temperature range, carry out especially about-80 to about 40 ℃ in the pact-100 of routine.Carry out although described reaction is desirably under the normal pressure, it also can be chosen wantonly under pressurization or decompression and carry out.
In being prepared method (c), reacting in thinner such as methyl alcohol by formula (III) compound and can obtain target compound 0.25 to 2 mole borohydride sodium and 1 mole.
Can handle all plants and plant part according to the present invention.Plant in this article is interpreted as being meant all plants and plant population, for example need with unwanted wild plant or crop (comprising the crop that nature grows).Crop can be by conventional plant breeding and optimization method, or the plant that can obtain by biotechnology and recombination method or the combination by these methods, and it comprises genetically modified plants and comprises by plant breeder's protection or unprotected cultivar.Plant part is interpreted as referring on the ground and all parts and the organ of underground plant, for example branch, leaf, Hua Hegen, and its example that can mention is blade, needle, petiole, stem, flower, fruit body, fruit, seed, root, stem tuber and rhizome.Plant part also comprises the results material, and asexual and sexual propagation material, for example cuttage bar, stem tuber, basis, offsets and seed.
The present invention with reactive compound handle plant and plant part be directly carry out or by conventional method allow compound effects around it, environment or storage area, for example by flooding, spray, evaporate, haze, scatter, spray thereon, and at propagating materials, especially in the seed, can also use one or more coatings.
The reactive compound of the above-mentioned formula of the present invention (I) can be preferred for controlling weeds in paddy field.Can followingly mention by the weeds in paddy field example that utilizes reactive compound of the present invention to control:
Dicotyledon as the subordinate:Polygonum (Polygonum), Han Lepidium (Rorippa), joint Lepidium (Rotala), Vandellia (Lindernia), Bidens bipinnata belong to (Bidens), the horsefly eye belongs to (Dopatrium), sweet wine intestines genus (Eclipta), Elatine ambigua (Elatine), Gratiola (Gratiola), Vandellia (Lindernia), ludwigia (Ludwigia), Oenanthe (Oenanthe), Ranunculus (Ranunculus), damp chilly genus (Deinostema) etc.
Monocotyledon as the subordinate:Echinochloa (Echinochloa), Panicum (Panicum), annual bluegrass belong to (Poa), Cyperus (Cyperus), Monochoria (Monochoria), genus fimbristylis (Fimbristylis), arrowhead genus (Sagittaria), Eleocharis (Eleocharis), Fischer grass genus (Scirpus), Waterplantain (Alisma), Aneilema, water screening spp (Blyxa), eriocaulon buergerianum (Eriocaulon), Potamogeton (Potamogeton) etc.
The above-mentioned formula of the present invention (I) reactive compound can be used to be specifically related to following representative weeds in paddy field:
The plant latin name
Dicotyledon:
Mexicana (Rotala indica Koehne),
Procumbent Falsepimpernel (Lindernia procumbens Philcox),
Lindernia dubia L.Penn.，
Lindernia micrantha (Lindernia angustifolia),
False loosestrife (Ludwigia prostrata Roxburgh),
Pondweed (Potamogeton distinctus A.Benn),
Three stamen waterworts (Elatine triandra Schk),
Chinese celery (Oenanthe javanica).
Monocotyledon:
Paddy field barnyard grass (Echinochloa oryzicola Vasing),
Lunge needle spikesedge herb (Eleocharis acicularis L.),
Eleocharis kuroguwai Ohwi，
Difformed galingale herb (Cyperus difformis L.),
Herba Cyperi Glomerati (Cyperus serotinus Rottboel),
Firefly Lin (Scirpus juncoides Roxburgh),
Monochoria vaginalis (Monochoria vaginalis Presl),
Short arrowhead (Sagittaria pygmaea Miq),
Wear leaf rhizoma alismatis (Alisma canaliculatum A.Br.Et Bouche),
Sagittaria trifolia，
Monochoria korsakowii (Monochoria korsakowii).
In addition, the above-mentioned formula of the present invention (I) reactive compound can be effective to control example as sulfonylurea herbicide being shown the above-mentioned weeds of resistance.
Yet the purposes of above-mentioned formula of the present invention (I) reactive compound is not limited to be used to control these weeds kinds, and the weeds that can be used to control the weeds in paddy field of other kind in the same manner and be different from the sulfonylurea herbicide resistant weed.
In actual using, reactive compound of the present invention can be mixed with the conventional formulation type.This class preparation type can be mentioned be for example solution, wetting powder, emulsion, suspending agent, pulvis, water dispersion granule, tablet, granule, suspension emulsion, with the microcapsule formulations of polymeric material form, jet preparation etc.
These preparations can make by original known method, for example by with reactive compound and bulking agent, i.e. and liquid or solid diluent or carrier, and optional and surfactant, promptly emulsifier and/or dispersant and/or foaming agent mix mutually.
