CA1099127A - Herbicidal compositions - Google Patents
Herbicidal compositionsInfo
- Publication number
- CA1099127A CA1099127A CA282,130A CA282130A CA1099127A CA 1099127 A CA1099127 A CA 1099127A CA 282130 A CA282130 A CA 282130A CA 1099127 A CA1099127 A CA 1099127A
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- group
- alkyl
- formula
- herbicidal compositions
- alanine
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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
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A B S T R A C T
Herbicidal compositions comprising as active in-gredients an R-(+)-isomer of a phenoxy-alkanoic acid derivative, e.g., a (dimethylamine) salt of R-(+)-(4-chloro-2-methylphenoxy)propionic acid or R-(+)-(2,4-dichlorophenoxy)propionic acid, and an N,N-di-substituted alanine derivative, e.g., N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine esters, especially the methyl and isopropyl ester, exhibit a significantly reduced antagonism with respect to the effect of the alanine compound on oats whilst maintaining the activity against broad-leaved weeds which makes a single post-emergence application effective.
Herbicidal compositions comprising as active in-gredients an R-(+)-isomer of a phenoxy-alkanoic acid derivative, e.g., a (dimethylamine) salt of R-(+)-(4-chloro-2-methylphenoxy)propionic acid or R-(+)-(2,4-dichlorophenoxy)propionic acid, and an N,N-di-substituted alanine derivative, e.g., N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine esters, especially the methyl and isopropyl ester, exhibit a significantly reduced antagonism with respect to the effect of the alanine compound on oats whilst maintaining the activity against broad-leaved weeds which makes a single post-emergence application effective.
Description
2~
The present invention relates to herbicidally-active compositions comprising a phenoxy-alkanoic acid derivative and an alanine derivative.
For many years the broad-leaved weeds which infest cereal crops have been successfully controlled by foliar application of plant growth regulakor herbicides, such as phenoxy-alkanoic acid derivatives, known as hormone weed killers.
It is known, for example from British patent speci-fications Nos. 1,164,160 and 1,289,283 that certain alanine derivatives have a herbicidal action upon wild oats and furthermore, that these compounds may be used selectively in cereal crops to control wild oats growing alongside the cereal crops.
It would be most desirable to eradicate both broad-leaved and grass weeds by a single post-emergence application to a cereal crop but it has been observed that the presence of a hormone weed killer has an antagon-istic effect on the activity of the alanine derivative grass weed herbicide so that the latter's effectiveness is greatly reduced leading to much poorer control of the grass weeds than is normally achieved by applying the two types of herbicides separately.
It has now surprisingly been found that applying a specific optical isomer of a phenoxy-alkanoic acid or phenoxy-alkanoic acid derivative in combination with an ~.~
9~
alanine derivative gives a virtually unaffected activity with respect ko grass weeds whilst maintaining the activity against broad-leaved weeds.
The present invention provides herbicidal com-positions comprising as active ingredients at least one R-(-~)- isomer of a phenoxy-alkanoic acid derivative of the general forrnula - ~ indicating the asymmetric carbon atorn -m ~ o ~C-C- O -Rl (I) (R)n H
wherein R represents an alkyl group of up to 4 carbon atoms; n is O or an integer up to 4; m is O or an integer up to 5; Rl represents a hydrogen atom, a metal-salt forming or an optionally alkyl-substituted ammonium ion, or an optionally substituted alkyl, cycloalkyl~ alkenyl, aryl or aralkyl group; and R2 represents an alkyl group of up to 4 carbon atoms and at least one N,N-disubstituted alanine compound of the general formula:
N / ~ (II) \ CH-CoR3 wherein X represents a fluorine or chlorine atom; Y
represents a hydrogen, fluorine or chlorine atom; Q
represents an oxygen or sulphur atom and R~ represents a group of formula -oR4, wherein R represents a hydrogen atom, a metal-salt forming or an optionally alkyl-substituted ammonium ion, an optionally substituted alkyl, cycloalkyl, alkenyl, aryl or aralkyl group;
a group of formula -SR5, in which R5 represents an optionally substituted alkyl, cycloalkyl, alkenyl, aryl or aralkyl group; or a group of formula -NR6R7 or -oN=CR6R7, in which R6 and R7 each individually represents a hydrogen atom, a hydroxy group, an optionally substituted alkyl, alkenyl, aryl, aralkyl, heterocyclic, alkoxy, alkylthio or amino group or R6 and R7 together represent a polymethylene group optionally inter-rupted by one or more hetero atoms.
The optional substituents in the alanine derivatives of formula II are preferably one or two chlorine or fluorine atoms, or alkyl or alkoxy groups containing up to 4 carbon atoms. The alkyl, alkenyl, alkoxy, and alkyl-thio groups referred to in formula II suitably contain up to 6 carbon atoms, preferably up to 4 carbon atoms.
The aryl, aralkyl, cycloalkyl, heterocyclic and poly-methylene groups suitably contain up to 10 carbon atoms, 2~7 preferably up to 7 carbon atoms. The hetero-atoms which may be in the polymethylene group or in the heterocyclic groups can be oxygen, nitrogen or sulphur atoms and preferably one or two oxygen and/or nitrogen atoms.
Preferred compositions according to the present invention comprise R-(-~)-phenoxy-alkanoic acid derivatives of formula I, wherein n is 0 or 1; rn is 1, 2 or 3; R represents a methyl group; R1 represents a hydrogen atom, a sodium or potassium ion, an optionally alkyl-substituted ammonium ion, wherein the alkyl groups contain up to 18 carbon atoms or an alkyl group of up to 18 carbon atoms; and R2 represents a methyl group.
More preferred compounds according to formula I
to be used in the compositions according to the in-vention are potassium- and dimethylamine salts of R-(+)-(4-chloro-2-methylphenoxy)propionic acid, R-(+)-(2,4-dichlorophenoxy)propionic acid; and R-(~)-(2,4,5-trichlorophenoxy)propionic acid~
Examples of N,N-disubstituted alanine compounds and their method of synthesis can be found, for instance, in the following German patent specifications --6~
OLS 1 643 527; Ol,S 2 109 910; OLS 2 ~02 029;
OLS 2 349 970; OLS 2 504 319 and OI.S 2 L~60 691.
