NO780714L - PLANT GROWTH STIMULATORS AND PLANT PROTECTION AGENTS BASED ON OXIMETERS AND ESTERS - Google Patents

Description

Plant growth stimulants and plant protection agents

based on oximeters and esters.e.

The present invention relates to new oximeters and esters with the general formula I

production of these, as well as new agents based on these compounds and use of these agents, respectively compounds for plant growth stimulation and protection of cultivated plants.

In the formula I means

Ar - a phenyl radical of formula

- an α- or 3-naphthyl residue, or - a heterocyclic ring of formula

X=- CN, -NC>2 1 halogen, lower alkanoyl, a carboxylic acid residue,

hydrogen, a carboxylic acid residue or lower alkyl,

0 = - lower -alkyl which is linear or branched or interrupted by heteroatoms or may be substituted with halogen,

- lower alkenyl or haloalkenyl,

- lower alkynyl,

- optionally with halogen-substituted C^-C^-cycloalkyl, lower cyanoalkyl,

- lower alkanecarboxylic acid ester group,

- lower alkanecarboxylic acid ester group,

- lower alkanecarboxylic acid amide group,

aliphatic acyl residue,

- araliphatic, cycloaliphatic or optionally substituted aromatic or heterocyclic acyl residue,

- alkylsulfonic acid or

- a sulphonic acid amide residue,

R-^ - hydrogen, halogen, lower alkyl, lower alkoxy or an optionally at most twice by halogen, -CN, NC^CF^substituted para phenoxy radical, I?2 and R.. - independently of each other hydrogen, halogen, NC^ ,

lower alkyl, haloalkyl, lower alkoxy,

R 4 and - independently of each other hydrogen, halogen, NC^,

lower alkyl,

Z - oxygen or sulfur,

with the restriction that if Ar means an unsubstituted phenyl residue and Q the residue - CP^CN, X stands for NC^, halogen, lower alkanoyl, a carboxylic acid residue. a carboxylic acid ter-res t, H, a carboxylic acid amide residue or lower alkyl.

Depending on the substitution, these oxime derivatives are obtained

with the general formula I with various plant biological • properties that can be used as plant growth regulators or also as pesticide antidotes in general in agriculture or in special sectors within plant protection.1 formula I is understood to mean halogen fluorine, chlorine, bromine or iodine.

The term alkyl alone or as part of a substituent includes branched or unbranched Cl 1 - to C 8 -alkyl groups, lower alkyl means C -C -C -alkyl. Examples are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. butyl, tert. butyl, . as well as the higher homologues amyl, isoamyl, hexyl, heptyl, octyl and isomers thereof. Preferably, alkanoyls or cyanoalkyls contain an additional C atom. A lower alkane carboxylic acid ester consists of a lower alkyl part with 1-4 C atoms, the carbonyl group and an alcoholic or phenolic residue with 1-0 C atoms. Special mention must be made of vinegar

-CH2COOT (T = C1-Cg residue) and-1-propion ester -CH(CH3)-

COOT where OT = lower aliphatic alcohol residue is preferred in both cases.

Alkenyls mean aliphatic residues with one or two double bonds ("alkadienyls") and a maximum of 6>preferably 4 C atoms, haloalkenyls contain up to 3 halogen atoms, preferably chlorine or bromine. Lower alkynyl means propynyl (=propargyl) and butynyl.

Carbonic acid amides and sulfonic acid amides also include mono- or symmetrical or unsymmetrical di-substituted amides whereby the substituents may optionally be lower alkyl, lower alkenyl, propynyl or butynyl and once a phenyl ring zone according to the definition for R^/R^ may be substituted or unsubstituted.

C^-C^ cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl, cycloaliphatic residues corresponding to these ring systems may however, depending on the possibility, contain ..one or more double bonds.

An araliphatic residue comprises an aryl group which, according to F^/R-^, is one to three times substituted phenyl or also .naphthyl, fluorenyl, indanyl which is bound to the rest of the molecule via lower alkyl or lower alkenyl. Examples are the base elements benzyl, phenethyl, phenylallyl and homologues.

Aromatic carboxylic acids, which can form aromatic acyl residues are derived from aromatics such as above all phenyl and can be substituted as indicated under I^/R^•

Heterocyclic carboxylic acids are derived from mono- or bicyclic rings with 1 to 3 identical or different heteroatoms 0, S and N. Mention must be made of 3- to 6-, above all 5- or 6-membered heterocycles•which can be saturated, partially saturated or unsaturated and may optionally be substituted as indicated under R^/R,.. Non-limiting examples include: furan, nitrofuran, bromofuran, methylfuran, thiophene, chlorothiophene, pyridine, 2,6-dichloropyridine , pyrimidine, pyridazine, pyrazine, piperidine, methylpiperidine, morpholine, thiomorpholine, tetrahydrofuran, oxazole, pyrazole, pyrrole, pyrroline, pyrrolidine, thiazole, 2,3-dihydro-4H-pyran, pyran, dioxane, 1,4-oxati -(2)-in.

Examples of aliphatic chains which are interrupted by heteroatoms are methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl, ethylthioethyl, methylaminoethyl, tert. butylaminoethyl, alkoxyalkyloxyalkyl such as methoxyethoxyethyl.

It has been shown that oximeters and oximesters of formula

I has extremely advantageous properties in practice for plant growth stimulation without entailing adverse consequences for the plants treated in this way. The active substance with formula I has, in small doses, a particular ability to stimulate both the germinating seeds and also the further developed young plants. This, at certain dosages, leads to a clearly enlarged root system, to an increased photosynthesis rate and to a faster development of aboveground plant parts. The effect of the oximes of formula I is not, however, restricted to the earlier stage of the plants' development, but can also be observed in later application or by partial application to specific plant parts (e.g. seed dressing, seed application, root treatment, sprout treatment, foliar application). This technique leads to faster growth of the treated plants, better fruit bearing, an earlier ripening and harvesting time and an increased and at the same time improved harvest quantity. The application of the active substances can in principle be carried out on plants, on plant parts, on the seeds or in the soil and corresponds to the usual application or pickling technique. Another very important advantage is the improvement of the competitiveness of the thus treated plant vis-à-vis the non-growth-stimulated weed flora. However, in such cases the application of the active substance of formula I must take place on the seeds or sprouts of the desired plant culture and not in the cultivation area. A third important advantage resulting from the substantially enlarged root system of the plant treated in this way consists in the possibility of achieving a satisfactory development of the plant culture and a sufficient amount of harvest even under less favorable environmental conditions. Examples of such environmental disturbance factors include: nutrient-poor soil, drought, low temperatures during the plant's early development, short-term frost, reduced solar radiation as a result of an unfavorable season or unfavorable growing location.

