DD146593A5 - PROCESS FOR PRODUCING NEW OXIMAETHERS AND ESTERS - Google Patents

Abstract

Processes for the preparation of new oxime ethers and esters of the formula I mentioned herein. These substances have various beneficial effects of plant growth stimulation, especially in the early stages of plant development. In addition, such compounds make plant-aggressive (phytotoxic) agrochemicals more plant-compatible in terms of antidote activity. Unsuitable selective herbicides can be used, for example, in the presence of such oxime derivatives for certain crops without harmful consequences for weed control.

Description

, 21.5 9

Process for the preparation of new oxime ether and ester. Field of the invention

The invention relates to a process for the preparation of new plant growth-promoting and plant-protecting oxime ether and ester. ,

Characteristic of the known technical solutions

Means for influencing the plant growth, especially for growth inhibition have been described variously; For example, chlorocholine chloride is particularly suitable for Halmy clarification and stalk stabilization on wheat. According to DT-OS 2,458,165, bis (p-chlorophenyl) acetic acid or its salts, esters, amides bzv /. their nitrile similar Halrnverkürzung effect in grain. In DT-OS 2,407,148, 2,6-disubstituted phenoxyacetic acid esters or propionic acid esters are recommended as growth regulators. However, the mode of action of these substances is unsatisfactory, especially at low application rates and concentrations. The situation is similar with p-chlorophenyldimethylacetic acid (DL-PS 113.890), as well as with the ^ -cyano-bicyclo / 2-, 2,77-heptane (PR-PS 2,256,722). As experiments have shown, their effect is very great unsatisfactory.

The arylglyoxylnitriloximes of the general formula proposed in US Pat. No. 3,799,757

C = TT-OH (X = H, Cl, Br,

Zn C = iT _:

, 18,9.1979

56 141 12

are insufficient as growth inhibitors and plant regulators: moreover, they are not stable and decompose already after a shorter time ·

There have also been proposed various substances which are capable of specifically antagonizing the harmful effect of a herbicide on the crop, i. H. to protect the crop without appreciably affecting the herbicidal action on the weeds to be controlled. Depending on its properties, such an antidote (= antidote) can be used to pretreat the seed of the cultivated plant (seed or seed dressing) or seed into the seed furrows or as a tank mixture on its own or together with the herbicide before or after emergence the plants are used. The treatment with the antidote can be done before, after or at the same time as the herbicide treatment. Preliminary treatment includes both pre-sowing cultivation (ppi) and the treatment of sown, but not overgrown, acreage. '

Thus, British Patent 1,277,557 describes the treatment of seeds or sprouts of wheat and sorghum with certain oxamic acid esters and amides from N ~ methoxymethyl-2 ', 6'-diethylchloroacetanilide (alachlor) attack. Other references (DT -OS 1 · 952'91Ο, DT-OS 2 * 245.471, FR-PS 2 · Ο21 · 611) propose antidotes for the treatment of cereals, maize and rice seeds for protection against attack by herbicidal thiocarbamates «In DT No. 1,576,676 and US Pat. No. 3,131,570, hydroxyaminoacetanilides and hydantoins are proposed for the protection of cereal seeds from carbamates such as IPG, CIPC, etc.

18.9.1979 56 141 12

In the literature, however, no class of substances has been described which, on the one hand, is able to give strong growth-stimulating impulses to plants and, on the other hand, has the ability to protect plants against aggressive agricultural chemicals in the sense of an antidote effect.

Object of the invention

It is an object of the invention to overcome this disadvantage and to provide processes for the preparation of compounds which combine both.

D olegung of the invention of the invention

In accordance with the invention, new oxime ethers and esters of general formula I are prepared

Ar-C-X (I) η

N-O-Q

In the formol I means

Ar - a phenyl radical of the formula

18.9.1979 56 141

a c <or ß-naphthyl radical, or a heterocyclic ring der'formula

X = - CN, -NOp, halogen, lower alkanoyl, a carboxylic acid radical, hydrogen, a Carbonsäureamxdrest, or Uiederalkyl,

Q = - lower alkyl which is straight-chain or branched or which may be interrupted by heteroatoms or substituted by halogens,

lower alkenyl or haloalkenyl,

lower alkynyl,

optionally substituted by halogen Cv-Cy-cycloalkyl, lower cyanoalkyl,

lower alkane carboxylic acid ester group,

lower alkanecarboxamide group,

aliphatic acyl radical,

- araliphatic cycloaliphatic or optionally subst * aromatic bezw. heterocyclic acyl radical,

- Alkylsulfonic acid or

18.9.1979 56 141 12

a sulphonic acid amide radical,

R is hydrogen, halogen, lower alkyl, lower alkoxy or a para-phenoxy radical which may be substituted twice or more by halogen, -CN, .UOp, CP-,

Rp and R ^ independently of one another hydrogen, halogen,

, Lower alkyl, haloalkyl, haloalkoxy,

R. and RJ - W _a sserstoff independently halogen, HOp, lower alkyl,

Z - oxygen or sulfur,

with the proviso that when Ar is unsubstituted phenyl and Q is -CHPCH, then X is HOp, halo, lower alkanoyl, carboxylic acid, carboxylic acid ester, hydrogen, carboxylic acid amide or haloalkyl.

Depending on the substitution of these oxime derivatives of the general formula I, products having various properties influencing plant growth are obtained which can be used as plant growth regulators or else as pesticide antidotes in general in agriculture or in special sectors of plant protection.

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

The term alkyl, alone or as part of a substituent, includes branched or unbranched C. to Cg alkyl groups; Lower alkyl means C ..- C, alkyl. Examples are methyl,

• 18.9 * 1979

56 141 12

Ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, and the higher homologues amyl, isoamyl, hexyl, heptyl, octyl together with their isomers. Analogously, alkanoyloes or cyanoalkyls contain an additional carbon atom. A lower alkanecarboxylic acid ester consists of a Hiederalkylteil with 1-4 carbon atoms, the .Carbonylgruppe and an alcoholic or phenolic radical having 1 to 8 carbon atoms. • Particularly mention should be made of ethyl acetate -CH ₂ -COOT (T = C ₁ -C ₈ -ReSt) and 1-propionic ester -CH (CH ₃ ) -COOT, where OT = lower aliphatic alcohol radical is preferred in both cases.

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

Carboxylic acid amides and sulfonic acid amides also include mono- or symmetric or unsymmetrical di-substituted amides wherein the substituents may optionally be lower alkyl, lower alkenyl, propynyl or butynyl and once a phenyl ring which may be substituted or unsubstituted as defined for R 1 / R 2.

C 1 -C ₇ cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl; cycloaliphatic radicals correspond to these ring systems, but they may also contain, depending on the possibility, one or more double bonds.

An araliphatic radical comprises an aryl group, as appropriate. according to Rp / R ^ mono- to trisubstituted phenyl, or naphthyl, fluorenyl, indanyl, the above

18.9.1979 56 141 12

Uiederalkyl or lower alkenyl is attached to the remainder of the molecule. Examples are the basic substances benzyl, phenethyl, phenylallyl and homologs.

Aromatic carboxylic acids which can form aromatic acyl radicals are derived from aromatics such as, above all, phenyl and may be substituted as defined under R0 / R3.

Heterocyclic carboxylic acids are derived from mono- or bicyclic rings containing 1 to 3 identical or different heteroatoms 0, S and N. Mention should be made of 3- to 6-, especially 5- or 6-membered heterocycles which may be saturated, partially saturated or unsaturated and optionally as defined under R, / R ₁ -. Examples that should not be limiting are:

Furan, ITitrofuran, bromofuran, methylafuran, thiophene, chlorothiophene, pyridine, 2,6-dichloropyridine, pyrimidih, pyridazine, pyrazine, pyrazine, piperidine, methylpiperidine, morpholine, thiomorpholine, tetrahydrofuran, oxazole, pyrazole, pyrrole, pyrroline, pyrrolidine, thiazole , 2,3-dihydro-4H-pyran, pyran, dioxane, 1,4-oxathi- (2) -in. /

Examples of aliphatic chains interrupted by heteroatoms are methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl, ethylthioethyl, methylaminoethyl, tert. Butylaminoethyl, alkoxyalkoxyalkyl such as methoxy-ethoxyethyl.

The compounds of the formula I are prepared by processes known per se (Organic Reactions 1953, Vol. 7, pages 343 and 373, Journal of Practical Chemistry, 66, p.353, Liebig, Ann., 25_O, 1616) by etherification or acylation an oxime of the formula V

e - 215 93 4

.18.9.1979 56 141 12

Ar-C-X (V)

Il

N-OH

or its oxime salt with a halide of the formula HalG-Q, where Ar, X and Q have the meaning given for formula I and Hal represents halogen, preferably chlorine or bromine.

The condensation of substituted ex-oximino compounds takes place during the etherification expediently in the form of their salts, especially their alkali metal or ammonium salts, as shown below in selected examples:

a) Ar - C - X + Hal - CH ₀ - CO - KH ₀ Ar - CX _ _ L L L L ^η

NO-Saiz 'NO-CH ₂ -CO-M ₂

Oximacetamides of the formula I.

b) Ar - C - X + Hal - CH - COOCH ^ Ar - C - X

it\ 3 It

N-O-salt CHo N-O-CH-COOCHo

J ι j

Oxime Cane Carbon Ester \ of Formula I

215934

c) Ar - C - X

ti

U-O-Saiz

+ Hal-CHp-CH = CHp

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Ar-C-X

It

NO-CH ₂ -CH = CH ₂

Oxime ether of the formula I.

The acylation is conveniently carried out with the free oximes of the formula V, as the following schemes show:

d) Ar -

C-X

ti

N-O-H

Acid-

Ha Io not

Ar-C-X

Il

'N-O-CO-

heterocycle

Acyloxime of the formula I.

(Cyclo)

Aliphatic, aromatic,

e) Ar -

C-X

Il

N-OH

Sulfuric acid · halide

Ar -

C-X

51

NO-SO ₂ -

(Cyclo)

Aliphat, kroniat, heterozygus

Sulfonyloxime of the formula I

(In the formula scheme above, "Hal" stands for halogen, especially Cl or Br).

Suitable solvents for obtaining the compounds of the formula I are, in principle, all representatives which behave indifferently under the conditions of the reaction. For example, hydrocarbons, but especially polar solvents such as acetonitrile, dioxane, Cellosolve, DMF, but also ketones such as Me thy la ketone, acetone, etc. Hydroxyl-containing solvents are excluded.

The temperatures are in the range of ~ 1O C to about 150 ⁰ C, preferably between 20 ° and 120 ⁰ G.

