CN86105662A - 2-[1-(3-chloroallyloxyimino) alkylidene]-5-alkyl alkylthio base-hexanaphthene-1,3 dione herbicides - Google Patents

2-[1-(3-chloroallyloxyimino) alkylidene]-5-alkyl alkylthio base-hexanaphthene-1,3 dione herbicides Download PDF

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CN86105662A
CN86105662A CN86105662.0A CN86105662A CN86105662A CN 86105662 A CN86105662 A CN 86105662A CN 86105662 A CN86105662 A CN 86105662A CN 86105662 A CN86105662 A CN 86105662A
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塔塔奥·鲁欧
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Chevron USA Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/10—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
    • C07C251/16—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings

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Abstract

2-[1-(3-chloro enyl propoxy amido) propylidyne]-hexanaphthene-1 that 5-replaces, the 3-derovatives is disclosed.These compounds have before the bud and bud after phytotoxicity, be useful selective herbicide.

Description

2-[1-(3-chloroallyloxyimino) alkylidene]-5-alkyl alkylthio base-hexanaphthene-1,3 dione herbicides
This application is the part continuation application of the U.S. Patent Application Serial 768,301 submitted on August 23rd, 1985.
The present invention relates to some trans-2-[1-(3-chloro enyl propoxy amidos) propylidyne]-the 5-(alkyl alkylthio base) hexanaphthene-1,3-diketone and salt thereof and these compounds are as herbicide applications.
We disclose the following compound of structural formula in the US Patent No of issuing on April 3rd, 1,984 4,440,566:
Figure 86105662_IMG2
The preferably alkyl of 1-3 carbon atom, preferably ethyl or propyl group of R in the formula;
R 1Preferably 3-trans-chlorallyl or 4-benzyl chloride base;
R 2And R 3The alkyl or the R of 1-3 carbon atom respectively do for oneself 2Or R 3In one be hydrogen and another is the alkyl alkylthio base of 2-8 carbon atom, best R 2And R 3Methyl or R respectively do for oneself 2Or R 3In one be hydrogen and another is a 2-ethyl thiopropyl.
It is safe to the weeding activity of weeds and to the broad-leaved farm crop that our patent has also been set forth these compounds.
Have been found that in US Patent No some compounds that comprise in 4,440,566 (that is, below general formula 1 compound) are compared with other compound, present unexpected ground excellent herbicidal.Though the included compound of top general formula (X) generally has good weeding activity, these compounds of the present invention have outstanding weeding activity, and this is not expect in advance.
Compound of the present invention present before the bud for weeds and bud after phytotoxicity, have weeding activity behind the good especially bud for Herba Setariae Viridis, duck bud, yard grass, volunteer plant, barnyard grass grass, broad-leaved Signalgrass, Herba Eleusines Indicae, red rice, Sprangletop, about Han Xuncao.
Even the compound of logical formula I also presents good phytotoxicity for the weeds amount of application is very low, and be to be safe for the broad-leaved farming.Therefore, The compounds of this invention is useful especially for weeds in the conduct of control broad-leaved, especially for the weeds in the conduct of control beans.
Compound of the present invention can be represented with following general formula:
R in the formula 1Be 3-trans-chlorallyl, R 2Be 2-methyl thiopropyl or 2-propylthio ethyl.
The present invention also comprises the corresponding salt of generalformula.
There is tautomer in generalformula.Such compound has two unsymmetrical carbons, and optically active isomer is also arranged.Formula of I of the present invention comprises corresponding tautomer and independent optically active isomer and composition thereof, also comprises, corresponding tautomer and optically active isomer and their mixture.
Another aspect of the present invention provides a kind of herbicidal composition, and this herbicidal composition comprises The compounds of this invention or its mixture of appropriate carriers and herbicidally effective amount.
The present invention also provides a kind of method that stops or control undesired plant growth, and this method comprises with the The compounds of this invention of herbicidally effective amount or the growth matrix and/or the foliage spray of their this kind of plant of mixture process.