Oximeters and esters with formula I, however, have plant-regulating properties to a greater extent, depending on the time of application and the type of plant.

Various further application possibilities of the oximes of formula I are indicated in the following which are, however, not limiting: - application for improved leaf development in cultures such as tobacco, charcoal or lettuce and avoidance of unwanted germination. - Application for yield increase in leguminous cultures (e.g. with peas, beans, soya and peanuts) by stimulating the generative growth (increase of grafting).

Application for increasing the storage capacity of storage-unstable crops such as cereals (preventing the plants from breaking under adverse weather conditions such as storms or

persistent rain)

- Application to facilitate the harvesting of fruits by increasing the formation of the separating tissue between fruit and branch in the plants. - Application for increasing the storage capacity of substances in plants (sugars, proteins, oils and other) or for temporary retention of what was once stored.

Storability of plant constituents includes the possibility of maintaining the stored longer than under natural conditions. Thus, e.g. the storage capacity of potatoes is increased. Furthermore, the sugar content in the sugarcane shortly before harvesting can be kept constant by the application of certain oxymeters with formula I, whereby the plant's efforts towards further side bud formation at the expense of the sugar content are counteracted.

Agents for influencing plant growth, especially for growth inhibition, have already been described several times, and e.g. Chlorocholine chloride is particularly suitable for straw shortening and straw stabilization in wheat. According to DOS 2,458,165, bis(p-chlorophenyl) acetic acid or salts, esters, amides or nitriles thereof must cause similar straw shortening in grain. In DOS 2,407,148, 2,6-disubstituted phenoxyacetic acid esters or pronionic acid esters are recommended as growth regulators. However, the mode of action of these substances is not satisfactory, particularly at low application quantities and concentrations. A similar relationship exists with p-chlorophenyldimethylacetic acid (German patent 113,890) and also with 2-cyano-bicyclo[2,2,1] heptane (French patent 2,256,722). As experiments show, their effect is very unsatisfactory.

The arylglyoxynitrile proposed in US patent 3,799,757-. oximes of the general formula

are growth inhibitors and plant regulators with insufficient effect, and in addition they are not stable and decompose already after a short time. Surprisingly, the oximes of formula I have a further very important property. They are excellently suited for protecting cultivated plants such as cultivated millet, rice, maize, cereals (wheat, rye, barley, harrow), cotton, sugar beet, sugarcane, soya etc. against attack by plant-aggressive agricultural chemicals, especially herbicides of various substance classes such as triazines, phenylurea derivatives, carbamates, thiol carbamates, halogen-acetanilides, halophenoxyacetic acid esters, substituted phenoxyphenoxyacetic acid esters and -propionic acid esters, substituted pyridineoxyphenoxyacetic acid esters and -propionic acid esters, benzoic acid derivatives, etc. if these do not act selectively or sufficiently selectively, i.e. also damage the cultivated plants more or less next to the weed to be controlled. The invention also relates to agents containing these oximeters of formula I together with biologically active additives such as herbicides, fungicides or insecticides. To solve this problem, various substances have already been proposed that are able to specifically counteract it. harmful effect of a herbicide on the cultivated plant, i.e. to protect the cultivated plant without thereby noticeably affecting the herbicidal effect of the grasses to be controlled. Thereby, such a counteracting agent (=Antidote) can, depending on its properties, be used for pre-treatment of the cultivated plant's seeds (pickling of seeds or cuttings) or before sowing in the seed tracks or as a tank mixture alone or together with the herbicide before or after the growth of the plants.

The treatment with the counteracting agent can take place before, after or at the same time as the herbicide treatment. Prior treatment includes both the treatment of the cultivation surface before sowing (ppi = "pre plant incorporation") and treatment of the sown but not yet vegetated cultivation surfaces.

Thus, British patent 1,277,557 describes the treatment of seeds or sprouts of wheat and sorghum with certain oxamic acid esters and amides before attack by N-methoxymethyl-2',61-diethyl-chloroacetanilide (Alaclor). Other literature citations

(DOS 1.952.910, DOS 2,245,471, French patent 2,021,611)

suggests weeding agents for the treatment of grain, maize and rice seeds for protection against attack by herbicidal thiol carbamates. In German patent 1. 576 . 676 and US Patent 3,131. 509, hydroxy-amino-acetanilides and hydant ions are proposed for the protection of cereal seeds against carbamates such as IPC, CIPC, etc.

In the literature, however, so far no class of substances has been proposed which, on the one hand, has strong growth-stimulating impulses on plants and, on the other hand, has the ability to protect plants against aggressive agricultural chemicals in the form of an antidote effect.

Particular emphasis must be placed on such compounds of formula I in which Ar has the indicated meaning and the other substituents have the following meaning: X = - cyano, nitro, halogen, lower alkanoyl, a carboxylic acid ester residue of a lower aliphatic alcohol, a carboxylic acid amide residue or lower alkyl,

= - lower alkyl which is linear or branched or may be interrupted by a heteroatom or substituted by a halogen atom,

- lower alkneyl,

- lower alkynyl,

- lower cyanoalkyl,

- lower alkanecarboxylic acid ester group,

- lower alkanecarboxylic acid amide group,

- lower aliphatic acyl residue,

- cycloaliphatic acyl residue with 4 to 6 C atoms, or - an unsubstituted or, in the case of a lower aliphatic residue, one or two times substituted sulphonic acid amide residue, = - hydrogen or a para-standing phenoxy residue,

R2 and R^- independently of. each other hydrogen, halogen or

lower alkyl, R^ and R, - - hydrogen,

z = - oxygen or sulfur.

Among these, the compounds of formula Ia are preferred

where the substituent has the following meaning:

X = - cyano, nitro, halogen, lower alkanoyl, a carboxylic acid ester residue of a lower aliphatic alcohol, a carboxylic acid amide residue or lower alkyl,

Q = - lower rectilinear alkyl chain which is interrupted by

oxygen,

-,lower alkenyl,

- lower alkynyl,

- lower cyanoalkyl,

- lower alkanecarboxylic acid ester group,

- lower alkanecarboxylic acid amide group,

- lower aliphatic.acyl residue,

- unsubstituted or with a lower aliphatic residue than-

or twice substituted sulphonic acid amide residue,

R^= - hydrogen, R2=- hydrogen, halogen, lower alkyl or lower alkoxy,

=- hydrogen, halogen, lower alkyl or lower alkoxy.

