DD145362A5 - PROCESS FOR PROTECTING CULTURAL PLANTS - Google Patents

Abstract

A method for protecting crops from aggressive agricultural chemicals is described, using oxime derivatives of the formula (with the substituents R1, X, and O as defined herein) as inhibitors. Either the area under which the crops are grown, or the crops themselves, or parts of the plant (seeds, tubers, stem pieces, etc.) can be treated with these oxime derivatives as a dressing.

Description

Berlin, 23.1.1979 AP A 01 ίί / 207 605 (54 148/1

Process for the protection of crop plants

Field of application of the invention

The invention relates to a process for the protection of crop plants from phytotoxic agrochemicals, for example herbicides with insufficient selectivity.

The invention further relates to agents used for the protection of crop plants and propagation material, such as seeds, roots, fruits, tubers, rhizomes, stem parts, cuttings, sprouted seedlings, etc., which have been treated with the agents according to the invention.

Characteristic of known technical solutions

As antidotes or antidotes, various substances have already been proposed which are capable of specifically antagonizing the damaging effect of a herbicide on the crop, i. to protect the crop without significantly affecting the herbicidal action on the weeds to be controlled. In this case, such an antidote, also called safener, depending on its properties for the pretreatment of the seeds of the crops (dressing of the seed or cuttings) or before sowing be used in the seed furrows or as a tank mixture by itself or together with the herbicide before or after emergence of the plants. Pre-emergence treatment includes both the treatment of the cultivated area before sowing (ppi =

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AP A 01 U / 207 (54 H8 / 11)

"pre-plant incorporation") as well as the treatment of the sown, but not yet overgrown cultivated areas.

Thus, British Patent 1,277,557 describes the treatment of seeds bzv7 · sprouts of wheat and sorghum with certain oxalic acid esters η and amides before attack by N-Ivie thoxyme thy 1-2 ', б • -diethyl-chloroacetanilide (alachlor) , Other references (DE-OS 1,952,910, DE-OS 2,245,471, FR-PS 2,021,611) disclose antidotes for the treatment of cereals, corn and rice seeds for protection against the attack herbicidal thiolcarbamates before. DE-PS 1,576,676 and US-PS 3,131,509 propose hydroxyamino-acetanilides and hydantoins for the protection of cereal seeds from carbamates such as IPC, CIPC, etc. In the further development, however, all these preparations have proved to be insufficient.

Object of the invention

The aim of the invention is to provide a method for the protection of crops, with both crops and the propagation material from the harmful influence of phytotoxic agrochemicals, such as insufficiently selective herbicides can be protected, without affecting the herbicidal action is impaired.

Explanation of the essence of the invention

The object of the invention is to find new compounds which are suitable as antidotes or antidotes and specifically antagonize the harmful effect of a herbicide on the cultivated plant.

-3- 23.1.1979

AP A 01 U / 207 (54 148/11)

According to the invention as antidotes oxime derivatives of the general formula I.

R ₁ -CO-CX

' Fr

KOQ ^U;

for the protection of crops against aggressive agrochemicals ·

In the formula I means

R ^ optional

- A radical -ORp, v / orin Rp for an aliphatic group having a maximum of 8 carbon atoms or araliphatic group having a maximum of 15 carbon atoms or a cycloaliphatic or aromatic group each having a maximum of 10 carbon atoms, where as substituents of the aromatic radicals or the cycloaliphatic radical halogen, -CN, -NOp, lower alkyl, lower alkoxy, haloalkyl come into question,

- a residue -HH-CO-IiH-R. or

- a radical -N (R ₃ ) (R *), wherein R, is hydrogen or iJiederalkyl and R, hydrogen or an aliphatic group having a maximum of 8 carbon atoms or araliphatic group having a maximum of 15 carbon atoms or a cycloaliphatic or aromatic Group each having a maximum of 10 carbon atoms, suitable halogen, -CN, NO ₂ , lower alkyl, lower alkoxy, haloalkyl being possible as possible substituents of the aromatic groups or the cycloaliphatic radical,

- a radical -N (Ro) (R /) »wherein R ^ and R * together form a 5- or 6-membered heterocyclic ring, which may still contain oxygen as a possible further heteroatom,

-4- 23.1.1979

AP A 01 N / 207 (54 148/11)

