CA1108639A - Herbicidally active n-ethylcarbanilic acid (3- methoxycarbonylamino)-phenyl ester and its manufacture and use - Google Patents
Herbicidally active n-ethylcarbanilic acid (3- methoxycarbonylamino)-phenyl ester and its manufacture and useInfo
- Publication number
- CA1108639A CA1108639A CA326,275A CA326275A CA1108639A CA 1108639 A CA1108639 A CA 1108639A CA 326275 A CA326275 A CA 326275A CA 1108639 A CA1108639 A CA 1108639A
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- Prior art keywords
- acid
- substituted
- methoxycarbonylamino
- phenyl ester
- formula
- Prior art date
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-
- 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
- A01N47/22—O-Aryl or S-Aryl esters thereof
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- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A novel carbanilic acid derivative, namely N-ethyl-carbanilic acid (3-methoxycarbonylamino)-phenyl ester of the formula
A novel carbanilic acid derivative, namely N-ethyl-carbanilic acid (3-methoxycarbonylamino)-phenyl ester of the formula
Description
11~8639 The present invention is concerned with a new carbanilic acid ester, with the process for the manufacture of this compound, and also with its use as a selective herbicide especially for the control of weeds in cotton, ground-nut and rice crops.
Carbanilic acid derivatives having a selective herbi-cidal action are already kno~n (German Patent Specification No.
1,567,151). Active substances of this kind that are known in practice, for example methyl-N-~3-~(3-methylphenyl)-carbamoyloxy]-phenyl~-carbamate (phenmedipham), have outstanding selectivity with reg;ard to beet crops but beyond that, however, possess only a narrow spectrum of action.
The problem upon which the present invention is based has, therefore, been to provide a selective herbicidal agent that has a broad spectrum of action and may be used in other agricultural crops, for example cotton, ground-nut and rice crops, This problem is now solved in accordance with the present invention.
The present invention provides N-ethylcarbanilic acid (3-methoxycarbonylamino)-phenyl ester of the formula O-CO-N _~~~~~~~~~C2H5 The herbicidal action of the new compound of the present invention extends to many plant genera, for example, Valerianella, Portulaca, Papaver, Kochia, Solanum, Escholtzia, Euphorbia, Brassica, Datura, ~pomea, Setaria, Echinochloa, Digitaria, Stellarla, Senecio, Matricaria, Lamium, Centaurea,
Carbanilic acid derivatives having a selective herbi-cidal action are already kno~n (German Patent Specification No.
1,567,151). Active substances of this kind that are known in practice, for example methyl-N-~3-~(3-methylphenyl)-carbamoyloxy]-phenyl~-carbamate (phenmedipham), have outstanding selectivity with reg;ard to beet crops but beyond that, however, possess only a narrow spectrum of action.
The problem upon which the present invention is based has, therefore, been to provide a selective herbicidal agent that has a broad spectrum of action and may be used in other agricultural crops, for example cotton, ground-nut and rice crops, This problem is now solved in accordance with the present invention.
The present invention provides N-ethylcarbanilic acid (3-methoxycarbonylamino)-phenyl ester of the formula O-CO-N _~~~~~~~~~C2H5 The herbicidal action of the new compound of the present invention extends to many plant genera, for example, Valerianella, Portulaca, Papaver, Kochia, Solanum, Escholtzia, Euphorbia, Brassica, Datura, ~pomea, Setaria, Echinochloa, Digitaria, Stellarla, Senecio, Matricaria, Lamium, Centaurea,
- 2 -'~
~i86~
- Amaranthus and Polygonum.
The quantities applied for a selective control of weeds are within the ran~e of from approximately 0.5 to 5 kg of active substance per hectare.
In contrast to the known active substances of analogous constitution, the compound of the present invention, when applied in the quantities specified above, can surprisingly be used in other crops, for example cotton, ground-nut, rice and other crops, instead of in beets, without damaging then, which is of great economic significance.
The present invention accordingly also provides a herbicidal preparation which comprises N-ethylcarbanilic acid (3-methoxycarbonylamino)-phenyl ester in admixture or con-junction with a suitable carrier.
The present invention further provides a method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with N-ethylcarbanilic acid (3-methoxycarbonylamino)-phenyl ester.
The present invention further provides a method of protecting a crop area against weeds, wherein the crop area is treated with N ethylcarbanilic acid (3-methoxycarbonylamino)-phenyl ester.