The liquid diluent that can mention or carrier are for example aromatic hydrocarbons (for example dimethylbenzene, toluene or Fluhyzon etc.), chlorinated aromatics or chlorinated aliphatic hydrocarbon (as chlorobenzene, vinyl chloride or carrene etc.), aliphatic hydrocarbon is [as cyclohexane etc., or paraffin (as mineral oil fractions etc.)], alcohols (as butanols, ethylene glycol etc.) and ether, ester etc., ketone (as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone etc.), intensive polar solvent (as dimethyl formamide, methyl-sulfoxide etc.), water etc.Water is being used as under the situation of bulking agent, and for example organic solvent can be used as cosolvent.
The solid diluent that can mention or carrier are: the natural mineral matter (for example kaolin, clay, talcum, chalk, quartz, Attagel, imvite or diatomite etc.) through grinding for example, the synthetic material (for example finely divided silica, aluminium oxide and silicate etc.) through grinding.Can mention that the solid carrier that is applicable to particle is: that for example pulverize and natural rock classification (as calcite, marble, float stone, sepiolite and dolomite etc.), the synthetic particle of inorganic and organic powdery, organic material particle (as sawdust, cocoa husk, corncob or tobacco rods etc.) etc.
The emulsifier that can mention and/or foaming agent are: for example nonionic and anion emulsifier [as polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether (for example alkylaryl polyglycol ether, alkyl sulfonic ester, alkyl sulfate, aromatic yl sulphonate)], protein hydrolysate etc.
Dispersant comprises for example lignin sulfite waste liquor, methylcellulose etc.
Thickener can be used for preparation (pulvis, granule, missible oil).The described thickener that can mention is for example carboxymethyl cellulose, natural and synthetic polymer (for example gum Arabic, polyvinyl alcohol or polyvinyl acetate etc.).
Can also use colouring agent.The described colouring agent that can mention is inorganic pigment (for example iron oxide, titanium oxide and Prussian blue etc.), and organic dyestuff such as alizarin dyes, azo dyes or metal phthalein cyanine dye, and other the micronutrient salt of iron, manganese, boron, copper, cobalt, molybdenum and zinc etc. for example.
Said preparation comprises formula (I) reactive compound between 0.01 and 95 weight % usually, preferably between 0.1 and 90 weight %.
Formula of the present invention (I) reactive compound can be used for weeds control with itself or its dosage form.Formula (I) reactive compound can also be used for other known weed killer herbicide combined.Can make in advance with final dosage form with the Herbicidal combinations that known weed killer herbicide mixes mutually, or can get by bucket is mixed in use.Can be used for can mentioning following weed killer herbicide with the weed killer herbicide of the combined mixed herbicidal composite of formula (I) compound, it represents that with common name representative instance is:
Acetyl herbicide: for example third careless amine, butachlor, P DimethenamidP, alachlor etc.;
Acetamide-group herbicides: for example clomeprop, ethobenzanid etc.;
Benzofurans weed killer herbicide: benfuresate etc. for example;
Indandione class weed killer herbicide: indanofan etc. for example;
Pyrazoles weed killer herbicide: for example pyrazolate, benzofenap, pyrazoxifen etc.;
Oxazine ketone weed killer herbicide: example is as the oxazine humulone etc.;
Sulfonylurea herbicide: for example bensulfuron-methyl-methyl esters, azimsulfuron, imidazoles sulphur are grand, pyrazosulfuron ethyl ester, AC322140, ethoxysulfuron, halosulfuronmethyl methyl esters etc.;
Dithiocarbamate herbicide: for example benthiocarb, molinate, pyributycarb etc.;
Triazine herbicide: for example dimethametryn, symetryne etc.;
Triazole herbicide: azoles acyl grass amine etc. for example;
Quinolines weed killer herbicide: dichloro quinolinic acid etc. for example;
Isoxazole herbicide: isoxazole humulone etc. for example;
Dithio acid esters weed killer herbicide: the home country of anilofos for example;
Oxyacetamide weed killer herbicide: for example mefenacet, flufenacet etc.;
Tetrazolinone herbicides: fentrazamide etc. for example;
Dicarboximide class weed killer herbicide: Huan Wu Evil humulone etc. for example;
Oxadiazole ketone weed killer herbicide: oxadialgyl, Evil humulone etc. for example;
Three ketones weed killer herbicide: for example sulphur humulone, benzobicyclon etc.;
Phenoxy propionic acid ester herbicide: cyhalofop-butyl etc. for example;
Benzoic acid herbicide: for example KIH 6127, two careless ethers etc.;
Diphenylether weed killer herbicide: for example chlomethoxynil, Oxyfluorfen etc.;
Pyridine dicarboxyl thioesters class weed killer herbicide: dithiopyr etc. for example;
Phenoxy herbicide: for example MCPA, MCPB etc.;
Carbamide herbicides: for example vanilla is grand, cumyluron etc.;
Naphthalenedione class weed killer herbicide: quinoclamine etc. for example;
Isoxazole dione herbicides: clomazone etc. for example.
