CA1100987A - Herbicidally active carbanilic acid esters - Google Patents
Herbicidally active carbanilic acid estersInfo
- Publication number
- CA1100987A CA1100987A CA276,170A CA276170A CA1100987A CA 1100987 A CA1100987 A CA 1100987A CA 276170 A CA276170 A CA 276170A CA 1100987 A CA1100987 A CA 1100987A
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- CA
- Canada
- Prior art keywords
- compound
- acid
- ester
- protecting
- treated
- 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
-
- 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
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
-
- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
- C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/32—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C271/38—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of rings other than six-membered aromatic rings with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
-
- 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
- A01N2300/00—Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention provides herbicidally active carbanilic acid esters of the general formula I
The present invention provides herbicidally active carbanilic acid esters of the general formula I
Description
The present invention relates to herbicidally active carbanilic acid esters, with a process for the manufacture of these compounds and with their use.
It has been known that certain carbanilic acid esters, for e~ample carbanilic acid isopropyl ester and 3-chlorocarbanilic acid isopropyl es-ter, are herbicidally active (German Patent : Specification No. 833,274). However, these compounds do not act satisfactorily at low ra~es of application against dicotyle-donous weeds and also have the disadvantage of a very limited selectivity towards crop pIants.
The problem upon which the present invention is based has, therefore, been to provide an agent of the type referred to, which has a strong herbicidal action against dicotyledonous weeds even at low rates of application and al.so.good selective properties.
This problem has now been solved in accordance with the present invention by the compounds of the general formula I, as defined below.
I'he present invention accordingly provides compounds of the general formula I
~N
Xn ~ H-CO-OR (I) in which R represents an aliphatic or cycloaliphatic hydrocarbon group, ~ represents an alkyl or alkoxy group or a halogen atom and n represents 0 or 1. .
The co~pounds of the present invention are distinguished by an outstanding herbicidal action against dicotyledonous and ~, , 9~7 also agains-t monocotyledonous weeds (including certain undesired plants not normally considered as weeds) amongst which there ¦
may be mentioned, for example, Stellaria media, Senecio Vulgaris, I
Matricarla chamomilla, Lamium amplexicaule, Centaurea cyanus, Amaranthus ret oflexus, Galium aparine, Chrysanthemum segetum, Ipomoea purpurea, Poly~onum lapathi-folium, Avena fatua, Alopecurus myosuroides, Echinochloa crus galli, Setaria italica, Digitaria sanguinal_s and Poa annua. : ;
Owing to their excellent selective properties these compounds can be used directly in agricultural crops amongst which there may be mentioned, for example, lucerne, bus~-beans, cotton, soya beans, ground-nut and wheat crops.
It has also been found that the compounds o the present invention have in a narrower sense a defoliating. action and growth regulating properties.
The compounds of the present invention act satisfactor-ily even at rates of application from 0.5 kg per hectare and, depending on the purpose of use, can be applied without damaging crops of useful plants at up to 5 kg per hectare or more both by pre-emergence and also by post-emergence methods. When two or more compounds of the general formula I are used the rat~s of 0.5 kg and 5 kg o.r more refer oE course to the total amount applied of these compounds. ~-:
The present invention also provides a herbicidal prep-aration which comprises a compound of the general formula I, inladmixture or conjunction with a suitable carrier. The preparation may of course contain one or more compounds of the general formula I.
The present invention further provides a method of protecti.ng a living plant against weeds, wherein this area in the vicinity of a living plant is treated with a compound of the general formula I.
, The present invention further provides a method of protecting a crop area against weeds, wherein a crop area is treated with a compound of the general formula I.
The present invention further provides a pack which ~;
comprises a compound of the general formula I together with instructions for its use as a selective herbicide. ¦~
The compounds of the present invention can be used either alone, or in admixture with one another or with other acti~e substances.
Depending on the purpose desired there may be mentioned in this connection, for example, the following herbicidally active substances, which, if desired, may be added to the compounds of the present invention immediately be~ore use:
substituted anilines, substituted aryloxy-carboxylic acids and also salts, esters and amides thereof, substituted ethers, substituted arsonic acids and also salts, esters and amides thereof, substituted benzimidazoles, substituted benzisothiazoles, substituted benzthiadiazinone dioxidesj substituted benzoxazines, substituted benzoxazinones, substituted benzthiazoles, substituted
It has been known that certain carbanilic acid esters, for e~ample carbanilic acid isopropyl ester and 3-chlorocarbanilic acid isopropyl es-ter, are herbicidally active (German Patent : Specification No. 833,274). However, these compounds do not act satisfactorily at low ra~es of application against dicotyle-donous weeds and also have the disadvantage of a very limited selectivity towards crop pIants.
The problem upon which the present invention is based has, therefore, been to provide an agent of the type referred to, which has a strong herbicidal action against dicotyledonous weeds even at low rates of application and al.so.good selective properties.
This problem has now been solved in accordance with the present invention by the compounds of the general formula I, as defined below.
I'he present invention accordingly provides compounds of the general formula I
~N
Xn ~ H-CO-OR (I) in which R represents an aliphatic or cycloaliphatic hydrocarbon group, ~ represents an alkyl or alkoxy group or a halogen atom and n represents 0 or 1. .
The co~pounds of the present invention are distinguished by an outstanding herbicidal action against dicotyledonous and ~, , 9~7 also agains-t monocotyledonous weeds (including certain undesired plants not normally considered as weeds) amongst which there ¦
may be mentioned, for example, Stellaria media, Senecio Vulgaris, I
Matricarla chamomilla, Lamium amplexicaule, Centaurea cyanus, Amaranthus ret oflexus, Galium aparine, Chrysanthemum segetum, Ipomoea purpurea, Poly~onum lapathi-folium, Avena fatua, Alopecurus myosuroides, Echinochloa crus galli, Setaria italica, Digitaria sanguinal_s and Poa annua. : ;
Owing to their excellent selective properties these compounds can be used directly in agricultural crops amongst which there may be mentioned, for example, lucerne, bus~-beans, cotton, soya beans, ground-nut and wheat crops.