The present invention also provides a kind of method of coordinate plant growth, this method comprises that this is effective for the normal growth that changes plant with the The compounds of this invention of coordinate plant growth significant quantity or the growth matrix and/or the foliage spray of their this kind of plant of mixture process.
The present invention also provides the preparation method of some chemical intermediates and The compounds of this invention.
The present invention is specified in down.
Generalformula can prepare easily by the method for illustrating below:
Figure 86105662_IMG4
R in the formula 1And R 2Implication the same.
This method can contact easily and carry out, preferably react in inert organic solvents by-chlorallyl oxygen amine (B) trans with 3-by compound (A).
Typical method is at about 0-80 ℃, preferably under 20-40 ℃, reacts approximately 1-48 hour, and preferably about 4-12 hour, every mol compound (A) was with about 1-2 mol, preferably 1.05-1.2 mol 3-trans-chlorallyl oxygen amine (B).Operable suitable inert organic solvents comprises, for example low-grade alkane alcohol (as methyl alcohol, ethanol), ethers (as ether), methylene dichloride.Biphase water and immiscible organic solvent (as, hexane) etc. and their suitable mixture also can be used as reaction medium.
Trans-chlorallyl oxygen amine is known compound, can pass through currently known methods, and for example US Patent No 4,440, the preparation of method described in 566.With alkali metal alcoholates on the spot in and 3-trans-hydrochloride of chlorallyl oxygen amine can prepare trans-chlorallyl oxygen amine reagent.
General formula (A) compound can be by US Patent No 4,440, and 566 general method prepares.
The corresponding salt of logical formula I compound can be prepared by ordinary method, and for example, general formula 1 compound makes with wanting cationic alkali (for example sodium hydroxide, potassium hydroxide etc.) reaction to some extent.This salt cation also can be by carrying out with wanting the ion-exchange of cationic ion exchange resin to some extent.
Reaction product can reclaim from its mixture of reaction products by any suitable separation and method of purification (for example, chromatography).Suitable separation and method of purification are for example narrated among some embodiment below.
In general, above-mentioned reaction is carried out in liquid phase, so the generalized case overdraft is inessential, unless pressure influence refluxes during the temperature (boiling point) of reaction down.These reactions are carried out under about 300-3000mmHg pressure usually, and it is more suitable to carry out under normal atmosphere or environmental stress.
Typically or preferably reaction conditions (as the mole ratio of temperature of reaction, time, reactant, solvent etc.) has given, but also can adopt other reaction conditions.The optimum reaction conditions (as temperature, reaction times, mole ratio, solvent etc.) can be improved with specific reaction reagent or organic solvent, but can be determined by the best approach of routine.
When acquiring mixture of optical isomers, each optically active isomer can separate with conventional Split Method, and this depends on physical property qualitative difference between the geometric object.But preferably in reaction, use required foreign body object to make starting raw material.
Be the definition of some terms of using in the literary composition below, unless narration is specially arranged in addition:
" 2-methyl thiopropyl " is meant the group of following structure:
Figure 86105662_IMG5
" 2-propylthio ethyl " is meant that structure is-CH 2-CH 2-S-CH 2CH 2CH 3Group.
Suitable salt is meant that those do not show the salt that changes the parent compound herbicidal properties.The salt that is fit to comprises as cationic salts such as lithium, sodium, potassium, alkaline-earth metal, copper, zinc, ammonia, quaternary ammonium salts.
" room temperature " or " envrionment temperature " refers to about 20-25 ℃.
Generalformula and salt thereof present before the bud and bud after weeding activity, show good especially weeding activity for weeds.These compounds are cut weeds for some difficulties, have good especially phytotoxicity as Herba Setariae Viridis, duck bud, yard grass, about Han Xun grass with as the spontaneous cereal of weed growth.