X is hydrogen, -CN, halogen, lower alkyl, lower alkanoyl, -COOH, a carboxylic ester residue, a carboxylic acid amide residue,

Q - hydrogen,

lower alkyl which may be interrupted by heteroatoms or substituted by halogen or cyano,

lower alkenyl or haloalkenyl,

lower alkynyl,

- optionally substituted by halogen

lower alkanecarbonyic acid ester group,

lower alkane carboxylic acid thioester group,

lower alkane carboxylic acid amide group,

aliphatic acyl radical,

araliphatic cycloaliphatic or optionally subst aromatic or heterocyclic acyl radical,

- Alkylsulfonyl

- Sulfonsäureamidrest

- a metal salt

a quaternized ammonium salt.

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

Carboxylic acid esters and thioesters are carboxylic acid lower alkyl esters and lower alkyl thioesters · Acyl radicals are carboxylic acid radicals · Carboxylic acid amides, in addition to -COML, also denote monoalkyl-substituted or symmetrically or asymmetrically dialkyl-substituted amides, the alkyl groups being alkylkyl ·

20 7 6 05 - ⁵ - 23.1.1979

AP A 01 N / 207 605 (54 148/11)

The term alkylHin or as part of a substituent includes branched or unbranched C to Cg alkyl groups; Lower alkyl, alone or as part of a substituent, means C ₁ -C. Alkyl. Examples are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert. Butyl, and the higher homologues amyl, isoamyl, hexyl, heptyl, octyl together with their isomers · Analogously contain Alkanoyle or Cyanalkyle an additional carbon atom. Accordingly, lower alkenyl or alkynyl groups contain a maximum of 4 carbon atoms »

The term aliphatic group includes saturated (alkyls) as well as unsaturated (alkenyls, alkadienyls, alkynyls), halo-substituted, cyano-substituted, and oxygen-interrupted radicals containing a maximum of 8 carbon atoms. "

The term aromatic group includes phenyl and naphthyl.

An araliphatic radical includes an optionally monosubstituted to trisubstituted phenyl or naphthyl bonded via lower alkyl or lower alkenyl to the remainder of the molecule. Examples are the bases benzyl, phenethyl, phenylallyl and homologues ·

The term heterocyclic acyl radical includes 5- or 6-membered heterocyclic carboxyl compounds having a ring heteroatom from the series Ii, O or S. Examples are the radicals of furancarboxylic acid, thiophenecarboxylic acid, nicotinic acid, isonicotinic acid and others, cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, Cyclohexyl and cycloheptyl. Cycloaliphatic radicals correspond to these ring systems, but may also contain, depending on the possibility, one or more double bonds.

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^ AP A 01 Ή / 207 605

As metal salts are cations of the I. to IV. Groups of the periodic table and heavy metal salts to understand · Examples are Na, K, Ca, Mg, Al, Zn, Cu, Fe, Mn, Co, Ni.

Quaternary ammonium salts contain, as identical or different substituents, hydrogen, C 1 -C 4 -alkyl, lower-hydroxyalkyl, benzyl, amino, di-lower alkylamino, or form two valences and the N atom a 5- or 6-membered heterocyclic ring with optionally one further heteroatom N, 0 or S.

Oximes of the formula I are outstandingly suitable for protecting crops such as rice, sharks, cereals (millet, wheat, rye, barley, oats) from the attack of plant-aggressive agrochemicals, in particular herbicides of various substance classes, provided that they do not act or are not sufficiently selective So, in addition to the weeds to be controlled, the crop plants also more or less damage ·

Particularly noteworthy as antidotes are those compounds of formula I wherein

R ₁ denotes a radical -N (Ro) (R 1) in which R ₁ denotes hydrogen or lower alkyl and R * denotes hydrogen or a lower aliphatic group or optionally a maximum of three times by halogen, -CN, NO 9 _f lower alkyl, lower alkoxy, CP, substituted phenyl radical,

V 23.1.1979

AP A 01 N / 207 (54 148/11)

X is hydrogen, -CN, lower alkyl, acetyl, -COOH lower alkyl, -COOKH ₂ , -COOHH lower alkyl or -COON (lower alkyl) p, and