It has also been found that the compounds o the present invention have in a narrower sense a defoliating. action and growth regulating properties.
The compounds of the present invention act satisfactor-ily even at rates of application from 0.5 kg per hectare and, depending on the purpose of use, can be applied without damaging crops of useful plants at up to 5 kg per hectare or more both by pre-emergence and also by post-emergence methods. When two or more compounds of the general formula I are used the rat~s of 0.5 kg and 5 kg o.r more refer oE course to the total amount applied of these compounds. ~-:
The present invention also provides a herbicidal prep-aration which comprises a compound of the general formula I, inladmixture or conjunction with a suitable carrier. The preparation may of course contain one or more compounds of the general formula I.
The present invention further provides a method of protecti.ng a living plant against weeds, wherein this area in the vicinity of a living plant is treated with a compound of the general formula I.
, The present invention further provides a method of protecting a crop area against weeds, wherein a crop area is treated with a compound of the general formula I.
The present invention further provides a pack which ~;
comprises a compound of the general formula I together with instructions for its use as a selective herbicide. ¦~
The compounds of the present invention can be used either alone, or in admixture with one another or with other acti~e substances.
Depending on the purpose desired there may be mentioned in this connection, for example, the following herbicidally active substances, which, if desired, may be added to the compounds of the present invention immediately be~ore use:
substituted anilines, substituted aryloxy-carboxylic acids and also salts, esters and amides thereof, substituted ethers, substituted arsonic acids and also salts, esters and amides thereof, substituted benzimidazoles, substituted benzisothiazoles, substituted benzthiadiazinone dioxidesj substituted benzoxazines, substituted benzoxazinones, substituted benzthiazoles, substituted
2~ benzthiadiazoles, substituted biurets, substituted quinolines, substituted carbamates, substituted aliphatic carboxylic acids and also salts, esters and amides thereof, substituted aromatic carboxylic acids and also salts, esters and amides thereof, .
substituted carbamoylalkyl-thio- or dithio-phosphates, substituted quinazolines substituted cycloalkylamidocarbonthiolic acids and also salts, esters and amides thereof, substituted cycloalkyl-carbonamido-thiazoles, substituted dicarboxylic acids and also salts, esters and àmides thereof, substituted dihydrobenzofuranyl- ~;
sulphonates, substituted disulphides, substituted dipyridylium salts, substituted dithiocarbamates, substituted dithiophospho~ic acids and also salts, esters and amides thereof, substituted ureas, substituted hexahydro-lH-carbothioates, substituted .
substituted carbamoylalkyl-thio- or dithio-phosphates, substituted quinazolines substituted cycloalkylamidocarbonthiolic acids and also salts, esters and amides thereof, substituted cycloalkyl-carbonamido-thiazoles, substituted dicarboxylic acids and also salts, esters and àmides thereof, substituted dihydrobenzofuranyl- ~;
sulphonates, substituted disulphides, substituted dipyridylium salts, substituted dithiocarbamates, substituted dithiophospho~ic acids and also salts, esters and amides thereof, substituted ureas, substituted hexahydro-lH-carbothioates, substituted .
- 3 -Q~ 7 hydantoins, substituted hydraziedes, substituted hydrazonium salts, substituted isoxazolepyrimidones, substituted imidazoles, substituted isothiazole-pyrimidones, substituted ketones, substituted naphthoquinones, substituted aliphatic nitriles, substituted aromatic nitriles, substituted oxadiazoles, substituted oxadiazinones, substituted oxadiazolidine-diones, substituted oxadiazine-diones, substituted phenols and also ~
salts and esters thereof, substituted phosphonic acids and also .
salts, esters and am.ides thereof, substituted phosphonium chlorides, substituted phosphonalkylglycines, substituted ~:
phosphites, substituted phosphoric acids and also salts, esters ;:
and amides thereoE, substituted piperidines, substituted pyrazoles, substituted pyrazole-alkyl-carboxylic acids and also : :
salts, esters and amides thereof, substituted pyrazolium salts, substituted pyrazolium alkyl sulphates, substituted pyridazines, substituted pyridazones, substituted pyridine caxboxylic acids and also salts, esters and amides thereofj substituted pyridines, ~ ;.
substituted pyridine carboxylates, substituted pyridinones, ~ substituted pyrimidones, substituted pyrrolidine carboxylic acids and also salts, esters and amides thereof, substituted ~
pyrrolidines, substituted aryl sulphonic acids and also salts, .
esters and amides thereof, substituted styrols, substituted tetrahydro-oxadiazine-diones, substituted tetrahydromethanoindenes, substituted tetrahydro-diazole-thiones, substituted tetrahydro-thiacliazine-thiones, substituted tetrahydro-thiadiazole-diones, substituted thiadiazoles, substituted aromatic thiocarboxylic acid amides, substituted thiocarboxylic acids and also salts, esters and amides thereof, substituted thiolcarbamates, substituted thiophosphoric acids and also salts, esters and amides thereof !
substituted triazines, substituted triazoles, substituted uracils and substituted uretidine-diones. .
Furthermore, other additives may also be used, for .
salts and esters thereof, substituted phosphonic acids and also .
salts, esters and am.ides thereof, substituted phosphonium chlorides, substituted phosphonalkylglycines, substituted ~:
phosphites, substituted phosphoric acids and also salts, esters ;:
and amides thereoE, substituted piperidines, substituted pyrazoles, substituted pyrazole-alkyl-carboxylic acids and also : :
salts, esters and amides thereof, substituted pyrazolium salts, substituted pyrazolium alkyl sulphates, substituted pyridazines, substituted pyridazones, substituted pyridine caxboxylic acids and also salts, esters and amides thereofj substituted pyridines, ~ ;.
substituted pyridine carboxylates, substituted pyridinones, ~ substituted pyrimidones, substituted pyrrolidine carboxylic acids and also salts, esters and amides thereof, substituted ~
pyrrolidines, substituted aryl sulphonic acids and also salts, .
esters and amides thereof, substituted styrols, substituted tetrahydro-oxadiazine-diones, substituted tetrahydromethanoindenes, substituted tetrahydro-diazole-thiones, substituted tetrahydro-thiacliazine-thiones, substituted tetrahydro-thiadiazole-diones, substituted thiadiazoles, substituted aromatic thiocarboxylic acid amides, substituted thiocarboxylic acids and also salts, esters and amides thereof, substituted thiolcarbamates, substituted thiophosphoric acids and also salts, esters and amides thereof !
substituted triazines, substituted triazoles, substituted uracils and substituted uretidine-diones. .