Usually, be other position that herbicidal compound directly is sprayed on blade face or plant during dispenser behind the bud.Be to impose on herbicidal compound in the growth matrix of plant or in following growth matrix during dispenser before the bud.The optimal dose of herbicidal compound or composition is with the specified plant kind, plant-growth degree (if growing) and the specified plant position that contacts and exposure level and change.Optimal dose also can with place or environment (as, the such shaded areas in greenhouse is different from such open country zone, land for growing field crops) and the types of the weeds that will prevent and kill off and degree and change.In general, no matter be dispenser behind preceding dispenser of bud or the bud, the consumption of The compounds of this invention is approximately the preferably about 0.02-10kg/ha of 0.02-60kg/ha.
Though these compounds can just not dilute and use theoretically, in fact generally are to use with composition or dosage form, contain the active compound and the acceptable carrier of significant quantity in composition and the preparation.Acceptable or compatible carrier (acceptable carrier on the agricultural) is meant the not obviously influence of biological effect to active compound, and can dilute the carrier of active compound.Typical composition comprises about 0.05-95%(weight) logical formula I compound or their mixture.Also can make dense dose that wants high density to some extent, use preceding redilution.Carrier can be solid, liquid or aerosol.Actual composition can adopt forms such as granule, pulvis, pulvis subtilis, solution, missible oil, paste, aerosol.
Spendable suitable solid carrier comprises natural clay (as kaolin, U.S.'s atlapulgite, polynite etc.), talcum powder, pyrophyllite, diatomite, synthetic smart silica, ca aluminosilicate, tricalcium phosphate etc.Organic substance, for example, walnut parting, cotton seed hulls, flour, wood powder, tree bark powder etc. also can be used as carrier.Spendable suitable liquid diluent comprises water, organic solvent (as benzene, toluene, dimethyl sulfoxide (DMSO), kerosene, diesel oil, oil fuel, petroleum naphtha etc.), or the like.Spendable suitable aerosol carrier comprises as fontanel for conventional aerosol carriers such as alkane.
Said composition also can comprise variously can improve promotor and the tensio-active agent that active compound enters plant tissue speed, for example, and organic solvent, wetting agent and oil, for the composition of using before the bud, can reduce the degree of leached of compound, or improve soil stability.Vegetables oil for example soya-bean oil, paraffin oil and olefinic oil is useful especially carrier or additive for the phytotoxicity that improves composition.
Said composition can also contain various compatible auxiliarys, stablizer, conditioning agent, sterilant, sterilant, if necessary, also can contain other weeding active compound.
A kind of suitable dense preparation comprises 23-27%(weight) active weedicide of the present invention, 2-4%(weight) emulsifying agent, for example, alkyl benzene calcium sulfonate, octylphenol ethoxylate etc., or their mixture and about 70-75% organic solvent, for example, dimethylbenzene etc.Before using, this dense preparation and water and preferably a vegetable oil mix, and use with the aqueous emulsion that contains the 0.5-2% vegetables oil of having an appointment (for example, soya-bean oil), paraffin oil and olefinic oil.This weedicide is to contain about 0.02-0.6%(weight), 0.07-0.15%(weight preferably) weedicide of the present invention, about 0.001-0.01%(weight) emulsifying agent, approximately 0.08-2.5%(weight) organic solvent and about 95-99%(weight) aqueous emulsion of water use more suitable.Best herbicidal compound also contains about 0.25-2%(weight) vegetables oil.The herbicidal composition of this use can be by first mixture preparation and the required water of about 1/4-1/2, and then, the adding vegetables oil also adds the water of residual content and makes easily.If without vegetables oil, so, dense preparation and water mixed simply get final product.
The present invention can further be understood by following non-limiting preparation and example.If there is not explanation specially, below all temperature and temperature range be meant centigradetemperature, " envrionment temperature " and " room temperature " is meant about 20-25 ℃, " percentage ratio " or " % " is meant weight percentage." mole " or " moles " is meant mol." equivalent " be meant the reagent that adds earlier in the mole number of amount of reagent and the example or after the equimolal of the reagent that adds.