Particularly preferred is this latter group are such compounds where the substituents in formula Ia have the following

importance:

X = '- cyano, nitro, halogen, lower alkanoyl, a carboxylic acid ester residue of a lower alkanol, a carbonic acid amide residue, Q = - lower alkynyl,

- lower cyanoalkyl,

- lower alkanecarboxylic acid ester group,

- lower alkanecarboxylic acid amide group,

=- hydrogen,

R2hydrogen, halogen or lower alkyl,

R3= hydrogen, halogen or lower alkyl.

Within the latter group, in a narrower sense, the compounds are preferred in which the substituent of formula Ia has the following meaning: X - cyano, chlorine, bromine, acetyl, propionyl, -COOCH^, -COOC^H,.,

-CO-NH2, -CO-NHCH3, -CO-N (CHg )'2 ,

0 = - propynyl or butynyl,

- cyanomethyl or cyanoethyl,

- methoxycarbonylmethyl, ethoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylethyl, - an optionally substituted acetamide or propionamide residue at one or two lower aliphatic groups on the N atom, R^= - hydrogen,

R^- hydrogen, halogen or methyl,

R =- hydrogen, halogen or methyl.

• Among these, such are an important subgroup where X means a cyano group.

Another preferred range of plant-stimulating and plant-protecting active substances with formula I is that covered by formula I:

where R-^, R 2 and R^ independently of each other mean hydrogen,

halogen, N02 r lower alkyl, haloalkyl, lower alkoxy and

X = - CN, N02, halogen, the acetyl group, a carbonic acid ester-

residue of a lower aliphatic alcohol or a carboxylic acid amide residue, whereas

n is 1, 2 or 3,

Rg is hydrogen or lower alkyl, R0 means -CONH2, -CO-NH-(lower aliphatic residue), -C0-NH-cycloalkyl, -CONH-(CgH5_m) (halogen,.lower

_alkyl) or -CN, and

m is an integer 0, 1, 2 or 3.

Within the scope of formula II are compounds of formula

III preferred

where

X1 means -CN, NO2, chlorine, acetyl, lower alkoxycarbonyl,

allyloxycarbonyl, carbamoyl or di-lower alkyl-carbamoyl and

R, . -CN, -CO-NH-, -CO-NH-lower alkyl or -CONH(C,H[r ) 10 z 6 5-m (Cl, Br, CH3) and m is an integer 0,1 or 2 .

The preferred individual compounds include:

- α-cyanobenzylidene-amino-oxaacetamide of formula

- a-c.yanobenzylidene-amino-oxyacetic acid ethyl ester

(connection 1.4)

- a-(cyanoethoxyimino)-benzacetonitrile (compound 1.44) virulent chloroacetanilides which are partly not sufficiently tolerable on cultivated plants such as cereals, rice, refined sorghum-millet and others but which in cooperation with the oximeters with formula

In the present invention, such cultivated plants are spared

without losing its other weeding effect is e.g. known from the US patents 3,547,620 , 3 . 403,994, 3. 442 . 945.

The antidotes with the formulas I, II or III are preferably used with herbicidal chloroacetanilides of the formula

where

R^^ means lower alkyl, alkoxy, alkoxyalkyl, trifluoromethyl or halogen,

R , R 1 and R 1 independently of each other mean hydrogen, lower alkyl, alkoxy, alkoxyalkyl, trifluoromethyl or halogen, and R 1 - means a C 1 -C 4 alkyl, which is optionally substituted

by carboxy, carboxylic acid ester,.carbonamide, by a

or two lower aliphatic "residues substituted carbonamide or by -CN, or wherein is pro<p>inyl, butynyl, an acetalized carbonyl group, 1,3-dioxo-lan-2-yl-alkyl, 1,3-dioxolan- 5-yl-alkyl, 1,3-dioxan-2-yl-alkyl, furanylmethyl, tetrahydrofuranylmethyl or alkoxyalkyl of the formula -A-O-R^ , where A means an alkylene chain with 1 to 4 C atoms of which.. 1 or 2 belong the direct chain oq R-^g lower alkyl,

alkenyl or also cycloalkyl or cycloalkylmethyl with 3 to 6 C atoms in the ring-

The terms "lower alkyl" or "lower aliphatic residue" mean groups with a height of 4 carbon atoms and correspond to the definition given above for formula I, likewise the term "halogen".

Some of the chloroacetanilides particularly suitable for use with the antidotes specified according to the invention are mentioned in the following: N-ethoxymethyl-2-methyl-6-ethyl-chloroacetanilide, N-methoxymethyl-2,6-diethyl-chloroacetanilide, N-( 2<1->methoxyethyl)-2,6-dimethyl-chloroacetanilide, N-(2<1->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-[3'-methoxyprop-(2')-yl]-2-methyl-chloroacetanilide, N -[3<1->methoxyprop<p->(2<1>)-yl]-2,6-dimethyl-chloroacetanilide, N-[3'methoxyprop-(2<1>)-yl]-2-methyl -6-ethyl-chloroacetanilide, N-[3'-methoxy<p>rop-(2<1>)-yl]-2,6-diethyl-chloroacetanilide, N-(2'-ethoxyethyl)-2,6- diethyl-chloroacetanilide, N-(2'-n-propoxyethyl)-2-methyl-6-ethyl-chloroacetanilide, N-(2'-n-propoxyethyl)-2,6-diethyl-chloroacetanilide, N-(2'- isopropoxyethyl)-2-methyl-6-ethyl-chloroacetanilide, N -chloroacetyl-2,6-diethylanilino-acetic acid ethyl ester, N-chloroacetyl-2,6-diethylanilino-acetic acid ethyl ester, N-chloroacetyl-2,6-dimethylanilino-acetic acid iriethyl ester, N-chloroacetyl-2-methyl-6-ethylanilino-acetic acid isopropyl 'ester, 2-[N-(α-chloroacetyl)-2,6-dimethylanilino]acetaldehyde-diethyl acetal, N-[3<1->methoxyprop-(2<1>)-yl]-2,3-dimethyl- chloroacetanilide, N-(2'-ethoxyethyl)-2-methyl-chloroacetanilide,

