CN1053786A - Has urea derivatives of weeding activity and preparation method thereof - Google Patents
Has urea derivatives of weeding activity and preparation method thereof Download PDFInfo
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- CN1053786A CN1053786A CN91100563A CN91100563A CN1053786A CN 1053786 A CN1053786 A CN 1053786A CN 91100563 A CN91100563 A CN 91100563A CN 91100563 A CN91100563 A CN 91100563A CN 1053786 A CN1053786 A CN 1053786A
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- alkyl
- definition
- logical formula
- alkoxyl group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/42—One nitrogen atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D521/00—Heterocyclic compounds containing unspecified hetero rings
Abstract
The present invention relates to a kind of new general formula with weeding activity (I) (all substituent definition are referring to specification sheets) compound and salt thereof, and contain the composition that these compounds reach optional toxinicide.The invention still further relates to the method for preparing general formula (I) compound.The present composition has excellent weeding activity to some weeds.
Description
The present invention relates to the salt as leading to the described replacement sulfonylurea derivative of formula I and forming new, that have weeding activity with basic metal, alkaline-earth metal, amine or quaternary amine alkali.
Wherein
R
1Represent hydrogen, halogen, C
1-4Alkoxyl group, halo-C
1-4Alkoxyl group, C
1-3Alkane alkylsulfonyl, or COR
6Group;
R
2Represent hydrogen, C
1-3Alkyl, or phenyl;
R
3Represent C
1-6Alkyl, C
3-6Alkenyl, C
1-3Alkoxyalkyl, the C that is replaced by one or more halogen atoms
2-4Alkyl, or benzyl;
R
4And R
5Represent C independently of each other
1-4Alkyl, C
1-4Alkoxyl group, halogen, C
1-3Alkylamino or two-(C
1-3Alkyl) amino, or C
1-3Alkylthio;
R
6Represent C
1-4Alkoxyl group, C
3-6Alkenyloxy, C
3-6Alkoxyalkyl, C
1-3Alkylamino, two-(C
1-3Alkyl) amino, piperazinyl, or morpholinyl;
X represents oxygen or sulphur;
E represents methyne or nitrogen.
The invention still further relates to the herbicidal composition that contains these compounds and alternative toxicide.
The invention still further relates to the logical formula I compound of preparation (R wherein
1, R
2, R
3, R
4, R
5, R
6, X and E definition the same) method.
In above-mentioned definition (and whole specification sheets):
-" alkyl " comprises straight chain and branched-chain alkyl, as methyl, ethyl, propyl group, sec.-propyl and any butyl;
-" alkoxyl group " is often referred to any in methoxyl group, oxyethyl group, propoxy-, isopropoxy or the four kinds of isomery butoxy, particularly methoxyl group, oxyethyl group or propoxy-;
-" alkenyl " can be for example allyl group, pseudoallyl, 1-propenyl, 1-butylene base, crotyl, 3-butenyl, 1-isobutenyl or amylene group, particularly allyl group or 4-amylene group;
Halogen atom in-" halogen " itself or the halogenated alkoxy can be fluorine, chlorine or bromine, particularly chlorine.
Can be potassium, sodium, magnesium or calcium oxyhydroxide with the basic metal or the alkaline earth metal hydroxides of logical formula I compound formation salt, mainly be sodium and potassium oxyhydroxide.
Salifiable amine comprises primary, the second month in a season or tertiary amine, as any, the dimethylamine in methylamine, ethamine, propylamine, Isopropylamine, the four kinds of isomery butylamine, diethylamine, Isopropylamine, Diisopropylamine, tetramethyleneimine, piperidines, morpholine, Trimethylamine 99, pyridine, quinoline or isoquinoline 99.9, particularly Isopropylamine and diethanolamine.
Being used for salifiable quaternary amine alkali is, for example, and any in halogenation Tetrylammonium, halogenation three second benzyl ammoniums, halogenation three methylbenzyl ammoniums or the tetrabutylammonium halogenide.
Sulfonyl urea derivates with weeding activity is a compound known.
Known sulfonylurea is characterised in that on its 3-position nitrogen-atoms that is replaced by heterocyclic group and has hydrogen or C
1-4Alkyl, particularly methyl; Or C
1-4Alkoxyl group, particularly methoxyl group; Or C
2-8Alkenyl, C
2-4Alkynyl group or aralkyl.Disclosed other substituting group seldom in document or the patent specification.
Such sulfonylurea is at for example European patent specification NO.152,378 and Japanese Patent Application Publication Nos.J5 8126872 and J6 0078981 on the books.
Sulfonylurea derivative has good Chinese People's Anti-Japanese Military and Political College's amount unifacial leaf and dicotyledons weeds, mainly be herbicide effect (the J.M.Green et al.:proc.S.Weed Sci.Soc.34 of broad-leaved and pasture weeds, 214(1981)), particularly in wheat and barley field.Its advantage is very low significant quantity (being generally 5-50 gram/hectare).Its shortcoming is that raise crop more or less suffers damage in use.In practice, when using these sulfonylurea derivatives, as be used for the paddy field, preferably use toxinicide, as be used for corn field, must use toxinicide.At european patent application NO.127, in 469, the toxinicide that can use in earlier stage in bud is after planting disclosed, this toxinicide can protect wheat and broomcorn millet to avoid the harmful effect of sulfonylurea herbicide.Best toxinicide is 2-((aminocarboxyl) amino-sulfonyl) methyl benzoate and an ammonium salt thereof, and 3-((aminocarboxyl) amino-sulfonyl)-2-Thiophene Carboxylic Acid methyl esters.
According to US Patent specification NO.4,343,649, available 1,8-naphthalic anhydride, α-(cyano group methoxyimino) benzyl cyanide or N, N-diallyl-dichloro acetamide improves 2-chloro-N-((the 4-methoxyl group-6-methyl isophthalic acid with weeding activity, 3,5-triazine-2-yl) benzsulfamide, 2 aminocarboxyl), 5-two chloro-N-((4,6-dimethoxy-pyridine-2-yl) selectivity of benzsulfamide benzsulfamide or 2-methoxycarbonyl-N-(4,6-dimethyl pyrimidine-2-yl) aminocarboxyl aminocarboxyl)).
At Hungarian patent specification NO.201, in 445, disclose and contained as the sulfonyl urea derivates of active ingredient and as the herbicidal composition of the glycine derivative of toxinicide.
The objective of the invention is to develop the herbicidal composition that contains new active ingredient, compare with known sulfonylurea, it has more superior physics and chemical property, higher selectivity and lower persistent.
In research process, develop the composition that contains logical formula I sulfonyl urea derivates.This sulfonyl urea derivates is characterised in that, the N of the sulfonylurea group that is replaced by heterocyclic group
3Have one on the atom (3-position nitrogen-atoms)
Group (R wherein
2And R
3Definition the same).
Have been found that, the composition that contains logical formula I new compound is particularly suitable for controlling weeds, because said composition has excellent herbicide effect under suitable low dosage, cultivated plant there is suitable selectivity, maybe can make it have selectivity by using known toxinicide, simultaneously, said composition also is easy to decompose in soil.
