CA1149398A - Compositions, which promote plant growth and protect plants, based on oxime ethers and oxime esters - Google Patents

Abstract

Abstract of the Disclosure Novel oxime ethers and oxime esters of the formula I given herein have various advantageous effects with regard to stimulation of plant growth, particularly in the early stage of development of the plant. Furthermore, such compounds have the property of rendering, in the sense of an antidote action, agricultural chemicals which would otherwise damage the plants (phytotoxic chemicals) more compatible with the cultivated plants.
Herbicides that are insufficiently selective can be used for example in the presence of such oxime derivatives in specific cultivated crops for combating weeds, without disadvantageous consequences for the cultivated plants.

Description

~ 3.~ ~

The present invention relates to novel oxime ethers and oxime esters of the general formula I

Ar - C - X (I) N-O-Q

to their production, and also to novel compositions based on these compounds, and to the application of these compositions or compounds for promoting plant growth or for protecting cultivated plants.
In the formula I
Ar represents a phenyl group of the formula

2 ~

an - or ~-naphthyl group, or a heterocyclic ring of the formula Rs X represents -CN, -N02, halogen, lower alkanoyl, a carboxylic acid ester group, hydrogen, a ca:rboxylic acid amide group, or lower alkyl, Q represents lower alkyl which is straight-chain or branched chain, or which can be interrupted by hetero atoms or sub-stituted by ha]ogen, or represents lower aLkenyl or haloalkenyl lower alkynyl, C3-C7-cycloalkyl optionally substituted by - 2 - ~

halogen, or represents lower cyanoalkyl, a lower alkanecarboxylic acid ester group, a lower alkanecarboxylic acid amide group, a lower aliphatic acyl group, a phenyl group optionally substituted by halogen or lower alkoxy, or an alkylsulphonic acid or a sulphonic acid amide group, Rl represents hydrogen, halogen, lower alkyl, lower alkoxy, or a phenoxy group which is in the para position and which is optionally substituted a maximum of twice by halogen, -CN, N02 or CF3, R2 and R3 independently of one another represent hydrogen, halogen, N02, lower alkyl, halogenoalkyl or lower alkoxy, 0 R4 and R5 independently of one another represent hydrogen, halogen N02 or lower alkyl, and Z represents oxygen or sulphur, with the proviso that, if Ar represents an unsubstituted phenyl group and Q
represents the radical -CH2CH, X represents N02, halogen, lower alkanoyl, a carboxylic acid group, a carboxylic acid ester group, hydrogen, a carboxylic acid amide group or lower alkyl and with the further proviso that, if Q is a lower alkane carboxylic acid ester or amide group and X is hydrogen or methyl, Ar is other than mono- or dihalo-substituted phenyl.
Depending on substitution of these oxime derivatives of the genera].
formula I, there are obtained products which have various properties influencing plant growth, and which can be used, in agriculture general].y or in special areas of plant protection, as plant-growth regulators or alternatively as antidotes (safeners) for pesticides.

9~98 By halogen in the formula I is meant fluorine, chlorine, bromine or iodine.
The expression alkyl on its own or as part of a substituent embraces branched-chain or straight-chain Cl- to C8-alkyl groups; and lower alkyl denotes Cl-C4-alkyl. Examples are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, as well as the higher homologues amyl, isoamyl, hexyl, heptyl or octyl, together with their isomers. Analogously, alkanoyls or cyanoalkyls contain an additional C atom. A lower alkanecarboxylic acid ester consists of a lower alkyl part having 1-4 C atoms, the carbonyl group and an alcoholic or phenolic radical having 1 to 8 C atoms. To be mentioned in particular are acetic ester -CH2-COOT (T = Cl-C8-radical) and l-propion ester -CH(CH3)-COOT, with OT = a lower aliphatic alcohol radical being preferred in both cases.
Alkenyls denote aliphatic radicals having one or also two double bonds ("alkadienyls") and a maximum of 6, preferably 4, C atoms. Halogenoalkenyls contain up to 3 halogen atoms, preferably chlorine or bromine. ~ower alkynyl denotes propynyl (= propargyl) and butynyl.
Carboxylic acid amides andisulphonic acid amides embrace also monosubstituted or symmetrically or unsymmetrically disubstituted amides, with the substituents being optionally lower alkyl, lower alkenyl, propynyl or butynyl, and also once a phenyl ring, which can be substituted or unsubstituted according to ~ 8 the definition for R2/R3.
C3-C7-cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. Cycloaliphatic radicals correspond to these ring systems, but they can also contain, depending on possibility, one or more double bonds.
An araliphatic radical includes an aryl group, such as phenyl, optionally mono- to tri.substituted according to R2/R3, or naphthyl, fluorenyl, or indanyl, which is bound by way of lower alkyl or lower alkenyl to the radical of the molecule.
Examples are the fundamental substances benzyl, phenethyl, phenylallyl, as well as homologues.
Aromatic carboxylic acids, which can form the aromatic acyl groups, are derived from aromatic substances, such as in particular phenyl, and can be substituted as defined under R2/R3.
Heterocyclic carboxylic acids are derived from mono- or bicyclic rings having 1 to 3 identical or different hetero atoms 0, S and N. To be mentioned are 3- to 6-membered, especially 5- or 6-membered, heterocycles, which can be saturated, partially saturated or unsaturated, and can be optionally substituted as defined under R4/R5. Examplès which may be mentioned but which do not constitute any limitation are: furan, nitrofuran, bromofuran, methylfuran, thiophene, chlorothiophene, pyridineS
2,6-dichloropyridine, pyrimidine, pyridazine, pyrazine, piperidine, methylpiperidine, morpholine, thiomorpholine, tetrahydrofuran, ~ 8 oxazole, pyrazole, pyrrole, pyrroline, pyrrolidine, thiazole, 2,3-dihydro-4H-pyrane, pyrane, dioxane or 1,4-oxathi-(2)-ine.
Examples of aliphatic chains interrupted by hetero atoms are methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl, ethylthioethyl, methylaminoethyl, tert-butyl-aminoethyl or alkoxyalkoxyalkyl, such as methoxyethoxyethyl.
It has been shown that oxime ethers and oxime esters of the formula I have for practical purpos~s extraordinarily advantageous properties for promoting plant growth, without there being any disadvantageous consequences for the plants treated therewith.
Applied in small dosage amounts, active substances of the formula I have in particular the ability to stimulate both the germinating seed and the young plants which are developing.
With specific dosage amounts, this leads to a clearly enlarged root system, to an increased rate of photosynthesis and to a more rapid development of parts of plants above the soil. The action of the oximes of the formula I is however not restricted to the early stage of plant development, but can be observed also in the case of later application, or in the case of a partial application to specific parts of plants (seed dressings, pre-swelling of the seed, root`treatment, treatment of shoots or leaf application). This manner of treatment leads to a more rapid growth of the treated plant, to improved fruit setting, to an earlier point of time of ripening and of harvesting and to an increased or otherwise improved crop yield. The active substances can be applied to the plant, to parts of the plant, 939~3 to the seed or to the soil, and the mode of application corresponds to customary techniques of application or of dressing. A further very important advantage is the improvement in the power to compete of the plant treated in this manner compared with that of the weed flora which has not been growth-stimulated. The active substance of the formula I must of course be applied in this case to the seed or to the seedlings of the desired crop of plants and not to the crop area in general. A
third important advantage, which is a result of the greatly expanding root system of a plant thus treated, is the possibility, even under environmental conditions that are not particularly favourable, of achieving a satisfactory development of the crop of cultivated plants and thus an adequate crop yield.
Examples which may be mentioned of such disturbance factors hostile to the environment are: soils low in nutrients, drought, low temperatures during the early development of the plant, sudden frosts, and reduced sunlight in consequence of an unfavourable time of the year or of an unfavourable location.
Oxime ethers and oxime esters of the formula I possess however to a very great extent properties for regulating plant growth, depending on the point of time of application and on the type of plant.
Various other possibilities of application of the oximes of the formula I may be listed as follows, but they do not constitute a limitation:

39~3 - application for improved leaf formation in crops of tobacco, cabbage or lettuce, and avoidance of undesirable side shoots;
- application for increasing yield in crops of leguminosae (e.g. in crops of peas, beans, soya beans and peanuts) by promoting generative growth (increase of tillering);
- application for increasing the rigidity of crops prone to flat~ening, such as cereals (prevention of the sagging of plants under unfavourable weathe~r conditions, such as storms or continual rain);
- application for facilitating harvesting of fruit by promoting the formation of abscission layers between the fruit and the shoot part of the plant; and - application for raising the storage capacity for plant substances (sugar, proteins, oils, and so forth), or for temporarily maintaining that which has been stored.

The storage capacity for plant substances includes the possibility of retaining that already stored for longer than under natural conditions. Thus, the storability of potatoes can be improved. Furthermore, the sugar content in sugar cane shortly before harvesting can be kept constant by application of specific oxime ethers of thè formula I, whereby the tendency of the plant to form further side shoots at the expense of the sugar content is counteracted.
Compositions for influencing plant growth, especially for inhibiting growth, have already been described at various times;

9;398 thus, chlorocholine chloride in particular is suitable for the shortening and stabilising of the stems in wheat crops.
According to German Offenlegungsschrift No. 2,458,165, bis-(p-chlorophenyl)-acetic acid, or salts, esters amides or nitriles thereof, are said to effect a similar shortening of stems in cereal crops. In German Offenlegungsschrift No.
2,407,148, 2,6-disubstituted phenoxyacetates or 2,6-disubstituted phenoxypropionates are recommended as growth regulators.
The mode of acting of these substances, particularly with low applied amounts and low concentrations, is however not satlsfac-tory. The position is similar in the case of p-chlorophenyl-dimethylacetic acid (East German Patent Specification No. 113,890), and also in the case of 2-cyano-bicyclo[2,2,1]heptane ~French Patent Specification No. 2,256,722). As was shown by tests, the action of these compounds is very unsatisfactory.
The arylglyoxilnitrile oximes, suggested in the U.S. Patent Specification No. 3,799,757, of the general formula C=N-OH (X = H,Cl, Br, N02) C-N
Xn are insufficiently effective as growth inhibitors and plant-growth regulators; they are moreover not stable and decompose after a fairly short period of time.
Oximes of the formula I surprisingly possess a further very important property. They are excellently suitable for protecting cultivated plants, such as cultivated millet, rice, maize, varieties of cereals (wheat, rye, barley or oats), cotton, sugar beet, sugar cane, soya bean, etc., against being attacked by agricultural chemicals, particularly by herbicides of the widest variety of classes of substances, such as triazines, phenylurea derivatives, carbamates, thiolcarbamates, halogenoacetanilides, halogenophenoxyacetates, substituted phenoxyphenoxyacetates and -propionates, substituted pyridine-oxyphenoxyacetates and -propionates, benzoic acid derivatives, etc., in cases where these do not act selectively or not sufficiently selectively, that is to say, damage to a greater or lesser extent the cultivated plants in addition to the weeds to be combated. The invention relates also to compositions which contain these oxime ethers of the formula I, together with biologically acting additives, such as herbicides, fungicides or insecticides.
Various substances have already been suggested for overcoming this problem, which substances are able to specifically antagonise the harmful action of a herbicide on the cul1:ivated plant, i.e. to protect the cultivated plant without noticeably affecting the herbicidal action on the weeds to be combated.
Depending on its properties, such an antidote can be used for the preliminary treatment of the seed of the cultiva~ed plant (dressing of the seed or of the seedlings); or it can be applied into the seed furrows before sowing; or it can be applied as a tank mixture, on its own or together with the herbicide, before or after ernergence of the plants. The treatment with the antidote can be carried out before or after, or simultaneously with, the herbicidal treatment. The pre-emergence treatment includes both the treatment of the cultivated area before sowing (ppi = pre plant incorporation) and the treatment of the sown cultivated area before emergence of the plants.
Thus, the British Patent Specification No. 1,277,557 describes the treatment of seed and seedlings of wheat and sorghum with certain esters and amides of oxamic acid before the attack by N-methoxymethyl-2',6'-diethyl-chloroacetanilide (Alachlor). Other publications (German Offenlegungsschriften Nos.
1,952,910 and 2,245,471, and French Patent Specification No.
2,021,6Ll) suggest antidotes for the treatment of cereals, maize seed and rice seed to protect them against the attack from herbicidal thiolcarbamates. In German Patent Specification No.
1,576,676 and U.S. Patent Specification No. 3,131,509, hydroxy-amino-acetanilides and hydantoins are suggested for protecting cereal seeds against carbamates, such as IPC, CIPC, etc.
However, there has not hitherto been suggested in the literature a class of substancès which on the one hand are able to impart to plants strong growth-stimulating impulses, and on the other hand have the ability to protect, in the sense of an antidote effect, plants against aggressive agricultural chemicals.