N-(21-methoxyethyl)-2-methyl-chloroacetanilide,

N-[2'-methoxyprop-(1<1>)-yl]-2,6-dimethyl-chloroacetanilide, N-[2<1->methoxyprop-(1')-yl]-2-methyl-6- ethyl1-chloroacetanilide, N-[3<1->ethoxyprop-(2')-yl]2-methyl-6-ethyl1-chloroacetanilide, N-[1'-methoxybut-(2<1>)-yl]-2 ,6-dimethyl-chloroacetanilide, N-(2')-methoxyethyl)-2-methyl-6-methoxy-chloroacetanilide, N-(n-butoxymethyl)-2-tert.butyl-chloroacetanilide, N-[3<1- >ethoxyprop-(2<1>)-yl]-2,6-dimethyl-chloroacetanilide, N-(2<1->methoxyethyl)-2-chloro-6-methyl-chloroacetanilide, N-(2'-ethoxyethyl) -2-chloro-6-methyl-chloroacetanilide, N-(2<1->ethoxyethyl-2,3,6-trimethyl-chloroacetanilide, N-(2'methoxyethyl)-2,3,6-trimethyl-chloroacetanilide, N -(2<1->isopropoxyethyl)-2,3,6-trimethyl-chloroacetanilide, N-cyanomethyl-2,6-dimethyl-chloroacetanilide,

N-(but-1-yn-3-yl)-chloroacetanilide,

N-propynyl-2-methyl-6-ethyl-chloroacetanilide,

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<1->furanyl-methyl-2,6-dimethyl-chloroacetanilide, N-(2<1->furan< y>l-methyl)-2-chloro-6-methyl-chloroacetanilide, IJ- (2 1 - te tr ahydr of ur anyl-methyl)-2 , 6-dimethyl-chloroacetanilide , N-(N<1-> propargylcarbamylmethyl)-2,6-dimethyl-chloroacetanilide, N-(N',N<1->dimethylcarbamylmethyl)-2,6-dimethyl-chloroacetanilide, N-(n-butoxymethyl)-2,6-diethyl-chloroacetanilide, N -(2'-n-butoxyethyl)-2,6-diethyl-chloroacetanilide, N-[3'-methoxybut-(2<1>)-yl]-2,6-dimethylchloroacetanilide, 2-chloro-N-isopropylacetanilide.

Suitable herbicidal thiolcarbamates which were used in grain, rice or refined sorghum-millet can be made culturable together with compounds of formula I, II or III preferably correspond to the formulas

where

R _ means lower alkyl, alkenyl, chloroallyl, dichloroallyl,

trichloroallyl, benzyl or p-chlorobenzyl,

R18C2-C4-alkyl and R19C3-C4-alkyl or cyclohexyl, or where R-^g and R^g together with the N-atom form a hexahydro-1H-azepine-, a decahydroquinoline- or a 2-methyl-decahydroquinoline- -ring.

The following thiolcarbamates are mentioned as examples of such compounds: 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-d'isopropylthiolcarbamate, S-propyl-N,N-dipropylthiolcarbamate,

S-ethyl-N-ethyl-N-cyclohexylthiocarbamate,

S-ethyl-N-hexahydro-1H-azepine-1-carbothioate, S-isopropyl-N,N-hexamethylene thiolcarbamate,

S-(p-chlorobenzyl)-N,N-diethylthiocarbamate,

N-ethylthiocarbonyl-cis-decahydroquinoline,

N-propylthiocarbonyl-decahydroquinaldine,

S-ethyl-N,N-bis(n-but<y>l)-thiolcarbamate, S-tert-butyl-N,N-bis(n-propyl)-thiolcarbamate.

Further examples of applicable thiol carbamates are described in US patents 2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786 and 3,582,314.

As further preparations which can be made culturable with compounds of formula I are mentioned: α-[4-(2,4-dichlorophenoxy)-phenoxy}-propionic acid methyl ester, α-[4-(4-trifluoromethylphenoxy)-phenoxy]-propionic acid -methyl ester, α-[4-(2-chloro-4-trifluoromethylphenoxy)-phenoxy]-propionic acid methyl ester, α-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionic acid methyl ester.

The amount of antidote used varies between approx. 0.01 and approx. 15 parts by weight per weight part herbicide. You decide on a case-by-case basis, i.e. depending on the type of herbicide used, which ratio is most suitable for optimal effect with the particular cultivated plant.

As already mentioned, different methods and techniques are used for the application of the new pesticides with formulas I - III for the protection of cultivated plants against agrochemicals or for plant growth stimulation: .

1) Seed pickling

a) Pickling the seeds with an active substance that is formulated as a spray powder by shaking in a container for even distribution on the seed surface (dry pickling). Under this, approx. 10 to 500 g active ingredient with formula i (40 g to 2 kg spray powder) per 100 kg of seed. b) Pickling the seeds with an emulsion concentrate of the active substance with formula I according to method a) (wet pickling). c) Pickling by immersing the seeds in a brew with 50 - 3,200 ppm active substance with formula I- for 1 - 72 hours and

possibly subsequent drying of the seeds (dip pickling) . ■

The pickling of the sowing seeds or the treatment of the germinated seeds are of course the preferred application methods because the active substance treatment is completely directed towards the desired culture. As a rule, 10 g to 500 g, preferably 50 to 250 g AS per 100 kg of seed, whereby depending on the methodology which also enables the addition of other active substances or micronutrients, deviations can be upwards or downwards from the specified limit concentrations (repetitive pickling).

2) Application from tank mix

A liquid preparation of a mixture of antidote and herbicide (reciprocal quantity ratio between 10 .: 1 and 1 10) is used whereby the amount of herbicide used amounts to 0.1 to 10 kg per hectares. Such tank mixture is preferably applied before or immediately after sowing or incorporated 5 - 10 cm deep into the soil while it has not yet been sown.

3) Application in the seed furrow

The antidote is applied as an emulsion concentrate, spray powder or as granules in the previously sown seed furrow and then the herbicide is applied after covering the seed furrow in the normal way.

In principle, the antidote can therefore be applied before, together with or after the pesticide, and the application of this can be carried out on the seeds or on the field before or after sowing or in certain cases also after burning the seeds. In particular, the invention also relates to agents that contain

next to the antidotes with formula I at least one agrochemical active ingredient, e.g. a herbicide from the chloroacetanilide or thiol carbamate series. These agents also contain carriers and/or distribution agents.

