CS223867B2 - Means for the growth stimulation of plants and means for protection of plants and method of making the active substances - Google Patents

Abstract

Novel compositions which are suitable in agriculture for crop protection contain, together with suitable carrier material, at least one active ingredient from the series comprising oxime ethers, oxime esters or oxime carbamates, the active substance having the formula I <IMAGE> in which the substituents are as defined in Claim 1. The compositions can be used advantageously for crop protection. Such compositions have antidote properties for protecting plants against aggressive agrochemicals and, besides, have other plant-regulating and pesticidal properties.

Description

CIBA-GEIGY AG ^, BASIL switzerland] (54) Plant growth promoter and plant protection product and process for the manufacture of active substances

Present in ^Y finding relates ^p grate presents ^of e ^d ing to promote plant growth and protect plants containing the novel oxime ethers and oxime esters as active methacrylate ^to y, j and ^k of ^{Iz Pooh} with ^b in productions ^b y these new computer ^{H EFFECTIVE} nnýc ^{h methacrylate} e ^k .

New oximethers and oximesethers corresponding to the general formula I have been found

Ar - C - X

II

Y N — O — Q (I) wherein

Ar represents a phenyl group of the formula

«-Ňaftytovou slku ^pi nu ^b not on ^the heterocyclic group of formula ou

X is cyano, nitro, halogen, alkylcarbonyl having 1 to 4 carbon atom ^Y u ^hlík UV alk ^y Love "times, and ^o ox ^y carbonyl group having 1-4 carbon atoms in the alkoxy part, hydrogen, aminocarbonyl optionally mono- - or disubstituted by (C1-C4) alkyl, or by (C1-C4) alkyl,

Q represents a (C1-C4) alkyl group, a (C1-C4) alkyl group interrupted by 1 or 2 oxygen atoms or sulfur atoms; furthermore is C1-C4alkyl substituted with cyano; a (C 1 -C 4) alkyl group which is substituted with a carboxylic acid ester moiety, the ester moiety being selected from the group consisting of C 1 -C 4 alkyl, benzyl, or mononitrobenzyl; furthermore represents a C1-C4 alkyl group which is substituted by a carboxamido group, wherein the carboxamido group is optionally mono- or disubstituted by a C1-C4 alkyl group or a C1-C4 alkenyl group or is optionally monosubstituted (C 2 -C 4) alkynyl, phenyl or mono- or dihalophenyl; furthermore represents ^alkene-yl verifies SKU yne · ^p is ² and ^{Z 4} represents ^Y uhlíkp alkinyiovou group having 2-4 carbon atoms; alkylcarbonyl having 1 to 4 carbon atom of the ^alkyl hunting ai ^s st ^{and Ca; b} enzo ^yl verifies group which is optionally substituted with 1 to 3 substituents · selected from the group consisting of halogen, nitro, alkyl skupmou ^{1 and 4} of ^Y uMíkp alkoxystopinou having ¹ to ⁴ carbon atoms and halogenoalkyl having 1 to 4 carbon atoms; a benzylcarbonyl group which is substituted with a halogen atom; ^b styrylkar verifies ^l · Gr ^{i nu; f} uro ^y ló · group; alk ^{y y} sulfone alkoxycarbonyl having 1-4 · · carbon atoms; aminosulphonyl ^f he verifies ^yl SKU ^p m e ^{j u} that ^after pnpa ^ga mono- or ^di · su ^b The substituted alkyl group having 1 to 4 carbon atoms;

R 1 represents hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, nitro or para-phenoxy optionally substituted with 1 to 2 substituents selected from from the group consisting of halogen and haloalkyl of 1 to 4 carbon atoms;

R 11 is hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy;

R a is hydrogen, halogen or nitro;

R 5 represents hydrogen or halogen and

Z represents an oxygen atom or a sulfur atom, S ^{^, Z} e ^when Ar represents an unsubstituted ^phenyl verifies hundred ^{l p} mu and Q is -CH 2 CN Stopnete ^p and ^the symbol X is a nitro group, a halogen, an alkylcarbonyl group having from ^{1 and 4} carbon ulihku · va ^{plurality of projections} moieties of ^ · and ^LK oxycarbonyl group having 1 to 4 carbon atoms va ^o oxides by ^Star cmstg as ^thanks, aminotorbonylovou group which is optionally monosubstituted or disubstituted by alkyl having 1-4 carbon atoms, or represents alkyl having 1 to 4 carbon atoms.

According to the method of substitution of these derivatives, the oxime of the formula I a to ^d in ^KTY sr ^s to different ^even in the ^L and ^T nose ^t m ⁱ · Poku ^d j ^d eo biological activity to plants which may be used as plant growth regulators or ^which just Jato proájety ^p ESTICA ^Ids generally in agriculture or in special areas of crop protection.

In formula I, halogen is fluorine, chlorine, bromine or iodine.

^In ýrazem "alk ^y T 'itself · Neto Jato any part of a substituent refers to a branched or nerozv ^of branching and a ^{plurality of projections} hunting SKU ^{p s} in ^y with 1 to 4 carbon atoms. Jato examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, ^s sek.tarc.but radical.

^p redmi ^{ive out of five} em ^{Pla d} en ^Star LO ^from it in the ^Y n and ^l is the cut means to promote plant growth and plant protection agents, which comprises, as an active ingredient comprises from 0.01 to 90 weight percent of at least one compound ^No. enyne ^The general formula ( ^I) together with the carrier (s) and / or surfactant.

The oximethers and oximesethers of the formula I have been found to have particularly advantageous growth promoting properties in practice, without causing disadvantageous consequences for the vegetable soils ^{which have been found to be} present in the crop ¹ . · in which ^the YC ^{h can be} in the ch ^ka · particular the ability to stimulate the germination of seeds · · ·. as well as developing young plants. This leads, at certain doses, to an apparently enlarged root system, to an increase in photosynthesis and to a faster development of above-ground parts. · O ^C ine ^the oxime ^of formula ¹ but is not limited to the early stage of plant development, but can also be observed during the subsequent application or in the partial application to certain parts of the plant (seed dressing, before swelling of the seed, root treatment, Shoot treatment, application on plant leaves). This technique results in faster growth ošetfene rosthn-ene glued ^to deploy pktap r ^y s ^l EJ zrárá ^width and determine c ^{y s hl} en stozně and increased or otherwise improved harvest. The active compounds can in principle be carried out on the plant, to parts of plants, the seed or to ^UD p y ^p rov ^{ADI p} o ^d le obv ^YKL YC ^hp Ostu ^P U pn aphtorn Neto sea. Gave ^{very d} ůležitou Preferably the improved ability of the treated grew tontorovat: evel ftórá ^ ^ ^kt ERA ^was no growth and stimulated. In takovýc ^ht op ^d pa ^{of manufacture} ec ^h must VSA ^{to I} and ^{P to} U ^or litoce nn ^{e la} t ^ky formula ^{1 p} t Eq ^Ade the ^seeds, the

no. 113890], as well as 2 ^ J ^ ⁱ ^ _(ainbic / | ko [2,2,1he ^p tan ^(f rancouz ^to ý patent SPK town

256,722). Experiments show that their effect is very inadequate.

In U.S. Pat. No. 3,799,757 proposed arylglyoxylnitriloximes of the general formula of the seedlings of the desired crop plant and not on the sown area. A third important advantage is at the ^{DU dk} u ^ sie tetataě zvřeného ^to him ořenov ^Star system treated plants possibility that such plants have even less favorable environmental conditions for the satisfactory development and to sufficient yield of crops. Examples of such environmental disturbing factors are: nutrient-deficient soils, drought, low temperatures during the development of a young plant, short-term frost, reduced sunlight due to unfavorable time of year or unfavorable location.

However, the oxime ethers and oximesters of the formula (I) have to a large extent plant control properties, depending on the period of application and the plant species.

The various other possibilities of applying oximes of formula I are given below without representing any limitation:

use to improve leaf formation in cultures such as tobacco, cabbage or lettuce and to prevent unwanted shoots;

use for increasing the harvest yields in cultures histenin (e.g. ad ^kl of peas ^f azoh, soybeans and rape potoemmce) ^{p dp} of weakened resistance generative growth (improved rooting);

use to increase the resistance of crops to lodging, such as cereals (preventing the crushing of plants under adverse weather conditions such as storms and permanent rain);

use to facilitate the harvesting of fruits by promoting the formation of dividing tissue between the fruit and part of the shoots of plants;

use in enhancing the ability of the in ^puts m & obrnch ^acrylate in plants through e ^{to e} (Cutò proteins, oils etc.) or to temporarily maintain storage substances already acquired.

The ability to store stockpiles in plants also includes the ability to maintain stocks once they have been purchased longer than under natural conditions. Thus, for example, the shelf life of the potatoes can be increased. Further, it is possible to maintain the sugar content of the sugar cane shortly before harvest by applying certain oximeters of formula ¹ to ^a constant value, thereby counteracting the plant's attempts to produce additional side shoots and thus to prevent loss of sugar content.

Means for influencing the growth of plants, especially^witht^E к^pot^land^Cov^andn^and rMhi^by^ly j^iž difer^{ě p}O^psled^y.^Tand^to is in^hO^dný zejm^Ena c^hlorc^h° Linear chloride to discourage staa^toe wrong^pšMeasurement of stalk stability in wheat. According to DOS No. 2,458,165 bis- (p-chlorophenyl) acetic acid or its salts, esters, amides or nitrile thereof has a similar ability to shorten the stalk in cereals. In DOS 2,407,148 2,6-disubstituted phenoxyacetate esters are recommended^yselrn^ypO^eventand^dě -^pro^Frionové^kyselmy^jako re^Gulátor^y r^atstu rosthn. Effect^to However, this is not always the case, especially at lower application rates and concentrations^postačující. It behaves similarly^p-chlorophenyl · dimethylacetic acid^toyselin^y (GDR Pat

in which

X is a ^ of chloro, ^{b b} a ROM not nitros at ^{the p-well, the} owner ^and I ^p of the grate ^before the poDačujím ^alkyl, growth, and I ^to the re ^g u ^la tor ^y Imst rosthn insufficient effect. Moreover, these substances are not stable and decompose in a short time.

Surprisingly, oximes of formula I have another very important property. These substances are excellent for protecting crop plants such as millet, rice, maize, various other cereals (wheat, rye, barley, oats), sugar beet, sugar cane, soybean etc. from agrochemicals, are agresivi backlash ^or ros ^{tl INAM} zejnmna herbimdy various groups of substances, such as triazines, phenylurea derivatives, carbamates, thiocarbamates, haloacetanilides halogenfenoxyoctové esters acids, esters of substituted acids and esters fenoxyfenoxyoctové substituted phenoxyphenoxypropionic acid esters substituted pyridino.xyfenoxyoctové acid - propionic acid, benzoic acid derivatives etc., where these substances are selective or insufficiently selective in that ^dl e combated ^pl eve ^profiles more or less harmful to the crop plants as well.

The invention also relates to compositions comprising these oxime ethers of the formula I together with biologically active additives such as herbicides, fungicides or insecticides.

The above problem ^yls b j ^Iz navrMny various ЫШу, ^kt ns are capable of specifically antagonizing the harmful effect of the herbicide on the cultivated plant, i.e. to protect the cultivated plant without noticeably affecting the herbicidal while the effect on weed control. It is possible to use such a composition to counteract the harmful vHvům ^h er ^bi c ^Ids (antidote) Dist ^yp of ^dl e properties for the purpose of pre-treating seed of the crop plant (dressing the seed or the seedlings) or before sowing the soil for sowing, or as a mixture prepared immediately before use, alone or together with the herbicide before or after emergence of the plants. The antidote treatment may be performed before, after, or concurrently with the herbicide treatment. Pre-emergence treatment includes both pre-sowing (ppi = 'pre plant incorporatton') treatment and sown but not yet grown areas.

