CA1271644A - 2-¬1-(3-chloroallyloxyamino) alkylidene|-5- alkylthioalkyl-cyclohexane-1,3-dione herbicides - Google Patents
2-¬1-(3-chloroallyloxyamino) alkylidene|-5- alkylthioalkyl-cyclohexane-1,3-dione herbicidesInfo
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- CA1271644A CA1271644A CA000516351A CA516351A CA1271644A CA 1271644 A CA1271644 A CA 1271644A CA 000516351 A CA000516351 A CA 000516351A CA 516351 A CA516351 A CA 516351A CA 1271644 A CA1271644 A CA 1271644A
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Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
2-[1-(3-chloroallyloxyamino)propylidene]-5-(sub-stituted-cyclohexane-1,3-dione derivatives are disclosed.
The compounds exhibit pre- and post-emergent phytotoxicity and are useful as selective herbicides against grasses.
2-[1-(3-chloroallyloxyamino)propylidene]-5-(sub-stituted-cyclohexane-1,3-dione derivatives are disclosed.
The compounds exhibit pre- and post-emergent phytotoxicity and are useful as selective herbicides against grasses.
Description
~;~7~L~4~
Z-[1-(3-CHLOROALLY~OXYAMINO) ALKYLIDENE]-5-ALKYLTHIOALKYL-CYCLOHEXANE-1,3-~IONE EERBICIDES
BACKGROUND OF-THE INVENTION
This invention relates to certain trans 2-11-(3-chloroallyloxyamino) propylidene~-5-(alkylthioalkyl)cyclo-hexane-1,3-dione and salts thereo~ and to the use of such compounds as herbicides.
U.S. Patent No. 4,440,566, issued April 3, 1984, discloses compounds having the formula:
\C~
() q/q, oR 5 ~2 R3 ~X) wherein R is most preferably alkyl of 1 to 3 carbon atoms, most pre~erably ethyl or propyl;
Rl is most preferably 3-trans-chloroallyl or 4-chlo-robenzyl;
R2 and R3 are preferably each alkyl o 1 to 3 carbon atoms or one of R2 or R3 is hydrogen and the other i5 alkylthioalkyl having 2 through 8 carbon atoms, ~ost pre~
ferably R2 and R3 are each methyl or one of R2 or R3 is hydrogen and the other is 2-ethylthiopropyl.
This patent also teaches that these compounds exhibit herbicidal activity against grasses and are sa~e with respect to broad-leaf crops.
SUMMARY OF THE INVENTION
I~ is has now been discovered that certain o~
~0 the compounds (i.e., see Formula I below) encompassed within U.S. Patent No. 4,440,566, exhiblt surprisingly ., .
~L2'7~L644 ~1 -2-~ superior herbicidal activity as compared with others.
; Although, the compounds encompassed within Formula (X) 05 above, generally exhibit very good herbicidal activity, the outstanding herbicidal activity possessed by the present compounds rarely exists and cannot be predicted beforehand.
The present compounds exhibit both pre-emergence and post-emergence phytotoxicity with respect to grasses and exhibit excellent especially post-emergence herbicidal activity against Bermudagrass, foxtail, crabgrass, volun-teer corn, volunteer sorghum, barnyardgrass, broad-leaf signalgrass, goosegrass, red rice, sprangletop, seedling Johnsongrass and Rhizome Johnsongrass.
The compounds of Formula I exhibit excellent phytotoxicity against grasses at even very low application rates and may be safely applied with respect to broad-leaf crops at such rates. Thus, the present compounds are ~U especially useful for controlling grassy weeds in broad-leaf crops and are especially useful to control grassy weeds in soybean crops.
The compound of the present invention can be represented by the following formula:
NOR
C~
CH3CH~
O ~ - OH
~ ~
~; /\
(I) wherein Rl is 3-trans-chloroallyl and R2 is 2-methyl-thiopropyl or 2-propylthioethyl.
The invention also comprises compatible salts of the compound of Formula I.
~0 ~27~64~
~1 -3-As is well recognized, compounds of the nature of Formula (I) exist as tautomers~ The compounds also have two asymmetric carbon atoms and can also exist as optical isomers. The above formula is intended to encom-pass the respective tautomeric forms as well as the indi-vidual optical isomers as well as mixtures thereof and the respective tautomers and optical isomers as well as mix-tures thereof are encompassed within the invention~
In a further aspect the invention provides aherbicidal composition comprisin~ a compatible carrier and a herbicidally effective amount of the compound(s) of the invention or mixtures thereof.
The present invention also provides a method for preventing or controlling the growth of unwanted grassy vegetation, which comprises treating the growth medium and/or the foliage of such vegetation with a herbicidally effective amount of the compound(s) of the invention or ~U mixtures thereof.
The present invention also provides a method for regulating plant growth which comprises treating the growth medium and/or the foliage of such vegetation with a plant growth reyulating effective amount of the com-pound(s) of the invention or mixtures thereof, effectiveto alter the normal growth pattern of said plants.
The present invention also provides chemical intermediates and processes for preparing the compounds of the invention.
The invention will be further described herein-below.
FURTHER DESCRIPTION OF THE
INVENTION AND THE PREFERRED EMBODIMENTS
The compound of Formula (I) can be conveniently prepared by the following schematically represented pro-cess:
., ~.~7~4~
CH3CH2 ~
O ~ OH
~J + H2NORl >
~ lB) H R
(A) wherein ~1 and R2 are as defined hereinabove.
This process can be conveniently effected by contacting Compound (A) with 3-trans-chloroallyloxyamine (B), preferably in an inert organic solvent.
Typically, this process is conducted at tempera-tures in the range of about from 0 to 80C, preferably about from 20 to 40C, for about from 1 to 48 hours, pre-ferably about from 4 to 12 hours, using about from 1 to 2, preferably 1.05 to 1.2 moles of 3-trans-chloroallyloxy-amine ~B) per mole of Compound (A). Suitable inert organic solvents which can be used include, for example, lower alkanols, e.g., methanol, ethanol, ethers, e.g., ethyl ether; methylene chloride. Two-phase water and immiscible organic solvent (e.g., hexane), and mixtures thereof can also be used as the reaction medium.
Trans-chloroallyloxyamine is a known compound and can be prepared via known procedures, such as, for example, described in V~S. Patent No. 4,440,566. The trans-chloroallyloxyamine reactant can be provided by neutralizing a hydrochloride salt of trans-chloroallyloxy-amine in situ with an alkali metal alkoxide.
The starting materials of Formula (A) can also be prepared via the general procedure described in U.S.
Patent No. 4,440,566.
The compatible salts of Formula (I) can be pre-pared by conventional procedures, for example, via the reaction of the compound of Formula I with a base, such as, for example, sodium hydroxide, potassium hyclroxide and ~L~716~
Ol _5_ the like, having the desired cation. Additional varia-tions in the salt cation can also be effected via ion 05 exchange with an ion exchange resin having the desired cation.
General Process Conditions The reaction product can be recovered from its reaction product mixture by any suitable separation and purification procedure, such as, for example~ chromato-graphy. Suitable separation and purification procedures are, for example, illustrated in the Examples set forth hereinbelow, Generally, the reactlons described above are conducted as liquid phase reaction and hence pressure is generally not significant except as it affects temperature (boiling point) where reactions are conducted at reflux.
Therefore, these reactions are generally conducted at pressures of about from 300 to 3,000 mm of mercury and ~V conveniently are conducted at about atmospheric or ambient pressure.
It should also be appreciated that where typical or preferred process conditions (e.g., reaction tempera-tures, times, mole ratios of reactants, solvents, etc.) have been given, that other process conditions could a~so be used. Optimum reaction conditions (e.g., temperature, reaction time, mol ratios, solvents, etc.) may vary with the particular reagents or organic solvents used but can be determined by routine optimization procedures.
