GB2058055A - Herbicidal substituted diphenyl ethers - Google Patents
Herbicidal substituted diphenyl ethers Download PDFInfo
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- GB2058055A GB2058055A GB8025861A GB8025861A GB2058055A GB 2058055 A GB2058055 A GB 2058055A GB 8025861 A GB8025861 A GB 8025861A GB 8025861 A GB8025861 A GB 8025861A GB 2058055 A GB2058055 A GB 2058055A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
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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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
- A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
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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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/48—Nitro-carboxylic acids; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
- C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/59—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
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- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
The herbicidal diphenyl ethers are of the general formula I <IMAGE> wherein: A is halogen, cyano or nitro; X is hydrogen or halogen; Y hydrogen, halogen, cyano, trifluoromethyl, or C1-4 alkyl; Z is oxygen or sulfur; R is C1-3 alkylidene or monosubstituted C1-3 alkylidene, wherein the substituent is selected from C1-4 alkyl, C1-4 oxyalkyl or C1-4 hydroxyalkyl; and R<1> is hydrogen, alkyl or C1-10 alkoxy, C3-8 cycloalkyl, an agronomically acceptable ionic species, phenyl, or mono-, di-, or trisubstituted phenyl wherein the substituent(s) is (are) selected from halogen, C1-10 alkyl or C1-10 alkoxy, cyano, nitro, or trifluoromethyl, or an optical or stereo isomer thereof.
Description
SPECIFICATION
Substituted diphenyl ethers, their preparation and use
This invention concerns certain substituted diphenyl ethers having herbidical activity, their preparation, and the control of weeds therewith.
According to the present invention there are provided substituted diphenyl ethers which are represented by the formula:
wherein:
A is nitro, halogen or cyano,
X is hydrogen or halogen;
Y is hydrogen, halogen, cyano, trifluoromethyl or alkyl containing 1 to 4 carbon atoms;
Z is oxygen or sulfur;
R is alkylidene or monosubstituted alkylidene containing 1 to 3 carbon atoms, wherein the substituent is
selected from alkyl, oxoalkyl or hydroxyalkyl containing 1 to 4 carbon atoms; and
R1 is hydrogen, alkyl or alkoxy containing 1 to 10 carbon atoms, cycloalkyl containing 3 to 8 carbon atoms,
an agronomically acceptable ionic species, phenyl, or mono-, di-, or trisubstituted phenyl wherein the
substituent(s) is (are) selected from halogen, alkyl or alkoxy containing 1 to 10 carbon atoms, cyano,
nitro, or trifluoromethyl.
Exemplary of halogens represented in the above formula are, for example, bromine, chlorine, iodine, or fluorine, preferably bromine or chlorine. Some alkyl and cycloalkyl groups represented in the above formula are, for example, methyl, ethyl, isobutyl, n-butyl, t-butyl, n-amyl, heptyl, octyl, iso-octyl, nonyl, decyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like. Suitable alkoxy, oxoalkyl and hydroxyalkyl groups are, for example, methoxy, ethoxy, butoxy, octoxy, oxoethyl, oxopropyl, oxobutyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, and the like. Methylidene, ethylidene, or propylidene are exemplary of suitable alkylidene groups.As examplesof agronomically acceptable ionic species, there may be mentioned alkali metals such as sodium, potassium, or lithium; alkaline earth metals such as barium or calcium; ammonium; or alkylammonium or alkanolammonium containing 1 to 4 carbon atoms.
Preferred compounds of this invention are those wherein Z is oxygen, A is nitro, R1 is alkyl of up to 4 carbon atoms, X is hydrogen, and Y is halogen.
Compounds of the above formula are believed to have herbicidal activity in accordance with this invention. Some specific examples of compounds within the scope of said formula and preferred in accordance with this invention are 1 '-(ethoxycarbonyl )ethyl 5-(2-chloro-4-trifluoromethyl-phenoxy)-2- nitrobenzoate; 1 '-(ethoxyca rbonyl methyl )ethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate; 2'ethoxycarbonyl 5-(2-chloro-4-tri-fluoromethylphenoxy)-2-nitrobenzoate; 2'-(ethoxycarbonyl)ethyl 5-(2ch lo ro-4-trifl u oromethyl phenoxy)-2-nitrobenzoate; 1 '-(ethoxycarbonyl) methyl 5-(2-ch lo ro-4trifluoromethylphenoxy)-2-nitrobenzoate; 1 '-ethoxycarbonyl-2-oxopropyl 5-(2-chloro-4trifluoromethylphenoxy)-2-nitrobenzoate; 1'-(ethoxycarbonyl)-butyl 5-(2-chloro-4-trifluoromethylphenoxy)2-nitrobenzoate; 1 '-(phenoxy-carbonyl)ethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate; 1' (ethoxycarbonyl)propyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate; 1 '-ethoxycarbonyl-3'- methyl butyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate, 1 '-(ethoxycarbonyl )ethyl 5-(2-chloro-4trifluoromethylphenoxy)-2-bromobenzoate; 1 '-(ethoxycarbonyl)-2'-hydroxypropyl 5-(2-chloro-4 trifluoromethylphenoxy)-2-nitrobenzoate; 1 '-(ethoxycarbonyl)ethyl 5-(2-chloro-4-trifl uoromethylphenoxy)2-cyanobenzoate; l'-(ethoxycarbonyl )ethyl 5-(2,6-dichloro-4-trifl uoromethyl phenoxy)-2-nitrobenzoate; 1' (ethoxycarbonyl)ethyl 5-(2-ch loro-6-bromo-4-trifluoromethylphenoxy)-2-cyanobenzoate; and 1' (thioethylcarbonyl)ethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate.
It is, of course, to be further understood that the stereo and optical isomers of compounds represented by the above formula are within the scope of this invention.