The proton NMR spectrum of being given (p.mr or NMR) is measured at 60mHz, (s) refers to unimodally, and (bs) finger beam is unimodal, d refers to bimodal, (dd) refers to bimodally, and t refers to triplet, (dt) refer to that two three peaks refer to quartet, refer to that (m) multiplet and CPS refer to number of cycles per second.
Example 1
Trans-the 2-[1-(3-chloro enyl propoxy amido) propylidyne]-5-(2-first thiopropyl)-hexanaphthene-1, the 3-diketone
(a) containing 48g(1.0mole) in the cold soln of the 250ml methylene dichloride of thiomethyl alcohol, add 82.4g crotonic aldehyde solution, contain 15% water and 85% crotonic aldehyde (1.0mole) in this solution, then add the 2ml triethylamine.Exothermic heat of reaction refluxed reaction about 2 minutes.This mixture at room temperature stirs spend the night (about 18 hours), uses dried over mgso, filters.Solution evaporation concentrates, and gets the 142.4g enriched material, wherein contains 78%(weight) β-methylthio group butyraldehyde and 22% methylene dichloride.
(b) with 71.2g(0.5mole) β-methylthio group butyraldehyde is dissolved in the 500ml methylene dichloride, then, adds 159.18g(0.5mole) triphen phosphinidene 2-acetone, mixture stirs spend the night (about 18 hours) under room temperature.Steam methylene dichloride, remaining solid residue.Add hexane and make the resistates pulp, filter.Remaining solid is used the hexane thorough washing again, filters.Merging filtrate is evaporated to driedly, obtains 70.6g 6-methylthio group-3-hepten-2-one, is oily matter.(during general molded being equipped with, also can adopt US Patent No 4,355, the general method in 184 prepares this product easily, or adopts the U.S. Patent application series No655 that September in 1984,27 days ' Cleveland submitted, and therefore 776 method is herein incorporated and does reference.）
(c) under 0-5 ℃, containing 27g(0.5mole) drip 66.0g(0.5mole in about 300ml methanol solution of sodium methylate) dimethyl malonate, then drip 79.5g(0.5mole) 6-methylthio group-3-hepten-2-one.Make the temperature of this mixture rise to room temperature, and under room temperature, stir spend the night (about 18 hours).Evaporate this mixture to dried, and resistates is mixed with 300ml water.The aqueous solution with ether washing gained is acidified to PH2 with concentrated hydrochloric acid then, uses dichloromethane extraction again.Use the dried over mgso dichloromethane extract, be evaporated to driedly, obtain 4-methoxycarbonyl-5-(2-first thiopropyl-hexanaphthene-1, the 3-diketone.
(d) contain 129g(0.5mole in the 300ml ethanol) 4-methoxycarbonyl-5-(2-first thiopropyl)-hexanaphthene-1,3-diketone and 65g 85%(weight) mixture of potassium hydroxide (1mole) aqueous solution, refluxed 2 hours, and then, under room temperature, stirred spend the night (about 18 hours).Evaporate this mixture to dried, and resistates is dissolved in the water.Wash this aqueous solution with the 100ml ether, then, be acidified to pH1, with twice of dichloromethane extraction with the 6N aqueous hydrochloric acid.The combined dichloromethane extracting solution with water washing, with dried over mgso, is evaporated to driedly, reaches 60g 5-(2-first thiopropyl) hexanaphthene-1, the 3-diketone is oily matter, places curing in 3～4 days.
(e) contain 16.0g(0.08mole) 5-(first thiopropyl) hexanaphthene-1, in the 200ml toluene of 3-diketone, in 5 minutes, slowly add 8.8g(0.088mole) triethylamine, and then, add 2.4g(0.02mole) Dimethylamino pyridine.In 20 minutes, drip 7.7g(0.084mole) propionyl chloride.65～70 ℃ of reactions 3 hours, then, be chilled to room temperature and place spend the night (about 18 hours).With water and 10%(weight) aqueous hydrochloric acid washs this mixture in succession, then, separates water layer and toluene layer.With the methylbenzene extraction water layer, and methylbenzene extraction liquid and the toluene layer told previously merged.With 1%(weight) aqueous sodium hydroxide solution extraction toluene phase.With the washed with dichloromethane extracting solution, then, with hcl acidifying to pH1, again with dichloromethane extraction.With the dried over mgso dichloromethane extract, be evaporated to driedly, obtain 2-propionyl-5-(2-first thiopropyl) and hexanaphthene-1, the 3-diketone.