Where optical isomer mixtures are obtained, the respective optical isomers can be obtained by conventional resolution procedures. Geometric isomers can be separated by conventional separation procedures which depend upon differences in physical properties between the geometric isomers. ~owever, it is generally preferable to use the desired isomeric starting material in the reaction.
Definitions _ As used herein the following terms have the following meanings unless expressly stated to the contrary:
1~716~
The term "2-methylthiopropyl" refers to the group having the formula:
The term "2-propylthioethyl" refers to the group having the formula -cH2-cH2-s-cH2cH2cH3~
The term "compatible salts" refers to salts which do not significantly adversely alter the herbicidal properties of the parent compound. Suitable salts include cation salts such as, for example, the cation salts of lithium, sodium, potassium, alkali earth metals, copper, zinc, ammonia, quaternary ammonium salts, and the like.
The term "room temperature" or "ambient tempera-ture" refers to about 20-25C.
Utility ~0 The compounds of Formula (I) and their salts exhibit both pre- and post-emergent herbicidal activity and exhibit especially good herbicidal activity against grasses. The compounds exhibit especially good phyto-toxicity against foxtail, Bermudagrass, crabgrass, rhizone, Johnsongrass and volunteer corn. These weed species are generally very diEficult to control and hence, the present compounds provide a significant advantage which respect to the control of such weeds.
Generally, for post-emergent applications, the herbicidal compounds~are applied directly to the foliage ~ or other plant parts. For pre-emergence applications, the ^~ herbicidal compounds are applied to the-growth medium, or prospective growth medium, for the plant. The optimum amount of the herbicidal compound or composition will vary with the particular plant species, and the extent of plant growth, if any, and the particular part of the plant which is contacted and the extent of contact. The optimum dosage can also vary with the general location, or environment (e.g., shelte~ed areas such as greenhouses compared to exposed areas such as Eields), and type and ol -7-degree of control desired. Generally, for both pre- and post-emergent control, the present compounds are applied at rates of about from 0.02 to 60 kg/ha, preferably about from 0.02 to 10 kg/ha.
Also, although in theory the compounds can be applied undiluted, in actual practice they are generally applied as a composition or formulation comprising an effective amount of the compound(s) and an acceptable car-rier. An acceptable or compatible carrier (a~riculturally acceptable carrier) is one which does not significantly adversely affect the desired biolog~cal ef~ect achieved by the active compounds, save to dilute it. Typically, the composition contains about ~rom 0.05 to 95% by weight of the compound of Formula (I) or mixtures thereof. Concen-trates can also be made having high concentrations designed for dilution p-ior to application. The carrier can be a solid, liquid, or aerosol. The actual composi-tions can take the form of granules, powders, dusts, solu-tions, emulsions, slurries, aerosols, and the like.
Suitable solid carriers which can be used include, for example, natural clays (such as kaolin, atta pulgite, montmorillonite, etc.), talcs, pyrophyllite, diatomaceous silica, synthetic fine silica, calcium alumi-nosilicate, tricalcium phosphate, and the like. Also, organic materials, such as, for example, walnut shell flour, cotton-seed hulls, wheat flour, wood flour, wood bark flour, and the like can also be used as carriers.
Suitable liquid diluents which can be used include, for example, water, organic solvents (e.g., hydrocarbons such as benzene, toluene, dimethylsulfoxide, kerosene, diesel fuel, fuel oil, petroleum naphtha, etc.), and the like.
Suitable aerosol carriers which can be used include con-3~ ventional aerosol carriers such as halogenated al~anes,etc.
The composition can also contain various promo-ters and surface-active agents which enhance the rate of transport of the active compound into the plant tissue 4~ such as, for example, organic solvents, wetting agents and oils, and in the case of compositions designed for pre-emergence application agents which reduce the leachability 05 of the compound or otherwise enhance soil stability. Crop oils, such as, for example, soybean oils, paraffin oils and olefinic oils, are especially advantageous as carriers or additives in that they enhance phytotoxicity.
The composition can also contain various com-patible adjuvants, stabilizers, conditioners, insecti-cides, fungicides, and if desired, other herbicidally active compounds.
One convenient concentrate formulation which can be used comprises 23-27% by weight of the active herbicide of the invention, 2 to 4% by weight of an emulsifier, for example, calcium alkylbenzene sulfonates, octylphenol-ethoxylate, etc., or mixtures thereof, and about 70~75~
organic solvent, for example, xylene, etc. The concen-trate is mixed with water and preferably a crop oil prior to application and applied as a water emulsion containing ~; about 0.5 to 2~ of a crop oil, for example, soybean oils, and paraffinic oils and olefinic oils. Conveniently, the herbicide is applied as water emulsion containing about 0.02-0.6 wt. %, preferably 0.07-0~15 wt. ~ of the herbi-cide, of the invention; about 0~001-0.01 wt. % of an emul-sifier; about 0.08-2.5 wt. % of an organic solvent and about 95 to 99 wt. % water. Preferably, the composition , also contains about 0.25 to 2 wt. % of a crop oil. The application composition can be conveniently prepared by mixing the concentrate formulation with about 1/4 to 1/2 the desired amount of water. Then admixing the crop oil ; and then adding the remaining amount of water. IE no crop oil is used, then the water and concentrate formulation are simply admixed together.
3~ A further understanding of the invention can be had in the following non-limitin~ Preparation(s) and Example(sl. Wherein, unless expressly stated to the con-trary, all temperatures and temperature ranges refer to the Centigrade system and the term "ambient" or "room temperature" refers to about 20-25C. The term "percent"
or "~" refers to weight percent and the term "mole" or "moles" refers to gram moles. The term "equivalent"
refers to a quantity of reagent equal in moles, to the moles of the preceding or succeeding reactant recited in that example in terms of finite moles or finite weight or vo~ume. Where given, proton-magnetic resonance spectrum (p.m.r. or NMR) were determined at &0 mHz, signals are assigned as singlets (s), broad singlets (bs), doublets (d), double doublets (dd), triplets (t), double triplets (dt), quartets (q), and multiplets (m); and cps refers to cycles per second. Also where necessary examples are repeated to provide additional starting material for sub-sequent examples.
EXA~PLES
Example 1 Trans-2-[1-(3-chloroallyloxyamino) propylidene]~5-(2-methylthiopropyl)-cyclohexane-1,3-dione (a) To a cooled solution containing 48 g (1.0 mole) of methylmercaptan in 250 ml of methylene chlo-ride was added 82.4 g of crotonaldehyde solution, contain-ing 15~ water 85% crotonaldehyde (1.0 mole) followed by the addition of 2 ml of triethylene amine. The resulting exothermic reaction caused the mixture to reflux for about
Z-[1-(3-CHLOROALLY~OXYAMINO) ALKYLIDENE]-5-ALKYLTHIOALKYL-CYCLOHEXANE-1,3-~IONE EERBICIDES
BACKGROUND OF-THE INVENTION
This invention relates to certain trans 2-11-(3-chloroallyloxyamino) propylidene~-5-(alkylthioalkyl)cyclo-hexane-1,3-dione and salts thereo~ and to the use of such compounds as herbicides.
U.S. Patent No. 4,440,566, issued April 3, 1984, discloses compounds having the formula:
\C~
() q/q, oR 5 ~2 R3 ~X) wherein R is most preferably alkyl of 1 to 3 carbon atoms, most pre~erably ethyl or propyl;
Rl is most preferably 3-trans-chloroallyl or 4-chlo-robenzyl;
R2 and R3 are preferably each alkyl o 1 to 3 carbon atoms or one of R2 or R3 is hydrogen and the other i5 alkylthioalkyl having 2 through 8 carbon atoms, ~ost pre~
ferably R2 and R3 are each methyl or one of R2 or R3 is hydrogen and the other is 2-ethylthiopropyl.
This patent also teaches that these compounds exhibit herbicidal activity against grasses and are sa~e with respect to broad-leaf crops.