The compounds of this invention are typically synthesized by, for example, reacting an appropriately substituted benzoyl halide with an alcohol (or thiol) or an appropriately substituted a-hydroxycarboxylic ester or by reacting an appropriately substituted benzoic acid with an appropriately substituted a-halocarboxylic ester using techniques known to the art. The substituted benzoyl halides (or acids) and the substituted a-hydroxy (or ct-halo) carboxylic esters may be obtained from commercial sources or prepared by known techniques.More particularily, an at least stoichiometric amount of substituted benzoyl halide is added with stirring to the substituted a-hydroxycarboxylic acid, preferably in the presence of an acid acceptor, such as, for example, triethylamine, pyridine, N,N-dimethyl aniline, or the like. Since the reaction is typically exothermic, the substituted benzoyl halide is added incrementally so that the temperature of the reaction mixture does not appreciably exceed about 35"C. When the compounds of this invention are prepared by reacting a substituted benzoic acid with an a-halocarboxylic ester, the latter is preferably added to the former in the presence of an azo compound, such as, for example, 1 ,5-diazobicyclo (5.4.0.) undec-5-ene (DBU).In either method of synthesis, the reaction may, if desired, by conducted in the presence of an inert solvent, such as, for example, benzene, methylene chloride, chloroform, ethyl acetate, tetrahydrofuran, or the like. At the completion of addition of the substituted benzoyl halide to the a-hydroxycarboxylic ester (or the completion of addition of the a-halocarboxylic ester to the substituted benzoic acid), the reaction mixture is heated to reflux and maintained at reflux until the reaction attains the desired extent of completion. The reaction mixture is then cooled to ambient temperature and typically washed consecutively with dilute acid, dilute base and water, and allowed to phase separate. Substituted diphenyl ether is recovered from the organic phase by any known technique, such as, for example, evaporation, crystallization, vacuum drying, or the like.If desired, the product, substituted diphenyl ether, may be further purified by, for example, recrystallization.
The compounds of this invention have been found effective in regulating the growth of a variety of undesirable plants, i.e. weeds, when applied, in an herbicidally effective amount, to the growth medium prior to emergence of the weeds or to the weeds subsequent to emergence from the growth medium. The term "herbicidally effective amount" is that amount of compound or mixture of compounds required to so injure or damage weeds such that the weeds are incapable of recovering following application. The quantity of a particular compound or mixture of compounds applied in order to exhibit a satisfactory herbicidal effect may vary over a wide range and depends on a variety of factors such as, for example, hardiness of a particular weed species, extent of weed infestation, climatic conditions, soil conditions, method of aplication, and the like.Typically, as little as 0.2 or less pound per acre to 10 or more pounds per acre of compound or mixtures of compounds may be required. Of course, the efficacy of a particular compound against a particular weed species may readily be determined by relatively straightforward laboratory or field testing in a manner well known to the art.
The compounds of this invention may be used as such or in formulation with agronomically acceptable adjuvants, inert carriers, other herbicides, or other commonly used agricultural compounds, for example, pesticides, stabilizers, safeners, fertilizers, and the like. The compounds of this invention, whether or not in formulation with other agromonically acceptable materials, are typically applied in the form of dusts, granules, wettable powders, solutions, suspensions, aerosols, emulsions, dispersions or the like in a manner well known to the art. When formulated with other typically used agronomically acceptable materials, the amount of compound or compounds of this invention present in the formulation may vary over a wide range, for example, from about 0.05 to about 95 percent by weight on weight of formulation.Typically such formulations will contain from about 5 to about 75 percent by weight of compound or compounds of this invention.
The compounds of this invention have been found effective in controlling a variety of broadleaf and grassy weeds at application rates of two (2) pounds per acre or less pre- or postemergence while not significantly damaging desirable crops such as, for example, corn, wheat, rice, and soybeans. Exemplary of weeds that may be effectively controlled by the application of compounds of this invention are wild mustard (Brassica kaber); yellow foxtail (Setaria glauca); crabgrass (Digitaria sanguinalis); coffeeweed (Sesbania spp.); velvetleaf (Abutilon theophrasti); johnsongrass (Sorghum halepense); barnyardgrass (Echinochloa crusgal li); jimsonweed (Datura stramonium); teaweed (Sida spinosa); tall morningglory (Roth); and the like.
The invention will now be further illustrated by reference to the following Examples in which:
Examples I through XII are illustrative of the synthesis of certain specific substituted diphenyl ether compounds ofthis invention, and
Example XIII is illustrative of the effectiveness of the compounds of the invention.
EXAMPLE I 1 '-lEfhoxycarb on ylleth y/ 5-(2-chloro-4- trifluornmed?yfphenoxy)-2-nftrnbenzoate A 100-milliter, 3-necked flask, provided with an addition funnel, a reflux condenser, and a magnetic stirring bar, was charged with 1.18 grams (0.01 mole) of ethyl lactate and 0.79 grams (0.01 mole) of pyridine in 30 milliliters of benzene. To the stirred solution, at ambient temperature (about 20"C.), was added dropwise 3.79 grams (0.01 mole) of 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzOyl choride in 20 milliliters of benzene. Exothermic heating was observed. After addition was complete, the reaction mixture was heated to reflux and maintained at reflux for 6 hours. The reaction mixture was then cooled, transferred to a separatory funnel and washed consecutively with 30-milliliter portions of 1 Normal hydrochloric acid, water, 1 Normal sodium hydroxide and water. The washed organic phase was dried over magnesium sulfate and concentrated on a rotary evaporator at 550C. to yield 2.89 grams of a light yellow oil identified as 1 '-(ethoxycarbonyl)ethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate having:
NMR (acetone, D6) 7.3-8.35 (complex multiplet, 6H); 5.355 (quartet, H); 4.285 (quartet, 2H); 1.626 (doublet, 3H); 1.256 (triplet,3H).