The present invention further provides a pack which comprises M-ethylcarbanilic acid (3~methoxycarbonylamino)-phenyl ester together with instructions for its use as a herbicide.
The compound of the present invention may be used either alone or with other active substances.
Depending on the desired aim, the following herbi-cidally active substances, for example, may be used concomitantly and may even, if desired, be added to the compound of the pre-sent invention immediately prior to application:
. . . .
' 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 dioxides, substituted benzoxazines, substituted benzoxazinones, substituted benzthiazoles, substituted 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 thereo~, substituted cycloalkylcarbonamido-thiazoles, substituted dicarboxylic acids and also salts, esters and amides thereof, substituted dihydrobenzofuranyl sulphonates, substituted disulphides, substituted dipyridylium salts, substituted dithiocarbamates, substituted dithioph~sphoric ac~ds and also salts, esters and amides thereof, substituted ureas, substituted hexahydro~lH carbothioates, substituted hydantoins, substituted hydrazides, : substituted hydrazonium salts, substituted isoxazolepyrimidones, substituted imidazoles, substituted isothiazolepyrimidones, substituted ketones, substituted naphthoquinones, substituted aliphatic nitriles, substituted aromatic nitriles, substituted oxadiazoles, substituted oxadiazinones, substituted oxadiazolidinediones~ :
substituted oxadiazinediones, substituted phenols and also salts and esters thereof, .substituted phosphonic acids and alæo salts, esters and amides 20 thereof, substituted piperidines, substituted pyrazoles, substituted pyrazolalkylcarboxylic acids and also salts, esters and amides thereof, substituted pyrazolium salts, substituted pyrazolium alkyl sulphates, substituted pyridazines, substituted pyridazones, substituted pyridine carboxylic acids and also salts, esters and amides thereof, substituted pyridines, substituted pyridine carboxylates, ii39 :` :
substituted pyridinones, substituted pyrimidones, substituted pyrrolidine carboxylic acids and also salts, esters and amides thereof, ; substituted pyrrolidines, substituted arylsulphonic acids and also salts, esters and amides thereof, substituted styrenes, substituted tetrahydro-oxadiazinediones, substituted tetrahydromethanoindenes, substituted tetrahydro-diazole-thiones, substituted tetrahydro-thiadiazine-thiones, substituted tetrahydro-thiadiazolediones, 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 uretidinediones.
- Furthermore, other additives may alsobe usedj for example non-phytotoxic additives which with herbicides produce a synergistic increase in action, for example wetting agents, emulsifiers, solvents and oily additives.
The compound of the present invention or a mixture thereof with other herbicidally active substances is advantag-eously applied in the form of herbicidal preparations, for example powders, strewable preparations, granules, solutions, emulsions :~f~8~39 or suspensions, with the addition of liquid and/or solid vehicles or diluents and, if desired, of surface~active agents, for example wetting, adhesive, emulsifying and/or dispersing agents.
Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, for example benzene, toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide and dimethylformamide and also mineral oil fractions.
Suitable solid carriers are, for example, mineral earths, for example tonsil, silica gel, talcum, kaolin, atta-clay, limestone and silicic acid, and vegetable products, for example meals.
As surface-active agents there may be mentioned,for example, calcium lignin sulphonate, polyoxyethylene-alkyl-phenyl ethers, naphthalenesulphonic acids and salts, thereof, phenolsulphonic acids and salts thereof, formaldehyde conden-sates, fatty alcohol sulphates and also substituted benzenesul-phonic acids and salts thereof.
The proportion of the active substance(s) in the various herbicidal preparations may vary within wide limits.
For example, the preparatlons may contain approximately 10 to 80 by weight of active substance(s), approximately 90 to 20% by weight of liquid or solid carrier and, if desired, up to 20%
by weight of surface~active agentts).
The active substances may be applied in the usual manner, for example with water as carrier in quantities of spray liquor ranging from approximately 100 to 1000 litres per hectare. It is equally possible to apply the active substances by the so-called "low-volume methodl' and "ultra-low-volume method"
and also to apply them in the form of so-called microgranules.