Compounds of the formula I to be particularly emphasised are those wherein Ar has the given meaning, and the other substituents have the following meanings:.
X represents cyano, nitro, halogen, lower alkanoyl, a ~ carboxylic acid ester group of a lower aliphatic alcohol, a carboxylic acid amide group, or lower alkyl, Q represents lower alky]. which is straight-chain or branched-chain, or which can be interrupted by a hetero atom or substituted by halogen, or Q represents lower alkenyl, lower alkynyl, lower cyanoalkyl, a lower alkanecarboxylic acid ester group, a lower alkanecarboxylic acid amide group, a lower aliphatic acyl group, a cycloaliphatic acyl group having 4 to 6 C atoms, or an unsubstituted sulphonic acid amide group or a sulphonic acid amide group mono- or disubstituted by a lower aliphatic radical, Rl represents hydrogen, or a phenoxy group in para-position, R2 and R3 independently of one another represent hydrogen, halogen or lower alkyl, R4 and R5 represent hydrogen, and Z represents oxygen or sulphur.

Preferred compounds amongst these are compounds of the formula Ia R2 ~ C - X (Ia) ~ g39 ~

wherein the substituents have the following meanings:
X represents cyano, ni.tro, halogen, lower alkanoyl, a carboxylic acid ester group of a lower aliphatic alcohol, a carboxylic acid amide group or lower alkyl, Q represents a lower straight-chain alkyl chain which is interrupted by oxygen, or Q represents lower alkenyl, lower alkynyl, lower cyanoalkyl, a lower alkanecarboxylic acid ester group, a lower alkanecarboxy]ic acid amide group, a lower aliphatic acyl group, a sulphonic acid amide group which is unsubstituted or is mono- or disubstituted by a lower aliphatic radical, Rl represents hydrogen, ~2 represents hydrogen, hàlogen, lower alkyl or lower alkoxy, and R3 represents hydrogen, halogen, lower alkyl or lower alkoxy.
Particularly preferred compounds of this last-mentioned group are those compounds wherein the substituents of the formula Ia have the following meanings:
X represents cyano, nitro, halogen, lower alkanoyl, a carboxylic acid ester group of a lower alkanol, or a carboxylic acid amide group, Q represents lower alkynyl, lower cyanoalkyl, a lower alkane-carboxylic acid ester group, a lower alkanecarboxylic acid amide group, Rl represents hydrogen, ~ 9 39 ~ -R2 represents hydrogen, halogen or lower alkyl, and R3 represents hydrogen, halogen or lower alkyl.
Preferred compounds within the last-mentioned group are, within narrower limits, those compounds wherein the substituents of the formula Ia have the following meanings:
X represents cyano, chlorine, bromine, acetyl, propionyl, -COOCH3, -COOC2H5, -CO-NH2, -CO-NHCH3 or -CO-N(CH3)2, Q represents propynyl or butynyl, cyanomethyl or cyanoethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, methoxy-. carbonylethyl or ethoxycarbonylethyl, an acetamide orpropionamide group optionally substituted on the N atom by one or two lower aliphatic groups, Rl represents hydrogen, R2 represents hydrogen, halogen or methyl, and R3 represents hydrogen, halogen or methyl.
Compounds amongst these which form an important subgroup are those wherein X represents a cyano group.
Another preferred range of active substances of the formula I
which promote plant growth and protect plants is that embraced by the formula II

R2 ~ C-X (II).
R3 N-O-(CH)n R10 wherein Rl, R2 and R3 independently of one another represent hydrogen, halogen, NO2~ lower alkyl, halogenoalkyl or lower alkoxy, X represents -CN, -N02, halogen, the acetyl group, a carboxylic acid ester group of a lower aliphatic alcohol or a carboxylic acid amide group, n represents 1, 2 or 3, Rg represents hydrogen or lower alkyl, Rlo represents -CON~2, -CO-NH-(lower aliphatic radical) 7 -CO-NH-cycloalkyl, -CONH-(C6H5 m) (halogen, lower alkyl)m or -CN, and m represen~s an integer, O, 1, 2 or 3.

Pre~erred compounds within the compass of the formula II are compounds of the formula III

C-X' (III) . N-o-cH2-RlO
wherein X' represents -CN, -N02, chlorine, acetyl, lower alkoxy-carbonyl, allyloxycarbonyl, carbamoyl or di-lower-alkyl-carbamoyl, Rlo represents -CN, -CO-NH2, -CO-NH-lower alkyl or -CONH(C6H5_m) (Cl, Br~ CH3)m~
m represents an integer, 0~ 1 or 2.
The preferred individual compounds include:
~-cyanobenzylidene-amino-oxacetamide of the formula C-CN
N_o_cl~2_co_NH2 a-cyanobenzylidene-amino-oxyacetic acid ethyl ester (Comp. 1.4), a-(cyanoethoximino)-benzacetonitrile (Comp. 1.44).
Effective chloroacetanilides, which in some cases are not sufficiently tolerated bycultivated plants, such as cereals, rice, cultivated sorghum, and so forth, but which, when acting together with the oxime ethers of the formula I of the present invention, leave such cultivated plants unharmed, without losing any of their normal effectiveness against weeds, have become known, for example, from the U.S. Patent Specifications Nos.

3,547,620, 3,403,994, 3,442,945, 3,637,847, 3,598,859, 3,819,661, 3,946,045 and 3,983,174, and from the German Offenlegungsschriften Nos. 2,212,268, 2,305,495, 2,328,340, 2,402,983, 2,405,183 and 2,405,479.
The antidotes of the formula I, II or III are used preferably together with hérbicidal chloroacetanilides of the formula R
Rl13l11 R
(IV) ~F~' Co-cH
wherein Rl/ R 12 Rll represents lower alkyl, alkoxy, alkoxyalkyl, trifluoro-methyl or halogen, R12, R13 and R14 independently of one another represent hydrogen, lower alkyl, alkoxy, alkoxyalkyl, trifluoromethyl or halogen, and R15 represents a Cl-C4-alkyl which is optionally substituted ~93~8 by carboxy~ carboxyli.c acid ester, carbonamide, or carbonamide substit~ed by one or two l.ower ali.phatic radicals, or by -CN; or wherein R15 represents propynyl, butynyl, an acetalised carbony~ group, 1,3-dioxolan-2-yl-alkyl, 1,3-dioxolan-5-yl-alkyL, 1,3-dioxan-2-yl-alky]., furanylmethyl, tetrahydro~uranylmethyl, or alkoxyal~yl o~
t~le form -A-O-R16, wherein A reprecents an alkylene c'nain having 1 to 4 C atoms, of which L or 2 belong to the direct chain, and R16 represents lower alky]., alkenyl, or cycloalkyl or cycloalkylmethyl having 3 to 6 C atoms in the ring.
The expressions "lower alkyl" cr "lower aliphatic radical' denote groups having at most 4 carbon a~oms, and correspond to the aforementioned defini~ion for the formula I, and likew;se the term "halogen".
Some chloroacetanilides which are particularly suitable for use with the antidotes according to the invention are listed below:
N-ethoxymethyl-2-methyl-6-ethyl-chloroacetanilide, N-methoxymethyl-2,6-diethyl-chloroacetanilide, N-(2'-methoxye~hyl.)-2,6-dimethyl-chloroacetanilide, N-(2'-allyloxyethyl)-2,6 dimethyl-chloroacetanilide, N-(2'-n.-propoxyethyl)-2,6-dimethyl-chloroacetanilide, N-(2'-isopropoxyethyl)~2,6-dimethyl-chloroacetanilide, N-(2'-methoxyethyl)-2-methyl-6-ethyl-chloroacetanilide, N-(2'-methoxyethyl)-2,6-diethyl-chloroacetanilide, N-(2'-ethoxyethyl)-2-methyl-6-ethyl-chloroacetanilide, N-l3'-methoxyprop-(2')-yl]-2-methyl-chloroacetanilide, N-13'-methoxyprop-(2')-yl]-2,6-dimethyl-chloroacetanilide, N-[3'-methoxyprop-(2')-yl]-2-methyl-6-ethyl-chloroacetanilide, N-13'-methoxyprop-(2')-yl]-2,6-diethyl-chloroacetanilide, N-(2'-ethoxyethyl)-2,6-diethyl-chloroacetanilide, N-(2'-n-propoxyethy])-2-methyl-6-ethyl-chloroacetanilide, N-(2'-n-propoxyethyl~--2,6-diethyl-chloroacetanilide, N-(2'-isopropoxyethyl.)-2-methyl-6-ethyl-chloroac.etanilide, N-chloroacetyl-2,6-dimethyl.anilino-acetic acid ethyl ester, N-chloroacetyl-2,6-diethylanilino-acetic acid ethyl ester, N-chloroacetyl-2,6-dimethylanilino-acetlc acid methyl ester, N-chloroacetyl-2-methyl-6-ethylanilino-acetic acid isopropyl ester, - 1N- (~-chloroacetyl)-2,6-dimethylanilino]acetaldehyde-diethyl-acetal, N-l3'-methoxyprop-(2')-yl]-2,3-dimethyl-chloroacetanilide, N-(2'-ethoxyethyl)-2-methyl-chloroacetanilide, N-(2'-methoxyethyl)-2-methyl-chloroacetanilide, N-[2'-methoxyprop-(1')-yl]-2,6-dimethyl-chloroacetanilide, N- [2~ -methoxyprop-(1')-yl]-2-methyl-6-ethyl-chloroacetanilide, N-[3'-ethoxyprop-(2')-yl]-2-methyl-6-ethyl-chloroacetanilide, N-[l'-methoxybut-(2')-yl]-2,6-dimethyl-chloroacetanilide, N-(2'-methoxyethyl)-2-methyl-6-methoxy-chloroacetanilide, N-(n-butoxymethyl)-2-tert.butyl-chloroacetanilide, N-[3'-ethoxyprop-(2')-yl]-2,6-dimethyl.-chloroacetanilide, ~ ~Y:~l39 ~