Thus it is disclosed in British Pat. No. 1,277,557 the treatment of seeds or shoots of wheat and sorghum with certain oxamic acid esters and amides of oxamic acid from attack by N-methoxymethyl-2 ^', 6 ⁱ - ^{d Thy} lchloracetanilidem IE [Maclilor]. In other places in the literature (DOS No. 1 952 910, DOS 2 245 471, French Patent No. 2 021 611), antidotes are proposed for the treatment of cereals, corn seeds and rice to protect against herbicide attack. with active thiolcarbamates. German Patent 1,576,676 and U.S. Patent 3,131,509 suggest hydroxyaminoacetanilides and hydantoins to protect cereal seeds against carbamates such as IPC, CIPC, and the like.

In the literature, no group of substances has been described which, on the one hand, exert a strong stimulus on the growth of plants and, on the other hand, have the ability to protect plants from aggressive agrochemicals in terms of antidote effect.

Of particular note are those compounds of formula I wherein Ar and Z are as defined above and the other substituents are as follows:

X is cyano, nitro, halogen, alkylcarbonyl with 1 to 4 carbon alkyl, alkoxycarbonyl having 1 to 4 carbon atoms in alkoxytévé amino ^for R ^b online ^yl verifies skuprnu which is optionally monosubstituted or disubstituted by alkyl having 1 to 4 carbon atoms, or represents an alkyl group having 1 to 4 carbon atoms;

Q is C 1 -C 4 alkyl; (C 1 -C 4) alkyl group interrupted by 1 or 2 oxygen or sulfur atoms; (C 1 -C 4) alkyl substituted with cyano; a (C 1 -C 4) alkyl group which is substituted with a carboxylic acid ester moiety, the ester moiety selected from the group consisting of C 1 -C 4 alkyl, benzyl, or mononitrobenzyl; alkyl having 1 to 4 carbon atoms which is substituted by a carboxamido, which is optionally monosubstituted or disubstituted by alkyl having 1 to 4 atoms in ^hlík with no ^b a / aa ^o en ^yl verifies a ^to u ^p another 2 to 4 carbon atoms or is optionally monosubstituted with (C 2 -C 4) alkynyl, phenyl or mono- or dihalophenyl; (C 2 -C 4) alkenyl; (C 2 -C 4) alkynyl; ^o and y ^{o p} arbonylovou SKU yne with C1 -C4 alkyl Uhl ^Cart uv or aminosulfone verifies ^yl group which is optionally mono- or disubstituted by alkyl having 1-4 carbon atoms;

Ri is hydrogen, halogen, alkyl with u ^{p to 1} yne ^{and 4} utofau atoms or p-position bonded phenoxy;

R 2 is hydrogen, halogen or C 1 -C 4 alkyl;

R 1 is hydrogen and

R 5 is hydrogen.

Of these, compounds of formula Ia are preferred

(in which

X is cyano, nitro, haloalkane^yl^toarbonyl group with 1 to⁴ atom^y at^hl^íku v al^keelu, a^lkoxy^toarbonyto vou s^toat^pinu s 1 a⁴ carboxylic acid alkoxy, an aminocarbonyl group which is optionally mono- or disubstituted with (C 1 -C 4) alkyl; alkyl group^pinu s 1 a⁴ utofau atoms;

Q represents a C 1 -C 4 alkyl group^y at^hlíkat,^toter^and it is submerged^kyand noskupinou; C 1 -C 4 alkyl substituted with an ester moiety^toarbox^ytov^E tyselm ^ whereby^bythe ester is a radical selected from the group consisting of C 1 -C 4 alkyl, benzyl or mononitrobenzyl; (C 1 -C 4) -alkyl which is substituted with carboxamido R 3^toter^and Yippee^pO^eventand^dě mono- or tosubstituted by C 1 -C 4 alkyl and / or C 2 -C 4 alkenyl or optionally monosubstituted by C 2 -C 4 alkynyl, phenyl or mono- or dihalophenyl; (C 2 -C 4) alkenyl; (C 2 -C 4) alkynyl; (C 1 -C 4) alkylcarbonyl or aminosulfonyl, optionally mono- or disubstituted with (C 1 -C 4) alkyl,

R 1 is hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy; and

R 2 is hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy.

Particularly preferred from the following groups are those compounds in which the substituents in Formula Ia have the following meanings:

X is cyano, nitro, halogen, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl or aminocarbonyl optionally mono- or disubstituted with C 1 -C 4 alkyl carbon atoms;

Q is C1-C4alkyl substituted with cyano; a (C 1 -C 4) -alkyl group substituted with a carboxylic acid ester moiety, the ester moiety selected from the group consisting of C 1 -C 4 alkyl, benzyl, or mononitrobenzyl; alkyl having 1 to 4 carbon atoms which is substituted by a carboxamido, which is optionally mono- or disubstituted with an alkyl skupmou ^{1 and 4 h} at a hydrogen ^Y 'Zu / or azenyl group with 2-4 carbon atoms or optionally mono (C 2 -C 4) alkynyl, phenyl or mono- or dihalophenyl; or is (C 2 -C 4) alkynyl;

R 1 represents hydrogen, halogen or a C 1 -C 4 asylum group and

R 2 is hydrogen, halogen or C 1 -C 4 alkyl.

In the context of the latter group are preferred in the strict sense ^to the memory with the ^I ou ^No enyne ^where subssituenty formula Ia have the following meanings:

X is cyano, chloro, bromo, acetyl, propionyl, methoxy verifies ^the Arbon ^yl group and ^H ox ^yk art) onyl, aminocarbonyl N-methylamino ^the nominal SKU Arbon ^{y P} well, Ν, Ν-dimethylaminocarbonyl,

Q represents the ^y anmet ^HYL verifies the group ^Y or ^Y aneth talk group; methoxycarbonylmethyl, ethoxycarbonylmethyl, methoxycarbonylethyl or ethoxycarbonylethyl; alkyl having 1-2 carbon atoms which is substituted karboxamidoskupmo ^ ^{k Ter} _ ^p op ^case mono ^- or disubstituted with an alkyl group having 1 to 4 carbon atoms and / or alkenyl having 2 to 4 carbon atoms, or which is ^p oprípa monosubsthuována al ^{ki ga} n ^y or with an alkyl with 2-4 carbon atoms; or represents a propynyl group or a butynyl group,

R 1 is hydrogen, halogen or methyl;

R 2 represents hydrogen, halogen or methyl.

Of these compounds, an important sub-group of compounds are those in which X is k ^y ano.

Another preferred range of effective aunts

formula I having the ability to stimulate plant growth and protect plants is included in formula II:

c-x

R (ID in which

X is cyano, nitro, halogen, acetyl, C 1 -C 4 alkoxycarbonyl or aminocarbonyl optionally mono- or disubstituted with C 1 -C 4 alkyl, n is 1, 2 or 3,

Ra is hydrogen or a ^5- keel group having 1 to 3 carbon atoms,

R 10 represents an aminocarbonyl group which is optionally monosubstituted with C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl or phenyl which is itself optionally further substituted by 1 or 2 halogen atoms; or is cyano, with a portion of the formula

- (CH) "- I 9 consists highest ^e of four atoms ^at uhhku.

Within the scope of formula II, compounds of formula III are preferred

CX II NO-CH 2 -R _Q (III)

in which

X is cyano, chloro, acetyl, alkoxycarbonyl ^l verifies SKU ^p yne with ^1-4 carbon uh'í'ku or aminocarbonyl optionally a ^{plurality of projections} dfeubstituována 'verifies sk: u ^p another 1 to 4 C atoms , and

Rio is aminocarbonyl, ^{kt ER} is ^p o ^or ad ^e monosubstituted alkyl group having 1 to 4 carbon atoms or by phenyl which is itself popři223867

is still substituted with 1 or 2 halogen atoms; or is cyano.

Preferred individual compounds include:

α-cyanobenzylideneaminooxacetamide of the formula

-C-CN

N-O-CH 2 CO-NH 2 α-cyanobenzylideneaminooxyacetic acid ethyl ester (Compound 1.4) α- (cyanoethox.imino) benzacetonitrile (Compound 1.44)

Effectively ^E c ^hl oracetani ^{Lidy, kt} ns of the ^part are crop plants such as cereals, rice, cultural, millet, and other sufficiently tolerated, but while using oxime ethers of the formula I according to ^ e ^ ostenVo in ^y n and ^l cut tatovéto kukurrn plants saving without otherwise suffering in its effect on ^{the UCI p} level ^of m ^are Zn ^and m ^y such ^IKL and ^d from US Pat. No. 3,547,620, 3,403,994, 3,442,945, 3,637,847, 3,598 859,

819 661, 3 946 045, 3 983 174 and from DOS number 2 212 268, 2 305 495, 2 328 340, 2 402 983,

405 183 and 2 405 479.

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

^R _{2 is} ^R 1if ^R 12.

(IV) in which:

Rit ^implies in ntérn and verifies ^lkyl groups alkoxy, alkoxyalkyl, ^having trifluormetbylovou to ^P inu not ^b ^ en the halls,

R12, R13, and R14 are each independently hydrogen, lower alkyl, alkoxy, alkoxyalkyl, trifluoromethyl or halogen, and

Rts is alkyl having 1 to 4 carbon ^yl UHN ^ ^k TERA ^p op ^Rip ad ^e substhuována carboxy ester, carboxylic ^alkyl SEL ⁱ n ^y ami ^d em ^to Ar ^b ox ^y nominal tyseliny ^forward e is ^d him or two ^MZ MENTAL ali ^f ATIC ^to YMI radicals substituted carboxylic acid amide, or cyano, or in which

^Implies in rtf до п ^ ^ ^ butyn acetatovanou carbonyl group, a 1,3-dioxolan-2-ylaikyl l, ^3-yl-5- dinxnlαn lαlkyl, ^{1,3-dioxan-2-yy-alk-yl,} furanylmethyl, tetrahydrofuran ^-yl meth ^yl or ^alk ox ^y al ^alkyl formula -A-O-Rab, ^the de

A is alkylene having 1 to 4 carbon atom of ^Y ^ UHN rnch ¹ or 2 ^ i PMS straight chain, and

R 16 represents a lower alkyl group, an alkenyl group or a cycloalkyl group or a cycloalkylmethyl group having 3 to 6 carbon ring atoms.

^In ýraz ^y ,, ^also lower alkyl "or" lower ^{also to} alifatm characterized ZB ^y te ^k "represent: ⁱ with u ^{p to s} in the most 4 carbon atoms, and further correspond to the definition given above for formula I. The same applies to the term" hatogien ".