The new compound of the present invention may be manufactured, for example, by the process of the present in-86~9 vention, as defined belQw, The present invention accordingly further providesa process for the manufacture of N=ethylcarbanilic acid (3-methoxycarbonylamino)-phenyl ester, wherein a) chloroformic acid 3-methoxycarbonylamino-phenyl ester of the formula O-CoC 1 ~ NH-COOCH3 is reacted with N-ethylaniline of the formula ~3 in the presence of an acid acceptor,for example with the addition of excess amine or an inorganic base, for example a sodium hydroxide solution, sodium carbonate or potassium car- :
bonate, or a tertiary organic base, for example triethylamine, or b) 3-hydroxy-carbanilic acid methyl ester of the formula OH
~ NH-COOCH3 is reacted in the presence of a tertiary organic base, for example triethylamine or pyridine, or in the form of an alkali metal salt thereof with N-ethyl-N-phenyl-carbamoyl chloride of the formula . ~ - 8 -~ -CO-Cl the reaction being carried out at a temperature within the range of from 0 to 100C, or c) N-ethylcarbanilic acid 3-nitrophenyl ester of the formula C H
~ CO - N
is catalytically hydrogenated, for example by using nickel in methanol, to form the corresponding 3-amino-phenyl ester which is then reacted with chloroformic acid methyl ester of the formula Cl ~ COOCH3 in the presence of an acid acceptor, for example an inorganic base, for example a sodium hydroxide solution, sodium carbonate or potassium carbonate, or a tertiary organic base, for example triethylamine.
The product of process variants (a), (b) and (c) may be isolated in the usual manner.
The new compound of the present invention is soluble in acetone, cyclohexanone, methylene chloride, ethyl acetate and dimethylformamide. It is insoluble in water and benzine.
The following Examples illustrate the invention.
Examples 1 to 3 illustrate the manufacture of the new compound of the present invention and Example 4 illustrates the possible ways of usin~ the new c~mpound.
.
36~9 Example 1 To a solution of 18,2 ~ (0 15 mole) of N-ethyl-aniline in 50 ml of ethyl acetate were added 50 ml of water.
A solution of 34.4 g (0.15 mole) of chloroformic acid 3-methoxy-carbonylamino-phenyl ester in 100 ml of ethyl acetate and, simultaneously, a solution of 20.7 g (0.15 mole) of potassium carbonate in 70 ml of water were then added dropwise, while stirring, during which the temperature was maintained at 10-15C
by cooling. Stirring was continued for 30 m~nutes while cooling with ice. The organic phase was then separated and washed at 0C with dilute hydrochloric acid and water. After drying with magnesium sulphate, it was evaporated under reduced pressure.
The oily residue crystallized from isopropyl ether/pentane.
Yield: 36.2g = 76.8% of the theoretical yield of N-N-ethyl-carbanilic acid (3-methoxycarbonylamino)-phenyl ester.
M.p.: 110-110.5C. ~, calculated: C: 64.96% H; 5.i7% N: 8.91%
found: C: 64.93% H: 6.08% N: 9.08%
Example 2 The sodium salt prepared from 16.7 g (0.1 mole) of
~i86~
- Amaranthus and Polygonum.
The quantities applied for a selective control of weeds are within the ran~e of from approximately 0.5 to 5 kg of active substance per hectare.
In contrast to the known active substances of analogous constitution, the compound of the present invention, when applied in the quantities specified above, can surprisingly be used in other crops, for example cotton, ground-nut, rice and other crops, instead of in beets, without damaging then, which is of great economic significance.
The present invention accordingly also provides a herbicidal preparation which comprises N-ethylcarbanilic acid (3-methoxycarbonylamino)-phenyl ester in admixture or con-junction with a suitable carrier.
The present invention further provides a method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with N-ethylcarbanilic acid (3-methoxycarbonylamino)-phenyl ester.
The present invention further provides a method of protecting a crop area against weeds, wherein the crop area is treated with N ethylcarbanilic acid (3-methoxycarbonylamino)-phenyl ester.
The present invention further provides a pack which comprises M-ethylcarbanilic acid (3~methoxycarbonylamino)-phenyl ester together with instructions for its use as a herbicide.
The compound of the present invention may be used either alone or with other active substances.
Depending on the desired aim, the following herbi-cidally active substances, for example, may be used concomitantly and may even, if desired, be added to the compound of the pre-sent invention immediately prior to application:
. . . .
