CN1105023A - Substituted benzoyl cyclic enone, process for preparation, and herbicide - Google Patents
Substituted benzoyl cyclic enone, process for preparation, and herbicide Download PDFInfo
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- CN1105023A CN1105023A CN94101552.1A CN94101552A CN1105023A CN 1105023 A CN1105023 A CN 1105023A CN 94101552 A CN94101552 A CN 94101552A CN 1105023 A CN1105023 A CN 1105023A
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Abstract
A compound, the herbicide containing said compound as active component, and a method for using said herbicide to prevent unnecessary plant from growing are disclosed.
Description
The present invention is the benzoyl cyclic enone derivative about new replacement, and its preparation method contains this compound and plants special method of growing as the herbicidal composition of effective constituent with this herbicidal composition control.
In the past at U.S. Pat P5, once disclosed the benzoyl-1 that 2-replaces in 006,158,3-cyclohexanedione compound has certain weeding activity.
U.S. Pat P4,762,551 have disclosed the sulfo-that some comprise that 3-(replaces)-2-benzoyl ring-compound of 2-ketone and European patent EP 338,992 disclosed the aryl dicyclo diketone that replaces and can be used as weeding active compound.But, compound of the present invention they chemical structure and substituent in conjunction with aspect be different from those compounds that before disclosed.Never related in their former documents, so the compound of the present invention newfound compound that is some.In addition, above the known compound mentioned paddy rice is had very high phytotoxicity, so they are difficult to use as herbicides for use in paddy.
The compound of the present invention of logical formula I representative has weeding activity and very low to the phytotoxicity of paddy rice to a lot of weeds below; because it has best movability and water-soluble in soil; so compare with other cyclohexadione compounds of being reported in the former document; consider that from point of view of environment protection they are to be considered to can be the more practical weedicide that the world accepts.
For example, after being added to this compound in the surface water of paddy field, allow then paddy field water either by every day discharge depth be the speed discharging 3 days (3 days total emit the water that the degree of depth is 9cm) of 3cm, the compound of being given in the table of discovery 3 its degree of depth of moving in soil under these conditions is 1 to 5cm, and by contrast, at USP5,006,158, USP4, its degree of depth of moving in soil of dione compounds of the known tool weeding activity of being reported in 762,551 and EP338,992 is 6-9cm.
Many compounds of the present invention also have such excellent characteristic, and are promptly water-soluble little, only be equivalent to 1/tens to several ten thousand of known dione compounds with weeding activity recited above/.
New compound provided by the present invention is shown in logical formula I
A representative in formula
One-S(O) nR
1Group, wherein n is O or 2 and R
1Represent a low alkyl group that has 1-4 carbon atom, its carbon atom can be replaced by an elementary alkoxy carbonyl that has 2-3 carbon atom;
A group of naphthene base that has 3-6 carbon atom;
A benzyl group, it can be by 1 to 3 halogen atom, and methyl and/or nitro replace;
A phenyl group, it can be by 1-5 halogen atom, 1 to 3 low alkyl group of 1-4 carbon atom of band, the lower alkoxy of 1-4 carbon atom of a band, a halogenated methyl, a nitro, cyano group and/or quilt have 1 or 2 alkyl of 1-2 carbon atom or the amino that alkyl sulphonyl replaces; Or
One-OR
2Group, R in formula
2Represent one by 1 to 5 halogen atom and/or 1 to 3 phenyl that has the low alkyl group replacement of 1-3 carbon atom;
B represents a halogen atom, a nitre worker, a low alkyl group that has 1-2 carbon atom, or a low alkyl group alkylsulfonyl that has 1-2 carbon atom;
D represents a hydrogen atom, a low alkyl group that has 1-2 carbon atom, a lower alkoxy that has 1-4 carbon atom, a lower alkoxy methyl that has 2-4 carbon atom, or an elementary alkoxy carbonyl that has 2-5 carbon atom;
E represents a halogen atom; a lower alkoxy that has 1-3 carbon atom; carbon atom on this lower alkoxy can be replaced by 1-3 fluorine atom; a lower alkylthio that has 1-3 carbon atom; a low alkyl group alkylsulfonyl that has 1-3 carbon atom; carbon atom on this alkyl sulphonyl can be replaced by 1 to 3 fluorine atom, or a low alkyl group alkylsulfonyl oxygen base that has 1-3 carbon atom.
The actual weedicide that uses, be main food particularly at those rice, paddy rice is that the weedicide that staple crops countries uses must possess following good characteristics, (1) high herbicidal activity for example, and (2) herbicidal spectrum is wide, (3) to the low phytotoxicity of farm crop (as rice plant), (4) appropriateness is water-soluble, the soil flowability of appropriateness, and (5) are to fish and Mammals low toxicity, (6) in soil, have certain stability and the certain period after easily in the occurring in nature decomposition, or the like.