Furthermore, other additives may also be used, for .
- 4 -7 I ~
.
example non-phytotoxic additives, which impart to herbicides a synergistic increase in action, for example wetting agents, `
emulsifiers, solvents and oily additives.
Advantageously, the active compounds o the yeneral formula I or mixtures containing them are used in the form of herbicidal preparations, for example, powders, strewable preparations, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid vehicles or diluents, and, if desired, of surface-active agents, for example wetting 1~ adherent, emulsifying and/or dispersing agents.
Suitable liquid carriers are, for example, water, aliphatic hydrocarbons, aromatic hydrocarbons, for example benzene, toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide and dimethylformamide, and also mineral oil fractions. :
As solid carriers there are suitable, for example, mineral earths, for example tonsil, silica gel, talcum, kaolin, attaclay, limestone and silicic acid, and vegetable products, for example meals.
As surface-active agents there may be mentioned, .;
for example, ca.Lcium lignin sulphonate, polyoxyethylene-alkyl-phenyl ethers, naphthalene sulphonic acids and salts thereof, phenol sulphonic acids and salts thereof, formaldehyde condensates, .
fatty alcohol sulphates and also substituted henzene sulphonic acids and salts thereof. ::
The total amount of the ac-tive substance or substances in the various herbicidal preparations may vary within wide .
limits. By way of example, the preparations may contain approximately 10 to ~0% by weight of active compound(s), approximately 90 to 20% by weight of liquid or solid carrier and also, iE desired, up to 20~ by weight of surface-active agen-t(s). .
.
example non-phytotoxic additives, which impart to herbicides a synergistic increase in action, for example wetting agents, `
emulsifiers, solvents and oily additives.
Advantageously, the active compounds o the yeneral formula I or mixtures containing them are used in the form of herbicidal preparations, for example, powders, strewable preparations, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid vehicles or diluents, and, if desired, of surface-active agents, for example wetting 1~ adherent, emulsifying and/or dispersing agents.
Suitable liquid carriers are, for example, water, aliphatic hydrocarbons, aromatic hydrocarbons, for example benzene, toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide and dimethylformamide, and also mineral oil fractions. :
As solid carriers there are suitable, for example, mineral earths, for example tonsil, silica gel, talcum, kaolin, attaclay, limestone and silicic acid, and vegetable products, for example meals.
As surface-active agents there may be mentioned, .;
for example, ca.Lcium lignin sulphonate, polyoxyethylene-alkyl-phenyl ethers, naphthalene sulphonic acids and salts thereof, phenol sulphonic acids and salts thereof, formaldehyde condensates, .
fatty alcohol sulphates and also substituted henzene sulphonic acids and salts thereof. ::
The total amount of the ac-tive substance or substances in the various herbicidal preparations may vary within wide .
limits. By way of example, the preparations may contain approximately 10 to ~0% by weight of active compound(s), approximately 90 to 20% by weight of liquid or solid carrier and also, iE desired, up to 20~ by weight of surface-active agen-t(s). .
- 5 -The active compounds may be applied in the usual manner, for example with water as carrier in quantities of ~ ;~
spray liquor of approximately 100 to 1000 litres per hectare.
It is also possible to use the active compounds in the so-called "low volume" and "ultra-low volume" methods and also to apply them in the form of so-called microgranules~ ¦
Among the compounds of the present invention those ¦;
of the general formula I, in which R represents an alkyl, alkenyl or alkynyl group containing up to 6 carbon atoms, X ¦
represents a methyl or methoxy group or a chlorine atom and n represents 0 or 1, are especially distinguished by an outstanding herbicidal action.
As such alkyl, alkenyl and alkynyl groups there may be mentioned, for example, methyl, ethyl, propyl,~ isopropyl, neopentyl, allyl, 2-methyl-2-propenyl, 2-propynyl and l-methyl-2-propynyl groups.
Among -the compounds o~ the present invention r 3-cyanocarbanilic acid isopropyl ester is outstanding with regard to its herbicidal selective properties.
The new compounds of the present invention of the general formula I may be prepared, for example, by the process o the present invention, as defined below~
The present invention accordingly further provides a process for the manufacture of a compound of the general formula I, wherein (aj a 3-aminobenzonitrile of the general formula fN
n~LNH2 in which X and n have the meanings given above, is reacted in the presence of an acid binding agent with a c~loroformic acid ester of the general ~ormula
spray liquor of approximately 100 to 1000 litres per hectare.
It is also possible to use the active compounds in the so-called "low volume" and "ultra-low volume" methods and also to apply them in the form of so-called microgranules~ ¦
Among the compounds of the present invention those ¦;
of the general formula I, in which R represents an alkyl, alkenyl or alkynyl group containing up to 6 carbon atoms, X ¦
represents a methyl or methoxy group or a chlorine atom and n represents 0 or 1, are especially distinguished by an outstanding herbicidal action.
As such alkyl, alkenyl and alkynyl groups there may be mentioned, for example, methyl, ethyl, propyl,~ isopropyl, neopentyl, allyl, 2-methyl-2-propenyl, 2-propynyl and l-methyl-2-propynyl groups.
Among -the compounds o~ the present invention r 3-cyanocarbanilic acid isopropyl ester is outstanding with regard to its herbicidal selective properties.
