CA1151184A - 4-thioparabanic acid derivatives, process of preparing the same, and use as herbicides - Google Patents
4-thioparabanic acid derivatives, process of preparing the same, and use as herbicidesInfo
- Publication number
- CA1151184A CA1151184A CA000367841A CA367841A CA1151184A CA 1151184 A CA1151184 A CA 1151184A CA 000367841 A CA000367841 A CA 000367841A CA 367841 A CA367841 A CA 367841A CA 1151184 A CA1151184 A CA 1151184A
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- CA
- Canada
- Prior art keywords
- acid
- methyl
- imide
- thioparabanic
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/96—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Indole Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE 4-Thioparabanic acid derivatives of the formula in which R stands for an aromatic radical, which may be substituted. The invention also comprises a process for making the compounds by reacting the corresponding thio-oxanilic acid nitriles with methylisocyanate. The compounds according to the invention have herbicidal effectiveness.
Description
The present invention relate~ to com~ounds from the group of 2-oxo-4-thiono~5-imino-imidazolidines and, in particular, 4-thioparabanic acid derivatives, a process of preparing the same and herbicides containing the same.
It is an object of the invention to provide new 4-thioparabanic acid derivatives which are applicable as herbicidal agents against undesirable weeds in cultivated plantings, which have the necessary tolerance toward useful plant:s, and to also provide methods for preparing such compounds by reactions easy, as well as inexpensive to carry out.
The 4-thioparabanic acid derivatives of this invention have the formula R ~S
N - C
C C = ~ - ~
~ ~ /
~H3 in which R stands for an aromatic radical, which may be substituted.
Preferred compounds of the invention are such in which R is an aromatic radical of up to 10 C-atoms, a substituted aromatic radical having up to 9 C-atoms, and 0-3 hetero-atoms.
Especially preferred are compourlds in which R is an aromatic radical with up to 6 C-atoms, a substituted aromatic radical with up to 9 C-atoms, and 0-3 herero-atoms.
- 1 - .~
'rhe erfective agents according to the ir~vention may be used for selective weed control, while leaving useful and decorative plants in agricultural and hort;cultural plant:ings unaffected, when applied in appropriate amounts.
The herbicidal effectiveness also applies to high].y yield-reducing weed grasses and dicotyledonous weeds. From the group of sweet weed grasses, e.g., Lolium-species, Poa annua, Alopecurus myosuroides, Avena fatua, some millets, e.g., Digitaria sanguinalis and Echinochloa crus-galli, and from the ~roup of "sour" grasses which are important in rice growing, e.g., Cyperus iria.
Other examples Çor dicotyledonous weeds are cruciferae, e.g., Sinapis arvensis, Capsella bursa-pastoris, Thlaspi arvense, Raphanus raphanistrum, and others, compositae, e.g., Centaurea cyanus, Matricaria inodora, Chrysanthemum segetum, Galinsoga parviflora, Senecio vulgaris, and others, knot weeds, e.g., Polygonum persicaria, labiatae, e.g., Lamium purpyreum, as well as Chenopodium album, Stellaria media, Galium aparine, Amaranthus retroflexus, and others.
~ he active compounds according to the invention have proven useful as herbicidal agents in cultivated plantings, such as summer barley, winter wheat, rice, cotton, soybean, potatoes, cultured millet especially sorghum millet~ corn and leguminous plants such as lucerns, beans, peas, and carrots.
The preparation of the compounds according to the invention is accomplished by reacting organic thio-oxanilic acid-nitriles with methylisocyanate.
The process for preparing compounds of the formula R S
N - C
C C = N - H
~\ /
O N
wherein R stands for an aromatic radical, which may be substituted, is characterized by:
(a) reacting a thio-oxanilic acid-nitrile of the formula R - NH - C
CN
with methylisocyanate (with R having the meaning explained above) and (b) adding, if desired, a solvent promoting cyclization during or after the reaction described under (a).
The chemical reaction occurring depends on the reaction temperature, the medium in which the reaction proceeds, and the purity of the starting materials (thio-oxanilic acid-nitrile or isocyanate) and, especially the HCl content thereoi, which may be present from the process of 1:~ 5~
producing the reactants and from the controlled, repro-ducible addition. The HCl has a reaction-retardant eEEect, provided that no basic reaction medium, such as pyridine, is used. However, an HCl content of up to 1000 ppm can generally be tolerated, calculated on the HCl-containing component. On the other hand, it is frequently desirable to add 50-1000 ppm, preferably 150-250 p~m HCl, calculated on the total amount of the methylisocyana~te to be reacted, in order to suppress a further Feaction at the imine-nitrogen ~in the 5-position) by ~xcessive isocyanate.
The reactions are advantageously carried out at a temperature range from ~-100C, pre~erably at temperatures about ~0C.
Pyridine or pyridine bases, such as the piccolines, used as reaction media, guarantee in general a rapid and smooth course of the reactions. However, it is frequently possible to-use the isocyanate to be reacted as the reaction medium, if the isocyanate has a sufficiently large capability of dissolving the thio-oxanilic acid-~0 nitrile. When the reaction is carried out in an aprotic,anhydrous solvent, e.g., benzene, toluene, tetrahydrofuran, and the lilce, as well as in reactions without a solvent, in the lower temperature range, cyclization, in general, does not occur and compounds of the formula R ~ S
N - C
¦ CN
O = C
NH
~ ~ _ _ _ . _ _ _ . . _ . . _ _ .... .. _ . , .. ., . . . .. . .. . ... . . . , .. _ _ . . _ s~
are formed which spontaneously are converted into the cyclic product when they are dissolved, or recrystallized in solvents promoting cyclization, such as ethanol, aqueous tetr~hydrofuran, but also in basic solvents, e.g., pyridine or pyridine bases.
The thio-oxanilic acid-nitriles are derivable from the corresponding isothiocyanates, which may be substituted at the aromatic radical. Their preparation is carried out according to or in an analogous manner to the prescription of A. Reissert and K. Bruggemann in Ber. dtsch. Chem. Soc.
57, 9~1 (192~).
Phenyl isothiocyanate, or phenyl isothiocyanate subst:ituted at the aromatic radical, is stirred in alcoholic solut:ion with an aqueous solution of KCN. After the reaction is complete (in general, after about three hours), the solution is diluted with water to twice its volume and precipitated with hydrochloric acid. If desired, the raw product obtained can be recrystallized, e.g., in a benzene/
cyclohexane mixture. This process is generally usable.
With this process, even thio-oxanilic acid-nitriles are obtainable, which have not yet been described in the literature.
The aromatic radical of the thio-oxanilic acid-nitri~e may be substituted in o-, m-, or p-position, in single or mu]tiple substitution. Principally, also condensed aromatic systems, such as, the naphthyl groups, are considered as aromatic radicals.