Above-mentioned reactive compound is known weed killer herbicide, and it is described in by British CropProtect Council in " Pesticide Manual " (agricultural chemicals handbook) of publishing in 2000.
In addition, when formula of the present invention (I) reactive compound is mixed mutually with safener, reduced phytotoxicity, and wideer weeds control spectrum is provided, and can enlarge application as selective herbicide by mixing.
Described safener can be mentioned is for example by the following compound of common name or coded representation:
AD-67, BAS-145138, benoxacor, cloquitocet_mexyl, cyometrinil, 2,4-D, DKA-24, dichlormide, vanilla are grand, fenclorim, fenchlorazole, separate careless amine, fluxofenim, separate careless amine, Shuan Ben oxazole acetoacetic ester, mefenpyrdiethyl, MG-191, naphthalic anhydride, oxavetrinil, PPG-1292, R-29148 etc.
Above-mentioned safener also is described in by British Crop Protect Council in " Pesticide Manual " (agricultural chemicals handbook) of publishing in 2000.
In addition, can also be further above-mentioned safener be mixed mutually with herbicidal composition through mixing, described herbicidal composition is made up of formula of the present invention (I) compound and above-mentioned weed killer herbicide.Reduced phytotoxicity by mixing, and wideer weeds control spectrum is provided, and can enlarge application as selective herbicide.
Surprisingly, the herbicidal composition of part through mixing of being made up of The compounds of this invention and known weed killer herbicide and/or safener can show synergy.
In utilizing formula (I) reactive compound, it can directly use with itself or use with dosage form, for example available at once solution, missible oil, tablet, suspending agent, pulvis, paste or granule, or use with the prepared type of service of further dilution.Reactive compound of the present invention can by for example water, spraying, atomizing, particle use to wait and use.
Formula (I) reactive compound can be before plantling and seedling after any stage use.It also can be sneaked in the soil prior to seeding.
The amount of application of formula (I) reactive compound can change within the specific limits.This difference fundamentally depends on the character of required effect.As under the situation of weed killer herbicide, can mention be the scope of amount of application for for example about 0.0001 to about 4kg, preferred reactive compound/hectare of about 0.01 to about 3kg.
Mentioned that as above the present invention can handle all plants and part thereof.In preferred embodiments, with wild plant kind and plant cultivation kind, or the biological breeding method by routine merges the plant variety and the part thereof that obtain as hybridization or protoplast and handles.In another preferred embodiment, handle, optionally conventional method genetically modified plants and plant cultivation kind and the plant part thereof that (genetic modified organism body) obtains that combine by gene engineering method.Term " part " or " part of plant " or " plant part " had been done explanation in the above.
According to the present invention, special preferred process is commercially available that get or the plant of the cultivar of using under concrete situation.Cultivar is interpreted as expression and has defined feature (" characteristic "), and by conventional breeding, by mutagenesis or the plant by recombinant DNA technology acquisition.They can be kind type, biotype or genotype.
According to floristics or plant cultivation kind, their habitat and growth conditions (soil, weather, vegetation period, nutrition), according to processing of the present invention also can cause super add and (" work in coordination with ") act on.Therefore, for example can reach reduce consumption and/or widen activity profile and/or improve compound used therefor of the present invention and with the activity of the combined composition of other agricultural chemical activity compound, improve plant growth, strengthen tolerance to high or low temperature, strengthen crop to the tolerance of drought or floods and soil salt amount, increase the performance of blooming, be easy to gather in the crops, hasting of maturity, raising harvest yield, improve the quality of results product and/or improve product nutritive value, improve the storage stability and/or the machinability of product, these have exceeded actual desired effect.