N-(2'-methoxyethyl)-2-chloro-6-methyl-chloroacetanllide, N-(2'-ethoxyethyl)-2-chloro--6-ln2thyl-chloroacetanilide, N-(2'-ethoxyethy])-2,3,6-trimethyl-chloroacetanilide, N-(2'-methoxyethyl)-2,3,6-trimethyl-chloroacetanilide, N-(2'-isopropoxyethyl)-?,3,6-trimethyl-chloroacetanilide, N-cyanomethyl-2,6-dimethyl-chloroacetanilide, N-(but-l-in-3-yl)-chloroacetanilide, N-propynyl-2-methyl~6-ethyl-chloroacetanil.ide, N-(1,3-dioxolan--2-ylmethyl)-2,6-dimethyl-chloroacetanilide, N-(1,3-dioxolan-2-ylmethyl)-2-ethyl-6-methyl-chloroacetanilide, N-(1,3-dioxan-2-ylmethyl)-2-methyl-6-ethyl chloroacetanilide, N-(2'-furanyl-methyl)-2,6-dlmethyl-chloroacetanilide, N-(2'-furanyl-methyl)-2-chloro-6-methyl-chloroacetallilide, N-(2'-tetrahydrofuranyl-methyl)-2,6-dimethyl-chloroacetanilide, N-(N'-propargylcarbamylmethyl)-2,6-dimethyl-chloroacetanilide, N-(N',N'-dimethylcarbamylmethyl)-2,6-dimethyl-chloroacetanilide, N-(n-butoxymethyl)-2,6-diethyl-chloroace~anilide, N-(2'-n-butoxyethyl)-2~6-diethyl-chloroacetanilide, N-[3'-methoxybut (2')-yl]-2,6-dimethyl-chloroacetanilide, and 2-chloro-N-isopropylacetanilide.
Suitable herbicidal thiolcarbamates which when used, in cro~s of cereals, rice or cultivated sorghurn, together with cornpounds of the formula I, II or III are made more compatible with the crops correspond preferably to the formula ~ 9 ~ 8 0 \ R18 or ~7-S0-C-N /

wherein R17 represents lo~er al~yl, alkenyl, chloroallyl, dichloroallyl, trichloroallyl, benzyl or p-chlorobenzyl, P~18 represents C2-C4-allcyl, and Rlg represents C2 C4-allcyl or cyclohexyl, or whe.rein R18 and R19 together with the N atom form a hexahyd~o-lH-aæepine ring, a decahydroqui.noline ring or a 2-methyl-decahydro-quinoline ring.
The ~ollowing thiolcarbamates may be mentioned as examples of such compoun.ds:
S ethyl-N,N-dipropylthiocarbamate, S ethyl-N,N-diisobutylthiocarbamate, S-2,3-dichloroallyl-N,N-diisopropylthiolcarbamate, S-propyl-N-butyl-N-ethylthiolcarbamate, S-2,3,3-trichloroallyl-N,N-diisopropylthiolcarbamate, S-propyl-N,N-dipropylthiolcarbamate, S-ethyl-N-ethyl-N-cyclohexylthiolcarbamate, ~-ethyl-N-hexahydro-lH-azepine-l-carbothioate, S-isopropyl-N,N-hexamethylene-thiolcarbamate, S-(p-cnlorobenzyl)-N,N-diethylthiolcarbamate, N-ethylthiocarbonyl-cis-decahydroquinoline, N-propylthiocarbonyl-decahydroquinaldine, S-ethyl-N,N-bi~-(n-butyl)-thiolcarbamate, and B

S-tert.butyl-l~ bis-(n-propyl)-thiolcarba~nate.
Further examples of thiolcarbamates that can be used are described in the U.S. Patent Specifications Nos. 2,913,327, 3,037,853, 3,175,897, 3,1~5,720, 3,198,786 and 3,582,314.
The following may be mentioned as further preparations which with compounds of the formula I can be made more compatible with the crops of cultivated plants:
a-[4-(2,4-dichlGrophenoxy)-phenoxy]:proplonic acid methyl ester, a- [4-(4-trifluoromethylphenox~)-phenoxy~propionic acid methyl ester, a- [4-(2-chloro-4-trifluoromethylphenoxy)-phenoxy]-propionic acid methyl ester, and a- [4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionic acid methyl ester.
The applied amount of antidote varies between about 0.01 and about 15 parts by weight per part by weight of herbicide.
Which ratio with regard to the optimum effect on the specific cultivated plant is most suitab]e is determined from case to case, i.e. depending on the type of herbicide used.
As already mentioned, various methods and techniques are suitable for the application of the novel antidotes of the formulae I-III for protecting cultivated plants against agricultural chemicals, or for stimulating plant growth 9~98 1.) Seed dressln~
-a) Dressing of ~he seed with an active substance formulated as a wettable powder by shaking in a vessel until there exists a uniform distribution over the surface of the seeds (dry dressing). The amount of active substance of the formula I
used for this purpose is about lO to 500 g (40 g to 2 '~g of wettable powder) per 100 Icg of seed b) Dressing of the seed wi~h an emulsion concentrate of the active substance of the formula I using rnethod a) (wet dressing).

c) Dressing by immersion of the seed in a liquor cGntaining 50-3200 ppm of active substance of the formula I for 1-72 hours and, optionally~ subsequent drying of the seed (immersion dressing)~

The dressing of the seed or the treatment of the germinated seedlings are naturally the preferred methods of application because the treatment with the active substance is directed completely at the target crop. There is used as a rule 10 g to 500 g, preferably 50 to 250 g, of active substance per 100 kg of seed, with it being possible, depending on the method used, which enables also the addition of other active substances or micronutrients to be made, to deviate either upwards or downwards from the given limiting concentrations (repeat dressings).

2) Application as a tank mixture A liquid preparatiGn of a mixture of antidote and herbicide (reciprocaL quantitative ratio between 10:1 and 1:10) is used, 3~

the applied amourlt OL herbicide belng 0.] to ].0 kg per hectare.A tank mi~ture of this kird is preferably appl.ied before or immediately after sowing, or it is worked into the unsown soil to a depth of 5 - 10 cm.

3) Application into the seed furrow The antidoLe is introduced, as an emulsion concentrate, ~ettable powder or granulate, into ~he open so~m seed furrow and, after the covering of the seed furrow in the normal manner, the herbi.cide is applied using the pre-emergence process.
Essentially, the antidote can therefore be applied before, together with, or after the pesticide, and its application to the seeds or to the field can be effected either before or after sowing, or in certain cases also after germination o.f the seed.
The invention relates in particular also to compositions which contain, besides the antidote of the formula I, at least one agrochemical active substance, e.g. a herbicide from the chloroacetanilide class or from the thiolcarbarnate class.
These cornpositions contain in addition also carrier substances and/or distributing agents.

4~ Controlled release of active substance The active substance in solution is absorbed onto m.ineral granulate carriers or onto polymerised granulates (urea/
formaldehyde), and the material is allowed to dry. It is possible if desired to apply a coatlng (coated granules), which enables the active substance to be released in controlled am.ounts over 93~

a specific period of time.
It is naturally possible to use also all other known methods of applying active substances. Examples in this respect are given further on in t-he text.
The process according to the invention for promoting plant growth or for protecting cultivated plants can be applied in par~icular to rice and to cultivated millet of the sorghum variety, also to maize, wheat, barley, oats, soya bean, cotton and sugar beet. It is however not limited to the promotlon and protection of annual plants, but is also very suitable for growth stimulation of perennial plants (fruit trees, ornamental shrubs, and so forth), where it is desired to promote root formation or the formation of side shoots, or to achieve improved fruit setting or improved inflorescence.

The compounds of the formula I are produced by processes known per se (Organic Reactions 1953, Vol. 7, pages 343 and 373;
Jou~nal f. prakt. Chemie 66, page 353; Liebigs Ann. 250, 165.), namely by etherification or acylation of an oxime of the formula V Ar - C - X (V), - N-OH

or of its oxime salt, with a halide of the formula Halg~Q, wherein Ar, X and Q have ~he meanings given for the formula I, and "Halg" denotes halogen, preferably chlorine or bromine.
The condensation of substituted ~~oximino compounds is ~1~939~3 effected in the case of etherification advantageously with the compounds in the form of their sal.ts, particularly in the form of their alkali metal salts or ammonium salts, as is shown in the following by selected examples:

a) Ar - C - X ~- Halg-CH2-CO--~ Ar - C - X
N~O-salt N-O-CH2-CO~ 2 oximacetamides of the formula I

b) Ar - S - X + Halg-CH-COOCH3 Ar - C - X
N-O~salt C~3 N-O-CH-COOC113 . CH3 oximealkanecar~oxylic acid esters of the formula I

~) Ar - C - X ~ Halg-C~12-CH-C~2 Ar - C - X
, N-O-salt N-O-CH2-CH=C~12 oxime ethers of the formula I

Acylation is effected advantageously with the free oximes of the fo~mula V, as is snown by the following diagrams:

Ar - C - X acid ______~ Ar - C - X (cyclo) N-O-H halide N-O-~O- aliphat, aromat, hetero-cycle acyloxirlles of the formula I

~.

~ 9 ~ 8 e) ~r - C - X sulphonic acicl Ar - C - X (cyclo) N~O~I ha1ide N-O-S02- aLiphat, hetero=
cycle sulphonyloximes of : the formula l (In the above diagrams, "Halg" denotes halo~en, especially Cl Gr P~r) S~ita~le as solvents Eor o~taining the compo~nds of the formula I are essentia]ly all representatives which bellave inertly under the conditions of the reaction. For example, hydrocarbons, particularly however polar solvents, such as acetonitrile, dioxane, cellosolve or DMF, but also letones, such as methyl ~thyl ketone, acetone, e~c. Solvents containing hydroxyl groups are excluded.
The temperatures are in the range of -10C to about 150~C, preferably between 20 and 120C.
As agents splitting off hydrogen halide, it is possible to use bases such as tert. amines (triethylamine, triethylene-diamine, piperidine, etc.). Also a suspension of sodium`carbonate in the anhydrous reaction medium suffices in some cases.
Oximes are present in two s~ereoisomeric forms, the syn-form and anti-form. Also the compounds of the formula I mentioned under a) to e) can be present in either of these forms in the pur~
state or as mixtures of both. By 'compounds of the formula Il are accordingly meant, within the scope of the present specifi-cation, both stereoisomeric forms on their own, or as mixtures with each other in any reciprocal quantitative ratio.
The following Examp1es lllustrate the production of the novel ~9~9B
oxi.mes of tlle for~,ula I.
Exa~ ple 1 17 g (0.1 mol) of phenylglyoxylonitrile-2-oxiMe sodiu~ salt is suspended in 170 ml of acetonitrile in a 350 ml sulphon,ti.ng flask. There is then added 23.8 g (0.1 mol) of chloroaceto-3,4 dichloroanilide, whereupon a slight reaction heating can be detected. The suspension is refluxed for 3 hours, with ~ne suspension chanc,ing in appearance. After cooling to room temperature, ~he formed sodium chloride is filtered off; the residue is su~sequently washed with acetonitrile, and the combined filtrates are then concentrated in vacuo to leaveas residue 3?.3 g of crude product. Recrystallisation frorn alcohol/water yields 20.4 g of final product of the formula C - N ~ 0 - CH2 ~ C0 ~ ~ ~ Cl C _ N Cl m.p. 143 - 144 C.
From the salt of 2,4-dimethylphenylhydroxamic acid chloride and allyl chloride, there is correspondingly obtained as an oily substance the product of the formula Cl~

~3C- ~ C-N-0-CH2-CH=CH2 In a similar manner is obtained from 2-thienylacetonitrile-oxime sodium salt and chloroace~onitrile the compound ~S ~ C-CN
N-0-Cll CN
as oily substance. 2 ~ 39 Example 2 33.6 g (0.2 mol) of yhenylglyoxy]oLlitrlle-oxime sodium salt and 25 g (0.22 mol) of chloroacetic acid methyl ester in 200 ml of acetonitrile are held for 3 hours at 60-70C with thorough stirring, in which time the suspension becomes greatly refined. After a further few hours, filtration is performed;
the residue is subsequently washed with acetonitrile, and the combined filtrates are concentrated-in vacuo to leave an oily residue, which becomes solid after about 24 hours, m.p. 68-70C;
Recrystallised from isopropanol: m.p. 71-72C.