SUMMARY OF THE INVENTION
I~ is has now been discovered that certain o~
~0 the compounds (i.e., see Formula I below) encompassed within U.S. Patent No. 4,440,566, exhiblt surprisingly ., .
~L2'7~L644 ~1 -2-~ superior herbicidal activity as compared with others.
; Although, the compounds encompassed within Formula (X) 05 above, generally exhibit very good herbicidal activity, the outstanding herbicidal activity possessed by the present compounds rarely exists and cannot be predicted beforehand.
The present compounds exhibit both pre-emergence and post-emergence phytotoxicity with respect to grasses and exhibit excellent especially post-emergence herbicidal activity against Bermudagrass, foxtail, crabgrass, volun-teer corn, volunteer sorghum, barnyardgrass, broad-leaf signalgrass, goosegrass, red rice, sprangletop, seedling Johnsongrass and Rhizome Johnsongrass.
The compounds of Formula I exhibit excellent phytotoxicity against grasses at even very low application rates and may be safely applied with respect to broad-leaf crops at such rates. Thus, the present compounds are ~U especially useful for controlling grassy weeds in broad-leaf crops and are especially useful to control grassy weeds in soybean crops.
The compound of the present invention can be represented by the following formula:
NOR
C~
CH3CH~
O ~ - OH
~ ~
~; /\
(I) wherein Rl is 3-trans-chloroallyl and R2 is 2-methyl-thiopropyl or 2-propylthioethyl.
The invention also comprises compatible salts of the compound of Formula I.
~0 ~27~64~
~1 -3-As is well recognized, compounds of the nature of Formula (I) exist as tautomers~ The compounds also have two asymmetric carbon atoms and can also exist as optical isomers. The above formula is intended to encom-pass the respective tautomeric forms as well as the indi-vidual optical isomers as well as mixtures thereof and the respective tautomers and optical isomers as well as mix-tures thereof are encompassed within the invention~
In a further aspect the invention provides aherbicidal composition comprisin~ a compatible carrier and a herbicidally effective amount of the compound(s) of the invention or mixtures thereof.
The present invention also provides a method for preventing or controlling the growth of unwanted grassy vegetation, which comprises treating the growth medium and/or the foliage of such vegetation with a herbicidally effective amount of the compound(s) of the invention or ~U mixtures thereof.
The present invention also provides a method for regulating plant growth which comprises treating the growth medium and/or the foliage of such vegetation with a plant growth reyulating effective amount of the com-pound(s) of the invention or mixtures thereof, effectiveto alter the normal growth pattern of said plants.
The present invention also provides chemical intermediates and processes for preparing the compounds of the invention.
The invention will be further described herein-below.
FURTHER DESCRIPTION OF THE
INVENTION AND THE PREFERRED EMBODIMENTS
The compound of Formula (I) can be conveniently prepared by the following schematically represented pro-cess:
., ~.~7~4~
CH3CH2 ~
O ~ OH
~J + H2NORl >
~ lB) H R
(A) wherein ~1 and R2 are as defined hereinabove.
This process can be conveniently effected by contacting Compound (A) with 3-trans-chloroallyloxyamine (B), preferably in an inert organic solvent.
Typically, this process is conducted at tempera-tures in the range of about from 0 to 80C, preferably about from 20 to 40C, for about from 1 to 48 hours, pre-ferably about from 4 to 12 hours, using about from 1 to 2, preferably 1.05 to 1.2 moles of 3-trans-chloroallyloxy-amine ~B) per mole of Compound (A). Suitable inert organic solvents which can be used include, for example, lower alkanols, e.g., methanol, ethanol, ethers, e.g., ethyl ether; methylene chloride. Two-phase water and immiscible organic solvent (e.g., hexane), and mixtures thereof can also be used as the reaction medium.
Trans-chloroallyloxyamine is a known compound and can be prepared via known procedures, such as, for example, described in V~S. Patent No. 4,440,566. The trans-chloroallyloxyamine reactant can be provided by neutralizing a hydrochloride salt of trans-chloroallyloxy-amine in situ with an alkali metal alkoxide.
The starting materials of Formula (A) can also be prepared via the general procedure described in U.S.
Patent No. 4,440,566.
The compatible salts of Formula (I) can be pre-pared by conventional procedures, for example, via the reaction of the compound of Formula I with a base, such as, for example, sodium hydroxide, potassium hyclroxide and ~L~716~
Ol _5_ the like, having the desired cation. Additional varia-tions in the salt cation can also be effected via ion 05 exchange with an ion exchange resin having the desired cation.
General Process Conditions The reaction product can be recovered from its reaction product mixture by any suitable separation and purification procedure, such as, for example~ chromato-graphy. Suitable separation and purification procedures are, for example, illustrated in the Examples set forth hereinbelow, Generally, the reactlons described above are conducted as liquid phase reaction and hence pressure is generally not significant except as it affects temperature (boiling point) where reactions are conducted at reflux.
Therefore, these reactions are generally conducted at pressures of about from 300 to 3,000 mm of mercury and ~V conveniently are conducted at about atmospheric or ambient pressure.
It should also be appreciated that where typical or preferred process conditions (e.g., reaction tempera-tures, times, mole ratios of reactants, solvents, etc.) have been given, that other process conditions could a~so be used. Optimum reaction conditions (e.g., temperature, reaction time, mol ratios, solvents, etc.) may vary with the particular reagents or organic solvents used but can be determined by routine optimization procedures.
Where optical isomer mixtures are obtained, the respective optical isomers can be obtained by conventional resolution procedures. Geometric isomers can be separated by conventional separation procedures which depend upon differences in physical properties between the geometric isomers. ~owever, it is generally preferable to use the desired isomeric starting material in the reaction.
Definitions _ As used herein the following terms have the following meanings unless expressly stated to the contrary:
1~716~
The term "2-methylthiopropyl" refers to the group having the formula:
The term "2-propylthioethyl" refers to the group having the formula -cH2-cH2-s-cH2cH2cH3~
The term "compatible salts" refers to salts which do not significantly adversely alter the herbicidal properties of the parent compound. Suitable salts include cation salts such as, for example, the cation salts of lithium, sodium, potassium, alkali earth metals, copper, zinc, ammonia, quaternary ammonium salts, and the like.
The term "room temperature" or "ambient tempera-ture" refers to about 20-25C.
Utility ~0 The compounds of Formula (I) and their salts exhibit both pre- and post-emergent herbicidal activity and exhibit especially good herbicidal activity against grasses. The compounds exhibit especially good phyto-toxicity against foxtail, Bermudagrass, crabgrass, rhizone, Johnsongrass and volunteer corn. These weed species are generally very diEficult to control and hence, the present compounds provide a significant advantage which respect to the control of such weeds.
Generally, for post-emergent applications, the herbicidal compounds~are applied directly to the foliage ~ or other plant parts. For pre-emergence applications, the ^~ herbicidal compounds are applied to the-growth medium, or prospective growth medium, for the plant. The optimum amount of the herbicidal compound or composition will vary with the particular plant species, and the extent of plant growth, if any, and the particular part of the plant which is contacted and the extent of contact. The optimum dosage can also vary with the general location, or environment (e.g., shelte~ed areas such as greenhouses compared to exposed areas such as Eields), and type and ol -7-degree of control desired. Generally, for both pre- and post-emergent control, the present compounds are applied at rates of about from 0.02 to 60 kg/ha, preferably about from 0.02 to 10 kg/ha.
Also, although in theory the compounds can be applied undiluted, in actual practice they are generally applied as a composition or formulation comprising an effective amount of the compound(s) and an acceptable car-rier. An acceptable or compatible carrier (a~riculturally acceptable carrier) is one which does not significantly adversely affect the desired biolog~cal ef~ect achieved by the active compounds, save to dilute it. Typically, the composition contains about ~rom 0.05 to 95% by weight of the compound of Formula (I) or mixtures thereof. Concen-trates can also be made having high concentrations designed for dilution p-ior to application. The carrier can be a solid, liquid, or aerosol. The actual composi-tions can take the form of granules, powders, dusts, solu-tions, emulsions, slurries, aerosols, and the like.