' 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 dioxides, substituted benzoxazines, substituted benzoxazinones, substituted benzthiazoles, substituted 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 thereo~, substituted cycloalkylcarbonamido-thiazoles, substituted dicarboxylic acids and also salts, esters and amides thereof, substituted dihydrobenzofuranyl sulphonates, substituted disulphides, substituted dipyridylium salts, substituted dithiocarbamates, substituted dithioph~sphoric ac~ds and also salts, esters and amides thereof, substituted ureas, substituted hexahydro~lH carbothioates, substituted hydantoins, substituted hydrazides, : substituted hydrazonium salts, substituted isoxazolepyrimidones, substituted imidazoles, substituted isothiazolepyrimidones, substituted ketones, substituted naphthoquinones, substituted aliphatic nitriles, substituted aromatic nitriles, substituted oxadiazoles, substituted oxadiazinones, substituted oxadiazolidinediones~ :
substituted oxadiazinediones, substituted phenols and also salts and esters thereof, .substituted phosphonic acids and alæo salts, esters and amides 20 thereof, substituted piperidines, substituted pyrazoles, substituted pyrazolalkylcarboxylic acids and also salts, esters and amides thereof, substituted pyrazolium salts, substituted pyrazolium alkyl sulphates, substituted pyridazines, substituted pyridazones, substituted pyridine carboxylic acids and also salts, esters and amides thereof, substituted pyridines, substituted pyridine carboxylates, ii39 :` :
substituted pyridinones, substituted pyrimidones, substituted pyrrolidine carboxylic acids and also salts, esters and amides thereof, ; substituted pyrrolidines, substituted arylsulphonic acids and also salts, esters and amides thereof, substituted styrenes, substituted tetrahydro-oxadiazinediones, substituted tetrahydromethanoindenes, substituted tetrahydro-diazole-thiones, substituted tetrahydro-thiadiazine-thiones, substituted tetrahydro-thiadiazolediones, 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 uretidinediones.
- Furthermore, other additives may alsobe usedj for example non-phytotoxic additives which with herbicides produce a synergistic increase in action, for example wetting agents, emulsifiers, solvents and oily additives.
The compound of the present invention or a mixture thereof with other herbicidally active substances is advantag-eously applied in the form of herbicidal preparations, for example powders, strewable preparations, granules, solutions, emulsions :~f~8~39 or suspensions, with the addition of liquid and/or solid vehicles or diluents and, if desired, of surface~active agents, for example wetting, adhesive, emulsifying and/or dispersing agents.
Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, for example benzene, toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide and dimethylformamide and also mineral oil fractions.
Suitable solid carriers are, for example, mineral earths, for example tonsil, silica gel, talcum, kaolin, atta-clay, limestone and silicic acid, and vegetable products, for example meals.
As surface-active agents there may be mentioned,for example, calcium lignin sulphonate, polyoxyethylene-alkyl-phenyl ethers, naphthalenesulphonic acids and salts, thereof, phenolsulphonic acids and salts thereof, formaldehyde conden-sates, fatty alcohol sulphates and also substituted benzenesul-phonic acids and salts thereof.
The proportion of the active substance(s) in the various herbicidal preparations may vary within wide limits.
For example, the preparatlons may contain approximately 10 to 80 by weight of active substance(s), approximately 90 to 20% by weight of liquid or solid carrier and, if desired, up to 20%
by weight of surface~active agentts).
The active substances may be applied in the usual manner, for example with water as carrier in quantities of spray liquor ranging from approximately 100 to 1000 litres per hectare. It is equally possible to apply the active substances by the so-called "low-volume methodl' and "ultra-low-volume method"
and also to apply them in the form of so-called microgranules.