C - C - N

In a similar manner is obtained, by condensation of 4-chlorophenylglyoxylonitrile-oxime sodium salt ~ith a-chloro-propionic acid ethyl ester, the coMpound of the formula Cl ~ C - CN

~13 in 99.3% yield in the form of oil.
If there is used, instead of the ~ chloropropionic acid ester, the chloroacetic acid isopropyl ester, there is obtained th~
compound of the formula Cl _ ~ C - CN m.p. 93-94C;
N-O-c~l2-coo-isoc3~l7 ~ ~f~9 ~

and with use of the unsubstituted phenylglyoxyloni~rile oxime (as Na salt) there is obtained the coMpound of the formula ~_C - ci~
~I m.p. 49-50C.
~-0-C~I2-C00-isoC3~7 Example 3 Production of ~ C-CN
N 0-CH2-C0-NH~
-CyanobenzylidPne-amino-oxacetamide 845 g (5 mols) of benz-acetonitrileoxime as Na salt is suspended in 2.5 litres of acetonitrile, and there is slowly added in the presence of catalytic amounts of KJ, with stirring, 468 g (5 mols) of chloroacetamide. The reaction mixt~re is refluxed for 12 hours; it is then cooled and su~sequently allowed to flow into about 12 litres of water. While the salts present are dissolving, the final product precipitates in crystalline form: 882 g (- 86.8% of theory), m.p. 128-129C (from ethanol).
There is correspondin~ly obtained, from the sodium salt of 3-furanylnitromethane-oxime and methanesulphonyl chloride, the compound of the formula 11~ ,11 N -O -S2 -CH3 in the form of viscous oil.

Example 4 8.0 g (0.037 mol) of the sodium salt of a-oximi.no-l-naphthylacetonitrile and 5.5 g (0,045 mol) of propargyl bromide in 50 ml of acetonitrile are heated for 4 hours at about 80C.
The suspension is afterwards concentrated in vacuo, and the residue is extracted with methylene chloride. The soluti.on is concentra~ed by evaporation to leave the compound of the formula ~

C-CN

N -O -C~2 ~C_CH
as oil.
Analysis for C15HloN20 calculated: C 76.9 % H 4.3 % N 11.96 %
found: C 76.4 % H 404 % N 11.8 % .

If there is used as reactant, instead of propargyl bromide, chloroacetonitrile, there is obtained the compound of the formula ~

C - CN
~-0-CH2-CN m.p. 81-82C .

~ ~93~8 Example 5 ~ .
0.1 ~nol of the sodiurn salt of a-o~imino-2-thienylacetonicrile with 0.12 mol of chloroacetamide is suspended in 150 ml of acetonitrile. Th~ suspension is heated for 3 hours at 50-60~C~
wi~h NaCl precipitating; this is filtered off and washed with acetonitrile. The filtrates are concentrated in vacuo to yield the cormpound of the formula _ C - CN

as a ligh~-yellow oily substance.

9~3 The temperat~lres ar~ giv~n in degrees Centigrad~ in the following Ta~l~s.

The following compounds can be produced by the methods described abov~:
.

~1 .

N-O-~

Comp. .
No. 1 R2 Q
~ _ __ ___ ~
~1.1 H H -CH2 CO-~.2 m.p. '28-129~
1.2 4-Cl H -CH2-CO-1~2 m.p. 12~-l23 1.3 H H -CH2-COC~3 . m.p. 71~72 1.4 H H -CH2-COOC2H5 m.p. 5~-56 1.5 H H -CH2-CO~(i-C3H7) m.p.49-50 1.6 4-CH3 H CH(C~3) 3 oil 1.7 4~Cl H -CH2-COO(i-C3H7) m.p.93 ~4 -- 1,8 ~-Cl 2-Cl -C~2-CC~C'~I3 oil . 1.9 4-Cl 2-Cl -C~2-CCOC2~l5 oll - 1.10 4-Cl 3-C] -CH2-COOCH3 oil.
1.11 4-Cl 3-Cl -CH2-COOC2H5 oil 1.12 4-Cl _ CH(C 3 C 2 5 oil _ _ .

- 32 _ 9;39~8 ~omp. ~
No . l P~ 2 ¦ Q
1,13 3 H -CH2-COOC2H5 m.p. 7~-81 t ,14 H H - -C~12 - C - Cl~ oi. 1 1.15 ~-~ 2-C.l -C i~ oil 1.16 4-CH3 H 3 1 oil 1.17 4~CH30 H -CH3 m.p. 75-77 1. 18 ~I- C~130 ~1 -C2ll5 oi]
1.19 4-~r H ~Cll -C--CH m . p . 90-92G
1 . 20 H 11 (,?l<C ' b . p . 118 -120 b / C

1 . 2 1 4 ~Cl 1-~ - Cil (C2}1s) -CO~)c 2ll5 oil 1. 22 4-Cl H -CH2 C_L~H semisolid 1, 23 4-Cl H -C}~ (CH3) COOCH3 oil1. 24 4-CH3 H C2~5 oil 1. 25 4 -C 1 . 2 -Cl -CH (CH3) -C--C}l oil ~ . 2 6 4 -Br H -CH3 m . p . 60 - 62 1. 27 3-CF3 H -CH2-COOC2H5 1. 28 3-CF3 H -CH2KC=CH2 1. 29 . H H nC4 9 1~ 30 H H -C112 -COO (isoC4H9) 1. 31 3-CF3 H -C~l (CH3) -COOC ~H5 1. 32 4-~12 H -CH2-COOCH3 1. 33 4-~02 H -CH2-CO-~12 1, 34 H H -CH2-CO -NH ~-C 1 m . p . 14 3 14-';
]. . 35 H H -S02~ (C113) 7 m . p . 88-89 1.3~ 4-~3r H -CH2-C~ m.p. 77-79 .. . .

~ 9 comp .
NO ~1 ¦R2 Q
_. __ _ , ~
1. 37 4-CH30 H -C2H5 solid 1. 38 H 11 ~CH3 m . p . 129-131 1. 39 H H ~C;~}15 oil 1.40 H H ~31~7 (iso) oil 1.41 . H . ~ H -CH(CH3)(,00CH3 oil I.42 H H -C~l(CH3)COOC2H5 I m.p. 36-37 1.43 H H -CH(C2H5) COOC2H5 ¦ solid 1. 4 4 H ~ H ~CH~ -CH2 -CN ¦ m . p . 12 3 - l2 6 1. 45 H H CH2 CH2 CH2 C oil 1. 4 6 . H H . -C0 -CH3 m . p . 68 -70 1. 47 3-C~3 H ~CH2-COOCl.'3 m . p . 107 -109 1. 48 2 -CH3 H C~12 1.49- 2-F H CH2 ~
1.-50 2 -~ H -CH2 -COi\~-l? oil 1.51 2-CH3 H -CH(CH3) COOCH;~L
1. S 2 4 -C 1 H C 1 m . p .15 8 - 7 ~C
1. 53 H H ~C0~ m . p .97-99 ~l3C0 Cl - . .
1.54 H : H -((,~2)7-CH3 m.p.131-133 1 . 5 5 4 9 H -CH2 ~ C',~l 1. 56 4-i~oC3H70 H -CH -CO-N112 1. 5 7 2 -CH3 H -CH2 ~ C0 -~H2 oil 1. 58 3-N02 H -CH2-C0-~'1-l2 1 59 3-~2 ~1 S2 3 m.p.133-135 .

9g'~3~

Comp, R 1 ~ R2 l ~_ 1. 60 ___ _ ~ -CH -CO ~CH3 m . p . 67 -6 8 1. 61 H H -CH (C~13) -CO N~2 m . p .144-146 1. 62 H H -S02 -rv~3 m . p . ~ ? 1-122 1. 6 3 }I 11 -CH2 ~ COOC4119 ( ter t . ) m . p . 7 6 -7 7 1. 64 H H ~CH (rlcl0~l2 1) CC2H5 m . p . 53 -54 1. 65 H 11 -C(~l3) 2~COOC2~ 5 oil 1. 66 H H -CH(CH3) -('OCC3~17 (iso) oil 1.67 H H -(CH2) l7 (~ 3 solid 1. 68 H H -CH ( CH3) ~C -CH oil 1. 69 H H -CH (CH3) -CO~ (v2115) 2 oil 1. 70 H H -CH2-CO-NH-CH3 1. 71 H H -CH2 -CO -N ( C~ 3) 2 1. 72 H H -CH2 -co~rl-cH2 -Cl-l CH2 1 . 7 3 H H -CH2 CONH -C-CH
] . 74 H H -CH2 -CON (C~3) ~CH2 -CH=C] 12 1.75 H H -CH2-cON(c~l3) -C2H5 1.76 H H -C~(C~3)-Co~H C~13 1.77 H H -CH(CH3) -CoN(cH3) 2 1.78 H H _cH2-CON(~11Y1) 2 solid 1. 7 9 H H -C6H3 (N02) 2 ( 2, 4) m ~ p .17 8 -17 9 1.80 H H CH2 C6H3C 2( ' ) m.p. 91-93 1. 81 H H -CH2 -COOCH2 C6H5 m . p . 61-62 1~ 82 H H -CH2 -COO -C6H~N02 (4) solid 1.83 H H -CH2-CONH-C6H3C12(3,5) m.p. 149-150 1.84 H H -CH2-CONH-C6'rl4F(4) m.p. 136-L37 1.85 H H -CO-C2H5 m.p. 53-55 1. 86 H H -CH (CH3) CN m . p .60 -62 1. 87 H H -CH2-CH=C~I-CH3 oil 1. 8 8 4 -CH 3 H C~ 2 m . p .82 - 84 .~9 4-C1~3 H -CH3 m.p. 44-46 1. 90 4-CH3 H -CH2-COOCH3 solid H -CH2 -CO()C2H5 s ol id . .