~8i Examples of substituents at the aromatic radical are saturated or unsaturated alkyl groups of 1-20 C-atoms, par~icularly the methyl-, ethyl-, propyl-, isopr~pyl-, butyl-, allyl- and crotyl-groups; also aliphatic radicals with a hetero-atom, e.g., ether or analogous thio-ether groups, especially methoxy-, ethoxy-allyloxy-crotyloxy- or methylmercapto-ethylmercapto-allylmercapto-crotylmercapto-radicals; the halogen groups (especially chlorides and bromides); organic and inorganic ester groups, as well as dialkylamino- and nitro-groups, the nitrile group, etc.
Examples of the compounds of the invention having the formula R S
N - C
C C = N - H
~ \ /
are:
l-Methyl-3-phenyl-~-thioparabanic acid-5-imide;
1-Methyl-3-p-chlorophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-o-chlorophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-m-chlorophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-o,p-dichlorophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-m,p-dichlorophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-fluorophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-(p-trifluoromethyl-phenyl)-4-thioparabanic acid-5-imide;
l-Methyl-3-p-nitrophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-o,p-dinitrophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-methylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-m-methylphenyl-4-thioparabanic acid~5-imide;
l-Methyl-3-o-methylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3~m,p-dimethylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-o,p-dimethylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-o,o,p-trimethylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-ethylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-m-ethylphenyl-4-thioparabanic acid-5-imide;
1-Methyl-3-o,p-diethylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-propylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-isopropylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-methoxyphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-ethoxyphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-propoxyphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-mercaptomethylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-mercaptoethylphenyl-4-thioparabanic acid-5-imide;
1-Methyl-3-p-mercaptopropylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-nitrilophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-m-ni~rilophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-carboxymethyl-phenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-carboxyethyl-phenyl-4-thioparabanic acid-5-imide;
l-Methy1-3-p-carboxypropyl-phenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-methylsulfonato-phenyl-4-thioparabanic acid-S-imide;
l-Methyl-3-p-ethylsulfonato-phenyl-~--thioparabanic acid-5-imide.
The effective compounds according to the invention may be used alone or in mixture with other substances. In general, they are used as mixtures with solid or liquid diluents or as solutions with solid or liquid solvents, the total content of effective agent being between 0.01 and 95%
by weight.
As a rule, the mixtures or solutions are applied as emulsion concentrates, pastes, spraying powders, granulates or micro-capsules.
Emulsion concentrates and pastes contain in general 10-90% by weight, preferably 15-50% by weight of effective agent, 2-25% by weight of auxiliary dispersing agents and organic solvents and/or water.
Spraying powders contain mostly 10-80% by weight , preferably 15-70% by weight of effective agent, 1-10% by weight of auxiliary dispersing agents and 10-89% by weight of inert components.
Granulates and micro-capsules contain 1-10% by weight, preferably 5-10% by weight of effective agent, in addition to inert components, binders and/or coatings.
According to the invention, the following are used:
As dispersing agents, e.g., alkyl- and aryl-sulfonates, methyl cellulose, polymer sulfonic acids, ~i5~
and their salts, polyalcohols, fatty acid esters, fatty alcohol ethers, fatty amines;
As organic solvents, e.g., alcohols, such as ethanol, butanol, dimethyl formamide tDMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone aromatics, such as toluene and xylene;
As inert components, e.g., kaolin, china clay, talcum, calcium carbonate, highly dispersed silicic acid, silicic gels, kieselgur, diatomateous earth, pumice, split brick, crushed corn, thickening agents, such as starch and carboxymethyl-cellulose; and As binders, e.g., magnesium sulfate, gypsum, and gum arabic.
The following formulation may be used as a herbicide:
1. Emulsion concentrate:
51.4% by weight of effective agent 30 ~/O by weight of Sillitin Z
10 % by weight of highly dispersed silicic acid (HDK) 6 % by weight of lignin sulfonate (cell pi~ch)
It is an object of the invention to provide new 4-thioparabanic acid derivatives which are applicable as herbicidal agents against undesirable weeds in cultivated plantings, which have the necessary tolerance toward useful plant:s, and to also provide methods for preparing such compounds by reactions easy, as well as inexpensive to carry out.
The 4-thioparabanic acid derivatives of this invention have the formula R ~S
N - C
C C = ~ - ~
~ ~ /
~H3 in which R stands for an aromatic radical, which may be substituted.
Preferred compounds of the invention are such in which R is an aromatic radical of up to 10 C-atoms, a substituted aromatic radical having up to 9 C-atoms, and 0-3 hetero-atoms.
Especially preferred are compourlds in which R is an aromatic radical with up to 6 C-atoms, a substituted aromatic radical with up to 9 C-atoms, and 0-3 herero-atoms.
- 1 - .~
'rhe erfective agents according to the ir~vention may be used for selective weed control, while leaving useful and decorative plants in agricultural and hort;cultural plant:ings unaffected, when applied in appropriate amounts.
The herbicidal effectiveness also applies to high].y yield-reducing weed grasses and dicotyledonous weeds. From the group of sweet weed grasses, e.g., Lolium-species, Poa annua, Alopecurus myosuroides, Avena fatua, some millets, e.g., Digitaria sanguinalis and Echinochloa crus-galli, and from the ~roup of "sour" grasses which are important in rice growing, e.g., Cyperus iria.
Other examples Çor dicotyledonous weeds are cruciferae, e.g., Sinapis arvensis, Capsella bursa-pastoris, Thlaspi arvense, Raphanus raphanistrum, and others, compositae, e.g., Centaurea cyanus, Matricaria inodora, Chrysanthemum segetum, Galinsoga parviflora, Senecio vulgaris, and others, knot weeds, e.g., Polygonum persicaria, labiatae, e.g., Lamium purpyreum, as well as Chenopodium album, Stellaria media, Galium aparine, Amaranthus retroflexus, and others.
~ he active compounds according to the invention have proven useful as herbicidal agents in cultivated plantings, such as summer barley, winter wheat, rice, cotton, soybean, potatoes, cultured millet especially sorghum millet~ corn and leguminous plants such as lucerns, beans, peas, and carrots.
The preparation of the compounds according to the invention is accomplished by reacting organic thio-oxanilic acid-nitriles with methylisocyanate.
The process for preparing compounds of the formula R S
N - C
C C = N - H
~\ /
O N
wherein R stands for an aromatic radical, which may be substituted, is characterized by:
(a) reacting a thio-oxanilic acid-nitrile of the formula R - NH - C
CN
with methylisocyanate (with R having the meaning explained above) and (b) adding, if desired, a solvent promoting cyclization during or after the reaction described under (a).
The chemical reaction occurring depends on the reaction temperature, the medium in which the reaction proceeds, and the purity of the starting materials (thio-oxanilic acid-nitrile or isocyanate) and, especially the HCl content thereoi, which may be present from the process of 1:~ 5~
producing the reactants and from the controlled, repro-ducible addition. The HCl has a reaction-retardant eEEect, provided that no basic reaction medium, such as pyridine, is used. However, an HCl content of up to 1000 ppm can generally be tolerated, calculated on the HCl-containing component. On the other hand, it is frequently desirable to add 50-1000 ppm, preferably 150-250 p~m HCl, calculated on the total amount of the methylisocyana~te to be reacted, in order to suppress a further Feaction at the imine-nitrogen ~in the 5-position) by ~xcessive isocyanate.