Some of the hypochlorite species which are particularly suitable for use with the antidotes of the invention are:

N-ethoxy ^y meth ^{yl-2-meth yl-6-eth yl} lchloracetanilid,

N-methoxy ^y meth ^{yl-2,6-dieth y} lchloracetanliid,

N- ⁽² '-me t ^h oxy et: LiY 1) - ^2, 6 c hloracetanilid,

N- (N-ethyl--altylox) - ^2, 6-dimettlylch nl'acetanilid ^{l, N} - (^ ^ -п-ргодох ЬУ) -2,6 - ^ 106 ^ 1 ^ t ^ chlorination inlid ^N - ( ² '- ^{i p} soprn oxyethylene ^l) - ^2.6 -dimethylchloracetanilid ^N - ^(2' -me th oxy eehy ^yl) - ^{2-methylbenzyl yl} -6-eth ^yl 1chloracetanilid,

N- ^{(2'-methoxy y} eth ^yl] - ^2, 6-diethyl Ichloracetanilid ^{yl, N} - ⁽² '-etlhoxy e ^ yl) - ² - MC Шу 1-6 -e ehylchtoracetanilid ^N - [3-methoxy ^{yp p} ro - ^{2 &apos; yl]} -2-NR- mettlylch ^l. acetanilide, ^N - [Bmetbox ^ ro ^ ² ^] -2 t ^ - <^ i ^ i ^ t: h ^y l ^^^ ^ β ηΐ ^ ^N - ^[3 '-methyl- nx ^{yp h} RN ^m - ^2' - ^yl] -2-meth ^yl-6eth ^ cMoracetanilid

N- [3'-methnx ^{yp p} ro - ² '- ^yl] -2,6 · - ^^^^ acetanilide, ^N - (^ -ethoxYeehy) acetanilide, ^N - ^(2-N-p for oxyethylene Шу ⁽¹ ) ^-2- methyl-6- ^ethyl- chloroacetanilide,

N- ^{(2 '- y} n ^p rnpox eth ^yl) - ^{2, 6-di} eth ^y lchloracetanilid ^N - ^[2' - ^{P 1} Sopro nx ^y eth ^y l] - ^{2-methyl-6-eth yl} lchloracetanilid, ethytester -c ^{N hl} oration ^butyl - ^{2,6-dimethylethyl y} lanihnooctové ^alkyl petroleum jelly, ethyl N-chloroacetyl-2,6-diethylanilinooctové acid methyl ester, N-chloroacetyl-2,6-dimethylanilinooctové acid isopropyl ester of N-chloroacetyl-2-methyl- 6-ethylanilinoacetic acid, 2- [N- (α-chloroacetyl) -2,6-dimethylanilino] acetaldehyde diethyl acetal,

N- [3‘-methoxyprop-2‘-yl] -2,3-dimethylchloroacetanilide,

N- (2-ethoxyethyl) -2-methylchloroacetanilide,

N- (2'-methoxyethyl) -2-methylchloroacetanide,

N- [2 ^; -methoxyprop-1'-yl] -2,6-dimethylchloroacetanilide,

N- [2'-methoxyprop-l ^<-yl] -2-methyl-6-ethylchloracetanilid,

N- [3 ^: -ethoxyprop-2'-yl] -2-methyl-6-ethylchloroacetanilide,

N- [3‘-ethoxyprop-2‘-yl] -2-methyl-6-ethylhloroacetanilide,

N- [1'-diethoxybut-2'-yl] -2,6-dimethylchloroacetanilide,

N- [2‘-methoxyethyl] -2-methyl-6-methoxychloroacetanilide,

N- (n-butoxymethyl) -2-tert-butylchloroacetanilide,

N-tS-ethoxyxypropiperazin-4-ylmethylchloroacetanilide,

N- (2'-methoxyethyl) -2-chloro-6-methylchloroacetanilide,

N- (2'-ethoxyethyl) -2-chloro-6-methylquinolin oracetanilid ^1,

N- (2'-ethoxy ethyl ^yl) -2,3,6-trimethylchloracetanilid,

N- (2‘-methoxyethyl) -2,3,6-trimethylchloroacetateBid,

N- (2'-isopropoxyethyl) -2,3,6-trimethylchloroacetanilide,

N-cyanomethyl-2,6-dimethylchloroacetanilide,

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

N-propynyl-2-methyl-6-ethylchloroacetanilide,

N- (1,3-dioxolan-2-ylmethyl) -2,6-dimethylchloroacetanilide,

N- (1,3-dioxolan-2-ylmethyl) -2-ethyl-6-methylchloroacetanilide,

N- (l, ^3-dioxo] an-2-ylmethyl) -2-methyl-6-ethylchloracetanilid,

N- (2‘-furanylmethyl) -2,6-dimethylchloroacetanilide,

N- (2'-furanylmethyl) -2-chloro-6-methylchloroacetanilide,

N- (2'-tetrahydrofuranylmethyl) -2,6-dimethylchloroacetanilide,

N- (N-propargylcarbamoylmethyl) -2,6-dimethylchloroacetanilide,

N- (N, N-dimethyl-carbamoylmethyl) -2,6-dimethylchloroacetanilide,

N- (n-butoxymethyl) -2,6-diethylchloroacetanilide

N- (2‘-n-butoxyethyl) -2,6-diethylchloroacetanilide,

N- [3'-methoxybut-2'-yl] -2,6-dimethyl-chloroacetanide,

2-chloro-N-isopropylacetanilide.

Suitable herbicidal thiolcarbamates which, when used in cereals, rice and cultural millet species together with the compounds of formulas I, II or III, are tolerated by crop plants, preferably correspond to the formula:

R17-S-C-N

R18

or /

R1.7 — SO — C — N

R18

in which

R 17 represents lower alkyl, alkenyl, chlorallyl, dichlorallyl, trichlorallyl, benzyl or p-chlorobenzyl,

R 18 is C 2 -C 4 alkyl

R 19 represents a C 2 -C 4 alkyl or cyclohexyl group, or in which:

R 18 and R 19 together with the nitrogen atom form a hexahydro-1H-azepine or decahydroquinoline or 2-methyldecahydroquinoline ring.

The following thiolcarbamates may be mentioned as examples of such compounds:

S-ethyl-N, N-dipropylthiocarbamate,

S-ethyl-N, N-diisobutylthiocarbamate,

S-2,3-dichlorallyl-N, N-diisopropylthiocarbamate,

S-propyl-N-butyl-N-ethylthiolcarbamate,

S-2,3,3-trichlorallyl-N, N-diisopropylthiolcarbamate,

S-propyl-N, N-dipropylthiolcarbamate,

S-ethyl-N-ethyl-N-cyclohexylthiolcarbamate,

S-ethyl-N-hexahydro-1H-azepine-1-carbothioate,

S-isopropyl-N, N-hexamethylenthiol carbamate,

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

N-ethylthiocarbonyl-cis-decahydroquinoline,

N-propylthiocarbonyldecahydroquinine,

S-ethyl-N, N-bis- (n-butyl) thiolcarbamate,

S-tert-butyl-N, N-bis (n-propyl) thiolcarbamate.

2 3 8 7

Further examples of useful thiolcarbamamates are described in U.S. Patent Nos. 2,913,327, 3,037,853, 3,175,897, U.S. Pat.

185,720, 3,198,786 and 3,582,314.

Other preparations which, in combination with the compounds of formula I, are compatible with crops include:

N- [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] methyl ester propionic acid, α- [4-3,5-dichloropyridyl-2-oxy] phenoxy] -propionic acid methyl ester.

The amount of antidote used varies between about 0.01 and about 15 parts by weight per 1 part by weight of the herbicide. This amount is determined on a case-by-case basis, i.e. depending on the type of herbicide used, so as to use the optimum ratio in relation to the optimum effect that is most suitable for the particular crop plant.

As already mentioned, various methods and techniques for using new antidotes of formulas I to III come to protect crop plants from agrochemicals or to stimulate plant growth:

1) Seed pickling

(a) Pickling of seeds with the active substance used in the form of a wettable powder by shaking in the container until evenly distributed on the surface of the seeds (dry pickling). About 10 to 500 g of active compound of the formula I (40 g to 2 kg of wettable powder) per 100 kg of seed are used.

(b) Seed pickling with the emulsion concentrate of the active compound of the formula I according to method (a) (wet pickling).

c) Pickling by dipping the seed in a suspension containing 50 to 3200 ppm of the active compound of the formula I for 1 to 72 hours and, optionally, subsequently drying the seeds (dipping).

Seed pickling or the treatment of sprouted seedlings are naturally preferred methods of application, since treatment with the active ingredient is entirely directed to the target crop plant. As a rule, 10 g to 500 g, preferably 50 to 250 g of active substance per 100 kg of seed are used, and according to the methodology which allows the addition of further active substances or micronutrients, it is possible to deviate upwards or downwards from said limit concentrations ( repeated pickling).

2) Applying the mixture prepared in a storage container

The liquid form of the antitumor and herbicide mixture is used (the ratio of the amount being between 10: 1 and 1:10), the amount of herbicide applied per ha being 0.1 to 10 kg. Such a mixture prepared in a tank is preferably applied before or immediately after sowing or 5-10 cm deep into the still unsown soil.

3) Application to grooves ready for sowing:

The antidote is applied in the form of an emulsion concentrate, wettable powder or granulate to the still sown grooves, and then after covering the grooves, the herbicide is applied in a normal manner by a pre-emergence process.

In principle, the antidote may be applied before, together or after the application of the pesticide, and may be applied to the seeds or field before or after sowing or, in certain cases, also after seed has emerged.

In particular, the invention also relates to compositions comprising, in addition to the antidote of the formula I, at least one agrochemical active substance, for example the chloroacetanilide or thiolcarbainate herbicide. These compositions additionally contain carriers and / or dispersants.

(4) Controlled release of active substance:

The active ingredient is applied in the form of a solution to a mineral granulate carrier or to a polymeric granulate (urea-formaldehyde) and then allowed to dry. Optionally, a coating (coated granules) may be formed which allows the active ingredient to be delivered in portions over a period of time.

Of course, all other methods of drug delivery can also be used. Examples are given below.

The process according to the invention for promoting plant growth or for the protection of crop plants can be used, in particular, on rice and useful sorghum (Sorghum), corn, wheat, barley, oats, soya, cotton, sugar beet. However, this procedure is not limited to the stimulation and protection of annual plants, but is also well suited to stimulate the growth of perennial plants (fruit trees, ornamental shrubs, etc.), stimulating the formation of roots or the formation of side shoots or improving deployment. fruits or improved state of flowers.

The compounds of formula I are prepared by methods known per se (Organic Reactions 1953, Vol. 7, pp. 343 and 373; Journal f. Praktie Chemie 66, p. 353; Liebigs Ann. 250, 165) by etherification or acylation of the oxime of formula V

Ar — С — X

N — OH (V)

(b)

Ar - C - X + Halg - CH - COOCH 3

N — O — salt СНз in which

Ar and X are as defined in formula I, or oxime salts by treatment with a halide of formula

Halg — Q in which

Q is as defined in formula I and

Halg is halogen, preferably chlorine or bromine.

The condensation of the substituted .alpha.-oximinoderivatives is effected in the etherification expediently in the form of their salts, in particular alkali metal or ammonium salts, as schematically indicated below in selected examples:

and)

Ar — C — X || + Halg-CH 2 -CO-NH 2

N — O — salt -----------------> Ar — C — X

II

N_O_CH2-CO-NH2 oximacetamides of formula I

Ar - C - X

II

------ N — O — CH — COOCH3

СНз ^yl ester of a carboxyalkyl ^{alkyl-voltage} Selin oximalkanů formula I

C)

Ar - C - X + Halg - CH 2 - CH = CH 2

N-O-salt

Ar - C - X

II

------ N - O - CH 2 - CH = CH 2 oximethers of formula I

The acylation is conveniently carried out with the free oximes of formula V, as shown in the following scheme:

d):

Ar — C — X acid halide || --------- N-O — H

Ar — C — X (cyclo) aliphatic,

II I aromatic residue,

N-O-CO hetericyclic acyloxime residue of formula I

E)

Ar - C - X sulfonic halide

N-OH acids

Ar - C - X

N — O — SO2 (cycloaliphatic, aromatic, heterocyclic sulfonyloxime of formula I

In the above. Halg represents halogen, especially chlorine or bromine.

As solvents to obtain compounds. Formula I principally ^h o ^{d p} and all extended ^{STARTUP EDL} and that for rea ^CZK --N ^{h a} r podnňnek behaves inertly. As pnklady ^l st of the ^loan: uhtevo ^d i ^K Y, ^Pr e ^{d eV mV} and ^the potarrn ^ro zpoušt ^of such dmxan, something ^{methylcarbazole-di formamide,} and ^N, and ^to this Toten Jato meth ^y lethyltoton, acetone ate. . ^{No howling} ou are extended ena ^{p STARTUP} and ^{EDL, kt} of the ER ^and the ^b! IUJ ^d rox ^y nominal ^hydroxy group.

The temperatures range from -10 ° C to about 150 ° C, preferably between 20 ° and 120 ° C.

As a hydrogen halide removing agent suitable base such as tertiary amines (triethyJamin, triethylene diamine ^y, piperidine etc.). In some cases, a suspension of sodium carbonate in an anhydrous reaction medium is also sufficient.

Oximes exist in two stereoisomeric forms, i.e., syn and anti. Also the compounds of formula I mentioned in paragraphs

a) to e) can be ^{characterized} with ^alkyl ova ^t in both ^f orm ^a c ^{h or} with ^the no ^b of Jato směsL ^Within toho2 2 3) 867 that disclosure is thus in terms of that mean both stereoisomeric forms themselves and as mixtures in any relative proportions.