Especially preferred N~N-disubstituted alanine compounds are those of the general formula II, wherein X and Y each individually represents a fluorine or chlorine atom; Q represents an oxygen atom; and R3 represents a group of formula --oR4, wherein R4 re-presents a hydrogen atom or an alkyl group of up to 6 carbon atoms, e.g. a methyl, ethyl or isopropyl group. When used in barley crops, preference is given to the use of compounds wherein X represents a fluorine atom; Y represents a chlorine atom; and R3 represents the group -oR4, wherein R4 represents an isopropyl group. For use in wheat preference is given to those compounds, wherein X represents a fluorine or chlorine atom, Y represents a chlorine atom; and R3 represents the group -oR4, wherein R4 represents a methyl or ethyl group.
The N,N-disubstituted alanine compounds can exist in optically active forms, and generally speaking, the leavo-rotatory isomer with the R-configuration is the most active form. Thus, where it is appropriate the N,N-disubstituted alanine compounds may be employed in their most active optically-active forms in the com-positions according to the present invention.
The present invention relates to herbicidally-active compositions comprising a phenoxy-alkanoic acid derivative and an alanine derivative.
For many years the broad-leaved weeds which infest cereal crops have been successfully controlled by foliar application of plant growth regulakor herbicides, such as phenoxy-alkanoic acid derivatives, known as hormone weed killers.
It is known, for example from British patent speci-fications Nos. 1,164,160 and 1,289,283 that certain alanine derivatives have a herbicidal action upon wild oats and furthermore, that these compounds may be used selectively in cereal crops to control wild oats growing alongside the cereal crops.
It would be most desirable to eradicate both broad-leaved and grass weeds by a single post-emergence application to a cereal crop but it has been observed that the presence of a hormone weed killer has an antagon-istic effect on the activity of the alanine derivative grass weed herbicide so that the latter's effectiveness is greatly reduced leading to much poorer control of the grass weeds than is normally achieved by applying the two types of herbicides separately.
It has now surprisingly been found that applying a specific optical isomer of a phenoxy-alkanoic acid or phenoxy-alkanoic acid derivative in combination with an ~.~
9~
alanine derivative gives a virtually unaffected activity with respect ko grass weeds whilst maintaining the activity against broad-leaved weeds.
The present invention provides herbicidal com-positions comprising as active ingredients at least one R-(-~)- isomer of a phenoxy-alkanoic acid derivative of the general forrnula - ~ indicating the asymmetric carbon atorn -m ~ o ~C-C- O -Rl (I) (R)n H
wherein R represents an alkyl group of up to 4 carbon atoms; n is O or an integer up to 4; m is O or an integer up to 5; Rl represents a hydrogen atom, a metal-salt forming or an optionally alkyl-substituted ammonium ion, or an optionally substituted alkyl, cycloalkyl~ alkenyl, aryl or aralkyl group; and R2 represents an alkyl group of up to 4 carbon atoms and at least one N,N-disubstituted alanine compound of the general formula:
N / ~ (II) \ CH-CoR3 wherein X represents a fluorine or chlorine atom; Y
represents a hydrogen, fluorine or chlorine atom; Q
represents an oxygen or sulphur atom and R~ represents a group of formula -oR4, wherein R represents a hydrogen atom, a metal-salt forming or an optionally alkyl-substituted ammonium ion, an optionally substituted alkyl, cycloalkyl, alkenyl, aryl or aralkyl group;
a group of formula -SR5, in which R5 represents an optionally substituted alkyl, cycloalkyl, alkenyl, aryl or aralkyl group; or a group of formula -NR6R7 or -oN=CR6R7, in which R6 and R7 each individually represents a hydrogen atom, a hydroxy group, an optionally substituted alkyl, alkenyl, aryl, aralkyl, heterocyclic, alkoxy, alkylthio or amino group or R6 and R7 together represent a polymethylene group optionally inter-rupted by one or more hetero atoms.
The optional substituents in the alanine derivatives of formula II are preferably one or two chlorine or fluorine atoms, or alkyl or alkoxy groups containing up to 4 carbon atoms. The alkyl, alkenyl, alkoxy, and alkyl-thio groups referred to in formula II suitably contain up to 6 carbon atoms, preferably up to 4 carbon atoms.
The aryl, aralkyl, cycloalkyl, heterocyclic and poly-methylene groups suitably contain up to 10 carbon atoms, 2~7 preferably up to 7 carbon atoms. The hetero-atoms which may be in the polymethylene group or in the heterocyclic groups can be oxygen, nitrogen or sulphur atoms and preferably one or two oxygen and/or nitrogen atoms.
Preferred compositions according to the present invention comprise R-(-~)-phenoxy-alkanoic acid derivatives of formula I, wherein n is 0 or 1; rn is 1, 2 or 3; R represents a methyl group; R1 represents a hydrogen atom, a sodium or potassium ion, an optionally alkyl-substituted ammonium ion, wherein the alkyl groups contain up to 18 carbon atoms or an alkyl group of up to 18 carbon atoms; and R2 represents a methyl group.
More preferred compounds according to formula I
to be used in the compositions according to the in-vention are potassium- and dimethylamine salts of R-(+)-(4-chloro-2-methylphenoxy)propionic acid, R-(+)-(2,4-dichlorophenoxy)propionic acid; and R-(~)-(2,4,5-trichlorophenoxy)propionic acid~
Examples of N,N-disubstituted alanine compounds and their method of synthesis can be found, for instance, in the following German patent specifications --6~
OLS 1 643 527; Ol,S 2 109 910; OLS 2 ~02 029;
OLS 2 349 970; OLS 2 504 319 and OI.S 2 L~60 691.
Especially preferred N~N-disubstituted alanine compounds are those of the general formula II, wherein X and Y each individually represents a fluorine or chlorine atom; Q represents an oxygen atom; and R3 represents a group of formula --oR4, wherein R4 re-presents a hydrogen atom or an alkyl group of up to 6 carbon atoms, e.g. a methyl, ethyl or isopropyl group. When used in barley crops, preference is given to the use of compounds wherein X represents a fluorine atom; Y represents a chlorine atom; and R3 represents the group -oR4, wherein R4 represents an isopropyl group. For use in wheat preference is given to those compounds, wherein X represents a fluorine or chlorine atom, Y represents a chlorine atom; and R3 represents the group -oR4, wherein R4 represents a methyl or ethyl group.
The N,N-disubstituted alanine compounds can exist in optically active forms, and generally speaking, the leavo-rotatory isomer with the R-configuration is the most active form. Thus, where it is appropriate the N,N-disubstituted alanine compounds may be employed in their most active optically-active forms in the com-positions according to the present invention.