18.9.1979 • 56 141 12

As Halogenwasserstoffabspaltende agent bases such as tert. Amines (triethylamine, triethylenediamine, Piperidin.ua) used /. In some cases, a suspension of soda in the anhydrous reaction medium is sufficient.

Oximes are present in two stereoisomeric forms of the syn- and anti-forms. The compounds of the formula I mentioned under a) to e) can also be present in pure form or as mixtures in both formulas. In the context of the present description, accordingly, both stereoisomeric forms are to be understood by themselves and as mixtures in any mutual mixing ratio.

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

example \

In a 350 ml sulfonation flask, 17 g (0.1 mol) of phenylglyoxylonitrile ~ 2 ~ oxime-IT-sodium were suspended in 170 ml of acetonitrile. Thereafter, 23.8 g (0.1 mol) of chloroaceto-3,4-dichloroanilide were added, with a slight heat of reaction was noted. The suspension was stirred at reflux for 3 hours, whereby the suspension changed in appearance. After cooling to room temperature, the product salt was filtered off, washed with acetonitrile and the filtrate was evaporated under vacuum. The residue obtained was 32.3 g of crude product. Recrystallized from alcohol / water gave 20.4 g of the final product of the formula

11 - 2

1-8.9.1979 56 141 12

N ~ O-CH ₂ -CO-HH _ / V-Cl

"egg

M.p. 143 - 144 ⁰ C.

Accordingly, the product of the formula is obtained from the salt of 2,4-dimethylphenylhydroxamic acid chloride and allyl chloride as the oily substance

Cl

C = NO-CK ₂ -CH = CH ₂

Similarly, the compound is obtained from 2-thienylacetonitrile oxime sodium and chloroacetonitrile

C-CN

as an oily substance.

Example 2.

33.6 g (0.2 mol) of phenylglyoxylonitrile oxime sodium and 25 g (0.22 mol) of methyl chloroacetate were kept in 200 ml of acetonitrile for 3 hours at 60-70 ° with good stirring, the suspension was highly refined After some for a further hour was filtered off, washed with acetonitrile and evaporated in vacuo, leaving an oily residue which became solid after about 24 hours.

18.9.1979 56 1.41 12

V O

Smp ". 68-70 ° C. Recrystallised from isopropanol: mp 71-72

/ 3-c-c,

Similarly, by condensation of 4-Chlorphenylglyoxylonitriloxim sodium with o-chloropropionic acid ethyl ester.die compound of the formula

Cl - (/ \> - C - CN

ti

HO-CH-COOC ₀ H, -t 2 5

CH ₃ in 99.3% yield as an oil.

If, instead of the c-chloropropionic acid ester, the isopropyl chloroacetate is employed, the compound of the formula ## STR1 ## is obtained

Cl ^ VC -. CN mp 93-94 ⁰ C

^^ NO-CH ₂ -COO-IsOC ₃ H ₇

and when using the unsubstituted Phenylglyoxvlonitriloxims (as Na salt) the compound of formula

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/ y_C - CN Mp. 49-50 ⁰ C

TO-CH ₀ -COO-ISoCJI ,.

Example 3 Preparation of

X = J I

KO-CH ₂ -CO-HH ₂

DC-Cyanobenzy liden-amino-ox acetamide

845 β (5 moles) of the sodium salt of benzo-acetonitrile oxime are suspended in 2.5 liters of acetonitrile and, in the presence of catalytic amounts of KI, 468 g (5 moles) of chloroacetamide are slowly added with stirring. The mixture is refluxed for 12 hours, cooled and the reaction mixture in about 12 liters of water run * While the salts are dissolved, the final product precipitates in crystalline form; 882 g (= 86.8 % of theory ), mp 128-129 ⁰ C (from ethanol).

Accordingly, the compound of the formula ## STR3 ## is obtained from 3-imuranylnitromethane-oxime-sodium and methanesulfonyl chloride

C-NO ₉

11 <-

NO-SO ₂ -CH ₃

as a viscous oil, Example 4

8.0 gi (0.037 mole) of o-O-imino-1-naphthylacetonitrile sodium and 5.5 g (0.045 g) of propargyl bromide were added 4 hours in 50 ml

21 593

09/18/1979. 56 141 12

Acetonitrile heated to about 80 ⁰ C · Thereafter, the suspension was concentrated in vacuo and the residue extracted with methylene chloride "The solution was evaporated to give the compound of formula

NO-CH ₂ -C =CH

as an oil remained.

analysis For ° 15 H _Λ Ν _ο 0 H O of fei 9.6 C 4, 4 % 11 ,8th about " 76 Q $> 4, 11 gef. 76 λ Cf

If, instead of propargyl bromide, the reaction partner used is chloroacetonitrile, the compound of the formula ## STR1 ## is obtained

λ Jh-G- CT mp. 81-82 ⁰ C

UO-CH ₂ -ClT

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Example 5

0.1 Mole © ^ -OsdLmino ^ -thienylacetonitrile sodium are suspended with 0.12 mol of chloroacetamide in 150 ml of acetonitrile. It is then heated to 50-60 ° for 3 hours, during which KaCl separates, which is filtered off and washed with acetonitrile. The filtrates are concentrated in vacuo. The compound of the formula remains

NO-CH ₂ -CO-M ₂ as a light yellow oily substance.

The following tables show the temperatures in degrees Centigrade.

The following compounds can be prepared by the methods indicated above:

R ₁

C-CN

Il

N-O-Q

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verb 9 R ₁ R ₂ Q. Mp. 128-129 ° Oei No* H H -CH ₂ -CO-KH ₂ mp " 126-128 ° Oei 1.1 4-C1 H -CH ₂ -CO-HH ₂ C 71-72 ° Oei 1.2 H H -CH ₂ -COOCH ₃ Mp. 54-56 ° 60-62 ° 1.3 H H -CH ₂ -COO ₂ H ₅ Smp β 49-50 ° 1.4 H H -CH ₂ -COO (IC ₃ H ₇ ) Oei 1.5 4-CH ₃ H -CH (CH ₃ ) COOCH ₃ I smp. 93-94 ° 1.6 4-01 H- -CH ₂ -OOO (IO ₃ H ₇ ) Oei 1 *. 7 '4-Cl 2-Cl -CH ₂ -COOCH ₃ Oei 1.8 4-Cl 2-01 -CH ₂ -COOC ₂ H ₅ Oei 1.9 4-Cl 3-01 -CH ₂ -COOCH ₃ Oei 1 * 10 4-Cl 3-01 -CH ₂ -COO ₂ H ₅ 0el_ ... 1 * 11 4-01 H -CH (CH ₃ ) -COOC ₂ H ₅ mp * 78-81 ° 1.12 4-CH ₃ O- H - - - -CH ₂ -COOC ₂ H ₅ Oei -1 * 13 H H -CHp-C = CH Oei 1.14 H 2-Cl ~ ^C 2 ^H 5 Oei 1.15 4-CH ₃ H mp * 75-77 ° 1.16 4-CH ₃ O H -CH ₃ Mp. OeI 90-92 ° 1 * 17 4-CH ₃ O 4-Br ' H H -O ₂ H ₅ -CH ₂ -C =CH Sap. 118-120 ° / 0 _e 8 Torr 1.18 1.19 H , H -CH ₀ -CH-CH ₀ ² X ² Cl Cl Oei 1.20 4-Cl H -OH (O ₂ H ₅ ) -COOC ₂ H ₅ semisolid 1.21 4-01 H -CH ₂ -C =CH 1.22 4_C1 H -CH (CHO-COOCH. 1 * 23 4-CH ₃ H- ^ y * s ~ ^G 2 ^H 5 1.24 4-Cl 2-Cl -CH (CH ₃ ) -C = CH Mp. 1o25 4-Br Ή -CH ₃ 1 * 26 3-CF ₃ H -CH ₂ -COOC ₂ H ₅ · 1.2Z 3-CP ₃ H -CHp-HC = GHP 1.28 H H. -JiC ₄ H ₉ 1 * 29

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Verb. ^R 1 R ₂ Q Mp. 143-144 ° feat- 129-131 123-126 ° Ur. H H -CH ₂ -COO (ISoC ₄ H ₉ ) Mp. 88-89 ° Snipe 1.30 3-CP ₃ H -CH (CH ₃ ) -COOC ₂ H ₅ Mp. 77-79 ° Oei 68-70 ° 1.31 4 ~ no ₂ H -CH ₂ -COOCH ₃ Oei 107-109 ° 1:32 4-NO ₂ H -CH ₂ -CO-KH ₂ Oei 36-37 ° 1:33 H H -CH ₂ -CO-KH -f-S- Cl mp · firmly 1:34 H H -S0 ₂ C (CH _{3) 2} Mp. 1:35 4-Br H -CH ₂ -CN Oei 1:36 4-CH ₃ O H .- ^C 2 ^H 5 mp · 158-160 ° 1:37 H H -CH ₃ Mp. 1:38 H H - ° 2 ^H 5 97-99 ° 1:39 H H -CO ₃ H ₇ (ISO) 1:40 H H -CH (CH ₃ ) COOCH ₃ Oei 131-133 ° 1:41 H H -CH (CH ₃ ) COOC ₂ H ₅ 1:42 H H -CH (C ₂ H ₅ ) COOC ₂ H ₅ Mp. 1 * 43 H H -CH ₂ -CH ₂ -CN 1:44 H H -CH ₂ -CH ₂ -CH ₂ -CN Mp. 1:45 H H -CO-CH ₃ 1:46 3-CF ₃ K -CH ₂ -COOCH ₃ Mp. 1:47 2-CH ₃ H ~ CH _? CN 1:48 2-F H -CH ₂ -CN 1:49 2-F H -CH ₂ -COKH ₂ - Oei 1 * 50 2-CH ₃ H -CH (CH ₃ ) -COOCH ₃ 1:51 4-Cl H -CH ₂ -CO-Im - {Ι / -σι 1:52 • Cl H H -CO-O 1:53 H ₃ CoIl H . H - (CH ₂ J ₇ -CH ₃ 1 * 54 4-XIC ₄ H ₉ O H -CH ₂ -CN 1:55 4-ISoC ₃ H ₇ O H -CH ₂ -CO-NH ₂ 1:56 2r-CH ₃ H -CH ₂ -CO-M ₂ , 1:57