EXAMPLE II
I '-(Ethoxycarbon ylmeth ylleth y/ 5-{2-chloro-4-trífluoromethylphenoxy)-2-nitrobenzoate A 100 milliliter, 3-necked flask, provided with an addition funnel, a reflux condenser, and a magnetic stirring bar, was charged with 1.32 grams (0.01 mole) of ethyl 3-hydroxybutyrate and 1.1 grams (0.01 mole) oftriethylamine in 30 milliliters of benzene. To the stirred solution, at ambient temperature (about 20"C.), was added dropwise 3.69 grams (0.01 mole) of 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoyl chloride in 20 milliliters of benzene. After addition was complete, the reaction mixture was heated to reflux and maintained at reflux for 6 hours.The reaction mixture was then cooled, transferred to a separatory funnel, and washed consecutively with 30-milliliter portions of 1 Normal hydrochloric acid, water, 1 Normal sodium hydroxide and water. The washed organic phase was dried over magnesium sulfate and concentrated on a rotary evaporator at 550C. to yield 3.75 grams of a brown oil identified as 1 '-(ethoxycarbonylmethyl)ethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate having:
NMR (acetone d6) 7.2- 8.36 (complex multiplet, 6H); 5.5 b (quartet, 1 H);
4.155 (quartet, 2H);
2.75 5 (doublet, 2H); 1.35 (doublet overlapping triplet, 6H).
EXAMPLE Ill 2'-Ethoxycarbonyl 5-(2-chloro-4-trffluoro-methylphenoxy)-2-nitrobenzoate A 250-milliliter, 3-necked flask, provided with an addition funnel, a reflux condenser, and a magnetic stirring bar, was charged with 2.70 grams (0.03 mole) of 3-hydroxypropionic acid and 2.38 grams (0.03 mole) of pyridine in 110 milliliters of methylene chloride. To the stirred solution, at ambient temperature (about 20"C.), was added dropwise 11.37 grams (0.03 mole) of 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoyl chloride in 30 milliliters of methylene chloride. Exothermic heating was observed. After addition was complete, the reaction mixture was heated to reflux and maintained at reflux for 22 hours.The reaction mixture was then cooled, transferred to a separatory funnel and washed twice with 100-milliliter portions of 1 Normal hydrochloric acid and once with 100 milliliters of water. The washed organic phase was dried over magnesium sulfate and concentrated on a rotary evaporator at 55 C. to yield 11.8 grams of a viscous yellow oil identified as 2'-ethoxycarbonyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate having:
NMR (acetone d6) 7.2 - 8.4 d (complex multiplet, 6H); 4.3 b (triplet, 2H); 2.67 5 (triplet, 2H).
EXAMPLE IV 2 '-(Ethoxycarbon yI)ethyl 5- (2-chloro-4-trifluoro-methylphenoxy)-2-nitrobenzoa te A 100-milliliter, 3-necked flask, provided with an addition funnel, a reflux condenser, and a magnetic stirring bar, was charged with 20 milliliters of ethanol and 5 milliliters of pyridine in 30 milliliters of methylene chloride. To the stirred solution, at ambient temperature (about 20"C.), was added dropwise 2.26 grams (0.005 mole) of 2'-(chlorocarbonyl )-ethyl 5-(2-chloro-4-trifl uoromethyl phenoxy)-2-nitrobenzoate in 15 milliliters of methylene chloride. After addition was complete, the reaction mixture was heated to reflux and maintained at reflux for 42.5 hours.The reaction mixture was then cooled and concentrated on a rotary evaporator at 55 C. The concentrated residue was taken up in 100 milliliters of methylene chloride, transferred to a separatory funnel and washed consecutively with 30-milliliter portions of 1 Normal hydrochloric acid, water, 7 percent aqueous ammonium hydroxide and water. The washed organic phase was dried over magnesium sulfate and concentrated on a rotary evaporator at 55to. to yield 1.3 grams of a yellow oil identified as 2'-(ethoxycarbonyl)ethyl 5-(2-chloro-4-trifl uoromethyl phenoxy)-2-nitrobenzoate, having:
NMR (chloroform) 7.0- 8.1 ò (multiplet, 6H); 4.3 ò (multiplet, 4H);
2.655 (triplet, 2H);
1.3 b (triplet, 3H).
EXAMPLE V 1'-KEthoxycarbonyl)methyl 5-r2-chloro-4-trifluoro-methylphenoxy)-2-nitrobenzoate A 100-milliliter, 3-necked flask, provided with an addition funnel, reflux condenser and a magnetic stirring bar, was charged with 1.25 grams (0.012 mole) of ethyl glycolate and 0.80 gram (0.01 mole) of pyridine in 35 milliliters of methylene chloride. To the stirred solution, at ambient temperature (about 20"C), was added dropwise 3.79 grams (0.01 mole) of 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzOyl chloride in 20 milliliters of methylene chloride. Exothermic heating was observed. After addition was complete, the reaction mixture was heated to reflux and maintained at reflux for 42.5 hours.The reaction was then cooled, transferred to a separatory funnel and washed consequently with 30-milliliter portions of 1 Normal hydrochloric acid, water, 7 percent aqueous ammonium hydroxide and water. The washed organic phase was dried over magnesium sulfate and concentrated on a rotary evaporator at 55 C. to yield 3.5 grams of a yellow oil identified as 1'-(ethoxycarbonyl)methyl 5-(2-chloro4-trifl uoromethyl-phenoxy)-2-nitrobenzoate having:
NMR (chloroform) 7.0-8.45 (multiplet, 6H); 4.825 (singlet, 2H);
4.255 (quartet, 2H);
1.31 5 (triplet, 3H).
EXAMPLE VI 1'-Ethoxycarbonyl-2'-oxopropyl 5-(2-chloro-4-trffluoro-methylphenoxy)-2-nitrobenzoate A 100-milliliter, 3-necked flask, provided with an addition funnel, reflux condenser, and magnetic stirring bar, was charged with 3.61 grams (0.01 mole) of 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoic acid and 1.53 grams (0.01 mole) of 1,5-diazobicyclo (5.4.0.) undec-5-ene (DBU) in 50 milliliters of benzene. To the stirred solution, at ambient temperature (about 20 C.), was added 1.65 grams (0.01 mole) of ethyl 2-chloroacetoacetate. The reaction mixture was then heated to reflux and maintained at reflux for 20.5 hours.