The new compound of the present invention may be manufactured, for example, by the process of the present in-86~9 vention, as defined belQw, The present invention accordingly further providesa process for the manufacture of N=ethylcarbanilic acid (3-methoxycarbonylamino)-phenyl ester, wherein a) chloroformic acid 3-methoxycarbonylamino-phenyl ester of the formula O-CoC 1 ~ NH-COOCH3 is reacted with N-ethylaniline of the formula ~3 in the presence of an acid acceptor,for example with the addition of excess amine or an inorganic base, for example a sodium hydroxide solution, sodium carbonate or potassium car- :
bonate, or a tertiary organic base, for example triethylamine, or b) 3-hydroxy-carbanilic acid methyl ester of the formula OH
~ NH-COOCH3 is reacted in the presence of a tertiary organic base, for example triethylamine or pyridine, or in the form of an alkali metal salt thereof with N-ethyl-N-phenyl-carbamoyl chloride of the formula . ~ - 8 -~ -CO-Cl the reaction being carried out at a temperature within the range of from 0 to 100C, or c) N-ethylcarbanilic acid 3-nitrophenyl ester of the formula C H
~ CO - N
is catalytically hydrogenated, for example by using nickel in methanol, to form the corresponding 3-amino-phenyl ester which is then reacted with chloroformic acid methyl ester of the formula Cl ~ COOCH3 in the presence of an acid acceptor, for example an inorganic base, for example a sodium hydroxide solution, sodium carbonate or potassium carbonate, or a tertiary organic base, for example triethylamine.
The product of process variants (a), (b) and (c) may be isolated in the usual manner.
The new compound of the present invention is soluble in acetone, cyclohexanone, methylene chloride, ethyl acetate and dimethylformamide. It is insoluble in water and benzine.
The following Examples illustrate the invention.
Examples 1 to 3 illustrate the manufacture of the new compound of the present invention and Example 4 illustrates the possible ways of usin~ the new c~mpound.
.
36~9 Example 1 To a solution of 18,2 ~ (0 15 mole) of N-ethyl-aniline in 50 ml of ethyl acetate were added 50 ml of water.
A solution of 34.4 g (0.15 mole) of chloroformic acid 3-methoxy-carbonylamino-phenyl ester in 100 ml of ethyl acetate and, simultaneously, a solution of 20.7 g (0.15 mole) of potassium carbonate in 70 ml of water were then added dropwise, while stirring, during which the temperature was maintained at 10-15C
by cooling. Stirring was continued for 30 m~nutes while cooling with ice. The organic phase was then separated and washed at 0C with dilute hydrochloric acid and water. After drying with magnesium sulphate, it was evaporated under reduced pressure.
The oily residue crystallized from isopropyl ether/pentane.
Yield: 36.2g = 76.8% of the theoretical yield of N-N-ethyl-carbanilic acid (3-methoxycarbonylamino)-phenyl ester.
M.p.: 110-110.5C. ~, calculated: C: 64.96% H; 5.i7% N: 8.91%
found: C: 64.93% H: 6.08% N: 9.08%
Example 2 The sodium salt prepared from 16.7 g (0.1 mole) of
3-hydroxy carbanilic acid methyl ester and sodium methylate (from 2.3 g of sodium) in absolute methanol was, after thoroughly removing the methanol in vacuo, suspended in 100 ml of dry methyl isobutyl ketone. A solution of 18.4 g (0.1 mole~ of N-ethyl-N~phenyl-carbamoyl chloride in approximately 80 ml of methyl isobutyl ketone was added dropwise, while stirring, during which the temperature rose to approximately 30C.
Stirring was then continued for one hour at 70C. After cooling to room temperature, approximately 200 ml of ethyl acetate were added to the mixture which was then washed at 0C with a dilute sodium hydroxide solution and water. It was then dried with ma~nes~um sulphate and evaporated under reduced pressure. The E~ - 10 _ . .
86~`9 ~ily residue crystallized fro~ is~propyl ether/pentane.
Yield: 27.3g = 87~ of the theoretical yield of N~ethyl~
carbanilic acid 3-(methoxycarbonylamino)-phenyl ester.
M.p.: 110-110.5C.
Example 3 a) 46.0 g (0.16 mole) of N-ethylcarbanilic acid 3-nitrophenyl ester were hydrogenated in 400 ml of tetrahydrofuran with 5 g of Raney nickel at 20-25C. After filtering off the Raney nickel, the mixture was evaporated under reduced pressure and the residue was recrystallized from ethyl acetate/pentane.
Yield: 25.4 g = 62% of the theoretical yield of N-ethylcar-banilic acid 3-amlnophenyl ester. M.p.: 68-70C.
b) 25 g (0.0975 mole) of N-ethylcarbanilic acid 3-aminophenyl ester were dissolved in a little ethyl acetate. After adding 20 ml of water and 4.0 g (0.1 mole) of magnesium oxide, there , were added dropwise, while stirring and cooling to 10-15C, 9.2 g (0.0975 mole) of chloxoformic acid methyl ester. Stirring was continued for 30 minutes at 15C, and the organic phase was separated, washed with dilute hydrochloric acid and water and, after dryin~ with magnesium sulphate, evaporated under reduced pressure. The oily residue crystallized from isopropyl ether/
pentane. Yield: 27.9 g = 91% of the theoretical yield of N-ethylcarbanilic acid 3-(methoxycarbonylamino)-phenyl ester.