Q is hydrogen, lower alkyl optionally substituted by halo Dder cyano, lower alkenyl, lower alkynyl, an alkanecarboxylic acid lower alkyl ester group having a maximum of 7 carbon atoms, acetamide (-CH ₂ -CONH ₂ ), a lower aliphatic acyl radical, an optionally substituted benzoyl radical 2 ~ furanoyl radical, an alkali or heavy metal salt or a quaternary ammonium salt, in which hydrogen, lower alkyl, benzyl or hydroxyethyl are suitable as substituents · This substance group should be named as linking group Ia »

Within the linking group Ia, such compounds are important as antidotes, wherein

R _{1 is} a radical -Iffl-R, wherein R * is hydrogen or

a lower alkyl group, X has the meaning given for Ia and Q is hydrogen, lower alkyl, lower cyanoalkyl, C ^ -C, alkenyl, propargyl, acetamide, -CH ₂ COO lower alkyl or -CH (CH ₃ ) COO lower alkyl. This subgroup should be called connection group Ib ·

- ί-

Another preferred linking group for its antidote effect is that in which

R _{1 represents} a radical -NH-CO-NH-R, in which R represents hydrogen or a lower alkyl group and in which X and Q have the meaning given for compound group Ia. This type of drug should be called compound group Ic. If Q within this group has the meaning given for compound group Ib, this type of active substance should be called compound group Id.

Another preferred linking group for its antidote effect is that in which

R- represents a radical -OR ₂ in which R _{2 is} an alkyl, alkenyl or alkynyl group having a maximum of 6 C atoms and in which X and Q have the meaning given for linking group Ia. This type of active substance should be called compound group Ie. If Q within this group has the meaning given for Ib, this type of active substance should be called compound group If.

Surprisingly, oximes of the formula I have the property of protecting crops from the attack of plant-aggressive agrochemicals, in particular against herbicides of the most varied classes, including 1,3,5-triazines, 1,2,4-triazinones, phenylurea derivatives, carbamates, thiocarbamates, phenoxyacetic acid esters, Phenoxypropionic acid esters, haloacetanilides, halophenoxyacetic acid esters, subst. Phenoxyphenoxyacetic acid esters and propionic acid esters, subst. Pyridinoxyphenoxy-acetic acid esters and propionic acid esters, benzoic acid derivatives, etc., if they are not or are insufficiently culturally tolerant.

- к - ft-

Such an antidote or antidote of the formula I can be used depending on the application for pretreatment of the seed of the crop (seed or seed dressing) or before or after sowing into the soil or on their own or together with the herbicide before or be applied after emergence of the plants. The treatment of the plant or of the seed with the antidote can therefore be carried out independently of the time of application of the phytotoxic chemical. However, it can also be carried out simultaneously (tank mix). Pre-emergence treatment includes both the pre-sowing cultivation (ppi ^β "pre-plant incorporation") and the treatment of the sown, but not overgrown, acreage.

The application rates of the antidote in relation to the herbicide depend largely on the type of application. If a field treatment is carried out, the amounts of antidote of formula I to phytotoxic chemical behave as l, 100 to 5: 1, preferably 1:20 to 1: 1. However, with seed dressing and similar targeted protective measures, far lower amounts of antidotes are compared with the e.g. amount of herbicide used per acre per acre (e.g., about 1: 3000 to 1: 1000). As a rule, protective measures such as seed dressing with an antidote of formula I and possible subsequent field treatment with agrochemicals are only loosely connected. Pre-treated seed and plant material may later come into contact with various chemicals in agriculture, horticulture and forestry.

The invention therefore also relates to crop protection agents which contain as active ingredient only an antidote of the formula I together with customary carriers

- * - 40-

contain. Such agents may optionally be additionally mixed with that agricultural chemical against which the crop is to be protected, e.g. with a herbicide.

In the context of the present invention, crop plants are all plants which produce yield materials in some form (seeds, roots, stems, tubers, leaves, flowers, ingredients such as oil, sugar, starch, albumen, etc.) and are grown and cultivated for this purpose. These crops include, for example, all cereals, corn, rice, sorghum, soy, beans, peas, potatoes, vegetables, cotton, sugar beet, sugar cane, peanuts, tobacco, hops, but then also ornamental plants, fruit trees and banana, cocoa and natural rubber -Gewächse. This list does not represent a limitation. In principle, an antidote can be used anywhere, \ oo a crop to be protected against the phytotoxicity of a chemical.