The reaction mixture was then cooled, transferred to separatory funnel, and washed consecutively with 30-milliliter portions of 1 Normal hydrochloric acid, water, 7 percent aqueous ammonium hydroxide and water. The washed organic phase was dried over magnesium sulfate and concentrated on a rotary evaporator at 55 C. to yield 3.1 grams of a brown oil identified as 1 '-ethoxycarbonyl-2'-oxopropyl 5-(2-chloro-4-trifluoromethyl phenoxy)-2-nitrobenzoate having:
NMR (acetone, d6) 7.2-8.25 (multiplet, 6H); 5.8 à (singlet, 1 H); 4.2 b (quartet, 2H); 2.3 à (singlet, 3H).
EXAMPLE VII 1 '-(EthoxycaThon yI)butyl 5-r2-chloro-4trifluoro-methylphenoxy)-2-nitrobenzoate A 100-milliter, 3-necked flask, provided with an addition funnel, a reflux condenser, and a magnetic stirring
bar, was charged with 3.61 grams (0.01 mole) of 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzOic acid and 1.53 grams (0.01 mole) of DBU in 50 milliliters of benzene. To the stirred solution, at ambient temperature, was added 2.19 grams (0.01 mole) of ethyl-2-bromovalerate. The reaction mixture was then heated to reflux and maintained at reflux for 22 hours. The reaction mixture was then cooled, transferred to a separatory funnel and washed consecutively with 30-milliliter portions of 1 Normal hydrochloric acid, water, 7 percent aqueous ammonium hydroxide and water.The washed organic phase was dried over magnesium sulfate and concentrated on a rotary evaporator at 55-C. to yield 2.2 grams of a brown oil identified as 1'-(ethoxycarbonyl)butyl 5-(2-chloro-4-trifluoromethyl )-2-nitrobenzoate having:
NMR (acetone d6) 7.2 - 8.2 ò (multiplet, 6H); 5.25 5 (triplet, 1 H); 4.28 b (quartet, 2H); 0.8- 1.9# (multiplet, 10H).
EXAMPLE VIII 7 '-IPhenoxycarbonyllethyl 5-(2-chloro-4-trifluoromethylphenoxy-2-nitrobenzoate A 100-milliliter, 3-necked flask, provided with an addition funnel, a reflux condenser, and a magnetic
stirring bar, was charged with 3.61 grams (0.01 mole) of 5-(2-chloro-4-trifluoromethylphenoxy)-2
nitrobenzoic acid and 1.53 grams (0.01 mole) of DBU in 50 milliliters of benzene. To the stirred solution, at
ambient temperature (about 20-C.), was added 2.29 grams (0.01 mole) of phenyl-2-bromoacetate. The
reaction mixture was then heated to reflux and maintained at reflux for 22.5 hours. The reaction mixture was then cooled, transferred to a separatory funnel and washed consecutively with 30-milliliter portions of 1
Normal hydrochloric acid, water, 1 Normal sodium hydroxide and water. The washed organic phase was dried over magnesium sulfate and concentrated on a rotary evaporator at 55-C. to yield 2.58 grams of a light green syrupy liquid identified as 1 '-(phenoxycarbonyl)ethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2
nitrobenzoate having:
NMR (acetone, d6) 7.0-8.255 (multiplet, 11 H); 5.5 b (quartet. 1H1;
1.685 (doublet, 3H).
EXAMPLE IX 1'-{Ethoxycarbonyl)propyl 5-(2-chloro-4-trifluoro-methylphenoxy)-2-nitrobenzoate A 100-milliliter. 3-necked flask, provided with an addition funnel, reflux condenser, and a magnetic stirring bar, was charged with 3.61 grams (0.01 mole) of 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoic acid and 1.53 grams (0.01 mole) of DBU in 35 milliliters of benzene. To the stirred solution, at ambient temperature (about 20 C.), was added dropwise 1.95 grams (0.01 mole)of ethyl-2-bromobutyrate in 15 milliliters of benzene. Exothermic heating was observed. After addition was complete, the reaction mixture was heated to reflux and maintained at reflux for 24 hours.The reaction mixture was then cooled, transferred to a separatory funnel and washed consecutively with 30-milliliter portions of 1 Normal hydrochloric acid, water, 7 percent aqueous ammonium hydroxide and water. The washed organic phase was dried over magnesium sulfate, concentrated on a rotary evaporator at 55 C. to yield 1.2 grams of a light brown syrupy liquid identified as 1 '-(ethoxyca rbonyl )propyl 5-(2-chloro-4-trifluoromethyl phenoxy)-2-nitrobenzoate having: NMR (acetone, d5) 7.2-8.2 6 (multiplet, 6H); 5.15 6 (triplet, H);
4.2 6 (quartet, 2H); 1.9 b (quartet, 2H); 0.8- 1.3 b (overlapping triplets, 6H).
EXAMPLE X 1'-Ethoxycarbonyl-3'-methy/butyl 5-(2-chloro-4-trffluoromethylphenoxy)-2-nitrobenzoate A 100-milliliter, 3-necked flask, provided with an addition funnel, a reflux condenser, and a magnetic stirring bar, was charged with 1.60 grams (0.01 mole) of ethyl ct-hydroxyisocaproate and 0.79 grams (0.01 mole) or pyridine in 40 milliliters of methylene chloride. To the stirred solution, at ambient temperature (about 20"C.), was added dropwise 3.79 grams (0.01 mole) of 5-(2-chloro-4-trifluoromethylphenoxy)-2nitrobenzoyl chloride in 10 milliliters of methylene chloride. Exothermic heating was observed. After addition was complete, the reaction mixture was heated to reflux and maintained at reflux for 46.5 hours.