(f) in 50ml ethanol, contain 4.2g(0.0117mole) 2-propionyl-5-(2-first thiopropyl) hexanaphthene-1, the solution of 3-diketone and the trans chlorine allyl of 2.7g 3-oxygen amine, stir about is 2.5 days under room temperature, is evaporated to dried then.Resistates is dissolved in methylene dichloride, and uses 1%(weight) aqueous sodium hydroxide solution extraction secondary.With ether washing water extracting solution, then, to pH1, and use dichloromethane extraction again with hcl acidifying.Use the dried over mgso dichloromethane extract, be evaporated to driedly, obtain the 2.1g motif compound, be oily matter.
Ultimate analysis:
Calculated value: C55.56% H6.99% N4.05%
Experimental value: C55.96% H7.32% N4.2%
Example 2
2-(1-(3-trans-chloro enyl propoxy amido) propylidyne)-5-(2-propylthio ethyl)-hexanaphthene-1, the 3-diketone
42.3%(weight) diluted hydrochloric acid aqueous solution of trans-chlorine allyl oxygen amine hydrochlorate is handled to pH8～10 with dilute sodium hydroxide aqueous solution, discharges unhindered amina.Then, with ether extraction twice, merge ether extracted liquid, wash twice with saturated sodium-chloride water solution, flow sour magnesium drying, evaporation gets light yellow liquid chlorine for allyl oxygen amine.
In 20ml ethanol, contain 3.2g 2-propionyl-5-(2-propylthio ethyl) hexanaphthene-1; 3-diketone and 1.3g be trans-mixture of chlorine allyl oxygen amine; stir under the room temperature spend the night (about 15～18 hours); then; evaporation concentration is also mixed with the 50ml ether, adds 5%(weight) aqueous sodium hydroxide solution regulates a little mixtures to pH11～12.Tell water and use 10%(weight) aqueous hydrochloric acid handles to pH2, then, usefulness ether extraction 2 times.Merge ether extracted liquid, wash twice with sodium chloride aqueous solution, dried over mgso, evaporation concentration obtains yellow liquid.This yellow liquid purifies through silicagel column, and the methylene dichloride wash-out gets the 3.1g motif compound, is oily matter.
Example 3
Trans-2-(1-(3-chloro enyl propoxy amido) propylidyne)-5-(2-ethyl thiopropyl)-hexanaphthene-1, the 3-diketone
With 17.2g(0.0636mole) 2-propionyl-5-(2-ethyl thiopropyl) hexanaphthene-1,3-diketone, 0.9g(0.0153mole) acetic acid and the 10.9g(0.075mole in 35ml water) 3-is trans-and chlorine allyl oxygen amine is added in the 20ml hexane and stirs.In about 15 minutes, slowly add 5%(weight) aqueous sodium hydroxide solution, 3.0g(0.0757mole is excessive slightly until adding) sodium hydroxide, the pH value of reaction mixture is about 6.Reaction mixture is heated to 40 ℃ and kept 2.5 hours, then, is chilled to room temperature.Tell organic phase (that is, hexane) and with 10ml 5%(weight) aqueous hydrochloric acid washes, and then, adds 6.25%(weight) aqueous sodium hydroxide solution is until pH12.Tell water and mix, under ice bath, drip 36%(weight with the 25ml hexane) aqueous hydrochloric acid transfers to pH value to 5.4.Tell organic phase, dried over mgso, evaporation concentration gets the 18.0g crude product.Purify this crude product with silica gel column chromatography, eluent is a hexanes/ch, obtains purely to inscribing compound, is oily matter.
Ultimate analysis
Theoretical value: C56.73% H7.28% N3.89%
Experimental value: C56.63% H7.55% N3.55%
Example 4
2-(1-(3-trans-chloro enyl propoxy amido) propylidyne)-3-oxo-5-(2-first thiopropyl)-hexamethylene-1-alkene-1-sodium alkoxide
This example is in order to set forth the method for preparing motif compound.
Under room temperature, the solution that is dissolved with 0.01 mol sodium hydroxide in the 2ml water is added to contains 0.01 mol 2-(1-(3-trans-chloro enyl propoxy amido) propylidyne-5-(2-first thiopropyl)-hexanaphthene-1, in the 3-diketone solution, after reaction is finished, the pressure reducing and steaming solvent obtains 2-(1-(3-trans-chloro enyl propoxy amido) propylidyne)-3-oxo-5-(2-first thiopropyl)-hexamethylene-1-alkene-1-sodium alkoxide.
Example 5
In this example with the motif compound of the sequence test example of narrating below 1～3, promptly, 2-(1-(3-trans-chloro enyl propoxy amido) propylidyne)-5-(2-methyl thiopropyl)-hexanaphthene-1,3-diketone (1), 2-(1-(3-trans-chloro enyl propoxy amido) propylidyne)-5-(2-propylthio ethyl)-hexanaphthene-1,3-diketone (2) and 2 (1-(3-trans-chloro enyl propoxy amido) propylidyne)-5-(2-ethyl thiopropyl)-hexanaphthene-1,3-diketone (3) comprises before the bud of a kind of cereal crop and a kind of broad leaf crop and phytotoxicity behind the bud for various weeds and broad-leaved farm crop.
Weeding test before the bud
Measure the preceding weeding activity of bud by the following method.