3~
Good results have been obtained with the ethyl esters of R-(+)-(2, Ll -dichlorophenoxy)propionic acid and R-(+)-(4-chloro-2-methylphenoxy)propionic acid, respectively, with N-benzoyl N-(3-chloro-4-f]uorophenyl)alanine methyl ester (racemic mixture);
N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine iso-propyl ester (racemic mixture);
N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine iso-propyl ester (leavo-rotatory isomer); and N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine ethyl ester (leavo-rotatory isomer).
Wild oat can be controlled in cereal crops by application of from 0.1 to 4 kg/ha of the compositions according to the present invention. The weight ratio of the alanine derivative to the R-(+)-phenoxy~alkanoic acid derivative is in the range from 1 : 0.2 to 1 : 25, preferably 1 : 0.5 to 1 : 15.
The invention also includes a method of eradicating or controlling both broad-leaved and grass weeds infesting cereal crops at a locus by applying to the locus a herbicidally effective amount of a R-(+~-isomer of a phenoxy-alkanoic acid derivative of formula I and an N,N-disubstituted alanlne compound of formula II.
The herbicidal compositions according to the in-vention may be formulated in such a way as to facilitate its application to the area to be tested and, con-veniently, the composition includes a carrier or a surfactant and usually a carrier and a surfactant.
The term "carrier" as used herein means a material, which may be inorganic or organic and of synthetic or natural origin, with which the active compound or compounds is mixed or formulated to facilitate its application to the plant, seed, soil or other object to be treated, or its storage, transport or handling. The carrier may be a solid or a fluid.
Any of the material usually applied in formulating pesticides may be used as a carrier.
Examples of suitable solid carrier are silicates, clays, for example, kaolinite clay, synthetic hydrate silicon oxides, synthetic calcium silicates, elements such as, for example, carbon and sulphur, natural and synthetic resins, such as,for example, coumarone resins, rosin, copal, shellac, dammar, polyvinyl chloride and styrene polymers and copolymers, solid polychlorophenols~
bitumen, asphaltite, waxes, such as for example, beeswax, paraffin wax, montan wax and chlorinated mineral waxes, and solid fertilizers, for example superphosphates.
Examples of suitable fluid carriers are water, alcohols, such as for example, isopropanol, ketones, such as for example, acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers, aromatic hydrocarbons, '7 _9_ such as for example, benzene and toluene, petroleum fractions, such as for example, kerosine, chlorinated hydrocarbons, such as for example, carbon tetra chloride, including liquefied normally vaporous gaseous compounds. Mixtures of different liquids are often suitable.
The surface-active agent rnay be a wetting agent, an emulsifying agent or a dispersing agent, it may be non-ionic or ionic. Any of the surface-active agents usually applied in formulating herbicides may be used.
Examples of suitable surface-active agents are the sodium or calcium salts of polyacrylic acids, the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide;
partial esters of the above fatty acids with glycerol, sorbitan, sucrose or pentaerythritol; condensation products of alkyl phenols, for example, p-octylphenol or ~-octylcresol, with ethylene oxide and/or propylene oxide; sulphates or sulphonates of these condensation products; and alkali metal salts, preferably sodium salts, of sulphuric acid esters or sulphinic acids containing at least 10 carbon atoms in the molecule, for example, sodium lauryl sulphate, sodium secondary alkyl sulphates, sodium salts of sulphonated castor oil, and sodium alkylaryl sulphonates, such as sodium dodecylbenzene sulphonate.
~he co~positions of the invention may be formu~ated as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emul.sions and pastes.
Wettable powders are usually compounded to contain 25, 50 or 75% of toxicant and usually contain, in addition to solid carrier, 3-10% of a dispersing agent and, where necessary, 0-10% of stabilizer(s) and/or other additives, such as penetrants or stickers. Dusts are usually ~ormulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and are diluted in the field with further solid carrier to give a composition usually containing 0.5-10% of toxicant. Granules are usually prepared to have a size between 0.15 and 1.68 mm and may be manufactured by agglomeration or impregnation techniques. Generally, granules will contain 0.5-25%
toxicant and 0-25% of additives, such as stabilizers, slow-release modifiers, binding agents, etc. Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, co-solvent, 10-50% w~v toxicant, 2-20% w/v emulsifiers and 0-20% of appropriate additives, such as stabilizers, penetrants and corrosion inhibitors.
Pastes are compounded so as to obtain a stable, flowable product and usually contain 10-60% toxicant, 2-20% of appropriate additives, and, as carrier, water or an organic liquid in which the toxicant is substantially insoluble.
z~
--ll--The composltions Or the invention may contain other ingredients, for example, protective colloids, such as gelatin, glue, casein, gums and polyvinyl alcohol; sodium polyphosphates; cellulose ethers, stabilizers, such as ethylene diamine tetra-acetic acid; other herbicides or pesticides; and stickers, for example, non-volatile oils.
Aqueous dispersions and emulsions, for example, compositions obtained by diluting a wettable powder or an emulsifiable concentrate according to the in-vention with water, also ]ie within the scope of the present invention. The said emulsions may be of the water-in-oil or of the oil-in-water type, and may have a thick "mayonnaise"-like consistency.
The notation to indicate the absolute configur-ation of the phenoxy-alkanoic acids and acid derivatives is as stated in Experientia, Volume 12, pages 81-9l~, 1956.
The invention is further illustrated by reference to the following Examples:--~2-EXAMPLE 1 - Demonstration of the efI'ect of phenoxy-propionic acid derivatives on the activity of N-benzoyl-N-(3-chloro-4-f'luorophenyl)-alanine methyl ester The following phenoxy propionate derivatives were formulated as 20% emulsifiable concentrates:
2,4-dichlorophenoxy propionic acid ethyl ester (racemic mixture) (~) R-(+)-(2,4-dichlorophenoxy)propionic acid ethyl ester (B) (4-chloro-2-methylphenoxy)propionic acid ethyl ester (racemic mixture) (C) R-(~)-(4-chloro-2-methylphenoxy)propionic acid ethyl ester (D) The compounds were applied as "in-tank mixtures" with a 15% emulsifiable concentrate of N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine methyl ester (racemic mixture) (E) to cultivated oat at the 1-1 2 leaf stage. The dosages used for compound (E) were 0.05, 0.1 or 0.2 kg/ha in all treat-ments. Sufficient amounts of the compounds A~ B, C and D
were added to produce mixtures with the ratios as indicated in the Table. The compound E was also applied alone.