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Verb. 58 ^R 1 ^R 2 Q - 133-13.5 ° No. 59 3-NO ₂ H -CH ₂ -CO-NH ₂ Smp β 67-68 ° 1. 60 3-nop H -SO ₂ -CH ₃ Mp. 144-146 ° 1. 61 H H -CH ₂ -CO-CH ₃ Mp. 121-122 ° 1. 62 H H . -CH (CH ₃ ) -CO-NH ₂ Mp., 76-77 ° 1. 63 H H -SO ₂ -CH ₃ Mp. 53-54 ° 1. 64 H H -CH ₂ -COOC ₄ H ₀ (tert.) Mp. 1" 65 H , H -CH (HC ₁ QH ₂₁ ) COOC ₂ H ₅ Oei 1. 66 .H H -C (OT ₃ ) 2-COOC ₂ H ₅ 1" H H -CH (CHO) -COOCoH ₇ Oei 1.· .67. (iso) ^{3 3} ' firmly , 68 H H '- (CH ₂ ) ₁₇ -CH ₃ Oei 1" .69 H H -CH (CH ₃ ) -C = CH Oei 1" .70 H H -CH (CHO) -CON (CpHc) P 1, , 71 H H -CH ₂ -CO-JIH-CH ₃ 1, 72 H H -CH ₂ -CO-N (CH ₃ ) ₂ 1, .73 H H -CH ₀ -COl] H-CH ₀ -CH = CH. 1 .74 H H -CH ₂ -CONH-C; eCH 1 H H -CH ₂ -CON (CH ₃ ) -CH ₂ - 1 .75 -CH = CHp .76 H H -CH ₂ -CON (CH ₃ ) -C ₂ H ₅ 1 .77. H H -CH (CH ₃ ) -COM-CH ₃ 1 .78 H H -CH (CH ₃ ) -CON (CH ₃ ) ₂ firmly 178-179 ° 1 .7.9 H H -CH ₂ -CON (AllyI) ₂ Mp ·. 91-93 ° 1 .80 H H -C ₆ H ₃ (NO ₂ ) ₂ (2,4) Mp. 61-62 ° 1 • 81 H H -CH ₂ -C ₆ H ₃ Cl ₂ (3,4) Mp. 1 .82. H H -CH ₂ -COOCH ₂ -C ₆ H ₅ firmly 1 .83 H H -CH ₂ -COO-C ₆ H ₄ NO ₂ (4) 149-150 ° 1 H H -CH ₀ -CONH-CrHoCl ₀ mp * 136-137 ° 1 .84 (3 ,?) ^{6 3 2} mp * 53-55 ° · • 85 H H -CH ₂ -CNH »C ₆ H ₄ F (4) Mp. 60-62 ° 1 .86 H H -CO-C ₂ H ₅ mp " 1 H H -CH (CH ₃ ) CN 1

- "21 593

18.9.1979 56 141 12

Verb. R ₁ ^R 2 Q Oei 82-84 ° No. H H • ~ CH ^ j-CH ⁼ CH ~ CH 0 Mp. 44-46 ° 1.87 4-CH ₃ H -CH ₂ -CN Mp. 1.88 4-CH ₃ H CH ^ firmly 1o89 4-CH ₃ H -CH ₂ -COOCH ₃ firmly 1.90 4-CH ₃ H -CH ₂ -COOC ₂ H ₅ Oei 1.91 4-CH ₃ H- -CH (CH ₃ ) COOC ₂ H ₅ Oei 162-164 ° 1.92 4-CH ₃ H -CH (C ₂ H ₅ ) COOC ₂ H ₅ Mp. 1.93 4-CH ₃ H -CH ₂ -COMI-C ₆ H ₃ Cl ₂ (3,4) - Oei 1.94 4-CH ₃ H CH (CH ₃ ) -COOC ₃ H ₇ (iso) firmly 1.95 4-CH ₃ H -CH ₂ -C =CH Oei 40 ° 1.96 4-CH ₃ H -CH ₂ -CH = CH-CH ₃ Mp. 1.97. 4-CH ₃ 3-CH ₃ -CH ₂ -CU Oei 1.98 4-CH ₃ 3-CH ₃ -CH ₃ Oei about 60 ° 1.99 4-CH ₃ 3-CH ₃ - ^C 2 ^H 5 OeI smp. about 50 ° 1100 4-CH ₃ 4-CH ₃ 3-CH ₃ 3 -CH ₃ -C ₃ H ₇ (n) -CH ₂ -COOCH ₃ mp " 1,101,1102 4-CH ₃ 3-CH ₃ -CH ₂ -COOC ₂ H ₅ Oei I0IO3 4-CH ₃ 3-CH ₃ -CH (CH ₃ ) COOCH ₃ Oei 75-81 ° 1104 4-CH ₃ , 3-CH ₃ -CH (CH ₃ ) COOC ₂ H ₅ Mp. 110 ° 1105 4-CH ₃ 3-CH ₃ -CH ₂ -C =CH Mp. 1106 4-CH ₃ 3-CH ₃ -CH ₂ -COIiH-C ₆ H ₃ Cli 3,4) Oei 1107 4-CH ₃ 3-CH ₃ -CH ₂ -COM-CH ₃ OeI OeI 91-93 ° 1..10 & 4-CH ₃ 4-CH ₃ 3-CH ₃ 3 -CH ₂ -CH ₂ -COFXCH ₃ 5CHp-CH = CH ₂ -CH ₂ -COM ₂ Mp. 1,109 1,110 4-OCH ₃ H -CH ₂ -ClT Oei 122-125 ° 1111 4-OCH ₃ H -C ₃ H ₇ (Ji) Mp. 50-53 ° 1112 4-OCH ₃ H -CH ₂ -COOCH ₃ Mp. 1113 4-OCH ₃ H -CH (CH ₃ ) COOCpH ₅ Oei 1114 4-OCH ₃ H -CH (CH ₃ ) COOCH ₃ OeI firm 1115 4-OCH ₃ 4-OCH ₃ ^H , H ' ^v -CH (C ₂ H ₅ ) COOC ₂ H ₅ '-CH (CH ₃ ) C = CH, 1,116 1,117

18.9.1979 56 141 12

Verb. R ₁ R ₂ "Q" firmly No. 4-OCH ₃ H -CH ₂ -COOC ₃ H ₇ (ISo) Oei 1118 4-OCH ₃ H -CH (CH ₃ ) COOC ₃ H ₇ (ISo) Oei 1119 4-OCH ₃ H - (CH ₂ ) ₇ -CH ₃ Smp.123-126 ° 1120 4-OCH ₃ H -CH ₂ -CO-NH ₂ firmly 1121 4-0CH ₃ H -CH ₂ -C = _CH Smp.ca ". 40 ° 1 · 122 4-OCH ₃ H -CH ₂ -CH = CH ₂ Smp.128-130 ° 1123 4-OCH ₃ H -CO-C ₆ H ₅ firmly 1124 4-0CH ₃ H -CH ₂ -CH = CH-CH ₃ Smp.69-71 ° 1125 4-Cl H - CH ₂ -CN Smp.70-71 ° 1126 4-Cl H -CH ₃ Smp.39-40 ° 1 * 127 4-Cl H -C ₂ H ₅ Oei 1128 4-Cl H -C ₃ H ₇ (Ii) Smp.81-82 ° 1129 4-Cl H -CH ₂ -COOCH ₃ Smp.79-80 ° 1130 4-Cl H -CH ₂ -COOC ₂ H ₅ Oei 1131 4-Cl H -CH (CHO COOC-.H ₇ (iso) Oei 1132 4-Cl H firmly 1133 4-Cl H -CH ₂ -CH = CH ₂ Smp.165-166 ° 1134 4-Cl H -CH ₂ -COm-C ₆ H ₃ Cl ₂ (3,4) Smp.199-201 ° 1135 4-Cl H -CH ₂ -CONH-C ₆ H ₄ Br (4) Smp.187-190 ° 1136 4-Cl · H -CH ₂ -COWH-C ₆ H ₄ CP ₃ O) Smp.204-205 ° 1137 4-Cl H -CH ₂ -CONH-C ₆ H ₄ Cl (4) Smp.51-53 ° 1138 2-Cl H -CH ₂ -CN Oei 1139 2-Cl H -CH ₃ Oei 1140 2-Cl H -C ₃ H ₇ (n) Smp.126-128 ° 1141 4-Cl 2-01 -CH ₂ -CN Mp. 95-96 ° 1 * 142 4-Cl 2-Cl -CH ₃ firmly 1143 4-Cl 2-Cl Oei 1144 4-Cl 2-Cl -CH (CH ₃ ) COOCH ₃ Oei 1145 4-Cl 2-01 -CH (CH ₃ ) COOC ₂ H ^ Oei 1 * 146 4-Cl 2.-01 -CH (C ₂ H ₅ ) COOC ₂ H ₅ firmly 1147 4-Cl 2-Cl -CH ₀ -C = CH 1148

18.9.1979 56 141 12

Verb. ^R 1 ^R 2 'Q OeI ... No. 4-Cl 2-01. -CH ₂ -CH = CH-CH ₃ Smp.84-85 ° 1 · 149 4-Cl 3-Cl -CH ₃ firmly 1150 4-Cl 3-Cl -C ₂ H ₅ Oei 1151 4-Cl 3-Cl -C ₃ H ₇ Cn) firmly 1152 4-Cl 3-Cl -C ₄ H ₉ (tert.) firmly 1153 4-Cl 3-Cl -CH (CH ₃ ) COOCH ₃ Oei 1154 4-Cl 3-Cl -CH (CH ₃ ) COOC ₂ H ₅ Oei 1155 4-Cl 3-Cl -CH (C ₂ H ₅ ) COOC ₂ H ₅ Smp »9O-93 ⁰ 1156 4-Cl 3-Cl -CH ₂ -CN firmly 1o15I 4-Cl 3-Cl -CH ₂ -C =CH firmly 1158 4-Br H -C ₂ H ₅ " firmly 1o159 4-Br H - C ₃ H ₇ U) firmly 1160 4-Br H -CH ₂ -COOCH ₃ Smp.ca. 40 ° 1161 4-Br H -CH ₂ -COOC ₂ H ₅ Oei 1162 4-Br H -CH (CH ₃ ) COOCH ₃ Oei 1163 4-Br H -CH (CH ₃ ) COOC ₂ H ₅ Oei 1164 4-Br H -CH (C ₂ H ₅ ) COOC ₂ H ₅ Smp.90-92 ° 1165 4-Br H -CH ₂ -CH = CH ₂ Smp.147-149 ° 1166 4-Br H -CH ₂ -CO-NH ₂ Smp.ca. 50 ° 1167 4-Br H -CH (CH ₃ ) -C = CH firmly 1168 4-Br H -CH ₂ -COOC ₃ H ₇ (ISo) Oei 1169 4-Br H -CH (CH ₃ ) -COOC ₃ H ₇ (iso) Oei 1170 4-Br H -CH ₂ -CH = CH-CH ₃ Mp, 152-155 ° 1 * 171 4-Br H -CH ₉ -CONH-CrH ^ Cl ₀ (3,4) 1172