The testing liquid of respective compound prepares in order to the below method: the 355.5mg test compound is dissolved in the 15ml acetone.The 2ml acetone that contains the 110mg nonionogenic tenside is added in this solution.Then, get this stock solution of 12ml and be added in the 47.7ml water, contain same nonionogenic tenside in the water, concentration is 625mg/l.
In a native basin, testing liquid evenly is sprayed on the soil surface the seed kind of test plant, if do not have explanation in addition in the table below, the test compound consumption is 27.5 μ g/cm 3Give native basin watering and be placed in the greenhouse.In three weeks, give native basin watering and observation seed germination and the healthy and strong situation of seedling etc. unceasingly.At three weekends, observe the herbicidal effect of evaluating compound on the basis at physiology.Be divided into 0～100 grade and evaluate, 0 grade of expression plant-less toxicity, 100 grades of complete kill plants of expression.These test-results are taken passages in table 1.
Weeding test behind the bud
Same quadrat method test preparation compound with narration in the test before the top bud.Test compound solution is sprayed on (wild avena sativa in long two similar basins that 2～3 inches high plants are arranged equably, soybean and pasture and water are 3～4 inches high) (every basin has 15～25 strain plants approximately), if not explanation in addition in the table below, the test compound consumption is 27.5 μ g/cm 2Be put in the greenhouse after the arid these plants, and water to soil matrix discontinuously as required.Routine observation is to phytotoxicity effect and physiology and the tissue reaction of these plants.After three weeks, the herbicidal effect of evaluation compound on the basis of these observations.Be divided into 0～100 grade and evaluate, 0 grade of expression plant-less toxicity, 100 grades of complete kill plants of expression.These test-results are taken passages in table 2.
Weeding activity before table 1 bud
Usage quantity: 27.5 μ g/cm 2(except as otherwise noted)
Compound number is to the phytotoxicity % of the broad leaved plant phytotoxicity % to weeds
Lamb's-quarters mustard amaranth soybean barnyard grass grass yard grass wild avena sativa paddy rice
1 0 20 0 0 100 100 100 100
2 0 0 0 50 100 100 100 100
3 25 30 25 30 100 100 100 100
Weeding activity behind table 2 bud
Usage quantity: 27.5 μ g/cm 2(except as otherwise noted)
Compound number is to the phytotoxicity % of the broad leaved plant phytotoxicity % to weeds
Lamb's-quarters mustard amaranth soybean barnyard grass grass yard grass wild avena sativa paddy rice
1 30 45 40 40 100 100 100 100
2 0 60 0 20 100 100 100 100
3 30 45 40 40 100 100 100 100
Example 6
This example has been estimated motif compound and trans-2-(1-(3-chloro enyl propoxy amido) butylidyne of example 1～3)-5-(2-ethyl thiopropyl)-hexanaphthene-1,3-diketone (" C-1 ") and 2-(1-(ethoxy amino) butylidyne)-5-(2-ethyl thiopropyl)-hexanaphthene-1,3-diketone (" C-2 ") is commodity weedicide " Sethoxydim "), under the low-down dosage to the bud of some weeds and two kinds of farm crop after weeding activity.
Test is undertaken by example 5 described same methods, but its consumption is as shown in table 3, and each test repeats to do four times.Test-results is taken passages in table 4, and 0 grade of expression does not have phytotoxicity, and 100 grades of expressions are killed fully.Generally, be lower than about 20～30% phytotoxicity do not think significant because in general plant may produce such injury.
Figure 86105662_IMG6
Figure 86105662_IMG7
As can be seen from Table 3, shown under the low dosage all compounds to Yellow nutsedge non-activity.Except that this weeds, compound 1～3 is all good than Compound C-1 to weeds shown in other, and is more superior than Compound C-2.
For control yard grass and Johnson grass, 0.05 μ g/cm 2The compound 1 of consumption or 2 herbicidal effect are equivalent to or are better than 0.28 μ g/cm 2The Compound C of consumption-1.For the barnyard grass grass, 0.05 μ g/cm 2The compound 1 or 2 of consumption equals 0.11 μ g/cm 2The effect of the Compound C of consumption-1.For wild avena sativa and yellow orchardgrass, 0.11 μ g/cm 2The compound 1 of consumption or 2 prevention effect are better than 0.28 μ g/cm 2The Compound C of consumption-1.From top data as can be seen, Compound C-1 is better than Compound C-2, and the superiority of compound 1 and 2 on consumption is more greater than Compound C-2.
Obviously, portion's disengaging the spirit and scope of the invention can not made many improvement and change.