Genetically modified plants that the present invention preferably handles or plant variety (promptly obtaining by gene engineering) comprise by the gene engineering of genetic material modifies all plants that obtain, and described genetic modification is given the particularly advantageous useful performance of these plants (" characteristic ").The example of this specific character is plant growing preferably, strengthen tolerance to high or low temperature, strengthen tolerance to drought or floods or soil salt amount, increase the performance of blooming, be easy to gather in the crops, hasting of maturity, higher crop, results product preferable quality and/or higher nutritive value, results product storage stability and/or machinability preferably.Further the example with ben described characteristic is to improve the insect of plant to animal and microorganism, as the property resisted of insect, mite, plant pathogenic fungi, bacterium and/or virus, and improves the tolerance of plant to some herbicidal active compounds.The example of the genetically modified plants that can mention is important crops, as cereal crops (wheat, rice), corn, soybean, potato, cotton, rape and fruit plant (apple, pears, oranges and tangerines and grape), ben is corn, soybean, potato, cotton and rape.Ben characteristic is by the toxin that produces in plant, and particularly those that produce in plant by the genetic stew (for example by gene C ryIA (a), CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and their associating) (hereinafter being called " Bt plant ") from bacillus thuringiensis,Bt (Bacillusthuringiensis) strengthen the performance of the anti-insect of plants.The characteristic that also requires emphasis especially is to improve the plant protection effect that the resistance (SAR), systemin (systemin), phytoalexin, elicitors and the resistant gene that obtain by system and corresponding expressed proteins and toxin come antimycotic, bacterium and toxin.In addition, ben characteristic is that plant is to some weeding active compound, as the tolerance of the enhancing of imidazolone type, sulfonylurea, glyphosate class or phosphino-triein (for example " PAT " gene).The gene that gives desired properties also can be united existence mutually in genetically modified plants.The example of " the Bt plant " that can mention is with trade name YIELD
Figure C20058000995500201
(for example corn, cotton, soybean),
Figure C20058000995500202
(for example corn),
Figure C20058000995500203
(for example corn), (cotton),
Figure C20058000995500205
(cotton) and
Figure C20058000995500206
Corn variety, cotton variety, soybean varieties and potato kind that (potato) sells.The plant of the herbicide-tolerant that can mention is with trade name Roundup
Figure C20058000995500207
(tolerance glyphosate, for example corn, cotton, soybean), Liberty
Figure C20058000995500208
(tolerance phosphino-triein, for example rape seed rape),
Figure C20058000995500209
(tolerance imidazolone type) and
Figure C200580009955002010
Corn variety, cotton variety, soybean varieties that (tolerance sulfonylurea, for example corn) sold.The plant of the antiweed that can mention (being generally used for the herbicide tolerant breeding) comprises with trade name
Figure C200580009955002011
The kind that (for example corn) sold.Be understood that these narrations also are applicable to plant that develop the future of the genetic characteristics that has described characteristic or also will improve in the future and/or the plant variety of putting on market in the future.
Listed plant can be handled with formula of the present invention (I) compound or active compound combinations in particularly advantageous mode, wherein except effective control weeds, genetically modified plants and plant cultivation kind is produced above-mentioned synergy.For active component or mixture, above-mentioned preferable range also is applicable to handles these plants.Ben is with compound or the mixture process plant mentioned especially herein.
The further concrete preparation of formula of the present invention (I) compound and use example with shown in the following embodiment.Yet the present invention not only is limited to this by any way.
Synthetic embodiment 1
Figure C20058000995500211
With 2-fluoro-6-[(4,6-dimethoxypyridin-2-yl) hydroxymethyl] aniline 1.6g (5.28mmol) is dissolved in the carrene (13ml), and to wherein adding pyridine 0.91g (11.46mmol).This solution is cooled to-5 ℃, and to carrene (2ml) solution that wherein adds difluoromethyl sulfonic acid chloride 1.73g (11.46mmol).At room temperature stirring reaction solution is 4 days, and uses dichloromethane extraction three times after adding entry.With 1N hydrochloric acid and water washing organic layer.After the drying, decompression distillates carrene, and the oily matter that the obtains mixed solvent by utilizing 1: 3 ethyl acetate and hexane is carried out purifying as the column chromatography of eluant, eluent, obtain target product 2-fluoro-6-[(4,6-dimethoxypyridin-2-yl) hydroxymethyl]-N-Difluoromethanesulfoanilide anilide 0.94g (productive rate 42%), it is a pale yellow crystals.
1H-NMR(300MHz，CDCl 3)δ3.99(6H，s)，4.97(1H，d)，5.99(1H，s)，6.13(1H，d)，6.61(1H，t)，7.07-7.13(1H，m)，7.23-7.29(1H，m)，7.51-7.53(1H，m)，10.57(1H，br)。
Synthetic embodiment 2
Figure C20058000995500221
2-chloro-6-[(4,6-dimethoxypyridin-2-yl) methyl] aniline 1.54g (5.51mmol) is dissolved in the carrene (12ml), and to wherein adding pyridine 0.87g (11.01mmol).This solution is cooled to-5 ℃, and to carrene (2ml) solution that wherein adds difluoromethyl sulfonic acid chloride 1.66g (11.01mmol).At room temperature stirring reaction solution is 4 days, and uses dichloromethane extraction three times after adding entry.After waiting to wash with water organic layer and drying, decompression distillates carrene, and obtain the target product 2-chloro-6-[(4 of white crystal, 6-dimethoxypyridin-2-yl) methyl]-N-Difluoromethanesulfoanilide anilide 1.2g (productive rate 55%), it is by utilizing 1: 6 the ethyl acetate and the mixed solvent of hexane to obtain as eluant, eluent column chromatography oily matter.
1HNMR(300MHz，CDCl 3)δ3.94(6H，s)，4.30(2H，s)，5.92(1H，s)，6.74(1H，t)，7.18-7.21(1H，m)，7.33-7.38(2H，m)，11.09(1H，br)。
Same procedure by above-mentioned synthetic embodiment 2 obtains following compound:
2-fluoro-6-[(4,6-dimethoxy-triazine-2-yl) methyl]-the N-Difluoromethanesulfoanilide anilide.