9;~

Comp ~ R 1 R2 Q
__ _ _~ _ 1. 92 4-CH3 H -CH(C113) COOC2H5 oil 1. 93 4-CH3 H -Cl~(C2H5) C00~2H5 oil 1.94 4-CH3 H CH2-CO~ C6113C12(3,4) m.p. 162-164 1. 95 4-CH3 H -CH(CH3) -COOC3H7 (iso) oil 1. 96 4-CH3 H -CH2-C_ CH solid 1. 97 4-CH3 H -CH2-CH=CH-CH3 oil 1. 98 4-CH3 3-CH3 -Cf~2 -CN m . p . 40 1. 99 4-CH3 3-CH3 -CH3 oi1 1 .100 4 -CH3 3 -CH3 -C2H5 oil 1.101 4-CH3 3-CH3 3 7 ( ) oil 1. 102 4-CH3 3 -CH3 -CH2 -COOCH3 m . p . ca . 60 1 .103 4-CH3 3 -CH3 -CH2 -COOC2H5 m . p . ca . 50 1.104 4-CH3 3-Cl13 -C~l(CH3) COOCH3 oil 1.105 4-CH3 3-CH3 -CH(CH3) COOC2H5 ~oil 1. 106 4-CH3 3-CH3 -CH2-C_CH m.p. 75-81 1.107 4 -CH3 3 -CH3 -CH2 CONH-C6H3C12 (3, 4) m . p . 110 1 .108 4 -CH3 3 -CH3 -CH2 -CONH -CH3 oil 1 .109 4 -CH3 3 -CH3 -C~l2 -CON ( C~13) CH2 -C~=C~ oil 1 .110 4 -C113 3 -CH3 CH2 -CONH2 oil 1. 111 4 -OCH3 H 2 m . p . 91-93 l ,112 4-OCH3 H C3 7 ( ) oil 1.113 4-OCH3 H -CH2-COOCH3 m.p. 122-125 1.114 4 -OCH3 H -CH(CH3) COOC~Hs m . p .50 -53 1.115 4-OCH3 H ~CH(cH3) COOCH3 oil 1 .116 4 ~0CH3 H CH (C2 5) 2 5 oil 1.117 4-OCH3 H -Cl-l(CH3) C CH solid 1. 118 4-OCH3 H -CH2 -cOOc3H7 ( iso) solid 1.119 4-OCH3 H -CHtCH3) cOOC3H7 (i~;o) oil 1.120 4-OCH3 H -(CH2) 7 -CH3 oil 1. 121 4 -OCH3 H -CH2 -CO ~NH2 In . p . 123 -126 1.122 4-OCH3 H -CH2-C- CH solid Q 9 ;3 9 8 c omp 1 R2 _ 1.123 4-OCH3 H -CH2-CH=CH2 m.p. ~a. 40 1.124 4-OCH3 H -CO-C6H5 m.p. 128-130 1,125 4-OCH3 H -CH -CH-CII-CH solid 1.126 4-Cl H CH2 CN m.p.69-71 1.127 4-Cl H -CH3 m.p.70-71 1.128 4-Cl H C2H5 m.p.39-40 1.129 4-Cl H C3H7( ) oi]
1.130 4-Cl H -CH2-COOCH3 m.p.81-82 1.131 4-Cl H -CH2-COOC2H5 m.p,79-80 1.132 4-Cl H -CH(CH3)COOC3H7(iso)oil 1.133 4-Cl H -(CH2)7-CH3 loil 1.134 4-Cl H -CH2-CII=CH2 ¦ solid 1.135 4-Cl H -CH2-CoNII-C6~T3C]2(3'4) m.p.165-166 1.136 4-Cl H -CH2-CONH-C6H4Br(4) m.p.199-201 1.137 4-Cl H -C~12-CONH-C61l4C~3(3) m-p.187-190 1.138 4-Cl H -CH2-CONH-C6H4Cl(4) m.p.204-205 1.139 2-Cl H CH2 CN m.p. 51-53 1.140 2-Cl H -CH3 oil 1.141 2-Cl H C3 7( ) oil 1.142 4-Cl 2-Cl CH2 m.p.l26-128 1.143 4-Cl 2-Cl -CH3 m.p. 95-96 1.144 4-Cl 2-Cl -C2H5 solid 1.145 4-Cl 2-Cl ( 3) 3 oil 1.146 4-Cl 2-Cl -CH(CH3)COOC2Hs oil 1.147 4-Cl 2-Cl -CH(C2~l5)COOC2H5 oil 1.148 4-Cl 2-Cl -cH2-c-cH solid 1.149 4-Cl 2-Cl -CH2-CH=CH-CH3 oil 1.150 4-Cl 3-Cl -CH3 m.p.84-85 1.151 4-Cl 3~Cl -C2H5 solid 1.152 4-Cl 3~Cl C3 7( ) oil 1.153 4-Cl 3-Cl ~ -c4H~( ert-) soLi 9~
., .

NoOmp. Rl R2 Q
. .
1.154 4-Cl 3-Cl -CH(CH3)COOCH3 solid 1.155 4-Cl 3-Cl -CH(CH3)COOC2H5 oil 1.156 4-Cl 3-Cl -CH(C2H5)COOC2H5 oil 1.157 4-Cl 3-Cl CH2 C m.p. 90-93 1.158 4-Cl 3-Cl -~12-C C~ solid 1.159 4-Br H -C2~lS solid 1.160 4-Br H C3H7(n) solid 1.161 4-Br H -C1l2-COOCH3 solid 1.162 4-Br H -CH2-COOC2H5 m.p.ca. 40 1.163 4-Br H -CH(CH3)COOCH3 oil 1.164 4-Br H -CH(CH3)COOC2H5 oil l.l65 4-Br H -CH(C2H5)COOC2H5 oil 1.166 4-Br H -C1~2-CH=CH2 m.p.90-92~
1.167 4-Br H -CH2-CO-NH2 m.p.147-149 1.168 4-Br H -CH(cH3)-c-cH m.p. ca. 50 1.169 4-Br H -CH2-COOC3H7(iso) solid 1.170 4-Br H -C~l(CH3)-COOC3H7(iso) oil 1.171 4-Br H -CH2-CH=CH-CH3 loil 1.172 4-Br H CH2 CO~H C6H3C12~,4) m.p.15 55 -9391~3 There are obtained ana]ogously also the ~ollow-lng compounds of the formula R

R2 ~= =~ C-Cl N-O-Q

N~mP Rl R2 . _ 1,173 H H -CH2-CN oil 1,174 H H -CH2-CO-NH2 oil 1.175 4-Cl H -CH2-CO-NH2 oil 1.176 H H -CH2-COOCH3 1.177 H H -CH2-COOC2H5 1.178 H H -CH2-COO(i-C3H7) 1.179 4-CH3 H -CH (CH3) COOCH3 1.180 4-Cl H -CH2-COO(i-C3H7) 1.181 4-Cl 2-Cl -CH2-COOCH3 1.182 4-Cl 2-Cl -CH2-COOC2H5 1.183 4-Cl 3-Cl -CH2-COOCH3 1.184 4-Cl 3-Cl -CH2-COOC2H5 1.185 4-Cl H -~H(CH3) -COOC2H5 1.186 4-CH30- H -CH2-COOC2H5 1.187 H H -C~I2-C--CH oil 1.188 H H -CH2-CON(CH3)2 1.189 4-CH3 H ~nC3H7 1.190 4-CH30 H -CH3 1.191 H H -CH2-CONHC_CH oil 1.192 4-Br H -CH2-C_CH
1.193 H H -CH2-cON(cH3) -C2H5 oil 1.194 H H -Cil2-CON(CH3)-C1~2-CH-CH2 oil 1.195 4-Cl H -CH2 C-CH
_~19_ ;f~

Comp . R 1 R2 ¦ _ __ _ __ 196 4-Cl 2-Cl -C~l(C~13~-C--Cl~
1 ,197 3 -CF3 1-1 -C112 -COOC211S
1,198 3 -CF3 ll -C112 -llC-C1l2 1.199 H 1-1 -C~-~2 -coNll -CH2 -Cll -C1~2 oil 1.200 3-CF3 H -cH(cH3) CC2H5 1 .201 4 -~12 ~l -C~12 -C0 -N112 oil 1.202 }I H -C112 C0 -NH -~ oil 1.203 4-C1 1-1 -Cll (C}~3) -COOCli3 oil 1.204 4 -N02 H -C112COOC113 solid 1. 205 H Jl C0 CH2 2 1. 206 3-CF3 5 -CF3 CH2-COOCH3 1. 207 2 -CH3 H -C}12-CN ; oil 1. 208 2 -F H CH2 C oil 1. 209 2 -F H -CH2-CON112 oil 1. 210 2 -CH3 H -Cll(CH3) -COOCH3 1. 211 4-nC41190 H CH2 CN oil 1. 212 4 -isoC3H70 H -CH2 -CO-N~12 oil 1. 213 2 -C~13 H -C1~12 -CO-N~12 oil 1. 214 3-N02 H -C112 -C0 -NH2 oil 1. 215 3-N02 H S2 3 1. 216 2 -CH3 4 -CH3 -CH2 -CH=C112 There are obtained analogously also the following compounds of the formula Rl ~ \\
~C-X

9;3~B

NomP 1 R2 X . ' __ _ 1~217 H H -COCH3 -C~2-CN oil 1.218 H H -COCH3 -C~12-CO-NH2 oil 1,219 H H -COCH3 -CH2-COOCH3 oil 1.220 . H H -COCH3 -C~l(C~13)-COOCH3 1.221 4-C1 H -COCH3 CH2 C
1.222 4-CH3 2-CH3 -COCH3 CH2 CN
1.223 3-CF3 H -COCH3 ~CH2-CO-NH2 1.224 4-C1 2-N02 -COCH3 -C~12-COOCH3 1.225 H H -COCH3 -C2H5 1.226 H H -COCH3 -CH2-Crl~CH2 1.227 H H -COOC2H5 CH2 C oil 1.228 H H -COOC2H5 -CH2-C--CH
1.229 H H -COOC2H5 -cH2-co-NH2 1.230 H H -COOC2H5 -CH2-CO-N(CH3)2 1.231 H H -COOC2H5 -C~13 oil 1.232 H H -No2 CH2 CN oil 1.233 H H -No2 -C~12-CONH2 oil 1.234 H H -No2 -CH2-CONH-C3H7(n) 1.235 H H -No2 -S02- ~ CH3 .1.236 H H -No2 -CH2-S02N(c~13)2 1.237 H H -No2 -CH2-COOC2H5 1.238 H 11 -No2 -CH(CH3)-COOCH3 1.239 H H -CO-NHCH3 2 oil 1.240 H H -CO-NHCH3 -CH2 CO-NHCH3 1.241 H H -CO-NHCH3 -CH3 1.242 H H -CO-NHCH3 -C112-C-cH oil 1.243 H H -CH3 CH2 C
1.244 H H -CH3 -CH2-CO-NH2 oil 1.245 H H -CH3 -CH2-COOCH3 1.246 H H -CH3 -cH(cH3)-coo(ic3H ) 1.247 H H -CH3 -cH2-co-N~l-cll3 3~3 Comp . R 1 R2 X Q
_ _~_ _ 1 248 H H -CEl3 CH2~C~ ~CE~2C-CH
1 . 24 9 H El -CH 3 CH -CONH -(,H -C~l=CH
1. 250 El H CH CH2 -CH=CH2 1. 251 2 -F H -CE13 CH2 COOC2H5 1. 252 2 -CE~3 5 -CH 3 -C~13 CH2 -CE~2 ~ -CH3 1. 253 H H -COOCH3 C112-CN
1. 254 3 -N02 H -COOG'H3 -CH2 -COOCH3 1. 255 H E~ -COOCH3 -CH2~CO-NH2 1. 256 H H -COOCH3 -CH3 1. 257 H H -COOCH3 nC5 11 1. 258 H H -COOCH3 -CH2 -CON ~ allyl) 2 1. 25 9 H H -COOCH3 CH ( CH3) 3 1. 260 H 2 -Cl -COOCH3 CH2 CN
1. 261 4-Cl 3 -Cl -COOt,H3 -CH2 -COOCH3 1. 262 2 -Cl 2 -N02 -COOC113 CH2 C
1. 263 2-Cl 2 -N02 -COOCH3 CH2 C
1. 264 H H H -CH2 -CN
1. 265 H H H -CH2-CONH2 1. 266 H HCO C~2~-CH -CH2 -C-CH
1. 267 H H-CO-CH2C-CH CH2 C
1. 268 H H-CO-CH2C-CH -CH2-CO-NH2 1. 269 H H-CO-CH2C-CH -C1-12 -CO -NHCH3 1. 270 H H-CO-CH2C-CH -CH2-CH=CH2 1. 271 H H-CO -CH2C_ CH -CH3 1. 27 2 H H-CO ~NH2 CH2 1. 273 H H-CO-N~12 -CH2-CO-NH2 1. 274 H HBr CH2 1. 275 H HBr -CH CO-NH2 1. 276 H HCl -CT12 -CH2 -CN
1. 27 7 H H-COC~13 -CH2 -CH2 -CN
1. 27 8 El H-COOG~13 -CH2 -CH2 -CN
1. 27 9 H H-C0~12 -C~12 -CH2 -CN