The new compounds of the present invention of the general formula I may be prepared, for example, by the process o the present invention, as defined below~
The present invention accordingly further provides a process for the manufacture of a compound of the general formula I, wherein (aj a 3-aminobenzonitrile of the general formula fN
n~LNH2 in which X and n have the meanings given above, is reacted in the presence of an acid binding agent with a c~loroformic acid ester of the general ~ormula
- 6 -Cl-CO-OR
in which R has the meaning given above, or (b) a 3-cyanophenyl isocyanate of the general formula 1 -CN
Xn ~L=c=o in which X and n have the meanings given above, is reacted with an alcohol of the general formula R-OH, in which R has the meaning given above.
The aompounds of the present invention readily dissolve in ethyl acetate, acetone and alcohol. On the other hand, they dissolve only moderately well in benzene and are practically insoluble in saturated hydrocarbons and water.
The following Examples illustrate the invention.
Examples 1 and 2 illustrate the manufacture of compounds of the general formula Iand Examples 3 to 5 illustrate the ~ossibilities of us~ of the compounds of the general formula I.
Example 1 3-Cyanocarbanillc ac d isopropyl ester.
To a mixture of 11.8 grams (0.1 mole~ of 3-aminobenzo-nitrile, 140 ml of ethyl acetate, 90 ml of water and 2.5 grams (0.053 mole) of magnesium oxide were added dropwise while stirring 13.5 grams (0.11 mole) of chloroformic acid isopropyl ester. The mixture was further stirred for 3 hours at room temperature, then the aqueous phase was acidified with dilute hYdrochloric acid, and the organic phase was washed until neutral with water. The ethyl acetate phase was separated, ~;
dried over magnesium sulphate, filtered and rotated. The crude product was recrystallized from ethyl acetate/hexane.
Yield: 15.3 grams = 75~ of the theoretical yield.
M.p.: 94 - 96~.
in which R has the meaning given above, or (b) a 3-cyanophenyl isocyanate of the general formula 1 -CN
Xn ~L=c=o in which X and n have the meanings given above, is reacted with an alcohol of the general formula R-OH, in which R has the meaning given above.
The aompounds of the present invention readily dissolve in ethyl acetate, acetone and alcohol. On the other hand, they dissolve only moderately well in benzene and are practically insoluble in saturated hydrocarbons and water.
The following Examples illustrate the invention.
Examples 1 and 2 illustrate the manufacture of compounds of the general formula Iand Examples 3 to 5 illustrate the ~ossibilities of us~ of the compounds of the general formula I.
Example 1 3-Cyanocarbanillc ac d isopropyl ester.
To a mixture of 11.8 grams (0.1 mole~ of 3-aminobenzo-nitrile, 140 ml of ethyl acetate, 90 ml of water and 2.5 grams (0.053 mole) of magnesium oxide were added dropwise while stirring 13.5 grams (0.11 mole) of chloroformic acid isopropyl ester. The mixture was further stirred for 3 hours at room temperature, then the aqueous phase was acidified with dilute hYdrochloric acid, and the organic phase was washed until neutral with water. The ethyl acetate phase was separated, ~;
dried over magnesium sulphate, filtered and rotated. The crude product was recrystallized from ethyl acetate/hexane.
Yield: 15.3 grams = 75~ of the theoretical yield.
M.p.: 94 - 96~.
- 7 -7 i~
Example 2 3-Cyanocarbanilic acid cyclopentyl ester.
A solu-tion of 7.2 grams (0.05 mole) of 3-cyanophenyl isocyanate in 50 ml of ether was added dropwise, while stirring, to a solution of 4.3 grams of (O.05 mole) of cyclopentanol and j~
0.1 ml of triethylamine in 50 ml of ether~ The reaction solution was heated to about 30C. To complete the reaction the mixture was stirred for abou~ S hours at room tempera~,ure. The solvent was then removed by rotation and the residue was recrystallized 10 ~ from methanol/water.
Yield: 9.3 grams = 8196 of the theoretical yield.
M~p.: 101 - 102C.
The following compounds of the present invention can be prepared in a manner analogous to that described in Example 1 or 2.
Name of the compound Phys~cal eonstant 3-Cyanocarbanilic acid methyl ester M.p.: 93 - 95C
3-Cyanocarbanilic acid ethyl ester M.p.: 48 - 50C
3-Cyanocarbanilic acid allyl ester M.p.: 67 - 68C
20 ~ 5-Cyano-2-methylcarbanilie aeid methyl esterM.p.:100 - 101C
5-Cyano-2-methylcarbanilie aeid ethyl ester M.p.: 96 - 97C
5-Cyano-2-methylearbanilie aeid propyl ester M.p.: 101 - 102C
5-Cyano-2-methylearbanilic aeid allyl ester M.p.: 94 - 95C
5-Cyano-2-methoxycarbanilic acid allyl ester M.p.: 90 - 91C
5-Cyano-2-methoxycarbanilic acid ethyl ester M.p.: 104 - 105C
5-Cyano-2-methoxycarbanilic acid methyl esterM.p.: 120 - 121C
5-Cyano-2-methylcarbanilic aeid isopropyl esterM.p.:127 - 128C
3-Cyanoearbanilie acid propyl ester M.p.: 38 - 39C
5-Cyano-2-methoxycarbanilic acid propyl esterM.p.: 60 - 61C
30 5-Cyano-2-methoxycarbanilic acid isopropyl esterM.p.: 111 - 112C
3-Cyanocarbanilic acid cyclohexyl ester M.p.: 72 - 74C
3-Cyanocarbanilic acid neopentyl ester M.p.: 125 - 126C
Example 2 3-Cyanocarbanilic acid cyclopentyl ester.
A solu-tion of 7.2 grams (0.05 mole) of 3-cyanophenyl isocyanate in 50 ml of ether was added dropwise, while stirring, to a solution of 4.3 grams of (O.05 mole) of cyclopentanol and j~
0.1 ml of triethylamine in 50 ml of ether~ The reaction solution was heated to about 30C. To complete the reaction the mixture was stirred for abou~ S hours at room tempera~,ure. The solvent was then removed by rotation and the residue was recrystallized 10 ~ from methanol/water.