Consider these characteristics, so in the compound of logical formula I representative, lead to the compound of formula II representative below preferred.
In formula
A ' represents one-S-(O) nR
3Group, wherein n is O or 2 and R
3Represent one can or be had the phenyl that 1-3 low alkyl group of 1-4 carbon atom replaces by 1-5 halogen atom,
B ' represent a halogen atom or nitro and
E ' represents a halogen atom, or a low alkyl group alkylsulfonyl that has 1-3 carbon atom, and the carbon atom on this group can be replaced by 1-3 fluorine atom.
Concrete example comprises following compound in most of preferred compound:
(1) 3-(2-chloro-4-methyl sulphonyl benzoyl)-4-thiophenyl-dicyclo [3.2.1]-Xin-3-alkene-2-ketone (compound N is o.95);
(2) 3-(2-chloro-4-methyl sulphonyl benzoyl)-4-(4-methylbenzene sulfenyl)-dicyclo [3.2.1] suffering-3-alkene-2-ketone (compound N is o.97);
(3) 3-(2-chloro-4-methyl sulphonyl benzoyl)-4-phenyl sulfonyl dicyclo [3.2.1] suffering-3-alkene-2-ketone (compound N is o.108);
(4) 3-(2-chloro-4-methyl sulphonyl benzoyl)-and 4-(2,6-dimethyl benzene sulfenyl)-dicyclo [3.2.1] suffering-3-alkene-2-ketone (compound N is o.79);
(5) 3-(2-chloro-4-methyl sulphonyl benzoyl)-4-(3-chlorinated benzene sulfenyl)-dicyclo [3.2.1] suffering-3-alkene-2-ketone (compound N is o.98); With
(6) 3-(2-nitro-4-methyl alkylsulfonyl benzoyl)-and 4-(2,6-dichlorobenzene sulfenyl)-dicyclo [3.2.1] suffering-3-alkene-2-ketone (compound N is o.68).
Those compounds that optimizes that is suitable for doing the herbicide for paddy field use as described above have been showed in the following table 1 with good activity and characteristics.
Table 1
A: to the weeding activity of barnyard grass grass, its EP
90Value
A:32-64 restrains effective constituent/hectare
B:64-125 restrains effective constituent/hectare
C: greater than 125 gram effective constituent/hectares
B: the flowability in soil
C:, use ID with the selectivity of paddy rice
10(paddy rice)/ED
90(barnyard grass grass) expression
A：＞8
D: ichthyotoxin, use TLm(48) expression
A：≥10ppm
B：0.5-10ppm
C：≤0.5ppm
Compound shown in the logical formula I can be produced, for example by following reactive mode preparation.Used in the back meet have in the above given implication, X represents a halogen atom.
Reactions steps (a) preferably is in the inert solvent under reaction conditions at one carries out, methylene dichloride for example, and chloroform, tetrahydrofuran (THF), toluene, acetonitrile or the like, reaction is preferably in an organic bases and exists down, for example, triethylamine.Suitable reaction temperature is in 0-40 ℃ of scope, as 20 ℃.
The rearrangement reaction of reactions steps b has catalyzer to exist, 4-dimethylaminopyridine for example, a lewis' acid or have the prussiate donor of irenine.
The acid catalyzer of suitable lewis used in rearrangement reaction can be that for example, aluminum chloride, zinc chloride or tin chloride (IV) and suitable prussiate donor can be for example, to be with the acetone cyanohydrin of triethylamine.
Suitable solvent for example comprises, methylene dichloride, acetonitrile or toluene.
Temperature of reaction from 0 ℃ to reflux temperature, preferred room temperature (20 ℃).
Table 2 is some benzoyl diketone (III), the specific example of the intermediate product of preparation.
Usually, in the halogenating reaction of step (c), the benzoyl diketone is to be dissolved in inert solvent, as chloroform, and tetracol phenixin, methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), dioxan, benzene, toluene is in the dimethylbenzene etc.Add excessive (being generally 100-300 mole %) thionyl halide or oxalyl halogen (thionyl chloride in fact commonly used or oxalyl chloride) then, the amine or the acid amides of the adding catalytic amount that continues are as dimethyl formamide or pyridine.Reaction mixture stirred 1 hour to 1 day under from room temperature to molten some boiling temperature.Use the ordinary method reaction product isolated then.
The compound shown in the logical formula IV is new compound above obtaining in step (c), and being easy in step (d) changes the compound of criticizing to shown in the formula I of the present invention with it.