~ 939~3 Similarly important products ar~ the compounds derived from n~phtl~ lyox~710nitrile and from analogous derivatives;
for example compounds of the formula <~ ~ N-O-Q

COMP. . .
NO . X Q
. ~ . _ _~
2.1 -CN -CH2~ m.p. 81-82 2,2 -CN CH2-CO-NH2 semisolid 2.3 -CN -C~l(C~13)-C-Cll oil 2.4 -CN -CH2-C-C~ oil 2.5 -CN -CH2-CH-CH2 oil 2.6 -CN -CH3 oil 2.7 -CN -C2H5 oil 2.8 -CN n~C3H7 oil 2.9 -CN -CH2-COOCH3 semisolid 2.10 -CN -CH2-COOC2~5 oil.
2.11 -CN -CU(CI13)-COOcH3 oil 2.12 -CN _C~ (CH3)-COOC~H5 oil 2.13 -CN -CH(c2Hs)-cooc2ll5 2.14 -CN : -CO-C~H5 m.p. 115-118 2.15 .-Cl~ -S2 ~ 1 L
2.16 -CN -S02-CH3 2.17 -CN -CH~CH3)-COO(isoC 3H7) oil 2.18 -CN -CH(CH3)-CO~(c2~l5)2 oil 2.19 ~CN -CH2-COO(isoc3u7) r oil _ 43 -Comp . .
No . X Q
___ ~ __ _ 2 . 20 - CN C}12 - CO ~ C 1 2 . 21 -CN -CO-NH-CH3 2 . 22 -Cl CH2 viscous 2 . 23 -C1 -~ CO ~ H2 oi1 2 . 24 -C1 -C2H5 2 . 2 5 -Br -C~ 2 ~ COO t er t C4~1 9 2 . 26 -C1. -Cll (Cll ) -COOCH3 2 . 27 ^C}12-CN oil ?, 28 -COCH3 -CH2-C0-~ 2 oil 2 . 29 -COCH3 -cH2-coocll3 2.30 -COC113 Cl Cl 2 . 31 COCIl3 C~12-C-CH
2 . 32 -COCI13 -CH3 oil 2 . 33 -COOCH3 CH2 oil 2 . 34 -COOCH3 -CH2-CO-NH2 2 . 36 -CO-NH2 -CH2-c0-~l;;2 2 . 37 -CH3 -CH2-CO -NH ~C1 oil 2.38 -C1 -C~2-CO-I~H~ C1 2 . 39 -CN CH2 -CH=C~l -CH3 oil 2 . 40 -CN -CH2 -CONH -CH3 oil 2 .41 CN -CH2-cON(cH3) 2 oil 2 . 42 -CN -CH2 -CON~ -CH2 -CH CH2 oil 2 . 43 -C1 -CH2 -CONH -CH2 -C-CH oil 2 . 44 -C1 -CH2 -CONH -CH3 oil 2 . 45 -COC~13 -CH2 -CONH -CH3 oil 2 . 46 -COCH3 -CH2 -CON ( CH3) C2 5 oil 2 . 47 -COOCH3 -CH2 -CONH-CH3 oil 2 . 48 -COOCH3 -CH2 -COOCH3 oil .

~ 39 8 Comp. X Q
~o.
.. . . _ 2.49 -COOCH3 -CH2-C.-CH Oel 2.50 -NO2 2 Oel 2.51 -NO2 -~12-CO-NH2 Oel Also the following groups of heterocyclic oxime derivatives are obtained in an analogous manner.

~Z Jl ,c, x N-O-Q

Comp.
No. R4 X Z Q
_ _ 3.1 H -CN S -CH2-CN oil 3.2 H -CN S -CH2-CON~I2 3.3 H -CN S CH2-COOCI-13 3.4 H -CN S -C~l(C~l3)-COOC113 3.5 5-Cl -CN S -CH2-CN
- - 3.6- 5 Cl -CN S -C~12-C0~12 3.7 5-Cl -CN S -CH2-COOC2H5 3.8 5-Cl -CN S -CH(CH3)-COOCIl3 3.9 5-Cl -CN S ~ -C~l(cH3)-coo(isoc3l7) 3.10 5-Cl -C~ S C~-l2-C-C~
3.11 H -CN S . -CH2~C~ -C~12 3.12 H -CN S -Cl~-COO(isoC3H7) 3.13 H -CN S -C2}15 3.14 H -CN S -C112-CH2 O CH3 3.15 11 -CH3 S -CH2-CN
3.16 H -C113 S -CH2~CO~H2 - ~5 -Comp . 4 X ~ Q
.. _ _ . I __ _ __ 3. 17 1~ -C113 S -Ci~2-COOC1~3 3 . 18 ~1 -C113 S -CH(CH3) ~COOCil3 3 . 19 H - CH3 S -CH 2 -C- C}I oil 3 . 20 H -CH3 S -CH2 -CH---CH2 3 . 21 H -CH3 S -CH2 -COO ( i~;oC31~7) 3 . 22 ~1 -Cll3 S -C2~15 3 . 23 11 -C~-13 S -C~12 -C~-12 -0-C~13 3 . 24 H -CN O -CH2 -CN oi 1 3 . 25 11 -CN O -C112 -CO-NH2 viscou~
3.26 H -CN O -CH2~ COOCH3 3 . 27 H -CN o ~nC3H7 3 . 28 H -CN O -CH2 -CH=CH2 3 . 29 H ~CN O -CH2-C-CH
3 . 30 }I -CN O -CH2 -CH2 0 CH3 3. 31 H -CN O -CO-~I-CH3 oil 3.32 H -CN O -CO-N~ C,H2 C-CH solid 3 . 33 H -CN O . -CO-NH--~ Cl 3 ~ 34 5 - N2 -CN o C 2 C oi1 3. 35 5-C1 -CN o C'112-CN oil 3 . 36 H ~C~13 O - -C~l2-CN oil 3 . 37 H -CH3 O -CH2-CO-NH2 oi1 3 . 3 8 H -CH3 O ~ -CH2 -COO ( iC3H7 ) 3 . 39 H -N02 O C 2 CN oi1 3 . 40 H - C1 . C 2 CN . oil 3~41 H Cl O -CH2-CO~lH2 oil 3 . 42 }I C1 S -CH2 -CN oil 3.43 H C1 S . ~C1~2-CO~J2 . oil 3 .44 4-C~3 _Cl13 _C'L-1(C~I3) -COOCH3 3~8 R5~-~ rr N-O-Q

NCOomp . R4 R 5 X Z . . _ 3. 45 . H H -CN S -CH2-CN oil 3. ~6 H H -CN S -C~-12-CO-iNil2 oil 3 . 47 H H -CN S -CH ~ -COOC173 3. 48 H H -CN S -C2H5 3. 49 11 H -CN S -CO-C2H5 3. 50 H . H -CN S -S02-CtH3 3. 51 11 H -CN S -CH2-C-CI-12 Cl 3. 52 H U -CN S -CH2-cON(c3H7)2 solid 3. 53 2-Cl 5-Cl -CN S -CH2-CN oil 3. S4 2-Cl 5-Cl -CN S -C~2-CO NH2 oil.
3, 55 5-N02 H -CN O -CH2-CN oil 3. 56 H H CH3 O -CH2-CN oil Cl 3. 57 H H CH3 O -CO-NH_~ Cl solid 3. 58 }I H -COCH3 O -CH2-COOCH3 3 . .59 H H -COCH3 O -CH (CH3) -COOCH3 3. 60 11 H -N02 -S2-C~3 3 . 61 H H . Cl O -CH2 -CN oil 3 . 62 H H Cl O -CH2-CO-N~il2 oil 3 . 63 H H Cl O -CH 2 -CONH ~C2H5 s ol id 3. 64 H H Cl S -CH2-CN oil 3 . 65 H H -CONH2 O C~12-CO-NH2 oil 3.66 H U COOCU3 0 -C 12 COOCU3 oil ~ 3~ 8 A fur~her impoLtant individllal ~-roup havi~, an action in~luencing plant growtil ~nd pro~c~in~ pl~nts is ~hat of the foi.lo~ing diphenyl etl~r d2rivatives of tlle -formula:

~ /~
~_ ~0 ~ C -X
N ~ 0 - Q

~ Nomp. Q _ __ ~ _ 4.1 -CN ~H2 CN
4.2 -CN -C~2-C0-~2 4.3 -CN -CH2-C00-CI13 4.4 -CN -CH(C~3)-coo c~3 4.5 -CN _CH(Cil3)-cO-c2H5 4.6 -CN -CH3 4.7 H -CH2-CN
4.8 H CH2-C0-~2 4.9 U -CH2-C00-CH3 4.10 CH3 C~l2 CN
4.11 CH3 CH(C~T3) C 3 4.12 C2H5 -CH2-COOC2H5 4.13 Cl -CH2-CN
- 4.14 Cl -CH2-G0-~2 4.15 Cl -C2H5 4.16 Cl -C~2-CH=CH2 4.17 N02 CH2 4.18 N02 CH2-C--CH
4.1~ N2 C0 N-tl CH
4,20 -C0-C~13 1 -CH2-COO(isoC3l^

4.21 -C.0-CH3 -C0-NH-4.22 C0-CIi3 -CH2-C0-NH2 4.23 -CN -CH2-CO~l ~ 3 4.24 . -CO-NH2 .-C112-CO-N~-2 - 4~ -.1. . .