The reaction mixture was then cooled, transferred to a separatory funnel and washed consecutively with 25-milliliter portions of 1 Normal hydrochloric acid, water, 3.5 percent aqeuous ammonium hydroxide and water. The washed organic phase was dried over magnesium sulfate and concentrated on a rotary evaporator at 55cm. to yield 3.99 grams of a viscous, brown oil identified as 1 '-ethoxycarbonyl-3'-methy.lbutyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate having:
NMR (acetone, d5) 7.2 - 8.3 (multiplet, 6H); 5.2 (triplet, 1H); 4.2 (quartet, 2H);
1.8 (multiplet 3H); 0.8- 1.45(multiplet,9H).
EXAMPLE XI 1 '-Ethoxycarbon4-2 '-h ydroxypropyl 5-(2-chloro-4-trifluorometh ylphenoxy)-2-nitrobenzoate A 500-milliliter, 3-necked flask, provided with an addition funnel, a reflux condenser, and a magnetic stirring bar, was charged with 19.56 grams (0.04 mole) of 1 '-ethoxycarbonyl-2'-oxopropyl 5-(2-chloro-4trifluoromethylphenoxy)-2-nitrobenzoate (prepared in accordance with Example VI) in 100 milliliters of methanol. To the stirred solution, at ambient temperature (about 20"C.), was added 3.14 grams (0.05 mole) of sodium cyanoborohydride and a few drops of methyl orange indicator. A 75:25 v/v solution of 2N hydrochloric acid and methanol was added dropwise at a rate sufficient to maintain the indicator color.The reaction mixture was then heated to reflux and maintained at reflux for 20 hours; after which the reaction mixture was cooled and concentrated on a rotary evaporator at 55"C. The concentrated residue was taken up in 200 milliliters of diethylether, transferred to a separatory funnel and washed consecutively with 100-milliliter portions of 1 Normal hydrochloric acid, water, 1 Normal sodium hydroxide and water.The washed organic phase was then dried over magnesium sulfate and concentrated on a rotary evaporator at 55"C. to yield 18.1 grams of yellow, syrupy liquid identified as 1'-ethoxycarbonyl-2'-hydroxypropyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate having: NMR(acetone,d6) 7.2- 8.3 ò (multiplet,6H); 4.2 5 (multiplet, 3H);
3.2 5 (quartet, 2H); 1.3 b (doublet overlapping triplet, 5H).
EXAMPLE XII 1' FEthoxycarbonyl)ethyl 5- (2-chloro-4-trffluorometh ylphenoxy)-2-bromobenzoate A 100-milliliter, 3-necked flask, provided with an addition funnel, a reflux condenser, and a magnetic stirring bar, was charged with 1.18 grams (0.01 mole) of ethyl lactate and 0.79 grams (0.01 mole) of pyridine in 50 milliliters of methylene chloride. To the stirred solution, at ambient temperature (about 20"C.), was added dropwise 2.07 grams (0.005 mole) of 5-(2-chloro-4-trifluoromethyl phenoxy)-2-bromobenzoyl chloride in 10 milliliters of methylene chloride. Exothermic heating was observed. After addition was complete, the reaction mixture was heated to reflux and maintained at reflux for 66 hours.The reaction mixture was then cooled, transferred to a separatory funnel and washed consecutively with 30-milliliter portions of 1 Normal hydrochloric acid, water, 7 percent aqueous ammonium hydroxide and water. The washed organic phase was dried over magnesium sulfate and concentrated on a rotary evaporator at 55"C. to yield 2.2 grams of a viscous, yellow, syrupy liquid identified as 1 '-(ethoxycarbonyl)ethyl 5-(2-chloro-4-trifluoromethylphenoxy)- 2-bromobenzoate having:
NMR (acetone, dg) 7.0 - 8.05 (multiplet, 6H); 5.255 (quartet, 1 H); 4.18 6 (doublet, 3H); 1.685 (doublet 3H); 1.185 (triplet, 6H).
Although syntheses of compounds of this invention have been illustrated in some detail by the foregoing
Examples I through XII, it is to be understood that any compound contemplated to be within the scope of this invention may be prepared by those skilled in the art simply by varying the choice of starting materials and using the illustrated techniques or any other suitable techniques.
EXAMPLE XIII Certain of the compounds prepared according to Examples I through XII were tested for herbicidal activity against certain weed species under controlled laboratory conditions of light, temperature, and humidity.
Seeds of selected weeds were planted in flats. For preemergence tests, the flats were treated with the selected compound immediately after planting. For postemergence tests, the flats were treated with the selected compound after a two-week's germination period. The compound was applied to the flats by spraying a solvent solution of the compound at the indicated rate of application, the state of growth of the weeds was observed, and the toxic effect of the compound was evaluated periodically after application.
The following shows, in tabular form, the weed species (identified by common name) and the compound applied (indicated by an "X" and identified by reference to the Example in which it was prepared) to the weed species. In each case, the compound was applied pre-emergent at a rate of two (2) pounds per acre.
Weed Compound
II IV V Vi VII Vlil IX X
Teaweed X X X X Jimsonweed X X X X X X X X X
Wild mustard X X X X X X X X Yellowfoxtail X X X X X X X X Largecrabgrass X X X X X X X X
Johnsongrass X X X X X X X
Coffeeweed X X X X X
Velvetleaf X X X X X
Tall morningglory X X X X X
Wild oats X X X
Barnyardgrass X X X X X X
In each of the foregoing tests, it was observed that all of the various weeds were either killed or injured beyond recovery within 21 to 22 days after application of the particular compound.
In the following table, the specified compound was applied post-emergent to the specified weed species at a rate of two (2) pounds per acre.