The reactions are advantageously carried out at a temperature range from ~-100C, pre~erably at temperatures about ~0C.
Pyridine or pyridine bases, such as the piccolines, used as reaction media, guarantee in general a rapid and smooth course of the reactions. However, it is frequently possible to-use the isocyanate to be reacted as the reaction medium, if the isocyanate has a sufficiently large capability of dissolving the thio-oxanilic acid-~0 nitrile. When the reaction is carried out in an aprotic,anhydrous solvent, e.g., benzene, toluene, tetrahydrofuran, and the lilce, as well as in reactions without a solvent, in the lower temperature range, cyclization, in general, does not occur and compounds of the formula R ~ S
N - C
¦ CN
O = C
NH
~ ~ _ _ _ . _ _ _ . . _ . . _ _ .... .. _ . , .. ., . . . .. . .. . ... . . . , .. _ _ . . _ s~
are formed which spontaneously are converted into the cyclic product when they are dissolved, or recrystallized in solvents promoting cyclization, such as ethanol, aqueous tetr~hydrofuran, but also in basic solvents, e.g., pyridine or pyridine bases.
The thio-oxanilic acid-nitriles are derivable from the corresponding isothiocyanates, which may be substituted at the aromatic radical. Their preparation is carried out according to or in an analogous manner to the prescription of A. Reissert and K. Bruggemann in Ber. dtsch. Chem. Soc.
57, 9~1 (192~).
Phenyl isothiocyanate, or phenyl isothiocyanate subst:ituted at the aromatic radical, is stirred in alcoholic solut:ion with an aqueous solution of KCN. After the reaction is complete (in general, after about three hours), the solution is diluted with water to twice its volume and precipitated with hydrochloric acid. If desired, the raw product obtained can be recrystallized, e.g., in a benzene/
cyclohexane mixture. This process is generally usable.
With this process, even thio-oxanilic acid-nitriles are obtainable, which have not yet been described in the literature.
The aromatic radical of the thio-oxanilic acid-nitri~e may be substituted in o-, m-, or p-position, in single or mu]tiple substitution. Principally, also condensed aromatic systems, such as, the naphthyl groups, are considered as aromatic radicals.
~8i Examples of substituents at the aromatic radical are saturated or unsaturated alkyl groups of 1-20 C-atoms, par~icularly the methyl-, ethyl-, propyl-, isopr~pyl-, butyl-, allyl- and crotyl-groups; also aliphatic radicals with a hetero-atom, e.g., ether or analogous thio-ether groups, especially methoxy-, ethoxy-allyloxy-crotyloxy- or methylmercapto-ethylmercapto-allylmercapto-crotylmercapto-radicals; the halogen groups (especially chlorides and bromides); organic and inorganic ester groups, as well as dialkylamino- and nitro-groups, the nitrile group, etc.
Examples of the compounds of the invention having the formula R S
N - C
C C = N - H
~ \ /
are:
l-Methyl-3-phenyl-~-thioparabanic acid-5-imide;
1-Methyl-3-p-chlorophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-o-chlorophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-m-chlorophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-o,p-dichlorophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-m,p-dichlorophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-fluorophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-(p-trifluoromethyl-phenyl)-4-thioparabanic acid-5-imide;
l-Methyl-3-p-nitrophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-o,p-dinitrophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-methylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-m-methylphenyl-4-thioparabanic acid~5-imide;
l-Methyl-3-o-methylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3~m,p-dimethylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-o,p-dimethylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-o,o,p-trimethylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-ethylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-m-ethylphenyl-4-thioparabanic acid-5-imide;
1-Methyl-3-o,p-diethylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-propylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-isopropylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-methoxyphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-ethoxyphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-propoxyphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-mercaptomethylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-mercaptoethylphenyl-4-thioparabanic acid-5-imide;
1-Methyl-3-p-mercaptopropylphenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-nitrilophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-m-ni~rilophenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-carboxymethyl-phenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-carboxyethyl-phenyl-4-thioparabanic acid-5-imide;
l-Methy1-3-p-carboxypropyl-phenyl-4-thioparabanic acid-5-imide;
l-Methyl-3-p-methylsulfonato-phenyl-4-thioparabanic acid-S-imide;
l-Methyl-3-p-ethylsulfonato-phenyl-~--thioparabanic acid-5-imide.
The effective compounds according to the invention may be used alone or in mixture with other substances. In general, they are used as mixtures with solid or liquid diluents or as solutions with solid or liquid solvents, the total content of effective agent being between 0.01 and 95%
by weight.
As a rule, the mixtures or solutions are applied as emulsion concentrates, pastes, spraying powders, granulates or micro-capsules.
Emulsion concentrates and pastes contain in general 10-90% by weight, preferably 15-50% by weight of effective agent, 2-25% by weight of auxiliary dispersing agents and organic solvents and/or water.
Spraying powders contain mostly 10-80% by weight , preferably 15-70% by weight of effective agent, 1-10% by weight of auxiliary dispersing agents and 10-89% by weight of inert components.
Granulates and micro-capsules contain 1-10% by weight, preferably 5-10% by weight of effective agent, in addition to inert components, binders and/or coatings.
According to the invention, the following are used:
As dispersing agents, e.g., alkyl- and aryl-sulfonates, methyl cellulose, polymer sulfonic acids, ~i5~
and their salts, polyalcohols, fatty acid esters, fatty alcohol ethers, fatty amines;
As organic solvents, e.g., alcohols, such as ethanol, butanol, dimethyl formamide tDMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone aromatics, such as toluene and xylene;
As inert components, e.g., kaolin, china clay, talcum, calcium carbonate, highly dispersed silicic acid, silicic gels, kieselgur, diatomateous earth, pumice, split brick, crushed corn, thickening agents, such as starch and carboxymethyl-cellulose; and As binders, e.g., magnesium sulfate, gypsum, and gum arabic.
The following formulation may be used as a herbicide:
1. Emulsion concentrate:
51.4% by weight of effective agent 30 ~/O by weight of Sillitin Z
10 % by weight of highly dispersed silicic acid (HDK) 6 % by weight of lignin sulfonate (cell pi~ch)
2 % by weight of polypropylene glycol 0.6% by weight of sodiumoleyl-methyltauride.
2. Spraying Powders:
20% by weight of effective agent 44% by weight of china clay 16% by weight of highly dispersed silicic acid l5% by weight oE lignin sulfonate (cell pitch) 5/O by weight of sodium-alkylnapthalinesulfonate-formaldehyde condensate (Atlox 4862, Registered trademark~
In general, the ef~ective compounds are used in amounts of 0.5-8 kg/ha, preferably 2-4 kg/ha.
The application as herbicide may be carried out both on the plants (post-emergence method) and on soil free vegetation (pre-emergence or pre-sowing method). The greater herbicidal effect is obtained with application to the soil, preferably before plant cultures have been sown, with subsequent flat, mechanical workin~ of the herbicides into the uppermost layers of the soil.