;398 _ Comp. ~ Q ^
..
4.25 -CO-OCH3 -CH2-CN
4.26 -CO-OCH3 -CH2-COOC2H5 4.27 -CO-OCH3 C2H5 4.28 -CO-OCH3 -CH2-C_CH
. _ _ A group of compounds which in the case of high applied amounts of 6 kg per hectare and more can shift the plant-growth-regulating action in the direc~ion of a herbicidal action, bu~
which in low applied amounts of l kg per hectare (and below) are eompletely tolerated by the crops, without the said eompounds losing their properties for regulating plan~ growth and for protecting plants, is that of the following substituted f~lt;Q9 w,thi~
diphenyl ether derivatives~of thc formula I:

` R23 ~3 0~ CI ~ - X
N ~ Q

`g;~8 ------~

No, R22 R23 X Q
_ . _

5,1 4-Cl 2-Cl -CN -CH2-CO~ 2 5,2 4-Cl 2-Cl -CN -CH2-COOCH~
5.3 4-Cl 2-C] -CN -Cll(cH3) C00C113 5.4 4-Cl 2-CN -C~ -CH2-COOC1~3 5,5 4-Cl 2-CN -CM -Cl~(C~13)-COOC~13 5.6 4-CF3 2-Cl -CN -C~l(CH3)-COOC~13 5.7 4-CF3 2-Cl -CN -CH2-COOC2115 . 5.8 4-N2 H -CN -CH(CH3) COOCH3 S.9 4-Cl 2-Cl -Cl -C~12-Cl~
5.10 4-Cl 2-Cl -Cl -Cl12~COOC113 5.11 4-Cl 2-Cl -Cl -C~l(CH3)-COOC~3 5.12 4-Cl 2-Cl -CEI3 -CH2-COOCH3 5.13 4-Cl 2-Cl -CH3 -CH(CH3)-COOCH~
5.14 4-Cl 2-Cl H -CH2-COOCH3 5.15 4-Cl 2-Cl H -CH(CH3)-COO~H3 S,16 4-CF3 2-Cl H -CH2-COOCH3 5,17 4-CF3 2-Cl H -CH(CH3)-COOC~3) .. . .. . ...

The compounds of the formula I can be used on their own or together with the active substances to be antagonised, and also together with suitable carriers ancl/or other additives. Suitable carriers and additives can be solid or liquid and they correspond to the substances common in formulation practice, such as natural or regenerated mineral substances, solvents, dispersing agents, wetting agents, adhesives, ~hickeners, binders and/or fertilisers.
The content of active substance in co~nerclal compositions is between 0.01 and 90 %.
For applicaLion, the compounds of the formula I can be in the following forms (the weight percentage figures in brackets signify advantageous amounts of active substance):
solid preparations: dusts and scattering agents (up to 10%~, -granulates [coated granules, impregnated granules and hornogeneous granules] and pellets (1 to 80%);
liquid preparations-.

) water-dispersible concentrates of active substance:
wettable powders and pastes (25 to 90% in the commercial packing, 0.01 to 15% in ready-for-use solutions);
emulsion concentrates and solution concentratès 10 to 50%~ 0.01 to 15% in ready-for-use solutions);
b) solutions (0.1 to 20%), e.g. for dressing, aerosols.
The active substances of the formula I of the present invention can be formulated for example as follows.

~ 39~

Du~st: The follo~ing s~bstances are usecl to produce a) a 5% dust and b) a 2% dust:
a) 5 parts of active substance, parts of talcum;
b) 2 parts of active substance, 1 part of highly dispersed silicic acid, and 97 parts of talcum.
The active substances are mixed and ground with the carriers, and in this form they can be applied by dusting.

Granulate: The following substances are used to produce a 5%
granulate:
parts of active substance, 0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, and ~1 parts of kaolin (particle size 0.3 - 0.8 mm).
The active substance is mixed with epichlorohydrin and dissolved in 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The solution thus obtained is sprayed onto kaolin, and the acetone is subsequently evaporated off in vacuo. A microgranulate of this kind can be advantageously worked into seed furrows.

~ettable powder: The following constituents are used to produce a) a 70% wettable powder, b) a 40% wettable powder, c) and d) a 25% ~ettable powder, and e) a 10% wettable powder:

~9~398 a) 70 parts of active substance, parts of sodium dibutylnaphthylsulphonate, 3 parts of naphthalenesulphonic acid/phc-nolsulphonic acid/formaldehyde condensate 3:2:1, parts o kaolin, and 12 parts of Champagne chalk;
b) 40 parts of active substclnce, parts of sodium lignin sulphona~e, 1 part of sodium dibutylnaphthalenesulphonate, and 54 parts of silicic acid;
c) 25 parts of active substance, 4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagne chalk/hydroxyethylcellulose mix~ure (1:1), - 1.5 parts of sodium dibutylnaphthalenesulphonate, 19.5 parts of silicic acid, 19.5 parts of Champagne chalk, and 28.1 parts of kaolin;
d) 25 parts of active substance, 2.5 par~s of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of Champagne chalk/hydroxyethylcellulose mixture (1:1), 8.3 parts of sodium al~ninium silicate, 16.5 parts of kieselguhr, and 46 parts of kaolin; and ~fl9398 e) 10 p?rts of active su~stance, 3 parts of a mixture of the sodium salt.s of saturated fatty alcohol sulphates, parts of naphthalenesulphonic acid/formaldehyde condensate, and 82 parts of kaolin.
The active substances are intimately mi.xed in suitable mixers with the addi~ives, and the mixture is then ground in the appropriate mills and rollers. There are obtained ~ettable powders ~hich have excellent ~etting alld suspension properties, which can be diluted with water to give suspensions of the deslred.
concentration; and which can be used in particular for leaf appli~
cation, for seed dressing or for the immersion treatment of seedlir.gs Emulsifiable concentrate: The follo~ing substances are used to , produce a 25% emulsifiable concentrate:
parts of active substance, 2.5 parts of epoxidised vegetable oil, parts of an alkylarylsulphonate/fatty alcohol polyglycol ether mixture, S parts of dimethylformamide, and 57.5 parts of xylene.
Emulsions of the desired colicentration can be prepared from these concentrates by dilution ~ith ~ater; and these emulsions are particularly suitable for seed dressing.

3~8 Biolo~ical Examples In order to determine the selective herbicidal action of a highly effective herbicidal leading product of the chloro-acetanilidine class, on its own and together with the antidote of the formula I according to the invention, the Eollowing tests were carried out; the herbicidal active substance used in the tests was N~L3'-methoxypropyl-(2')]-2-methyl-6-ethyl-chloroacetanilide (substance H) (German Offenlegungsschrift No 2,328,340).

1) Pre-emer~ence application as a tank mixture a) After sowing Aqueous suspensions were produced from formulated wettab]e powders of the herbicide (substance H) and from an antidote of the formula I (substance S) according to the invention, and these were then applied, singly and also as mixtures in amounts of 1 kg to 8 kg/hectare with mixture ratios H:S of 4:1 to 1:4, after the sowing of various varieties of cultivated millet of the Sorghum hybridum type (varieties "Funk", "Dekalb", "NK 222" and "DC 59"), in pots or in seed trays in a greenhouse, the said suspensions being applied to the surface of the soil in the sown vessels.
The vessels were then kept at 22 - 23C with customary watering.
The results were evaluated after 15 days on the basis of the following linea scale:
9 = plants undamaged (as untreated control plants) 1 - plants completely destroyed, 2 to 8 = intermediate stages of damage.

~ 33 b) Before sowin~ (PPI) In the same manner as under a), soil in pots and in seed trays was treated with the liquors containing the active substance, and immediately afterwards these vessels we.re sown with seeds of the millet variety "Funk".
Whereas the compound H when used alone i.n the given applied amounts damages or destroys the cultivated millet, its effect when an an.tidote of the formula I is present is neutralised either completely or to a great extent. This is achieved in particular with the compounds Nos. 1.1, 1.4, 1.14, 1.20 and 1.34.

2) Seed dressin~ (wet) Aqueous emulsion concentrates of an antidote of the formula I
were prepared, and each shaken in a bottle with 50 g of cultivated millet seed. The various concentrations of antidote amounted to between 20 and 150 g of antidote per 100 kg of seed. Shortly after the dressing treatment, the seed was sown in seed trays and treated in the customary manner with spray liquors of the herbicide H as described under la). The results were evaluated 15 days after appl.ication of the herbicide using the same ratings as before.
The results showed here too that protection of the cultivated millet is obtained where the concentration of herbicide is low, but sufficiently high to combat weeds, as a consequence of the antidote S. The following compounds were particularly effective as antidotes: Nos. 1.1, 1.4, 1.14, 1.20, 1.34, 1.44~ ]..70 to ~ 56 -~ ~9 ~3 L.75, 1.78, 1.82, 1.88, 1.91, 1.98, 1.103, 1.108, 1.110, 1.126,1.139, 1.173, 1.174, 1.177, 1.1~8, 1.191~ 1.199, 1.204, 1.207 to 1.209, 1.217, 1.218, 1.227, 1.230, 1.239, l 240, 1.253, 1.255, 1.267, 1.274, 1.275 to 1.279, and others. Compounds of the U.S. Patent Specification No. 3,799,757 did not act as antidotes.
The antagonistic action of an antidote of the formula I
does not extend as a rule to the main weeds, such as Echinochloa, Setaria italica, etc., which are destroyed practically to the same extent as they are when the antidote is not present.
Similarly good antidote effects are achieved also with other chloroacetanilides and thiolcarbamates, and also on other cul~ivated crops, such as rice, maize, wheat, cotton, soya bean or sugar cane.
Increase in yield of soYa bean croPS
In a field of soya bean plants of the "Lee 68" variety, plots each 50 square metres in size were sprayed with aqueous preparations of an active substance of the formula I when the plants were in the 5-6-leaf stage. The amount of active substance applied was 500 g per hectare. At the point of time of harvesting, it was established that untreated plants were for the most part broken (flattened), whilst on the treated plots all the plants were standing upright and displaying better pod setting. Compared with the control plots, the treated plots gave approximate]y 10-15% higher yields.
Significant increases in yield of 12% or more were achieved on plots which had been treated with the compounds Nos. 1.1, 1.3, 1.4, 1.167, or others.

Reduction of side shoots on tobacco crops Tobacco plants were grown in a greenhouse and topped as blossoming was beginning. One day later they were sprayed with aqueous spray liquors of the active substances Nos. 1.106 and 1.148. The concentration of the active substances was 0.66 and 1.32 % of active substance, respectivély.
Whereas in the case of the untreated plants, strong side shoots developed from the leaf axil buds, the growth of side shoots on the treated tobacco plants remained greatly reduced.
Similar results were obtained with other compounds of the formula I with a propargyl ether structure.
Biolo~ical tests under stress conditions Q
A) Plant ~rowth at below optimum temperature Rice plants in the 2- to 3-leaf stage were immersed with the roots and the lower part of the shoot for 45 minutes in a solution containing 10 ppm (= 0.001 %) of an active substance of the formula I. They were afterwards replanted in dripping wet soil in asbestos cement containers 70 x 70 cm in size, and kept at a temperature of only 18-22C instead of at 28-30C.
The surface of the soil in the containers was covered with 2-3 cm of water after 3 days. After a further 18 days, the trea.ed plants were compared with the untreated control plants.
The rice plants treated with compounds o the formula I or Ia had a root system which was on average 30 to 50 % larger.
Compounds of the U.S. Patent Specification No. 3,799,757 showed no such action.