Analogously, the following compounds of the formula

18.9 * 1979

56 141 12

N-O-Q

receive;

verbe R ₁ 2 H Q Oei Oei No. 1 H Oei 1173 H- H -CH ₂ -CN Oei 1,174 H H -CH ₂ -CO-NH ₂ 1175 4-Cl H -CH ₂ -CO-NH ₂ 1176 H H -CH ₂ -COOCH ₃ 1171 H H -CH ₂ -COOC ₂ H ₅ 1178 H H -CH ₂ -COOd-C ₃ H ₇ ) 1.17.9 4-CH ₃ 2-Cl -CH (CH ₃ ) COOCH ₃ 1180 4-C1 2-Cl -CH ₂ -COOd-C ₃ H ₇ ) 1181 4-Cl 3-Cl -CH ₂ -COOCH ₃ - 1182 4-Cl 3-Cl -CH ₂ -COOC ₂ H ₅ 1183 4-Cl H -CH ₂ -COOCH ₃ 1184 4-Cl H -CH ₂ -COOC ₂ H ₅ 1185 4-Cl H -CH (CH ₃ ) -COOC ₂ H ₅ Oei 1186 4-CH ₃ O- H -CH ₂ -COOC ₂ H ₅ 1187 H H -CH ₂ -C =CH 1188 H H -CHp-CON (CHO) ρ 1189 4-CH ₃ H Oei 1190 4-CH ₃ O H -CH ₃ 1191 H H -CH ₂ -CONHC = CH Oei 1 * 192 4-Br H -CH ₂ -C =CH -CHp-CON (CH -,) - CHp-CH = CHp OeI 1193 H H -CH ₂ -CON (CH ₃ ) -C ₂ H ₅ * ° ν rip-Vz = On. 1194 H 2-01 -CH (O) -C = CH 1195 4-Cl H 1196 4-Cl H • -CH ₂ -HC-CH ₂ 1.19.7 3-CF. H -Ch ₂ -CONH-CH ₂ -CH = CH ₂ 1198 1199 H

18.9.1979 56 141 12

Verb. ^R 1 R ₂ H Q- Oei No* H Oei 1200 3-CP ₃ H H - Oil V. Oil λ 7-O VjvJIj ptl j- Oei 1201 4-NO ₂ H 4-CH ₃ -CH ₂ -CO-NH ₂ firmly 1202 H H -CH ₂ -CO-NH- ^) 1203 4-Cl H -CH (CH ₃ ) -COOCH ₃ 1204 4-NO ₂ H -CH ₂ COOCH ₃ 'OeI 1205 H H -CO-CH ₂ -NH ₂ Oei 1206 3-CP ₃ 5-CP ₃ -CH ₂ -COOCH ₃ Oei 1207 2-CH ₃ H -CH ₂ -CN 1208 2-P H -CH ₂ -CN Oei 1 * 209 2-P H -CH ₂ -CONH ₂ Oei 1210 2-CH ₃ H -CH (CH ₃ ) -COOCH ₃ Oei 1211 4-11C ₄ H ₉ O H -CH ₂ -CN Oei 1212 4-1SoC ₃ H ₇ OH -CH ₂ -CO-NH ₂ 1213 2-CH ₃ -CH ₂ -CO-NH ₂ 1214 3-NO ₂ -CH ₂ -CO-BH ₂ 1215 3-NO ₂ -SO ₂ -CH ₃ 1216 2-ClI ₃ -CH ₂ -CH = CH ₂

The following compounds are analogous to the Pormel

receive:

18.9 * 1979 56 141 12

Verb «no. Y R ₂ X Q. Oei 1.21.7 H H -COCH ₃ -CH ₂ -CN OeI. 1218 H - H -COCH ₃ -CH ₂ -CO-NH ₂ Oei 1219 H H -COCH ₃ -CH ₂ -COOCH ₃ 1220 H H -COCH ₃ -CH (CH ₃ ) -COOCH ₃ 1221 4-Cl H -COCH ₃ -CH ₂ -CN 1222 4-CH-, 2-CH -COCH ₃ -CH ₂ -CN 1223 H -COCH ₃ -CH ₂ -CO-M ₂ 1 * 224 4-Cl 2-NO ₂ -COCH ₃ -CH ₂ -COOCH ₃ 1225 H H -COCH ₃ -C ₂ H ₅ 1226 ' H H -COCH ₃ -CH ₂ -CH = CH ₂ Oei 1227 H H- -COOC ₂ H ₅ -CH ₂ -CN 1228 H H -COOC ₂ H ₅ -CH ₂ -C =CH 1229 H H -COOC ₂ H ₅ -CH ₂ -CO-M ₂ 1230 H H -COOC ₀ H ₁ - -CH ₂ -CO-N (CH ₃ ) ₂ Oei 1 * 231 H H -COOC ₂ H ₅ -CH ₃ Oei 1232 H H NO ₂ -CH ₂ -CN Oei 1233 H H NO ₂ -CH ₂ -CONH ₂ 1234 H H NO ₂ -CH ₂ -CONH-C ₃ H ₇ (Ji) 1235 H H NO ₂ -SO ₂ - (O) -CH ₃ 1236 H H NO ₂ -CH ₂ -SO ₂ NCCH ₃ ) ₂ 1237 H H NO ₂ -CH ₂ -COOC ₂ H ₅ 1238 H H NO ₂ -CH (CH ₃ ) -COOCH ₃ Oei 1239 H H -CO-MCH ₃ -CH ₂ -CN 1240 H H -CO-MCH ₃ -CH ₂ -CO-MCH ₃ 1241 H H -CO-IiCH ₃ -CH ₃ Oei 1242 H H -CO-NHCH ₃ -CH ₂ -C =CH 1243 H H -CH ₃ -CH ₂ -CN Oei 1244 H H -CH ₃ -CH ₀ -CO-M ₀ 1245 H H -CH ₃ -CH ₀ -COOCHo 1246 H H -CH ₃ j-j 1 * 247 H H -CH ₃ -CH ₂ -CO-IIH-CH,

• 1-8.9.1979 56 141 12

Verb. ^R 1 H d H X Q No. I H H 1248 H H -CH ₃ -CH ₂ -CONH-CH ₂ C = CH 1249 2-F H -CH ₃ -CH ₂ -COIiH-CH ₂ -CH = CH ₂ 1250 2-CHO 5-CH ₃ -CH ₃ -CHp-CH = CHp 1251 H H -CH ₃ -CH ₂ -COOC ₂ H ₅ 1252 3 ~ N0 ₂ ^? H -CH ₃ -CH ₂ -CH ₂ -O-CH ₃ 1253 H H -COOCH ₃ -CH ₂ -CN 1254 H H -COOCH ₃ -CH ₂ -COOCH ₃ 1255 H H -COOCH ₃ -CH ₂ -CO-NH ₂ 1256 H H -COOCH ₃ -CH ₃ 1257 H H -COOCH ₃ -JiC ₅ H _{1 r} 1258 H 2-Cl -COOCH ₃ -CH ₂ -CON (AllyI) ₂ 1259 4-Cl 3-Cl -COOCH ₃ -CH (CH ₃ ) -COOCH ₃ 1260 2-C1 2-NO ₂ -COOCH ₃ -CH ₂ -CN 1261 2-Cl 2-NO ₂ -COOCH ₃ -CH ₂ -COOCH ₃ 1262 H H -COOCH ₃ -CH ₂ -CN 1263 H H -COOCHo -CH ₂ -CN 1264 H H H -CH ₂ -CN 1265 H H H -CH ₂ -COIlH ₂ 1266 H H -CO-CH ₂ C = CH -CH ₂ -C =CH 1.26.7 H H -CO-CH ₂ C = CH -CH ₂ -CN 1268 H H -CO-CH ₂ C = CH -CH ₂ -CO-IIH ₂ 1269 H H -C0-CH _? C = CH -CH ₂ -CO-ITHCH ₃ 1270 H H -CO-CH ₂ C _- = CH -CH ₂ -CH = CH ₂ 1271 H H -CO-CH ₂ C = CH -CH ₃ 1272 H H -CO-NH ₂ -CH ₂ -CN 1273 H -CO-NH ₂ -CH ₂ -CO-Im ₂ 1274 H H br -CH ₂ -CN 1275 H H br -CH ₂ -CO-NH ₂ 1276 H H Cl -CH ₂ -CH ₂ -CN 1277. H H -COCH ₃ -CH ₂ -CH ₂ -CN 1 * 278 -COOCH ₃ -CH ₂ -CH ₂ -CN 1279 -CONH ₂ -CH ₂ -CH ₂ -CN

18.9.1979 56 141 12

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

W-O-Q

Verb· X Q -CH ₂ -CN Mp. 81-82 ° No. CN -CH ₂ -C0_NH ₂ semisolid 2.1 CN -CH (CH ₁ ) -C = CH Oei 2.2 CN Oei 2.3 CN -CH ₂ -CH = CH ₂ Oei 2.4 CN CH ^ Oei 2.5 CN Oei 2.6 CN nC ₃ H ₇ Oei 2.7 CN , -CH ₂ -COOCH ₃ semisolid 2.8 CN -CH ₂ -COOC ₂ H ₅ Oei 2.9 "CN -CH (CH ₃ ) -COOCH ₃ Oei 2.10 CN -CH (CH) -COOC ₂ H ₅ Oei 2.11 CN -CH (C ₃ H ₅₎ -C00C ₂ H ₅ 2.12 CN -CO-C ₆ H ₅ Mp. 115-118 ° 2.13 CN -SO ₂ - (O) -Cl 2,14 - CN -SO ₉ -CH ₃ 2.15 CN -CH (CH-O-COO (ISoC ₃ H ₇ ) Oei 2 * 16 -CN. -CH (CH ₃ ) -CON (C ₂ H ₅ ) ₂ Oei 2.17 CN -CH ₂ -COO (X ₃ OC ₃ H ₇ J Oei 2.18 CN 2.19