M.p.: 110-110.5C.
Example 4 In a series of tests carried out in a greenhouse the plants listed in the Table below were treated by the post-emergence method with an application quantity of 1 kg of each of the active substances per hectare. Phenmedipham was used as the agent for comparison. The plants were at an early stage of development. The active substances were in each case applied in the form of an aqueous emulsion, us-ng a quantity of liquid i39 correspondiny to 500 litres per hectare. The degree of success of the treatment was eyaluated after 14 days and expressed by a numerical scale extending from 0 to lO, the value 0 repre-senting total destruction of the plant and the value lO repre-senting no damage.
As can be seen from the Table, the compound of the present invention achieved a good action against the weeds whilst having a good tolerability towards the crop plants, where-as the agent used for comparison severely damaged the crop plants whilst having less action against the weeds.
b~
~1~8639 C ~ ~ r~
o ~ ~ ~ ~ o ~s ~ ~ ~ t ~
~D ~ It ~ ~ g w~ ~-0 RJ
~n o P- ~ O ~ u ~ ~ O
3 ~ o o~ g ~
~ X I'-n ~ ~ o~ Cotton o ~ o Ground-nut o ~ o Rice o o o Stellaria o o o Senecio o o o Valerianella ~o ~ o Matricaria o o o Portulaca o ~ o Papaver o ~ o Kochia_ o~ ~ o Solanum o ~ o Escholtzia o ~ o Euphorbia o o o Brassica o o o Datura o o o Ipomea o ~ o Setaria o o o Lamium o ~ O Centaurea o o o Amaranthus o o o Echinochloa o ~ o Digitaria o o o Polygonum
Stirring was then continued for one hour at 70C. After cooling to room temperature, approximately 200 ml of ethyl acetate were added to the mixture which was then washed at 0C with a dilute sodium hydroxide solution and water. It was then dried with ma~nes~um sulphate and evaporated under reduced pressure. The E~ - 10 _ . .
86~`9 ~ily residue crystallized fro~ is~propyl ether/pentane.
Yield: 27.3g = 87~ of the theoretical yield of N~ethyl~
carbanilic acid 3-(methoxycarbonylamino)-phenyl ester.
M.p.: 110-110.5C.
Example 3 a) 46.0 g (0.16 mole) of N-ethylcarbanilic acid 3-nitrophenyl ester were hydrogenated in 400 ml of tetrahydrofuran with 5 g of Raney nickel at 20-25C. After filtering off the Raney nickel, the mixture was evaporated under reduced pressure and the residue was recrystallized from ethyl acetate/pentane.
Yield: 25.4 g = 62% of the theoretical yield of N-ethylcar-banilic acid 3-amlnophenyl ester. M.p.: 68-70C.
b) 25 g (0.0975 mole) of N-ethylcarbanilic acid 3-aminophenyl ester were dissolved in a little ethyl acetate. After adding 20 ml of water and 4.0 g (0.1 mole) of magnesium oxide, there , were added dropwise, while stirring and cooling to 10-15C, 9.2 g (0.0975 mole) of chloxoformic acid methyl ester. Stirring was continued for 30 minutes at 15C, and the organic phase was separated, washed with dilute hydrochloric acid and water and, after dryin~ with magnesium sulphate, evaporated under reduced pressure. The oily residue crystallized from isopropyl ether/
pentane. Yield: 27.9 g = 91% of the theoretical yield of N-ethylcarbanilic acid 3-(methoxycarbonylamino)-phenyl ester.
M.p.: 110-110.5C.
Example 4 In a series of tests carried out in a greenhouse the plants listed in the Table below were treated by the post-emergence method with an application quantity of 1 kg of each of the active substances per hectare. Phenmedipham was used as the agent for comparison. The plants were at an early stage of development. The active substances were in each case applied in the form of an aqueous emulsion, us-ng a quantity of liquid i39 correspondiny to 500 litres per hectare. The degree of success of the treatment was eyaluated after 14 days and expressed by a numerical scale extending from 0 to lO, the value 0 repre-senting total destruction of the plant and the value lO repre-senting no damage.