1H-NMR(300MHz，CDCl 3)δ4.05(6H，s)，4.22(2H，s)，6.56(1H，t)，7.07-7.28(3H，m)，10.16(1H，s)。
Synthetic embodiment 3
Figure C20058000995500231
With 2-chloro-6-[(4,6-dimethoxypyridin-2-yl) methyl]-N-Difluoromethanesulfoanilide anilide 0.4g (1.02mmol) is dissolved in the acetate (6ml), and to wherein adding chromium oxide (VI) 0.31g (3.05mmol).This solution is heated to 30 ℃ and stirred 6 hours.After at room temperature stirring 12 hours again, with the reaction solution dilute with water, and with diethyl ether extraction three times.The organic layer that washes with water.After the drying, decompression distillates diethyl ether, and obtain the target product 2-chloro-6-[(4 of white crystals, 6-dimethoxypyridin-2-yl) carbonyl]-N-Difluoromethanesulfoanilide anilide 0.28g (productive rate 67%), it is by utilizing 1: 3 the ethyl acetate and the mixed solvent of hexane to obtain as eluant, eluent column chromatography oily matter.
1H-NMR(300MHz，CDCl 3)δ3.93(6H，s)，6.19(1H，s)，6.34(1H，t)，7.37-7.43(1H，m)，7.63-7.69(2H，m)。
Same procedure by above-mentioned synthetic embodiment 3 obtains following compound:
2-fluoro-6-[(4,6-dimethoxy-triazine-2-yl) carbonyl]-the N-Difluoromethanesulfoanilide anilide.
1H-NMR(300MHz，CDCl 3)δ4.10(6H，s)，6.48(1H，t)，7.36(1H，m)，7.45(1H，t)，7.55(1H，d)，9.08(1H，s)。
Synthetic embodiment 4
Figure C20058000995500232
With 2-chloro-6-[(4,6-dimethoxypyridin-2-yl) carbonyl]-N-Difluoromethanesulfoanilide anilide 0.83g (2.04mmol) is dissolved among the methyl alcohol 30ml, and after treating that it is cooled to 5 ℃, when stirring to wherein adding borohydride sodium 0.15g (4.07mmol).At room temperature stirred this solution subsequently 2 hours.The decompression distillation reaction solution, and the crystallization that is obtained is dissolved in water and the carrene, and neutralize with citric acid.Separate organic layer, and with the further aqueous layer extracted of carrene 3 times.After washing organic layer and drying with water, decompression distillates carrene, obtains the target product 2-chloro-6-[(4 of white crystals, 6-dimethoxypyridin-2-yl) hydroxymethyl]-N-Difluoromethanesulfoanilide anilide 0.79g (productive rate 95%).
1H-NMR(300MHz，CDCl 3)δ3.99(6H，s)，4.99(1H，br)，5.99(1H，s)，6.24(1H，s)，6.76(1H，t)，7.27-7.30(1H，m)，7.39-7.42(1H，m)，7.64-7.67(1H，m)，10.62(1H，br)。
The compound that obtains with the same procedure of above-mentioned synthetic embodiment 1-4 is with being shown in the following table 1 with the synthetic compound of synthetic embodiment 1-4, and its physics and chemical property are as shown in table 2.
Table 1
Figure C20058000995500251
Figure C20058000995500252
Table 2
Compound number Physics and chemical property ( 1H-NMR(300MHz，CDC 3)δ)
1 3.99(6H，s)，4.97(1H，d)，5.99(1H，s)，6.13(1H，d)，6.61(1H，t)， 7.07-7.13(1H，m)，7.23-7.29(1H，m)，7.51-7.53(1H，m)，10.57(1H，br).
2 4.08(6H，s)，6.10(1H，s)，6.58(1H，t)，7.13(1H，t)，7.26-7.33(1H，m)， 7.47(1H，d)，9.60(1H，s).
3 3.99(6H，s)，4.99(1H，br)，5.99(1H，s)，6.24(1H，s)，6.76(1H，t)， 7.27-7.30(1H，m)，7.39-7.42(1H，m)，7.64-7.67(1H，m)，10.62(1H，br).
9 3.97(6H，s)，4.26(2H，s)，5.94(1H，s)，6.59(1H，t)，7.05-7.13(1H，m)， 7.16-7.23(2H，m)，11.14(1H，br).
10 4.05(6H，s)，4.22(2H，s)，6.56(1H，t)，7.07-7.28(3H，m)，10.16(1H，s).
11 3.94(6H，s)，4.30(2H，s)，5.92(1H，s)，6.74(1H，t)，7.18-7.21(1H，m)， 7.33-7.38(2H，m)，11.09(1H，br).
12 4.02(6H.s)4.34(2H，s)6.68(1H，t)7.22(1H)7.32(1H)7.41(1H)9.98(1H，br).