After spraying (single dose sprays in a total volume of 650 l/ha) the plants were set out in random-ized blocks in the glasshouse (there were 4 replicates of each treatment). Phytotoxicity was assessed visually on a 0-100 scale (where 0 = no effect and 100 = no visible growth after spraying) 7 and 13 days after spraying and by fresh shoot weight 20 days a~ter spraying.
The amounts of R-(+~p~noxyalkanoic acid derivatives used in the compositions according to the invention are lower than the amounts of the corresponding racemates in the compositions tested f'or comparative purposes so as to account for the higher activity of ~e R~ phenoxy alkanoic acid derivatives in the compositions according to the invention. The mean results obtained using 0.2 kg/ha of compound (E) are shown in Table I, the fresh weights being expressed as % reduction in total weight of untreated control.
-~4-~g~
r -- ~ o ~ N ~ ~:o ~l ~o O ~ l ~~ C~ t~l ~0 ~\ L~ ~1 ~
J ~ ~ rl rl _ _ _ SSI-O
u~ ~ r~ ~ o~ ~ O ~
rl h co ~I ~ ~D ~ Lr~ ~r-- u~
_ ~
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h . l Lr~ ~ ~ ~1 ~ ~I
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r~ rl ~ -- - - --- -D Q) ~ ~ C~ ~ ~ CO o~ LO ~ o~ ~
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S.r~ _ . ..... ~.,, rl ~ I I 3 co ~ t oc) ~ ~
3:~ ~ ~ ~ ~ ~ ~ ~ ~
,.. _ ~_ ~ m ~ ~
o o ~ ~ + +
v ~ __ r~
The results given in Table I clearly indicate that using the R-(+)-isomer of the phenoxy-propionic acid derivatives (B~ D) causes a significantly smaller re-duction in activity of the N,N-disubstituted alanine compound which makes it possible to use such a mixture in a single operation to eradicate or to control both broad-leaved and grass weeds.
EXAMPLE 2 - Demonstration of the effect of phenoxy propionic acid derivatives on the activity of N-benzoyl-_ N-(3-e~or~4~1uorophenyl)alanine isopropyl ester The compounds A, B, C and D as described in Example 1 were applied (20% emulsifiable coneentrates) as "in-tank" mixtures with 20% emulsifiable coneentrates of N-benzoyl-N-(3-ehloro-4-fluorophenyl)alanine iso-propyl ester (racemic mixture (~) and R-(-)-N~benzoyl-N-(3-ehloro-4-fluorophenyl)alanine isopropyl ester (leavo-rotatory isomer) (G) to eultivated oat at the 1-1~ leaf stage. The dosages used~for eompound (F) were 0.17 O. 2 or 0.4 kg/ha and for eompound (G) 0.05~ 0.1 or 0.2 kg/ha in all treatments. The compounds (F) and (G) were also applied alone.
The spraying was carried out as described in Example 1. Phytotoxicity on a 0-100 (visible) scale was assessed 7 and 14 days after spraying and by fresh shoot weight 15 days after spraying. The mean results obtained using 0.4 kg/ha of compound (F) and 0.2 kg/ha of compound (G) are given in Table II.
~6~9~
Again the results obtained indicate that using R~ )p~noxy propionic acid derivatives (B, D) causes a signifieantly smaller reduction in activity for the N,N-disubstituted alanine compounds. In combination with R-(-)-N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine isopropyl ester, virtually no reduction of activity has been found at all.
EXAMPLE 3 - Demonstration of the effect of phenoxy propionie aeid derivatives on the activity of R-(-)-N-benzoyl-N-(3-ehloro-4-fluorophenyl)alanine ethyl ester . .
The eompounds A, B, C and D (20% emulsifiable eoneentrates) as deseribed in the previous Examples were applied as "in-tank" mixtures with 20% emulsifiable eoneentrate of R-(-)-N-benzoyl-N-(3-ehloro-4-fluorophenyl)-alanine ethyl ester (H) to eultivated oat at the 1~1 leaf stage. The eompound (H) was also applied alone.
The spraying was earried out as deseribed in Example 1. Phytotoxieity on a 0-100 (visible) seale was assessed 7 and 14 days after spraying and by fresh shoot weight 15 days after spraying. The mean results ob-tained using 0.2 kg/ha of compound (H) are given in Table III.
Again the results obtained elearly indicate the signifieantly reduced antagonistie effect of R-(+)-phenoxy propionic aeids on the aetivity of N,N-di-substituted alanine derivatives.
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Good results have been obtained with the ethyl esters of R-(+)-(2, Ll -dichlorophenoxy)propionic acid and R-(+)-(4-chloro-2-methylphenoxy)propionic acid, respectively, with N-benzoyl N-(3-chloro-4-f]uorophenyl)alanine methyl ester (racemic mixture);
N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine iso-propyl ester (racemic mixture);
N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine iso-propyl ester (leavo-rotatory isomer); and N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine ethyl ester (leavo-rotatory isomer).
Wild oat can be controlled in cereal crops by application of from 0.1 to 4 kg/ha of the compositions according to the present invention. The weight ratio of the alanine derivative to the R-(+)-phenoxy~alkanoic acid derivative is in the range from 1 : 0.2 to 1 : 25, preferably 1 : 0.5 to 1 : 15.
The invention also includes a method of eradicating or controlling both broad-leaved and grass weeds infesting cereal crops at a locus by applying to the locus a herbicidally effective amount of a R-(+~-isomer of a phenoxy-alkanoic acid derivative of formula I and an N,N-disubstituted alanlne compound of formula II.
The herbicidal compositions according to the in-vention may be formulated in such a way as to facilitate its application to the area to be tested and, con-veniently, the composition includes a carrier or a surfactant and usually a carrier and a surfactant.
The term "carrier" as used herein means a material, which may be inorganic or organic and of synthetic or natural origin, with which the active compound or compounds is mixed or formulated to facilitate its application to the plant, seed, soil or other object to be treated, or its storage, transport or handling. The carrier may be a solid or a fluid.
Any of the material usually applied in formulating pesticides may be used as a carrier.
Examples of suitable solid carrier are silicates, clays, for example, kaolinite clay, synthetic hydrate silicon oxides, synthetic calcium silicates, elements such as, for example, carbon and sulphur, natural and synthetic resins, such as,for example, coumarone resins, rosin, copal, shellac, dammar, polyvinyl chloride and styrene polymers and copolymers, solid polychlorophenols~
bitumen, asphaltite, waxes, such as for example, beeswax, paraffin wax, montan wax and chlorinated mineral waxes, and solid fertilizers, for example superphosphates.