The invention also relates to a process for the protection of crops from aggressive (phytotoxic) agrochemicals by employing as an antidote oxime derivative of the formula I either before or after application of the agrochemical or simultaneously with the agrachemical.

The invention further relates to the propagation of such crops, which has been treated protectively with an oxime derivative of the formula I. The term "reproductive material" is to be understood as meaning all generative plant parts which can be used to propagate the crop. These include seeds (seeds in the strict sense), roots, fruits, tubers, rhizomes,

Stem parts, twigs (cuttings) and other plant parts. But it also includes germinated plants and young plants, which should be further transplanted after germination or emergence. Such young plants can be protected by a complete or partial dip treatment before transplanting targeted.

Compounds of the formula I can be prepared by methods known per se for the oximation of compounds of the formula II

R ₁ -CO-OT ₂ -X (II)

represent (with the meaning given for formula I) by reaction with nitrous acid (HNO ~) or an organic or inorganic nitrite and then convert the free oximes thus obtained optionally with bases in the salts or acylate with acids or acid halides or with halogenabspaltenden residues convert to other oxime ethers listed under Q. It may be cited as literature: DE-OS 2,312,956; DE-OS 2,350,910 and "Reports of the former German society" 42_, p., 738 f. {1909].

Oximes exist in two stereoisomeric forms, the syn and anti form. 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 two examples illustrate the preparation of oximes of the formula I. Temperatures are given in degrees Celsius.

Example Г Production of

H ₂ N-CO-NH-CO-C-CN N-OH

α-cyano-α-hydroxyimino-acetyl-urea

To 50 g of sodium nitrite in 250 ml of water are added at 80 ° with good stirring within 5 minutes 50 g Cyanacetylharnstoff and then heated to 100 °. After everything has dissolved, it is stirred for a further hour at room temperature and then cooled to 10 °. The resulting Na salt of the final product is filtered off and dissolved with heating in 200 ml of water. Now add the solution with 70 ml of concentrated hydrochloric acid, cool and filter. The resulting α-cyano-α-hydroxyiminoacetyl-urea melts at 210 ° -212 ° with decomposition,

Example 2

Production of

H ₉ N-CO-C-CN

NO-CH ₂ -CH = CH

α-Cyano-α-allyloximino-acetamide

To a solution of 11.3 g (0.1 mol) of α-cyano-ct-oximinoacetamide in 100 ml of acetonitrile is added 10.1 g (0.1 mol) of triethylamine and dropwise thereto 12.1 g (0.1 mol ) Allyl bromide. Then heated for 4 hours at reflux,

-12-43-

The solution is concentrated in vacuo and the residue is taken up in methylene chloride. The organic phase is washed several times with water, dried over sodium sulfate, stirred with charcoal and filtered clear. From the filtrate obtained on concentration 12.7 g (= 83.0 % of theory) of the final product, mp. 79-80 ° C.

207

- TS - АЦ-

In this way or after one of the methods will be the following connection

H ₂ N-CO-CX

Il

N-O-Q produced:

Verb.

Physical constant

CN

CN

CN

CN

CN

CN

CN

Cl Cl Cl Cl Cl Cl

-COCH-

-COCH-

-coch '-COCH- -COCH- -COCH- -CN

-CN -CN

-CH ₂ CN

-CH ₂ -CONH ₂

-CH ₂ -ChCH

-CH (CH ₃ ) COOCH ₃

-CH (CH ₃ ) COOC ₂ H ₅

-CH ₂ -CH = CH ₂

-CH ₂ CN

-CH ₂ -CONH ₂

-CH ₂ -COOCH ₃

-CH (CH ₃ ) COOCH ₃

-CH (CH ₃ ) COOC ₂ H

-CH ₂ -C =CH

-CH ₂ -CN

-CH ₂ -O = CH "

-CH ₂ -COOCH ₃

-CH (CH ₃ ) COOC ₂ H ₅

-CH ₂ -COOC ₃ H ₇ (ISo)