17 3.97(6H，s)，6.20(1H，s)，6.51(1H，t)，7.29-7.34(1H，m)，7.39-7.46(1H，m)， 7.55-7.58(1H，m)，11.14(1H，br).
18 4.10(6H，s)，6.48(1H，t)，7.36(1H，m)，7.45(1H，t)，7.55(1H，d)，9.08(1H，s)，
19 3.93(6H，s)，6.19(1H，s)，6.34(1H，t)，7.37-7.43(1H，m)，7.63-7.69(2H，m).
Reference example 1
Figure C20058000995500261
With 2-fluoro-6-[(4,6-dimethoxypyridin-2-yl) carbonyl] aniline 2.68g (9.67mmol) is dissolved among the methyl alcohol 80ml, and is and to be cooled after 5 ℃, at the general formula that stirs to wherein adding borohydride sodium 0.73g (19.33mmol).Subsequently solution was at room temperature stirred 2 hours.The decompression distillation reaction solution, and the crystallization that is obtained is dissolved in water and the carrene.Separate organic layer and use the dichloromethane extraction water layer again 3 times.After waiting to wash with water organic layer and drying, decompression distillates carrene, obtains the target product 2-fluoro-6-[(4 of white crystal, 6-dimethoxypyridin-2-yl) hydroxymethyl] aniline 2.66g (productive rate 98%).
1H-NMR(300MHz，CDCl 3)δ3.94(6H，s)，4.74(3H，m)，5.84(1H，d)，5.94(1H，s)，6.66-6.73(1H，m)，6.88-6.95(1H，m)，7.13-7.15(1H，m)。
Reference example 2
Figure C20058000995500271
Under 0-10 ℃, to the 2-of 10ml chloro-6-[1-(4,6-dimethoxypyridin-2-yl)-and the 1-methylthiomethyl] add 0.28g (7.37mmol) borohydride sodium in aniline 0.6g (1.84mmol) and the hexahydrated methanol solution of 0.88g (3.68mmol) nickel chloride (II), and reaction solution was at room temperature stirred 2 hours.The decompression distillation reaction solution adds ammoniacal liquor and carrene and leaches insoluble substance.Separate organic layer and use the dichloromethane extraction water layer again 3 times.After waiting to wash with water organic layer and drying, decompression distillates carrene, and the crystallization that is obtained with the n-hexane washing is to obtain the target product 2-chloro-6-[(4 of white crystals, 6-dimethoxypyridin-2-yl) methyl] aniline 0.48g (productive rate 93%).
1H-NMR(300MHz，CDCl 3)δ3.91(6H，s)，4.01(2H，s)，5.18(2H，s)，5.81(1H，s)，6.62-6.67(1H，m)，7.14-7.17(2H，m)。
Reference example 3
Figure C20058000995500272
2-chloroaniline 5.2g (26.0mmol) is dissolved in the carrene (200ml), and solution is cooled to-70 ℃.Drip the t-butyl hypochlorite's salt 2.82g (carrene of 26.0mmol (10ml) solution, and solution stirred 10 minutes down at-70 ℃ to the solution of cooling.In the reaction solution that is obtained, drip 2-methylthiomethyl-4, carrene (20ml) solution of 6-dimethoxypyridin 3.38g (26.0mmol), and this solution stirred 40 minutes down at-70 ℃.Add the methanol solution (9ml) of 28% sodium methoxide to the reaction solution that obtained, and stir this solution to reaching room temperature.Water is added in the reaction solution, and separate organic layer.Use the dichloromethane extraction water layer again 2 times.After waiting to wash with water organic layer and drying, decompression distillates carrene, and obtain target product 2-chloro-6-[1-(4,6-dimethoxypyridin-2-yl)-and the 1-methylthiomethyl] aniline 7.00g (productive rate 83%), it is by utilizing 1: 8 the ethyl acetate and the mixed solvent of hexane to obtain as the oily matter that the eluant, eluent column chromatography is obtained.
1H-NMR(300MHz，CDCl 3)δ2.04(3H，s)，3.93(6H，s)，5.07(1H，br)，5.14(1H，s)，5.90(1H，s)，6.67(1H，t)，7.19(1H，dd)，7.42(1H，dd)。
Control compounds
Figure C20058000995500281
(C-1 is the similar compound that is described among the WO 96/41799)
Figure C20058000995500282
(C-2 is described in the similar compound in the Japanese laid-open publication publication number 44546/2000)
Test implementation example 1:Test is to the herbicide effect of weeds in paddy field
The preparation active agent preparations
Carrier: DMF 5 weight portions
Emulsifier: benzyloxy polyglycol ether 1 weight portion
The reactive compound of 1 weight portion is mixed the active agent preparations that obtains the missible oil form mutually with the carrier and the emulsifier of above-mentioned weight.Preparation dilute with water with specified amount.