4) Controlled active ingredient release

The active ingredient is applied in solution to a mineral granule carrier or polymerized granules (urea/formaldehyde) and allowed to dry. Optionally, a coating can be applied (enveloping granules) which allows the active substance to be released in a dosed manner over a specific period of time.

Of course, all other methods for active ingredient application can also be used. Examples of this are given below.

The method according to the invention for plant growth stimulation or for the protection of cultivated plants can be particularly applied to rice and useful millet of the genus sorghum, further on. maize, wheat, barley, harrow, soya, cotton, sugar beet. However, it is not limited to the stimulation and protection of annual plants, but is also quite suitable for the growth stimulation of perennial plants (fruit trees, ornamental shrubs and the like). where root formation and shoot formation are stimulated or an improved fruit growth or improved flowering is to be achieved.

The preparation of the compounds of formula I takes place according to procedures known per se (Organic Reactions 1953, volume 1_, pages 343 and 373, Journal f. prakt. Chemie 66 page 353, Liebigs Ann. 250, 165.) by etherification or acylation of an oxime of formula V

or its oxime salt with a halide of formula Halg-O, whereby Ar, X and O. have the meaning given for formula I and Halg stands for halogen, preferably chlorine or bromine.

The condensation of substituted α-oximino compounds during the etherification takes place preferably in the form of their salts, in particular their alkali or ammonium salts, as outlined in the following selected examples:

The acylation takes place preferably with the free acids of formula I as the following scheme shows:

(In the formula above, "Halg" stands for halogen, especially chlorine or bromine).

As a solvent for extracting the compound of formula I, in principle all representatives are suitable which behave indifferently under the reaction conditions. For example, hydrocarbons, above all, however, polar solvents such as acetonitrile, dioxane, cellosolve, DMF, but also ketones such as methyl ethyl ketone, acetone, etc. Solvents containing hydroxyl groups are excluded.

Temperatures range from -10°C to approx. 150°C, preferably between 20°C and 120°C.

As hydrohalide of splitting agents, bases such as tertiary amines (triethylamine, triethylenediamine, piperidine, etc.) can be used. In some cases, it is also sufficient to suspend soda ash in an anhydrous reaction medium.

Oximere exists in two stereoisomeric forms, syn and anti. The compounds of formula I mentioned under a) to e) can also be present in both pure forms or as mixtures. Within the framework of the present description, both stereoisomeric forms are therefore to be considered individually or as mixtures in any mutual mixing ratio.

The following examples illustrate the preparation of new oximes of formula I:

EXAMPLE 1

In a 350 ml sulphide flask, 17 g (-0.1 mol) of phenylglyoxylonitrile-2-oxime sodium salt was suspended in 170 ml of acetonitrile. Then 23.8 g (0.1 mol) of chloroaceto-3,4-dichloroanilide were added, during which a slight heat tint could be observed. The suspension was stirred for 3 hours at reflux, whereby the suspension also took on a different appearance. After cooling to room temperature, the coke salt formed was filtered off, washed with acetonitrile and the filtrate evaporated under vacuum. 32.3 g of crude product was obtained as a residue. By alcohol/water recrystallization, 20.4 g of the final product with formula

Melting point: 143-144°C.

Similarly, from the salt of 2,4-dimethylphenylhydroxamic acid and allyl chloride as an oily substance, the product was obtained with

flour

In a similar way, the compound is obtained from 2-thienylacetonitrile oxime sodium salt and chloroacetonitrile

as an oily substance.

EXAMPLE 2

33.6 g (0.2 mol) of phenylglyoxylonitrile oxime sodium salt and 25 g (0.22 mol) of chloroacetic acid methyl ester were kept in 200 ml of acetonitrile for 3 hours at 60-70°C with good stirring, whereby the suspension

was greatly refined. After a further few hours, it was filtered off, washed with acetonitrile and evaporated in vacuo, during which an oily residue remained which solidified after approx.

24 hours.

Temp. 68-70°C. Recrystallized from isopropanol: m.p. 71-72°C

In a similar way, by condensation of 4-chlorophenylglyoxylonitrile-oxime-sodium salt with α-chloropropionic acid ethyl ester, the compound is obtained, with the formula -

in 99.3% yield as oil.

Using the chloroacetic acid isopropyl ester instead of the a-chloropropionic acid ester yields the compound with the formula

and using the unsubstituted phenylglyoxylonitrile oxime (as Na salt) the compound of formula EXAMPLE 3

g- cyanobenzylidene- amino- oxacetamide

845 g (5 mol) of the Na salt of benz-acetonitrile oxime are suspended in 2.5 liters of acetonitrile and in the presence of catalytic amounts of KJ, 468 g (5 mol) of chloroacetamide are slowly added while stirring. It is heated for 12 hours under reflux, cooled and the reaction mixture is allowed to flow in for approx. 12 liters of water. While the salts present dissolve, the final product precipitates out crystalline; 882 g (=86.8% of the theoretical), m.p. 128-129°C (from ethanol).

Similarly, from 3-furanylnitromethane oxime sodium salt and methanesulfonyl chloride, the compound with the formula is obtained

as viscous oil.

EXAMPLE 4

8.0 g (0.037 mol) of α-oximino-1-naphthylacetonitrile sodium and 5.5 g (0.04 5 ) of propargyl bromide were heated for 4 hours in 50 ml of acetonitrile to approx. 80° C. The suspension was then concentrated in vacuo and the residue extracted with methylene chloride. The solution was evaporated, leaving the compound of formula

returned as oil.

Analysis for ci5Hio<N>2°

Calculated: C, 76.9% H 4.3% N.11.96%

Found: C, 76.4% H 4.4% N'11.8%

If chloroacetonitrile is used as a reaction partner instead of propargyl bromide, the compound with formula is obtained

EXAMPLE 5

0.1 mol of α-oximino-2-thienylacetonitrile sodium salt is suspended with 0.12 mol of chloroacetamide in 150 ml of acetonitrile. It is then heated for 3 hours to 50-60°C, during which NaCl separates, which is filtered off and washed out with acetonitrile. The filtrates are concentrated in vacuo. It will return the connection with formula

as pale yellow, oily substance.

In the following tables, the temperatures are indicated in degrees Celsius.