B) Plant developl~en~ with slightly damal~ed seedlings Rice seed which had been pre-germinated in a quartz sand nutrient solutionwasimmersed wi~h the formed slightly yellowish shoots for 45 minutes in a solution containing 10 ppm of an active substance of the formula I; they were then replanted, with 42 plants in each case, in an asbestos cement vessel as described under A, and subsequently kept, until the time for gathering, a~ the normal temperature of 28-30C with the customary watering.
The final evaluation was with respect to dry weight of ~he parts of the plants above the soil, number of panicles and the dry grainweight compared with 42 correspondingly pre-germinated - but untreated control plants. The following mean values were obtained from several test series.
Control plants Treated plants I rease dry weight: 507 g 762-820 g 50.3 to 61.7 %
number of panicles: 242 284-352 g 17.4 to 45.5 %
dry grain weight: 182 g 220-290 g 20.9 to 59.3 %
The compounds Nos. 1.1, 1.4, 1.35, 1.44, 1.49, 1.78, 1.88, 1.173, 1.174, 1.207, 1.208, 1.217, 1.218, 1.253, 1.276, 1.277, 1.278, 2.1 and 3.1 were distinguished in this series of tests by .3 ~ 3~ ~

particularly high increases. Compounds from U.S. Pat~nt Specification No. 3,799,757 produced no such effects. The seeds of other cultivated plants, such as maize, cereals, soya bean and cotton, can be pretreated in a manner analogous to that described in the case of rice, and similar increases in yield are obtained.

Claims (32)

THE EMBODIMENTS OF THE INVENTION IN WHICII AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of the formula (I) wherein the substituents have the following meanings: Ar represents a phenyl group of the formula an .alpha.- or .beta.-naphthyl group, or a heterocyclic ring of the formula X represents cyano, nitro, halogen, lower alkanoyl, a carboxylic acid ester group, hydrogen, a carboxylic acid amide group, or lower alkyl; Q represents lower alkyl which is straight-chain or branched chain, or which can be interrupt-ed by hetero atoms or substituted by halogen, or Q represents lower alkenyl or haloalkenyl, lower alkynyl, C3-C7-cycloalkyl optionally substituted by halogen, or Q represents lower cyanoalkyl, a lower alkane carboxylic acid ester group, a lower alkanecarboxylic acid amide group, a lower aliphatic acyl group, a phenyl group optionally substituted by halogen or a lower alkoxy group, alkylsulphonic acid or a sulphonic acid amide group, R1 represents hydrogen, halogen, lower alkyl, lower alkoxy, or a phenoxy group which is in the para position and which is optionally substituted a maximum of twice by halogen, -CN, NO2 or CF3, R2 and R3 independently of one another represent hydrogen, halogen, NO2, lower alkyl, halogenoalkyl or lower alkoxy, R4 and R5 independently of one another represent hydrogen, halogen, NO2 or lower alkyl, and Z represents oxygen or sulphur, with the proviso that, if Ar represents an unsubstituted phenyl group and Q
represents the radical -CH2CN, X represents NO2, halogen, lower alkanoyl, a carboxylic acid ester group, hydrogen, a carboxylic acid amide group or lower alkyl, and with the further proviso that, if Q is a lower alkane carboxylic acid ester or amide group and X is hydrogen or methyl, Ar is other than mono-or dihalo-substituted phenyl.

2. A compound according to Claim 1 wherein Ar has the given meaning, and the other substituents have the following meanings:
X represents cyanom nitro, halogen, lower alkanoyl, a carboxylic acid ester group of a lower aliphatic alcohol, a carboxylic acid amide group, or lower alkyl, Q represents lower alkyl which is straight-chain or branched chain, or which can be interrupted by a hetero atom or substituted by halogen, or Q represents lower alkenyl, lower alkynyl, lower cyanoalkyl, a lower alkanecarboxylic acid ester group, a lower alkanecarboxylic acid amine group, a lower aliphatic acyl group, a cycloaliphatic acyl group having 4 to 6 C

atoms, or an unsubstituted sulphonic acid amide group or a sulphonic acid amide group mono- or disubstituted by a lower aliphatic radical, R1 represents hydrogen, or a phenoxy group in para-position, R2 and R3 independently of one another represent hydrogen, halogen or lower alkyl, R4 and R5 represent hydrogen, and Z represents oxygen or sulphur.

3. A compound according to Claim 1 of the formula Ia (la) wherein the substituents have the following meanings:
X represents cyano, nitro, halogen, lower alkanoyl, a carboxylic acid ester group of a lower aliphatic alcohol, a carboxylic acid amide group or lower alkyl, Q represents a lower straight-chain alkyl chain which is inter-rupted by oxygen, or Q represents lower alkenyl, lower alkynyl, lower cyanoalkyl, a lower alkanecarboxylic acid ester group, a lower alkanecarboxylic acid amide group, a lower aliphatic acyl group, a sulphonic acid amide group which is unsubstituted or is mono- or disubstituted by a lower aliphatic radical, R1 represents hydrogen, R2 represents hydrogen, halogen, lower alkyl or lower alkoxy, and R3 represents hydrogen, halogen, lower alkyl or lower alkoxy.

4. A compound according to Claim 3, wherein the substituents of the formula Ia have the following meanings:
X represents cyano, nitro, halogen, lower alkanoyl, a carboxylic acid ester group of a lower alkanol, or a carboxylic acid amide group, Q represents lower alkynyl, lower cyanoalkyl, a lower alkane-carboxylic acid ester group or a lower alkanecarboxylic acid amide group, R1 represents hydrogen, R2 represents hydrogen, halogen or lower alkyl, and R3 represents hydrogen, halogen or lower alkyl.

5. A compound according to Claim 4, wherein the substituents of the formula Ia have the following meanings:
X represents cyano, chlorine, bromine, acetyl, propionyl, -COOCH3, -COOC2H5, -CO-NH2, -CO-NHCH3 or -CO-N(CH3)2, Q represents propynyl or butynyl, cyanomethyl or cyanoethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, methoxy-carbonylethyl or ethoxycarbonylethyl, an acetamide or propionamide group optionally substituted on the N atom by one or two lower aliphatic groups, R1 represents hydrogen, R2 represents hydrogen, halogen or methyl, and R3 represents hydrogen, halogen or methyl.

6. A compound according to Claim 5, wherein X represents a cyano group, and Q, R1, R2 and R3 have the given meanings.

7. A compound according to Claim 1 of the formula II

(II) wherein R1, R2 and R3 independently of one another represent hydrogen, halogen, NO2, lower alkyl, halogenoalkyl or lower alkoxy, X represents -CN, -NO2, halogen, the acetyl group, a carboxylic acid ester group of a lower aliphatic alcohol, or a carboxylic acid amide group, n represents 1, 2 or 3, R9 represents hydrogen or lower alkyl, R10 represents -CONH2, -CO-NH-(lower aliphatic radical), -CO-NH-cycloalkyl, -CONH-(C6H5-m) (halogen, lower alkyl)m or -CN, and m represents an integer, 0, 1, 2 or 3.

8. A compound according to Claim 7 of the formula III

(III) wherein X' represents -CN, -NO2, chlorine, acetyl, lower alkoxy-carbonyl, allyloxycarbonyl, carbamoyl or di-lower-alkyl-carbamoyl, R10 represents -CN, -CO-NH2, -CO-NH-lower alkyl or -CO-NH(C6H5-m) (Cl, Br, CH3)m, and m represents an integer, 0, 1 or 2.

9. .alpha.-Cyanobenzylidene-amino-oxacetamide of the formula

10. A process for producing compounds of the formula I of claim 1 by etherification or acylation of an oxime of the formula V

(V) or of its oxime salt, with a halide of the formula Halg-Q, wherein Ar, X and Q
have the meanings given for the formula I, and "Halg" denotes halogen.

11. A process for producing compounds of formula Ia according to any one of claims 4 to 6 by etherification of an alkali salt or ammonium salt of the formula V

(V) with a halide Halg-Q, wherein Ar, X and Q correspond to one of the definitions given in any one of claims 4 to 6, and"Halg" denotes halogen.

12. A process for producing compounds of formula II or III according to claim 7 or 8 by etherification of an alkali salt or ammonium salt of the formula V

(V) with a halide Halg-Q, wherein Ar, X and Q correspond to one of the definitions given in claim 7 or 8, and "Halg" denotes halogen.

13. A process for promoting plant growth by treatment of the plant or of parts thereof, or of the habitat thereof, with a compound of the formula I
according to claim 1.

14. A process according to claim 13, in which the plant seed or the germinated seed is treated.

15. A process according to claim 14 for the treatment of sorghum-millet.

16. A process according to claim 14 for the treatment of rice.

17. A process according to claim 14 for the treatment of maize.

18. A process according to claim 14 for the treatment of wheat, rye, barley or oats.

19. A process according to claim 14 for the treatment of soya bean.

20. A process according to claim 14 for the treatment of cotton.

21. A process according to claim 14 for the treatment of sugar beet.

22. A process for protecting cultivated plants against the undesirable in-fluence of agricultural chemicals by applying an oxime derivative according to claim 1 to the plants, to parts of the plants or to their habitat, the applica-tion of the oxime being carried out before, simultaneously with, or after the application of the agricultural chemical.

23. A process according to claim 22, wherein the seed of the cultivated plants is treated with the oxime derivative.

24. A process according to claim 22, whereby the agricultural chemical is a herbicide.

25. A process according to claim 24, whereby the herbicide is an active ingredient of the chloroacetanilide class.

26. A process according to claim 25, whereby N-[3'-methoxy-propyl-(2')]-N-chloroacetyl-2-methyl-6-ethylaniline is used as the herbicide.

27. A process according to claim 24, whereby the herbicide is an active ingredient of the thiolcarbamate class.

28. A process according to claim 24, whereby,the herbicide is an active ingredient of the class comprising substituted phenoxyphenoxyacetic acid esters and phenoxyphenoxypropionic acid esters, or substituted pyridineoxyphenoxyacetic acid esters and pyridineoxyphenoxypropionic acid esters.

29. A compound according to claim 1 of the formula:

wherein R22 represents halogen, trifluoromethyl or nitro, R23 represents hydrogen, halogen or cyano, X represents hydrogen, halogen, cyano or lower alkyl and Q represents -CH2-CONH2,, -CH2CN, -CH2-COOCH3, CH2-COOC2H5, or CH(CH3)-COOCH.

30. A compound according to claim 1 of the formula:

wherein R22 represents chloro, trifluoromethyl or nitro, R23 represents hydrogen, chloro or cyano, X represents hydrogen, chloro, cyano or methyl and Q represents -CH2-CONH2, -CH2CN, -CH2-COOCH3, CH2-COOC2H5, or CH(CH3)-OOOCH3.

31. A compound of the formula:

32. A process for protecting cultivated plants against the undesirable influence of agricultural chemicals by applying an oxime derivative according to claim 29, 30 or 31 to the plants, to parts of the plants or to their habitat, the application of the oxime being carried out before, simultaneously with, or after the application of the agricultural chemical.