18 * 9o1979 56 141 12

Verb. X Q Cl viscous No. -CH ₂ -CO-NH - ^ 0 / -Cl Oei CN -CO-IJH-CH ₃ 2.20 CN -CH ₂ -CN 2.21 -Cl -CH ₂ -CO-NH ₂ 2.22 -Cl -C ₂ H ₅ Oei 2.23 -Cl -C -COOtertoC Hg Oei 2.24 Br -CH (CH ₃ ) ~ COOCH ₃ 2.25 -Cl -CH ₂ -CN 2.26 -COCH ₃ -CH ₂ -CO-NH ₂ 2.27 -COCH ₃ -CH ₂ -COOCTI ₃ . 2.28 -COCH ₃ -CH ₀ -CH-CH ₀ 2 χ 2 Oei 2.29 -COCH ₃ Cl Cl Oei 200 -CH ₀ -C = CH -COCH ₃ -CH ₃ 2.31 -COCH ₃ -CH ₂ -CN 2:32 -COOCH ₃ -CH ₂ -CO-NH ₂ Oei 2:33 -COOCH ₃ -CH ₂ -CN 2:34 -C ₂ H ₅ -CH ₀ -CO-NH ₀ 2 2 _cl Oei 2:35 -CO-NH ₂ -CH ₂ -CO-NH - (c ^ -Cl Oei 2:36 -CH ₃ -CH ₂ -CO-M - (E)? C1 Oei 2:37 -Cl -CHp-CH = CH-CH ^ Oei 2:38 CN Oei 2O9 CN -CH ₂ -CNO (CH ₃ ) ₂ Oei 2:40 CN -CH ₂ -CONH-CH ₂ -Ch = CH ₂ Oei 2:41 CN -CH ₂ -COIiH-CH ₂ -C =CH Oei 2:42 -Cl -CH ₂ -CONH-CH ^ Oei 2:43 -Cl -CH ₂ -CONH-CH ₃ 2:44 -COCH ₃ -CH ₂ -CON (CH ₃ ) -C ₂ H ₅ 2:45 -COCH ₃ -CH ₂ -COm-CH ₃ 2:46 -COOCH ₃ 2:47

18.9.1979 56 1.41 12

Verb" X Q Oei Mr · -COOCH ₃ -CH ₂ -COOCH ₃ Oei 2 * 48 -C00CH ₃ -CH ₂ -C =CH Oei 2:49 NO ₂ -CH ₂ -CU Oei 2 · 5Ο -M) ₂ -CHp-CO-Mp * Cm <- 2:51

Analogously, the following groups of heterocyclic oxime derivatives are also obtained *

 α - χ

If

N-O-Q.

Verb. ^R 4 X Z Q Oei -CH (CH,) - COO (isoC, H ₇ ) No * H CN S - -CH ₂ -CN 3 "1 H CN S -CH ₂ -COM ₂ -CH ₂ -CH = CH ₂ 3 * 2 H CN S. -CH ₂ -COOCH ₃ -CHp ~ C00 (i3oC., H ₇ ) 3.3 H CN S -CH (CH ₃ ) -COOCH ₃ - ° 2 ^H 5 3.4 5-Cl • -CN S -CH ₂ -CN -CH ₂ -CH ₂ -O-CH ₃ 3.5 5-Cl CN S -CH ₂ -COM ₂ -CH ₂ -CN 3.6 5-Cl CN S -CH ₂ -COOC ₂ H ₅ -CH ₂ -COM ₂ 3.7 5-Cl CN S -CH (CH ₃ ) -COOCH ₃ -CH ₂ -CGOGH ₃ . 3.8 5-Cl CN S 3.9 5-Cl CN S 3.10 H CN S 3 * 11 H CN S 3.12 H CN S 3.13 H · CN S 3 * 14 K -CK ₃ S 3.15 H- -CH ₃ S 3.16 H -CH ₃ S 3.17

18.9.1979 56 141 12

Verb. ^R 4 X Z Q Oei Oei No.. H -CH ₃ S -CH (CH ₃ ) -COOCH ₃ firmly 3.18 H -CH ₃ S -CH ₂ -C =CH 3.19 H -CH ₃ S -CH ₂ -CH = CH ₂ Oei 3.20 H -CH ₃ S '-CH ₂ -COO (ISoC-H ₇ ) Oei 3.21 H CH, S -C ₂ H ₅ Oei Oei 3.22 H S -CH ₂ -CH ₂ -O-CH ₃ viscous Oei 3.23 H CN 0 -CH ₂ -CN 3.24 H CN 0 -CH ₂ -CO-NH ₂ Oei 3.25 H CN 0 -CHp-COOCH, Oei 3.26 H CN 0 "JtIv 0 ^ ¹ V Oei 3.2Z H CN 0 PIT All HVt -WIp "" ν »n = unp Oei 3.28 H CN 0 -CH ₂ -C-CH Oei 3.29 H - CN 0 -CH ₂ -CH ₂ -O-CH ₃ 3.30 H CN 0 -CO-NH-CH ₃ 3.31 H CN 0 -CO-NH-CHp-C = CH 3:32 H CN 0 -CO-NH - <^ 5-Cl 3:33 5-NO ₂ CN 0 -CH ₂ -CN 3:34 5-Cl CN 0 -CH ₉ -CN 3:35 H -CH ₃ 0 -CH ₂ -CN 3:36 H -CH ₃ 0 -CH ₂ -CO-NH ₂ 3:37 H -CH ₃ 0 -CH ₂ -COO (IC ₃ H ₇ ) 3:38 H NO ₂ 0 -CH ₂ -CN 3:39 H Cl 0 -CH ₂ -CN 3:40 H Cl 0 -CH ₂ -CONH ₂ 3.41- H Cl S -CH ₂ -CN 3:42 H Cl S -CH ₂ -COm ₂ 3:43 4-CH ₃ -CH ₃ 0 -CH (CH ₃ ) -COOCH ₃ 3:44

C »ι

H-O-Q

18.9.1979 56 141

Verb * no, Λ ^R 5 X Z Q Cl Oei 3:45 H H CN S -CH ₂ -CN -CO-NH - / "X-Cl Oei 3:46 H H CN S -CH ₂ -CO-NH ₂ -CH ₂ -COOCH ₃ 3:41 H H CN S -CHp-COOCH-. G * J -CH (CH ₃ ) -COOCH ₃ 3:48 H Ή CN S - ^C 2 ^H 5 -SO ₂ -CH ₃ 3:49 H H CN S -CO-C ₂ H ₅ -CH ₂ -CN. 3:50 H H CN S -SO ₉ -CH- -CH ₂ -CO-NH ₂ 3 * 51 H H CN S "" 2 i ~ 2 -CH ₂ -COM-C ₂ H ₅ Cl -CH ₂ -CN firmly 3 * 52 H H CN S -CH ₂ -CON (C ₃ H ₇ ) ₂ -CH ₂ -CO-NH ₂ -CH ₂ -COOCH ₃ Oei 3:53 2_C1 5-Cl CN S -CH ₂ -CN Oei 3:54 2-Cl 5-C1 CN S -CH ₂ -CO-M ₂ Oei 3:55 5-NO ₂ H CN O -CH ₂ -CH Oei 3:56 H H / ΊΤΤ ViI Q O -CH ₂ -CN firmly 3:57 H H CH ₃ O 3:58 H H -COCH- O 3:59 H .H -cochI O 3 # 6Ο H H NO ₂ O Oei 3 * 61 H H φ Cl O Oei 3.62 H H Cl O firmly 3.63 H H . Cl O Oei 3.64 H H Cl S OeI OeI 3 * 65 3.66 H H H φ H -COM. -COOCH i O. 3 °

Another important single group with plant growth-influencing and plant-protective action is that of the following diphenyl ether derivatives of the formula:

18.9.1979 56 141 12

C-X η

H-O-Q

Verb. X Q Kr. CN -CH ₂ -CN 4.1 CN -CH ₂ -CO-NH ₂ 4.2 CN -CH ₂ -COO-CH ₃ 4.3 CN -CH (CH ₃ ) -COO-CH ₃ 4.4 CN -CH (CH ₃ ) -COO-C ₂ H ₅ 4.5 CN -CH ₃ 4.6 H -CH ₂ -CN 4.7 H -CH ₂ -CO-NH ₂ 4.8 H -CH ₂ -COO-CH ₃ 4.9 CH ₃ -CH ₂ -CN 4.10 CH ₃ -CK (CHO) -COOCH. ? -5 ν 4.11 C ₂ H -CH ₂ -COOC ₂ H ₅ 4.12 Cl -CH ₂ -CN 4.13 Cl -CH ₂ -CO-NH ₂ 4.14 Cl - ° 2 ^H 5 4.15 Cl -CH ^ j-CH = CHp 4.16 NO ₂ -CH ₂ -CN 4.17 NO ₂ -ΟΗλ-C-CH 4.18 NO ₂ -CO-NH-CH ₃ 4.19 -CO-CH ₃ -CH ₀ -COO (ISoCoH ₇ ), CF ^ ⁷ 4.20 -CO-CH ₃ -CO-NH- / q \ 4.21 -CO-CH ₃ -CH ₂ -CO-NH ₂ 4.22 CN -CH ₂ -CONH-CH ₃ 4.23 -CO-NH ₂ -CH ₂ -CO-NH ₂ 4.24 -CO-OCH ₃ -CH ₂ -CN 4.25 -CO-OCH ₃ -CH ₂ -CCOC ₂ H ₅ 4.26

18.9.1979 56 141 12

Verb no. X Q 4.27 .. 4 · 28 -CO-OCH ₃ -CO-OCH ₃ -C ₂ H ₅ -CH ₂ -C =CH

A Yerbindungsgruppe that can shift at high rates of 6 kg / ha and more the Pflanzenwuchsbeeinflusaenden effect in the direction of herbicidal.Wirkung, at low application rates of 1 kg / ha (and below), however, completely culturally tolerant, without their plant growth-regulating and plant growth-protecting properties is the one of the following substituted diphenyl ether derivatives of formula I:

N-O-Q

Verb no. « ^R 22 ^R 23 X Q 5 * 1 4-Cl 2-Cl CN -CH ₂ -CO-NH ₂ 5.2 4-Cl 2-01 CN -CH ₂ -COOCH ₃ 5 ··. 3 4-Cl 2-Cl CN -CH (CH ₃ ) -COOCH ₃ 5.4 4-Cl 2-CN CN -CH ₂ -COOCH ₃ 5.5 4-Cl 2-CH - CN -CH (CH ₃ ) -COOCH ₃ 5.6 4-CP ₃ 2-Cl CN -CH (CH ₃ ) -COOCH ₃ 5.7. 5.8 4-CP ₃ 4-NO ₂ 2-Cl H -CN -CN -CH ₂ -COOC ₂ H ₅ -CH (CH ₃ ) -COOCH ₃ 5.9 4-Cl 2-Cl -Cl -CH ₂ -CN 5.10 4-Cl 2-Cl -Cl -CH ₂ -COOCH ₃ 5.1.1 4-Cl 2-Cl -Cl -CH (CH ₃ ) -COOCH ₃

215934

 y ^R 23 X , 18.9.1979 i Q ' 2-Cl -CH ₃ 56 141 12 -CH ₂ -COOCH ₃ * Verb.Nr. ^R 22 2-Cl CH, -CH (CH ₃ ) -COOCH ₃ 5.12 4-Cl 2-Cl H -CH ₂ -COOCH ₃ 5.13 4-Cl 2-01 H -CH (CH ₃ ) -COOCH ₃ 5.14 4-Cl 2-Cl H -CH ₂ -COOCH ₃ 5 * 15 4-Cl 2-Cl H -CH (CH ₃ ) -COOCH ₃ ) 5.16 4-CP ₃ 5.17 4-CP ₃