Weed Compound
II Ill IV V VI VII VIII IX X
Teaweed X X X X
Jimsonweed X X X X X X X X X
Wild mustard X X X X X X X X X X
Yellow foxtail X X X X X X X Largecrabgrass X
Johnsongrass X X X X
Coffeeweed X X X X X X X X X X
Velvet leaf X X X X X X
Tall morningglory X X X X X X X X X
Wild oats X X X X
Barnyardgrass X X X
Cockleburr X X X X
In each of the foregoing tests, it was observed that all of the various weeds were either killed or injured beyond recovery within 21 to 22 days after application of the particular compound.
It has been observed that compounds of this invention wherein the 'A' substituent is other than nitro, for example, halogen and specifically, bromine (as typified by the compound prepared according to Example
XII), exhibit somewhat better herbicidal activity when applied postemergent rather than preemergent at rates below about 5 pounds per acre, for example, at 2 or less pounds per acre. The compounds of this invention wherein the 'A' substituent is nitro have been generally found effective either pre- or postemergent at application rates of 2 or less pounds per acre.
Although the invention has been described in considerable detail with reference to illustrative embodiments thereof, it is to be understood that it is not intended to be so limited since many variations may be made therein by those skilled in the art without departing from the spirit and scope thereof as defined in the appended claims.
Claims (21)
1. A compound represented by the general formula:
wherein:
A is halogen, cyano or nitro;
X is hydrogen or halogen;
Y is hydrogen, halogen, cyano, trifluoromethyl, or alkyl containing 1 to 4 carbon atoms;
Z is oxygen or sulfur;
R is alkylidene or monosubstituted alkylidene containing 1 to 3 carbon atoms, wherein the substituent is selected from alkyl, oxoalkyl or hydroxyalkyl containing 1 to 4 carbon atoms; and
R1 is hydrogen, alkyl or alkoxy containing 1 to 10 carbon atoms, cycloalkyl containing 3 to 8 carbon atoms, an agronomically acceptable ionic species, phenyl, or mono-, di-, ortrisubstituted phenyl wherein the substituent(s) is (are) selected from halogen, alkyl or alkoxy containing 1 to 10 carbon atoms, cyano, nitro, or trifluoromethyl, or an optical or stereo isomer thereof.
2. A compound as claimed in claim 1, wherein Z is oxygen.
3. A compound as claimed in claim 1 or 2, wherein R1 is alkyl containing up to 4 carbon atoms.
4. A compound as claimed in any one of the preceding claims, wherein A is nitro.
5. A compound as claimed in any one of claims 1 to 3, wherein A is halogen or cyano.
6. A compound as claimed in any one of claims 1 to 4, wherein A is nitro, Z is oxygen, R1 is alkyl of up to 4 carbon atoms, X is hydrogen, and Y is halogen.
7. A compound as claimed in claim 1, which is 1 '-(ethoxycarbonyl)ethyl 5-(2-chloro-4trifluoromethylphenoxy)-2-nitrobenzoate; 1 '-(ethoxycarbonylmethyl)-ethyl 5-(2-chloro-4trifluoromethyl phenoxy)-2-nitrobenzoate; 2'-ethoxycarbonyl 5-(2-chloro-4-trifl uoromethylphenoxy)-2nitrobenzoate; 2'-(ethoxyca rbonyl )ethyl 5-(2-chloro-4-trifl uoromethyl phenoxy)-2-nitrobenzoate; 1 '-(ethoxycarbonyl)methyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenxoate; 1 '-ethoxycarbonyl-2'-oxopropyl 5 (2-chloro-4-trifluoromethyl phenoxy)-2-nitrobenzoate; 1 '-(ethoxycarbonyl )butyl 5-(2-chloro-4trifluoromethylphenoxy)-2-nitrobenzoate; 1 '-(phenoxycarbonyl)ethyl 5-(2-chloro-4trifluoromethylphenoxy)-2-nitrobenzoate; 1 '-(ethoxycarbonyl )propyl 5-(2-chloro-4-trifluoromethylphenoxy)- 2-nitrobenzoate; 1 '-ethoxycarbonyl-3'-methylbutyl 5-(2-ch loro-4-trifluoromethyl phenoxy)-2-nitrobenzoate; 1 '-ethoxycarbonyl-2'-hyd roxypropyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate; or 1' (ethoxycarbonyl )-ethyl 5-(2-chloro-4-trifluoromethyl phenoxy)-2-bromobenzoate.
8. A compound as claimed in claim 1, wherein X is hydrogen, chlorine or bromine, Y is chlorine, A is nitro, R is -CH(CH3)-, Z is oxygen or sulfur and R' is a straight or branched chain alkyl of up to 10 carbon atoms or a cycloalkyl of from 5 to 7 carbon atoms.
9. A compond as claimed in claim 1, substantially as hereinbefore described in Example I.
10. A compound as claimed in claim 1, substantially as hereinbefore described in any one of Examples II to XII.
11. A method of making a compound as clainned in claim 1 ,which comprises reacting a substituted benzoyl halide of the formula:
wherein X, Y, and A have the meanings given in claim 1, and hal represents halogen, with a substituted o-hydroxycarboxylic ester of the general formula:
wherein R, Z and R' have the meanings given in claim 1.
12. A method as claimed in claim 11, wherein X, Y, A, R, Z and R1 have the meanings given in claim 8.
13. A method of making a compound as claimed in claim 1, which comprise reacting a compound of the general formula:
wherein X, Y, A and R have the meanings given in claim 1 and Hal has the meaning given in claim 11, with an alcohol oftheformula: R1-ZH wherein R1 and Z have the meanings given in claim 1, other than hydrogen.
14. A method of making a compound as claimed in claim 1, which comprises reacting a substituted benzoic acid of the general formula:
wherein X, Y and A have the meanings given in claim 1, with a substituted -halocarbaxylic ester of the general formula:
wherein R, Z and R1 have the meanings given in claim 1 and Hal has the meaning given in claim 11.
15. A method as claimed in claim 12, substantially as hereinbefore described in Example I.
16. A method as claimed in any one of claims 11 to 14 substantially as hereinbefore described in any one of Examples II to XII.