In reactions steps (d), accord with the halogenide (IV) and the mercaptan (R of the compound of wanting
1-SH) or phenol (R
2-OH) be dissolved in respectively in the inert solvent as tetrahydrofuran (THF) by stoichiometric quantity usually, methylene dichloride, toluene etc., the amount of then organic bases such as triethylamine being pressed starting raw material 100-200 mole % adds wherein.
Reaction is to carry out 1 hour to 1 day under (preferred room temperature) to the boiling temperature of solvent at 0 ℃, uses the ordinary method separated product then.
The oxidizing reaction of step (e) is carried out with an ordinary method, and (I-a) be dissolved in an inert solvent such as methylene dichloride will use an oxygenant such as m-chloro peroxybenzoic acid to carry out oxidizing reaction afterwards in chloroform or the tetracol phenixin vulcanizing writing paper.
The chemical preparation example
Be exemplary below from middle product (III) preparation The compounds of this invention.
Preparation example 1
3-(2-chloro-4-methyl sulphonyl benzoyl) dicyclo [3.2.1]-octane-2,4-diketone (0.99g) is dissolved in the 15ml methylene dichloride, adds the 0.8ml oxalyl chloride in this solution.Again to the dimethyl formamide that wherein adds a catalytic amount (1-2 drips).Reaction mixture at room temperature stirred 30 minutes, the backflow that continues 2 hours.Pressure reducing and steaming solvent and excessive oxalyl chloride are dissolved in resulting muriate in the 20ml tetrahydrofuran (THF) under not purified situation, muriate is purified and identify that respectively analytical data is as follows:
mp.154-157℃
δ（CDCl
3）7.7-8.0（3H，m），3.05（3H，s）2.8-3.4（2H，m），1.6-2.3（6H，m）。
Add 0.386g 2 in solution earlier, 6-dimethyl thiophenols adds the 0.39ml triethylamine then again under ice-cooled.
After at room temperature stirring 3-4 hour, reaction mixture is to be introduced in the water, uses ethyl acetate extraction.Use hydrochloric acid and the water washing organic phase of 1N respectively, use anhydrous sodium sulfate drying then.
The coarse crystallization that obtains after underpressure distillation boils off solvent obtains 1.11g target compound (compound number No.79 in table 3) with the Di Iso Propyl Ether washing.(from the resulting productive rate of diketone: 83.7%).
Preparation example 2
The 30ml tetrahydrofuran (THF) is dissolved in the method identical with top preparation example 1 with 3-(2-nitro-4-methyl alkylsulfonyl benzoyl)-dicyclo-[3.2.1] octane-2; in the resulting muriate of 4-diketone; muriate recited above is to identify respectively, and analytical data is as follows:
mp.120-123℃
NMR（CDCl
3）
δ8.4（1H，d，J＝2），8.15（1H，dd，J＝8.27），7.6（1H，d，J＝8），3.1（3H，s）;1.5-3.4（8H，m）
In this solution, add 0.674g 4-chlorophenyl mercaptan, add the 0.59ml triethylamine then.
At room temperature stir after the night, reaction mixture is handled by treatment step identical in the top preparation example 1, obtains 1.6g target compound (compound number No.63 in table 3).(productive rate 73.2%).
Preparation example 3
0.8g is dissolved in the 20ml methylene dichloride by the compound that obtains in the preparation example 2 (63), and gradation adds 0.68g m-chloro peroxybenzoic acid in this solution under ice-cooled.Reaction mixture stirred several hours under this situation.After confirming that with thin-layer chromatography reaction has been finished, with 50ml methylene dichloride diluted reaction mixture, with pyrosulphite hydrogen sodium water solution, wash with 5% wet chemical more earlier, that continues uses anhydrous sodium sulfate drying.
The crystallization that obtains behind the pressure reducing and steaming solvent obtains 0.7g target compound (compound number No.64 in table 3) with the Di Iso Propyl Ether washing.(productive rate: 82.3%).
Preparation example 4
Except using and the 1.92g 2-chloro-3-(2-nitro-4-methyl alkylsulfonyl benzoyl that obtains in the identical method of preparation example 1) dicyclo [3.2.1] oct-2-ene-4-ketone; 0.9g 2; 6-dichloro thiophenols, 0.7ml triethylamine and 35ml tetrahydrofuran (THF) repeat the method for preparation example 2 outward.So obtain 1.85g target compound (compound number No.68 in table 3), (productive rate: 67.8%).