As can be seen from the Table, the compound of the present invention achieved a good action against the weeds whilst having a good tolerability towards the crop plants, where-as the agent used for comparison severely damaged the crop plants whilst having less action against the weeds.
b~
~1~8639 C ~ ~ r~
o ~ ~ ~ ~ o ~s ~ ~ ~ t ~
~D ~ It ~ ~ g w~ ~-0 RJ
~n o P- ~ O ~ u ~ ~ O
3 ~ o o~ g ~
~ X I'-n ~ ~ o~ Cotton o ~ o Ground-nut o ~ o Rice o o o Stellaria o o o Senecio o o o Valerianella ~o ~ o Matricaria o o o Portulaca o ~ o Papaver o ~ o Kochia_ o~ ~ o Solanum o ~ o Escholtzia o ~ o Euphorbia o o o Brassica o o o Datura o o o Ipomea o ~ o Setaria o o o Lamium o ~ O Centaurea o o o Amaranthus o o o Echinochloa o ~ o Digitaria o o o Polygonum
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. N-Ethylcarbanilic acid (3-methoxycarbonylamino)-phenyl ester of the formula .
2. A process for the manufacture of N-ethylcarbanilic acid 3-(methoxycarbonylamino)-phenyl ester, wherein a) chloroformic acid 3-methoxycarbonylamino-phenyl ester of the formula is reacted in the presence of an acid acceptor with N-ethyl-aniline of the formula or b) 3-hydroxy-carbanilic acid methyl ester of the formula is reacted in the presence of a tertiary organic base or in the form of an alkali metal salt thereof with N-ethyl-N-phenyl-carbamoyl chloride of the formula the reaction being carried out at a temperature within the range of from 0° to 100°C, or c) N-ethylcarbanilic acid 3-nitrophenyl ester of the formula is catalytically hydrogenated to form the corresponding 3-amino-phenyl ester which is then reacted in the presence of an acid acceptor with chloroformic acid methyl ester of the formula Cl-COOCH3
3. A method of protecting a living plant against weeds, wherein the area is the vicinity of the living plant is treated with N-ethylcarbanilic acid (3-methoxycarbonylamino)-phenyl ester.
4. A method as claimed in Claim 3, wherein the amount of the N-ethylcarbanilic acid (3-methoxycarbonylamino)-phenyl ester used for the treatment is within the range of from approximately 0.5 to 5 kg per hectare.
5. A method of protecting a crop area against weeds, wherein the crop area is treated with N-ethylcarbanilic acid (3-methoxycarbonylamino)-phenyl ester.
6. A method as claimed in Claim 5, wherein the amount of the N-ethylcarbanilic acid (3-methoxycarbonylamino)-phenyl ester used for the treatment is within the range of from approx-imately 0.5 to 5 kg per hectare.
7. A method as claimed in Claim 5, 6 or 7 wherein the crop is a cotton, ground-nut or rice crop.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2819748A DE2819748C2 (en) | 1978-05-02 | 1978-05-02 | N-Ethylcarbanilic acid (3-methoxycarbonylamino) phenyl ester, a process for the preparation of this compound and a selective herbicidal agent containing it |
| DEP2819748.0 | 1978-05-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1108639A true CA1108639A (en) | 1981-09-08 |
Family
ID=6038754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA326,275A Expired CA1108639A (en) | 1978-05-02 | 1979-04-25 | Herbicidally active n-ethylcarbanilic acid (3- methoxycarbonylamino)-phenyl ester and its manufacture and use |
Country Status (31)
| Country | Link |
|---|---|
| JP (1) | JPS54144338A (en) |
| AR (1) | AR222653A1 (en) |
| AT (1) | AT365895B (en) |
| AU (1) | AU522366B2 (en) |
| BE (1) | BE875991A (en) |
| BR (1) | BR7902627A (en) |
| CA (1) | CA1108639A (en) |
| CH (1) | CH639946A5 (en) |