17. A herbicidal composition containing a herbicidally effective amount of a compound as claimed in any one of claims 1 to 7 or 10 or mixture of such compounds.
18. A herbicidal composition containing a herbicidally effective amount of a compound as claimed in claim 8 or 9, or a mixture of such compounds.
19. A method of controlling weed growth wherein a herbicidally effective amount of a compound as claimed in any one of claims 1 to 7 or 10, or a mixture of such compounds, is either applied to the growth medium prior to emergence of the weeds or applied to the weeds subsequent to emergence from the growth medium.
20. A method of controlling weed growth wherein a herbicidally effective amount of a compound as claimed in claim 8 or 9, or a mixture of such compounds is either applied to the growth medium prior to emergence of the weeds or is applied to the weeds subsequent to emergence from the growth medium.
21. A method of controlling weeds substantially as hereinbefore described in Example Xlil.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US6548079A | 1979-08-10 | 1979-08-10 | |
| US16346080A | 1980-06-27 | 1980-06-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2058055A true GB2058055A (en) | 1981-04-08 |
| GB2058055B GB2058055B (en) | 1984-06-13 |
Family
ID=26745647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8025861A Expired GB2058055B (en) | 1979-08-10 | 1980-08-08 | Herbicidal-substituted diphenyl ethers |
Country Status (31)
| Country | Link |
|---|---|
| KR (1) | KR840000739B1 (en) |
| AR (1) | AR230617A1 (en) |
| AT (2) | AT367966B (en) |
| AU (1) | AU527273B2 (en) |
| BE (1) | BE884698A (en) |
| BG (1) | BG36630A3 (en) |
| BR (1) | BR8004871A (en) |
| CH (1) | CH643808A5 (en) |
| CS (1) | CS235509B2 (en) |
| DD (1) | DD160269A5 (en) |
| DE (1) | DE3029728C2 (en) |
| DK (1) | DK343180A (en) |
| EG (1) | EG14309A (en) |
| ES (1) | ES494098A0 (en) |
| FI (1) | FI69057C (en) |
| FR (1) | FR2463119A1 (en) |
| GB (1) | GB2058055B (en) |
| GR (1) | GR70086B (en) |
| HU (1) | HU191024B (en) |
| IE (1) | IE50082B1 (en) |
| IT (1) | IT1132542B (en) |
| LU (1) | LU82699A1 (en) |
| NL (1) | NL8004475A (en) |
| NO (1) | NO149207C (en) |
| OA (1) | OA06698A (en) |
| PH (1) | PH17123A (en) |
| PL (1) | PL127425B1 (en) |
| PT (1) | PT71628A (en) |
| RO (1) | RO81103A (en) |
| SE (1) | SE441091B (en) |
| YU (1) | YU41936B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0063741A1 (en) * | 1981-04-23 | 1982-11-03 | Bayer Ag | Derivatives of 5-(2,6-dichloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoic acid, method for their preparation and their use as herbicides and plant growth regulators |
| EP0089538A1 (en) * | 1982-03-19 | 1983-09-28 | Bayer Ag | Optically active derivatives of phenoxy-benzoic acid, process for their preparation and their use as herbicides |
| EP0090204A1 (en) * | 1982-03-19 | 1983-10-05 | Bayer Ag | Optically active levorotatory derivatives of phenoxy-benzoic acid, method for their preparation and their use as herbicides |
| US4460402A (en) * | 1981-07-10 | 1984-07-17 | Rhone-Poulenc Agrochimie | Synergistic herbicide compositions of phenoxybenzoic acids and cyclohexanediones |
| US4667052A (en) * | 1981-06-16 | 1987-05-19 | Rhone-Poulenc Inc. | 2-nitro-5-(substituted phenoxy) benzoate esters of hydroxyalkanoic acids and derivatives thereof as herbicides |
| US4889946A (en) * | 1979-12-14 | 1989-12-26 | Bayer Aktiengesellschaft | Phenoxybenzoic acid compounds and herbicidal and plant growth regulant compositions |
| FR2640968A1 (en) * | 1988-12-27 | 1990-06-29 | Budapesti Vegyimuevek | (S) and (R,S)-1'-Alkoxycarbonylethyl 2-chloro-5-(2-chloro-4-trifluoromethylphenoxy)benzoates, process for their preparation and their use in herbicidal compositions |
| FR2640967A1 (en) * | 1988-12-27 | 1990-06-29 | Budapesti Vegyimuevek | (S)-1'-Methoxycarbonylethyl 2-bromo-5-(2-chloro-4-trifluoromethylphenoxy)benzoate and (S)-1'-ethoxycarbonylethyl 2-bromo-5-(2-chloro-4-trifluoromethylphenoxy)benzoate, process for their preparation and their use in herbicidal compositions |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK155935C (en) * | 1979-05-16 | 1989-10-16 | Rohm & Haas | SUBSTITUTED DIPHENYLETHERS, HERBICIDE PREPARATIONS CONTAINING THESE COMPOUNDS AND PROCEDURES TO COMBAT WEEDS |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3776715A (en) * | 1969-04-25 | 1973-12-04 | Mobil Oil Corp | Halophenoxy benzoic acid herbicides |
| US4164408A (en) * | 1971-02-11 | 1979-08-14 | Mobil Oil Corp. | Salts of substituted phenoxybenzoic acids, compositions of the same and herbicidal use thereof |
| JPS5610883B2 (en) * | 1973-12-27 | 1981-03-11 | ||
| CA1140563A (en) * | 1976-12-03 | 1983-02-01 | Wayne O. Johnson | Herbicidal esters of 4-trifluormethyl-3'- carboxy-4'-nitro diphenyl ethers |