Yield: 9.3 grams = 8196 of the theoretical yield.
M~p.: 101 - 102C.
The following compounds of the present invention can be prepared in a manner analogous to that described in Example 1 or 2.
Name of the compound Phys~cal eonstant 3-Cyanocarbanilic acid methyl ester M.p.: 93 - 95C
3-Cyanocarbanilic acid ethyl ester M.p.: 48 - 50C
3-Cyanocarbanilic acid allyl ester M.p.: 67 - 68C
20 ~ 5-Cyano-2-methylcarbanilie aeid methyl esterM.p.:100 - 101C
5-Cyano-2-methylcarbanilie aeid ethyl ester M.p.: 96 - 97C
5-Cyano-2-methylearbanilie aeid propyl ester M.p.: 101 - 102C
5-Cyano-2-methylearbanilic aeid allyl ester M.p.: 94 - 95C
5-Cyano-2-methoxycarbanilic acid allyl ester M.p.: 90 - 91C
5-Cyano-2-methoxycarbanilic acid ethyl ester M.p.: 104 - 105C
5-Cyano-2-methoxycarbanilic acid methyl esterM.p.: 120 - 121C
5-Cyano-2-methylcarbanilic aeid isopropyl esterM.p.:127 - 128C
3-Cyanoearbanilie acid propyl ester M.p.: 38 - 39C
5-Cyano-2-methoxycarbanilic acid propyl esterM.p.: 60 - 61C
30 5-Cyano-2-methoxycarbanilic acid isopropyl esterM.p.: 111 - 112C
3-Cyanocarbanilic acid cyclohexyl ester M.p.: 72 - 74C
3-Cyanocarbanilic acid neopentyl ester M.p.: 125 - 126C
- 8 -., i 7 ~:
Name of the compound Physical constant -- _ , , 3-Cyanocarbanilic acid (2-methyl-2-propenyl)ester M.p.: 75 - 76C
3-Cyanocarbanilic acid (l-methyl-2-propynyl)ester M.p.: 113 - 114C
3-Cyanocarbanilic acid 2-propynyl ester M.p.: 135 - 136C
2-Chloro-5-cyanocarbanilic acid isopropyl ester M.p.: 127 - 129C
2-Chloro-5-cyanocarbanilic acid allyl ester ~.p.: 84 - 85C
4-Chloro-3-cyanocarbanilic acid isopropyl ester M.p.: 95 - 96C
_xample 3 In a series of tests carried out in a greenhouse the compounds of the present invention listed in the following Table were sprayed over mustard, beetroots and tomatoes as test plants at the pre-emergence stage at the rate o~ 5 kg of the active substance being tested per hectare. For this purpose the active compounds were in each case applied in the form of a suspension using 500 litres of water per hectare. Three weeks after the treatment the results o~ the treatment were evaluated according to a numerical scale extending from 0 to 4, 0 representing no action and 4 representing destruction of the plants.
Compound of the invention Mustard Tomato Beetroot -3-Cyanocarbanilic acid methyl ester 4 3 -3-Cyanocarbanilic acid isopropyl ester 4 4 4 5-Cyano-2-methylcarbanilicacid ethyl ester 4 4 4 5-Cyano-2-methylcarbanilicacid methyl ester 4 4 3 5-Cyano-2-methylcarbanilicacid propyl ester 4 4 3 5 Cyano-2-methylcarballilicacid allyl ester - - 3 2-Methyl-5~yanocarbanilic acid i50propyl ester 4 4 4 3-Cyanocarbanilic acid ethyl ester 4 4 4 3-Cyanocarbanillc acid allyl ester 4 4 4 2-Chloro-5-cyanocar~lic acid isopropyl ester 4 4 3 3-Cyanocarbanilic acid propyl ester 4 4 4 2-Chloro-5~yanocarbanilic acid allyl ester 3 4 4 - means not tested _ 9 _ Example 4 In a series o~ ~ests carried out in a greenhouse the ~-plants listed in the following Table were treated before their emergence with the indicated active compounds being tested at a rate of 1 kg of active substance per hectare. For this t purpose the active compounds were in each case uniformly applied to the soil in the form of an aqueous suspension using 500 litres ¦~
per hectare. Three weeks after the treatment the results showed I ;
that the compound of the present invention was better than the agent used for comparison. The results are expressed by a .. -numerical scale extending from 0 to 10, the value 0 representing . ~' total destruction and the value 10 representing no damage. r Compound of the Agent used for invention comparison 3-Cyanocarbanilic ` 3-Chlorocarb-acid isopropyl . anilic acid ester isopropyl ester Cotton . 10 - 10 Soya 10 10 Stellaria media 0 0 Senecio vulgaris 0 8 .
Matricaria chamomilla 0 6 _ Lamium amplexicau]e 0 3 ___ Centaurea cyanus 0 8 Amaranthus retroflexus 0 2 .
Galium aparine 0 1 Chrysanthemum segetum 0 6 Ipomoea purpurea 0 3 Polygonum lapathifolium 0 0 Echinochloa crus galli 0 0 Digitaria sanguinalis 0 0 Example 5 .
In a series of tests carried out in a greenhouse the 9i~ t , i plants listed in the following Table were treated beforè their emergence with the indicated active compounds being tested at a rate of 1 kg of active substance per hectare. For this purpose the active compounds were in each case uniformly applied ,to the soil in the form of an aqueous suspension using 500 litres per hectare. Three weeks after the ~reatment the results showed that the compound of the present invention had a better selective action than the agent used for comparison~ The results are expressed by a numerical scale extending from 0 to 10, the value 0 representing total destruction and the value 10 representing no damaqe.