Examples of suitable fluid carriers are water, alcohols, such as for example, isopropanol, ketones, such as for example, acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers, aromatic hydrocarbons, '7 _9_ such as for example, benzene and toluene, petroleum fractions, such as for example, kerosine, chlorinated hydrocarbons, such as for example, carbon tetra chloride, including liquefied normally vaporous gaseous compounds. Mixtures of different liquids are often suitable.
The surface-active agent rnay be a wetting agent, an emulsifying agent or a dispersing agent, it may be non-ionic or ionic. Any of the surface-active agents usually applied in formulating herbicides may be used.
Examples of suitable surface-active agents are the sodium or calcium salts of polyacrylic acids, the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide;
partial esters of the above fatty acids with glycerol, sorbitan, sucrose or pentaerythritol; condensation products of alkyl phenols, for example, p-octylphenol or ~-octylcresol, with ethylene oxide and/or propylene oxide; sulphates or sulphonates of these condensation products; and alkali metal salts, preferably sodium salts, of sulphuric acid esters or sulphinic acids containing at least 10 carbon atoms in the molecule, for example, sodium lauryl sulphate, sodium secondary alkyl sulphates, sodium salts of sulphonated castor oil, and sodium alkylaryl sulphonates, such as sodium dodecylbenzene sulphonate.
~he co~positions of the invention may be formu~ated as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emul.sions and pastes.
Wettable powders are usually compounded to contain 25, 50 or 75% of toxicant and usually contain, in addition to solid carrier, 3-10% of a dispersing agent and, where necessary, 0-10% of stabilizer(s) and/or other additives, such as penetrants or stickers. Dusts are usually ~ormulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and are diluted in the field with further solid carrier to give a composition usually containing 0.5-10% of toxicant. Granules are usually prepared to have a size between 0.15 and 1.68 mm and may be manufactured by agglomeration or impregnation techniques. Generally, granules will contain 0.5-25%
toxicant and 0-25% of additives, such as stabilizers, slow-release modifiers, binding agents, etc. Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, co-solvent, 10-50% w~v toxicant, 2-20% w/v emulsifiers and 0-20% of appropriate additives, such as stabilizers, penetrants and corrosion inhibitors.
Pastes are compounded so as to obtain a stable, flowable product and usually contain 10-60% toxicant, 2-20% of appropriate additives, and, as carrier, water or an organic liquid in which the toxicant is substantially insoluble.
z~
--ll--The composltions Or the invention may contain other ingredients, for example, protective colloids, such as gelatin, glue, casein, gums and polyvinyl alcohol; sodium polyphosphates; cellulose ethers, stabilizers, such as ethylene diamine tetra-acetic acid; other herbicides or pesticides; and stickers, for example, non-volatile oils.
Aqueous dispersions and emulsions, for example, compositions obtained by diluting a wettable powder or an emulsifiable concentrate according to the in-vention with water, also ]ie within the scope of the present invention. The said emulsions may be of the water-in-oil or of the oil-in-water type, and may have a thick "mayonnaise"-like consistency.
The notation to indicate the absolute configur-ation of the phenoxy-alkanoic acids and acid derivatives is as stated in Experientia, Volume 12, pages 81-9l~, 1956.
The invention is further illustrated by reference to the following Examples:--~2-EXAMPLE 1 - Demonstration of the efI'ect of phenoxy-propionic acid derivatives on the activity of N-benzoyl-N-(3-chloro-4-f'luorophenyl)-alanine methyl ester The following phenoxy propionate derivatives were formulated as 20% emulsifiable concentrates:
2,4-dichlorophenoxy propionic acid ethyl ester (racemic mixture) (~) R-(+)-(2,4-dichlorophenoxy)propionic acid ethyl ester (B) (4-chloro-2-methylphenoxy)propionic acid ethyl ester (racemic mixture) (C) R-(~)-(4-chloro-2-methylphenoxy)propionic acid ethyl ester (D) The compounds were applied as "in-tank mixtures" with a 15% emulsifiable concentrate of N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine methyl ester (racemic mixture) (E) to cultivated oat at the 1-1 2 leaf stage. The dosages used for compound (E) were 0.05, 0.1 or 0.2 kg/ha in all treat-ments. Sufficient amounts of the compounds A~ B, C and D
were added to produce mixtures with the ratios as indicated in the Table. The compound E was also applied alone.
After spraying (single dose sprays in a total volume of 650 l/ha) the plants were set out in random-ized blocks in the glasshouse (there were 4 replicates of each treatment). Phytotoxicity was assessed visually on a 0-100 scale (where 0 = no effect and 100 = no visible growth after spraying) 7 and 13 days after spraying and by fresh shoot weight 20 days a~ter spraying.
The amounts of R-(+~p~noxyalkanoic acid derivatives used in the compositions according to the invention are lower than the amounts of the corresponding racemates in the compositions tested f'or comparative purposes so as to account for the higher activity of ~e R~ phenoxy alkanoic acid derivatives in the compositions according to the invention. The mean results obtained using 0.2 kg/ha of compound (E) are shown in Table I, the fresh weights being expressed as % reduction in total weight of untreated control.
-~4-~g~
r -- ~ o ~ N ~ ~:o ~l ~o O ~ l ~~ C~ t~l ~0 ~\ L~ ~1 ~
J ~ ~ rl rl _ _ _ SSI-O
u~ ~ r~ ~ o~ ~ O ~
rl h co ~I ~ ~D ~ Lr~ ~r-- u~
_ ~
~ ~ . ,__ .__ , ~ a~ ~ ~ ~ cr~ ~ a~ L~ o o t- ~
h . l Lr~ ~ ~ ~1 ~ ~I
~a~ _ _ _ rJ ~ C~ O O 0~ r~ c~ a~ o ~D
~ a~ ~ ~ o~ ~ ~ o~ ~
H I ~ ~ ~ _ ._ ___ . _ _ .. _ .
c~ O ~ O ~ u~ ~ u~
E~ ~ ~ o~
r~ rl ~ -- - - --- -D Q) ~ ~ C~ ~ ~ CO o~ LO ~ o~ ~
~ o~ a~ o~o~ o~co a~
S.r~ _ . ..... ~.,, rl ~ I I 3 co ~ t oc) ~ ~
3:~ ~ ~ ~ ~ ~ ~ ~ ~
,.. _ ~_ ~ m ~ ~
o o ~ ~ + +
v ~ __ r~
The results given in Table I clearly indicate that using the R-(+)-isomer of the phenoxy-propionic acid derivatives (B~ D) causes a significantly smaller re-duction in activity of the N,N-disubstituted alanine compound which makes it possible to use such a mixture in a single operation to eradicate or to control both broad-leaved and grass weeds.