| DK155935C (en) * | 1979-05-16 | 1989-10-16 | Rohm & Haas | SUBSTITUTED DIPHENYLETHERS, HERBICIDE PREPARATIONS CONTAINING THESE COMPOUNDS AND PROCEDURES TO COMBAT WEEDS |
-
1980
- 1980-07-17 FI FI802269A patent/FI69057C/en not_active IP Right Cessation
- 1980-07-18 NO NO802172A patent/NO149207C/en unknown
- 1980-07-29 AU AU60875/80A patent/AU527273B2/en not_active Expired
- 1980-07-29 YU YU1912/80A patent/YU41936B/en unknown
- 1980-07-30 AR AR281984A patent/AR230617A1/en active
- 1980-07-31 BG BG8048691A patent/BG36630A3/en unknown
- 1980-07-31 PT PT71628A patent/PT71628A/en unknown
- 1980-08-04 BR BR8004871A patent/BR8004871A/en not_active IP Right Cessation
- 1980-08-04 CS CS805392A patent/CS235509B2/en unknown
- 1980-08-05 GR GR62608A patent/GR70086B/el unknown
- 1980-08-05 PH PH24408A patent/PH17123A/en unknown
- 1980-08-05 IE IE1629/80A patent/IE50082B1/en not_active IP Right Cessation
- 1980-08-05 KR KR1019800003113A patent/KR840000739B1/en active
- 1980-08-05 OA OA57189A patent/OA06698A/en unknown
- 1980-08-06 NL NL8004475A patent/NL8004475A/en not_active Application Discontinuation
- 1980-08-06 DE DE3029728A patent/DE3029728C2/en not_active Expired
- 1980-08-06 EG EG480/80A patent/EG14309A/en active
- 1980-08-07 FR FR8017507A patent/FR2463119A1/en active Granted
- 1980-08-07 PL PL1980226124A patent/PL127425B1/en unknown
- 1980-08-07 DD DD80223176A patent/DD160269A5/en unknown
- 1980-08-07 RO RO80101924A patent/RO81103A/en unknown
- 1980-08-07 SE SE8005606A patent/SE441091B/en not_active IP Right Cessation
- 1980-08-07 AT AT0406780A patent/AT367966B/en not_active IP Right Cessation
- 1980-08-08 GB GB8025861A patent/GB2058055B/en not_active Expired
- 1980-08-08 HU HU801982A patent/HU191024B/en unknown
- 1980-08-08 ES ES494098A patent/ES494098A0/en active Granted
- 1980-08-08 IT IT24082/80A patent/IT1132542B/en active
- 1980-08-08 LU LU82699A patent/LU82699A1/en unknown
- 1980-08-08 CH CH604180A patent/CH643808A5/en not_active IP Right Cessation
- 1980-08-08 BE BE0/201690A patent/BE884698A/en not_active IP Right Cessation
- 1980-08-08 DK DK343180A patent/DK343180A/en unknown
-
1981
- 1981-12-15 AT AT0536081A patent/AT382760B/en not_active IP Right Cessation
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4889946A (en) * | 1979-12-14 | 1989-12-26 | Bayer Aktiengesellschaft | Phenoxybenzoic acid compounds and herbicidal and plant growth regulant compositions |
| EP0063741A1 (en) * | 1981-04-23 | 1982-11-03 | Bayer Ag | Derivatives of 5-(2,6-dichloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoic acid, method for their preparation and their use as herbicides and plant growth regulators |
| US4667052A (en) * | 1981-06-16 | 1987-05-19 | Rhone-Poulenc Inc. | 2-nitro-5-(substituted phenoxy) benzoate esters of hydroxyalkanoic acids and derivatives thereof as herbicides |
| US4460402A (en) * | 1981-07-10 | 1984-07-17 | Rhone-Poulenc Agrochimie | Synergistic herbicide compositions of phenoxybenzoic acids and cyclohexanediones |
| EP0089538A1 (en) * | 1982-03-19 | 1983-09-28 | Bayer Ag | Optically active derivatives of phenoxy-benzoic acid, process for their preparation and their use as herbicides |
| EP0090204A1 (en) * | 1982-03-19 | 1983-10-05 | Bayer Ag | Optically active levorotatory derivatives of phenoxy-benzoic acid, method for their preparation and their use as herbicides |
| FR2640968A1 (en) * | 1988-12-27 | 1990-06-29 | Budapesti Vegyimuevek | (S) and (R,S)-1'-Alkoxycarbonylethyl 2-chloro-5-(2-chloro-4-trifluoromethylphenoxy)benzoates, process for their preparation and their use in herbicidal compositions |
| FR2640967A1 (en) * | 1988-12-27 | 1990-06-29 | Budapesti Vegyimuevek | (S)-1'-Methoxycarbonylethyl 2-bromo-5-(2-chloro-4-trifluoromethylphenoxy)benzoate and (S)-1'-ethoxycarbonylethyl 2-bromo-5-(2-chloro-4-trifluoromethylphenoxy)benzoate, process for their preparation and their use in herbicidal compositions |
| GB2226561A (en) * | 1988-12-27 | 1990-07-04 | Budapesti Vegyimuevek | Herbicidal (S)-1-alkoxycarbonylethyl 2-bromo-5-(2-chloro-4-trifluoromethylphenoxy)benzoates |
| GR890100836A (en) * | 1988-12-27 | 1991-03-15 | Budapesti Vegyimuevek | Herbicidal diphenyl ethers substituted |
| GR890100837A (en) * | 1988-12-27 | 1991-03-15 | Budapesti Vegyimuevek | Herbicidac composition |
| BE1002794A4 (en) * | 1988-12-27 | 1991-06-11 | Budapesti Vegyimuevek | NEW HERBICIDE COMPOSITION. |
| BE1002811A4 (en) * | 1988-12-27 | 1991-06-18 | Budapesti Vegyimuevek | HERBICIDE COMPOSITION AND PROCESS FOR PREPARING THE SAME. |
| GB2226561B (en) * | 1988-12-27 | 1992-01-02 | Budapesti Vegyimuevek | Herbicidal (s)-1'-alkoxycarbonylethyl 2-bromo-5-(2-chloro-4-trifluoromethyl(phenoxy)benzoates |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930808 |