According to a further aspect in the invention, provide the method for the logical formula I new compound of preparation in inert organic solvents or its mixture, this method comprises:
(a) make isocyanic ester with logical formula IV or lsothiocyanates (R wherein
1Definition the same)
With the aminopyrimidine with logical formula III or amino-triazine (R wherein
2, R
3, R
4, R
5Identical with the definition of E) with the definition in the logical formula I
In 0-50 ℃ of temperature (preferred 20-30 ℃) reaction down, this reaction can be carried out in the presence of as the alkali of catalyzer; Perhaps
(b) make the have general formula sulfonamido carbamate derivatives (R wherein of (V)
1Definition identical with the definition in the logical formula I, R represents phenyl)
With the aminopyrimidine with logical formula III or amino-triazine (R wherein
2, R
3, R
4, R
5The same with the definition of E) in 25-120 ℃ of temperature (preferred 60-90 ℃) reaction down; Perhaps
(c) make urea chloride with logical formula VI (R wherein
2, R
3, R
4, R
5The same with the definition of E, R represents phenyl)
With (the R wherein of the sulphonamide an alkali metal salt with logical formula II
1Definition identical with the definition in the logical formula I)
In the presence of as the alkali of catalyzer, in-10-50 ℃ temperature (preferred 0-50 ℃) reaction down; Perhaps
(d) make the have general formula N-pyrimidinyl-amino manthanoate of (VII) or N-triazine radical amido manthanoate (R wherein
2, R
3, R
4, R
5The same with the definition of E, R represents phenyl)
With (the R wherein of the sulphonamide with logical formula II
1Definition identical with the definition in the logical formula I) in the presence of the alkali of catalytic amount, in 20-80 ℃ of temperature (preferred 20-40 ℃) reaction down; Perhaps
(e) make the have general formula SULPHURYL CHLORIDE (R wherein of (VIII)
1Definition identical with the definition in the logical formula I)
With the aminopyrimidine with logical formula III or aminotriazine (R wherein
2, R
3, R
4And R
5Definition the same) and alkali metal cyanate in 20-120 ℃ of temperature (preferred 60-90 ℃) reaction down.
If desired, available bases metal or alkaline earth metal hydroxides, amine or quaternary ammonium halide will be converted into its salt with the logical formula I compound of method for preparing, for example, in The suitable solvent, react, boil off solvent then by making required compound and suitable alkali.
In the process of the logical formula I compound of preparation, methylene dichloride, chloroform, tetracol phenixin, ethylene dichloride, trichloroethane, tetrahydrofuran (THF), acetonitrile, diox, benzene,toluene,xylene, chlorobenzene, dimethyl formamide, Nitromethane 99Min., nitroethane, N-Methyl pyrrolidone, glycol dimethyl ether, ether, diisopropyl ether, dibutyl ether, hexane, sherwood oil, ethyl acetate, ethyl acetate, dibutyl phthalate and mineral oil and vegetables oil can be used as inert organic solvents, but the available solvent is not limited thereto.
In aforesaid method, temperature of reaction can change in very wide scope, and is general at-20 ℃ of boiling points until solvent.But, be preferably between 0 ℃ to 90 ℃ and react, particularly between 45 ℃, react, because this temperature range also is suitable for preparing the thermo-sensitivity derivative with logical formula I at 15 ℃.React to be suitable under atmospheric pressure and carry out, also can improve or reduce pressure.Reaction also can be carried out in the presence of air or rare gas element (as nitrogen).
For shortening the reaction times or making reaction carry out to add several alkali as catalyzer fully.
As alkali with catalytic activity, can use tertiary amine, as triethylamine, Tributylamine, N, N-xylidene(s) and nitrogen-containing heterocycle compound such as pyridine or 1,4-diaza-bicyclo-(2.2.2) octane (DABCO), but also available bases metal hydroxides or alkali metal alcoholates such as sodium hydroxide or sodium methylate.The available catalyzer is not limited thereto when stating method on the implementation.
Can will separate with the product of method for preparing by evaporation or part evaporating solvent and recrystallization fully, or with the solvent or the solvent mixture grinding evaporation residue of slightly soluble product.If desired, the compound that can obtain with suitable carrier such as purifications such as aluminum oxide, silica gel by chromatography.
Herbicidal composition of the present invention generally contains logical formula I active ingredient 0.01-95%(weight), preferred 2-80%(weight), its formulation can be known formulation, but as solution, emulsion, dirt agent, pulvis, suspension, wettable powder, paste, soluble powder, granule, suspension concentrate or emulsifying concentrated solution, with the natural or synthetic materials of activity component impregnation or with the capsule of polymer overmold.
By active ingredient being mixed with binding agent, solvent and/or carrier and/or grinding the preparation present composition, also can add tensio-active agent and/or dispersion agent and adhesive accelerant simultaneously.
The available solvent is: aromatic hydrocarbon is preferably C
7-12Aromatic hydrocarbon is as the naphthalene of toluene, xylene mixture or replacement; Chloro aliphatic hydrocrbon or aromatic hydrocarbon are preferably vinylchlorid, methylene dichloride or chlorobenzene; Aliphatic hydrocrbon is as hexanaphthene, paraffin or mineral oil fractions; Mineral oil or vegetables oil; Alcohol is as ethanol or 1,2 ethylene glycol; Or its ether, as methyl glycol, ether; Ketone is as acetone, methylethylketone, mibk, pimelinketone; Intensive polar solvent is as N-Methyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl-sulphoxide; Phthalic ester is as dibutyl phthalate or phthalic acid two greases; And epoxidized vegetable oil, as epoxidation cocoa or soybean oil; Perhaps water.
Suitable carrier is: inorganic powder, as kaolin, calcite, talcum, chalk, quartz, attapulgite, montmorillonite, diatomite, perlite, amorphous silicas, aluminum oxide, high dispersive silicic acid, float stone, brick powder, sepiolite, wilkinite or sand; Organic dust is as certain a part of bits sprills as corn stalk, Exocarpium cocois (Cocos nucifera L) and Semen Maydis powder preparation with plant; Various starch, starch producing; Sugar is as glucose; Powdery or ground synthetic resins are as phenol or urea resin; In addition, also can use multiple inorganic or organic without the ground material.
Nonionic, positively charged ion and/or anion surfactant can be used as have good emulsifying, the tensio-active agent of dispersion and wet performance.The mixture of usable surface promoting agent also.Anion surfactant is water-soluble soap, as oleic acid or stearic sodium salt or sylvite, and the salt of natural acid mixture; But preferably use synthetic surfactant, particularly fatty alcohol sulfonate, aliphatic alcohol sulfate, sulphonate-benzimidizole derivatives or alkyl aryl sulfonate.Adducible example also has the calcium salt of lignosulfonic acid or triethanolamine salt, laurilsulfate, with the sulfonic acid of natural acid preparation and sulfuric ester and sulfonic acid, Witco 1298 Soft Acid or the tributyl naphthene sulfonic acid of fatty alcohol-ethylene oxide adduct.In addition, phosphoric acid salt (as to the salt of the phosphoric acid ester of ethylene oxide adduct of nonylphenol-(4-14)) also suits.
As cats product, can consider quaternary ammonium salt, this quaternary ammonium salt contains the low alkyl group that is replaced by halogen atom or hydroxyl and/or is connected in benzyl and C on the quaternary nitrogen atom
8-20Alkyl.The example of this class tensio-active agent is for example hard ester acyl trimethylammonium-ammonium chloride or benzyl-two (2-chloroethyl) ethyl-brometo de amonio.
Nonionogenic tenside is mainly the ester of polyoxyethylene glycol ether, polyoxyethylene glycol ester and polyvalent alcohol and condensation product thereof, nonylphenol polyethoxyethanols, Viscotrol C polyglycol ether and polypropylene-poly-oxyethylene affixture.
Sulfite lignin, sulphite liquid and methylcellulose gum are the examples of the dispersion agent that suits.
Can contain adhesive accelerant in the composition, for example, carboxymethyl cellulose, natural or synthetic, powdery, granular or emulsion state polymkeric substance such as polyvinyl alcohol, polyvinyl acetate and natural phospholipid such as kephalin, Yelkin TTS or synthetic phospholipid.