In the greenhouse, the seed or the stem tuber of firefly Lin, Monochoria vaginalis, annual broadleaf weed (Procumbent Falsepimpernel, mexicana, three stamen waterworts, spend more water amaranth (Ammannia multiflora Roxb) etc.), Herba Cyperi Glomerati is being filled with the 500cm of paddy soil 2Basin in inoculate.It is dark to be filled to about 2-3cm subsequently.After waiting to inoculate 5 days and 13 days, the dilute solution of each active agent preparations that will make according to above-mentioned preparation method is applied to water surface.After pending, keep depth of water 3cm, and after 3 weeks, measure herbicide effect by handling.
Herbicide effect with complete death be 100% and no herbicide effect be 0% to estimate.When demonstration is higher than 80% herbicide effect, think that it has the practicality of weed killer herbicide.
With specific embodiment to compound number 1,3,11 and 17, and the result of study of control compounds C-1 is shown in following table 3 and table 4.
Table 3:Inoculate and use after 5 days
Figure C20058000995500291
Table 4: inoculate and use after 13 days
Figure C20058000995500301
Test implementation example 2:Test is to the residual effect of weeds in paddy field
In the greenhouse, with 1000cm 2Basin fill with paddy soil, and be filled to about 2 to 3cm dark.With as above test implementation example 1 described appointment, dilute solution is applied to water surface.After the pending fixed time (handle 1 week, 2 weeks, 3 weeks, 4 weeks, 5 weeks, 6 weeks and 7 week the back), inoculate seed or the stem tuber of firefly Lin to be tested, Monochoria vaginalis, annual broadleaf weed (Procumbent Falsepimpernel, mexicana, three stamen waterworts, spend more water amaranth (Ammannia multiflora Roxb) etc.), Herba Cyperi Glomerati and short arrowhead weeds.After waiting to inoculate 3 weeks, measure each herbicide effect.
After treating to carry out the evaluation of herbicide effect with the same way as of the foregoing description 1, to the evaluation of residual effect with shown in the period (all numbers) that is kept above 80% herbicide effect.
To compound number 1 and 11, and the result of study of control compounds C-1 and C-2 is as shown in table 5 below with specific embodiment.
Table 5:
Figure C20058000995500302
Test implementation example 3:The herbicide effect of test antagonism sulfonylureas resistant weed
In the greenhouse, firefly Lin is (collected in the Iwamizawa area, Hokkaido), Procumbent Falsepimpernel is (collected in the Kazo area, Saitama Pref.), Procumbent Falsepimpernel is (collected in the Higashi-Hiroshima area, Hiroshima Pref.), three stamen waterworts (collected in the Kazo area, Saitama Pref.) seed is being filled with the 20cm of paddy soil 2Basin in inoculate.Be filled to about 2 to 3cm dark subsequently.When treating that each weeds begins to emerge, the appointment of each active agent preparations that will make with the same procedure of above-mentioned test implementation example 1, dilute solution is applied to water surface.After processing, keep the depth of water of 3cm, and after 3 weeks, measure the herbicide effect of handling.Carry out the evaluation of herbicide effect with the same procedure of above-mentioned test implementation example 1.When demonstration is higher than 80% herbicide effect, think that it has the practicality of weed killer herbicide.Consider the different biological nature of plant resistance to environment stress possibility that comprises the plant that grows in different regions, will collect sulfonylureas resistance Procumbent Falsepimpernels two different regions and be used for this test.With specific embodiment to compound number 1,3,11 and 17, and the result of study of control compounds C-1 is as shown in table 6 below.
Table 6:
Figure C20058000995500311
Test implementation example 4:Test is to the phytotoxicity of transplanting rice
Phytotoxicity to transplanting rice is to estimate under the condition with planting depth more shallow than the 2cm degree of depth of routine, and weed killer herbicide is simulated these harsh conditions to cause the paddy rice injury.In the greenhouse, with three kinds of different degree of depth the paddy rice (mutation Nipponbare) of 2 to 2.5 leaf phases is transplanted and to be filled with the 1000cm of paddy soil 2In the basin.Be filled to about 2 dark subsequently to about 3cm.Transplant after 5 days, the appointment of each active agent preparations that will make with the same procedure of above-mentioned test implementation example 1, dilute solution is applied to water surface.After processing, keep the depth of water of 3cm, and after 2 weeks, measure the paddy rice injury by handling.
Paddy rice injury is 100% and not have injury be 0% to estimate with complete death.When demonstration is lower than 20% injury, think that it has the practicality of rice herbicide.
To compound number 11, and the result of study of control compounds C-1 and C-2 is as shown in table 7 below with specific embodiment.