In the fol]owing, a number of examples will describe both the preparation of the compounds according to the invention and their herbicidal effects. It should, however, be understood that the examples are given by way of illustration and not of limitation.
~ le 1 Preparation of l-methyl-3-phenyl-4-thioparabanic acid-5-imide (III) 1st Step 20 g of thio-oxanilic acid-nitrile (1) purified by recrystallization from benzene/cyclohexane (1:1) are dissolved at 20C in 30 ml freshly distilled, HCl-free methylisocyanate. When standing overnight, compact, reddish-~15~
yellow crysta:Ls are deposited. After 24 hours, excess methylisocyanate is distilled oEE and the resi(lue is recrystalliæed in benzene. The yield is 25 g (92% of the theoretical amount) of N-meti-ylcarbamoyl-thio-oxanilic acid-nitrile (II) having a m.p. of 116C (decomposition).
_nd S_~p 20 g (II) are dissolved in a suffic;ent amount oE
boiling ethanol. Upon cooling, 19 g (95% of the theoretical amount) of yellow crystals of l-methyl-3-phenyl-4-thioparabanic acid-5-imlde (III) are obtained, having a m.p. of 132C.
Exampl _ Preparation of l-methyl-3-phenyl-4-thioparabanic acid-5-imide (III) 60 g crude, non-recrystalli~ed thio-oxanilic acid--nitrile (IA) prepared according to the prescription of A. Reissert and K. Bruggemann appearing in Ber. dtsch. chem.
Ges. 57, 981 (1924) are covered by pouring thereon 90 ml methylisocyanate at 20C, to which 8 ml HGl gas had been previously added. After standing for 24 hours, excess methylisocyanate is distilled off and the residue is recrystallized in ethanol. In a yield of 55.7 g, the product (III) as given above, is obtained. M.p. 129-131C.
Comparison Example 1 10 g pure thio-oxanilic acid-nitrile (I) ~analo-gous to Example 1) are dissolved in 15 ml methylisocyanate, ~ ~5~
to which are added 0.45 ml gaseous HCl. After standing for 24 hours, a black, tarry residue is obtained. It was not possible to isolate the thioparabanic acid product.
Example 3 -Preparation of l-methyl.-3-o-chlorophenyl-4-thioparabanic acid-5-imide (IV) R = o-ClC6H4 5 g o-chloro-thio-oxanilic acid-nitrile are covered by pouring thereon 20 ml HCl-free methylisocyanate and the same ;s allowed to stand 24 hours at 20C.
Subsequently, excess methylisocyanate is dis~;lled o~E and finally the residue is recrystallized in ethanol. Obtained are 3.35 g of yellow crystals of (IV), m.p. 129-131C.
Example 4 Preparation of l-methyl-3-o-chlorophenyl-4-thioparabanic acid-5-imide (IV) R = o-ClC6H4 Operation is carried out in a manner ana]ogous to Example 3, with the difference that instead of treating at 20C, the mixture is reacted for 2 hours in boiling methylisocyanate. The operation leads to the same result as Example 3.
Example 5 Preparation of l-methyl-3-p-fluorophenyl-4-thioparabanic acid-5-imide (V) R = p-F-C6~l ~ ~5~
5 g p-Eluoro-thio-oxanilic acid-nitrile are reacted with 20 ml methylisocyanate at 20C. The further process is carried out as in Example 3. Obtained are yellow crystals of (V) in a yield oE 5.2 g; m.p. l22-124C.
Exampl _ Preparation of l-methyl-3-o-methoxyphenyl-~l-thioparabanic acid-5-imide (Vl) o CH30C6H~
38.4 g o-methoxy-thio-oxanilic acid-nitrile are dissolved in 60 ml pyridine and added thereto are 11.4 g methylisocyanate. The mixture is allowed to stancl for 24 hours at 20C. Pyridine is subsequently distilled off and the residue is recrystallized in ethanol. Obtained are 29 g of (VI) with a m.p. of 124-127C.
Exampl _ Preparation of l-methyl-3-(3,4 dichlorophenyl)-4-thio-parabanic acid-5-imide (VII) R = o,p-Cl2C6H3 10 g 3,4-dichloro-thio-oxanilic acid-nitrile are dissolved in 60 ml pyridine and added thereto are 2.5 g methylisocyanate. After 24 hours of standing, the pyridine is distilled off under vacuum, and the residue is dissolved in a small quantity of hot ethanol. Obtained are 8.1 g of raw (VII). After renewed recrystallization in 100 ml ethanol, 5.8 g of yellow crystals (VII) remain; m.p.
135-137C.
Example 8 Preparation of l-methyl-3-para-tolyl-4-thioparabanic acid-5 imide (VIII) R = p-CH3C6H4 10 g p-methyl-thio-oxanilic acid-nitrile, dissolved in 20 ml pyridine, are reacted while cooled with
2. Spraying Powders:
20% by weight of effective agent 44% by weight of china clay 16% by weight of highly dispersed silicic acid l5% by weight oE lignin sulfonate (cell pitch) 5/O by weight of sodium-alkylnapthalinesulfonate-formaldehyde condensate (Atlox 4862, Registered trademark~
In general, the ef~ective compounds are used in amounts of 0.5-8 kg/ha, preferably 2-4 kg/ha.
The application as herbicide may be carried out both on the plants (post-emergence method) and on soil free vegetation (pre-emergence or pre-sowing method). The greater herbicidal effect is obtained with application to the soil, preferably before plant cultures have been sown, with subsequent flat, mechanical workin~ of the herbicides into the uppermost layers of the soil.
In the fol]owing, a number of examples will describe both the preparation of the compounds according to the invention and their herbicidal effects. It should, however, be understood that the examples are given by way of illustration and not of limitation.
~ le 1 Preparation of l-methyl-3-phenyl-4-thioparabanic acid-5-imide (III) 1st Step 20 g of thio-oxanilic acid-nitrile (1) purified by recrystallization from benzene/cyclohexane (1:1) are dissolved at 20C in 30 ml freshly distilled, HCl-free methylisocyanate. When standing overnight, compact, reddish-~15~
yellow crysta:Ls are deposited. After 24 hours, excess methylisocyanate is distilled oEE and the resi(lue is recrystalliæed in benzene. The yield is 25 g (92% of the theoretical amount) of N-meti-ylcarbamoyl-thio-oxanilic acid-nitrile (II) having a m.p. of 116C (decomposition).
_nd S_~p 20 g (II) are dissolved in a suffic;ent amount oE
boiling ethanol. Upon cooling, 19 g (95% of the theoretical amount) of yellow crystals of l-methyl-3-phenyl-4-thioparabanic acid-5-imlde (III) are obtained, having a m.p. of 132C.
Exampl _ Preparation of l-methyl-3-phenyl-4-thioparabanic acid-5-imide (III) 60 g crude, non-recrystalli~ed thio-oxanilic acid--nitrile (IA) prepared according to the prescription of A. Reissert and K. Bruggemann appearing in Ber. dtsch. chem.