-CH ₂ -CONH ₂

© NH (CH ₃ ) 2 " ^c i2 ^H 25 ⁽ⁿ⁾ CUNH ₃ -CH ₃

Mp.185-187 ° Mp.165-167 ° Mp.194-196 ° Mp.101-103 ° OeI OeI Mp. 79-80 °

OeI OeI OeI viscosities OeI OeI OeI OeI OeI viscos Smp.74-75.5 '

Smp.136-138 "Smp.153 °

Verb. X

Physical constant

CN

1/3 FeSmp. > 3OO ° (Zeis)

CN

25 CN CH ₃ 26 CN CH ₅ 27 CN C ₃ H ₇ CiSO) 28 CN 2-furanoyl 29 CN -COCH ₃ CH ₂ CH ₂ -OH 30 CN CH ₂ CH ₂ OH

CN

CN

-CN -CN

-CN -CN

© NH ₃ -sek.C ₄ H ₉

NH ₂ CCH ₃ )

C ₆ H ₅ CH ₂ -

CH ₂ CH ₂ -OH

0H ₂ N (CH ₂ CH ₂ -OH) ₂ © HNCCH ₃ ) ₃ mp 1.33-134 °

Smp.171 ° Smp.126 ° viscos

Smp.200 ° Czers) mp.141-143 °

Oei

Mp.91-97 ° Mp.145-147 °

Smp.24O ° ccers) wax

Oei

Mp. 138-142 '

as well as following the formula

R.-NH-CO-C-XKN-O-Q

Verb. ^R 4 X Q physical Oei No. constant Oei 37 H ₂ N-CO CN -CH ₂ CN Oei Oei 38 H ₅ C ₂ NH-CO- CN -QI ₂ CN Oei Oei 39 HcC.-NH-CO- CN -CH ₂ CN Oei Oei 40 H ₂ N-CO- CN -CH ₂ -CONH ₂ Oei Oei 41 H ₂ N-CO- CN -CH ₂ -COOCH ₃ Oei Oei 42 H ₅ C ₂ -NH-CO- CN -CH ₂ -COOC ₂ H ₅ Oei Oei 43 H ₂ N-CO- CN -CH (QI ₃ ) -COOCH ₃ viscos Smp.l76 ° (dec) 44 H ₅ C ₂ -NH-CO- CN -CH (CH ₃ ) -COOC ₂ H с viscos 45 H ₅ C ₆ -NH-CO- CN -CH ₂ -COOCH ₃ Oei 46 H ₂ N-CO- Cl -CH ₂ CN Oei 47 H ₃ C-NH-CO- Cl -CH ₂ CN Oei 48 H ₅ C ₂ -NH-CO- Cl -CH ₂ CONH ₂ viscos 49 H ₂ N-CO- Cl -CH ₂ -COOCH ₃ Oei 50 H ₂ N-CO- Cl -Q1 (CH ₃ COOC ₃ H ₇ ( iso) OeI 51 H ₅ C ₂ -NH-CO- Cl -CH (CH ₃ ) COOC ₂ H ₅ Oei 52 H ₂ N-CO- -COCH ₃ -CH ₂ CN 53 пНдСд-NH-CO- -COCH ₃ -CH ₂ CN 54 H ₃ C-NH-CO- -COCH ₃ -CH ₂ CN 55 H ₂ N-CO- -COCH ₃ -CH ₂ COOCH ₃ 56 H ₅ C ₂ -NH-CO- -COCH ₃ -CH ₂ COOC ₂ H ₅ 57 H ₅ C ₂ -NH-CO- -COCH ₃ -CH (CH ₃ ) COOC ₂ H ₅ 58 H ₃ C-NH-CO- -COCH ₃ -CH (CH ₃ ) COOCH ₃ 59 H ₂ N-CO- -COCH ₃ -CH ₂ -CONH ₂ 60 H ₂ N-CO- CN 0H ₃ NCH ₃

- Kl

Verb. R, no.