In addition, the present composition also can contain other additive, as stablizer, foam preventer, viscosity modifier, sanitas and inorganic or pigment dyestuff.
Activator, synergistic agent and toxinicide also can be added in the composition of the present invention.
Contain known toxinicide; as DKA-24(N-dichloro-acetyl-N-allyl group glycyl N '-allyl amine); AD-67(N-dichloro-acetyl-1-oxa--4-azaspiro (4; 5) decane); R-25788(N; N-diallyl-dichloro acetamide); MG-191; the herbicidal composition of TI-35 or CGA-92194 is (TI-35 is the N-(dichloro-acetyl)-hexamethylene imine also within the scope of the invention; CGA-92194 is N-(1; 3-dioxolane-2-ylmethoxy)-imino--benzyl cyanide; MG-191 is 2-dichloromethyl-2-methyl isophthalic acid, the 3-dioxolane).
If desired, logical formula I compound of the present invention and contain these compound compositions and can use with other agricultural chemicalses, these agricultural chemicalses can be weedicide, fungicide insecticide, miticide, nematocides, antiviral agent, plant-growth regulator or attractive substance.
Compound of the present invention preferably contains 0.01-95%(weight), 2-80%(weight particularly) logical formula I active ingredient or all active ingredients and toxinicide, 5-99.9%(weight) liquid state or solid-state carrier and 0-30%(weight), 0.1-25%(weight particularly) tensio-active agent and other additives.When also containing toxinicide in the composition, toxinicide can be 1: 1 to 50: 1 with the ratio of active ingredient.
Composition with following composition is particularly preferred composition (all per-cents is weight percentage):
1. solution
Active ingredient 1-30%, preferred 5-25%
Solvent 1-90%, preferred 0-85%
Tensio-active agent 0-99%, preferred 0-95%
2. but emulsifying concentrated solution
Active ingredient 1-20%, preferred 5-10%
Tensio-active agent 1-30%, preferred 5-20%
Liquid carrier 50-94%, preferred 70-85%
3. wettable powder
Active ingredient 0.5-90%, preferred 20-80%
Tensio-active agent 0.5-20%, preferred 5-15%
Solid-state carrier 5-95%, preferred 15-90%
4. suspension concentrate
Active ingredient 5-75%, preferred 10-50%
Water 25-95%, preferred 30-80%
Tensio-active agent 1-40%, preferred 5-20%
5. pulvis
Active ingredient 0.5-10%, preferred 0.5-5%
Solid-state carrier 90-99.5%, preferred 95-99%
6. granule
Active ingredient 0.5-30%, preferred 1-15%
Solid-state carrier 70-99.5%, preferred 85-95%
Before use, used water is a 0.01%(weight with the concentration that composition of the present invention is diluted to active ingredient).The composition that available currently known methods will dilute back or not diluted is applied to the zone that needs processing, as spraying, dusting, atomizing, distribution, sprinkling or ultralow pressure method.The composition that contains the logical new sulfonyl urea derivates of formula I of the present invention is to unifacial leaf and weeding activity dicotyledonous, annual and that perennial weeds all has excellence.Composition of the present invention can be used with the bud later stage before sowing or before the bud.
As handling the bud early stage (not growing plant) in soil in weeds, the germination plant send bud and grow to that cotyledon (Seed-leaf) phase stops growing and in 3-6 week rear section or all wither.As handling in the weeds bud later stage, handle the back weeds and stop growing, 1-4 after week weeds partly or entirely withered.The present composition is characterised in that under very low amount of application and can plays a role.Weeds according to need are handled have good effect under the dosage that is low to moderate 0.01-2.0 kilogram/hectare.Find the farm crop of important implant mass, be not subjected to the influence of said composition as wheat, corn, barley, rice and beans.Therefore, composition of the present invention can be used for controlling effectively unifacial leaf and dicotyledonous, annual and perennial weeds, and but being difficult to maybe can not the above-mentioned farm crop of infringement.Carry the training crop and be not limited to above-mentioned a few class.According to used active ingredient, also can use the present composition of 0.05-2.0 kilogram/hectare dosage and control whole weeds.
A special advantage that contains as the logical formula I sulfonylurea composition of active ingredient is, impose in the soil after, said composition is decomposed rapidly.As using composition behind the bud, other raise crop can be sowed immediately in the zone after the processing after the results farm crop, or through sowing again after the time that contains the required weak point of composition of discussing the known sulfonylurea of selling than other.
Further describe active ingredient of the present invention (logical formula I compound) and preparation of compositions and purposes by following indefiniteness embodiment.
Embodiment 1
Preparation 3-ethoxyl methyl-1-(2-methoxycarbonyl benzenesulfonyl)-and 3-(4-methoxyl group-6-methyl isophthalic acid, 3,5-triazine-2-yl) urea (compound 8)
To containing 3.96g(20mmol) 2-ethoxyl methyl amino-4-methoxyl group-6-methyl isophthalic acid, 3, after adding 0.01g DABCO catalyzer in the solution of the 50ml anhydrous diethyl ether of 5-triazine, under room temperature and the agitation condition in this solution Dropwise 5 .3g(22mmol) be dissolved in the 2-methoxycarbonyl benzenesulfonyl isocyanate of 20ml anhydrous diethyl ether.This reaction mixture was stirred 6 hours, and product begins to separate out simultaneously.The precipitate that second day filtering for crystallizing goes out washs it under rearmounted room temperature dryly with a little ether, producing the 6.5g(productive rate is 74%) title compound, m.p.:105-106 ℃.
Embodiment 2
Preparation 3-ethoxymethyl-1-(2-chlorinated benzene alkylsulfonyl)-and 3-(4-methoxyl group-6-methyl isophthalic acid, 3,5-triazine-2-yl) urea (compound 4)
With 3.96g(20mmol) the 2-(ethoxyl methyl) amino-4-methoxyl group-6-methyl isophthalic acid, 3, the 5-triazine is added to 6.23g(20mmol) N-(2-chlorinated benzene alkylsulfonyl) in the solution of 120ml dry-out benzene of phenyl carbamate.Stirred this mixture 8 hours in 75-80 ℃, then with its evaporate to dryness.After with the ether recrystallization, obtain 5.06g(61%) title compound, m.p.:123-123 ℃.
Embodiment 3
Preparation 3-(4,6-dimethyl pyrimidine-2-yl)-1-(2-chlorinated benzene alkylsulfonyl)-the 3-(ethoxyl methyl) urea (compound 2)
Under 5-10 ℃ and agitation condition, to be dissolved in the 4.87g(20mmol of 10ml dimethyl formamide) N-(4,6-dimethyl pyrimidine-2-yl)-the N-(ethoxyl methyl) urea chloride is added drop-wise to 4.27g(20mmol) 25ml of 2-chlorinated benzene sulphonamide sodium salt is anhydrous, heavily steam in the solution of dimethyl formamide.After adding, this mixture was at room temperature stirred 3 hours, be poured into then in the 250ml frozen water.Filter precipitate, it is washed after drying with less water, the mixture with ethyl acetate and ether carries out recrystallization then, thereby obtains 3.34g(42%) title compound, m.p.:118-119 ℃.
Embodiment 4
Preparation 3-(4,6-dimethyl pyrimidine-2-yl)-3-ethoxyl methyl-1-(2-methoxycarbonyl benzenesulfonyl) urea (compound 6)
To 2.15g(10mmol) 2-methoxycarbonyl benzsulfamide and 1.52g(10mmol) 1, add 3.1g(10mmole in the no Shui dioxane solution of 25ml of 8-diazabicyclo (5.4.0) 11-7-alkene) N-(4,6-dimethyl pyrimidine-2-yl)-the N-(ethoxyl methyl) phenyl carbamate.In 30-35 ℃ this reaction mixture was stirred 10 hours, pour into then in the 200ml water.After its pH value is transferred to 6.5, filter out throw out, be dried and carry out recrystallization with the mixture of chloroform and hexane, obtain 1.59g(37.6%) title compound, m.p.:124-126 ℃.