Ges. 57, 981 (1924) are covered by pouring thereon 90 ml methylisocyanate at 20C, to which 8 ml HGl gas had been previously added. After standing for 24 hours, excess methylisocyanate is distilled off and the residue is recrystallized in ethanol. In a yield of 55.7 g, the product (III) as given above, is obtained. M.p. 129-131C.
Comparison Example 1 10 g pure thio-oxanilic acid-nitrile (I) ~analo-gous to Example 1) are dissolved in 15 ml methylisocyanate, ~ ~5~
to which are added 0.45 ml gaseous HCl. After standing for 24 hours, a black, tarry residue is obtained. It was not possible to isolate the thioparabanic acid product.
Example 3 -Preparation of l-methyl.-3-o-chlorophenyl-4-thioparabanic acid-5-imide (IV) R = o-ClC6H4 5 g o-chloro-thio-oxanilic acid-nitrile are covered by pouring thereon 20 ml HCl-free methylisocyanate and the same ;s allowed to stand 24 hours at 20C.
Subsequently, excess methylisocyanate is dis~;lled o~E and finally the residue is recrystallized in ethanol. Obtained are 3.35 g of yellow crystals of (IV), m.p. 129-131C.
Example 4 Preparation of l-methyl-3-o-chlorophenyl-4-thioparabanic acid-5-imide (IV) R = o-ClC6H4 Operation is carried out in a manner ana]ogous to Example 3, with the difference that instead of treating at 20C, the mixture is reacted for 2 hours in boiling methylisocyanate. The operation leads to the same result as Example 3.
Example 5 Preparation of l-methyl-3-p-fluorophenyl-4-thioparabanic acid-5-imide (V) R = p-F-C6~l ~ ~5~
5 g p-Eluoro-thio-oxanilic acid-nitrile are reacted with 20 ml methylisocyanate at 20C. The further process is carried out as in Example 3. Obtained are yellow crystals of (V) in a yield oE 5.2 g; m.p. l22-124C.
Exampl _ Preparation of l-methyl-3-o-methoxyphenyl-~l-thioparabanic acid-5-imide (Vl) o CH30C6H~
38.4 g o-methoxy-thio-oxanilic acid-nitrile are dissolved in 60 ml pyridine and added thereto are 11.4 g methylisocyanate. The mixture is allowed to stancl for 24 hours at 20C. Pyridine is subsequently distilled off and the residue is recrystallized in ethanol. Obtained are 29 g of (VI) with a m.p. of 124-127C.
Exampl _ Preparation of l-methyl-3-(3,4 dichlorophenyl)-4-thio-parabanic acid-5-imide (VII) R = o,p-Cl2C6H3 10 g 3,4-dichloro-thio-oxanilic acid-nitrile are dissolved in 60 ml pyridine and added thereto are 2.5 g methylisocyanate. After 24 hours of standing, the pyridine is distilled off under vacuum, and the residue is dissolved in a small quantity of hot ethanol. Obtained are 8.1 g of raw (VII). After renewed recrystallization in 100 ml ethanol, 5.8 g of yellow crystals (VII) remain; m.p.
135-137C.
Example 8 Preparation of l-methyl-3-para-tolyl-4-thioparabanic acid-5 imide (VIII) R = p-CH3C6H4 10 g p-methyl-thio-oxanilic acid-nitrile, dissolved in 20 ml pyridine, are reacted while cooled with
3.25 g methylisocyana~e. After 24 hours at 20C, the mixture is evaporated and the residue recrystallized in 50 ml ethanol. Obtained are yellow crystals of (VIII) in a yield of 7.9 g; m.p. 135-137C.
Example 9 Herbicidal effectiveness of l-methyl-3-phenyl-4-thio-parabanic acid-5-imide (III) The herbicidal effectiveness of this compound according to the invention was tested with a single application in green houses. In the test described, first the seed grains of the cultured plants and of the weeds were sown in arable soîl rich in minerals and poor in humus, and then lightly covered with soil particles. Immediately after the sowing (and, in any case before germination of the seeds in the soil), the effective compound according to the învention was evenly sprayed onto the surface Eree of vegetation, by means of spraying powders or emulsion concentrates. Four weeks later, the plants were finally evaluated as to damage or destruction, while untreated control plants, which had grown up in the meanwhile, served as a reference.
5~ 8~
Effectiveness in % with application o-f 0.5-2 kg/ha of active substance in the pre-emergence process is shown in the table below.
KG/HA ACTIVE SUBSTA~CE
0.5 1.0 2.0 Useful Plants Cotton 0 0 10 Sorghum millet 0 0 20 Corn 0 0 10 Lucerne 0 0 lO
Peas 0 10 20 Common beans 10 30 40 Dicotyledonous Weeds Sinapis arvensis 98 100 100 Chenopodium album 75 95 98 Chrysanthemum segetum 100 100 100 Galinsoga parviflora 85 100 100 Centaurea cyanus 30 75 98 Stellaria media 100 100 100 Polygonum persicaria 75 95 100 Galium aparine 85 95 98 Amaranthus retroflexus 100 lO0 100 Lamium purpureum 75 100 100 Senecio vulgaris 30 75 100 Capsella bursa-pastoris 95 98 100 Matricaria inodora 100 100 100 Weed Grasses Poa annua 100 100 100 Alopecurus myosuroides 95 98 100 Avena fatua 95 98 100 Digitaria sanguinalis 98 100 100 Echinochloa crus-galli 85 98 100 5~
Example 10 Herbicidal effectiveness of l-methyl-3-p-chlorophenyl-4-thioparabanic acid-5-imide The effective agent is tested in an analogous manner to ~xample 9 in the pre-emergence process.
Effectiveness in % with amounts of 0.5-2 kg/ha active substance in the pre-emergence process:
KG/HA ACTIVE SUBSTANCE
0.5 1.0 2.0 Useful Plants Cotton 0 0 10 Sorghum millet 0 0 0 Corn 0 0 0 Lucerne 0 10 20 Dicotyledonous Weeds Sinapis arvensis 85 100 100 Chenopodium album 80 95 100 Chrysanthemum segetum 95 100 1.00 Galinsoga parviflora 98 100 100 Centaurea cyanus 70 85 100 Stellaria media 90 98 100 Amaranthus retroflexus 60 100 100 Capsella bursa-pastoris 100 100 100 Matricaria inodora 98 100 100 Solanum nigrum 80 98 100 Viola tricolor 85 98 100 - 1~ -5~l18~
KG / HA ACT I VE SUB STANCE
0.5 1.0 2.0 Weed Grasses Poa annua 95 100 100 Alopecurus myosuroides85 95 100 Avena fatua 50 95 100 Setaria viridis 70 100 100 Apera spica-venti 100 100 100 Example 11 Herbicidal effectiveness of l-methyl-3-(3',4'-dichloro-phenyl)-4-thioparabanic acid-5-imide The ef~ective agent is tested in an analagous manner to Example 9 in the pre-emergence process.