| CS (1) | CS207787B2 (en) |
| DD (1) | DD143200A5 (en) |
| DE (1) | DE2819748C2 (en) |
| EG (1) | EG13834A (en) |
| ES (1) | ES478923A1 (en) |
| FI (1) | FI790909A (en) |
| FR (1) | FR2424905A1 (en) |
| GB (1) | GB2020283B (en) |
| GR (1) | GR73571B (en) |
| HU (1) | HU184202B (en) |
| IL (1) | IL57073A (en) |
| IN (1) | IN150828B (en) |
| IT (1) | IT1166730B (en) |
| MX (1) | MX5787E (en) |
| NL (1) | NL7901680A (en) |
| PH (1) | PH14259A (en) |
| PL (1) | PL116642B1 (en) |
| PT (1) | PT69398A (en) |
| RO (3) | RO78022A (en) |
| SE (1) | SE7902441L (en) |
| SU (1) | SU852167A3 (en) |
| TR (1) | TR20603A (en) |
| YU (1) | YU40364B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1567151C3 (en) * | 1965-04-09 | 1974-02-21 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Diurethanes, processes for the preparation of these compounds and herbicidal compositions containing them |
| US3535101A (en) * | 1966-09-07 | 1970-10-20 | Schering Ag | Herbicide and algicide means |
| US3901936A (en) * | 1966-10-15 | 1975-08-26 | Schering Ag | Process for the preparation of n-carbamoyloxyphenyl carbamates |
| JPS5140073A (en) * | 1974-06-28 | 1976-04-03 | Siemens Ag | SHIRIKONNODOOPINGUHOHO |
| DE2557552C2 (en) * | 1975-12-18 | 1984-12-20 | Schering AG, 1000 Berlin und 4709 Bergkamen | Diurethanes and herbicidal agents containing these compounds as active ingredients |
-
1978
- 1978-05-02 DE DE2819748A patent/DE2819748C2/en not_active Expired
-
1979
- 1979-03-02 NL NL7901680A patent/NL7901680A/en not_active Application Discontinuation
- 1979-03-16 FI FI790909A patent/FI790909A/en not_active Application Discontinuation
- 1979-03-19 YU YU667/79A patent/YU40364B/en unknown
- 1979-03-19 SE SE7902441A patent/SE7902441L/en unknown
- 1979-03-23 ES ES478923A patent/ES478923A1/en not_active Expired
- 1979-03-27 PT PT69398A patent/PT69398A/en unknown
- 1979-03-29 IN IN208/DEL/79A patent/IN150828B/en unknown
- 1979-04-06 IT IT21636/79A patent/IT1166730B/en active
- 1979-04-07 GR GR58833A patent/GR73571B/el unknown
- 1979-04-15 IL IL7957073A patent/IL57073A/en unknown
- 1979-04-18 AR AR276229A patent/AR222653A1/en active
- 1979-04-20 CS CS792753A patent/CS207787B2/en unknown
- 1979-04-23 GB GB7914092A patent/GB2020283B/en not_active Expired
- 1979-04-25 CA CA326,275A patent/CA1108639A/en not_active Expired
- 1979-04-25 DD DD79212488A patent/DD143200A5/en unknown
- 1979-04-26 MX MX797937U patent/MX5787E/en unknown
- 1979-04-27 HU HU79SCHE677A patent/HU184202B/en unknown
- 1979-04-27 SU SU792757223A patent/SU852167A3/en active
- 1979-04-30 TR TR20603A patent/TR20603A/en unknown
- 1979-04-30 PH PH22442A patent/PH14259A/en unknown
- 1979-04-30 RO RO7987405A patent/RO78022A/en unknown
- 1979-04-30 PL PL1979215274A patent/PL116642B1/en unknown
- 1979-04-30 BR BR7902627A patent/BR7902627A/en unknown
- 1979-04-30 RO RO79104234A patent/RO80177A/en unknown
- 1979-04-30 AT AT0323279A patent/AT365895B/en not_active IP Right Cessation
- 1979-04-30 CH CH405879A patent/CH639946A5/en not_active IP Right Cessation
- 1979-05-01 AU AU46578/79A patent/AU522366B2/en not_active Ceased
- 1979-05-01 JP JP5256679A patent/JPS54144338A/en active Pending
- 1979-05-02 BE BE0/194952A patent/BE875991A/en not_active IP Right Cessation
- 1979-05-02 FR FR7911009A patent/FR2424905A1/en active Granted
- 1979-05-02 EG EG254/79A patent/EG13834A/en active
- 1979-05-30 RO RO79104223A patent/RO80176A/en unknown
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| MKEX | Expiry |