It has been found that oxime ethers and oxime esters of the formula I have extraordinarily advantageous properties for the promotion of plant growth in practice, without producing adverse effects on the plants thus treated. Active ingredients of the formula I possess, in particular at low dosages, the ability to stimulate both the germinating seeds and the further developing young plants. This leads at certain doses to a significantly increased root system, to an increased photosynthesis rate and to a faster development of aerial plant parts. However, the effect of the oximes of the formula I is not limited to the early stage of plant development, but can also be applied later or at par-. observed on certain plant parts (seed pickling, seed swelling, root canal treatment, shoot treatment, foliar application). This technique results in faster growth of the treated plant, improved fruit set, an earlier ripening and harvesting time and an increased or otherwise improved crop yield. The application of the active ingredients can in principle be carried out on the plant, on plant parts, on the seed or in the soil and corresponds to customary application or pickling technique. Another very important advantage is the improvement of the competitive power of the plant thus treated compared to the non-growth-stimulated weed flora. However, in such a case, the application of the active ingredient of the formula I to the seed or the seedlings of the

34 - O 1 ζ Ο % A

18.9.1979 56 141 12

v / Loggerhead crops and do not take place on the acreage. A third important advantage due to the significantly increased root system of such a treated plant is the possibility of obtaining a satisfactory development of the plant culture and sufficient crop yield even under less favorable environmental conditions. Examples of such environmentally unfavorable disruptive factors include: poor soil, dryness, low temperatures during the youth development of the plant, short-term cheers, reduced solar radiation due to unfavorable seasons or unfavorable location.

Oxime ethers and esters of the formula I, however, to a greater extent have plant regulatory properties, depending on the time of application and the nature of the plant.

Various other possible uses of the oximes of the formula I are enumerated below, which, however, do not represent a limitation:

- Use for improved leaf formation in crops such as tobacco, cabbage or lettuce and avoidance of unwelcome Geiztriebe.

- Use to increase yield in legume crops (eg in peas, beans, soy and peanut) by promoting generative growth (increase tillering).

- Use to increase the stability of storage-prone crops such as cereals (preventing the kneeling of plants under adverse weather conditions such as storms or continuous rain).

09/18/1979

* "'.' 56 141 12

- Use for harvest relief of fruits by promoting the formation of separating tissue between 'fruit and shoot part of the plants.

- Use to increase the storage capacity of plant ingredients (sugars, proteins, oils, etc.) or to temporarily keep the once stored.

The storage capacity of phytochemicals includes the possibility of preserving once stored longer than under natural conditions. For example, the shelf life of potatoes can be increased. Furthermore, the sugar content in sugar cane can be kept constant shortly before harvest by application of certain oxime ethers of the formula I, thus counteracting the plant's endeavor for further sidestring formation at the expense of the sugar content.

Surprisingly, oximes of the formula I have another very important property. They are excellent, crops such as millet, rice, corn, cereals (stains, rye, barley, oats), cotton, sugar beets, sugar cane, soy, etc. from the attack of plant-aggressive agrochemicals, especially herbicides of various classes, such as triazines, phenylurea derivatives , Carbamates, thiolearbamates, haloacetanilides, halophenoxyacetic acid esters, subst. Phenoxyphenoxyacetic acid ester and propionic acid ester, subst. Protect pyridineoxyphenoxy-acetic acid esters and propionic acid esters, benzoic acid derivatives, etc., provided that they do not act or not sufficiently selective, so in addition to the weeds to be controlled and the crops damage more or less. The invention also relates to compositions, - which oxime ethers of the formula I together with biological

36 -215

.18.9.1979 56 141 12

acting additives, such as herbicides, fungicides or insecticides.

Particular mention should be made of those compounds of the formula I in which Ar has the meaning indicated and the other substituents have the following meanings:

X »cyano, nitro, halogen, mederalkanoyl, a carboxylic acid ester radical of a lower aliphatic alcohol, a carboxylic acid amide radical or alkylalcohol,

Q is lower alkyl which is straight-chain or branched or which may be interrupted by a heteroatom or substituted by halogen,

lower alkenyl,

lower alkynyl,

lower cyanoalkyl,

lower alkane carboxylic acid ester group,

lower alkanecarboxamide group,

lower aliphatic acyl radical,

- Cycloaliphatic acyl radical having 4 to 6 carbon atoms, or

an unsubstituted or by a lower aliphatic radical mono- or disubstituted sulfonic acid amide,

R ₁ '= s-hydrogen or a para-phenoxy radical,

R ^ - independently of one another hydrogen, halogen or

Mederalkyl, '

R / and

R ₁ - - hydrogen,

18.9.1979 56 141

Zs - oxygen or sulfur. ί

Among these, compounds of the formula Ia are preferred

^R 3 - ^ p / - S - ^x

N-O-Q in which the substituents have the following meanings:

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

Q = - lower straight-chain alkyl chain interrupted by oxygen,

lower alkenyl,

lower alkynyl,

lower cyanoalkyl,

lower alkane carboxylic acid ester group,

lower alkanecarboxamide group,

lower aliphatic acyl radical,

unsubstituted or by a lower aliphatic radical ein¬. or twice substituted sulfonic acid amide,

R = hydrogen,

R s - hydrogen, halogen, lower alkyl or Ni ederalkoxy,

R-a = - hydrogen, halogen, lower alkyl or

18.9.1979 56 141

Lower.

Particular preference is given from the latter group to those compounds in which the substituents of the formula Ia have the following meanings:

X = cyano, nitro, halogen, lower alkanoyl, a carboxylic acid ester radical of a lower alkanol, a carboxylic acid amide radical,

Q = lower alkynyl,

lower cyanoalkyl,

lower alkane carboxylic acid ester group,

lower alkanecarboxamide group,

R ₁ = - hydrogen,

R ₂ = - hydrogen, halogen or lower alkyl, R, = - hydrogen, halogen or Ni ed er alkyl ..

Within the latter group, in a narrower sense, those compounds are preferred in which the substituents of the formula Ia have the following meanings:

X = - cyano, chlorine, bromine, acetyl, propionyl, -COOCH ₃ , -COOC ₂ H ₅ , -CO-NH ₂ , -CO-NHCH ₃ , -CO-NCCHO ₂ ,

Q = - propynyl or butynyl,

- Cyanomethyl or cyanäthyl, '...'.

- methoxycarbonylmethyl, xthoxycarbonylmethyl, methoxycarbonylathy1, ethoxycarbonylethyl,

- 39 - 2.15 93 4

18.9.1979 .56 141 12

an acetamide or propionamide radical optionally substituted by one or two lower aliphatic groups on the atom;

R ₁ = hydrogen,

Rp = hydrogen, halogen or methyl, R = hydrogen, halogen or methyl.

Among them, those are an important subgroup in which X represents a cyano group.

Another preferred range of plant-promoting and plant-protecting active substances of the formula I is that encompassed by the formula II:

wherein

R 1, R p and R independently of one another are hydrogen, halogen, NO ₂ , lower alkyl, halogenoalkyl, lower alkoxy,

X = '-. --CN, NO ₂ , halogen, the acetyl group, one

Carboxylic ester residue of a low acid phosphate. :

Alcohol or a carboxylic acid amide mean while

η is 1, 2 or 3,

18.9.1979 56 141

Rq represents hydrogen or lower alkyl,

-COHH ₂ , -CO-NH-lower aliphato radical), -CO-NH-cycloalkyl, -COHH- (CgIk _1n ) (halogen, lower alkyl) _m

or -CN, and m represents an integer 0, 1, 2 or 3 «

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

(III)

NO-CH ₂ -R ₁₀

X ¹ -CN, NOp, chlorine, acetyl, lower alkoxycarbonyl,

Allyloxycarbonyl, carbamoyl or di-lower alkylcarbamoyl, and

R _{10 is} -CN, -CO-NH ₂ , -CO-NH-lower alkyl or

-COTM (CAIr _m ) (Cl, Br, CH ,,), and

m is an integer 0, 1 or 2 »

Among the preferred individual compounds:

- C <-Cyanobenzylidene-amino-oxacetamide of the formula

41 - '21 593 4

18.9.1979 56 141 12

NO-CH ₂ -CO-NH ₂ ... '

- oc-cyanobenzylidene-amino-oxyessigsäureäthylester (Verb.

1/4)

- o <- (cyanoethyl 3-imino) benzacetonitrile 1 (Compound 1.44)

Effective chloroacetanilides, some of which are based on crops such as cereals, rice, refined sorghum millet, and the like. a. are not sufficiently tolerant, but spare in conjunction with the oxime ethers of the formula I present invention such crops without losing their other weed effect, are, for. See, for example, U.S. Patents 3,547,620, 3,403,994, 3,442,945, 3,637,847, 3,598,859, 3,819,661, 3,946,045, 3,983,174, and DT-OS Ur. 2,212,268, 2,305,495, 2,328,340, 2,402,983, 2,405,183 and 2,405,47? known.

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

^R 13 ^R 11

(IV)

CO-CH ₂ Cl

used in which

lower alkyl, alkoxy, alkoxyalkyl, tri fluorine thy I or halogen, '.

and R ₁ . independently hydrogen, lower

18.9.1979 56 141 12

res is alkyl, alkoxy, alkoxyalkyl, trifluoromethyl or halogen, and

Ii _{15 is} a C ₁ -C, alkyl which is optionally substituted by carboxy, carboxylic acid ester, carbonamide, by one or two lower aliphatic ^ substituted carbonamide or by -CN; or in which R ₁ , - is propynyl, butynyl, an acetalated carbonyl group, 1, 3-dioxolan-2-yl-alkyl, 1,3-dioxolan-5-ylalkyl, 1,3-dioxan-2-yl-alkyl, puranylmethyl, Tetrahydrofurany! Methyl or alkoxyalkyl of the form -AOR ^ g, where A is an alkylene chain having 1 to 4 carbon atoms, of which 1 or 2 belongs to the direct chain, and R 1 is lower alkyl, alkenyl or also Cycloalkyl or cycloalkyl methyl with 3 to 6 carbon atoms in the ring.