Embodiment 5
Preparation 3-(4,6-dimethyl pyrimidine-2-yl)-3-methoxymethyl-1-(2-methoxycarbonyl benzene sulfonyl) urea (compound 5)
Will be at the 4.3g(20mmol in the 30ml anhydrous acetonitrile) 2-methoxycarbonyl benzene sulfonyl chloride, 3.67g(22mmol) 4,6-dimethyl-2-(methoxymethyl)-aminopyrimidine and 3.24g(40mmol) mixture of potassium cyanate is in 81 ℃ of vigorous stirring 2 hours.Filter out the inorganic salt that are settled out, evaporated filtrate is resuspended in its resistates in the 30ml water.The precipitation that goes out of dry filter then, and it is carried out recrystallization with the mixture of ethyl acetate and ether, finally obtain 5.4g(66.2%) title compound, m.p.:133-135 ℃.
Listed compound all is to prepare by method similar to the aforementioned embodiment in the table 1.
Embodiment 6
Preparation wettable powder (10WP)
Each composition weight g
Press the activeconstituents 20 of embodiment 2 preparations
Silicate carrier (Zeolex 444) 80
Diatomite 80
Aliphatic sulfonic acid sodium wetting agent (Netzer IS) 4
Cresoform sulphonate dispersion agent (Dis-
pergiermittel 1494） 6
Sulphite liquid-powder (Borresperse NA) 10
Place the laboratory ball mill to pulverize 30 minutes powdered mixture, in the contraplex grinding machine of Alpine 63C type laboratory, be ground into fine particle then with 70 velocity stages.The wettable powder composition that obtains thus contains compound 4 in the table 1 of 10% weight part as activeconstituents.
Floatability (concentration is 1%): 86.5%.
Wet screening slag (in the DIN10 sieve): 0.27%.
Embodiment 7
Preparation wettable powder (50WP)
Each composition weight: g
Press the active ingredient 150 of example 3 preparations
Synthetic silicate carrier (Zeolex 444) 30
Diatomite 50
Aliphatic sulfonic acid sodium (Netzer IS) 4
Cresols-formaldehyde sulphonate 6
Sulphite liquid-powder 10
Use-case 6 described methods.The wettable powder composition that so obtains contains 10%(weight) as the compound 2 in the table I of active ingredient.
Floatability (concentration is 1%): 82.9%.
Wet screening slag (in the DIN100 sieve): 0.43%.
Embodiment 8
Preparation wettable powder (85WP)
Component is heavy: g
Press the active ingredient 170 of example 4 preparations
Synthetic silicon carrier (Sipernat 50s) 20
Oil methyl sodium laurate (Arkopon T plv) 4
Cresols-formaldehyde sulphonate 6
Use-case 6 described methods.Resulting wettable powder composition contains 85%(weight) table 1 compound 6 as active ingredient.
Floatability (concentration is 1%): 82.9%.
Wet screening slag (in the DIN100 sieve): 0.43%.
Embodiment 9
Preparation emulsifiable concentrate (5EC)
Component is heavy: g
Press the active ingredient 5 of example 1 preparation
Dimethylbenzene 70
Pimelinketone 15
Calcium dodecylbenzene sulphonate (Emulsogen
IP 400） 8
Cithrol (Emulsogn EL 400) 2
Under agitation condition with solubilization of active ingredient in the mixture of dimethylbenzene and pimelinketone, and add 8g Emulsogen IP 400 and 2g Emulsogen EL 400 emulsifying agents.Treat its even after-filtration mixture.
The emulsifiable concentrate that so obtains contains 5%(weight) as the table I compound 8 of active ingredient.
Emulsifying stability (1% enriched material in CIPAC A and CIPAC D water): stable after 2 hours.
Observe the formation of reversible emulsion after 24 hours.
Embodiment 10
Preparation dusting (5D)
Component is heavy: g
Talcum 20
Silicate (Sipernat 50s) 30
Press the active ingredient 50 of example 5 preparations
Limestone powder (M10) 900
To in the ball mill of laboratory, pulverize by active ingredient, synthetic silicate carrier and the steatitic mixture of example 5 preparations, in the contraplex grinding machine of Alpine 63C type laboratory, grind to form fine particle then.In a laboratory powder blenders with limestone powder with the powder mixing that obtains.
The dusting that so obtains contains 5%(weight) as the table I compound 5 of active ingredient.
Screening reject (in the DIN100 sieve): 0.12%.
Embodiment 11
Preparation suspending concentrate (5FW)
Component is heavy: g
Press the active ingredient 10 of example 2 preparations
Trisun Oil R 80 168
Organophilic bentonite (Ivegel) 2
Polyethylene alkyl ether, polyoxyethylenated castor oil,
Ethoxylated fatty acid and sulfo-sodium succinate (Sorpol 3815) 20
Active ingredient, Trisun Oil R 80, close organic substance wilkinite (Ivegel) and Sorpol 3815 emulsifying agents are weighed in the laboratory ball mill.With suspending concentrate with the 65%(volume) diameter be that the granulated glass sphere filler of 1.0-1.5mm ground 30 minutes with the speed of 775rpm.
So the suspending concentrate of gained contains 5%(weight) as the table I compound 4 of active ingredient.
Stability (1% enriched material in CIPAC and CIPAC D water): stable after 30 minutes.
Embodiment 12
Preparation suspending concentrate (40FW)
Component is heavy: g
Press the active ingredient 80 of embodiment 1 preparation
Synthetic silicate (Zeolex 444) 6
Oil methyl sodium laurate (Arkopan T plv.) 4
Nonyl phenyl polyglycol ether (Arkopal N100) 10
2% xanthan gum (Kelzen S) solution 10
Water 80
80g is weighed in the ball mill of laboratory by active ingredient, synthetic silicate (Zeolex 444), oil methyl sodium laurate (Arkopon T plv.) and nonyl phenyl polyglycol ether (Arkopal N 100) wetting dispersing agent and the 80g water of embodiment 1 preparation.After the homogenizing, with suspending concentrate with the 70%(volume) diameter be that the granulated glass sphere filler of 1.0-1.5mm ground 30 minutes.Through grinding and with after filler separates, in a Ultra turrax equipment by vigorous stirring with 20g2% xanthan gum (Kelzen S) solution homogenizing mixture.
The suspending concentrate of so preparing contains 40%(weight) as the table I compound 8 of active ingredient.
Floatability (concentration is 1%): 97.3%.
Granularity (being lower than 10 μ): 91.6%
Embodiment 13
Preparation water dispersible granular (75WDG)
Component is heavy: g
Table 1 compound 3 375 as active ingredient
Synthetic silicate carrier 55
Polyvinylpyrrolidone (the K30 product that BASF produces) 20
Alkyl phenol ether phosphoric acid ester (Atlox 5330 products that ICI produces) 30
Polymethylene glycol ethers and polymethylene alkyl aryl ether
(Atlox 4896 products that ICI produces) 20
Water 180
375g is carried out precomminution (the pre-grinding) as the table I compound 3 of activeconstituents with 55g synthetic silicate carrier in the ball mill of laboratory, in Alpine 63C type Contraplex grinding machine, this mixture is ground to form fine particle then with 80 velocity stages.The mixture of 20g polyvinylpyrrolidone, 30g alkyl phenol ether phosphoric acid ester and 20g polyalkylene glycol ethers and polymethylene alkyl aryl ether is dissolved in the 180ml water and prepares granulating liquid.Powdered mixture after will grinding then is added in the FPG0.5 type periodical operation that has the atomisation unit that liquefies (operation regularly) granulator, and is 60-65 ℃ entering of airflow and it is transferred to fluidized by attemperation.When temperature out reached 30 ℃, granulation liquid is start vaporizer under 1.5 bar pressures.Increase the flow that increases air-flow according to particulate.Continue drying after adding granulation liquid, reach 36-38 ℃ until temperature out
The particle that so makes contains 75%(weight) as the table I compound 3 of active ingredient.