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

Example 1

In a 350 ml sulfonation flask, 17 g (0.1 mol) of phenylglyoxylonitrile-2-oxime sodium are suspended in 170 ml of acetonitrile. Then, 23.8 g (0.1 mol) of chloroaceto-3,4-dichloroanilide were added to show a slight thermal coloration. The suspension was stirred at reflux for 3 hours, changing the appearance of the suspensions. After cooling to room temperature, the reaction solution was filtered from the resulting sodium chloride, the filter residue was washed with acetonitrile, and the filtrate was evaporated in vacuo. 32.3 g of crude product are obtained in the form of a residue. After recrystallization from an alcohol / water mixture, 20.4 g of the reaction product of the formula chloroacetic acid are obtained, kept in 200 ml of acetonitrile at 60 DEG-70 DEG C. for 3 hours with good stirring, the suspension becoming very fine. After a few more hours, the product was filtered off, washed with acetonitrile and dried in vacuo to give an oily residue after about 24 hours.

Melting point 68-70 ° C. After recrystallization from isopropyl alcohol, the melting point is 71-72 ° C.

C ~ C — N

NO-CH 2 COOCH _Z

Similarly, by condensation of 4´Chlorophenylglyoxylonitriloxime sodium salt with α-chloropropionic acid ethyl ester, a compound of the formula:

- ^ - C-N-O-Cl = CO-NH-C = N

Cl

mp 143-144 ° C.

Correspondingly, the product of the formula ^H is obtained from the salt of 2,4-dimethylphenylhydro-oxamic acid chloride and allyl chloride in the form of an oily substance: Cl ^H 3 ^C = 33-C = N-O-CH 2 CH = CH _{2 -}

In a similar manner, a compound of formula is obtained from the sodium salt of 2-thienylacetonitriloxime and chloroacetonitrile

II

N-O-CH 2 CN as an oil.

Example 2

33.6 g (0.2 mol) of phenylglyoxylonitriloxime sodium salt and 25 g (0.22 mol) of methyl ester in 99.3% yield as an oil.

When chloroacetic acid isopropyl ester is used in place of the ^α -chloropropionic acid ester, a compound of the formula ^ci- O-f ^{cN is obtained}

N-0-CH-C00 ISOC £ ₃ Hi mp 93-94 ° C, using an unsubstituted fenylglyoxylonitriloximu (as sodium salt) is reached to the compound of formula

O 'u' ^CN

N-O-CH 2 COO-C 1 H 3?

mp 49-50 ° C.

Example 3

Preparation of compound of formula

α-cyanobenzylideneaminooxacetamide

845 g (5 mol) of benzacetonitriloxime sodium are suspended in 2.5 liters of acetonitrile and 468 g (5 mol) of chloroacetamide are slowly added with stirring in the presence of a catalytic amount of potassium iodide. The reaction mixture is heated at reflux for 12 hours, then cooled and then allowed to flow to about 12 liters of water. While the salts present dissolve, the reaction product precipitates in crystalline form. Yield 882 g [i.e. 86.8% of theory). Mp 128-129 ° C (from ethanol).

Correspondingly, the compound of the formula is obtained from the sodium salt of 3-furanylnitromethanoxime and methanesulfonyl chloride.

ГТ'Г ^{02 0} NO-SO ^CH ^ in the form of a viscous oil.

Example 4

8.0 g (0.037 mol) of the sodium salt of α-oximino-1-naphthylacetonitrile and 5.5 g (0.045 mol) of propargyl bromide are heated to about 80 ° C in 50 ml of acetonitrile for 4 hours. The suspension was concentrated in vacuo and the residue was extracted with methylene chloride. The solution was evaporated to give the title compound as an oil

calculated:

C: 76.9%, H: 4.3%, N: 11.96;

ПЯ1 О7ППП *

C: 76.4 ’%, H: 4.4%, N: 11.8%.

When chloroacetonitrile is used as the reactant instead of propargyl bromide, the compound of formula (I) is obtained.

(γ-C-GN n-o-chlorine, m.p. 81-82 ° C).

Example 5

0.1 mol of sodium α-oximino-2-thienylacetonitrile is suspended in 150 ml of acetonitrile together with 0.12 mol of chloroacetamide. Thereafter, the reaction mixture is heated at 50-60 ° C for 3 hours, whereupon sodium chloride precipitates, which is filtered off and washed with acetonitrile. The filtrates were concentrated in vacuo. There remains a compound of formula ## STR2 ## as a light yellow oil.

The following tables show temperatures in degrees Celsius.

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

Analysis for

C15H10N2O

W-O-Q

compound number R1 R2 Q physical data 1.1 H H —CH2 —CO — NH2 t 128-139 1.2 4-Cl H —CH2 —CO — NH2 126-128 1.3 H H —CH2 — COOCH3 71-72 1.4 H H —CH2 — COOC2H5 54-56 1.5 H H —CH2 — COO (C1-C3H7) 49-50 1.6 4-CH3 H —CH (CH3) COOCH3 oil 1.7 4-Cl H —CHa — COO (C1-C3H7) t. 93-94 1.8 4-Cl 2-C1 —CH2 — COOCH3 oil 1.9 4-Cl 2-C1 —CH2COOC2H5 oil 1.10 4-Cl 3-C1 —CHa — COOCH3 50-52 1.11 4-Cl 3-C1 —CH2 — COOC2H5 46-48 1.12 4-Cl H —CH3 CH3 - —COOC3 H5 oil 1.13 4-CH3O- H —CH2 — COOC2H5 78-81 1.14 H H —CH2— CeeCH n _D 22 1.5597 1.15 H 2-C1 —C2H5 oil 1.16 4-CH3 H -nC3H7 n _D 22 1.53 5 9 1.17 4-CH3O H —CH3 75-77 1.18 4-CH3O H —C2H5 oil 1.19 4-Br H —CH2C-CH 90-92 1.20 H H —CH3 — CH — CH2 \ / X / \ Cl Cl t 118-120/107 Bye 1.21 4-Cl H —CH (C2 H5) - COOC2 H5 oil 1.22 4-Cl H —CH2 — C = CH 75-77 1.23 4-Cl H —CH (CH3) —COOCH3 oil 1.24 4-CH3 H —C2H5 no ²² 1.5426 1.25 4-Cl 2-C1 —CH (CH3j — C = CH oil 1.26 4-Br H —CHs 60-62 1.27 3-CF3 H —CH2 — COOC2H5. 1.28 3-CF3 H —CH2 — HC = CH2 1.29 H H -nCaH9 1.30 H H —CH2 — COO (ISCO4H9) 1.31 3-CF3 H —CH (CH3) —COOC2 H5 1.32 4-NO2 H —CH2 — COOCH3 1.33 4-NO2 H —CH2 —CO — NH2 Cl / 1.34 H H -CH2CO-NH4 ^- Cl2 143-144 1.35 H H - SO 2 N (CH 3) 2 88-89 1.36 4-Br H —CH — CN 77-79 1.37 4-CH3O H —CaHs solid product 1.38 H H —CH3 129-131 1.39 H H —C2H5 oil 1.40 H H —C3H7 (1SO) n _D ²² 1.5 3 4 0 1.41 H H —CH (CH3) COOCH3 oil 1.42 H H —CH (CH3) COOC2 H5 36-37 1.43 H H —CH (C2 H5) COOC2 H5 solid product 1.44 H H —CH2 — CH2 — CN 123-126 1.45 H H —CH2 — CH2 — CH2 — CN n _D 22 1.5352 1.46 H H —CO — CH3 68-70 1.47 3-CF3 H —CH2 — COOCH3 107-109 1.48 2-CH3 H —CHa— CN 1.49 2-F H —CH — CN 1.50 2-F H —CH2 — CONH2 oil 1.51 2-CH3 H -CH (CH 3) -COOCH 3

WHOSE

Н _Ъ СО Cl

1.54 Η Н - (СНг) 7 — СНз 131-133 1.55 4-пС4НэО Н —СН2 — CN 1.56 44soC3H7O Н —СН2 — СО — ΝΗ2 1.57 2-СНз Н —СНг— СО — ΝΗ2 oil 1.58 3-ΝΟ2 Н —СНг — СО — ΝΗ2 1.59 3-ΝΟ2 Н -SO 2 -CH 3 133-135 1.60 Н Н —СНг — СО — СНз 67-68 1.61 Н Н —СН (СНз) - СО — ΝΗ2 144-146 1.62 Н Н —S? - СНз 121-122 22 1.63 Н Н —СНг — СООС4Нэ (target) 76-7 ' 1.64 Н Н —СН (пС.10Н21) СООСгН5 53 - 51 1.65 Н Н - (СНз) г — СООС2Н5 oil 1.66 н Н —СН (СНз) —СООС3Н7 (ISO) n _D 22 1.5112 1.67 н Н - (СНг) 17 — СНз solid product 1.68 н Н —СН (СНз) - С = СН oil 1.69 н Н —CH (CH3) —CON (С? Н ₅ ) г n _D ²² 1,5300 1.70 н Н —СНг — СО — NH — СНз 1.71 н н —СНг — СО — N (CH3) 2 1.72 н н —СНг — CONH — СНг — СН = СНг 1.73 н н —СНг — CONH — С = СН 1.74 н н —СНг — СОЫ (СНз) - СНг — СН = СНг 1.75 н н —СНг — CON (CHs) - С2Н5 1.76 н н —СН (СНз) —CONH — СНз 1.77 н н —СН (СНг) - СОЫ (СНз) г. 1.78 н н —СНг — СОЩаПуПг 46-48 1.79 н н —СбНз (N02) 2 (2.4) t 178-179 1.80 н н -СНг — СбНзС1г (3.4) 91-93 1.81 н н —СНг — СООСНг — СбН5 61-62 1.82 н н —СНг — СОО — C6H4NOž (41 solid product 1.83 н н —СНг — CONH — СбНзС1г (4) 149-150 1.84 н н —СНг— CONH — C6H4F (3) 136-137 1.85 н н —СО — С2Н5 53-55 1.86 н н CH (CH 3) CN 60-62 1.87 н н —СНг — СН = СН — СНз Пг> 22 1.5477 1.88 4-СНз н —СНг — CN 82-84 1.89 4-СНз н —СНз 44-46 1.90 4-СНз н —СНг — СООСНз solid product 1.91 4-СНз н —СНг — СООС2Н5 solid product 1.92 4-СНз н —СН (СНз) СООС? Н5 oil 1.93 4-СНз н —СН (С2Н5) СООСгН5 n _D 22 1.5128 1.94 4-СНз н —СНг — COONH — СбНзС1г (3.4) tt 162-164 1.95 4-СНз н - СН (СНз) —COOC5H7 (iso) n _D 22 1,5100 1.96 4-СНз н —СНг — С = СН solid product 1.97 4-СНз н —СНг — СН = СН — СНз oil 1.98 4-СНз 3-СНз —СНг — CN 40 1.99 4-СНз 3-СНз —СНз oil 1.100 4-СНз 3-СНз -С2Н5 oil 1.101 4-СНз 3-СНз —СзН7 (п) oil 1.102 4-СНз 3-СНз —СНг — ССОСНз 60 ° C 1.103 4-СНз 3-СНз —СНг — СООС2Н5 50 ° C