Claims (19)

1, logical formula I compound and compatibility salt thereof,
Figure 86105662_IMG1
R ' is 3-in the formula trans-chlorallyl, R 2Be 2-methyl thiopropyl or 2-propylthio ethyl.
2, the compound of stipulating according to claim 1, wherein R 2It is 2-methyl thiopropyl.
3, be 2-(1-(3-trans-chloro enyl propoxy amido) propylidyne according to the compound of claim 2 regulation)-5-(2-methyl thiopropyl)-hexanaphthene-1, the 3-diketone.
4, the compound of stipulating according to claim 1, wherein R 2It is 2-propylthio ethyl.
5, be 2-(1-(3-trans-chloro enyl propoxy amido) propylidyne according to the compound of claim 4 regulation)-5 '-(2-propylthio ethyl)-hexanaphthene-1, the 3-diketone.
6, a kind of herbicidal composition is characterized in that containing compound and a kind of suitable carrier of claim 1 regulation of herbicidally effective amount.
7, a kind of herbicidal composition is characterized in that containing compound and a kind of suitable carrier of claim 2 regulation of herbicidally effective amount.
8, a kind of herbicidal composition is characterized in that containing compound and a kind of suitable carrier of claim 4 regulation of herbicidally effective amount.
9, a kind of herbicidal composition is characterized in that containing the compound and a vegetable oil of claim 1 regulation of herbicidally effective amount.
10, a kind of method of controlling weeds, this method comprise that the compound of claim 1 regulation of using herbicidally effective amount is on the blade face of this plant or in the growing environment.
11, a kind of method of controlling weeds, this method comprise that the compound of claim 2 regulation of using herbicidally effective amount or its mixture are on the blade face of this plant or in the growing environment.
12, a kind of method of controlling weeds, this method comprise that the compound of claim 4 regulation of using herbicidally effective amount or its mixture are on the blade face of this plant or in the growing environment.
13, a kind of method of preventing and treating Herba Setariae Viridis, orchardgrass, yard grass, broad-leaved Signalgrass, red rice, defeated approximately inferior grass, spontaneous corn or spontaneous jowar, this method comprises that the compound of the claim 1 of using herbicidally effective amount is on this plant or in its growing environment.
14, a kind of herbicidal composition wherein contains 0.02～0.6%(weight) compound of claim 1 regulation, 0.001～0.15%(weight) emulsifying agent, 0.08～2.5%(weight) organic solvent and about 95～99%(weight) water.
15, the herbicidal composition of claim 14 regulation wherein contains about 0.25～2%(weight) vegetables oil.
16, a kind of concentrate herbicidal composition wherein contains 23～27%(weight) compound of claim 1 regulation, 2～4%(weight) emulsifying agent and about 70～75%(weight) organic solvent.
17, a kind of method for preparing the compound of claim 1 regulation; this method is included in 2-propionyl under the reaction conditions-5-(2-methyl thiopropyl)-hexanaphthene-1,3-diketone and 3-be trans-and the reaction of chlorine allyl oxygen amine obtains the reactions steps of corresponding generalformula.
18, the method for claim 17 regulation, reaction is to carry out in about 0～80 ℃ of temperature range in inertia oxygen based solvent.
19, the method for the compound of preparation claim 1 is substantially as described here.
CN86105662A 1985-08-23 1986-07-30 Process for preparing 2-[1-(3-chloroallyloxyimino)alkylidene]-5-alkylthioalkyl-cyclohexane-1,3-dione Expired CN1011782B (en)