Floatability (after the concentration 1%, 30 minute): 93.7%
The particle of granularity between 0.2-1mm: at least 75%.
Embodiment 14
Preparation water dispersible granular (25WDG)
Component is heavy: g
Table I compound 7 125 as active ingredient
Synthetic silicate carrier 250
Star Dri 5 tackiness agent 75
Sulfite lignin (Sorpol 9047K product, TOKO produces) 30
Polyoxyethylene gathers alkaryl phenyl ether sulfuric ester
(Sorpol 5096 products that Toko produces) 20
Will be as table I compound 7, synthetic silicate carrier, Star Dri 5 tackiness agent and Sulfite lignin (the Sorpol 9047K product of active ingredient, Toko produces) and the poly-alkaryl phenyl ether sulfuric ester of polyoxyethylene (Sorpol 5096, the Toko product) tensio-active agent weighing to the ball mill of laboratory.Grind after 30 minutes, this powdered mixture is ground to form fine particle in Alpine 63C type Contraplex grinding machine.This end is added in FPG 0.5 type periodical operation (operation regularly) the fluidisation device that has the atomisation unit that liquefies, and by regulating air-flow it is transferred to fluidized state, temperature in is about 60 ℃.
When temperature out reaches 28-30 ℃, carry out granulation by atomized water.After obtaining about 0.5mm desired particle size, stop the atomizing of water.Continue drying, reach 36-38 ℃ until temperature out.
The particle that so makes contains 25%(weight) as the table I compound 7 of active ingredient.
Floatability (after the concentration 1%, 30 minute): 91.85%
The particle of granularity between 0.2-1.0mm: at least 95%.
Embodiment 15
Preparation suspending concentrate (14.5FW)
Component is heavy: g
Table I compound 82 as active ingredient
As the DKA-24(N-dichloro-acetyl of toxinicide-
N-allylglycine N '-allyl acid amides) 12.5
Zeolex 444 carriers 11.6
Monoethylene glycol 15
Arkopon T wetting agent 3
Arkopol N-090(nonyl phenyl polyglycol ether)
Dispersion agent 6
Water 39.9
2%(weight as thickening material) xanthan gum solution 10
Preparing total content by embodiment 12 is 14.5%(weight) the suspending concentrate of active ingredient (table I compound 8) and DKA-24 toxinicide (its weight ratio is 1: 6.25).
Embodiment 16
Preparation suspending concentrate (27.0FW)
Component is heavy: g
Table 1 compound 82 as active ingredient
As the R-25788(N of toxinicide, N
-diallyl-dichloro acetamide) 25
Zeolex 444 carriers 5
Monoethylene glycol 10
Arkopon T wetting agent 2.5
Arkopol N-090 dispersion agent 5.5
Water 42
2%(weight) xanthan gum solution thickening material 8
Repeat example 12 described methods, obtaining total content is 27%(weight), weight ratio is 1: 12.5 the active ingredient (table I compound 8) and the suspending concentrate of R-25788 toxinicide.
Embodiment 17
Preparation wettable powder (20.25WP)
Component is heavy: g
Table I compound 4 1.5 as active ingredient
As the AD-67(N-dichloro-acetyl of toxinicide-
1-oxa--4-azaspiro (4.5) certain herbaceous plants with big flowers alkane) 18.75
Zeolex 444 carriers 34.75
Diatomite 33.0
Netzer IS wetting agent 3
Dispergiermittel 1494 dispersion agents 4
Sulphite liquid-powder dispersion agent 5
Repeat the method for example 6, obtaining total content is 20.25%(weight), weight ratio is 1: 12.5 the active ingredient (table I compound 4) and the wettable powder composition of AD-67 toxinicide.
Embodiment 18
But preparation water discrete particles (13.5WDG)
Component is heavy: g
Table I compound 61 as active ingredient
As the CGA-92194 of toxinicide (N-(1,
3-dioxolane-2-ylmethoxy) imino--benzyl cyanide) 12.5
Synthetic silicate carrier 61.5
Star Dri 5 tackiness agent 15
Sulfite lignin (Sorpol 9047K) 6
Polyoxyethylene gathers alkaryl phenyl ether vitriol
（Sorpol 5096） 4
Repeat embodiment 14 described methods, obtaining total content is 13.5%(weight), weight ratio is 1: 12.5 the active ingredient (table I compound 6) and the water dispersible granular of toxinicide (CGA-92194).
Embodiment 19
Preparation wettable powder (51.2WP)
Component is heavy: g
Table I compound 2 20 as active ingredient
DKA-24 31.2 as toxinicide
Zeolex 444 carriers 14.4
Diatomite wetting agent 24.4
Netzer IS wetting agent 2
Cresols-formaldehyde sulfonate 3
Sulphite liquid grain end dispersion agent 5
Repeat the method for example 6, obtaining total content is 51.2%(weight), weight ratio is 1: 1.56 the active ingredient (table I compound 2) and the wettable powder composition of toxinicide (DKA-24).
Embodiment 20
Preparation wettable powder (24.75WP)
Component weighing: g
Table I compound 26 as active ingredient
As the MG-191(2-dichloromethyl of toxinicide-
The 2-methyl isophthalic acid, the 3-dioxolane) 18.75
Zeolex 444 carriers 33
Diatomite support 32.25
Netzer IS wetting agent 2
Dispergiermittel 1494 dispersion agents 3
Sulphite solution powder dispersing agent 5
Repeat the method for embodiment 6, obtaining total content is 24.75%(weight), weight ratio is 1: 3.125 the active ingredient (table I compound 2) and the wettable powder mixture of toxinicide (MG-191).
Embodiment 21
Preparation dusting (5.2D)
Component is heavy: g
Table I compound 52 as active ingredient
AD-67 50 as toxinicide
Talcum 19
Synthetic silicate carrier (Sipernat 50s) 29
Limestone powder (M 10 types) 900
Repeat the method for example 10, obtaining total content is 5.2%(weight), weight ratio is 1: 25 the active ingredient (table I compound 5) and the dusting of toxinicide (AD-67).
Embodiment 22
Preparation wettable powder (21WP)
Component is heavy: g
Table 1 compound 61 as active ingredient
DKA-24 20 as toxinicide
Zeolex 444 carrier 30 as one kind
Diatomite support 39.5
Dispergiermittel 1494 dispersion agents 3
Netzer IS wetting agent 2
Sulphite liquid-powder 4.5
Repeat example 6 described methods, obtaining total content is 21%(weight), weight ratio is 1: 20 the active ingredient (table 1 compound 6) and the wettable powder of toxinicide (DKA-24).
Embodiment 23
Preparation dusting (6D)
Component is heavy: g
Table 1 compound 4 10 as active ingredient
DKA-24 50 as toxinicide
Talcum 15
Synthetic silicate carrier (Sipernat 50S) 25
Limestone powder (M10 type) 900
Repeat the method for example 10, obtaining total content is 6%(weight), weight ratio is 1: 5 the active ingredient (table I compound 4) and the dusting composition of toxinicide (DKA-24).