Suitable solid carriers which can be used include, for example, natural clays (such as kaolin, atta pulgite, montmorillonite, etc.), talcs, pyrophyllite, diatomaceous silica, synthetic fine silica, calcium alumi-nosilicate, tricalcium phosphate, and the like. Also, organic materials, such as, for example, walnut shell flour, cotton-seed hulls, wheat flour, wood flour, wood bark flour, and the like can also be used as carriers.
Suitable liquid diluents which can be used include, for example, water, organic solvents (e.g., hydrocarbons such as benzene, toluene, dimethylsulfoxide, kerosene, diesel fuel, fuel oil, petroleum naphtha, etc.), and the like.
Suitable aerosol carriers which can be used include con-3~ ventional aerosol carriers such as halogenated al~anes,etc.
The composition can also contain various promo-ters and surface-active agents which enhance the rate of transport of the active compound into the plant tissue 4~ such as, for example, organic solvents, wetting agents and oils, and in the case of compositions designed for pre-emergence application agents which reduce the leachability 05 of the compound or otherwise enhance soil stability. Crop oils, such as, for example, soybean oils, paraffin oils and olefinic oils, are especially advantageous as carriers or additives in that they enhance phytotoxicity.
The composition can also contain various com-patible adjuvants, stabilizers, conditioners, insecti-cides, fungicides, and if desired, other herbicidally active compounds.
One convenient concentrate formulation which can be used comprises 23-27% by weight of the active herbicide of the invention, 2 to 4% by weight of an emulsifier, for example, calcium alkylbenzene sulfonates, octylphenol-ethoxylate, etc., or mixtures thereof, and about 70~75~
organic solvent, for example, xylene, etc. The concen-trate is mixed with water and preferably a crop oil prior to application and applied as a water emulsion containing ~; about 0.5 to 2~ of a crop oil, for example, soybean oils, and paraffinic oils and olefinic oils. Conveniently, the herbicide is applied as water emulsion containing about 0.02-0.6 wt. %, preferably 0.07-0~15 wt. ~ of the herbi-cide, of the invention; about 0~001-0.01 wt. % of an emul-sifier; about 0.08-2.5 wt. % of an organic solvent and about 95 to 99 wt. % water. Preferably, the composition , also contains about 0.25 to 2 wt. % of a crop oil. The application composition can be conveniently prepared by mixing the concentrate formulation with about 1/4 to 1/2 the desired amount of water. Then admixing the crop oil ; and then adding the remaining amount of water. IE no crop oil is used, then the water and concentrate formulation are simply admixed together.
3~ A further understanding of the invention can be had in the following non-limitin~ Preparation(s) and Example(sl. Wherein, unless expressly stated to the con-trary, all temperatures and temperature ranges refer to the Centigrade system and the term "ambient" or "room temperature" refers to about 20-25C. The term "percent"
or "~" refers to weight percent and the term "mole" or "moles" refers to gram moles. The term "equivalent"
refers to a quantity of reagent equal in moles, to the moles of the preceding or succeeding reactant recited in that example in terms of finite moles or finite weight or vo~ume. Where given, proton-magnetic resonance spectrum (p.m.r. or NMR) were determined at &0 mHz, signals are assigned as singlets (s), broad singlets (bs), doublets (d), double doublets (dd), triplets (t), double triplets (dt), quartets (q), and multiplets (m); and cps refers to cycles per second. Also where necessary examples are repeated to provide additional starting material for sub-sequent examples.
EXA~PLES
Example 1 Trans-2-[1-(3-chloroallyloxyamino) propylidene]~5-(2-methylthiopropyl)-cyclohexane-1,3-dione (a) To a cooled solution containing 48 g (1.0 mole) of methylmercaptan in 250 ml of methylene chlo-ride was added 82.4 g of crotonaldehyde solution, contain-ing 15~ water 85% crotonaldehyde (1.0 mole) followed by the addition of 2 ml of triethylene amine. The resulting exothermic reaction caused the mixture to reflux for about
2 minutes. The mixture was stirred at room temperature overnight (aoout 18 hours) and then dried over magnesium sulfate and filtered. The filtrate was concentrated by evaporation affording a 142.4 g of concentrate containing 78 wt. ~ beta-methylthiobutyraldehyde and 22~ methylene chloride, (b) 71.2 Grams (0.5 mole) of beta-methylthio-butyraldehyde was dissolved in 500 ml of methylene chloride. 159.18 Grams ~0.5 mole) of triphenylphosphor-anylidene 2-propanone was then added and the mixture stirred at room temperature overnight (about 18 hours~.
The methylene chloride was evaporated off leaving a solid residue. ~he residue was slurried in hexane, filtered.
The remaining solids were thoroughly washed with hexane and filtered. The combined filtrates were evaporated to ~1~44 dryness affording 70.6 g of 6-me~hylthio-3-hepten-2-one as an oil. (For large scale operations this product can also 05 be conveniently prepared by the general procedures described in U.S. Pa~ent No. 4,35~,184 and PCT/US 85/
01853, published April 10, 1986 as WO 86/02065.
I0 (c~ 66.0 Grams (0.5 mole~ of dimethyl malonate was added dropwise to a solution cont~ining 27 9 ~0.5 mole3 of sodium methoxide in about 300 ml of methanol at 0-5C followed by the dropwise addition 79.5 9 (0.5 mole) of 6-methylthio-3-hepten-2-one. The temperature of the mixture was allowed to rise to room temperature. The mixture was stirred overnight (about 18 hours) at room temperature. The mixture was evaporated to dryness and the residue mixed wlth 300 ml of water. The re~ulting aqueous solution w~s washed with ethyl ether, then acidi~
fied with concentrated hydrochlorlc acid to pH2 and extracted with methylene chloride. The methylene chloride extract was dried over magnesium sulfate and evaporated to dryness affording 4-methoxycarbonyl-5-(2-methylthiopropyl)-cyclohexane 1,3-dione.
(d) A mixture containing 129 g (0.5 mole) of 4-methoxycarbonyl-5-(2-methylthiopropyl)-cyclohexane-1,3-dione and 65 g of aqueous 85 wt.% potassium hydroxide (1 mole) in 300 ml of ethanol was refluxed for 2 hours and then stirred overnight (about 18 hours) at room tempera-ture. The mixture was evaporated to dryness and the resi-due dlssolved in water. The resulting aqueous solution was washed with 100 ml of ethyl ether, then acidified to pHl with 6N aqueous hydrochloric acid and extracted twice with methylene chloride. The combined methylene chloride extract was washed with water, dried over magnesium sul-fate and evaporated to dryness affording 60 9 of 5-(2-methylthiopropyl) cyclohexane-1,3-dione as an oil which solidieied upon standing for 3 or 4 days.
(e) 8.8 Grams ~0.088 mole) of trlethylamine was slowly added over a five-minute period to a mixture . .
6~
~
containing 16.0 g (0.08 mole) of 5-(methylthiopropyl)cyclo-hexane-1,3-dione in 200 ml of toluene after which 2.4 g 05 (0.02 mole) of dimethylaminopyridine was added. 7.7 Grams (0.084 mole) of propionyl chloride was added dropwise to this mixture over a 20-minute period. The mixture was maintained at 65-70C for 3 hours and then cooled to room temperature and allowed to stand overnight (about 18 hours). The mixture was washed first with water and then with aqueous 10 wt. % hydrochloric acid. The resulting aqueous and toluene liquid phase layers were then separated. The aqueous layer was extracted with toluene and the axtract combined with the previously separated toluene layer. The toluene phase was extracted with aqueous 1 wt. ~ sodium hydroxide. The extract was washed ~ with methylene chloride, then acidified to pHl with hydro-; chloric acid, and extracted with methylene chloride. The methylene chloride extract was dried over magnesium sulfate and evaporated to dryness affording 2-propionyl-5-t2-methyl-thiopropyl)cyclohexane-1,3-dione.