compound number Rl R2 Q physical data 1.104 4-CH3 3-CH3 —CH (CH3) COOCH3 oil 1.105 4-CH3 3-CH 3 —CH (CH3) COOC2 H5 oil 1.106 4-CH3 3-CH 3 —CH2 — C = CH 75-81 1.107 4-CH3 3-CH3 —CH.2 — CONH — C6H3Cl2 (3.4) 110 1.108 4-CH 2 3-CH 3 —CHa — CONH — CH3 oil 1.109 4-CH3 3-CH3 —CH2 — CON (CH3) CH2 — CH = CH2 oil 1.110 4-CH3 3-CH 3 —CH2 — CONH2 oil 1.111 4-CH3 H —CH2— CN 91-93 1.112 4-OCHs H —C3H7 (n) oil 1.113 4-OCHs H —CH2 — COOCH3 122-125 1.1141, 4-OCH3 H HH (HH ₃₎ COOC H5 50-53 1.115 4-OCH3 H —CH (CH3) COOCH3 oil 1.116 4-OCHs H —CH (C2’H5) COOC2H5 oil 1.117 4-OCH3 H —CH (CH3) Cl = CH solid product 1.118 4-OCH3 H —CH2 — OCCO2H7 (iso) solid product 1.119 4-OCH3 H —OH (OHz) OCCCzH7 (iso) oil 1.120 4-OCH3 H ^ ^ 7 ^ 3 oil 1.121 4-OCH3 H —CH2 —CO — NH2 123-126 1.122 4-OCH3 H —OH2 —O = OH solid product 1.123 4-OCH3 H —CH2 — CH = CH2 mp about 40 ° C 1.124 4-OCH3 H —CO — CoHs mp 128-130 1.125 4-OCH3 H —OHc — OH = OH — OH 2 88-93 1.126 4-Cl H —CH2 — CN 69-71 1.127 4-Cl H —CH3 70-71 1.128 4-Cl H —C2: H5 39-40 1.129 4-Cl H oil 1.130 4-Cl H —OH2 — OCOOHз 81-82 1.131 4-Cl H —OH2 — OCCO2H5 89 - · 90 1.132 4-Cl H - CH (CHz) OCOCzH7 ((so) oil 1.133 4-Cl H - (CH 3 -CH 2 oil 1.134 4-Cl H —OH2 — OH = OH2 solid product 1.135 4-Cl H - ·. — Of ^ c — CONH · —O6H5C (1 (3,4) t. - t. 165 - · 166 1.136 4-Cl H —CH2 — OONH — C6H4Bг (3) 199 -. 201 1.137 4-Cl H —OHc — CCNH — OβШCFз (2) 187-190 1.138 4-Cl H ·, · - ·  —OH2 — C (CŇH-C: eHiOO (4)) ·. 204-205 1.139 2-C1 H -  - · · =. ”—— CN 51 -: 53 1.140 2-C1 H · .......— CHs oil 1.141 2-C1 H  - λ — CsH ^ n] oil 1.142 4-Cl 2-C1 ^: —OH2 — ON t - 126 - 128 1.143 4-Cl 2-C1 ·· '......— CHs 95-96 1.144 4-Cl 2-C1 .- · solid product 1.145 ·. ·. · 4-C1 2-C ^ 1: ..... —OH (OH5) CCCOHз n _D 22 1.5460 1.146 ; 4-C1 2-C1. :  —OH (CH 2) OOO O 2 H 5 oil 1.147 '.' 4-Cl 2-C1 . -OH (C 6 H 5) COOC 2 H 5 oil 1.148 4-Cl 2-C1 —CHC-O = OH 75 - · 76 1.149 ^: 4-C1 2-C1 —CH 2 --CH 2 CH-CH oil 1.150 4-C1 3-C1 —CH3 84-85 1.151 4-Cl 3-C1 —C2H5 solid product 1.152 4-Cl 3-C1 —Csl ^ n) oil 1.153 4-Cl 3-C1 —CdlHíterc.) solid product 1.154 4-Cl 3-C1 —OH (CHз) OOOOHз solid product 1.155 4-Cl 3-C1 —CH (CH 2) OOO O 2 H 5 oil 1.156 4-Cl 3-C1 —CH (O2H5) OOCOcH5 oil 1.157 4-Cl 3-C1 —CH2 — CN 90-93 1.158 3-C1 3-C1 —CH2O = OH solid product 1.159 4-Br H solid product 1.160 4-Br H - ^з ^ п) solid product 1.161 4-Br H —OHc — OOCOHз 79-80

merge-Ri to a number

R2 physical data

1.162 4-Br H 1.163 4-Br H 1.164 4-Br H 1.165 4-Br H 1.166 4-Br H 1.167 4-Br H 1.168 4-Br H 1.169 4-Br H 1.170 4-Br H 1.171 4-Br H 1.172 4-Br H 1.172 / 1 4-C1 2-C1

1.172 / 2 4-СНз H — CHž — COOC2H5 —СН (СНз) СООСНз —СН (СНз) СООС2Н5 —CH (C2H5) COOC2H5 —CH2 — CH = CH2 —СН (СНз) —с ^ сн —СН (СНз) = СН —СН2 — COOC3H7 (iso) —СН (СНз) —COOC3H7 (iso) —СН2 — СН = СН — СНз —СН2 — CONH — СбНзС12 (3,4) —SO2N (CH3) 2

about 40 ° C oil oil oil

tt 90-92 tt 147 J 149 t, t. 50 ° C n _D 22 1.5310 oil oil

152-155

По ²⁰ 1.5646

128-130

1.174 / 3 4-СНз H

Cl

163-164

1.173 / 4 4-СНз H 1.173 / 5 4-C1 2-C1

СН ₃ О - ^co ^ Ie

tt 159-161

1.173 / 6ΗH

1.1. 108-110

150-151

1.173 / 7

1.173 / 8

2-C1 cl

63-66 —СО — С (СНз) з

93-96

1.173 / 9 4-C1 2-C1 —CH2CH2 — S — СНз n _D 2? 1.5740 1.173 / 10 H H —CH2CH2 — S — СНз ηθ ²⁷ 1.5600 1.173 / 11 4-C1 2-C1 —CH2 — S — СНз 70-72 1.173 / 12 H H —CH2 — S — СНз По ²⁷ 1.5780 1.173 / 13 H H —СН (ОСНз) СООСНз oil 1.173 / 14 H H —СН2СН (ОСНз) 2 mp 35 ° C 1.173 / 15 H H —CH2 — СН (СНз) 2 oil

The following compounds of the formula are also obtained analogously

^R 1 Q —C-c ¹¹ NOQ. compound Ri Rž Q physical data

number

1.173 H Η —СН2 — CN oil 1.174 H Η —СНг — CO — ΝΗζ oil 1.175 4-Cl Η —СНг — CO — NH2 oil 1.176 H Η —СН2 — СООСНз 1.177 H Η —СНг— СООС2Н5 1.178 H Η —СН2 — СОО (I-C3H7) 1.179 4-СНз Η —СН (СНз) СООСНз 1.180 4-Cl Η —СНг — СОО (1-СзН7) 1.181 4-Cl 2-С1 —СНг — СООСНз 1.182 4-Cl 2-С1 —СНг — СООС2Н5 1.183 4-Cl 3-С1 —СНз — СООСНз 1.184 4-Cl 3-С1 —СНг — СООС2Н5 1.185 4-Cl Η —СН (СНз) —СООС2Н5 1.186 4-СНзО— Η —СНг — СООС2Н5 1.187 H Η —СНг — С ^ СН oil 1.188 H Η —СНг — CON (СНз) г. 1.189 4-СНз Η -ПС3Н7 1.190 4-СНзО Η —СНз 1.191 Η Η —СНг — CONHC = CH oil 1.192 4-Br Η —СНг — С = СН 1.193 Η Η —СНг — CON (СНз) —С2Н5 oil 1.194 Η Η —СНг — СОИ (СНз) —СН — СН = СНг oil 1.195 4-Cl Η —СНг — С = СН 1.196 4-Cl 2-С1 —СН (СНз) —С = СН 1.197 3-CFs Η —СН2СООС2Н5 1.198 3-CFs Η —СНг — НС = СНг 1.199 H Η —СНг — COONH — СНг — СН = СНг oil 1.200 3-CF3 Η —СН (СНз) —СООС2Н5 1.201 4-NO2 Η —СНг — CO-NH2 oil 1.202 H Η -CH _from CO-NH4-y oil 1.203 4-Cl Η —СН (СНз) —СООСНз oil 1.204 4-NO2 Η —СНгСООСНз solid product 1.205 H Η —СО — СНг — NH2 1.206 3-CF3 5-CFs —СНг — СООСНз 1.207 2-СНз Η —СНг — CN oil 1.208 2-F Η —СНг — CN oil 1.209 2-F Η —СНг — CONH2 oil 1.210 2-СНз Η —СН (СНз) - СООСНз 1.211 4-ПС4Н9О Η —СНг — CN oil 1.212 4-ISOC3H7O Η —СНг — СО — NH2 oil 1.213 2-СНз Η —СНг — СО — NH2 oil 1.214 3-NO2 Η —СНг — СО — NH2 oil 1.215 3-NO2 Η —SO2 — СНз 1.216 2-СНз 4-СНз —СНг— СН = СНг

The following compounds of the formula are likewise obtained analogously

ί2

Honors those ‘S

CD

СЛ> L>

I do it do it do it do it to ac x x x x x x x x x x

Ш Ш m -X X X X X

N см <* i се ем ем ем «χι to CM xawacO ^^ xssxxxssss x

I t

04 ax to X ^е ?

XXXXXXXXXX

CM CM CM CM cm cm cm cm cm cm cm cm cm cm cm cm cm HHiHHt-IHHhHh HH rl Η H · rl I-I rl

LO

CM it

X ⁷ ? ο XE ο U ο Ζ υ ω ^Z § ^{1 1} O φ Γ ') IX Ε I ^{Ε U} λ X' | X ϋ Η! G I g ¹ I to

X ο

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I ¢ 0

X ω

I to X ω

AND

X ω

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CM. χ X ω

C\)

X to X to X X X X to ω ω ω ω CM CM CM X X X to X OOOgzzzII Z Z Z I I I o O i i i i I I I uuuu

XXXXXXXXX hm O | mm нт τ mt * mm mm mm μι Πη Fh HH HM-hM wt

CDsOCOOHNOOtF

04 04 04 04 04 04 04 04 γΗΗγΗΗΗΗΗΗΗ compound Rl R2 X Q physical data number to

To to to OU OU OU OU OU OU OU OU OU OU OU OU OU OU OU OU OU OU OU OU OU OU OU OU

tO ΐζζζζ ± ω ω о ^ 1111

Ν t ΟΚ ΟΚ Ε Ο Ο Ο-H U-н---и W <<W U <W W T T T T T T T T T T T T T T

OJ t-4

PQ

LocDOcoOTOrHCMoo ^ incDtxoooor-íoqoo ^ ^ INCO-cooDOr ioqcoxjiincDt ^ ^^^^ oocno xtlinininminininiDininCDCDCDCOCOCOCOCOCDCDt ^ C ^ r ^ t ^ t ^ t ^ l ^ OO ^ bstxř c4C4CMCMCMCMC4CM <Ni (xioq (NCM (NC4CMc <io <ioqoqoqc4CMoqcMC4 (NCMC4] cqc4CMeac ^ C4] cs3 Η r r l Η I I I Η I I I I 1 1 1 1 1 1 1 1 1 1 1 1 1 — — — — — — — — —

PL (Compound R1 R2 X Q Physical Data Number

1.281 Η Η H — СОСбНз (СНз) 2 (3,5) oil

1.282 5-СНз 3-СНз H —СОСбНзС12 (3,5) T. 140-141 co o

. ·? cm cm

O o τ τ τ .г2 it .52 _H N- (i-1 μ_ (ь- ».T1-1 нч T> - <йн of ω ω о о о ~ ω ω ω т Λ ^ 4 * 44 400 14 014 ^ж