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

Some of the chloroacetanilides which are particularly suitable for use with the antidotes according to the invention are mentioned below:

H-Aethoxymethyl-2-methyl-6-ethyl-chloroacetanilide, N-methoxymethyl-2,6-diethy1-chloroacetanilide, N- (2 ^l -methoxyethyl) -2,6-dimethyl-chloroacetanilide, N ~ ( ^2f- Allyloxyäthyl 2,6-dimethyl-chloroacetanilide, N- (2- ^t- n-propoxyethyl) -2,6-dimethyl-chloroacetanilide, N- (2'-isopropoxyethyl) -2,6-dimethyl-chloroacetanilide, H- ( ^2f -methoxyethyl) -2-methyl-6-ethyl-chloroacetanilide, H "(2 ^l ~ methoxyethyl) -2,6-diethyl-chloroacetanilide,

43 - 21 593 4

18.9.1979 56 141 12

N- (2 ^f -Aethoxyäthyl) -2-methyl-6-ethyl-chloroacetanilide, N-ZJ ^l -Methoxyprop- (2 x) -y! 7-2-niethyl-chloroacetanilide, N-· Z3'-Methoxyprop- ( 2 ·) -y 37-2,6-dimethyl-chloroacetanilide, N-Z 3 '-methoxyprop- (2') -yl / -2-methyl-6-ethyl-chloroacetanilide, K »3i" methoxyprop- (2 ^l ) -yl7-2,6-diethyl-chloroacetanilide, N- ( ^2f- ethoxyethyl) -2,6-diethyl-chloroacetanilide, N- (2 ¹ -n-propoxyethyl) -2-methyl-6-ethyl-chloroacetanilide, N- (2 ^l -n-propoxyethyl) -2,6-diethyl-chloroacetanilide, N- (2 ^l -isopropoxyethyl) -2-methyl-6-ethyl-chloroacetanilide, N-chloroacetyl-2,6-dimethylanilino-acetic acid ethyl! esters, N-chloroacetyl-2,6-diethylanilino-e3-acetic acid ether, N-chloroacetyl-2, β-dimethylanilino-acetic acid methyl ester, N-chloroacetyl-2-methyl-6-ethylanilino-acetic acid isopropyl

ester, 2- ^ N- (ex, -chloroacetyl) - dimethylanilinoyacetaldehyde diethyl acetal,

N- / 5 ^f -ethoxyprop- (2 ') - yl7-2,3-dimethyl-chloroacetanilide, N- (2 ^l -ethoxyethyl) -2-methyl-chloroacetanilide, N- ( ^2f- methoxyethyl) -2- methyl-chloroacetanilide, N - ^ '- methoxyprop-d') -yl-7,6-dimethyl-chloroacetanilide, NZ? ^1- Methoxyprop- (1 ') - yl7-2-methyl-6-ethyl-chloroacetanilide, N-Z3'-ethoxyprop- (2') - yl7-2-methyl-6-ethyl-chloroacetanilide, N-Zi "' -Methoxybut (2 ^I ) -yl-7,6-dimethyl-chloroacetanilide, N- (2'-methoxyethyl) J-methyl-O-methoxy-chloroacetanilide, N- (n-butoxymethyl) -2-tert-butyl-chloroacetanilide , N-ZJ'-Aethoxyprop- (2 ') - yl7-2s6-dimethyl-chloroacetanilide, N- (2'-methoxyethyl) -2-chloro-6-methyl-chloroacetanilide, N- (2 ^l -ethoxyethyl) - 2-chloro-6-methyl-chloroacetanilide, N- (2'-ethoxyethyl) -2,3 '6-triraethyl-chloroacetanilide, N- (2 ^l -Methoxyäthyl) -2 _i 3,6-trimethyl-chloroacetanilide, N- ^(1: 2 -Isopropoxyäthyl) -2 _s 3,6-trimethyl-chloroacetanilide, N-cyanomethyl-2,6-diInethyl-chloroacetanilide _^ y- (but-1-in-3-yl) - ohloracetanilid, N-propynyl 2 ~ methyl ~ 6 ~ äthy! -chloroacetanilide,

44 - £ ] 5 Υ ό 4

18.9.1979 56 141 12

N- (1,3-dioxolan-2-ylmethyl) -2, G-dimethyl-chloroacetanilide, IT- (1,3-dioxolan-2-ylmethyl) -2-ethyl-6-methyl-chloroacetanilide, N - (1,3-dioxan-2-ylmethyl) -2-methyl-6-ethyl-chloroacetanilide, 1- (2 ^? -Puryl-ethyl) -2,6-dimethyl-chloroacetanilide, Li (2 ^t - Furanylmethyl) -2-chloro-6-methyl-chloroacetanilide, N- (2 ^! -Tetrahydrofuranylmethyl) -2,6-dimethyl-chloroacetanilide, _$ Ii- (U '-propargylcarbamylmethy1) -2, S-dimethyl- chloroacetanilide, H- (N ^1, N Dimethylcarbamy! methyl) -2,6-dimethyl-chloroacetanilide. , , , , ,

N- (n-butoxymethyl) -2,6-diethyl ~ chloroacetanilide, N- (2 ^-n-l Butoxyäthyl) -2,6-diethyl-chloroacetanilide, N-Z3'-Methoxybut- (2 ^t) -yl7-2 _i 6-dimethylchloroacetanilide, 2-chloro-isopropylacetanilide.

Suitable herbicidal thiocarbamates, which are rendered more compatible with crops when used in cereals, rice or refined sorghum millet together with compounds of the formulas I, II or III, preferably correspond to the formula

or R ₁₇ -SO-CN

O ^R 19

R ₁₇ denotes lower alkyl, alkenyl, chlorallyl, dichloroallyl, trichloroallyl, benzyl or p-chlorobenzyl,

R ₁₀ C ₀ -Cy ₁ -alkyl and to c. f

R ^ q represents Cp-C * -alkyl or cyclohexyl, or in which R-o and R ^ q together with the N-atom form a hexahydro-1H-azepine, a decahydroquinoline or a 2-methyl-decahydroquinoline ring »

- 45 -

, 09/18/1979

- 56 141 12

As examples of such compounds, mention may be made of the following thiolcarbamates; ·

S-ethyl-N ^ N-dipropylthiocarbamate,

S-ethyl-N, N-diisobutylthiocarbamate,.

S ^^ - Dichloroallyl-TJjN-diisopropylthiolcarbaiiiat, S-propyl-ii-butyl-N-ethylthiolcarbainate, S-2,3,3-trichloroallyl-N, N-diisopropylthiolcarbamate, S-propyl-l, N-dipropylthiolcarbamate, S Ethyl-N-ethyl-H-cyclohexylthiolearbamate, S-ethyl-U-hexahydro-IH-azepine-i-carbothioate, S-isopropyl-utero-hexamethylene-thiocarbamate, S-Cp-chlorobenzyl-1-N-diethylthiolcarbamate, K- Ethylthiocarbonyl-cis-decahydroquinoline, N-propyl-thiocarbonyl-decahydro-quinaldine, S-ethyl-1,2-bis-n-butyl-thiocarbainate, S-tert-butyl-1-bis-bis-propyl-1-thiocarbamate.

Further examples of useful thiolcarbamates are described in U.S. Patent Nos. 2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786 and 3,582,3H.

As further preparations that can be made more compatible with compounds of formula I, may be mentioned

oi '.- / Ä- (2,4-dichlorophenoxy) -phenoxy_7-proplonsäureinethy ester ok- ^ 2 - (4-Trif luorme thy! phenoxy) phenoxy_7-propionic acid

methyiester, ............ · ....

© £ -Z4- (2 ~ chloro-4-trifluoromethylphenoxy) -phenoxx7-piOpion-

acid methyl ester,. -.... , -:

c <-> i5- (3,5-dichloropyridyl-2-oxy) -phenoxy-7-propionic acid methyl ester.

46 ν-21 5934

09/18/1979

   · 56 141 12

The amount of antidote employed will vary between about 0.01 and about 15 parts by weight per part by weight herbicide. One determines from case to case, d. H. depending on the type of herbicide used, which ratio is the most appropriate in terms of optimum effect on the particular crop

As already mentioned, different methods and techniques are possible for the use of the new antidotes of Formulas I-III for the protection of crops from agrochemicals or for plant growth stimulation:

1 ») Seed pickling g

a) seed dressing with a formulated as a wettable powder by shaking in a vessel until evenly distributed on the seed surface (dry dressing) e is used about 10 to 500 g of active ingredient of formula I (40 g to 2 kg spray powder) per 100 kg seed.

b) dressing the seeds with an emulsion concentrate of the active ingredient of the formula I by the method a) (wet pickling),

c) pickling by dipping the seed into a broth with 50-3200 ppm of active ingredient of the formula I for 1-72 hours and optionally subsequent drying of the seeds (dip dressing).

The dressing of the seed or the treatment of the germinated seedling are naturally the preferred methods of administration, while the active ingredient treatment is completely directed to the target culture. As a rule, 10 g to 500 g of _9, preferably 50 to 250 g of AS per 100 kg are used

• - 47 - 21 5 93 4

18.9.1979 56 141 12

Seeds, whereby, depending on the methodology, which also allows the addition of other active substances or micronutrients, may deviate upwards or downwards from the stated limit concentrations (repeating stains).

2) Application from tank mix

A liquid work-up of a mixture of antidote and herbicide (mutual ratio between 10: 1 and 1:10) is used, the rate of application of herbicide is 0.1 to 10 kg per hectare. Such tank mix is preferably applied before or immediately after sowing or incorporated 5 - 10 cm deep in the not yet sown soil.

3) Application in the seed furrow

The antidote is introduced as emulsion concentrate, wettable powder or granules in the open seeded seed furrow and then applied after covering the seed furrow in the normal manner, the herbicide in pre-emergence.

In principle, therefore, the antidote may be applied before, together with or after the pesticide, and its application may be to the seeds or to the field before or after sowing or, in some cases, after emergence of the seed. The invention also relates, in particular, to compositions comprising, in addition to the antidote of the formula I, at least one agrichemical active substance, eg. As a herbicide from the chloroacetanilide or thiolcarbamate series. These agents also contain carriers and / or distribution agents.

⁴⁸ - 215

18.9.1979 56 1.41 12.

4) Controlled drug delivery

The active ingredient is applied in solution to mineral granules or polymerized granules (urea / formaldehyde) and allowed to dry. Optionally, a coating can be applied (granules) which allows the active substance to be dispensed over a certain period of time «

Of course, all other methods of drug administration can be applied. For this, examples are given below.

The inventive method for plant growth or to protect crops can be applied in particular to rice and nuts millet of Gattum sorghum, also on corn, wheat, barley, oats, soy, cotton, sugar beets "It is not only on the promotion and the Protection of annual plants limited, but also for growth stimulation of perennial plants (fruit trees, ornamental shrubs o. The like) very well suited in which the 'rooting or side shoots promoted or improved fruit set or improved inflorescences are to be achieved.