Table 7: transplant and use after 5 days
Test implementation example 5:Test is to the phytotoxicity of lineal rice shoot paddy rice with to the herbicide effect of weeds in paddy field
In the greenhouse, with firefly Lin, Monochoria vaginalis, difformed galingale herb, annual broadleaf weed ( On the footpath between fields Dish, Mexicana, three stamen waterworts, spend more the water amaranth), and paddy rice (mutation: seed Nipponbare andRD-23) is being filled with the 500cm of paddy soil 2Basin in inoculate.Be filled to subsequently about 0 dark to about 0.5cm, to reach moistening environment.In the two leaf phases of paddy rice, the appointment of each active agent preparations that will make with the same procedure of above-mentioned test implementation example 1, dilute solution is sprayed at the circumference pelvic with plant.After handling 2 days, keep the depth of water of 3cm, and after pending 3 weeks and 2 weeks, estimate the injury of herbicide effect and paddy rice respectively.
The injury of herbicide effect and paddy rice is 100% and not have injury be 0% to estimate with complete death.When demonstration is higher than 80% herbicide effect and be lower than 20% injury, think that it has the practicality of rice herbicide.
To compound number 3 and 11, and the result of study of control compounds C-2 is as shown in table 8 below with specific embodiment.
Table 8: use (spraying) in the two leaf phases of paddy rice
Figure C20058000995500331
Example of formulations 1(granule)
In the mixture of The compounds of this invention number 1 (0.4 part), bentonite (montmorillonite) (39.6 parts), talcum (58 parts) and lignosulfonates (2 parts), add entry (25 parts); well mediate; make 10 to 40 purpose particles by the extrusion granulator machine, and dry down at 40 to 50 ℃ to obtain granule.
Example of formulations 2(granule)
The clay mineral particle (99.8 parts) that will have the distribution of 0.2 to 2mm particle diameter places impeller.In rotation, The compounds of this invention number 1 (0.2 part) is sprayed with liquid diluent, evenly moistening and dry down to obtain granule at 40 to 50 ℃.
Example of formulations 3(missible oil)
The compounds of this invention number 1 (30 parts), dimethylbenzene (55 parts), polyoxyethylene alkyl phenyl ether (8 parts) are mixed mutually with alkyl benzene calcium sulfonate (7 parts), and stir to obtain missible oil.
Example of formulations 4(wetting powder)
Mixture (80 parts), alkyl benzene calcium sulfonate (2 parts) and the alkyl naphthalene sulfonic acid ester-formalin-condensation product (3 parts) of The compounds of this invention number 1 (15 parts), hard charcoal (moisture amorphous silicon oxidation thing fine powder) and powdered clay (1: 5) are mixed mutually with powder, obtain wetting powder.
Example of formulations 5(water-dispersible granules)
The compounds of this invention number 1 (20 parts), sodium lignin sulfonate (30 parts), bentonite (15 parts) and the diatomite powder (35 parts) through calcining adding under water well mixing, are extruded with the screen cloth of 0.3mm, and carried out drying to obtain water-dispersible granules.

Claims (7)

1. by the difluoromethyl sulfamide derivative shown in the following formula
Figure C2005800099550002C1
Wherein
X represents halogen,
Y represents CH or N,
R 1The expression hydrogen and
R 2Expression hydrogen or hydroxyl, or
R 1And R 2Carbon atom with their bondings forms C=0.
2. according to the compound of claim 1, wherein
X represents fluorine or chlorine,
Y represents CH or N,
R 1The expression hydrogen and
R 2Expression hydrogen or hydroxyl, or
R 1And R 2Carbon atom with their bondings forms C=0.
3. method for preparing formula (I) compound of claim 1
Figure C2005800099550003C1
Wherein X, Y, R 1And R 2Such as claim 1 definition, it is characterized in that a) formula (II) compound
Figure C2005800099550003C2
Wherein
X, Y, R 1And R 2Have above-mentioned identical definition,
With the reaction of difluoromethyl sulfonic acid chloride, this is reflected under the atent solvent existence and carries out, and optionally has acid cement,
Or
B) at R 1And R 2Carbon atom with their bondings forms under the situation of C=0:
With formula (Ib) compound
Figure C2005800099550003C3
Wherein
X has above-mentioned identical definition with Y,
With oxidant reaction, this is reflected under the atent solvent existence and carries out, and optionally has acidic catalyst,
Or
C) at R 1Expression hydrogen, and R 2Under the situation of expression hydroxyl:
With formula (Ic) compound
Wherein
X has above-mentioned identical definition with Y,
With alkali metal hydride complex compound or borane complex reaction, this is reflected under the atent solvent existence and carries out.
4. Herbicidal combinations is characterized in that it comprises the formula of at least a claim 1 (I) compound.
5. be used to control the method for weeds in paddy field, formula (I) compound effects that it is characterized in that making at least a claim 1 is in weeds in paddy field and/or its habitat.
6. formula (I) compound of claim 1 is used to control the purposes of weeds in paddy field.
7. be used to prepare the method for Herbicidal combinations, it is characterized in that formula (I) compound of claim 1 is mixed mutually with bulking agent and/or surfactant.
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