The following compounds can be prepared according to the above methods:

Analogously, the following compounds are also obtained with the formula

Analogously, the following compounds are also obtained with the formula

Similarly important products are those derived from naphthylglyoxylonitrile and analogous derivatives; for example those with the formula

In an analogous manner, the following groups of heterocyclic oxime derivatives were also recovered.

A further important individual group with plant growth influencing and plant protective effects is that of the following diphenyl ether derivatives with the formula:

A compound group which, at high consumption amounts of 6 kg/ha and more, can store the plant growth-influencing effect in the direction of a herbicidal effect, but which at lower consumption amounts of 1 kg/ha (and below) is still completely culturally tolerant, without losing its plant growth regulating and plant growth protective properties, are those of the following substituted diphenyl ether derivatives with formula I: The compounds of formula I can be used alone or together with the active substances to be antagonized as well as together with suitable carriers and/or other additives. Suitable carriers and additives can be solid or liquid and correspond to the usual substances in the formulation technique such as. for example, natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders and fertilizers.

The content of active substance in products that can be marketed is between 0.01 and 90%.

For use, the compounds of formula I can be present in the following processing forms (whereas the weight percentages in brackets are advantageous amounts of active substance).

Fixed processing forms: Powder and liquid (up to

10%); granules, encapsulated granules,

impregnation granules and homogeneous granules, pellets (grains) (1 to 80%);

Liquid processing forms:

a) water-dispersible active substance concentrates:

Spray powders (wettable powders) and

pastes (25-90% in commercial packaging, 0.01 to 15% in ready-to-use solution).; emulsion and solution concentrates (10 to 50%; 0.01 to 15% in ready-to-use solution);b) Solutions (0-, 1' to 20%); e.g. for' pickling, aerosols.

The active substances with formula I according to the present invention can e.g. is formulated as follows: Powder: For the production of a) 5% and b) 2%

powder, the following substances are used:

a) 5 parts active substance

95 parts talc

b) 2 parts active substance

1 part highly dispersed silicic acid

97 parts talc;

The active substances are mixed and ground with the carrier substances and can be atomized in this form of application.

Granulate: For the production of a 5% granulate, the following substances are used:

5 parts active substance

0.25 parts apichlorohydrin

0.25 parts cetyl polyglycol ether,

3.50 parts polyethylene glycol

91 parts kaolin (grain size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts acetone, and then polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed onto kaolin and the acetone is then evaporated in a vacuum. Such microgranules can be advantageously incorporated into seed furrows.

Spray powder: For the production of a) 70%, b) 40% c) and d) 25%, e) 10% spray powder, the following ingredients are used:

a) 70 parts • active substance

5 parts sodium dibutyl naphthyl sulfonate

3 parts naphthalene sulfonic acids-phenol sulfonic acids-formaldehyde condensate 3:2:1,

10 parts kaolin

12 parts Champagne chalk;

b) 40 parts active substance

5 parts lignin sulfonic acid sodium salt

1 part dibutyl naphthalene sulfonic acid sodium salt

54 parts silicic acid;

c) 25 parts active substance 4.5 parts calcium lignin sulphonate

1.9 parts champagne chalk/hydroxyethyl cellulose mixture (1:1),

1.5 parts sodium dibutyl naphthalene sulfonate

19.5 parts silicic acid

19.5 parts champagne chalk

2 8.1 parts kaolin;

d) .25 parts active substance 2.5 parts 'isooctylphenoxy-polyoxyethylene-ethanol

1.7 parts champagne chalk/hydroxyethyl cellulose mixture (1:1)

8.3 parts sodium aluminum silicate

16.5 parts diatomaceous earth

46 parts kaolin

e) 10 parts of active substance

3 parts mixture of sodium salts of saturated fatty alcohol sulphates 5 parts naphthalene sulphonic acid/formaldehyde condensate

82 parts kaolin.

The active substances are carefully mixed in suitable mixers with additional substances and ground on corresponding mills and rollers, resulting in a spray powder of excellent wettability and suspension, which can be diluted with water to form suspensions of the desired concentration and can be used especially for foliar application, for seed stains or for dipping cuttings.

Emulsifiable concentrates: For the production of a 25% emulsifiable concentrate, the following substances are used:

25 parts active substance

2.5 parts epoxidized vegetable oil

10 parts of an alkylaryl sulfonate/fatty alcohol-polyglycol ether mixture

.5 parts dimethylformamide

57.5 parts xylene.

From such concentrates, by diluting with water, emulsions of any desired concentration can be obtained, which are particularly suitable for seed stains.

Biological examples

To determine the selective herbicidal effect of a highly active herbicidal top product from the chloracetanilide series alone and together with the antidotes with formula I according to the invention, the following experiments were carried out: N-[3<1->methoxy was used as the herbicidal active ingredient -propyl-(2<1>)]-2-methyl-6-ethyl-chloroacetanilide (substance H) (DOS 2 328 340).

1) Preparatory investigations of tank mixture

a) After sowing

Of the herbicide (substance H) and of an antidote with formula I (substance S) according to the invention, aqueous suspensions were prepared from formulated spray powders and these were used individually or as mixtures in amounts from 1 kg to 8 kg/ha and mixing ratio H: S = 4:1 to 1:4 after sowing different types of Sorghum hybridum (varieties "Funk", "Dekalb",

"NK 222 " and "DC 59") in pots or seed trays in greenhouses on the soil surface of the sown containers. The containers were then kept under normal watering at 22-23°C. The results are observed after 15 days and are divided according to the following linear scale: 9 = undamaged plants (as untreated control plants)

1 = total killed plants

2 to 8 = intermediate level of damage.

b) Before sowing (PPI)

In the same way as under a), the soil in the pots and seed trays is treated with the brews containing the active ingredient and is only sown immediately after this with seeds of millet "Funk".

While the compound H, used alone, damages or destroys cultivated millets in the quantities used, this effect is canceled by the presence of an antidote of formula I either completely or to a large extent. In particular, this is achieved with compounds no. 1.1, 1.4, 1.14, 1.20, 1.34.

2) Seed pickling (wet)

Aqueous emulsion concentrates of an antidote of formula I are prepared and shaken in a bottle with 50 cultured millet seeds. The different concentrations of antidote are between 20 and 150

g antidote per 100 kg of seeds. Shortly after pickling, the seeds are sown,

in seed trays and treated in the usual way with a spray brew of the herbicide H as indicated under 1 a). The assessment of the results took place 15 days after application of the herbicide according to the same division.