Embodiment 24
Preparation suspending concentrate (22FW)
Component is heavy: g
Table 1 compound 22 as active ingredient
Toxinicide DKA-24 20
Zeolex 444 carriers 6
Arkopon T wetting agent 4
Arkopol N-100 wetting agent 10
2%(weight as thickening material) xanthan gum solution 10
Water 48
Repeat example 12 described methods, obtaining total content is 22%(weight), weight ratio is 1: 10 the active ingredient (table I compound 5) and the suspending concentrate of toxinicide (DKA-24).
Embodiment 25
The greenhouse test of effect (to the effect of the plant that emerges) behind the bud
The mixture of the floresca chernozem soil of 1/3 part sand, 1/3 part clay and 1/3 part its bottom of packing into is had in the 200ml Plastic Bottle in 4 holes, then the seed of sowing test plant.
After the sowing, under normal illumination, the soil and the plantlet of emerging are respectively sprayed, and replenish 4 hours illumination 20-26 ℃ of every day.Use greenhouse sprayer will be sprayed onto on the 2-4 leaf plant by per hectare 1000 premium on currency from the 10WP composition that table I compound 3,5,6,7 and 8 makes respectively by example 6 methods under 4 bar pressures.
Around the spraying back second and the infringement (damage) of test plant is assessed.The degree of damage of various test plant is by percentage ratio: 0% representative is harmless, and 100% representative is withered fully.
It the results are summarized in the table II.As can be seen, composition of the present invention has good herbicidal effect, and cultivated plant is had good selectivity.Wherein compound 3,7 and 8 has been proved to be especially effective.
The table II and after in each table, the Roman number I on first hurdle refers to show I, Arabic numerals refer to show the compound number in the I.
The table II
Act on behind the bud
Abbreviation in the table II:
ORYS Oryza sativa STEM Stellaria media
ECHC Echinochloa c.g. GALA Galium aparine
MATI Matricana inodor ZEAM Zea mays
HELA Helianthus annuus GLYM Glycine max
TRIE Triticum aesticum
Embodiment 26
The greenhouse test that the bud previous crops is used
Dividing 3 parts of planting seeds with test plant is 200cm to placing high 7cm, bottom area
2The carton of bottom perforated in saturating medium forest soil in.The chest of handling is respectively placed on the plastics tray that has wet cloth.Before plant emerged after the sowing, the 10WP composition that will prepare from table I compound 7 by embodiment 6 with the greenhouse miniaturised nebuliser was sprayed onto soil surface the chest with water by the amount of 1200 liters of per hectares.Guarantee replenishing of water by the moisture state of keeping wet cloth.Under normal illumination and additional illumination in four hours, experimentize in 20-28 ℃.Spraying the herbicidal effect of back the 4th and the 6th all his-and-hers watches 1 compounds 7 assesses.It the results are summarized in the table III.
The table III
The bud previous crops is used
The destructiveness (%) of compound number dosetest plant
(in the table I) g/ha Solanum Digitaria ECHC STEM TRIE
migrum adans
I/7 250 70 50 20 100 0
1000 100 60 40 100 0
Embodiment 27
Research to cultivated plant effect in the plant growing case
The ground surface soil (pH value is 6.5, and penetration degree is 50, and humus content is 1.4%) of every part of 400g is weighed into lining, and (area is 0.8dm with the plastic culture bottle of PVC paillon foil
2) in.In soil, sow 10 Pi-3737 corn seeds, 100 streaky sunflowers " IREG " seed, 50 SA-114 jowar seeds and 1g red rice respectively.
Handle after these kinds subcovering with 100g soil respectively.In this treating processes, to use by the dosage of per hectare 10,20,40,80,160 and 320g respectively from water dispersible granular (75WDG) and Ally in contrast, Tell, Granstar, Glean, Logran and the SL-950 of compound 2,4,5,6 and 8 preparations respectively by the method for example 13, every part is repeated 4 times.Treated soil surface covers with 100g soil more in addition in every bottle.
Bottle is placed plant incubator, be sprayed to its water capacity every day, and carry out shining in 16 hours following every day at HGMF/D 400 fluorescent lamps.Experiment was assessed after determined when the fresh weight of sunflower, jowar and millet and corn fresh weight and seedling are long in after planting the 10th day.Gained the results are summarized in the table IV, is named as " sowing I ".
Divide 6 repeat sowings in evaluated experiment soil in the seed of corn, sunflower and millet.The assessment result of these subsequent experimental is summarized in the table V to IX, respectively called after " sowing II III, IV, V, VI ".
To sowing IV, assessment continues 76 days altogether from the sowing I.
Embodiment 28
The weeding activity test of the field experiment that in the winter wheat farm crop, carries out
At every 10m near the Sebes-Koeroes river
2Tanaka to the winter wheat back weeds control experiment of emerging.
Test is is 6.3 at pH value, contain on the 3.4% organic pasture clay soil and carry out.With winter wheat as green crop.In October 24 through on the drying kind bed of fining-off with planting seed to the 6-7cm depths, form line-spacing by the straight line sowing.
Experiment after emerging April 20.Kind of weeds and the vegetative period when handling thereof be: burweed (Galium aparine is abbreviated as GALAP) is in the 4-6 impeller phase; Redly educate nettle (Lamium purpureum LAMPU) is flowering period; Meadow veronica (Veronica arvensis, VERAR) the budding phase when blooming; (Fumaria officinalis FUMOF) was 6 leaf phases to medicinal native goitre; Chickweed (Stellaria media; STEME) be flowering period; (for stem forms the phase, (Chenopodium album CHEAL) is the 2-6 leaf phase to white Chenopodium plant to the east Root of Rocket Consolida for Consolida orientalis, CONOR) high 10cm; (Bilder-dyckia Convolvulus BILCO) is the 2-3 leaf phase to fallow flax ground weeds.For experimentizing, use the parcel atomizer that has propane-butane air pressure.The compound 4,5,6 and 8 of table I is used by the dosage of per hectare 10-80g activeconstituents respectively, and with the spraying fluid sprinkling of 500 liters of per hectares, this spraying fluid is for pressing the 5FW suspending concentrate of example 11 preparations.Logran 75 DF of use same dose and Granstar 75 DF are in contrast.
By the 0(non-activity)-100(is withered fully) level herbicide effect and the phytotoxicity effect of these experiments are assessed.After the processing, pass through to measure spike number (bar/cm in the vegetative phase
2), the weight (g) of spike length (cm) and 1000 grains carries out four assessments (April 27, May 4, May 25 and June 18).After 4 repeated experiments institute values are averaged, will the results are summarized in the table X to showing the X VI.
Table X VI
Detect the result of each fringe
Can know and find out to showing result shown in the X VI from the table X, the present composition and with existing difference between the commercial available composition that compares.Contain in the table I compound 4 and 8 composition by the weeds that grown the aftertreatment of emerging being proved to be extremely effective with extremely strong infection.These two kinds of compounds also are desirable to the selectivity of cultivated plant.Because contain the phytotoxicity height of the herbicidal composition of table 1 compound 5 and 6, to (almost useless) a little less than the weeds control action kou, thereby they are not suitable at the winter wheat culture and carry out weeds control.