Preparation example 5
Except using and the 1.87g 2-chloro-3-(2-nitro-4-methyl alkylsulfonyl benzoyl that obtains in the identical method of preparation example 1) dicyclo [3.2.1] oct-2-ene-4-ketone; 0.52g THIOGLYCOL acid formic acid; 0.68g outside triethylamine and the 35ml tetrahydrofuran (THF); repeat the method for preparation example 2, reaction mixture is handled (eluent: ethyl acetate/normal hexane: 1: 4 to 1: 1) through silica gel chromatography and is obtained 0.52g target compound (compound number No.71 in table 3) (productive rate: 23.4%) thereafter.
Preparation example 6
Will be by the method identical by 1.0g 3-(2-nitro-4-methyl alkylsulfonyl benzoyl with preparation example 1)-dicyclo [3.2.1] octane-2, the 1.0g muriate that the 4-diketone obtains is dissolved in the 20ml tetrahydrofuran (THF).In this solution, add 0.58g 2,4,6-Trichlorophenol and 0.41g triethylamine then respectively.
At room temperature stir after the night, reaction mixture is handled by treatment process identical in preparation example 1, and thick extract obtains 0.5g target compound (the numbering No.113 of compound in table 4), (productive rate: 32.7%) with the ether crystallization.
Preparation example 7
3-(2-chloro-4-methyl sulphonyl benzoyl)-and dicyclo [3.2.1]-octane-2,4-diketone (1.0g) is to be dissolved in the 10ml methylene dichloride, adds the 0.3ml thionyl chloride in this solution.The dimethyl formamide (1-2 drips) that adds a catalytic amount again, reaction mixture refluxed 6 hours.Pressure reducing and steaming solvent and excessive thionyl chloride are dissolved in the muriate that obtains in the 10ml methylene dichloride.
Under ice-cooled, in this solution, successively add 0.31g thiophenol and 0.392g triethylamine.Solution at room temperature stirred 2-3 hour, reaction mixture is water and salt water washing respectively, and use anhydrous sodium sulfate drying, the coarse crystallization that obtains behind the pressure reducing and steaming solvent obtains 1.2g target compound (compound number No.95 in table 3), (productive rate: 95.2%) after with ether and/or washing with acetone.
Reference example
Intermediate product, 3-(2-nitro-4-methyl-alkylsulfonyl benzoyl)-dicyclo [3.2.1] octane-2, the preparation of 4-diketone.
To containing 10g dicyclo [3.2.1] octane-1,2, drip the 70ml dichloromethane solution that contains 19.1g 2-nitro-4-methyl alkylsulfonyl benzoyl chlorine in the 100ml methylene dichloride of 4-diketone under ice-cooled.
After dripping,,, wash with water, use anhydrous sodium sulfate drying again with the methylene dichloride dilution ice-cooled down reaction mixture restir 1 hour.
The evaporated under reduced pressure solvent obtains the coarse crystallization of an enol ester of 25.2g.
Unpurified enol ester is dissolved in the 160ml acetonitrile, adds 20ml triethylamine and 4.3ml acetone cyanohydrin in this solution.Reaction mixture at room temperature stirs a night.Behind the concentrating under reduced pressure, reaction mixture is poured in the water, uses dichloromethane extraction, with 10% hydrochloric acid and saturated brine washing, uses anhydrous sodium sulfate drying more respectively.
Pressure reducing and steaming solvent, residue obtain the 19g target compound with the ether crystallization, 3-(2-nitro-4-methyl alkylsulfonyl benzoyl)-dicyclo [3.2.1] octane-4-diketone.(productive rate: 71.8%).
Provided object lesson in table 3-1 to 3-9 and the table 4 with the compound of top described method preparation.But the present invention is not limited to this.
Compound of the present invention shown in the logical formula I can be used for preventing and kill off multiple injurious weed.Compare with the compound that known two ketones have weeding activity, compound of the present invention has shown selective herbicidal activity and has reduced phytotoxicity to rice plant simultaneously considerably.The characteristics of The compounds of this invention are that the annual and perennial weeds that is grown in the rice terrace is all had quite high weeding activity, barnyard grass grass (it is the popular name of main representative weeds in the paddy field) for example, Sheathed Monochoria, (the serious weeds of annual harm in the paddy field), Herba Cyperi Difformis (the serious cyperus weeds of annual harm in the paddy field), Herba Eleocharitis acicularis (perennial cyperus weeds, grow in the marsh, water channel, the paddy field, representational perennial weeds), short arrowhead (grows in the paddy field, the marsh, a kind of perennial weeds in the irrigation canals and ditches), the sugarcane grass, Herba Cyperi Glomerati (the perennial weeds that belongs to cyperus, be grown in the paddy field, the marsh is in the irrigation canals and ditches) etc., they have demonstrated very low phytotoxicity to rice plant.
