Claims
- 1. A method of protecting rice crops from the phytotoxic action of haloacetanilide herbicides, which comprises adding to the herbicide or applying to the locus of the crops, as antidote, a compound of the formula ##STR83## wherein R.sub.1 is hydrogen or cyano, and
- R.sub.10 is lower alkyl or phenyl optionally substituted by halogen or trifluoromethyl,
- in a plant-protecting amount.
- 2. A method according to claim 20 in which, in the compound, R.sub.10 is methyl, phenyl, chlorophenyl, trifluoromethylphenyl or dichlorophenyl.
- 3. A method according to claim 1 in which the herbicide is N-(1-methyl-2-methoxyethyl)-N-chloroacetyl-2-ethyl-6-methylaniline
- 4. A method according to claim 2 in which the compound is phenylacetonitrile-oxime-(2'-meta-trifluoromethyl-anilidocarbonyloxyethyl) ether.
- 5. A method according to claim 4 in which the herbicide is N-(1-methyl-2-methoxyethyl)-N-chloroacetyl-2-ethyl-6-methylaniline.
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 9201/78 |
Aug 1978 |
CHX |
|
Parent Case Info
This is a divisional of application Ser. No. 68,263 filed on Aug. 20, 1979, now U.S. Pat. No. 4,353,735.
The present invention relates to a method of protecting plant crops from the phytoxic action of potent herbicides by means of oxime derivatives and also to a number of novel oxime derivatives.
The oxime derivatives employed as active compounds have the formula I ##STR2##
wherein
n is 0, 1 or 2 and m is 0 or 1, and
Ar is a phenyl radical ##STR3## a naphthyl radical substituted by R.sub.2 and R.sub.3, a 5- to 10-membered hetorcyclic radical which contains not more than 3 identical or different heteroatoms N, O and/or S and which is substituted by R.sub.2, R.sub.3 and R.sub.4 and can be substituted by oxo or thiono, or if m is 0, Ar is a radical R--CO, wherein R is a radical --OR.sub.5, in which R.sub.5 is an aliphatic group containing not more than 8 carbon atoms or is an araliphatic group containing not more than 15 carbon atoms or is a cycloaliphatic or aromatic group, each containing not more than 10 carbon atoms, while the possible substituents of the aromatic radicals or of the cycloaliphatic radical are halogen, --CN, --NO.sub.2, lower alkyl, lower alkoxy, haloalkyl; or R is a radical --NH--CO--NH--R.sub.7 or a radical --N(R.sub.6)(R.sub.7), wherein R.sub.6 is hydrogen or lower alkyl and R.sub.7 is hydrogen or an aliphatic group containing not more than 8 carbon atoms or an araliphatic group containing not more than 15 carbon atoms or a cycloaliphatic or aromtic group containing not more than 10 carbon atoms, while possible substituents of the aromatic groups or of the cycloaliphatic radical are halogen, --CN, NO.sub.2, lower alkyl, lower alkoxy, or haloalkyl; or R is a radical --N(R.sub.6)(R.sub.7), wherein R.sub.6 and R.sub.7 together form 5- or 6-membered heterocyclic ring which can additionally contain oxygen as possible further heteroatom,
R.sub.1 is a hydrogen, halogen, lower alkyl, lower alkoxy or a p-phenoxy radical which is unsubstituted or at most disubstituted by halogen, CN, NO.sub.2, CF.sub.3,
R.sub.2, R hd 3 and R.sub.4, each independently of the other, are hydrogen, halogen, CN, NO.sub.2, lower alkyl, lower alkoxy, haloalkyl, haloalkoxy, lower alkanoyl, OH, phenyl, halophenyl, lower carbalkoxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy, lower carbamoyloxy, lower alkylthio, lower alkylsulfonyl, phenalkoxy, cyclohexyl, NH.sub.2, --NH--lower alkyl, --N(di-lower alkyl), lower alkanoylamino, carbomayl, sulfamoyl,
X is hydrogen, --CN, halogen, lower alkyl, lower alkanoyl, --COOH, a carboxylic acid ester radical, a carbamoyl radical, and
Q is the radical --C.sub.a H.sub.2a --R.sub.8, wherein a is an integer between 1 and 6, while the corresponding radical can also be branched and R.sub.8 is one of the following radicals: ##STR4## wherein R.sub.9 is hydrogen, a cycloapliphatic, araliphatic or aromatic group which is unsubstituted or mono- or polysubstituted at the ring by CN, NO.sub.2, halogen, lower alkyl, lower alkoxy or haloalkyl, or is lower alkenyl, lower haloalkenyl or lower akhynl, R.sub.10 is an aliphatic group or a cycloaliphatic, araliphatic or aromatic group which is unsubstituted or mono- or polysubstituted at the ring by CN, NO.sub.2, halogen, lower alkyl, lower alkoxy or haloalkyl, R.sub.11 is hydrogen, lower alkyl or cycloalkyl, R.sub.11 or an aromatic group, while Y is O, S, SO, SO.sub.2 or ##STR5## and A is C.sub.2 -C.sub.3 alkylene or C.sub.2 -C.sub.3 alkenylene which is unsubstituted or substituted by halogen, CN or lower alkyl and which together with a carbon chain which is unsubstituted or substituted by halogen, CN or lower alkyl can form a fused ring, and Hal is halogen.