А ^Ю * 2 ^ гЧ ^Ю * Т о

ОО ^ inCDSCOOJOHOJCn ^ inCDS 00 СОСОсОСОООоООО} СПСЯСТ> СТ) СЭСЯ сч C4NCMCMCs3CM <N! O4C \! CMC4C \ l (NiOJ

г-i тЧННгИНгНтЧгНгННННгI г-1

Similarly important compounds are analogous derivatives, for example, those derived from naphthyloxynitrile and

physical data

X compound number

2.1 —CN —СН2 — CN 81-82 2.2 —CN —СН2 — СО — NH2 47-49 2.3 —CN —СН (СНз) - СэСН oil 2.4 —CN —СНг — Се = СН oil 2.5 —CN —СНг — СН = СН2 oil 2.6 —CN —СНз oil 2.7 —CN -С2Н5 oil 2.8 —CN П-СЗН7 oil 2.9 —CN —СНг — СООСНз semi-solid product 2.10 —CN —СНг — СООС2Н5 oil 2.11 —CN —СН (СНз) —СООСНз oil 2.12 —CN —СН (СНз) —СООС2Н5 oil 2.13 —CN —СН (С2Н5) —СООС2Н5 2.14 —CN —СО — СеНэ 115-118 2.15 —CN 2.16 —CN —SO2 — СНз 2.17 —CN -СН (СНз) —СОО (IS0C3H7) oil 2.18 —CN —CH (CH3) -CON (C2 H5) 2 oil 2.19 —CN —СН2 — COO (isoC3H6) n _D ²² 1.5650 2.20 —CN —CHgCO-NH — —Cl 2.21 —CN —CO — NH — СНз 2.22 —Cl —CH2 — CN viscous product 2.23 —Cl —CH2 —CO — NH2 oil 2.24 —Cl —C2H5 2.25 —Br —CH2—COOterc.C4H9 2.26 —Cl —СН (СНз) - СООСНз 2.27 —СОСНз —СНг — CN oil 2.28 —СОСНз —CH2 —CO — NH2 oil 2.29 —СОСНз —СНг — СООСНз 2.30 —СОСНз —СНг — СН — СНг X Cl Cl 2.31 —СОСНз —СНг — С ^ СН 2.32 —СОСНз —СНз oil 2.33 —СООСНз —СНг — CN oil 2.34 —СООСНз —СНг — CO-NH2 2.35 —С2Н5 —СНг — CN 2.36 —СО — NH2 —СНг — СО — ^NHz А ^С1 2.37 —СНз —СНг — СО — NH— <О / —С1 oil

2.38 —Cl —CH2 —CO — NH — W / —Cl 2.39 —CN —СНз — CH — CH — СНз 2.40 —CN —СНг — CONH — СНз

oil oil

Q ^f yz ^IKA NAL data composite number

X

2.41 —CN —CH2 — CON (CH3) 2 oil 2.42 —CN —CH2 — CONH — CH2 — CH = CH2 oil 2.43 —Cl —CH2 — CONH — CH2 — C = CH oil 2.44 —Cl —CH2 — CONH — CH3 oil 2.45 —COCH3 —CH2 — CONH — CH3 oil 2.46 —COCH3 —CH2 — CON (CH3) —C2H5 oil 2.47 —COCH3 —CH2 — CONH — CH3 oil 2.48 —COOCH3 —CH2 — COOCH3 oil 2.49 —COOCH3 —CH2 — C = CH oil 2.50 —NO2 —CH2 — CN oil 2.51 —NO; —CH2 —CO — NH2 oil 2.52 —CN —CH2CH2 —S — CH3 nD ²⁷ 1 ^, 534 2.53 —CN —CH2 —S — CH3 nD ²⁸ 1.6351

By analogy will also gain X the following groups of heterocyclic oxime derivatives; v- _z i z cx compound number Ri of II N-O-Q Q physical data 3.1 H —CN WITH —CH2 — CN T. 36 3.2 H —CN WITH —CH2 — CONH2 123 - 124 / / 156-158 3.3 H —CN WITH —CH2 — COOCH3 nD ²⁵ 1.557 3.4 H —CN WITH —CH (CH3) —COOCH3 Hd ²⁵ 1.540 3.5 5-C1 —CN WITH —CH2 — CN t 68 3.6 5-C1 —CN WITH —CH2 — CONH2 t. 158 3.7 5-CI —CN WITH —CH2 — COOC2H5 37-43 3.8 5-C1 —CN WITH —CH (CH3) —COOCH3 nD ²⁶ 1.5435 3.9 5-C1 —CN WITH —CH2 CH3 --COO (isoC3H7 3.10 5-C1 —CN WITH —CH2 — C = CH 53-70 3.11 H —CN WITH —CH2 — CH = CH2 nD ²⁵ 1.567 3.12 H —CN WITH —CH2 — COO (1SOC3H7 3.13 H —CN 3 —C2H5 3.14 H —CN 3 —CH2 —CH2 —O — CH3 3.15 H —CN 3 —CH — CN n-, 26 1.5581 3.16 H —CH3 3 —CH2 — CONH2 t .t 82-92 3.17 H —CH3 3 —CH2 — COOCH3 3.18 H —CH3 3 —CH (CH3) —COOCH3 nD ²⁵ 1.5335 3.19 H —CH3 3 —CH2 — C = CH oil 3.20 H —CH3 3 —CH2' — CH = CH2 3.21 H —CH3 3 —CH2 — COO (ISCO3H7 3.22 H —CH3 3 —C2H5 3.23 H —CH3 3 —CH2 — CH2 —O — CH3 3.24 H —CH3 3 —CH2 — CN 98 3.25 H —CH3 0 —CH2 —CO — NH2 94 3.26 H —CN 0 —CH2 — COOCH3 3.27 H —CN 0 -11C3H7 3.28 H —CN 0 —CH2 — CH = CH2 3.29 H —CN 0 —CH2 — C = CH 3.30 H —CN 0 —CH2 — CH2 —O — CH3 3.34 5-NOž —CN 0 —CH2 — CN oil

combining X Z to a physical data number

Q

3.35 5-C1 —CN 0 —CH — CN oil 3.36 H —CH3 0 —CH2 — CN oil 3.37 H —CH3 0 —CH2 —CO — NH2 oil 3.38 H —CH3 0 —CH2 — COO (iCsH7) 3.39 H -So what 0 —CHa— CN oil 3.40 H Cl 0 —CH2 — CN oil 3.41 H Cl 0 —CH2 — CONH2 oil 3.42 H Cl with —CH2 — CN oil 3.43 H Cl with -CH 2 - CONH 2 oil 3.44 4-CH3 —CH3 0 —CH (CH3) —COOCH3 3.44 / 1 H —CN with —COC2H5 3.44 / 2 H —COOC2H5 0 —CH2 — CN n _D 25 1.509 3.44 / 3 H —COOC2H5 0 —CH2CH = CH2 n _D 25 1,510

C-X

N-O-Q

compound number R4 R5 X of Q physical data 3.45 H H —CN with —CH2 — CN oil 3.46 H H —CN with —CH2 —CO — NH2 oil 3.47 H H —CN with —CH2COOCH3 3.48 H H —CN with —C2H5 3.49 H H —CN with —CO — C2H5 3.50 H H —CN with —SO2 — CH3 3.51 H H —CN with —CH2 — C = CH2 1 Cl 3.52 H H —CN with —CH — CON (C5H7) 2 solid product 3.53 2-C1 5-C1 —CN with —CH2 — CN oil 3.54 2-C1 5-C1 —CN with —CH2 —CO — NH2 oil 3.55 5-NO.2 H —CN 0 —CH2 — CN oil 3.56 H H CH3 0 —CH? —CN oil 3.58 H H —COOCH3 0 - CH2COOCH3 3.59 H H —COOCH3 0 —CH (CH3) —COOCH3 3.60 H H —NO2 0 —SO2 — CH3 3.61 H H Cl 0 —CH2 — CN oil 3.62 H H Cl 0 —CH2 —CO — NH2 oil 3.63 H H Cl 0 —CH2 — CONH — C2H5 solid product 3.64 H H Cl with —CH2 — CN oil 3.65 H H —CONH2 0 —CH2 — co — NH2 oil. 3.66 H H —C00CH3 0 —CH2COOCH3 oil

are follow! Derivatives ^{and Y} t ^if d en ce pattern ^yl ether:

Another important single group of substances manifesting their ability to influence the ^{growth of} plants and the ability to protect plants,

c-x

N-o-q compound number

4.1 —CN —CH2 — CN 4.2 —CN —CH2 —CO — NH2 4.3 —CN —CH2 — COO — CH3 4.4 —CN —CH (CH3) —COO — CH3 4.5 —CN —CH (CH5) —COO — C2H5 4.6 —CN - CH5 4.7 H —CH2 — CN 4.8 H —CH2 —CO — NH2 4.9 H —CH2 — COO — CH3 4.10 CHs —CH2 — CN 4.11 CH3 —СН (СНз) —COOCH3 4.12 C2H5 —CH2 — COOC2H5 4.13 Cl —CH2 — CN 4.14 Cl —CH2 —CO — NH2 4.15 Cl —C2H5 4.16 Cl —Ch2 — ch = ch2 4.17 NOž —CH2 — CN 4.18 NO2 —CH2 — C = CH 4.20 —CO — CH3 —CH2 — COO (isoC3H7) 4.22 —CO — CH3 —CH2 —CO — NH2 4.23 —CN —CH2 — CONH — CH3 4.24 —CO — NH2 —CH2 —CO — NH2 4.25 —CO — OCH3 —CH2 — CN 4.26 —CO — OCH3 —CH2 — COOC2H5 4.27 —CO — OCH3 —C2 — H5 4.28 —CO — OCH3 —CH2 - C = CH

Group of compounds with a high and ^PL and ^the crosslinked with ^é m Fifejdy City Hospital 6 ^{kg / hr.} · And vfce may e ^f e ^k t ^p rojevuj ^s c ^s is ovhvňovárnm RAST plants convert direction herbicidal effect and which at low applied amount M M ^{1 k} g ^{/ h} and (and ^lower m are generally tolerated by crop plants without losing the ability to regulate plant growth and plant protection properties, the following are substituted diphenyl ether derivatives of formula I:

N-O-GL

compound number R22 R23 X Q physical data

5.1 4-C1 2-C1 —CN —СН2 — СО — ΝΗ ₂ 5.2 4-C1 2-C1 —CN —СН2 — СООСНз 5.3 4-C1 2-C1 —CN —СН (СНз) СООСНз По ⁴¹ 1.5792 5.4 4-C1 2-CN —CN —СН2— СООСНз 5.5 4-C1 2-CN —CN —СН (СНз) СООСНз 5.6 4-CF3 2-C1 —CN —СН (СНз) СООСНз По ³¹ 1.5402 5.7 4-CF3 2-C1 —CN —СН2 — СООС2Н5 n _D ²⁴ 1.5422 5.8 4-NO2 H —CN —СН (СНз] СООСНз 5.9 4-C1 2-C1 —Cl —СН2 — CN 5.10 4-C1 2-C1 —Cl —СН2 — СООСНз 5.11 4-C1 2-C1 —Cl —СН (СНз) СООСНз 5.12 4-C1 2-C1 —СНз —СНг — СООСНз 5.13 4-C1 2-C1 -СНз —СН (СНз) СООСНз 5.14 4-C1 2-C1 Η —СН2— СООСНз 5.15 4-C1 2-C1 Η —СН (СНз) СООСНз 5.16 4-CF3 2-C1 Η —СНг — СООСНз По ²⁴ 1.5472 5.17 4-CF3 2-C1 Η —СН (СНз) СООСНз oil 5.18 4-C1 2-C1 —CN —CH2CN По ⁴¹ 1.599 5.19 4-CF3 2-C1 —CN —CH2CN 1.1. 110 5.20 4-CF3 2-C1 —CN —CH (CH3) CN n _D ³¹ 1.545

The compounds of the formula I can be used alone or together with the active substances whose action is to be antagonized, as well as together with suitable carriers and / or other additives.

Suitable carriers and additives may be solid or liquid and correspond to those customary in the preparation of such compositions, such as natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizer.

The active ingredient content of the formulations marketed is between 0.01 and 90 percent.

For application, the compounds of formula (I) may be present in the following forms of processing (whereby percentages by weight in brackets mean the preferred amounts of active ingredient:

solid forms of processing:

dusting, spreading (up to 10%), granules, coated granules, impregnated granules and homogeneous granules, pellets (grains) (1 to 80%);

Liquid processing:

(a) water-dispersible concentrates of the active substance:

wettable powders and pastes (25-90% in commercial packaging, 0.01-15% in ready-to-use solutions); emulsion concentrates and concentrated solutions (10 to 50%, 0.01 to 15% in directly applied solution);

b) solutions (0.1 to 20%), for example for pickling, aerosols.