The compounds of the formula I can be used alone or together with the active ingredients to be antagonized and together with suitable carriers and / or other additives. Suitable carriers and adjuvants can be solid or liquid and correspond to the substances customary in formulation technology, such as, for example, natural or regenerated mineral substances, solvents, dispersants, disintegrants, adhesives, thickeners, binders or fertilizers.

215 9 3 4

18.9.1979 56 141 12

The content of active substance in marketable agents is between 0.01 to 90%.

For application, the compounds of the formula I can be present in the following work-up forms (where the weight percentages in brackets represent advantageous amounts of active ingredient):

Solid reprocessing forms: Dusts and scattering agents (up to 10 Si) Granules, coating granules, impregnated granules and homogenous granules, pellets (grains) (1 to 80 $);

Liquid reprocessing forms:

a) water-dispersible active substance concentrates:

Wettable powders and pastes (25-90 % in the commercial pack, 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 %) ; z. B. for stains, aerosols

The active compounds of the formula I of the present invention can be formulated, for example, as follows:

Dusts: The following materials are used to prepare a) 5% and b) 2% dust.

a) .5 parts of active ingredient 95 parts of talc;

18.9.1979 56 141 12

b) 2 parts of active ingredient

1 part of highly dispersed silicic acid, 97 parts of talc;

The active ingredients are mixed with the carriers and ground and can be dusted in this form for use.

Granule at? The following substances are used to prepare a follow 5 granules:

5 parts active ingredient

0.25 parts of epchlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol.

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

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The resulting solution is sprayed on kaolin, and then the acetone is evaporated in vacuo. Such microgranules can be incorporated advantageously in seed furrows.

Wettable powder; To prepare a) 70% b) 40% c) and d) 25% e) 10% wettable powder, the following constituents are used *

a) 70 parts of active ingredient

5 parts of sodium dibutylnaphthylsulfonate,

3 parts of Uaphthalenesulfonic acids-phenolsulfonic acids-

. ...... formaldehyde condensate 3ϊ1ϊ1,

10 parts kaolin,

12 parts Champagne chalk;

215 93

40 parts 5 parts 1 part

54 parts

18.9.1979 56 141

active substance

Lignin sulfonic acid sodium salt,

Dibutylnaphthalenesulfonic acid-sodium

aalz,

silica;

25 parts active substance 4 , 5 parts Calcium lignosulfonate,. 1 , 9 parts Champagne chalk / hydroxyethylcellulose Geraisch (1: 1), 1 , 5 parts Sodium dibutyl-naphthalene sulfonate, ' 19 , 5 parts silica, , 5 parts Champagne chalk, 28 _S 1 parts Kaolin·, 25 parts active substance 2, 5 parts Isooctylphenoxy-polyoxyethylene-ethanol, 1" 7 parts Champagne chalk / Hydroxyäthylcellulose- Mixture (1: 1), 8th, 3 parts Sodium aluminum silicate, 16 5 parts diatomaceous earth, 46 parts Kaolin, 10 parts Active ingredient ... , , , 3 parts Mixture of sodium salts of saturated ..... , Pettalkoholsulfaten, 5 parts Naphthalenesulfonic acid / Pormaldehyde Condensate, 82 parts Kaolin;

The active ingredients are intimately mixed in appropriate mixers with the aggregates and ground on appropriate mills and rollers. It gives spray powder of excellent wettability and suspension, which can be combined with

⁵² .. '. - 215934

18 * 9.1979 56 141 12

Dilute water to suspensions of the desired concentration and use in particular for foliar application, for seed dressing or for dipping seedlings »

Emulsifiable concentrates ^ To produce a 25 follow emulsifiable concentrate The following substances are used:

25 parts of active ingredient

2.5 parts of epoxidized vegetable oil, 10 parts of an alkylaryl sulfonate / fat

alcohol polyglycol ether mixture, 5 parts dimethylformamide,

57.5 parts xylene.

From such concentrates emulsions of any desired concentration can be prepared by dilution with water, which are particularly suitable for seed dressing.

Claims (3)

53 - 215 93 18, SU1979 56 141 12 invention claim 1 · Process for the preparation of compounds of the general formula Ar-C-X (I) I » N-O-Q contains, wherein the substituents have the following meaning: Ar = - a phenyl radical of the formula R ₂ a C 1 - or B -lithaphyl radical, a heterocyclic ring of the formula ^R 4 X = - cyano, nitro, halogen, mederalkanoyl, a carboxylic acid ester radical, hydrogen ,. a carboxylic acid amide residue or lower alkyl, Q = - a lower alkyl which is straight-chain or is branched or may be interrupted by heteroatoms or substituted by halogen, lower alkenyl or haloalkenyl,  18.9.1979 56 141 12 lower alynyl, optionally substituted by halogen lower cyanoalkyl, lower alkane carboxylic acid ester group, lower alkanecarboxamide group, aliphatic acyl radical, _- araliphatic, cycloaliphatic or optionally subst. aromatic or heterocyclic acyl radical, - Alkylsulfonic acid or a sulphonic acid amide radical, R .. - hydrogen, halogen, lower alkyl, Lower alkoxy or an optionally max. twice by halogen, -CN, NOp, CF-5 substituted para-phenoxy,. p and R, independently of one another, are hydrogen, halogen, , Lower alkyl, haloalkyl, lower alkoxy, and Rc independently of one another are hydrogen, halogen, , Lower alkyl and Z. mean oxygen or sulfur, with the proviso that when Ar is an unsubstituted phenyl radical and Q is the radical -CHgCB ", X is 215 93 4 B) with the proviso (Proviso) that if Ar is a halogen- or nitro-substituted phenyl radical or unsubstituted naphthyl radical and Q is propynyl, then X is not hydrogen and c) with the proviso that when Ar is an optionally substituted phenyl radical, Q is not an aliphatic or aromatic aoyl radical, characterized in that an etherification or acylation of an oxime of the formula V Ar-C-X ti V NOH
or an oxime salt with a halide of the formula HaIg - Q where Ar, X and Q have the abovementioned meaning and Hal represents halogen, preferably chlorine or bromine, is carried out » Process according to item 1 for the preparation of compounds of the general formula E- Ia -j ww in - υ - Q in the X "t - cyano, nitro, halogen, lower alkanoyl, a carboxylic acid ester radical of a lower alkanol, a carboxylic acid amide radical, Qw- lower AlHLnyl, lower cyanoalkyl, lower alkanoic acid ester G-group, lower alkanecarboxamide group, R "- hydrogen, R _? a hydrogen, halogen or lower alkyl, R ~ s hydrogen, halogen or ETiederalkyl, with the provisos a), b) and o) according to point 1, characterized in that an etherification of an alkali metal or ammonium salt of the general Pormel V with a halide of the general formula ! HaIg - Q where Ar, X and Q are as defined above and Hal is halogen, preferably chlorine or bromine. Process according to item 2 for the preparation of compounds of the general formula (Ia) in which X s is cyano, chloro, bromo, acetyl, propionyl, -COOCH ₃ , -COOC ₂ H ₅ , -CO-NH ₂ , -CO-NHCH ₃ , -CO-N (CH ₃ ) ₂ ,
Qβ-propynyl or butynyl, Cyanomethyl or cyanäthyl,
Methoxycarbonylmethyl, ethoxyo-carbonylmethyl, Methoxycarbonylethyl, ethoxycarbonylethyl, an acetamide or propionamide radical optionally substituted by one or two lower aliphatic groups on the N atom, R 2 -hydrocarbons, R ₂ - hydrogen, halogen or methyl, R ₃ a - hydrogen, halogen or methyl with the provisos a) and b) according to point 1, characterized in that an etherification of an alkali or ammonium salt of the general formula V with a halide of the general formula HaIg - Q -57- 215934 wherein Ar, X and Q have the abovementioned meaning and Hal is halogen, preferably chlorine or bromine, is carried out. 4 · Process according to item 2 for the preparation of compounds of general formula (Ia) in which X represents a cyano group and Q, R, R ₂ and R- have the abovementioned meaning with the provisos a) and b) according to item 1, characterized in that an etherification of an alkali metal or ammonium salt of the general formula V with a halide HaIg - Q wherein Ar, X and Q have the meanings given above and HaIg is halogen, preferably chlorine or bromine, is carried out. 5 · Process according to item 1 for the preparation of compounds of general formula II C-X in the R ₂ and R-5 are independently hydrogen, halogen, NO ₂ , lower alkyl, haloalkyl, lower alkoxy and 58 - 2 18.9.1979 56 141 12 X -CN, N0 ' ₂ , halogen, the acetyl group, ^ mean a carboxylic acid ester radical of a niederali phat «Alkohpls or a carboxamide, while η is 1, 2 or 3, Rq represents hydrogen or lower alkyl, R ₁₀ -COISH ₂ , -CO-NH- (lower aliphatic radical), -CO-NH-cycloalkyl, - g ₅ (Halogen, lower alkyl) or -CN, and m is an integer 0, 1, 2 or 3, characterized in that an etherification of an alkali metal or ammonium salt of the general formula V with a halide of the general formula Haig-Q wherein Ar, X and Q have the abovementioned meaning and Hal is halogen, preferably chlorine or bromine, is carried out. , , 6. Process according to item 5 for the preparation of compounds of general formula III (III) in the X ¹ -CN, NO ₂ , chlorine, acetyl, lower alkoxycarbonyl, allyloxycarbonyl, carbamoyl or di-lower alkylcarbamoyl, and 59 - 'd. Y 3 ' y 3 ^; , 18.9.1379 56 141  v -CU, -CO-NH ₂ , -GO-MH-lower alkyl or -CO-KH (C ₆ H ₅ _ _m ) (Cl, Br, CH ^) _m and m is an integer 0, 1 or 2, characterized in that an etherification of an alkali metal or ammonium salt of the general formula V with a halide of the general formula HaIg-Q, where Ar, X and Q have the abovementioned meaning and Hal represents halogen, preferably chlorine or bromine. 7 · Process according to item 6 for the preparation of benzylidene-amino-oxacetamide of the formula NO-CH ₂ -CO-KH ₂ characterized in that an etherification of an alkali or ammonium salt of the general formula N-O-Saiz in the salt for alkali or ammonium group is associated with a halide of the formula Hal-CH ₂ -CO-KH ₂ Hal is halogen, preferably chlorine or bromine. 6ο 8, Process according to item 1, characterized in that one prepares / Q (2-butene-1-yl) -oximino-7-P-methoxybenzylcyanide » 9 «A method according to item 1, characterized in that one-OE6 rZ0- ^(M e * fchoxycarbonyl-oxyiminoJ7- °° - 2-thienyl ^ manufactures (acetonitrile. 10. The method according to item 1, characterized in that. (%. ~ / 0- (Cyanomethyl-oxyimino) 7- ° C ~ (5-chloro-2-thienyl) -acetonitrile.