Effectiveness in % with amounts at 1-4 kg/ha active substance:
KG/HA ACTIVE SUBSTA~CE
1.0 2.0 4.0 20 Useful Plants _ _ Sorghum-millet 0 0 0 Corn 0 0 0 Lucerne 0 0 10 Summer barley 0 0 10 Dicotyledonous Weeds Chenopodium album 100 100 100 Chrysanthemum segetum 98 100 100 Galinsoga parviflora 98 100 100 Stellaria media 90 100 100 Amaranthus retroflexus 60 100 100 ~s~
KG/HA ACTIVE SUBSTANCE
1.0 2.0 4.0 Capsella bursa-pastoris 100 100 100 Matricaria inodora 90 100 100 Solanum nigrum 100 100 100 Viola tricolor 75 100 100 Weed Grasses Poa annua 98 100 100 Setaria viridis 85 95 100 Apera spica-venti 95 100 100 Comparison Example 2 For purposes of comparison, a commercial herbicide of the urea group, e.g, Afalon with the effective agent Linuron [3-(3,4-dichlorophenyl)-1-methoxy-1-methyl-urea] was tested. Otherwise, the procedure was the same as followed in Example 9.
Effectiveness in % when applying from 0.5-2.0 kg/ha active substance in the pre-emergence process:
LINURON (AFALON) KG/HA ACTIVE SUBSTANCE
0.5 1.0 2.0 Useful Plants Winter-wheat O 10 50 Cotton O 0 10 Sorghum-millet 0 20 70 Corn O 10 40 Lucerne 95 100 100 Peas 0 40 70 Common beans 10 70 100 - 18 ~
~S~
NURON (AFALON) KG/HA ACTI~lE SUBSTANCE
0.5 1.0 2.0 Dicotyledonous Weeds Sinapis arvensis 98 100 100 Ghenopodium album 70 95 98 Chrysanthemum segetum 85 98 100 Galinsoga parviflora 98 100 100 10 Centaurea cyanus 0 3U 70 Stellaria med ia 100 100 100 Polygonum persicaria 50 95 100 Galium aparine 35 45 50 Amaranthus retroflexus 100 100 100 Lamium purpureurn 90 98 100 Senecio vulgaris 30 80 98 Capsella bursa-pastoris 98 98 100 Matricaria inodora 95 100 100 Weed Grasses Poa annua 70 80 95 Alopecurus myosuroides 60 70 85 Avena fatua 40 50 80 Digitaria sanguinalis 70 80 95 Echinochloa crus-galli 80 95 100 The comparison of the results of Examples 9, 10 and 11 with Comparison Example 2, shows the improved compatibility with useful plants of the act-ive agents according to the invention, especially in the group of the fami].y leguminosae, a.s compared to the standard herbicide.
The herbicide superiority is also remarkable especia]ly against weed grasses and cleavers, where the compounds according to the invention are of exceedingly high activity.
_ 19 _ Comparison Example 3 In a further test series, comparison was made with the commercial product Lasso having an active agent Alachlor [2'-chloro-2,6-diethyl-N-(methoxymethyl)-acetanilide].
Otherwise, the procedure was the same as followed in Example 9.
Effectiveness in % with application of 0.5-2 kg/ha of active substance in the pre-emergence process:
LASSO (ALACHLOR) KG/HA ACTIVE SUBSTANCE
0.5 1.0 2.0 Useful Plants Corn 0 10 30 ':
Sorghum-millet 85 98 100 Dicotyledonous Weeds . :
Stellaria media 40 60 75 Galium aparine 0 10 20 Centaurea cyanus 0 20 40 Chrysanthemum segetum 0 30 70 Senecio vulgaris 20 40 75 Raphanus raphanistrum 0 10 20 Weed Grasses Avena fatua 60 70 85 Alopecurus myosuroides 50 6~ 98 Comparison of the results of Examples 9, 10 and 11 with Comparison Example 3 show a considerably improved effectiveness of the compounds according to the invention, particularly in combating the dicotyledonous plants with comparable tolerance to corn and even decisively improved compatibility with sorghum-millet.
Example 12 Herbicidal effectiveness of l-methyl~3-p-chlorophenyl-4-thioparabanic acid 5-imide The possibilities of application of the compound according to the invention in the post-emergence process (application to the leaves of the plants) were tested in a further test series in the greenhouse. In this process, the effective agent was sprayed onto the plants which had reached a certain growth: in dicotyledonous plants in addition to the primary cotyledons, the first, genuine pair of leaves was developed; and in monocotyledonous plants, at least two leaves were formed.
The treated plants were evaluated for the last time after 1~ days of spraying for damage and destruction.
Herbicidal effectiveness in % at 1.2 and 4 kg/ha application of active substance in the post-emergence process:
KG/HA ACTIVE SUBSTANCE
Useful Plants Summer Barley 0 0 20 Corn o o Q
Sorghum-millet 0 0 20 Lucerne Q lQ 20 Dicotyledonous Weeds Stellaria media 75 9~ 100 Chrysanthemum segetum 50 95 lQQ
Galinsoga pa-rviflora 60 98 lQ0 5~
KG/HA ACTIVE SUBSTANCE
Senecio vulgaris . 50 70 98 Capsella bursa-pastoris 95 100 100 Chenopodium album 90 98 100 Solanum nigrum 75 90 100 Polygonum persicaria 60 85 98 Weed Grasses Poa annua 70 98 100 Apera spica-venti 70 95 100 Example 13 Herbicidal effectiveness of l-methyl-3-(3',4'-dichloro-phenyl)-4-thioparabanic acid-5-imide in the post-emergence process The effective agent is tested in an analogous manner to Example 12 in the post-emergence process.
Herbicidal effectiveness in % with application of 0.5-2 kg/ha of active substance in the post-emergence process:
KG/HA ACTIVE SUBSTANCE
0.5 1 2 -Useful Plants Summer Barley 0 0 0 Corn 0 0 0 Sorghum-millet 0 0 0 Lucerne 0 0 20 5~
K(,/}IA ACT[VLI, SUBSTANC~
0.5 l 2 Dicotyledonou~s Weec]s . . .
Stellaria media 80 95 100 Chrysanthemum segetum 90 98 100 Galin~oga parvif.Lora 85 90 98 Centaurea cyanus 60 95 98 Capsella bursa-pastoris 95 :L00 100 Chenopodium alburn 98 100 100 Solanum nigrum 75 80 100 Polygonum persicaria 95 98 100 Amaranthus retroflexus 95 100 100 Galium aparine 70 85 95 Thus, while only several examples of the present invention have been shown and describecl, it will be obvious that many changes and modi~ications may be made thereunto, without departing from the spirit and scope of the invention.
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Example 9 Herbicidal effectiveness of l-methyl-3-phenyl-4-thio-parabanic acid-5-imide (III) The herbicidal effectiveness of this compound according to the invention was tested with a single application in green houses. In the test described, first the seed grains of the cultured plants and of the weeds were sown in arable soîl rich in minerals and poor in humus, and then lightly covered with soil particles. Immediately after the sowing (and, in any case before germination of the seeds in the soil), the effective compound according to the învention was evenly sprayed onto the surface Eree of vegetation, by means of spraying powders or emulsion concentrates. Four weeks later, the plants were finally evaluated as to damage or destruction, while untreated control plants, which had grown up in the meanwhile, served as a reference.