(f) A solution containing 4.2 g (0.0117 mole) of 2~propionyl-5-(2-methylthiopropyl)cyclohexane-1,3-dione and 2.7 9 of 3-trans-chloroallyloxyamine in 50 ml of ethanol was stirred at room temperature over the weekend (about 2-1/2 days) and then evaporated to dryness. The residue was dissolved in methylene chloride and extracted twice with aqueous 1 wt. % sodium hydroxide. The aqueous extract was washed with ethyl ether, then acidified to pHl with hydrochloric acid and then extracted with methylene chloride. The methylene chloride extract was dried over magnesium sulfate and then evaporates to dryness affording 2.1 9 of the title compound as an oil.
Elemental analysis Carbon: calc. 55.56%, found 55.96~; Hydrogen: calc. 6.99~, found 7.32%; Nitrogen calc. 4.05 %, found 4.2~.
qO
Example 2 2-[1-(3-trans-chloroallyloxyaminc))propylidene]-5-(2-propylthioethyl)-cyclohexane-1,3-dione _ 05 A 42.3 wt.% solution of the hydrochloride salt of trans-chloroallyloxyamine in dilute aqueous hydrochlo-ric acid solution was treated with dilute aqueous sodium hydroxide to pH 8-10 to liberate the free amine. The solution was then extracted twice with ethyl ether. The ~ ether extracts were combined, washed twice with saturated aqueous sodium chloride and then driad over magnesium sulfate and evaporated yielding chloroallyloxyamine as a pale yellow liquid.
A mixture containing 3.2g of 2-propionyl-S-(2-IS propylthioethyl)cyclohexane-1,3-dione and 1.3g or trans-chloroallyloxyamine in 20 ml of ethanol was stirred over-night (about 15-18 hrs.) at room temperature and then concentrated by evaporation and mixed with 50 ml of ethyl ether. The pH of the mixture was adjusted to pH 11-12 by the addition of aqueous 5 wt. % sodium hydroxide. The aqueous phase was separated and treated with aqueous 10 wt.% hydrochloric acid to pH 2 and then extracted twice with ethyl ether. The ethyl ether extracts were combined, washed twice with aqueous sodium chloride, dried over magnesium sulfate and concentrated by evaporation to a yel;low liquid. The yellow liquid was chromatographed through a silica gel column eluting with methylene chlo-ride affording 3.1 g of the title compound as an oil.
Example 3 Trans-2-[1-(3-chloroallyloxyamino) propylidene]-5-(2-ethylthiopropyl)-cyclohexane-1,3-dione In this example, 17.2 g (0.0636 mol) of 2-pro-; pionyl-5-(2-ethylthiopropyl)cyclohexane-1,3-dione; 0.9 g (0.0153 mol) of acetic acid, and 10.9 g (0.0757 mol) of 3S 3-trans-chloroallyloxyamine in 35 ml of water were added to 20 ml of hexane and stirred. Agueous 5 wt. ~ sodium hydroxide was slowly added over about 15 minutes until 3.0 g (0.0757 m ~ small excess) of sodium hydroxide had been added - pH of reaction mixture about 6. The mixture was heated to and maintained at 40C for 2-1/2 hours and then cooled to room temperature. The or~anic (i.e., hexane) phase was separated and washed with 10 ml of aqueous 05 5 wt % hydrochloric acid and then aqueous 6.25 wt. %
sodium hydroxide added until pH12. The aqueous phase was separated and admixed with 25 ml of hexane and the pH
adjusted to 5.4 by the dropwise addition of aqueous 36 wt. ~ hydrochloric acid over an ice bath. The organic phase was separated, dried over magnesium sulfate and then concentrated by evaporation affording 18.0 ~ of a crude product. The crude product was purified by column chroma-tography over silica gel eluting with hexane:methylene chloride affording the purified title compound as an oil.
IS Elemental analysis carbon calculated 56.73~, found 56.63~;
Hydrogen calculated 7.28%, found 7.55~; Nitrogen 3.89%, found 3.55%.
Example 4 Sodium 2-~1-(3-trans-chloroallyloxyamino) propylidene-3-oxo-5-(2-methylthiopropyl)-~U _ cyclohex-l-en-l-olate This example illustrates a procedure which can be used to prepare the title compound.
A solution containing 0.01 mole of sodium hydroxide dissolved in 2 ml of water is added to a solu-tion containing 0.01 mole of 2-~1-(3-trans-chloroallyl-oxyamino~ propylidene-5-(2-ethylthiopropyl)-cyclohexane 1,3-dione at room temperature. After the reaction is completed, the solvents are evaporated off under vacuum affording the l-hydroxy sodium salt of 2-[1-(3-trans-chlo-roallyloxyamino) propylidene-3-oxo-5-(2-methylthiopropyl)-cyclohex-l-en-l-ol, Example 5 In this example, the title compound of Examples 1-3, i.e., 2-~1-(3-trans-chloroallyloxyamino) propylidene]-5-(2-~ethylthiopropyl)-cyclohexane-1,3-dione (1); 2-[1-(3-trans-chloroallyloxyamino) propylideneJ-5-(2-propylthioethyl)-cyclohexane-1,3-dione (2~;and 2-11-(3-trans-chloroallyloxyamino)propylidene]-5-(2-ethylthio-propyl) cyclohexane-1,3-dione (3); were tested, u~ing the procedures described hereinbelow, for pre-emergent and ~27~L6~
post-emergent phytotoxic activity against a variety of grasses and broad-leaf plants including one grain crop and one broad-leaf crop.
Pre-Emergent Herbicide Test Pre-emergence herbicidal activity was determined in the following manner.
Test solutions of the respective compounds were prepared as follows:
355.5 mg of test compound was dissolved in 15 ml of acetone. 2 ml of acetone containing 110 mg o~ a non-ionic surfactant was added to the solution. 12 ml o~ this stock solution was then added to 47.7 ml of water which contained the same nonionic surfactant at a concentration of 625 mg/l.
Seeds of the test vegetation were planted in a pot of soil and the test solution was sprayed uniformly onto the soil surface at a test compound dose of 27.5 micrograms/cm2 unless otherwise specified in the following Tables. The pot was watered and placed in a greenhouse. The pot was watered intermittently and observed for seedling emergence, health of emerging seed-lings, etc., for a 3-week period. At the end of this period, the herbicidal effectiveness of the compound was rated based on the physiological observations. A 0-to-100 scale was used, 0 representing no phytotoxicity, 100 t; representing complete kill. The results of these tests are summarized in Table 1.
Post-Emergent Herbicidal Test The test compound was formulated in the same manner as described above for the pre-emergent test.
This formulation was uniformly sprayed on 2 similar pots containing plants 2 to 3 inches tall (except wild oats, soybean and watergrass which were 3 to 4 inches tall) (approximately 15 to 25 plants per pot) at a test compound dose of 27.5 microgram/cm2 unless otherwise specified in the following Tables~ After the plants had dried, they were placed in a ~reenhouse and then watered intermit-tently at their bases as needed. The plants were observed ~L~7.~ E;`~
periodically for phytotoxic effects and physiological and morphological responses to the treatment. After 3 weeks, 05 the herbicidal effectiveness of the cornpound was rated based on these observations. A O-to-100 scale was used, O representing no phytotoxicity, 100 representing complete kill. The results of these tests are summarized in Table 2.
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The methylene chloride was evaporated off leaving a solid residue. ~he residue was slurried in hexane, filtered.
The remaining solids were thoroughly washed with hexane and filtered. The combined filtrates were evaporated to ~1~44 dryness affording 70.6 g of 6-me~hylthio-3-hepten-2-one as an oil. (For large scale operations this product can also 05 be conveniently prepared by the general procedures described in U.S. Pa~ent No. 4,35~,184 and PCT/US 85/
01853, published April 10, 1986 as WO 86/02065.