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CN86105662A Expired CN1011782B (en) 1985-08-23 1986-07-30 Process for preparing 2-[1-(3-chloroallyloxyimino)alkylidene]-5-alkylthioalkyl-cyclohexane-1,3-dione

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Cited By (2)

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CN106187841A (en) * 2016-07-08 2016-12-07 山东润博生物科技有限公司 A kind of industrialized process for preparing of clethodim
CN112225682A (en) * 2020-10-19 2021-01-15 中国科学院大连化学物理研究所 Method for improving reaction speed of synthesizing clethodim

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NL193944C (en) * 1985-08-23 2001-03-02 Tomen Corp Weed control agents based on 2- 1- (3-chloro-alloxyamino) -alkylidene-5-alkylthioalkyl-1,3-cyclohexanedione.
ES2014493B3 (en) * 1986-04-24 1990-07-16 Ciba-Geigy Ag ACIL-CICLOHEXANDIONAS AND ITS OXYME ETERS WITH HERBICIDIC EFFECT AND REGULATOR OF PLANT GROWTH.
GB8722838D0 (en) * 1987-09-29 1987-11-04 Shell Int Research Oximino ether compounds
JP2536075B2 (en) * 1988-06-27 1996-09-18 住友化学工業株式会社 Herbicidal composition
US5108488A (en) * 1989-07-21 1992-04-28 Valent U.S.A. Corporation Synergistic herbicidal composition
US6300281B1 (en) * 2000-07-03 2001-10-09 Valent U.S.A. Corporation Optically pure(−) clethodim, compositions and methods for controlling plant growth comprising the same
BRPI0917511B8 (en) 2008-08-19 2022-10-11 Dow Agrosciences Llc PROCESS FOR PREPARATION OF ALDEHYDES, KETONES, ESTERS AND SULFONES SUBSTITUTED WITH ALKYLTIO
CN105418470B (en) * 2015-11-17 2017-12-15 江苏长青农化股份有限公司 A kind of synthetic method of clethodim
WO2020172219A1 (en) * 2019-02-20 2020-08-27 Valent U.S.A. Llc Clethodim compositions and methods of use thereof
CN113024425B (en) * 2019-12-24 2022-05-17 沈阳科创化学品有限公司 Preparation method of clethodim

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US4440566A (en) * 1982-08-05 1984-04-03 Chevron Research Company Herbicidal substituted 2-(1-(oxyamino)-alkylidene)-cyclohexane-1,3-diones
AU556148B2 (en) * 1982-01-29 1986-10-23 Ici Australia Limited Cyclohexane -1,3- dione derivatives
NL193944C (en) * 1985-08-23 2001-03-02 Tomen Corp Weed control agents based on 2- 1- (3-chloro-alloxyamino) -alkylidene-5-alkylthioalkyl-1,3-cyclohexanedione.

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106187841A (en) * 2016-07-08 2016-12-07 山东润博生物科技有限公司 A kind of industrialized process for preparing of clethodim
CN106187841B (en) * 2016-07-08 2018-01-30 山东润博生物科技有限公司 A kind of industrialized process for preparing of clethodim
CN112225682A (en) * 2020-10-19 2021-01-15 中国科学院大连化学物理研究所 Method for improving reaction speed of synthesizing clethodim
CN112225682B (en) * 2020-10-19 2022-02-25 中国科学院大连化学物理研究所 Method for improving reaction speed of synthesizing clethodim

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FR2586416B1 (en) 1989-06-02
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