5~ 8~
Effectiveness in % with application o-f 0.5-2 kg/ha of active substance in the pre-emergence process is shown in the table below.
KG/HA ACTIVE SUBSTA~CE
0.5 1.0 2.0 Useful Plants Cotton 0 0 10 Sorghum millet 0 0 20 Corn 0 0 10 Lucerne 0 0 lO
Peas 0 10 20 Common beans 10 30 40 Dicotyledonous Weeds Sinapis arvensis 98 100 100 Chenopodium album 75 95 98 Chrysanthemum segetum 100 100 100 Galinsoga parviflora 85 100 100 Centaurea cyanus 30 75 98 Stellaria media 100 100 100 Polygonum persicaria 75 95 100 Galium aparine 85 95 98 Amaranthus retroflexus 100 lO0 100 Lamium purpureum 75 100 100 Senecio vulgaris 30 75 100 Capsella bursa-pastoris 95 98 100 Matricaria inodora 100 100 100 Weed Grasses Poa annua 100 100 100 Alopecurus myosuroides 95 98 100 Avena fatua 95 98 100 Digitaria sanguinalis 98 100 100 Echinochloa crus-galli 85 98 100 5~
Example 10 Herbicidal effectiveness of l-methyl-3-p-chlorophenyl-4-thioparabanic acid-5-imide The effective agent is tested in an analogous manner to ~xample 9 in the pre-emergence process.
Effectiveness in % with amounts of 0.5-2 kg/ha active substance in the pre-emergence process:
KG/HA ACTIVE SUBSTANCE
0.5 1.0 2.0 Useful Plants Cotton 0 0 10 Sorghum millet 0 0 0 Corn 0 0 0 Lucerne 0 10 20 Dicotyledonous Weeds Sinapis arvensis 85 100 100 Chenopodium album 80 95 100 Chrysanthemum segetum 95 100 1.00 Galinsoga parviflora 98 100 100 Centaurea cyanus 70 85 100 Stellaria media 90 98 100 Amaranthus retroflexus 60 100 100 Capsella bursa-pastoris 100 100 100 Matricaria inodora 98 100 100 Solanum nigrum 80 98 100 Viola tricolor 85 98 100 - 1~ -5~l18~
KG / HA ACT I VE SUB STANCE
0.5 1.0 2.0 Weed Grasses Poa annua 95 100 100 Alopecurus myosuroides85 95 100 Avena fatua 50 95 100 Setaria viridis 70 100 100 Apera spica-venti 100 100 100 Example 11 Herbicidal effectiveness of l-methyl-3-(3',4'-dichloro-phenyl)-4-thioparabanic acid-5-imide The ef~ective agent is tested in an analagous manner to Example 9 in the pre-emergence process.
Effectiveness in % with amounts at 1-4 kg/ha active substance:
KG/HA ACTIVE SUBSTA~CE
1.0 2.0 4.0 20 Useful Plants _ _ Sorghum-millet 0 0 0 Corn 0 0 0 Lucerne 0 0 10 Summer barley 0 0 10 Dicotyledonous Weeds Chenopodium album 100 100 100 Chrysanthemum segetum 98 100 100 Galinsoga parviflora 98 100 100 Stellaria media 90 100 100 Amaranthus retroflexus 60 100 100 ~s~
KG/HA ACTIVE SUBSTANCE
1.0 2.0 4.0 Capsella bursa-pastoris 100 100 100 Matricaria inodora 90 100 100 Solanum nigrum 100 100 100 Viola tricolor 75 100 100 Weed Grasses Poa annua 98 100 100 Setaria viridis 85 95 100 Apera spica-venti 95 100 100 Comparison Example 2 For purposes of comparison, a commercial herbicide of the urea group, e.g, Afalon with the effective agent Linuron [3-(3,4-dichlorophenyl)-1-methoxy-1-methyl-urea] was tested. Otherwise, the procedure was the same as followed in Example 9.
Effectiveness in % when applying from 0.5-2.0 kg/ha active substance in the pre-emergence process:
LINURON (AFALON) KG/HA ACTIVE SUBSTANCE
0.5 1.0 2.0 Useful Plants Winter-wheat O 10 50 Cotton O 0 10 Sorghum-millet 0 20 70 Corn O 10 40 Lucerne 95 100 100 Peas 0 40 70 Common beans 10 70 100 - 18 ~
~S~
NURON (AFALON) KG/HA ACTI~lE SUBSTANCE
0.5 1.0 2.0 Dicotyledonous Weeds Sinapis arvensis 98 100 100 Ghenopodium album 70 95 98 Chrysanthemum segetum 85 98 100 Galinsoga parviflora 98 100 100 10 Centaurea cyanus 0 3U 70 Stellaria med ia 100 100 100 Polygonum persicaria 50 95 100 Galium aparine 35 45 50 Amaranthus retroflexus 100 100 100 Lamium purpureurn 90 98 100 Senecio vulgaris 30 80 98 Capsella bursa-pastoris 98 98 100 Matricaria inodora 95 100 100 Weed Grasses Poa annua 70 80 95 Alopecurus myosuroides 60 70 85 Avena fatua 40 50 80 Digitaria sanguinalis 70 80 95 Echinochloa crus-galli 80 95 100 The comparison of the results of Examples 9, 10 and 11 with Comparison Example 2, shows the improved compatibility with useful plants of the act-ive agents according to the invention, especially in the group of the fami].y leguminosae, a.s compared to the standard herbicide.
The herbicide superiority is also remarkable especia]ly against weed grasses and cleavers, where the compounds according to the invention are of exceedingly high activity.
_ 19 _ Comparison Example 3 In a further test series, comparison was made with the commercial product Lasso having an active agent Alachlor [2'-chloro-2,6-diethyl-N-(methoxymethyl)-acetanilide].
Otherwise, the procedure was the same as followed in Example 9.
Effectiveness in % with application of 0.5-2 kg/ha of active substance in the pre-emergence process:
LASSO (ALACHLOR) KG/HA ACTIVE SUBSTANCE
0.5 1.0 2.0 Useful Plants Corn 0 10 30 ':
Sorghum-millet 85 98 100 Dicotyledonous Weeds . :
Stellaria media 40 60 75 Galium aparine 0 10 20 Centaurea cyanus 0 20 40 Chrysanthemum segetum 0 30 70 Senecio vulgaris 20 40 75 Raphanus raphanistrum 0 10 20 Weed Grasses Avena fatua 60 70 85 Alopecurus myosuroides 50 6~ 98 Comparison of the results of Examples 9, 10 and 11 with Comparison Example 3 show a considerably improved effectiveness of the compounds according to the invention, particularly in combating the dicotyledonous plants with comparable tolerance to corn and even decisively improved compatibility with sorghum-millet.
Example 12 Herbicidal effectiveness of l-methyl~3-p-chlorophenyl-4-thioparabanic acid 5-imide The possibilities of application of the compound according to the invention in the post-emergence process (application to the leaves of the plants) were tested in a further test series in the greenhouse. In this process, the effective agent was sprayed onto the plants which had reached a certain growth: in dicotyledonous plants in addition to the primary cotyledons, the first, genuine pair of leaves was developed; and in monocotyledonous plants, at least two leaves were formed.