The results also showed that at a low, but sufficient herbicide concentration for weed control, a sparing of cultivated millet is achieved with antidote S. The compounds no. 1.1, 1.4, 1.14, 1.20, 1.34, 1.4.4, 1.70 to 1.75, 1.78, 1.82, 1.88, 1.91, <:>1.98, 1.103, 1.108, 1.110, 1.126, 1.1139, 1.174, 1.177, 1.188, 1.191, 1.199, 1.204, 1.207 to 1.209, 1.217, 1.218, 1.227, 1.230, 1.239, 1.240, 1.253, 1.255, 1.267, 1.275 to 1.274, and others Compounds from US patent no.

3,799,757 did not act as antidotes.

The antagonistic effect of an antidote with formula I does not, as a rule, extend to main weeds such as Echinochloa, Setaria italica etc., which are damaged to approximately the same extent as without an antidote.

Similar good antidote effects are also achieved with other chloroacetanilides and with thiol carbamates and also on other crops such as rice, maize, wheat, cotton, soya or sugar cane.

Yield increase in soy

In a field of soya plants of the variety "Lee 68", 50 m 2 plots were sprayed with aqueous preparations of an active substance of formula I when the plants were in the 5-6-leaf stage. The amount of active ingredient used was 500 g/ha. At the time of harvest, it was determined that untreated plants were largely broken, while in the treated plots all plants stood straight up and showed improved pod weight. The treated plots showed 10 to 15%. higher yield than the control plots. Significant yield increases of 12%' or more were obtained on plots treated with compounds No. 1.1,

1.3, 1.4, 1.67 or other others.

' Géiztrieb"- inhibition in tobacco

Tobacco plants were grown in greenhouses and the flowers were cut

off at the beginning of flowering. A day later, they were sprayed with aqueous spray mixtures of active substances no. 1,106 and 1,148. The active ingredient concentration was 0.66 per cent. 1.32% active substance.

While the untreated plants developed vigorous "Geiztrieb" from the leaf axil buds, "Geiztrieb" growth remained severely inhibited in the treated tobacco plants. - Similar effects were shown by other compounds of formula I with a propargyl ether structure.

Biological experiments under stress conditions

A) Plant growth under suboptimal temperature

Rice plants in the 2- to 3-leaf stage are dipped for 45 minutes with the roots and the lower part of the stem in a solution containing 10 ppm (= 0.001%) of an active substance of formula I. They are then propagated in completely wet soil for 70 x 70 cm asbestos cement containers and are kept at a temperature of only 18-22°C instead of 28-30°C. The soil in the containers is covered after 3 days with 2-3 cm of water. After a further 18 days, the treated plants are compared with untreated control plants.

The rice that has been treated with the compounds of the formula I acc. Ia had an average 30 to 50% enlarged root system. The compounds from US Patent No. 3,799,757 showed no such effect.

B) Plant development with slightly damaged seeds

Rice seeds that were pre-germinated in a quartz sand nutrient solution are dipped with the formed slightly yellowish stems for 45 minutes in a solution with 10 ppm of an active substance of formula I, after which 42 plants are propagated as described under A in an asbestos cement container and kept until harvest at a normal temperature of 28-30°C under normal watering.

The final assessment referred to the dry weight of the above-ground plant parts, the number of panicles and the dry grain weight compared to 42 similarly germinated but untreated control plants. From several series of experiments, the following average values were obtained.

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, 2.277, 1.278,

2.1, 3.1 excelled in this trial series with particularly high growth. The compounds from US Patent 3,799,757 produced no such effects. The seeds from other cultivated plants such as e.g. corn,

grain, soya, cotton can be pre-treated in the same way and lead to similar yield increases.

Claims (35)