Physical constant

61 H ₂ N-CO-CN

62 H ₂ N-CO-CN

63 H ₂ N-CO-CN

(+ JNH,

© NH (CHO ₀ -NH ₀

JZZ

© H _o tsi0 ζ \ /

Mp.2O9 ° (Zers) Mp.125-126 °

Smp.160-165 °

64 H ₂ N-CO-CN

65 H ₂ N-CO-CN

66 H ₂ N-CO-CN

67 H ₂ N-CO-CN

68 H ₂ N-CO-CN

69 H ₂ N-CO-CN

70 H ₂ N-CO-CN

71 H ₂ N-CO-CN

72 H ₂ N-CO-CN

73 H ₂ N-CO-CN

74 H ₂ N-CO-CN

75 H ₂ N-CO-CN

76 H ₂ N-CO-CN

77 H ₂ N-COCOOQ ₃

78 H ₃ C-NH-CO COOCH ₃

79 H ₃ C-NH-CO COOCH ₃

80 H ₃ C-NH-CO COOCH ₃

81 HcC.-NHCO COOCH-j

-> D ό

82 H ₅ C ₆ NH-CO COOCH ₃

83 H ₂ N-CO CN

84 H ₅ C ₂ NH-CO CN

85 H ₅ C ₂ NH-CO CN

86 cycloCN propyl

87 cycloCN-propyl

88 cyclo-CN hexyl -H-

Na ^

k Zn

h Co

2-furanoyl

h Fe

Э NH (CHJ ₀ -C

© NH

Mp.

Mp.

Mp.

Mp.

Mp.

Mp.

M.p. (n) m.p.

Mp. © NH (CH ₃ ) ₂ -CH ₂ CH ₂ OH m.p.

Mp.

Mp.

Mp.

Oei

Oei

Oei

Oei

Oei

Oei

^ Mn '' Mp.

H Mp.

© NH (CH ₃ ) ₃ -CH ₂ CN -Ql ₂ COOCH ₃ -CH ₂ CN

25O ° (Zers) 210-212 ° 200 ° (Zers)> 300 ° £ ers) 198 ° (Zers)> 300 ° £ ers) 176-181 ° 110-113 ° 149 °

125-128 ° 136-138 ° 171-172 ° 160 ° (Zers)

-CH (CH ₃ ) COOCH ₃

-CH ₂ CN

-CH (QI ₃ ) COOC ₂ H ₅

h Cu h co

-H-

Mp. Mp.

Mp. Mp.

> 300 ° 166-168 ° 162 °

149.5 ° (decomp.)

> 300 ° (Zers)

202 °

Verb. OT ₃ X Q physical No. OT ₃ constant 89 nC ₄ H ₉ CN ₂ H _2n Q ₅ Smp.121-123 ° 90 OT ₃ CN © H ₃ NN (OT ₃ ) ₂ firmly 91 OT ₃ CN H Smp.125-126,5 ° 92 cyclopropyl CN 2-furanoyl Smp.l87 ° (dec) 93 CN -OT ₂ CN Smp.91-93 ° "94 CN H Mp. 181 ° OT ₀ OT ₀ OH

100 101 102 103 104 105

106 107 108 109 110

CH.

CH.

CH

OT

2-H ₃ CO-C ₆ H ₄ - ^С бѴ

3,5 (Cl ₂ ) C ₆ H ₃ -3-CF ₃ -C ₆ H ₄ -

4-CF ₃ -C ₆ H ₄ -4-Cl, 3-CF ₃ -C ₆ H ₃ -2 -OT ₃ , 4 -Cl-C ₆ H ₃ -3 -Cl-C ₆ H ₄ -3- OT ₃ ) C ₆ H ₄ -

H H H H H OeI

OT ₃ ) ₂ C ₁₂ H ₂₅ (n) Mp.92-93 'Mp.146-148 °

© NH ₃ -sek.C ₄ H ₉

QNH ₃ --OT ₃ 175 ° mp.

© NH ₂ (CH ₃ ) ₂ M.p. 75-78 ° -CO-C ₆ H ₃ Cl ₂ (3.4) M.p. 167-168 °

Hp.166-168 °

H Smp.181.5 °

H Smp.167 °

H Smp.196 °

H Smp.137 °

H H H H H

Smp.171 ° Mp.178 ° Mp.170-174 ° Mp.146-150 ° Mp.125-129 °

and the following compounds of the formula

Verb no.

^ N-CO-C-CN N-O-Q

Physical constant

Ul 112 113 114 115 116 117 118

HCO

h Mn

⁴⁴ "

H Mp.225 ° (decomp.)