Embodiment 29
The detoxifcation composition is to the research of cultivated plant effect in the plant incubator
It is 0.8dm with PVC paillon foil, area that the ground surface soil (pH value is 6.5, and penetration degree is 50, and humus content is 1.4%) of every part of 40g is weighed to lining
2The plastic culture bottle in.Respectively at 10 Pi-3737 corn seeds of this native upper seeding wheel and 10 bar shaped sunflowers " IREC " seed.Soil with 100g covers these seeds.Handle then, each is handled and repeats 4 times.The active ingredient 2,4,5,6 and 8 that to show I in these treating processess is combined into by the form of example 15 composition prepared with toxinicide DKA-24, AD-67, R-25788, MG-191 and the CGA-92194 of per hectare 250-500g respectively by the amount of per hectare 20-160g to be used.Soil surface treated in each bottle covers with the soil of 100g in addition.
Bottle is placed plant incubator, and cultivate by illumination 16 hours every days.Be sprayed to its water capacity to plant every day.
Experiment is assessed by measuring (measurement) seedling length, fresh weight in handling back the 13rd day.It the results are summarized in table X VII to showing the X IX.
Embodiment 30
The detoxifcation composition is to the test of cultivated plant effect in the plant incubator
It is 0.8dm with PVC paillon foil, area that the ground surface soil (pH value is 6.5, and penetration degree is 50, and humus content is 1.4%) that takes by weighing every part of 400g is put into lining
2The plastic culture bottle in.On this soil, sow 10 Pi-3737 corn seeds and 50 SA-114 jowar seeds respectively, 100g soil in the covering.Begin then to handle, every part is repeated 4 times.The compound 2,4,5,6 and 8 that to show I in these treating processess is combined into by example 22 to 24 composition prepared forms with the DKA-24 toxinicide of per hectare 400g respectively by the amount of per hectare 20,40 and 80g to be used.Glean, Granstar, Ally or the Tell of same dose combined with the DKA-24 toxinicide respectively use to make comparisons.Cover the soil of 100g on the soil surface that in each bottle, sprayed again.
Bottle is placed plant incubator, and cultivated under the illumination condition 16 hours every days.Spray plant every day, until its water capacity.
Handling back the 12nd day assesses experiment by measuring (measurement) seedling length and fresh weight.Gained the results are summarized in the table XX.
Claims (6)
1, a kind of replacement sulfonyl urea derivates and salt thereof with general formula (I):
R wherein
1Represent hydrogen, halogen, C
1-4Alkoxyl group, halo-C
1-4Alkoxyl group, C
1-3Alkane alkylsulfonyl, or COR
6Group;
R
2Represent hydrogen, C
1-3Alkyl, or phenyl;
R
3Represent C
1-6Alkyl, C
3-6Alkenyl, C
1-3Alkoxyalkyl, the C that is replaced by one or more halogen atoms
2-4Alkyl, or benzyl;
R
4And R
5Represent C independently of each other
1-4Alkyl, C
1-4Alkoxyl group, halogen, C
1-3Alkylamino or two-(C
1-3Alkyl) amino, or C
1-3Alkylthio;
R
6Represent C
1-4Alkoxyl group, C
3-6Alkenyloxy, C
3-6Alkoxyalkyl, C
1-3Alkylamino, two-(C
1-3Alkyl) amino, piperazinyl, or morpholinyl;
X represents oxygen or sulphur;
E represents methyne or nitrogen.
2, a kind of herbicidal composition that replaces sulfonylurea that contains replaces sulfonyl urea derivates comprising the logical formula I as active ingredient:
Wherein
R
1Represent hydrogen, halogen, C
1-4Alkoxyl group, halo-C
1-4Alkoxyl group, C
1-3Alkane alkylsulfonyl, or COR
6Group;
R
2Represent hydrogen, C
1-3Alkyl, or phenyl;
R
3Represent C
1-6Alkyl, C
3-6Alkenyl, C
1-3Alkoxyalkyl, the C that is replaced by one or more halogen atoms
2-4Alkyl, or benzyl;
R
4And R
5Represent C independently of each other
1-4Alkyl, C
1-4Alkoxyl group, halogen, C
1-3Alkylamino or two-(C
1-3Alkyl) amino, or C
1-3Alkylthio;
R
6Represent C
1-4Alkoxyl group, C
3-6Alkenyloxy, C
3-6Alkoxyalkyl, C
1-3Alkylamino, two-(C
1-3Alkyl) amino, piperazinyl, or morpholinyl;
X represents oxygen or sulphur;
E represents methyne or nitrogen.
3, the described composition of claim 2, its existence form is a wettable powder.
4, the described composition of claim 2, its existence form is a granule.
5, a kind of contain as the replacement sulfonylurea of active ingredient and toxinicide contain the toxinicide herbicidal composition, said composition comprises the sulfonyl urea derivates that the logical formula I as active ingredient replaces (R wherein respectively
1, R
2, R
3, R
4, R
6The definition of X and E is identical with claim 1) or its salt; and toxinicide; the preferred DKA-24(N-dichloro-acetyl of this toxinicide-N-allyl group glycyl N '-allyl amine); AD-67(N-dichloro-acetyl-1-oxa--4-azaspiro (4; 5) decane); R-25788(N; N-diallyl-dichloro acetamide); MG-191(2-dichloromethyl-2-methyl isophthalic acid; the 3-dioxolane); CGA-92194(N-(1; 3-dioxolane-2-ylmethoxy) imino--benzyl cyanide) or the TI-35(N-(dichloro-acetyl)-hexamethylene imine); both total amounts are 0.01-95%(weight); preferred 2-80%(weight), the ratio of active ingredient and toxinicide be 1: 1 to 1: 50(weight).
6, a kind of method for preparing logical formula I replacement sulfonylurea and salt thereof,
Wherein
R
1Represent hydrogen, halogen, C
1-4Alkoxyl group, halo-C
1-4Alkoxyl group, C
1-3Alkane alkylsulfonyl, or COR
6Group;
R
2Represent hydrogen, C
1-3Alkyl, or phenyl;
R
3Represent C
1-6Alkyl, C
3-6Alkenyl, C
1-3Alkoxyalkyl, the C that is replaced by one or more halogen atoms
2-4Alkyl, or benzyl;
R
4And R
5Represent C independently of each other
1-4Alkyl, C
1-4Alkoxyl group, halogen, C
1-3Alkylamino or two-(C
1-3Alkyl) amino, or C
1-3Alkylthio;
R
6Represent C
1-4Alkoxyl group, C
3-6Alkenyloxy, C
3-6Alkoxyalkyl, C
1-3Alkylamino, two-(C
1-3Alkyl) amino, piperazinyl, or morpholinyl;
X represents oxygen or sulphur;
E represents methyne or nitrogen;
This method comprises:
(a) make isocyanic ester with logical formula IV or lsothiocyanates (R wherein
1Definition the same)
With the aminopyrimidine with logical formula III or amino-triazine (R wherein
2, R
3, R
4, R
5Identical with the definition of E) with the definition of logical formula I
In 0-50 ℃ of temperature (preferred 20-30 ℃) reaction down; Perhaps
(b) make the have general formula sulfonamido carbamate derivatives (R wherein of (V)
1Definition identical with the definition in the logical formula I, R represents phenyl)
With the aminopyrimidine with logical formula III or amino-triazine (R wherein
2, R
3, R
4, R
5The same with the definition of E) in 25-120 ℃ of temperature (preferred 60-90 ℃) reaction down; Perhaps
(c) make urea chloride with logical formula VI (R wherein
2, R
3, R
4, R
5The same with the definition of E, R represents phenyl)