Compound of the Agent used for invention comparison 3-Cyanocarbanilic 3-Chlorocarbanilic acid isopropyl ~acid isopropyl ester ester Wheat 10 6 Alopecurus myosuroides 0 0
Name of the compound Physical constant -- _ , , 3-Cyanocarbanilic acid (2-methyl-2-propenyl)ester M.p.: 75 - 76C
3-Cyanocarbanilic acid (l-methyl-2-propynyl)ester M.p.: 113 - 114C
3-Cyanocarbanilic acid 2-propynyl ester M.p.: 135 - 136C
2-Chloro-5-cyanocarbanilic acid isopropyl ester M.p.: 127 - 129C
2-Chloro-5-cyanocarbanilic acid allyl ester ~.p.: 84 - 85C
4-Chloro-3-cyanocarbanilic acid isopropyl ester M.p.: 95 - 96C
_xample 3 In a series of tests carried out in a greenhouse the compounds of the present invention listed in the following Table were sprayed over mustard, beetroots and tomatoes as test plants at the pre-emergence stage at the rate o~ 5 kg of the active substance being tested per hectare. For this purpose the active compounds were in each case applied in the form of a suspension using 500 litres of water per hectare. Three weeks after the treatment the results o~ the treatment were evaluated according to a numerical scale extending from 0 to 4, 0 representing no action and 4 representing destruction of the plants.
Compound of the invention Mustard Tomato Beetroot -3-Cyanocarbanilic acid methyl ester 4 3 -3-Cyanocarbanilic acid isopropyl ester 4 4 4 5-Cyano-2-methylcarbanilicacid ethyl ester 4 4 4 5-Cyano-2-methylcarbanilicacid methyl ester 4 4 3 5-Cyano-2-methylcarbanilicacid propyl ester 4 4 3 5 Cyano-2-methylcarballilicacid allyl ester - - 3 2-Methyl-5~yanocarbanilic acid i50propyl ester 4 4 4 3-Cyanocarbanilic acid ethyl ester 4 4 4 3-Cyanocarbanillc acid allyl ester 4 4 4 2-Chloro-5-cyanocar~lic acid isopropyl ester 4 4 3 3-Cyanocarbanilic acid propyl ester 4 4 4 2-Chloro-5~yanocarbanilic acid allyl ester 3 4 4 - means not tested _ 9 _ Example 4 In a series o~ ~ests carried out in a greenhouse the ~-plants listed in the following Table were treated before their emergence with the indicated active compounds being tested at a rate of 1 kg of active substance per hectare. For this t purpose the active compounds were in each case uniformly applied to the soil in the form of an aqueous suspension using 500 litres ¦~
per hectare. Three weeks after the treatment the results showed I ;
that the compound of the present invention was better than the agent used for comparison. The results are expressed by a .. -numerical scale extending from 0 to 10, the value 0 representing . ~' total destruction and the value 10 representing no damage. r Compound of the Agent used for invention comparison 3-Cyanocarbanilic ` 3-Chlorocarb-acid isopropyl . anilic acid ester isopropyl ester Cotton . 10 - 10 Soya 10 10 Stellaria media 0 0 Senecio vulgaris 0 8 .
Matricaria chamomilla 0 6 _ Lamium amplexicau]e 0 3 ___ Centaurea cyanus 0 8 Amaranthus retroflexus 0 2 .
Galium aparine 0 1 Chrysanthemum segetum 0 6 Ipomoea purpurea 0 3 Polygonum lapathifolium 0 0 Echinochloa crus galli 0 0 Digitaria sanguinalis 0 0 Example 5 .
In a series of tests carried out in a greenhouse the 9i~ t , i plants listed in the following Table were treated beforè their emergence with the indicated active compounds being tested at a rate of 1 kg of active substance per hectare. For this purpose the active compounds were in each case uniformly applied ,to the soil in the form of an aqueous suspension using 500 litres per hectare. Three weeks after the ~reatment the results showed that the compound of the present invention had a better selective action than the agent used for comparison~ The results are expressed by a numerical scale extending from 0 to 10, the value 0 representing total destruction and the value 10 representing no damaqe.
Compound of the Agent used for invention comparison 3-Cyanocarbanilic 3-Chlorocarbanilic acid isopropyl ~acid isopropyl ester ester Wheat 10 6 Alopecurus myosuroides 0 0
Claims (51)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A carbanilic acid ester of the general formula I
(I) in which R represents an alkyl, alkenyl, alkynyl or cycloalkyl group having up to 6 carbon atoms, X represents an alkyl or alkoxy group or a halogen atom and n represents 0 or 1.
(I) in which R represents an alkyl, alkenyl, alkynyl or cycloalkyl group having up to 6 carbon atoms, X represents an alkyl or alkoxy group or a halogen atom and n represents 0 or 1.
2. A compound as claimed in claim 1, wherein R
represents an alkyl, alkenyl or alkynyl group containing up to 6 carbon atoms.
represents an alkyl, alkenyl or alkynyl group containing up to 6 carbon atoms.
3. A compound as claimed in claim 2, wherein X
represents a methyl or methoxy group or a chlorine atom.
represents a methyl or methoxy group or a chlorine atom.