By halogen in formula I is meant fluorine, chlorine, bromine or iodine.
Carboxylic acid esters are lower alkyl esters. Carbomoyl radicals, in addition to --CONH.sub.2, are also monoalkyl-substituted or symmetrically or unsymmetrically dialkyl-substituted amides, while the alkyl groups are lower alkyl groups.
The term alkyl by itself or as moiety of another substituent comprises branched or unbranched alkyl groups of 1 to 8 carbon atoms. Lower alkyl by itself or as moiety of another substituent denotes C.sub.1 -C.sub.4 alkyl. Examples are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, as well as the higher homologues amyl, isoamyl, hexyl, heptyl, octyl, together with their isomers. By analogy, alkanoyl or cyanoalkyl groups contain an additional carbon atom. Lower alkenyl or alkynyl groups accordingly contain not more than 4 carbon atoms.
The term "aliphatic group" comprises saturated radicals (alkyls), and unsaturated radicals (alkenyls, alkadienyls, alkynyls), halogen-substituted radicals, cyano-substituted radicals, and radicals which are interrupted by oxygen. These radicals contain not more than 8 carbon atoms.
The term "aromatic group" comprises phenyl and naphthyl, which can in principle be mono- or polysubstituted by CN, NO.sub.2, halogen, lower alkyl, lower alkoxy or haloalkyl. An arapliphatic radical comprises an unsubstituted or mono- to trisubstituted phenyl or naphthyl radical which is bonded through lower alkyl or lower alkenyl to the radical of the molecule. Examples are benzyl, phenethyl, phenylallyl and their homologues.
Unsubstituted or substituted heterocyclic radicals can be mono- ot bicyclic. Examples are: furan, nitrofuran, bromofuran, methylfuran, thiophene, chlorothiophene, pyridine, 2,6-dichloropyridine, pyrimidine, pyridazine, pyrazine, piperidine, methylpiperidine, morpholine, thiomorpholine, tetrahydrofurane, oxazole, pyrazole, pyrrole, pyrroline, pyrrolidine, thiazole, 2,3-dihydro-4H-pyrane, pyrane, dioxane, or 1,4-oxathi-(2)-ine, benzthiazole, benzoxazole, bensimidazole, quinoline, benz-1,3-dioxolane. Cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cycohexyl and cycloheptyl. Cycloapliphatic radicals correspond to these ring systems, but, where possible, can additionally contain one or more double bonds.
The compounds of the formula I can be obtained
(a) with the exception of compounds, wherein Q is --C.tbd.C hal, by reacting a compound of the formula II ##STR6## with a compound of the formula III
(b) where Q is --C.tbd.C Hal, by reacting a compound of the formula IV ##STR7## with halogen in the presence of a base. In the above formulae II, III and IV, Ar, X, Q, m and n are as defined for formula I, Hal' is halogen, preferably chlorine or bromine, and Me is hydrogen or a metal cation, preferably an alkali metal or alkaline earth metal cation.
The compounds of the formula IV can be obtained by a process analogous to that of process (a).
The reactions can be carried out in the presence or absence of solvents which are inert to the reactants. Examples of suitable solvents are: alcohols, such as ethanol; ketones, such as acetone; nitriles, such as acetonitrile; N,N-dialkylated amides, such as dimethyl formamide; dimethyl sulfoxide, pyridine, or, in process (b), also water as well as mixtures of these solvent with one another.
Where Me is hydroge, the process is carries out in the presence of a base. Examples or suitable bases are inorgance bases, such as the oxides, hydroxides, hydrides, carbonates and bicarbonates of alkali metals and alkaline earth metals, as well as e.g. tertiary amines, such as trialkylamines (e.g. triethylamine), and pyridine. The reaction temperature are in the range between 0.degree. and 150.degree. C. The reaction are carried out under normal pressure and, in (a), optionally in a nitrogen atmosphere.
The compounds of the formula II are prepared by methods analogous to known ones. Processes (a) and (b) also constitutes an object of the invention.
The compounds of the formula I can be used by themselves or together with suitable carriers and/or other adjuvants. Suitable carriers and adjuvants can be solid or liquid and correspond to the substances normally used in the art of formulation, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.
The content of active substances in commercial compositions is between 0.1% and 90% by weight.
For application, the compounds of the formula I may be process to the following formulations (in which the percentages by weight in brackets refer to advantageous amounts of active ingredient):
Such compositions also constitute an object of the invention.