I0 (c~ 66.0 Grams (0.5 mole~ of dimethyl malonate was added dropwise to a solution cont~ining 27 9 ~0.5 mole3 of sodium methoxide in about 300 ml of methanol at 0-5C followed by the dropwise addition 79.5 9 (0.5 mole) of 6-methylthio-3-hepten-2-one. The temperature of the mixture was allowed to rise to room temperature. The mixture was stirred overnight (about 18 hours) at room temperature. The mixture was evaporated to dryness and the residue mixed wlth 300 ml of water. The re~ulting aqueous solution w~s washed with ethyl ether, then acidi~
fied with concentrated hydrochlorlc acid to pH2 and extracted with methylene chloride. The methylene chloride extract was dried over magnesium sulfate and evaporated to dryness affording 4-methoxycarbonyl-5-(2-methylthiopropyl)-cyclohexane 1,3-dione.
(d) A mixture containing 129 g (0.5 mole) of 4-methoxycarbonyl-5-(2-methylthiopropyl)-cyclohexane-1,3-dione and 65 g of aqueous 85 wt.% potassium hydroxide (1 mole) in 300 ml of ethanol was refluxed for 2 hours and then stirred overnight (about 18 hours) at room tempera-ture. The mixture was evaporated to dryness and the resi-due dlssolved in water. The resulting aqueous solution was washed with 100 ml of ethyl ether, then acidified to pHl with 6N aqueous hydrochloric acid and extracted twice with methylene chloride. The combined methylene chloride extract was washed with water, dried over magnesium sul-fate and evaporated to dryness affording 60 9 of 5-(2-methylthiopropyl) cyclohexane-1,3-dione as an oil which solidieied upon standing for 3 or 4 days.
(e) 8.8 Grams ~0.088 mole) of trlethylamine was slowly added over a five-minute period to a mixture . .
6~
~
containing 16.0 g (0.08 mole) of 5-(methylthiopropyl)cyclo-hexane-1,3-dione in 200 ml of toluene after which 2.4 g 05 (0.02 mole) of dimethylaminopyridine was added. 7.7 Grams (0.084 mole) of propionyl chloride was added dropwise to this mixture over a 20-minute period. The mixture was maintained at 65-70C for 3 hours and then cooled to room temperature and allowed to stand overnight (about 18 hours). The mixture was washed first with water and then with aqueous 10 wt. % hydrochloric acid. The resulting aqueous and toluene liquid phase layers were then separated. The aqueous layer was extracted with toluene and the axtract combined with the previously separated toluene layer. The toluene phase was extracted with aqueous 1 wt. ~ sodium hydroxide. The extract was washed ~ with methylene chloride, then acidified to pHl with hydro-; chloric acid, and extracted with methylene chloride. The methylene chloride extract was dried over magnesium sulfate and evaporated to dryness affording 2-propionyl-5-t2-methyl-thiopropyl)cyclohexane-1,3-dione.
(f) A solution containing 4.2 g (0.0117 mole) of 2~propionyl-5-(2-methylthiopropyl)cyclohexane-1,3-dione and 2.7 9 of 3-trans-chloroallyloxyamine in 50 ml of ethanol was stirred at room temperature over the weekend (about 2-1/2 days) and then evaporated to dryness. The residue was dissolved in methylene chloride and extracted twice with aqueous 1 wt. % sodium hydroxide. The aqueous extract was washed with ethyl ether, then acidified to pHl with hydrochloric acid and then extracted with methylene chloride. The methylene chloride extract was dried over magnesium sulfate and then evaporates to dryness affording 2.1 9 of the title compound as an oil.
Elemental analysis Carbon: calc. 55.56%, found 55.96~; Hydrogen: calc. 6.99~, found 7.32%; Nitrogen calc. 4.05 %, found 4.2~.
qO
Example 2 2-[1-(3-trans-chloroallyloxyaminc))propylidene]-5-(2-propylthioethyl)-cyclohexane-1,3-dione _ 05 A 42.3 wt.% solution of the hydrochloride salt of trans-chloroallyloxyamine in dilute aqueous hydrochlo-ric acid solution was treated with dilute aqueous sodium hydroxide to pH 8-10 to liberate the free amine. The solution was then extracted twice with ethyl ether. The ~ ether extracts were combined, washed twice with saturated aqueous sodium chloride and then driad over magnesium sulfate and evaporated yielding chloroallyloxyamine as a pale yellow liquid.
A mixture containing 3.2g of 2-propionyl-S-(2-IS propylthioethyl)cyclohexane-1,3-dione and 1.3g or trans-chloroallyloxyamine in 20 ml of ethanol was stirred over-night (about 15-18 hrs.) at room temperature and then concentrated by evaporation and mixed with 50 ml of ethyl ether. The pH of the mixture was adjusted to pH 11-12 by the addition of aqueous 5 wt. % sodium hydroxide. The aqueous phase was separated and treated with aqueous 10 wt.% hydrochloric acid to pH 2 and then extracted twice with ethyl ether. The ethyl ether extracts were combined, washed twice with aqueous sodium chloride, dried over magnesium sulfate and concentrated by evaporation to a yel;low liquid. The yellow liquid was chromatographed through a silica gel column eluting with methylene chlo-ride affording 3.1 g of the title compound as an oil.
Example 3 Trans-2-[1-(3-chloroallyloxyamino) propylidene]-5-(2-ethylthiopropyl)-cyclohexane-1,3-dione In this example, 17.2 g (0.0636 mol) of 2-pro-; pionyl-5-(2-ethylthiopropyl)cyclohexane-1,3-dione; 0.9 g (0.0153 mol) of acetic acid, and 10.9 g (0.0757 mol) of 3S 3-trans-chloroallyloxyamine in 35 ml of water were added to 20 ml of hexane and stirred. Agueous 5 wt. ~ sodium hydroxide was slowly added over about 15 minutes until 3.0 g (0.0757 m ~ small excess) of sodium hydroxide had been added - pH of reaction mixture about 6. The mixture was heated to and maintained at 40C for 2-1/2 hours and then cooled to room temperature. The or~anic (i.e., hexane) phase was separated and washed with 10 ml of aqueous 05 5 wt % hydrochloric acid and then aqueous 6.25 wt. %
sodium hydroxide added until pH12. The aqueous phase was separated and admixed with 25 ml of hexane and the pH
adjusted to 5.4 by the dropwise addition of aqueous 36 wt. ~ hydrochloric acid over an ice bath. The organic phase was separated, dried over magnesium sulfate and then concentrated by evaporation affording 18.0 ~ of a crude product. The crude product was purified by column chroma-tography over silica gel eluting with hexane:methylene chloride affording the purified title compound as an oil.
IS Elemental analysis carbon calculated 56.73~, found 56.63~;
Hydrogen calculated 7.28%, found 7.55~; Nitrogen 3.89%, found 3.55%.
Example 4 Sodium 2-~1-(3-trans-chloroallyloxyamino) propylidene-3-oxo-5-(2-methylthiopropyl)-~U _ cyclohex-l-en-l-olate This example illustrates a procedure which can be used to prepare the title compound.
A solution containing 0.01 mole of sodium hydroxide dissolved in 2 ml of water is added to a solu-tion containing 0.01 mole of 2-~1-(3-trans-chloroallyl-oxyamino~ propylidene-5-(2-ethylthiopropyl)-cyclohexane 1,3-dione at room temperature. After the reaction is completed, the solvents are evaporated off under vacuum affording the l-hydroxy sodium salt of 2-[1-(3-trans-chlo-roallyloxyamino) propylidene-3-oxo-5-(2-methylthiopropyl)-cyclohex-l-en-l-ol, Example 5 In this example, the title compound of Examples 1-3, i.e., 2-~1-(3-trans-chloroallyloxyamino) propylidene]-5-(2-~ethylthiopropyl)-cyclohexane-1,3-dione (1); 2-[1-(3-trans-chloroallyloxyamino) propylideneJ-5-(2-propylthioethyl)-cyclohexane-1,3-dione (2~;and 2-11-(3-trans-chloroallyloxyamino)propylidene]-5-(2-ethylthio-propyl) cyclohexane-1,3-dione (3); were tested, u~ing the procedures described hereinbelow, for pre-emergent and ~27~L6~
post-emergent phytotoxic activity against a variety of grasses and broad-leaf plants including one grain crop and one broad-leaf crop.