Since the compound of the present invention shown in the logical formula I for bud before and the weeds of growing period demonstrated excellent herbicidal, so they can be used as the weedicide that soil treatment is used before and after the shoot transplanting equipment, also can do farm crop transplant before the weedicide used of soil treatment and before farm crop are transplanted and growing period handle the cauline leaf of farm crop.
Usually, containing The compounds of this invention was to be processed to suitable formulation for use before their are used as the composition with herbicidal performance of effective constituent.
That is exactly that compound recited above is to mix with suitable inert support, if necessary, make their energy dissolved with auxiliary material with a suitable ratio, separate, suspend, mix dipping, absorption or bonding, so that they can be processed to suitable form, suspension agent for example, emulsion, solution, wettable powder, the flowable pulvis of exsiccant, granule, tablet etc.
Can make both solids of material that carrier uses in the present invention, also liquid.But solid carrier material soyflour, flour, wood powder, tree bark powder, sawmilling, the tobacco rod powder, walnut parting,, fiber powder, the residue after elite is extracted in plant powder such as the plant materials; Fibrous matter such as paper, waved plate, friperie; Synthetic polymer such as powdery synthetic resins; Inorganic mineral powder such as clay (as, kaolin, bentonite, acid clay), talcum (talcum, pyrophyllite), silica (diatomite, silica sand, mica, white carbon, (silicic acid of synthetic polymolecularity is also referred to as aqueous tiny silicon or aqueous silicic acid, is its main component and some product contains Calucium Silicate powder)), activated carbon, SULPHUR POWDER, float stone, incinerating diatomite, brickbat, flying dust, sand, lime carbonate, calcium phosphate, or the like; Chemical fertilizer such as ammonium sulfate, ammonium phosphate, ammonium nitrate, the urea element, ammonium chloride, Repone K, saltpetre, composite fertilizer etc., they also can be separately or in them 2 or a plurality ofly use with mixed form.
Liquid support should be selected from like this some materials, though promptly they itself have solvate ability and those they itself do not have a solvate ability, by adding auxiliary material effective constituent is scatter.Example comprises water, and alcohol (as methyl alcohol, ethanol, Virahol, butanols, ethylene glycol), ketone is (as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), diisobutyl ketone, cyclohexanone), and ether (as ether, dioxan, cellosolve, dipropyl ether, tetrahydrofuran (THF)), aliphatic hydrocarbon (as gasoline, mineral oil), aromatic hydrocarbon is (as benzene, toluene, dimethylbenzene, solvent naphtha, alkylated naphthalene), and halohydrocarbon (as ethylene dichloride, chlorinated benzene, chloroform, tetracol phenixin), ester is (as ethyl acetate, dibutyl phthalate, o-benzene butyl phthalate ester, phthalic acid dioctyl ester), acid acylamide (as dimethyl formamide, diethylformamide, N,N-DIMETHYLACETAMIDE), nitrile (as acetonitrile), dimethyl sulfoxide (DMSO), etc.These can use separately or they in 2 or more use with mixed form.
Auxiliary agent comprises following material: auxiliary agent can use by purpose.In some cases, 2 or a plurality of auxiliary agent mix and use.In other cases, used additives not.
Tensio-active agent can be used for emulsification, disperses solubilising and/or wetting effective constituent.For example, the available tensio-active agent is a polyoxyethylene alkylaryl ether, Voranol EP 2001, the polyoxyethylene high-grade aliphatic ester, polyoxyethylene resinate, polyoxyethylene sorbitol acid anhydride glycerine-laurate, polyoxyethylene sorbitol acid anhydride-oleic acid ester, alkyl aryl sulfate, napsylate condensation product, lignin sulfonate, higher alcohol sulfates etc. are in order to reach dispersion, stable, adhere to, purposes such as bonding can be used casein, pectin, starch, alginic acid, methylcellulose gum, carboxy methyl cellulose, gum arabic, polyvinyl alcohol, asbolin, sucrose oil, bentonite, sulfonated lignin etc.
In order to promote the flowability of solid product, can use, for example, wax, stearate, alkyl phosphate etc.
As the anti-wadding agent of product suspension, can use, for example, naphthene sulfonic acid condensation product, the phosphoric acid of condensation etc.
Also may add defoamer such as silicone oil.
If desired, can regulate the amount of effective constituent in the formulation.Under the situation of pulvis or granule, the amount of effective constituent is generally the 0.2-20%(weight percent), and, be approximately the 0.1-50%(weight percent for emulsion and wettable powder).
The formulation preparation example
Be according to representative dosage forms examples more of the present invention below.Need not to point out that content of effective can change in the described scope in the above.Below all data by weight percentage.