Different compounds which are are able to antagonise the harmful action of a herbicide on cultivated plants specifically have already been proposed as antidotes, i.e. compounds which protect cultivated plants without noticeably influencing the herbicidal action on the weeds which it is desired to control. Depending on their properties, such antidotes, also known as safeners, can be used for pretreating the seeds of the cultivated plants (dressing seeds or seedlings) or before sowing seeds n furrows or as tank mixture, by themselves or together with the herbicide or after emergence of the plants. The pre-emergence treatment includes both treatment of the crop area before sowing (ppi=pre-plant incorporation) and treatment of the crop areas after sowing but before emergence of the plants.
Thus, British patent specification 1 277 557 discloses the treatment of seed and seedlings of wheat and sorghum with certain esters and amides of oxamic acid before attack by N-methoxymethyl-2'-6'-diethyl-chloroacetanilide (Alachlor). Other publications (German Offenlegungsschriftne Nos. 1 952 910 and 2 245 471, and French patent specification No. 2 021 611), propose antidotes for the treatment of cereals, maize seeds and rice seeds to protect them against attack by herbicidal thiolcarbamates. In German patent specification No. 1 576 676 and U.S. Pat. No. 3,131,509, hydroxyamino-acetanilides and hydantoins are suggested for protecting cereal seeds against carbamates, such as IPC, CIPC, etc.
The further development, however, has shown all these preparations to be unsatisfactory.
Surprisingly, oximes of the formula I have the property of protecting cultivated plants from attack by aggressinve agricultural chemicals, in particular herbicides, of the most diverse compound classes, including 1,3,5-triazines, 1,2,4-triazinones, phenylurea derivatives, carbamates, thiolcarbamates, phenoxyacetates, phenoxypropionates, haloacetanilides, halophenoxyacetates, substituted phenoxyphenoxyphenoxycetates and -propionates, benzoic acid derivatives, where these compounds are not tolerated or insufficently tolerated by plants.
The rates of application of the antidote with respect to the herbicide depend largely on the mode of applications. Where a field treatment is carried out, the ratio of antidote of the formula I to phytotoxic chemical is 1:100 to 5:1, preferably 1:20 to 1:1. When dressing seeds and taking similar specific protective measures, however, much lower amounts of antidote and required in comparison with e.g. the amounts of herbicide later employed per hectare of crop area (e.g. about 1:3000 to 1:1000). As a rule, protective measures such as seed dressing wih an antidote of the formula I and possible later field treatment with agricultural chemicals are only loosely connected. Pretreated seeds and plants can later come into contact with different chemicals in agriculture, horticulture and forestry.
Accordingly, the invention relates to plant protection compositions which contain, as active ingredients, solely an antidote of the formula I together with conventional carriers. If appropriate or desired, such compositions can additionally be mixed with the chemical against the acton of which it is desired to protect the cultivated plant, for example with a herbicide.
Cultivated plants within the scope of this invention are all plants which, in any form, can be harvested (seeds, roots, stalks, tubers, leaves, blossoms) and from which extracts can be obtained (oils, sugar, starch, protein) and which for this purpose are cultivated and tended. To these plants belong e.g. all species of cereals, maize, rice, millet, soybeans, beans, peas, potatoes, vegetables, cotton, sugar beet, sugar cane, ground nuts, tobacco, hops, and also ornamentals, fruit trees and bananas, cocoa and natural rubber plants.
In principle, an antidote can be employed wherever it is desired to protect a cultivated plant from the phytotoxicity of a chemical.
The invention also relates to a method of protecting cultivated plants from aggressive (phytotoxic) chemicals, which comprises applying an oxime derivative of the formula I which acts as antidote, optionally before or after application of the chemical, or also simultaneously with the chemical.
The invention also relates to the propagation products of such cultivated plants which are given a protective treatment with an oxime derivative of the formula I. By propagation products are meant all generative parts of plants which can be used for the propagation of the cultivated plant, for example grains (seeds in the narrow sense), roots, fruit, tubers, rhizomes, parts of stalks, branches (seedlings) and other parts of plants. Propagation products also include pregerminated plants and young plants which, after pregermination or emergence, will be further transplanted. Such young plants can be selectively protected by means of a complete or partial immersion treatment before transplantation.
The following types of substituent or combinations thereof with one another are preferred:
The invention is illustrated by the following Examples, but without any restriction to what is described therein. Temperatures are in degrees centigrade, pressures in millibars, and parts and percentages are by weight.
US Referenced Citations (10)
Foreign Referenced Citations (1)
| Number |
Date |
Country |
| 2808317 |
Sep 1978 |
DEX |
Divisions (1)
|
Number |
Date |
Country |
| Parent |
68263 |
Aug 1979 |
|
Patent Grant
4486224