Pre-Emergent Herbicide Test Pre-emergence herbicidal activity was determined in the following manner.
Test solutions of the respective compounds were prepared as follows:
355.5 mg of test compound was dissolved in 15 ml of acetone. 2 ml of acetone containing 110 mg o~ a non-ionic surfactant was added to the solution. 12 ml o~ this stock solution was then added to 47.7 ml of water which contained the same nonionic surfactant at a concentration of 625 mg/l.
Seeds of the test vegetation were planted in a pot of soil and the test solution was sprayed uniformly onto the soil surface at a test compound dose of 27.5 micrograms/cm2 unless otherwise specified in the following Tables. The pot was watered and placed in a greenhouse. The pot was watered intermittently and observed for seedling emergence, health of emerging seed-lings, etc., for a 3-week period. At the end of this period, the herbicidal effectiveness of the compound was rated based on the physiological observations. A 0-to-100 scale was used, 0 representing no phytotoxicity, 100 t; representing complete kill. The results of these tests are summarized in Table 1.
Post-Emergent Herbicidal Test The test compound was formulated in the same manner as described above for the pre-emergent test.
This formulation was uniformly sprayed on 2 similar pots containing plants 2 to 3 inches tall (except wild oats, soybean and watergrass which were 3 to 4 inches tall) (approximately 15 to 25 plants per pot) at a test compound dose of 27.5 microgram/cm2 unless otherwise specified in the following Tables~ After the plants had dried, they were placed in a ~reenhouse and then watered intermit-tently at their bases as needed. The plants were observed ~L~7.~ E;`~
periodically for phytotoxic effects and physiological and morphological responses to the treatment. After 3 weeks, 05 the herbicidal effectiveness of the cornpound was rated based on these observations. A O-to-100 scale was used, O representing no phytotoxicity, 100 representing complete kill. The results of these tests are summarized in Table 2.
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l -18-Example 6 In this example, the title compounds of Examples 05 1-3 were tested for post-emergence herbicidal activity at very low dosage rates side by side with trans-2-[1-(3-chloroallyloxyamino)butylidene]-5-(2-ethylthiopropyl)-cyclohexane-1,3-dione ("C-l") the commercial herbicide Sethoxydim ("C-2") (i.e., 2-[1-~ethoxyamino)butylidene]-5-10 (2-ethylthiopropyl)-cyclohexane-1,3-dione against an expanded list of weed grasses and two crops.
The tests were conducted in the same manner as described in Example 5, hereinabove, with the exception that the dosages indicated in Table 3 were used and four l5 replicates were used per test. The results of this r testing are summarized in Table 4 wherein O indicates no phytotoxicity and 100 indicates complete kill. Generally, phytotoxicities below about 20-30% are not considered meaningful because generally the plant can grow out of this amount of injury.
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Ol -21-As can be seen from Table 3, all of the com-pounds were inactive against yellow nutsedge at these S dosage rates. With this one exception, Compounds 1-3 were superior to Compound C-l with respect to each of the other weed species in the test and were greatly superior to Compound C-2.
In terms of dosages required to evoke equivalent responses, an application rate of Compound 1 or 2 of 0.05 y/cm2 was about equivalent or superior to an application rate of Compound C-l of 0.28 y/cm2 to control crabgrass and Johnsongrass. An application rate of 0.05 y/cm2 of Compound 1 or 2 was equivalent to an application rate of 0.11 y/cm2 of Compound C-l to control barnyardgrass. With respect to wild oats and yellow foxtail, an application rate of 0.11 y/cm2 of Compound 1 or 2 provided superior control over application rate of 0.28 y/cm2 of Compound C-l. As above noted, Compound C-l was superior to Compound C-2 and the dosages advantages afforded by Compounds 1 and 2 were even greater with respect to Compound C-2.
Obviously, ~any modifications and variations of the invention described hereinabove and below can be made without departing from the essence and scope thereof.
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l -18-Example 6 In this example, the title compounds of Examples 05 1-3 were tested for post-emergence herbicidal activity at very low dosage rates side by side with trans-2-[1-(3-chloroallyloxyamino)butylidene]-5-(2-ethylthiopropyl)-cyclohexane-1,3-dione ("C-l") the commercial herbicide Sethoxydim ("C-2") (i.e., 2-[1-~ethoxyamino)butylidene]-5-10 (2-ethylthiopropyl)-cyclohexane-1,3-dione against an expanded list of weed grasses and two crops.
The tests were conducted in the same manner as described in Example 5, hereinabove, with the exception that the dosages indicated in Table 3 were used and four l5 replicates were used per test. The results of this r testing are summarized in Table 4 wherein O indicates no phytotoxicity and 100 indicates complete kill. Generally, phytotoxicities below about 20-30% are not considered meaningful because generally the plant can grow out of this amount of injury.
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r~ ~ E~a X o~ ~ ~ ~ c ~ u~ co ~ o C~ ~ t a:~ a~
E~ ~ ~~ N C U) O U:~ ~ Ocn IJ ) C~
u) o ~ O ~ ~ ~ ~ cr~
3 'O IX ~
O ~ ~D ~ O ~ D O ~1 ~ S3 o ~ CO ~ ~ I` ~ ~ er ~1) C ~C ~ u~ O O ~ ~ cn ~ ~ o o oo O
r ~ a~
a~ 0 ~ ~ ~1 0 UQ U~ CO ~ ~ l P u~ ~ c~ ~ a) ~ 0 Co ~ U~
a ~I ~ ~1 0 0 t~ O O ~ r-~ O O
O O O O O O O O O O O O ~
~;
C ~ ~ ~ ~ ~ ~ ~ ~ f'~
U ~ Z ~
~1 0 ~ O ~
COOOO ~oo O ~
U~ X .~
o~ o ~ V C
,~ ~, V oooo oooo ps~ ~o ~ U~
O ~, o o o o o o o o ~1~
Z
3 ~1 O ~ or~oo c~c~oo ,~ v cou~
O
.~ ~
o ~o ~ I o~ C 0 a~o ~00 ,~ S 0 u~ ~r t~J 1~ ~
~' ~ ~ a 0 C~
X ~1 0 o ~ u~ o ~ O O
nS 0 '3 ~
~7 O O
P~ C~ 0 ~DOOCO OCOOO
s~ 0 a~
~ ~ ~ ~a :1 ~ ~ h 0 ~ In o ~ u~ o o E
J~
~ l o o ~ ~ o o :~ o O e 0OOO oooo c )Q
Ol -21-As can be seen from Table 3, all of the com-pounds were inactive against yellow nutsedge at these S dosage rates. With this one exception, Compounds 1-3 were superior to Compound C-l with respect to each of the other weed species in the test and were greatly superior to Compound C-2.
In terms of dosages required to evoke equivalent responses, an application rate of Compound 1 or 2 of 0.05 y/cm2 was about equivalent or superior to an application rate of Compound C-l of 0.28 y/cm2 to control crabgrass and Johnsongrass. An application rate of 0.05 y/cm2 of Compound 1 or 2 was equivalent to an application rate of 0.11 y/cm2 of Compound C-l to control barnyardgrass. With respect to wild oats and yellow foxtail, an application rate of 0.11 y/cm2 of Compound 1 or 2 provided superior control over application rate of 0.28 y/cm2 of Compound C-l. As above noted, Compound C-l was superior to Compound C-2 and the dosages advantages afforded by Compounds 1 and 2 were even greater with respect to Compound C-2.