Example 1 wettable powder
Compound (50 parts) in table 2,20 parts of diatomite, 22 parts of clays, 3 parts of white carbon, 2 parts of sodium lignosulfonates and 3 parts of sodium alkyl naphthalene sulfonates be mixed and grind, and obtains active constituent content and be 50% wettable powder.
Example 2 granules
Compound (0.35 part) in table 2,25 parts of bentonite, 70.65 parts of talcums mix mutually with 2 parts of Sodium dodecylbenzene sulfonatees.Mixture and about 20 parts of water integrate in a kneading device, use a tablets press granulation then, and the drying that continues is also repaired particle, obtains containing the granule of effective composition 0.35%.
Weedicide of the present invention can by the amount that can produce phytotoxicity or control growing directly make water or other material it is done suitably dilution or suspend after be applied to the cauline leaf of weeds or weeds or be applied in the soil that does not need weed growth or germination.
The using dosage of weedicide of the present invention depends on different factors, for example, and purpose, the weeds kind that is killed or controls, the situation that weeds or farm crop germinate or grow, the trend that weeds germinate, weather, formulation, using method, place to use, duration of service etc.
When using weedicide of the present invention to make the rice terrace selective herbicidal, the consumption of The compounds of this invention is 5-1000g/ha, preferred 10-500g/ha.
When weedicide of the present invention and one or more other herbicide mixture, the consumption of The compounds of this invention should be lower than dosage recited above, because use with than its independent use synergism is arranged.
Though weedicide of the present invention is particularly suitable in the rice terrace before germinateing and the growing period controlling weeds, it also may mix with its weedicide so that enlarges the weeds spectrum, prolongation drug effect phase or minimizing using dosage, and this measure does not exceed category of the present invention.
Effect of the present invention
Weedicide of the present invention can be prevented and treated multiple injurious weed usually, has particularly reduced the phytotoxicity to rice plant significantly, can optionally prevent and kill off paddy field weed.
Biological Examples
Biological Examples described below will explain the present invention, but the present invention is not limited to this.
The test of test example 1 granule
One 1/5000 are Wager basin is filling of water paddy soils and ploughing and weeding.The depth of water is 4cm, broadcast into the barnyard grass grass Sheathed Monochoria, the seed of Amonannia Multiflora and Scirpus hotarui, the short arrowhead of Sagittaria, the bulb of Cyperes Serotimis Rottb and Eleocharisf Kuroguhai is to be planted in the basin.Then with the rice plants of 2 leaf phases (kind: Koshihikari) transplant to basin (it is dark that 3 marks are planted 1cm, and it is dark that 3cm is planted in 3 strains) by every basin six strains.After transplanting the 10th day, the granule of The compounds of this invention was about to be numbered 63,65,66,68,70,88,89,90,91,93,95,96,97, the granule that 98,100 and 104 compound is processed into by example 2 methods and with compound (A) in the Japanese Unexamined Patent Publication No 152642/1986, compound in the Japanese Unexamined Patent Publication No 202755.1987 (B) and Japanese patent application 3 with the number of opening 6425/1990 in the prepared granule of compound (C) be applied to the surface of water.
After handling second day and the 3rd day, it was 3cm/ days that seepage is operated its speed, counts the 21st day from processing, carries out O﹠A according to following standard, and the result is in showing 5-1 and 5-2.
0: invalid, no vegetable poison bamboo
10: all kill
Test example 2: wettable powder test
A 325cm
2Flowerpot with loading on the farmland, the seed of various weeds, i.e. lady's-grass, barnyard grass grass, Herba Setariae Viridis, Polygonum blumei, lamb's-quarters, piemarker, artemisiifolia, Amaranthus retroflexus, Xanthium Strumarium Pharbitis purpurea, with the seed of various farm crop, as soybean, corn, wheat, cotton and sweet grass sowing are in basin.Soil treatment before sowing was carried out bud in 1 day was carried out foliar treatment at after planting 10 days, the compound of handling usefulness is a compound of the present invention, compound number is 62,64,67,68,71,90,91,93,95,97,100 and 104, will do to spray with the aqueous solution of the wettable powder of the aqueous solution of the wettable powder of these compound and the compd A that is used for comparison above-mentioned and handle.Handle back 21 days by following standard O﹠A, test-results is given in table 6.