EXAMPLE 2 - Demonstration of the effect of phenoxy propionic acid derivatives on the activity of N-benzoyl-_ N-(3-e~or~4~1uorophenyl)alanine isopropyl ester The compounds A, B, C and D as described in Example 1 were applied (20% emulsifiable coneentrates) as "in-tank" mixtures with 20% emulsifiable coneentrates of N-benzoyl-N-(3-ehloro-4-fluorophenyl)alanine iso-propyl ester (racemic mixture (~) and R-(-)-N~benzoyl-N-(3-ehloro-4-fluorophenyl)alanine isopropyl ester (leavo-rotatory isomer) (G) to eultivated oat at the 1-1~ leaf stage. The dosages used~for eompound (F) were 0.17 O. 2 or 0.4 kg/ha and for eompound (G) 0.05~ 0.1 or 0.2 kg/ha in all treatments. The compounds (F) and (G) were also applied alone.
The spraying was carried out as described in Example 1. Phytotoxicity on a 0-100 (visible) scale was assessed 7 and 14 days after spraying and by fresh shoot weight 15 days after spraying. The mean results obtained using 0.4 kg/ha of compound (F) and 0.2 kg/ha of compound (G) are given in Table II.
~6~9~
Again the results obtained indicate that using R~ )p~noxy propionic acid derivatives (B, D) causes a signifieantly smaller reduction in activity for the N,N-disubstituted alanine compounds. In combination with R-(-)-N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine isopropyl ester, virtually no reduction of activity has been found at all.
EXAMPLE 3 - Demonstration of the effect of phenoxy propionie aeid derivatives on the activity of R-(-)-N-benzoyl-N-(3-ehloro-4-fluorophenyl)alanine ethyl ester . .
The eompounds A, B, C and D (20% emulsifiable eoneentrates) as deseribed in the previous Examples were applied as "in-tank" mixtures with 20% emulsifiable eoneentrate of R-(-)-N-benzoyl-N-(3-ehloro-4-fluorophenyl)-alanine ethyl ester (H) to eultivated oat at the 1~1 leaf stage. The eompound (H) was also applied alone.
The spraying was earried out as deseribed in Example 1. Phytotoxieity on a 0-100 (visible) seale was assessed 7 and 14 days after spraying and by fresh shoot weight 15 days after spraying. The mean results ob-tained using 0.2 kg/ha of compound (H) are given in Table III.
Again the results obtained elearly indicate the signifieantly reduced antagonistie effect of R-(+)-phenoxy propionic aeids on the aetivity of N,N-di-substituted alanine derivatives.
_ _ _ _ _ ,_ _, I ~
a~ l ~ O ~ O O O O O l ~ O
h . ~I ~ ~\1 ~
:æ ra rl rl ___ . . . , . _ _ ., .
I rl u~~ o ~~ ~ ~ ~ ~D OD CO ~ 0~ ~
J (~J 1~ N ~ ~ ~ ~ ~ ~\
~t ~3 IP5! ~
__ _____ ~ , ~ .. ....... ....... _._ _ .. ~
. ________. ~__ .. _ .__.. _. ~.... ____.. ._ ~ ~ I
~d I ,1 c~
a ~ C) rl I ~ C~ O ~ OC) O O O l r~
3 ~ ~ ~ Ir~ ~J ~1 ~ ~: ~ rl r~
___.___._ _...... _._.. _ __.. _.. _... . .. _.. ... ........ ._.... ._.... _ rl ~ ~ ~ ~ ~ O C~ O ~ L~ ~ 00 ~ U~ ~ ~ ~ L~ ~ ~ ~ ~D L
____ ___ _______ .--.. _.. ,,, ..... . . .
H _ __ I
m ~ a ¢ ~ ~ l Lr~ ~ o ~ ~ ~ o E~ ~ ~ ~ ~ ~ ~ ~ r~
~-rl ~
~ ......... _.. .. .... _ _ .. .. _ _____ _ _ __ __ ._ rl ~ ~ O ~ O O ~ U~ ~ ~ U~ ~ CO
~ n ~ u~ oo ~D ~ U~ 0~ ~ 00 ~D ~
------~ - ~ ---~
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ o~
rl J~ l .. .. .. .. .. .. .. .. l .. ..
~ s~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
m ~ ~ cC
~ ~ + + + + ~ +
o ~ F4 ~ F~l ~
. I . ._ I
9~ 7 ~ ~ J~ O O ~ U~ O L~
~rl ~rl ~ o ~ _, .. .. . _~.
I ~rl u~ u~
L~ o ~ o o ~ a) .. _._. .. ... ,__, rl ~ U~ ~ ~ ~ OC~ C~
~ ~ ~ Lr~ C- ~D ~ ~O
_. _.. . .. .,. ...... ...
H¦ O ~ ___ ____ ~ _... _ ¢~1 ~ o ~ o ~ o E~ ~ rl rl _ _ .
~ ~ ~ Lr~ ~ t- ~D CC) o~
s o .......... ... ...
~1 t~J 3 3 00 t~J 3 ...._ . .
._ I
I ~ rl C) :~
~ C) rl l J 0~ ~ r~ ~1 ~ O O
Ll~ ~ ~ ~I
~1~ ~ ~rl rl __ _____ _ .... ,. ..... _ .... _. .____ O
u~ ~ o ~ ~D ~ =r o~ C-(I) rl ~ C) ~ ~ ~\ ~ ~O ~ 1-- 1~
__ ~ . ... ....... .. ... .. ....... . . _ _ __._ .
_ _.. __ ._.. _.... ............ _ ._.. __.... __ I
I ~ rl C) ai ~r ~ ~ ~ lr~ co ~ ~ o 1--~1 ~ rl rl N ~1 __ _.. _._ __ .. .. , ., , _._.. _ ___ .__._. _ _~
r-l rl h ~n oot:~ coOJ t--CO ~ ~J t--~ ~ m oo ~o ~ cot-- ~ oO o~ ~
H ¦ _ _ ___ ~ _ _ ___ __ __ ._.. .. ..... _.. , . _ _ ~ ~4 01 E~ ~ Q) ~ td ~
~ r~ ~ l 1~ OC)~I Lr~ o Lr~ O O
C~ ~ rl rl ____ _. __. . _ __. ____ _.__ ____. ___._, ___ rl h J~ ~q O 1~ 3 O ~~J 0~ I CO
U~ rl C) Ci~a~ CO ~ 0~ ~ C~ Ci~
.