Obviously, ~any modifications and variations of the invention described hereinabove and below can be made without departing from the essence and scope thereof.
3~
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A herbicidal composition comprising a herbicidally effective amount of a compound having the formula:
wherein R1 is 3-trans-chloroallyl; and R2 is 2-methylthio-propyl or 2-propylthioethyl; and agro chemically acceptable salts thereof, together with a compatible carrier.
wherein R1 is 3-trans-chloroallyl; and R2 is 2-methylthio-propyl or 2-propylthioethyl; and agro chemically acceptable salts thereof, together with a compatible carrier.
2. The composition of claim 1 wherein R2 is 2-methyl-thiopropyl.
3. The composition of claim 2 wherein said compound is 2-[1-(3-trans-chloroallyloxyamino)propylidene]-5-(2-methylthio-propyl)-cyclohexane-1,3-dione.
4. The composition of claim 1 wherein R2 is 2-propyl-thioethyl.
5. The composition of claim 4 wherein said compound is 2-[1-(3-trans-chloroallyloxyamino)propylidene]-5-(2-propylthio-ethyl)-cyclohexane-1,3-dione.
6. The composition of claim 1 comprising a herbicidally effective amount of the compound according to claim 1 and a crop oil.
- 22a - 61936-1715
- 22a - 61936-1715
7. A method for controlling grassy plants which comprises applying a herbicidally effective amount of a composition according to claim 1, to the foliage or habitat of said plants.
8. A method for controlling grassy plants which comprises applying a herbicidally effective amount of the composition of claim 2, or mixtures thereof, to the foliage or habitat of said plants.
9. A method for controlling grassy plants which comprises applying a herbicidally effective amount of the composition of claim 4, or mixtures thereof, to the foliage or habitat of said plants.
10. A method for controlling the grass species of foxtail, Bermudagrass, volunteer sorghum, broad-leaf signalgrass, goose-grass, red rice, sprangletop, Johnsongrass or volunteer corn which comprises applying a herbicidally effective amount of the composition of claim 1 to said grass species or their habitat.
11. The composition of claim 1 comprising 0.02-0.6 wt. %
of a compound according to claim l; 0.001-0.15 wt. % of an emulsifier; 0.08-2.5 wt. % of an organic solvent and about 95 to 99 wt. % water.
of a compound according to claim l; 0.001-0.15 wt. % of an emulsifier; 0.08-2.5 wt. % of an organic solvent and about 95 to 99 wt. % water.
12. The composition of claim 1 wherein said composition comprises about 0.25-2 wt. % of a crop oil.
13. A herbicidal concentrate composition comprising 23-27 wt. % of a compound according to claim l; 2 to 4 wt. % of an emulsifier and about 70-75 wt. % of an organic solvent.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76830185A | 1985-08-23 | 1985-08-23 | |
| US768,301 | 1985-08-23 | ||
| US79867085A | 1985-11-15 | 1985-11-15 | |
| US798,670 | 1985-11-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1271644A true CA1271644A (en) | 1990-07-17 |
Family
ID=27118040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000516351A Expired - Fee Related CA1271644A (en) | 1985-08-23 | 1986-08-20 | 2-¬1-(3-chloroallyloxyamino) alkylidene|-5- alkylthioalkyl-cyclohexane-1,3-dione herbicides |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0236313A1 (en) |
| KR (1) | KR920010518B1 (en) |
| CN (2) | CN1021282C (en) |
| AU (2) | AU586200B2 (en) |
| BE (1) | BE903349A (en) |
| CA (1) | CA1271644A (en) |
| CH (2) | CH666890A5 (en) |
| DE (1) | DE3627410A1 (en) |
| FR (1) | FR2586416B1 (en) |
| GB (2) | GB2188321B (en) |
| NL (2) | NL193944C (en) |
| NO (1) | NO162555C (en) |
| SE (1) | SE458683B (en) |
| WO (1) | WO1987001699A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP5320465B2 (en) | 2008-08-19 | 2013-10-23 | ダウ アグロサイエンシィズ エルエルシー | Improved method for adding thiolates to α, β-unsaturated carbonyl or sulfonyl compounds |
| 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 |
| 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 |
| AU2020226507A1 (en) * | 2019-02-20 | 2021-09-23 | Sumitomo Chemical Company, Limited | 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 |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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. |
-
1985
- 1985-09-19 NL NL8520309A patent/NL193944C/en not_active IP Right Cessation
- 1985-09-19 WO PCT/US1985/001786 patent/WO1987001699A1/en active Application Filing
- 1985-09-19 KR KR1019860700645A patent/KR920010518B1/en not_active IP Right Cessation
- 1985-09-19 AU AU49541/85A patent/AU586200B2/en not_active Expired
- 1985-09-19 EP EP85904913A patent/EP0236313A1/en active Pending
- 1985-09-19 CH CH1974/87A patent/CH666890A5/en not_active IP Right Cessation
- 1985-09-19 GB GB8708127A patent/GB2188321B/en not_active Expired
- 1985-09-30 BE BE0/215661A patent/BE903349A/en not_active IP Right Cessation
-
1986
- 1986-06-30 AU AU59380/86A patent/AU585999B2/en not_active Ceased
- 1986-07-22 NL NL8601900A patent/NL8601900A/en not_active Application Discontinuation
- 1986-07-30 CN CN90107624A patent/CN1021282C/en not_active Expired - Lifetime
- 1986-07-30 CN CN86105662A patent/CN1011782B/en not_active Expired
- 1986-08-13 DE DE19863627410 patent/DE3627410A1/en not_active Withdrawn
- 1986-08-18 FR FR8611806A patent/FR2586416B1/en not_active Expired
- 1986-08-19 CH CH3344/86A patent/CH667086A5/en not_active IP Right Cessation
- 1986-08-20 CA CA000516351A patent/CA1271644A/en not_active Expired - Fee Related
- 1986-08-21 GB GB8620373A patent/GB2179352B/en not_active Expired
- 1986-09-15 SE SE8603868A patent/SE458683B/en not_active IP Right Cessation
- 1986-09-18 NO NO86863733A patent/NO162555C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2586416A1 (en) | 1987-02-27 |
| CH667086A5 (en) | 1988-09-15 |
| CN1021282C (en) | 1993-06-23 |
| GB2179352B (en) | 1989-08-09 |
| NO863733D0 (en) | 1986-09-18 |
| GB2188321A (en) | 1987-09-30 |
| AU5938086A (en) | 1987-02-26 |
| CH666890A5 (en) | 1988-08-31 |
| GB2179352A (en) | 1987-03-04 |
| FR2586416B1 (en) | 1989-06-02 |
| NL193944C (en) | 2001-03-02 |
| GB8620373D0 (en) | 1986-10-01 |
| KR920010518B1 (en) | 1992-12-04 |
| NL193944B (en) | 2000-11-01 |
| BE903349A (en) | 1986-04-01 |
| CN86105662A (en) | 1987-04-08 |
| WO1987001699A1 (en) | 1987-03-26 |
| NO162555B (en) | 1989-10-09 |
| NO162555C (en) | 1990-01-17 |
| DE3627410A1 (en) | 1987-02-26 |
| EP0236313A1 (en) | 1987-09-16 |
| GB8708127D0 (en) | 1987-05-13 |
| SE8603868L (en) | 1987-03-20 |
| KR870700287A (en) | 1987-12-28 |
| NL8601900A (en) | 1987-03-16 |
| SE458683B (en) | 1989-04-24 |
| NO863733L (en) | 1987-03-26 |
| NL8520309A (en) | 1985-09-19 |
| SE8603868D0 (en) | 1986-09-15 |
| CN1051285A (en) | 1991-05-15 |
| GB2188321B (en) | 1989-08-31 |
| AU586200B2 (en) | 1989-07-06 |
| CN1011782B (en) | 1991-02-27 |
| AU4954185A (en) | 1987-04-07 |
| AU585999B2 (en) | 1989-06-29 |
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