0: to no effect, plant-less toxicity
10: all kill
Abbreviation:
ECCP.: the barnyard grass grass
SCHO.: the sugarcane grass
CYSR.: Herba Cyperi Glomerati
ELKO.: pin Lin
MOVP. Sheathed Monochoria
AMMR.: Ammannia multiflora Roxb
SAPM.: short arrowhead
SATL.: wild arrowhead
DIAH.: lady's-grass
SEVP.B.: Herba Setariae Viridis
POBME.: knotweed
CHAL.: lamb's-quarters
AMAL.: artemisiifolia
AMRL.: Amaranthus retroflexus
XASL.: Siberian cocklebur
ABTM.: piemarker
PHPVO.: Pharbitis purpurea
Claims (12)
1, the benzoyl cyclic enone derivative of the replacement shown in logical formula I
A representative in formula
One-S (O) nR
1Group, wherein n is 0 or 2 or R
1Represent a low alkyl group that has 1-4 carbon atom, its carbon atom can be replaced by an elementary alkoxy carbonyl that has 2-3 carbon atom;
A group of naphthene base that has 3-6 carbon atom;
A benzyl group, it can be by 1 to 3 halogen atom, and methyl and/or nitro replace;
A benzyl group, it can be by 1-5 halogen atom, 1-3 low alkyl group of 1-4 carbon atom of band, lower alkoxy of being with 1-4 carbon atom, halogenated methyl, nitro, cyano group and/or quilt have 1 or 2 alkyl of 1-2 carbon atom or the amino of alkyl sulphonyl replacement; Or
One-OR
2Group, R in formula
2Represent one by 1 to 5 halogen atom and/or 1 to 3 phenyl that has the low alkyl group replacement of 1-3 carbon atom;
B represents a halogen atom, a nitro, and a low alkyl group that has 1-2 carbon atom, or one shown off the low alkyl group of 1-2 carbon atom alkylsulfonyl arranged;
D represents a hydrogen atom, a low alkyl group that has 1-2 carbon atom, a lower alkoxy that has 1-4 carbon atom, a lower alkoxy methyl that has 2-4 carbon atom, or an elementary alkoxy carbonyl that has 2-5 carbon atom;
E represents a halogen atom; a lower alkoxy that has 1-3 carbon atom; carbon atom on this lower alkoxy can be replaced by 1-3 fluorine atom; a lower alkylthio that has 1-3 carbon atom; a low alkyl group alkylsulfonyl that has 1-3 carbon atom; carbon atom on this alkyl sulphonyl can be replaced by 1 to 3 fluorine atom, or a low alkyl group alkylsulfonyl oxygen base that has 1-3 carbon atom.
2, the benzoyl cyclic enone derivative of the replacement shown in logical formula II
In formula
A represents one-S-(O) nR
3Group, wherein n is 0 or 2 and R
3Represent one can or be had the phenyl that 1-3 low alkyl group of 1-4 carbon atom replaces by 1-5 halogen atom,
B
1Represent a halogen atom or nitro and
E
1Represent a halogen atom or a lower alkoxy acyl group that has 1-3 carbon atom, the carbon atom on this group can be replaced by 1-3 fluorine atom.
3,3-(2-chloro-4-methyl sulphonyl benzoyl)-4-thiophenyl dicyclo [3.2.1] suffering-3-alkene-2-ketone.
4,3-(2-chloro-4-methyl sulphonyl benzoyl)-and 4-(4-methylbenzene sulfenyl) dicyclo [3.2.1] suffering-3-alkene-2-ketone.
5,3-(2-chloro-4-methyl sulphonyl benzoyl)-4-phenyl sulfonyl dicyclo [3.2.1] suffering-3-alkene-2-ketone.
6,3-(2-chloro-4-methyl sulphonyl benzoyl)-and 4-(2,6-dimethyl benzene sulfenyl)-dicyclo [3.2.1] suffering-3-alkene-2-ketone.
7,3-(2-chloro-4-methyl sulphonyl benzoyl)-4-(3-chlorinated benzene sulfenyl)-dicyclo [3.2.1] suffering-3-alkene-2-ketone.
8,3-(2-nitro-4-methyl alkylsulfonyl benzoyl)-and 4-(2,6-dichlorobenzene sulfenyl)-dicyclo [3.2.1] suffering-3-alkene-2-ketone.
9, herbicidal composition, it contains just like claim and requires acceptable carrier on the benzoyl cyclic enone derivative of the replacement shown in the logical formula I in 1 and the agricultural.
10, control does not need the method for plant-growth in the paddy field, and it comprises that using one requires the benzoyl cyclic enone derivative of the replacement of an effective amount of herbicide shown in 1 formula of (I) as claim.
11, method that the benzoyl cyclic enone derivative of the replacement shown in the formula I is led in preparation
Respectively meet in the formula to have in claim and require determined implication in 1, the preparation method comprises:
(a) with a compound shown in the logical formula III of a halogenating agent halogenation
(B, D have as requiring determined identical implication in 1 in claim with E in the formula)
Obtain a compound shown in the logical formula IV
X represents a halogen atom in formula, other symbol above having given identical implication;
(b) with the compound shown in the said logical formula IV and mercaptan or phenol reaction; With
(c) make this product stand oxidizing reaction.