The treated plants were evaluated for the last time after 1~ days of spraying for damage and destruction.
Herbicidal effectiveness in % at 1.2 and 4 kg/ha application of active substance in the post-emergence process:
KG/HA ACTIVE SUBSTANCE
Useful Plants Summer Barley 0 0 20 Corn o o Q
Sorghum-millet 0 0 20 Lucerne Q lQ 20 Dicotyledonous Weeds Stellaria media 75 9~ 100 Chrysanthemum segetum 50 95 lQQ
Galinsoga pa-rviflora 60 98 lQ0 5~
KG/HA ACTIVE SUBSTANCE
Senecio vulgaris . 50 70 98 Capsella bursa-pastoris 95 100 100 Chenopodium album 90 98 100 Solanum nigrum 75 90 100 Polygonum persicaria 60 85 98 Weed Grasses Poa annua 70 98 100 Apera spica-venti 70 95 100 Example 13 Herbicidal effectiveness of l-methyl-3-(3',4'-dichloro-phenyl)-4-thioparabanic acid-5-imide in the post-emergence process The effective agent is tested in an analogous manner to Example 12 in the post-emergence process.
Herbicidal effectiveness in % with application of 0.5-2 kg/ha of active substance in the post-emergence process:
KG/HA ACTIVE SUBSTANCE
0.5 1 2 -Useful Plants Summer Barley 0 0 0 Corn 0 0 0 Sorghum-millet 0 0 0 Lucerne 0 0 20 5~
K(,/}IA ACT[VLI, SUBSTANC~
0.5 l 2 Dicotyledonou~s Weec]s . . .
Stellaria media 80 95 100 Chrysanthemum segetum 90 98 100 Galin~oga parvif.Lora 85 90 98 Centaurea cyanus 60 95 98 Capsella bursa-pastoris 95 :L00 100 Chenopodium alburn 98 100 100 Solanum nigrum 75 80 100 Polygonum persicaria 95 98 100 Amaranthus retroflexus 95 100 100 Galium aparine 70 85 95 Thus, while only several examples of the present invention have been shown and describecl, it will be obvious that many changes and modi~ications may be made thereunto, without departing from the spirit and scope of the invention.
L ~-,T~C . ~ !~T`~!~ T~ LT ~.r ~ a~ f L'.~'::~LL .~LLU~ ~S~ r~ ~!.e~ .~ UL~L ~ C~ ~."~L ~LL7"~
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the formula in which R denotes a phenyl- or a naphthyl-group, optionally substituted in single or multiple substitution in o-, m- or p-position by substituents selected from the group consisting of saturated or unsaturated alkyl having from 1-20 carbon atoms, methoxy, ethoxy, allyloxy, crotylmercapto, carboxymethyl, carboxyethyl, carboxypropyl, methylsulfonato, ethylsulfonato, halogen, nitro and nitrile.
2. A process for preparing a compound of the formula in which R denotes a phenyl- or a naphthyl-group, optionally substituted in single or multiple substitution in o-, m- or p-position by substituents selected from the group consisting of saturated or unsaturated alkyl having from 1-20 carbon atoms, methoxy, ethoxy, allyloxy, crotylmercapto, carboxymethyl, carboxyethyl, carboxypropyl, methylsulfonato, ethylsulfonato, halogen, nitro and nitrile, comprising the steps of:
reacting a thio-oxanilic acid-nitrile of the formula wherein R has the meaning above with methylisocyanate.
reacting a thio-oxanilic acid-nitrile of the formula wherein R has the meaning above with methylisocyanate.
3. The process according to Claim 2, additionally comprising the step of adding a solvent promoting cyclization during said reacting step.
4. The process according to Claim 3, additionally comprising the step of adding a solvent promoting cyclization after said reacting step.
5. A method for combatting weeds and weed grasses by applying to the area to be controlled a herbicidal effective amount of a compound of the formula in which R denotes a phenyl- or a naphthyl-group, optionally substituted in single or multiple substitution in o-, m- or p-position by substituents selected from the group consisting of saturated or unsaturated alkyl having from 1-20 carbon atoms, methoxy, ethoxy, allyloxy, crotylmercapto, carboxymethyl, carboxyethyl, carboxypropyl, methylsulfonato, ethylsulfonato, halogen, nitro and nitrile.
6. The method according to Claim 5, wherein said application is carried out on said weeds and weed grasses.
7. The method according to Claim 5, wherein said application is carried out on soil free of vegetation.
8. The method according to Claim 5, wherein said compound is applied in an amount of 0.5 - 8. n kg/ha.
9. The method according to Claim 5, wherein said compound is applied in an amount of 0.5 - 2.0 kg/ha.
10. The method according to Claim 5, wherein said compound is applied in an amount of 0.5 - 1.0 kg/ha.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803000130 DE3000130A1 (en) | 1980-01-04 | 1980-01-04 | 4-THIOPARABANIC ACID DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS AN HERBICIDE AGENT |
| DEP3000130.0 | 1980-01-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1151184A true CA1151184A (en) | 1983-08-02 |
Family
ID=6091504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000367841A Expired CA1151184A (en) | 1980-01-04 | 1981-01-02 | 4-thioparabanic acid derivatives, process of preparing the same, and use as herbicides |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0032366B1 (en) |
| JP (1) | JPS56100767A (en) |
| AT (1) | ATE4594T1 (en) |
| CA (1) | CA1151184A (en) |
| DE (2) | DE3000130A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1618240B1 (en) | 2003-05-01 | 2006-08-30 | Johnson and Johnson GmbH | Patterned sheet products |
| JP5350217B2 (en) * | 2006-03-29 | 2013-11-27 | ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア | Diarylthiohydantoin compounds |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3854925A (en) * | 1971-05-12 | 1974-12-17 | Chevron Res | 1,3-disubstituted-5-(substituted thio) imino-2,4-imidazolidine diones and the 4-thio analogs |
| US3843677A (en) * | 1972-05-08 | 1974-10-22 | Chevron Res | 5-chlorothioimino imidazolidines |
-
1980
- 1980-01-04 DE DE19803000130 patent/DE3000130A1/en not_active Withdrawn
- 1980-12-26 JP JP18418280A patent/JPS56100767A/en active Pending
-
1981
- 1981-01-02 EP EP81100004A patent/EP0032366B1/en not_active Expired
- 1981-01-02 AT AT81100004T patent/ATE4594T1/en active
- 1981-01-02 DE DE8181100004T patent/DE3160824D1/en not_active Expired
- 1981-01-02 CA CA000367841A patent/CA1151184A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3160824D1 (en) | 1983-10-13 |
| EP0032366A1 (en) | 1981-07-22 |
| ATE4594T1 (en) | 1983-09-15 |
| JPS56100767A (en) | 1981-08-12 |
| DE3000130A1 (en) | 1981-07-09 |
| EP0032366B1 (en) | 1983-09-07 |
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| MKEX | Expiry | ||
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Effective date: 20000802 |