4. A compound as claimed in claim 1 which is 3-cyanocarbanilic acid methyl ester.
5. A compound as claimed in claim 1 which is 3-cyanocarbanilic acid ethyl ester.
6. A compound as claimed in claim 1 which is 3-cyanocarbanilic acid allyl ester.
7. A compound as claimed in claim 1 which is 5-cyano-2-methylcarbanilic acid ethyl ester.
8. A compound as claimed in claim 1 which is 5-cyano-2-methylcarbanilic acid methy] ester.
9. A compound as claimed in claim 1 which is 5-cyano-2-methylcarbanilic acid propyl ester.
10. A compound as claimed in claim 1 which is 5-cyano-2-methylcarbanilic acid allyl ester.
11. A compound as claimed in claim 1 which is 5-cyano-2-methoxycarbanilic acid allyl ester.
12. A compound as claimed in claim 1 which is 5-cyano-2-methoxycarbanilic acid ethyl ester.
13. A compound as claimed in claim 1 which is 5-cyano-2-methoxycarbanilic acid methyl ester.
14. A compound as claimed in claim 1 which is 5-cyano-2-methylcarbanilic acid isopropyl ester.
15. A compound as claimed in claim 1 which is 3-cyanocarbanilic acid propyl ester.
16. A compound as claimed in claim 1 which is 5-cyano-2-methoxycarbanilic acid propyl ester.
17. A compound as claimed in claim 1 which is 5-cyano-2-methoxycarbanilic acid isopropyl ester.
18. A compound as claimed in claim 1 which is 3-cyanocarbanilic acid cyclohexyl ester.
19. A compound as claimed in claim 1 which is 3-cyanocarbanilic acid isopropyl ester.
20. A compound as claimed in claim 1 which is 3-cyanocarbanilic acid cyclopentyl ester.
21. A compound as claimed in claim 1 which is 3-cyanocarbanilic acid neopentyl ester.
22. A compound as claimed in claim 1 which is 3-cyanocarbanilic acid (2-methyl-2-propenyl) ester.
23. A compound as claimed in claim 1 which is 3-cyanocarbanilic acid (1-methyl-2-propynyl) ester.
24. A compound as claimed in claim 1 which is 3-cyanocarbanilic acid 2-propynyl ester.
25. A compound as claimed in claim 1 which is 2-chloro-5-cyanocarbanilic acid isopropyl ester.
26. A compound as claimed in claim 1 which is 2-chloro-5-cyanocarbanilic acid allyl ester.
27. A compound as claimed in claim 1 which is 4-chloro-3-cyanocarbanilic acid isopropyl ester.
28. A process for the manufacture of a compound of the general formula I given in claim 1, in which R, X and n have the meanings given in claim 1, wherein (a) a 3-aminobenzonitrile of the general formula in which X and n have the meanings given above, is reacted in the presence of an acid-binding agent with a chloroformic acid ester of the general formula in which R has the meaning given above, or (b) a 3-cyanophenyl isocyanate of the general formula in which X and n have the meanings given above, is reacted with an alcohol of the general formula R-OH
in which R has the meaning given above.
in which R has the meaning given above.
29. A method of protecting a living plant against weeds, wherein the area in the vicinity of a living plant is treated with a compound as claimed in claim 1, 2 or 3.
30. A method of protecting a living plant against weeds, wherein the area in the vicinity of a living plant is treated with a compound as claimed in claim 4, 5 or 6.
31. A method of protecting a living plant against weeds, wherein the area in the vicinity of a living plant is treated with a compound as claimed in claim 7, 8 or 9.
32. A method of protecting a living plant against weeds, wherein the area in the vicinity of a living plant is treated with a compound as claimed in claim 10, 11 or 12.
33. A method of protecting a living plant against weeds, wherein the area in the vicinity of a living plant is treated with a compound as claimed in claim 13, 14 or 15.
34. A method of protecting a living plant against weeds, wherein the area in the vicinity of a living plant is treated with a compound as claimed in claim 16, 17 or 18.
35. A method of protecting a living plant against weeds, wherein the area in the vicinity of a living plant is treated with a compound as claimed in claim 19, 20 or 21.
36. A method of protecting a living plant against weeds, wherein the area in the vicinity of a living plant is treated with a compound as claimed in claim 22, 23 or 24.
37. A method of protecting a living plant against weeds, wherein the area in the vicinity of a living plant is treated with a compound as claimed in claim 25, 26 or 27.
38. A method of protecting a living plant against weeds, wherein a single compound as claimed in claim 1, 2 or 3 is used for the treatment of an area in the vicinity of the living plant in an amount within the range of from 0.5 to 5 kg per hectare.
39. A method of protecting a living plant against weeds, wherein two or more compounds as claimed in claim 1, 2 or 3 are used for the treatment of an area in the vicinity of the living plant in a total amount within the range of from 0.5 to 5 kg per hectare.
40. A method of protecting a crop area against weeds wherein a crop area is treated with a compound as claimed in claim 1, 2 or 3.
41. A method of protecting a crop area against weeds, wherein a crop area is treated with a compound as claimed in claim 4, 5 or 6.
42. A method of protecting a crop area against weeds, wherein a crop area is treated with a compound as claimed in claim 7, 8 or 9.
43. A method of protecting a crop area against weeds, wherein a crop area is treated with a compound as claimed in claim 10, 11 or 12.
44. A method of protecting a crop area against weeds, wherein a crop area is treated with a compound as claimed in claim 13, 14 or 15.
45. A method of protecting a crop area against weeds, wherein a crop area is treated with a compound as claimed in claim 16, 17 or 18.
46. A method of protecting a crop area against weeds, wherein a crop area is treated with a compound as claimed in claim 19, 20 or 21.
47. A method of protecting a crop area against weeds, wherein a crop area is treated with a compound as claimed in claim 22, 23 or 24.
48. A method of protecting a crop area against weeds, wherein a crop area is treated with a compound as claimed in claim 25, 26 or 27.
49. A method of protecting a crop area against weeds, wherein a single compound as claimed in claim 1, 2 or 3 is used for the treatment of the crop area in an amount within the range of from 0.5 to 5 kg per hectare.
50. A method of protecting a crop area against weeds wherein two or more compounds as claimed in claim 1, 2 or 3 is used for the treatment of the crop area in a total amount within the range of from 0.5 to 5 kg per hectare.