With (the R wherein of the sulphonamide an alkali metal salt with logical formula II
1Definition identical with the definition in the logical formula I)
In-10-50 ℃ temperature (preferred 0-50 ℃) reaction down; Perhaps
(d) make the have general formula N-pyrimidinyl-amino manthanoate of (VII) or N-triazine radical amido manthanoate (R wherein
2, R
3, R
4, R
5The same with the definition of E, R represents phenyl)
With (the R wherein of the sulfonamide with logical formula II
1Definition identical with the definition in the logical formula I) in 20-80 ℃ of temperature (preferred 20-40 ℃) reaction down; Perhaps
(e) make the have general formula SULPHURYL CHLORIDE (R wherein of (VIII)
1Definition identical with the definition in the logical formula I)
With the aminopyrimidine with logical formula III or amino-triazine (R wherein
2, R
3, R
4And R
5Definition the same) under 20-120 ℃ of temperature (preferred 60-90 ℃), in the mixture of inert organic solvents or inert organic solvents, react, available bases metal or alkaline earth metal hydroxides, amine or the quaternary ammonium halide logical formula I compound that will obtain thus is converted into its salt then, isolate the logical formula I compound or its salt that obtains by evaporating solvent, if desired, use the currently known methods recrystallization again.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU90600A HU206024B (en) | 1990-01-31 | 1990-01-31 | Herbicidal compositions comprising substituted sulfonylurea derivatives and optionally antidote, as well as process for producing the active ingredients |
| HU600/90 | 1990-12-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1053786A true CN1053786A (en) | 1991-08-14 |
Family
ID=10950375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91100563A Pending CN1053786A (en) | 1990-01-31 | 1991-01-31 | Has urea derivatives of weeding activity and preparation method thereof |
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|---|---|
| JP (1) | JPH069577A (en) |
| KR (1) | KR950013855B1 (en) |
| CN (1) | CN1053786A (en) |
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| BE (1) | BE1005348A3 (en) |
| BR (1) | BR9100399A (en) |
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| CS (1) | CS18891A2 (en) |
| DE (1) | DE4102905A1 (en) |
| DK (1) | DK16091A (en) |
| ES (1) | ES2033200B1 (en) |
| FI (1) | FI910456A (en) |
| FR (1) | FR2658193A1 (en) |
| GB (1) | GB2241699A (en) |
| GR (1) | GR910100041A (en) |
| HU (1) | HU206024B (en) |
| IE (1) | IE910321A1 (en) |
| IL (1) | IL97342A0 (en) |
| IN (1) | IN171736B (en) |
| IT (1) | IT1245018B (en) |
| LU (1) | LU87884A1 (en) |
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| DE10218704B4 (en) * | 2002-04-26 | 2006-11-30 | Bayer Cropscience Gmbh | Halosulfonylbenzoic acid halides, processes for their preparation and their use for the preparation of substituted phenylsulfonylureas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4371391A (en) * | 1980-09-15 | 1983-02-01 | E. I. Du Pont De Nemours And Company | Herbicidal sulfonamides |
| US4343649A (en) * | 1980-11-17 | 1982-08-10 | E. I. Du Pont De Nemours And Company | Herbicide antidotes |
| US4545811A (en) * | 1981-08-06 | 1985-10-08 | Ciba-Geigy Corporation | N-Phenylsulfonyl-N'-triazinyl-ureas |
| US4579584A (en) * | 1981-10-13 | 1986-04-01 | Ciba-Geigy Corporation | N-phenylsulfonyl-N'-triazinylureas |
| MA19680A1 (en) * | 1982-01-11 | 1983-10-01 | Novartis Ag | N- ARYLSULFONYL - N '- PYRIMIDINYLUREES. |
| JPS58126872A (en) * | 1982-01-22 | 1983-07-28 | Nippon Tokushu Noyaku Seizo Kk | Substituted phenylsulfonylurea derivative, its preparation and herbicide |
| EP0098569A3 (en) * | 1982-07-08 | 1984-12-19 | Hoechst Aktiengesellschaft | Heterocyclically substituted sulfonyl ureas, process for their preparation and their use in agriculture |
| CA1221689A (en) * | 1982-09-10 | 1987-05-12 | Mark E. Thompson | Herbicidal ortho-alkyl- and ortho-alkenyl-substituted benzenesulfonamides |
| EP0122231B1 (en) * | 1983-04-12 | 1990-01-17 | Ciba-Geigy Ag | Herbicidal agent |
| EP0147365A3 (en) * | 1983-11-03 | 1985-10-09 | Ciba-Geigy Ag | Herbicidal agent |
| US4685961A (en) * | 1984-02-14 | 1987-08-11 | Ciba-Geigy Corporation | Herbicidal sulfonylureas |
| DE3420769A1 (en) * | 1984-06-04 | 1985-12-05 | Bayer Ag, 5090 Leverkusen | SUBSTITUTED PHENYLSULFONYL UREAS |
| US4645527A (en) * | 1984-12-14 | 1987-02-24 | E. I. Du Pont De Nemours And Company | Herbicidal antidotes |
| EP0190105A3 (en) * | 1985-01-31 | 1988-10-26 | Ciba-Geigy Ag | Herbicidal agent |
| HU201445B (en) * | 1987-05-28 | 1990-11-28 | Eszakmagyar Vegyimuevek | Herbicide composition containing sulfonyl-urea derivative as active component and glycinamide derivative as antidotum |
-
1990
- 1990-01-31 HU HU90600A patent/HU206024B/en not_active IP Right Cessation
-
1991
- 1991-01-25 ZA ZA91583A patent/ZA91583B/en unknown
- 1991-01-28 CS CS91188A patent/CS18891A2/en unknown
- 1991-01-28 YU YU36391A patent/YU36391A/en unknown
- 1991-01-29 NO NO91910327A patent/NO910327L/en unknown
- 1991-01-29 GR GR910100041A patent/GR910100041A/en unknown
- 1991-01-29 GB GB9101825A patent/GB2241699A/en not_active Withdrawn
- 1991-01-30 IE IE032191A patent/IE910321A1/en unknown
- 1991-01-30 CA CA002035319A patent/CA2035319A1/en not_active Abandoned
- 1991-01-30 AU AU70082/91A patent/AU638533B2/en not_active Ceased
- 1991-01-30 BR BR919100399A patent/BR9100399A/en unknown
- 1991-01-30 PT PT96606A patent/PT96606A/en not_active Application Discontinuation
- 1991-01-30 BE BE9100088A patent/BE1005348A3/en not_active IP Right Cessation
- 1991-01-30 SE SE9100289A patent/SE9100289L/en not_active Application Discontinuation
- 1991-01-30 DK DK016091A patent/DK16091A/en not_active Application Discontinuation
- 1991-01-30 IT ITTO910059A patent/IT1245018B/en active IP Right Grant
- 1991-01-31 LU LU87884A patent/LU87884A1/en unknown
- 1991-01-31 FI FI910456A patent/FI910456A/en not_active Application Discontinuation
- 1991-01-31 ES ES9100250A patent/ES2033200B1/en not_active Expired - Fee Related
- 1991-01-31 DE DE4102905A patent/DE4102905A1/en not_active Withdrawn
- 1991-01-31 IN IN66/MAS/91A patent/IN171736B/en unknown
- 1991-01-31 KR KR1019910001821A patent/KR950013855B1/en active IP Right Grant
- 1991-01-31 CN CN91100563A patent/CN1053786A/en active Pending
- 1991-01-31 PL PL91293799A patent/PL293799A1/en unknown
- 1991-01-31 JP JP3098310A patent/JPH069577A/en active Pending
- 1991-01-31 NL NL9100166A patent/NL9100166A/en unknown
- 1991-01-31 NZ NZ236977A patent/NZ236977A/en unknown
- 1991-01-31 PL PL91288905A patent/PL288905A1/en unknown
- 1991-01-31 FR FR9101082A patent/FR2658193A1/en active Pending
- 1991-02-22 IL IL9197342A patent/IL97342A0/en unknown
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