S O
bD-rl 3 CO ~1 3 3 CO ~1 3 rl ~ l .... .... .. .. .. ..
3 ~ ~1 ~1 ~1~1 ~1 ~1 ~
U~
¢ m ~ ~
_ ~ ::c m rc
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Herbicidal compositions comprising as active ingredients at least one R-(+)-isomer of a phenoxy-alkanoic acid derivative of the general formule - ? indicating the asymmetric carbon atom -(I) wherein R represents an alkyl group of up to 4 carbon atoms; n is 0 or an integer up to 4; m is 0 or an integer up to 5; R1 represents a hydrogen atom, a metal-salt forming or an optionally alkyl-substituted ammonium, ion or an alkyl, cycloalkyl, alkenyl, aryl or aralkyl group; and R2 represents an alkyl group of up to 4 carbon atoms and at least one N,N-disubstituted alanine com-pound of the general formula:
(II) wherein X represents a fluorine or chlorine atom; Y represents a hydrogen, fluorine or chlorine atom; Q represents an oxygen or sulphur atom and R3 represents a group of formula -OR4, wherein R4 represents a hydrogen atom, a metal-salt forming or an optionally alkyl-substituted ammonium ion, an alkyl, cycloalkyl, alkenyl, aryl or aralkyl group which is unsubstituted or substituted by one or two chlorine or fluorine atoms or alkyl or alkoxy groups containing up to 4 carbon atoms;
a group of formula -SR5, in which R5 represents an alkyl, cycloalkyl, alkenyl, aryl or aralkyl group which is unsubstituted or substituted by one or two chlorine or fluorine atoms or alkyl or alkoxy groups containing up to 4 carbon atoms; or a group of formula -NR6R7 or -ON=CR6R7, in which R6 and R7 each individually represents a hydrogen atom, a hydroxy group, or an unsubstituted or substituted alkyl, alkenyl, aryl, aralkyl, heterocyclic, alkoxy, alkylthio or amino group substituted by one or two chlorine or fluorine atoms or alkyl or alkoxy groups containing up to 4 carbon atoms or R6 and R7 together repre-sent a polymethylene group optionally interrupted by one or more hetero atoms the weight ratio of the compounds of formual II:I being in the range of 1:0.2 to 1:25.
(II) wherein X represents a fluorine or chlorine atom; Y represents a hydrogen, fluorine or chlorine atom; Q represents an oxygen or sulphur atom and R3 represents a group of formula -OR4, wherein R4 represents a hydrogen atom, a metal-salt forming or an optionally alkyl-substituted ammonium ion, an alkyl, cycloalkyl, alkenyl, aryl or aralkyl group which is unsubstituted or substituted by one or two chlorine or fluorine atoms or alkyl or alkoxy groups containing up to 4 carbon atoms;
a group of formula -SR5, in which R5 represents an alkyl, cycloalkyl, alkenyl, aryl or aralkyl group which is unsubstituted or substituted by one or two chlorine or fluorine atoms or alkyl or alkoxy groups containing up to 4 carbon atoms; or a group of formula -NR6R7 or -ON=CR6R7, in which R6 and R7 each individually represents a hydrogen atom, a hydroxy group, or an unsubstituted or substituted alkyl, alkenyl, aryl, aralkyl, heterocyclic, alkoxy, alkylthio or amino group substituted by one or two chlorine or fluorine atoms or alkyl or alkoxy groups containing up to 4 carbon atoms or R6 and R7 together repre-sent a polymethylene group optionally interrupted by one or more hetero atoms the weight ratio of the compounds of formual II:I being in the range of 1:0.2 to 1:25.
2. Herbicidal compositions according to claim 1, wherein the R-(+) -phenoxy-alkanoic acid derivative is a compound according to the general for-mula (I), wherein n is 0 or 1; m is 1, 2 or 3; R represents a methyl group;
R1 represents a hydrogen atom; a sodium or potassium ion, an optionally alkyl -substituted ammonium ion, wherein the alkyl groups contain up to 18 carbon atoms or an alkyl group of up to 18 carbon atoms; and R2 represents a methyl group.
R1 represents a hydrogen atom; a sodium or potassium ion, an optionally alkyl -substituted ammonium ion, wherein the alkyl groups contain up to 18 carbon atoms or an alkyl group of up to 18 carbon atoms; and R2 represents a methyl group.
3. Herbicidal compositions according to claim 2, wherein the potas-sium or dimethylamine salts of R-(+)-(4-chloro-2-methylphenoxy)-propionic acid, R-(+)-(2,4-dichlorophenoxy)-propionic acid or R-(+)-(2,4,5-trichlorophenoxy) -propionic acid are used as active ingredient.
4. Herbicidal compositions according to claim 1, wherein the N,N-disubstituted alanine compound is a compound according to formula II, wherein X and Y each individually represents a fluorine or chlorine atom; Q represents an oxygen atom; and R3 represents a group of formula -OR4, wherein R4 repres-ents a hydrogen atom or an alkyl group of up to 6 carbon atoms.
5. Herbicidal compositions according to claim 4, wherein a compound according to formula II wherein X represents a fluorine atom; Y represents a chlorine atom; and R3 represents a group -OR4, wherein R4 represents an isopropyl group, is used as active ingredient.
6. Herbicidal compositions according to claim 4, wherein a com-pound according to formula II wherein X represents a fluorine or chlorine atom; Y represents a chlorine atom; and R3 represents a group -OR4, wherein R4 represents a methyl or ethyl group, is used as active ingredient.
7. Herbicidal compositions according to claim 1, wherein a leave-rota-tory isomer of a compound according to formula II is used as active ingredient.
8. Herbicidal compositions according to claim 7, wherein an ethyl ester of R-(+)-(2,4-dichlorophenoxy)-propionic acid or R-(+)-(4-chloro-2-methylphenoxy)-propionic acid is used as active ingredient together with the N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine isopropyl ester (leavo-rotat-ory isomer) or N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine ethyl ester (leavo-rotatory isomer).