1. A compound with the formula characterized in that the substituents have the following meaning: ' .r = - a phenyl residue of the formula - an α- or 3-naphthyIrest, - a heterocyclic ring of the formula X = - a cyano, nitro, halogen, lower alkanoyl, a carboxy- acid ester residue, hydrogen, a carboxylic acid amide residue or lower alkyl/ Q = - lower alkyl, which is straight or branched or may be interrupted with heteroatoms or substituted with halogen, - lower alkenyl or haloalkenyl, - lower alkynyl, - optionally with halogen-substituted C^-C^-cycloalkyl, lower cyanoalkyl, - lower alkanecarboxylic acid ester group, - lower alkanecarboxylic acid amide group, - aliphatic acyl residue, - araliphatic, cycloaliphatic or optionally substituted aromatic acc. heterocyclic acyl residue, - alkylsulfonic acid or - a sulphonic acid amide residue, R-^ - hydrogen, halogen, lower alkyl, lower alkoxy or an optional maximum twice with halogen, -CN, N02 , CF^ substituted para standing phenoxy residue, R 2 and R 2 -independently of each other mean hydrogen, halogen, NO 2 , lower alkyl, haloalkyl1, lower alkoxy, R 4 and R^ -independently of each other hydrogen, halogen, NO2 are lower alkyl and Z - oxygen or sulfur, under the condition that if Ar means an unsubstituted phenyl residue and Q the residue -CH2CN, X stands for NC>2, halogen, lower alkanoyl, a carboxylic acid ester residue, hydrogen, a carboxylic acid amide residue or lower alkyl. 2. Compounds according to claim 1, characterized in that Ar has the specified meaning and the other substituents have the following meanings: X = - cyano, nitro, halogen, lower alkanoyl, a carboxylic acid ester residue of a lower aliphatic alcohol, a carboxylic acid amide residue or lower alkyl, Q = - lower alkyl, which is straight or branched or may be interrupted by a heteroatom or substituted . with halogen, - lower alkenyl, - lower alkynyl, - lower cyanoalkyl/ - lower alkanecarboxylic acid ester group/ - lower alkanecarboxylic acid amide group, - lower aliphatic acyl residue, - cycloaliphatic acyl radical with 4 to 6 C atoms, or - an unsubstituted or with a lower aliphatic residue one or twice substituted sulphonic acid amide residue, = hydrogen or a para-standing phenoxy radical, R2 and R^ - independently of each other hydrogen, halogen or lower alkyl, R4 and R1- - hydrogen, Z = - oxygen or sulfur. 3. Compounds according to claim 1 with the formula Ia characterized in that the substituents have the following meaning: X = - cyano, nitro, halogen, lower alkanoyl, a car boronic acid ester residue of one lower aliphatic alcohol, a carboxylic acid amide residue or lower alkyl, Q = - lower straight-chain alkyl chain that is interrupted with oxygen^ - lower alkenyl, - lower alkynyl, - lower cyanoalkyl, - lower alkanecarboxylic acid ester group, - lower alkanecarboxylic acid amide group, - lower aliphatic acyl residue, - unsubstituted or, in the case of a lower aliphatic residue, one or two times substituted sulfonic acid amide residue,, R^ = - hydrogen, R2 = - hydrogen, halogen, lower alkyl or lower Alkoxy, R3 = - hydrogen, halogen, lower alkyl or lower Alkoxy. 4. Compounds according to claim 3, characterized in that the substituents with the formula Ia have the following meaning: X = cyano, nitro, halogen, lower alkanoyl, a carbon acid ester residue of a lower alkanol, a carboxylic acid amide residue Q = - lower alkynyl/ - lower cyanalkyL. - lower alkane carboxylic acid ester group, - lower alkanecarbonic acid amide group/ R-^ = - hydrogen, 'R2 = - hydrogen, halogen or lower alkyl, <1> R3 = - hydrogen, halogen or lower alkyl. 5. Compounds according to claim 4, characterized in that the substituents in formula Ia have the following meaning: X = - cyano, chlorine, bromine, acetyl, propionyl, -COOCH^ , -COOC2 H5 , -CO-NH2 , -CO-NHCH3 , -CO-N(CH3 )2 , Q = - propynyl or butynyl, - cyanomethyl or cyanoethyl, - methoxycarbonylmethyl, ethoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylethyl, - an optionally substituted acetamide or propionamide residue with one or two lower aliphatic groups on the N atom, R-^ = - hydrogen, R 2 = - hydrogen, halogen or methyl R3 = hydrogen, halogen or methyl 6. Compounds according to claim 5, characterized in that X means a cyano group and Q , R 1 , R 2 and R 3 have the indicated meaning. 7- Compounds according to claim 1 with formula II characterized in that R^ , R 2 and R^ independently of each other mean hydrogen, halogen, N02 , lower alkyl, haloalkyl, lower alkoxy, and X - -CN, N02 , halogen, the acetyl group, a carboxylic acid residue of a lower aliphatic alcohol or a carboxylic acid amide residue, and n is 1, 2 or 3, Rg is hydrogen or lower alkyl, R10 means -CONH2, -CO-NH-(lower aliphatic residue), -CO-NH-cycloalkyl, -CONH-(CgH5_m) (halogen, lower alkyl^ or -CN, and m is an integer 0, 1, 2 or 3. 8. Compounds according to claim 7 with the formula III characterized' by that X <1> means -CN, NO2, chlorine, acetyl, lower alkoxycar- bonyl, allyloxycarbonyl, carbamoyl or di-lower alkylcarbamoyl, and R10 means -CN, -C0-NH2, -CO-NH-lower alkyl or -CO-NH (CgH5_m) (Cl, Br, CH^ and m is an integer 0, 1 or 2. 9. α-cyanobenzylidene-amino-oxacetamide characterized by the formula 10. Process for the preparation of compounds with the formula I in claim 1, characterized in that an oxime with the formula V or the oxime salt thereof is etherified or acylated with a halide of the formula Halg-Q, where Ar, X and Q have the meanings given for formula I, and Halg stands for halogen, preferably chlorine or bromine. 11. Process according to claim 10 for the preparation of compounds according to one of claims 4 to 9, characterized in that an alkali or ammonium salt of formula V is etherified with a halide Halg-Q, where Ar, X and Q correspond to one of those in one of .claims 4 to 9 given definitions, and Halg stands for halogen, preferably chlorine or bromine. 12. Plant growth stimulating and plant protecting agent, characterized in that it contains as active substance 0.01-90% by weight of a compound of formula I according to claim 1, together with suitable carriers and/or surface-active additives. 13. Agent according to claim 12, characterized in that the active substance corresponds to a compound according to claim 2. 14. Agent according to claim 12, characterized in that the active substance corresponds to a compound according to claim 3. 15. Agent according to claim 12, characterized in that the active substance corresponds to a compound according to claim 4. 16. Means according to claim 12. characterized in that the active substance corresponds to a compound according to claim 5. 17. Agent according to claim 12, characterized in that the active substance corresponds to a compound according to claim 6. 18. Agent according to claim 12, characterized in that the active substance corresponds to a compound according to claim 7. 19. Means according to claim 12, characterized in that the active substance corresponds to a compound according to requirement 8. 20. Agent according to claim 12, characterized in that the active substance corresponds to a compound according to claim 9. 21. Method for plant growth stimulation, characterized in that the plants or parts thereof or the growth base thereof are treated with a compound of formula I according to one of claims 1 to 9. 22. Method according to claim 21, characterized in that the plant seeds or the germinated seeds are treated. 23. Method according to claim 22, characterized in that Sorghum millet is treated. 24. Method according to claim 22, characterized in that rice is processed. 25. Method according to claim 22, characterized in that corn is treated. 26. Method according to claim 22, characterized in that wheat, rye, barley or oats are treated. 27. Method according to claim 22, characterized in that soy is treated. 28. Method according to claim -22, characterized in that cotton is treated. 29. Method according to claim 22, characterized in that sugar beet is treated. 30. Method for the protection of cultivated plants against the unwanted effects of agricultural chemicals, characterized by the application of a compound according to one of claims 1 to 9 on the plants, on plant parts or the growth base in any desired order before, simultaneously or after the application of the agricultural chemical. . 31. Method according to claim 30, characterized in that the agricultural chemical is a herbicide. 32. Method according to claim 31, characterized in that the herbicide is an active substance from the series of chloroacetanilides. 33. Method according to claim 31, characterized in that N-[3'-methoxypropyl-(2 <1> )]-N-chloroacetyl-2-methyl-6-ethylaniline is used as herbicide. 34. Method according to claim 31, characterized in that the herbicide is an active substance from the class of thiol carbamates. 35. Method according to claim 31, characterized in that the herbicide is an active substance from the class of substituted phenoxyphenoxy-acetic acid esters and -propionic acid esters or the substituted pyridineoxyphenoxy-acetic acid esters and -propionic acid esters.