The active compounds of the formula I according to the invention can be used in compositions, for example of the following composition:

Dust:

The following substances are used to obtain a) 5% and b) 2% dusts:

(a) parts by weight of parts of talc;

(b) parts of active ingredient, part of highly dispersed silicic acid, parts of talc;

The active compounds are mixed with the carriers and the mixture is ground. In this form they can be used for dusting.

Granulate:

The following substances are used to produce 5% granulate:

parts of the active substance,

0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol, parts of kaolin (particle size 0.3-0.8 mm).

The active ingredient is mixed with epichlorohydrin and the mixture is dissolved in 6 parts of acetone, followed by addition of polyethylene glycol and cetyl polyglycol ether. The solution thus obtained is sprayed onto kaolin and then the acetone is evaporated in vacuo. Such microgranules may preferably be incorporated into grooves prepared for sowing.

Wettable powder:

For preparing a) 70%, b) 40%, c) and d) 25% and e) 10% wettable powder, the following ingredients are used:

(a) parts of the active substance, parts of sodium dibutylnaphthyl sulfonate, parts of the condensation product of naphthalenesulfonic acids and phenolsulfonic acids (3: 2: 1), parts of kaolin, parts of chalk (ex Champagne);

(b) parts of active substance, parts of lignin sulphonic acid sodium, parts of dibutylnaphthalenesulphonic acid sodium, parts of diatomaceous earth;

(c) parts of the active substance,

4.5 parts of lignin sulphonic acid calcium salt,

1.9 parts of a mixture of chalk (prov. Champagne) and hydroxyethylcellulose (1: 1),

1.5 parts of sodium dibutylnaphthalenesulfonate,

19.5 parts of diatomaceous earth,

19.5 part of chalk prov. Champagne,

28.1 parts of kaolin;

(d) parts of the active substance,

2.5 parts of isooctylphenoxypolyoxyethylenethanol,

1.7 parts of chalk (prov. Champagne) and hydroxyethylcellulose (1: 1),

8.3 parts of sodium aluminum silicate,

16.5 parts of diatomaceous earth, parts of kaolin.

(e) parts of active ingredient, parts of a mixture of sodium salts of saturated sulfated fatty alcohols, parts of a naphthalenesulfonic acid-formaldehyde condensation product, parts of kaolin;

The active ingredients are thoroughly mixed in suitable mixers with additives and ground in the corresponding mills and rollers. A wettable powder of excellent wettability and suspensibility is obtained, which is diluted with water to suspensions of the desired concentration and can be used, in particular, for foliar application, seed dressing or seedlings treatment.

Emulsifiable concentrates:

The following substances were used to prepare the 25% emulsifiable concentrate:

parts of the active substance

2.5 parts of epoxidized vegetable oil 10 parts of a mixture of alkylarylsulfonate and fatty alcohol polyglycol ether, parts of dimethylformamide,

57.5 parts xylene.

Emulsions of any desired concentration, which are particularly suitable for seed dressing, can be prepared from such concentrates by diluting with water.

Examples illustrating biological activity:

The following tests were performed to determine the selective herbicidal effect of the high performance herbicidal top product of the chloroacetanilide series alone and together with the antidotes of the invention of Formula I. N- [3‘-methoxypropyl-2‘-] -2-methyl-6-ethylchloroacetanilide (substance H) served as herbicidally active compound (cf. DOS No. 2 328 340).

1) Pre-emergence application of the mixture prepared in the tank immediately before use

a) After sowing

An aqueous suspension is prepared from the herbicide (compound H) and the active compound of the formula I according to the invention (compound S) in the form of wettable powders and this suspension is applied individually or also as mixtures in an amount of 1 kg to 8 kg / ha and H: S ratios. ~ 4: 1 to 1: 4 after the sowing of various cultivated varieties of millet species of sorghum hybrids (species "Funk ^u" Dekalb "," NK 222 "DC 59") in pots or trays in the greenhouse on soil sown vessels.

Thereafter, the containers are maintained at 22-23 ° C under normal irrigation. The results were evaluated after 15 days and evaluated according to the following linear scale:

= undamaged plants (as untreated control plants) = completely dead plants up to 8 - intermediate damage.

b) Before sowing (PPI)

In the same way as in (a), soil in pots and seeding pans shall be treated with suspensions containing the active substance and immediately after that the seeds of 'Funk' millet are sown.

While Compound H used alone damages or destroys the crop plant at the indicated application rates, this effect is either completely suppressed or far suppressed in the presence of the antidote of Formula I. · In particular, it achieves this result рй ^p ou ^f APPLICATION compounds Nos. 1.1, 1.4, 1.14, 1.20 and 1.34.

2) Seed pickling (wet)

An aqueous emulsion concentrate of safener of the formula I and shaken in a bottle with ^{50 g of} seeds kuhurmho dru ^h at ^p dew. Varying concentrations of antidote is between 20 and 150 g per ^{100 kg of} seeds. KMTC ^p motto of the seeds are sown in trays and seeding usually produced ^L YM ^PU with ^b em o ^with priority ^p including ^also verifies sus H ^p enzim herbicide as defined in the paragraph. Ia). Evaluation of the result is carried out 15 days after the herbicide application according to the same evaluation.

The results show here that at low, for combating weeds, however, sufficient concentrations of the herbicide with antidotes S ensures that cultivated millet is not over ^with leather. As antidotes ^Pooh with ^B i esp ^E on compounds Nos. 1.1, 1.4, 1.14, 1.20, 1.34, 1.44, 1.70 to 1.75, 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, 1.188, 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, 1.274, 1.275 to 1.279 and others. The compounds known from U.S. Pat. No. ^3,799,757 are not effective as antithotes.

The antagonistic effect of an antidote of formula I generally does not apply to major weeds, such as hedgehogs (Echinochloa), walnuts (Setaria italica), which are damaged approximately as much as in the absence of the antidote.

The effect of the herbicide without the use of an antidote and the use of an antidote in the cultivation of wet millet seeds as described above (Example 2) is also evident from the following results:

compound number effect of herbicide without / with antidote 1.1 4/8 1.4 4/8 1.14 4/8 1.20 4/7 1.34 4/7 1.44 4/8 1.70 (oil) 4/7 1.72 (oil) 4/7 1.75 (oil) 4/7 1.78 4/8 1.88 4/9 1.91 4/8 1.98 4/8 1.103 4/7 1.108 4Π 1.125 4/9 1.126 4/8 1.139 4/7 1.173 4/8 1.174 4/7 1.177 (oil) 4/7 1.188 (oil) 4/7 1.191 4/8 1.204 4/8 1.207 4/7 1.208 4/7 1.217 4/8 1.218 4/7 1.227 4/7 1.231 4/8 1.239 4/8 1.244 (t. 111 - 113 ° C 4/7 1.253 (oil) 4/7 1.255 (oil) 4/8 1.270 (oil) 4/7 1.273 (t. 167 - 168 ° C) 4/7 1.275 (oil) 4/7 1.277 (oil) 4/7 1.278 (oil) 4/7

Explanatory notes;

- dead plants considerable damage to plants

plant damage slight plant impact = healthy plant

Similarly good antidote effects are achieved with other chloroacetanilides and thiolcarbamates as well as on other cultures such as rice, corn, wheat, cotton, soybean or sugar beet.

Increase in soybean yield:

Field with rosthnami soy ^{hole h} u "Lee 68 'with ^p-rcelam vehkosti ^and about 50 m ^{2 d} APPLICABLE Lent in the formulations of the active ingredient of the formula I, once that grew ^yd axes ^and hnou stadrn 5-6 HSTR. Used ^LeVeLs Community ^account Inn ^and TK ^e l ^y varies ^{from 500} g ha. At the time of harvest, it was found that the untreated plants were largely broken (Dolezheni), while grown on the treated plots stand unbroken and. show improved deployment of pods. On treated plots is achieved in comparison. p. untreated control parcels of 'higher' yields by about 10 'to 15%.

^{P eh} odstatn for increase ^with EN ^s .výnosů about ^12% or more was achieved in the plots that were treated with compounds .C. . 1.1, 1.3, 1.4, 1.167 or others.

Suppression of side shoots of tobacco:

Tobacco plants are grown in a greenhouse, and when the flower begins to flow, the plants are cut off. One day later, plants are sprayed with aqueous spray suspensions of active ingredients Nos. 1.106 and 1.148. The active compound concentration is 0.66 and 1.32 percent, respectively.

While untreated plants from buds axis hste developed SIM ^{e p} knockout shoots of the treated plants was tobacco R ^{u TP} ostranmc ^{h h} above one ^{To strongly p} deformation. Similar effects were also obtained using other compounds of formula I having a propargyl ether structure.

3) Seed swelling using an antidote

IR 8 rice seeds are swollen for 48 hours in 10 or 100 ppm test solution solutions. The seeds are then allowed to dry for about 2 hours until they no longer stick. Rectangular plastic pots (8X8 cm ^HEAD 1 ⁰ cm) were filled up to 2 cm below the edge of a sandy-loamy soil. Then 4 g of seeds are sown in each pot and the seeds are covered with only a very small layer of soil (about seed grain diameter). The soil is kept moist. (but not muddy) condition. Then the herbicide, i.e. N- (1-methyl-2-ethoxyethyl) -N-chloroacetyl] ethyl-6-methylaniline, is applied in the form of a dilute solution and in an amount equivalent to 1.5 kg. active substances to. 1 ha. 18 days after. The offset is evaluated by a linear scale. from 1 to 9,. wherein 1 is complete. damage (destruction) of the plant. and 9 represents the unaffected state of healthy plants.

The compounds. you ^to formula I disclosed includes at azují test ^ ntidotický good effect. Examples include:

concentration compound herbicide impact assessment number (without / with anttoot)

100 ppm ppm

3.5

1.239

3.5

1.239

2.3

2/6

2/6

2/7

2/7

2/6

4) Test in nutrient solution using an antidote applied pre-emergence

Hewitt's nutrient solution is prepared containing the following amount of herbicide as well as the amount of test antidote.

Use the seeds of cultivated plants, which b ^y in Uve ^d ených-ncentoacmh used herbicide are expected to cause damage, and come in grained zonolitu (= expanded V ^ i ^ i ^ ii ^ i ^ lit), located in flower pot made of plastic, the bottom of which is provided with holes (diameter of the pot 6 cm). The pot was put into a transparent second ^to the ^EIT N ^AC ez ^pl astic ^Ké MOTs ^h (top diameter of 7 cm pots) in which about 50 ml of a nutrient solution prepared previously with the herbicide and antidote. This nutrient solution now capillaryly captures the filler material in a smaller pot and wets the seed of the germinating plant. Daily, the loss of liquid is supplemented to 50 ml with Hewitt's nutrient solution. Three weeks after the start of the experiment, the test result is evaluated on a linear scale of 1 to 9, with 1 indicating complete damage to the plant and 9 indicating unaffected healthy plants. The control solution used in parallel does not contain an antidote.

This test uses:

1) 4 ppm of Prometryne = 2,4-bis- (isopropylamino) -6-methylthio-s-triazine in sorghum of "Funk G-522"

2) 4 ppm 4-ethylamino-6-tert-butylamino-2-chloro-2-triazine in Farnese wheat

3) 4 ppm of α- [4- (p-trifluoromethylphenoxy) -phenoxy] propionic acid n-butoxyethyl ester in barley of the "Mazurka" species

4) 5 ppm Metolachlor = N- (1-methyl-2-methoxyethyl) -N-chloroacetyl-2-ethyl-6-methylaniline in sorghum (Sorghum) of "Funk G-522" type.

Using the compounds of formula I, the following results were obtained:

test variant compound number evaluation of herbicide effect (without / with antidote)

1 5.6 2/7 1 3.1 2/5 1 3.3 2/8 1 3.7 2/6 3 3.6 3/8 4 3.5 4/7

Biological experiments under stress conditions:

A) Growth of plants at a temperature that is optimum

2 to 3 leaf rice plants are immersed for 45 minutes with roots and the bottom of the sprout in a solution containing 10 ppm (= 0.001%) of the active ingredient of formula I. Then the plants are planted in moistened soil in asbestos-cement containers of 70 XX 70 cm and instead of at 28 ° to 30 ° C are kept at only 18 to 22 ° C. After 3 days the soil in the containers is covered with a layer of water 2 to 3 cm high. After another 18 ·. days, the condition of the treated plants is compared with that of the untreated control plants.