9. Herbicidal compositions according to claim 1, wherein the weight ratio of the alanine derivative to the R-(+)-phenoxy-alkanoic acid deriv-ative is in the range from 1:0.5 to 1:15.
10. Herbicidal compositions according to claim 1, wherein the amount of active ingredients is 0.5-75%w of the composition, together with a carrier, a surface-active agent or both a carrier and a surface-active agent.
11. A method of eradicating or controlling broad-leaved and grass weeds in cereal crops at a locus which comprises applying to the locus a herbicidally active amount of a R-(+)-isomer of a phenoxy-alkanoic acid derivative of formula I and an N,N-disubstituted alanine derivative of formula II.
12. A method according to claim 11, which comprises applying a R-(+) -isomer of a phenoxy-alkanoic acid derivative of formula I and a leavo-rotatory isomer of an N,N-disubstituted alanine derivative of formula II.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB32087/76A GB1586463A (en) | 1976-08-02 | 1976-08-02 | Herbicidal compositions |
| GB32087/76 | 1976-08-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1099127A true CA1099127A (en) | 1981-04-14 |
Family
ID=10333018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA282,130A Expired CA1099127A (en) | 1976-08-02 | 1977-07-06 | Herbicidal compositions |
Country Status (24)
| Country | Link |
|---|---|
| AT (1) | AT358864B (en) |
| AU (1) | AU511681B2 (en) |
| BE (1) | BE857377A (en) |
| BR (1) | BR7705038A (en) |
| CA (1) | CA1099127A (en) |
| CS (1) | CS196217B2 (en) |
| DD (1) | DD131122A5 (en) |
| DE (1) | DE2734684A1 (en) |
| DK (1) | DK344177A (en) |
| FI (1) | FI772334A (en) |
| FR (1) | FR2360251A1 (en) |
| GB (1) | GB1586463A (en) |
| GR (1) | GR64046B (en) |
| IT (1) | IT1085429B (en) |
| NL (1) | NL7708417A (en) |
| NO (1) | NO772714L (en) |
| NZ (1) | NZ184792A (en) |
| PL (1) | PL106611B1 (en) |
| PT (1) | PT66870B (en) |
| RO (1) | RO72715A (en) |
| SE (1) | SE7708783L (en) |
| SU (1) | SU730270A3 (en) |
| TR (1) | TR19742A (en) |
| ZA (1) | ZA774630B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6348434B1 (en) * | 1999-07-01 | 2002-02-19 | Basf Aktiengesellschaft | Herbicidal emulsifiable concentrate |
| US7129274B1 (en) | 1999-11-05 | 2006-10-31 | Emisphere Technologies Inc. | Phenoxy carboxylic acid compounds and compositions for delivering active agents |
| US7279597B1 (en) | 1999-11-05 | 2007-10-09 | Emisphere Technologies, Inc. | Phenyl amine carboxylic acid compounds and compositions for delivering active agents |
| TWI794369B (en) | 2017-12-14 | 2023-03-01 | 丹麥商Ｎｍｄ藥品公司 | Compounds for the treatment of neuromuscular disorders |
-
1976
- 1976-08-02 GB GB32087/76A patent/GB1586463A/en not_active Expired
-
1977
- 1977-07-06 CA CA282,130A patent/CA1099127A/en not_active Expired
- 1977-07-29 NL NL7708417A patent/NL7708417A/en not_active Application Discontinuation
- 1977-08-01 IT IT26382/77A patent/IT1085429B/en active
- 1977-08-01 PL PL1977200001A patent/PL106611B1/en unknown
- 1977-08-01 AT AT568077A patent/AT358864B/en not_active IP Right Cessation
- 1977-08-01 TR TR19742A patent/TR19742A/en unknown
- 1977-08-01 NZ NZ184792A patent/NZ184792A/en unknown
- 1977-08-01 RO RO7791238A patent/RO72715A/en unknown
- 1977-08-01 GR GR54077A patent/GR64046B/en unknown
- 1977-08-01 BR BR7705038A patent/BR7705038A/en unknown
- 1977-08-01 AU AU27512/77A patent/AU511681B2/en not_active Expired
- 1977-08-01 DD DD7700200369A patent/DD131122A5/en unknown
- 1977-08-01 SE SE7708783A patent/SE7708783L/en unknown
- 1977-08-01 FR FR7723615A patent/FR2360251A1/en active Granted
- 1977-08-01 DE DE19772734684 patent/DE2734684A1/en not_active Withdrawn
- 1977-08-01 ZA ZA00774630A patent/ZA774630B/en unknown
- 1977-08-01 BE BE179825A patent/BE857377A/en unknown
- 1977-08-01 CS CS775078A patent/CS196217B2/en unknown
- 1977-08-01 SU SU772510454A patent/SU730270A3/en active
- 1977-08-01 DK DK344177A patent/DK344177A/en unknown
- 1977-08-01 PT PT66870A patent/PT66870B/en unknown
- 1977-08-01 NO NO772714A patent/NO772714L/en unknown
- 1977-08-01 FI FI772334A patent/FI772334A/fi not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| ATA568077A (en) | 1980-02-15 |
| AU511681B2 (en) | 1980-08-28 |
| FI772334A (en) | 1978-02-03 |
| FR2360251A1 (en) | 1978-03-03 |
| NL7708417A (en) | 1978-02-06 |
| GR64046B (en) | 1980-01-19 |
| ZA774630B (en) | 1978-06-28 |
| AU2751277A (en) | 1979-02-08 |
| RO72715A (en) | 1982-09-09 |
| PT66870B (en) | 1979-01-23 |
| PL200001A1 (en) | 1978-03-28 |
| CS196217B2 (en) | 1980-03-31 |
| PT66870A (en) | 1977-09-01 |
| DK344177A (en) | 1978-02-03 |
| AT358864B (en) | 1980-10-10 |
| IT1085429B (en) | 1985-05-28 |
| NZ184792A (en) | 1980-05-08 |
| NO772714L (en) | 1978-02-03 |
| TR19742A (en) | 1979-10-25 |
| SE7708783L (en) | 1978-02-03 |
| DD131122A5 (en) | 1978-06-07 |
| FR2360251B1 (en) | 1981-06-12 |
| BE857377A (en) | 1978-02-01 |
| GB1586463A (en) | 1981-03-18 |
| BR7705038A (en) | 1978-05-02 |
| PL106611B1 (en) | 1980-01-31 |
| DE2734684A1 (en) | 1978-02-09 |
| SU730270A3 (en) | 1980-04-25 |
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