51. A method of protecting a crop area against weeds, the crop being a lucerne, bush-bean, cotton, soya bean, ground-nut or wheat crop, wherein a crop area is treated with a compound as claimed in claim 1, 2 or 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2619733.1 | 1976-04-30 | ||
| DE19762619733 DE2619733A1 (en) | 1976-04-30 | 1976-04-30 | CARBANILIC ACID ESTERS, PROCESS FOR PREPARING THESE COMPOUNDS AND THE HERBICIDAL AGENTS CONTAINING THESE AGENTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1100987A true CA1100987A (en) | 1981-05-12 |
Family
ID=5977066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA276,170A Expired CA1100987A (en) | 1976-04-30 | 1977-04-14 | Herbicidally active carbanilic acid esters |
Country Status (30)
| Country | Link |
|---|---|
| JP (1) | JPS52133946A (en) |
| AR (1) | AR218245A1 (en) |
| AT (1) | AT353549B (en) |
| AU (1) | AU2436577A (en) |
| BE (1) | BE854128A (en) |
| BG (1) | BG27715A3 (en) |
| BR (1) | BR7702183A (en) |
| CA (1) | CA1100987A (en) |
| CS (1) | CS200510B2 (en) |
| DD (1) | DD129732A5 (en) |
| DE (1) | DE2619733A1 (en) |
| EG (1) | EG12533A (en) |
| ES (1) | ES456423A1 (en) |
| FI (1) | FI771019A (en) |
| FR (1) | FR2349571A1 (en) |
| GB (1) | GB1582302A (en) |
| GR (1) | GR70655B (en) |
| IE (1) | IE44682B1 (en) |
| IL (1) | IL51971A0 (en) |
| IN (1) | IN155907B (en) |
| IT (1) | IT1075842B (en) |
| LU (1) | LU77225A1 (en) |
| NL (1) | NL7701416A (en) |
| NZ (1) | NZ183795A (en) |
| PL (1) | PL102202B1 (en) |
| PT (1) | PT66319B (en) |
| RO (1) | RO72522A (en) |
| SE (1) | SE7704519L (en) |
| SU (2) | SU652861A3 (en) |
| ZA (1) | ZA772586B (en) |
-
1976
- 1976-04-30 DE DE19762619733 patent/DE2619733A1/en not_active Withdrawn
-
1977
- 1977-02-10 NL NL7701416A patent/NL7701416A/en not_active Application Discontinuation
- 1977-03-01 ES ES456423A patent/ES456423A1/en not_active Expired
- 1977-03-01 SU SU772455512A patent/SU652861A3/en active
- 1977-03-15 CS CS771718A patent/CS200510B2/en unknown
- 1977-03-17 PT PT66319A patent/PT66319B/en unknown
- 1977-03-25 AR AR266999A patent/AR218245A1/en active
- 1977-03-30 RO RO7789860A patent/RO72522A/en unknown
- 1977-04-01 IN IN493/CAL/77A patent/IN155907B/en unknown
- 1977-04-01 FI FI771019A patent/FI771019A/fi not_active Application Discontinuation
- 1977-04-05 NZ NZ183795A patent/NZ183795A/en unknown
- 1977-04-06 BR BR7702183A patent/BR7702183A/en unknown
- 1977-04-06 BG BG7735930A patent/BG27715A3/en unknown
- 1977-04-14 CA CA276,170A patent/CA1100987A/en not_active Expired
- 1977-04-18 AU AU24365/77A patent/AU2436577A/en not_active Expired
- 1977-04-20 SE SE7704519A patent/SE7704519L/en unknown
- 1977-04-25 GB GB17085/77A patent/GB1582302A/en not_active Expired
- 1977-04-25 SU SU772473626A patent/SU655306A3/en active
- 1977-04-26 EG EG243/77A patent/EG12533A/en active
- 1977-04-27 IE IE849/77A patent/IE44682B1/en unknown
- 1977-04-28 IT IT22909/77A patent/IT1075842B/en active
- 1977-04-28 LU LU77225A patent/LU77225A1/xx unknown
- 1977-04-28 PL PL1977197702A patent/PL102202B1/en unknown
- 1977-04-28 DD DD7700198641A patent/DD129732A5/en unknown
- 1977-04-28 JP JP4978177A patent/JPS52133946A/en active Pending
- 1977-04-29 BE BE177153A patent/BE854128A/en unknown
- 1977-04-29 ZA ZA00772586A patent/ZA772586B/en unknown
- 1977-04-29 GR GR53331A patent/GR70655B/el unknown
- 1977-04-29 AT AT305977A patent/AT353549B/en not_active IP Right Cessation
- 1977-04-29 IL IL51971A patent/IL51971A0/en unknown
- 1977-05-02 FR FR7713169A patent/FR2349571A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| ZA772586B (en) | 1978-03-29 |
| IN155907B (en) | 1985-03-23 |
| SE7704519L (en) | 1977-10-31 |
| NL7701416A (en) | 1977-11-01 |
| PL197702A1 (en) | 1978-01-02 |
| ATA305977A (en) | 1979-04-15 |
| AT353549B (en) | 1979-11-26 |
| AU2436577A (en) | 1978-10-26 |
| DE2619733A1 (en) | 1977-11-17 |
| PL102202B1 (en) | 1979-03-31 |
| LU77225A1 (en) | 1977-08-18 |
| CS200510B2 (en) | 1980-09-15 |
| AR218245A1 (en) | 1980-05-30 |
| SU655306A3 (en) | 1979-03-30 |
| EG12533A (en) | 1979-06-30 |
| BG27715A3 (en) | 1979-12-12 |
| BR7702183A (en) | 1977-12-20 |
| ES456423A1 (en) | 1978-02-01 |
| FI771019A (en) | 1977-10-31 |
| GB1582302A (en) | 1981-01-07 |
| IE44682L (en) | 1977-10-30 |
| SU652861A3 (en) | 1979-03-15 |
| PT66319B (en) | 1978-08-14 |
| PT66319A (en) | 1977-04-01 |
| GR70655B (en) | 1982-12-03 |
| RO72522A (en) | 1982-09-09 |
| DD129732A5 (en) | 1978-02-08 |
| JPS52133946A (en) | 1977-11-09 |
| BE854128A (en) | 1977-10-31 |
| NZ183795A (en) | 1978-11-13 |
| IL51971A0 (en) | 1977-06-30 |
| FR2349571A1 (en) | 1977-11-25 |
| IT1075842B (en) | 1985-04-22 |
| IE44682B1 (en) | 1982-02-24 |
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| MKEX | Expiry |