The rice treated with the compounds of the formulas I and / or Ia has an enlarged root system by an average of 30 to 30. 50. ° / o. The compounds known from U.S. Pat. No. 3,799,757 show no such effect. ..........

B) Development of plants with slightly damaged seedlings

Rice seedlings pre-germinated in quartz sand containing nutrient solution with slightly yellowish shoots formed are immersed for 45 minutes in a solution containing 10 ppm of the active ingredient of the formula I, after which 42 plants are planted in the asbestos-cement container described in paragraph A). the plants are maintained at a normal temperature of 28-30 ° C and under normal irrigation conditions.

The final evaluation refers to the dry weight of the above-ground parts of the plant, the number of laths and the weight of the dry grain compared to the 42 plants that were appropriately germinated but not treated (control plants). The following average values were obtained from several series of experiments:

control plants treated plants increment (%) dry weight507 g number lat242 dry grain weight182 g

Compounds No. 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, 3.1 show a particularly high increment in this series of experiments. Using compounds known from U.S. Pat. No. 3,799,757

762 - 820 g 50.3 - 61.7

284 - 352 17.4 - 45.5

220 - 290 g 20.9 - 59.3 no such good results were achieved in any way.

Seeds of other crops such as corn, cereals, soybeans and cotton can be pre-treated in the same way and this treatment results in a similar treatment. yield increase.

Claims (11)

What is claimed is: 1. A plant growth promoting agent and a plant protection agent comprising as an active ingredient ^0, 01 to 90% by weight and ^L ESPO ^least one compound of formula I Ar - C - X II n - o - q (IL in which Ar represents a phenyl group of the formula α-naphthyl or a heterocyclic group of the formula X is cyano, nitro, halogen, alkylcarbonyl with 1 to ⁴ atoms in ^hlík UVA ^{plurality of projections} nominal MSTI and ^o ox ^yk arbonylovou group having 1 to 4 carbon atoms in the alkoxy part, hydrogen, aminocarbonyl having ^the u ^{pi nu, kt ER} is ^ ^ after IPA mono- or disubstituted by alkyl having 1-4 carbon atoms or an alkyl SKU ^pi comprising 1 to ⁴ carbon uhffiu, Q represents a (C1-C4) alkyl group, a (C1-C4) alkyl group interrupted by 1 or 2 oxygen or sulfur atoms; furthermore is C1-C4alkyl substituted with cyano; (C 1 -C 4) -alkyl which is substituted by a carboxylic acid ester residue; wherein the ester moiety is a moiety selected from the group consisting of C 1 -C 4 asylum, benzyl or mononitrobenzyl; furthermore represents alkyl having 1 to 4 carbon atoms which is substituted by a carboxamido, wherein the carboxamido optionally mono- or disubstituted asylum group having 1 to 4 carbon atoms and / or alkenyl group containing from 2 to 4 carbon atoms, or it ^is on and ^{if necessary ga-monosubstituted} and alknylovou group with 2-4 carbon atoms, phenyl or a mono- or dihalo-phenyl; C 2 -C 4 alkenyl is C 2 -C 4 alkynyl; alkylcarbonyl having 1. to 4 carbon atom of the Al ^alkyl MSTI b ^s benzoytovou SKU ^pi nu ,. which is optionally substituted with 1 to 5 carbon atoms 3 substituents selected from the group consisting of halogen, nitro, alkyl having 1 to 4 carbon atoms, a'koxyskupinou having 1 to 4 carbon atoms and halogen ^íkyl verifies Sapin having ^1-4 carbon ^hlík u ^u; a benzylcarbonyl group which is substituted with a halogen atom; a styrylcarbonyl group; a furoyl group; (C 1 -C 4) alkylsulfonyl; an aminosulfenyl group optionally mono- or disubstituted with (C 1 -C 4) alkyl; Ri is hydrogen, halogen, shelters Sapin having ¹ to ⁴ carbon ^y and ^o ox ^y with ^the oup having ^1-4 atom ^Y uN ^ M ^ enaZylovou group having 1 to 4 carbon atoms, nitro or para-position bound fenoxyskuplnu which optionally substituted with 1-2 substituents selected from ^Y tveгen ha ^{s l} o ^g ene and ha ^ ^ verifies enaZ group having 1 to 4 carbon atoms; R 2 is a C 1-4 alkyl or C 1-4 alkoxy group; R1 is hydrogen, halogen or nitro; R 5 represents hydrogen or halogen and Z represents an oxygen atom or a sulfur atom; provided that when Ar is unsubstituted phenyl and Q is —CH3 CN, X is nitro, halogen, C1-C4alkylcarbenyl, C1-C4alkoxycarbonyl, hydrogen, hydrogen is an aminocarbonyl group which is optionally monosubstituted or disubstituted with a (C1-C4) -alkyl or a (C1-C4) -alkyl, together with carriers and / or surfactants. 2. A composition according to claim 1, characterized in that Ппц I ^to about iičinnou skžku ^b of the U is ^H, at least one compound of formula I wherein Ar and Z have the meanings given in point 1, X is cyano, nitro, halo, ^b enyleveu alkylcarbonyl group having 1 to C4 alkyl alкoxyкarbenylevou group having 1 to 4 carbon atoms in the alkoxy ^l oic čMtJ ^b ar ^to amino he verifies ^yl ^^ n ^ of which is optionally monosubstituted or disubstituted asylum group with 1 to 4 carbon atoms, or represents alkyl C 1 -C 4; Q is Al ^alkyl alkoxycarbonyl having 1 to 4 carbon atoms; (C 1 -C 4) alkyl group interrupted by 1 or 2 oxygen atoms or ^s ; a (C 1 -C 4) alkyl group substituted with cyano; C 1 -C 4 alkyl which is substituted 223367 a carboxylic acid ester moiety wherein the ester moiety is selected from the group consisting of C 1-4 alkyl, benzyl, or mononitrobenzyl; C 1 -C 4 alkyl optionally substituted with carboxamido optionally monosubstituted or disubstituted with C 1 -C 4 alkyl and / or C 2 -C 4 alkenyl, or optionally monosubstituted with C 2 -C 4 alkynyl carbon, phenyl or mono- or dihalophenyl; (C 2 -C 4) alkenyl; (C 2 -C 4) alkynyl; (C 1 -C 4) alkylcarbonyl or animosulfonyl, which is optionally mono- or disubstituted with (C 1 -C 4) alkyl; R 1 is hydrogen, halogen, C 1 -C 4 alkyl - or phenoxy-bound in the β-position; R 2 is hydrogen, halogen or C 1 -C 4 alkyl; R 4 is hydrogen and R 5 is hydrogen. 3. A composition according to claim 1, wherein the active ingredient comprises at least one compound of formula (Ia) in which: X is cyano, nitro, halogen, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl, aminocarbonyl - which - is optionally mono- or disubstituted with C 1 -C 4 alkyl carbon; (C 1 -C 4) alkyl; Q is C1-C4alkyl substituted with cyano; a (C 1 -C 4) alkyl group which is substituted with a carboxylic acid ester moiety, the ester moiety being selected from the group consisting of C 1 -C 4 alkyl, benzyl, or mononitrobenzyl; C 1 -C 4 alkyl optionally substituted with carboxamido optionally mono- or disubstituted with C 1 -C 4 alkyl and / or C 2 -C 4 alkenyl or optionally monosubstituted with C 2 -C 4 alkynyl a carbon atom, a phenyl group or a mono or dihalophenyl group; (C 2 -C 4) alkenyl; (C 2 -C 4) alkynyl; (C 1 -C 4) alkylcarbonyl or aminosulfonyl, optionally mono- or disubstituted with (C 1 -C 4) alkyl, R1 is hydrogen, halogen, C1-C4alkyl or C1-C4alkoxy and R a represents hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy. 4. A composition according to claim 3, wherein the active ingredient comprises at least one compound of formula (Ia) wherein: X is cyano, nitro, halogen, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl or aminocarbonyl optionally mono- or disubstituted with C 1 -C 4 alkyl; Q is C1-C4alkyl substituted with cyano; (C 1 -C 4) alkyl substituted with a carboxylic acid ester moiety wherein the ester moiety is selected from the group consisting of C 1 -C 4 alkyl, benzyl, or mononitrobenzyl; C 1 -C 4 alkyl substituted with carboxamido optionally mono- or disubstituted with C 1 -C 4 alkyl and / or C 2 -C 4 alkenyl, or optionally monosubstituted with alkynyl a (C 2 -C 4) group, a phenyl group or a mono- or dihalophenyl group; or is (C 2 -C 4) alkynyl; R 1 represents hydrogen, halogen or a (C 1 -C 4) alkyl group; R 2 - represents hydrogen, halogen - or C 1 -C 4 alkyl. 5. A composition according to claim 4, wherein the active ingredient comprises at least one compound of formula (Ia) in which: X is cyano, - chloro, bromo, acetyl, propionyl -, methoxycarbonyl, ethoxycarbonyl, aminocarbonyl, N-methylaminocarbonyl, Ν, dim-dimethylaminocarbonyl, Q is cyanomethyl or cyanethyl; methoxycarbonylmethyl, ethoxycarbonylmethyl, methoxycarbonylethyl or ethoxycarbonylethyl; - (C 1 -C 2) -alkyl, - which is substituted by a carboxamido-2238В7 group, which is optionally mono- or disubstituted by (C 1 -C 4) -alkyl and / or (C 2 -C 4) -alkenyl, or optionally monosubstituted with (C 2 -C 4) alkynyl; or represents a propynyl group or a butynyl group, R 1 is hydrogen, halogen or methyl; R 2 represents hydrogen, halogen or methyl. 6. A composition according to claim 5, wherein the active ingredient comprises at least one compound of formula (Ia) wherein X is cyano and Q, R1 and R2 are as defined in point 5. 7. A composition according to claim 1, characterized in that it contains at least one compound of the general formula as active ingredient Steed Amino- (CH) _O-R R ₃ (II) wherein X is cyano, nitro, halogen, acetyl, C 1 -C 4 alkoxycarbonyl, or aminocarbonyl optionally mono- or disubstituted with C 1 -C 4 alkyl, n is 1, 2 or 3, R 9 is hydrogen or C 1 -C 3 alkyl, R 10 is an aminocarbonyl group which is optionally monosubstituted with C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl or phenyl optionally substituted with 1 or 2 halogen atoms itself ; or is cyano, with a portion of the formula - (CH) n R 9 consists of no more than 4 carbon atoms. 8. A composition according to claim 7, wherein the active ingredient comprises at least one compound of formula (III) _{-n 2} -r _1o (III) wherein: X is cyano, nitro, chloro, acetyl, C 1 -C 4 alkoxycarbonyl or aminocarbonyl, which is optionally disubstituted with C 1 -C 4 alkyl, and R 10 represents an aminocarbonyl group which is optionally monosubstituted with C 1 -C 4 alkyl or a phenyl group which is itself optionally substituted with 1 or 2 halogen atoms; or is cyano. 9. A composition according to claim 1, wherein the active ingredient is a compound of the formula no-ch ₂ -conh ₂ 10. A process according to claim 1, wherein the oxime of formula V is etherified or acylated. Ar — С — X N — OH in which (Vj, Аг and X have the meanings given in 1, or a salt thereof, by treatment with a halide of the formula Halg-Q in which Q is as defined in 1 a Halg is halogen, preferably chlorine or bromine. 11. The process of claim 10, wherein the alkali metal oxime salt of formula (V) or the ammonium salt of oxime of formula (V) is etherified by treatment with a halide of formula (I). Halg-Q where Ar, X and Q have the meanings given in any of points 4 to 9 and Halg is halogen, preferably chlorine or bromine.