Oxime derivatives for protecting plant crops

Oxime derivatives of the formula (I) ##STR1## wherein n is 0, 1 or 2 and m is 0 or 1, and Ar is a phenyl radical ##STR2## a naphthyl radical substituted by R.sub.2 and R.sub.3, a 5- to 10-membered heterocyclic 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 ##STR3## wherein R.sub.9 is hydrogen, 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, or is lower alkenyl, lower haloalkenyl or lower alkynyl, 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.12 is lower alkyl or an aromatic group, while Y is O, S SO, SO.sub.2 or ##STR4## 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. These compounds are used for protecting plant crops from the action of aggressive agricultural chemicals.

The present invention relates to a method of protecting plant crops from 
the phytotoxic 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 
##STR5## 
wherein n is 0, 1 or 2 and m is 0 or 1, and Ar is a phenyl radical 
##STR6## 
a naphthyl radical substituted by R.sub.2 and R.sub.3, a 5- or 
10-membered heterocyclic 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 aromatic 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 a 5- or 6-membered heterocyclic ring 
which can additionally contain oxygen as possible further heteroatom, 
R.sub.1 is 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.sub.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, carbamoyl, 
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: 
##STR7## 
wherein R.sub.9 is hydrogen, 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, or is lower 
alkenyl, lower haloalkenyl or lower alkynyl, 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.12 is lower alkyl or an aromatic group, 
while Y is O, S, SO, SO.sub.2 or 
##STR8## 
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. Carbamoyl 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 araliphatic 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- or 
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, benzimidazole, quinoline, 
benz-1,3-dioxolane. Cycloalkyl groups are cyclopropyl, cyclobutyl, 
cyclopentyl, cyclohexyl and cycloheptyl. Cycloaliphatic 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 
##STR9## 
with a compound of the formula III 
EQU Hal'-Q (III) 
or 
(b) where Q is -C.tbd.C Hal, by reacting a compound of the formula IV 
##STR10## 
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 solvents with one another. 
Where Me is hydrogen, the process is carried out in the presence of a base. 
Examples of suitable bases are inorganic 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 
temperatures are in the range between 0.degree. and 150.degree. C. The 
reactions 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 constitute 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 substance in commercial compositions is between 0.1% 
and 90% by weight. 
For application, the compounds of the formula I may be processed to the 
following formulations (in which the percentages by weight in brackets 
refer to advantageous amounts of active ingredient): 
Solid formulations: 
dusts, tracking agents, (up to 10%) granules (coated granules, impregnated 
granules and homogeneous granules); pellets (1 to 80%); 
Liquid formulations: 
(a) active substance concentrates which are dispersible in water: wettable 
powders, pastes; (25-90% in commercial packs, 0.01 to 15% in ready for use 
solutions; emulsifiable concentrates and concentrated solutions (10 to 
50%; 0.01 to 15% in ready for use solutions). 
(b) Solutions (0.1 to 20%); aerosols. 
Such compositions also constitute an object of the invention. 
Different compounds which 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 in 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 No. 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 Offenlegungsschriften Nos. 1 925 910 and 2 245 471, 
and French Pat. 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 Pat. 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 aggressive 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 phenoxyphenoxyphenoxyacetates and 
-propionates, benzoic acid derivatives, where these compounds are not 
tolerated or insufficiently tolerated by plants. 
The rates of application of the antidote with respect to the herbicide 
depend largely on the mode of application. 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 are 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 with 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 ingredient, 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 
action 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: 
for Q: 
(a) CH.sub.2 -C.tbd.CI 
(b) CH.sub.2 -O-phenyl (unsubstituted or substituted) 
(c) 
##STR11## 
-aryl (d) 
##STR12## 
(e) 
##STR13## 
(f) CH.sub.2 H.sub.2a -O-SO.sub.2 -lower alkyl (g) 
##STR14## 
A'=C.sub.2 -chain (h) 
##STR15## 
for Ar: (a) 
##STR16## 
(b) 1-naphthyl (c) 
##STR17## 
(d) benzoxazole (e) benzthiazole 
for X: 
(a) cyano 
(b) hydrogen 
(c) a carboxylic acid ester radical 
(d) lower alkyl 
for n and m: 
(a) n=2 m=1 
(b) m=0 
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.