12, the method in claim requirement 11, said halogenating agent is thionyl halide and oxalyl halogen.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08406393A JP3642497B2 (en) | 1992-03-18 | 1993-03-18 | Substituted benzoyl cyclic enone derivatives, herbicides containing the derivatives as active ingredients, and plant growth control methods |
| CN94101552A CN1041916C (en) | 1992-03-18 | 1994-01-08 | Substituted benzoyl cyclic enone, process for preparation, and herbicide |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9145492 | 1992-03-18 | ||
| JP08406393A JP3642497B2 (en) | 1992-03-18 | 1993-03-18 | Substituted benzoyl cyclic enone derivatives, herbicides containing the derivatives as active ingredients, and plant growth control methods |
| CN94101552A CN1041916C (en) | 1992-03-18 | 1994-01-08 | Substituted benzoyl cyclic enone, process for preparation, and herbicide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1105023A true CN1105023A (en) | 1995-07-12 |
| CN1041916C CN1041916C (en) | 1999-02-03 |
Family
ID=36940113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94101552A Expired - Lifetime CN1041916C (en) | 1992-03-18 | 1994-01-08 | Substituted benzoyl cyclic enone, process for preparation, and herbicide |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3642497B2 (en) |
| CN (1) | CN1041916C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104186476A (en) * | 2014-04-30 | 2014-12-10 | 广东中迅农科股份有限公司 | Herbicidal composition containing benzobicylon and pyriftalid |
| CN105211080A (en) * | 2014-07-02 | 2016-01-06 | 江苏龙灯化学有限公司 | A kind of Herbicidal combinations |
| CN105693569A (en) * | 2016-01-06 | 2016-06-22 | 江苏理工学院 | Synthesis method of 3-[4-(methyl sulfonyl)-2-chlorobenzoyl]bicyclo[3.2.1]-2.4-octanedione |
| CN106577683A (en) * | 2016-12-02 | 2017-04-26 | 安徽科技学院 | Herbicidal composition containing triafamone and benzobicylon |
| CN114728879A (en) * | 2020-10-20 | 2022-07-08 | Sds生物技术株式会社 | Method for producing dimethyl 2,3,5, 6-tetrachloro-1, 4-phthalate |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5536703A (en) * | 1995-01-13 | 1996-07-16 | Sandoz Ltd. | Herbicidal substituted benzoyl bicycloalkanediones |
| KR100415595B1 (en) * | 1995-07-25 | 2004-05-12 | 가부시키가이샤 에스디에스 바이오테크 | Power herbicide composition |
| DE102008037629A1 (en) | 2008-08-14 | 2010-02-18 | Bayer Cropscience Ag | Herbicide combination with dimethoxytriazinyl-substituted difluoromethanesulfonylanilides |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089046A (en) * | 1988-04-04 | 1992-02-18 | Sandoz Ltd. | Aryl and heteroaryl diones |
-
1993
- 1993-03-18 JP JP08406393A patent/JP3642497B2/en not_active Expired - Lifetime
-
1994
- 1994-01-08 CN CN94101552A patent/CN1041916C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104186476A (en) * | 2014-04-30 | 2014-12-10 | 广东中迅农科股份有限公司 | Herbicidal composition containing benzobicylon and pyriftalid |
| CN105211080A (en) * | 2014-07-02 | 2016-01-06 | 江苏龙灯化学有限公司 | A kind of Herbicidal combinations |
| CN105211080B (en) * | 2014-07-02 | 2017-06-20 | 江苏龙灯化学有限公司 | A kind of Herbicidal combinations |
| CN105693569A (en) * | 2016-01-06 | 2016-06-22 | 江苏理工学院 | Synthesis method of 3-[4-(methyl sulfonyl)-2-chlorobenzoyl]bicyclo[3.2.1]-2.4-octanedione |
| CN106577683A (en) * | 2016-12-02 | 2017-04-26 | 安徽科技学院 | Herbicidal composition containing triafamone and benzobicylon |
| CN114728879A (en) * | 2020-10-20 | 2022-07-08 | Sds生物技术株式会社 | Method for producing dimethyl 2,3,5, 6-tetrachloro-1, 4-phthalate |
| CN114728879B (en) * | 2020-10-20 | 2023-11-14 | Sds生物技术株式会社 | Method for producing 2,3,5, 6-tetrachloro-1, 4-dimethyl phthalate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0625144A (en) | 1994-02-01 |
| CN1041916C (en) | 1999-02-03 |
| JP3642497B2 (en) | 2005-04-27 |
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