Smp.210 ° (dec.) Mp.> 33O ° (dec.) Smp.28O ° (dec.) ° Smp.112 oil 0NH oil (CH _{3) 2} -C ₁₂ H ₂₅ (n) oil

© NH ₃ -sek.C ₄ H ₉

as well as following the formula

R ₁ -O-CO-CX * и

N-O-Q

Verb no. * 2 X Q Physical constant 119 C ₂ H ₅ CN , H Smp.133-136 ° 120 C ₂ H ₅ CN -SO ₂ CH ₃ Smp.81-83 ° 121 CH ₃ CN -CH ₂ COOCH ₃ Oei 122 123 C ₂ H ₅ C ₂ H ₅ -CN -CN -CH (CH ₃ ) COOCH ₃ -CH ₂ -COOc ₂ H ₅ OeI OeI 124 CH ₃ CN -CH ₂ CN ' Oei 125 CH ₃ '-CN -CH ₂ CONH ₂ viscos 126 1-C ₃ H ₇ CN -CH ₂ COC ₃ H ₇ (ISo) Oei 127 Cyclopropyl CN -CH ₂ CN Oei

207. 605 - Q physical Verb. Mv ^R 2 X constant INr. -CH ₂ CN viscos 128 CH ₃ Cl -CHoCOOCH ₃ viscos 129 CH ₃ Cl -CH ₀ CN Oei 130 cyclo Cl I propyl -CH (CH ₃ ) COOC ₂ H ₅ viscos 131 C ₂ H ₅ Cl -CH ₂ CN Oei 132 CH ₃ -COCH ₃ -CH ₂ CONH ₂ Oei 133 CH ₃ -COCH ₃ -CH ₂ COOC ₂ H ₅ Oei 134 C ₂ H ₅ -COCH ₃ -CH (CH ₃ ) COOCH ₃ Oei 135 CH ₃ -COCH ₃ -Ql ₂ CN Oei 136 CH ₃ -CO-OCH ₃ -CH ₂ CONH ₂ viscos 137 CH ₃ -CO-OQl ₃ -CH ₂ COOCH ₃ Oei 138 CH ₃ -CO-OCH ₃ -CH (CH ₃ ) COOCH ₃ Oei 139 CH ₃ -CO-OCH ₃ H Oei 140 CH ₃ -COCH ₃ H Smp.95-96 ° 141 C ₂ H ₅ CH ₃ H firmly 142 C ₂ H ₅ -COCH ₃ -CH ₂ -C-CH semicrystalline 143 CH ₃ -CO-OQl ₃ -CH ₂ -C =CH viscos 144 ^C 2 ^H 5 -CO-OC ₂ H ₅ CH ₃ Oei 145 ^C 2 ^H 5 -CO-OC ₂ H ₅ C ₂ H ₅ Oei 146 C ₂ H ₅ -CO-OC ₂ H ₅ -CH ₂ CN Oei 147 C ₂ H ₅ -CO-OC ₂ H ₅ CH ₃ Oei 148 ^C 2 ^H 5 -COCH ₃ C ₂ H ₅ Oei 149 C ₂ H ₅ -COCH ₃ -CH ₂ -C =CH Oei 150 C ₂ H ₅ -COQl ₃ -CH ₂ -CH = CH ₂ Oei 151 C ₂ H ₅ -COCH ₃ -CH ₂ -CH = CH ₂ Oei 152 C ₂ H ₅ -CO-OC ₂ H ₅ CH ₃ Oei 153 C ₂ H ₅ CN C ₂ H ₅ Oei 154 C ₂ H ₅ CN C ₃ H ₇ (ISO) Oei 155 C ₂ H ₅ CN -CH ₂ -CH = Ql ₂ viscos 156 ^C 2 ^H 5 CN -CH ₂ -ChCH viscos 157 C ₂ H ₅ CN

20 7 6 05 -20-11-

and the following compounds of the formula

R 'N-CO-C-X

N-O-Q

Verb. R ' X Q Physical. -OT ₂ CN Oei No. constant -OT ₂ -C = OT viscos 158 - (ch ₂ ) ₅ - CN -OT ₂ -COOOT ₃ Oei 159 - (ch ₂ ) ₅ - CN -OT ₂ CN Oei 160 - <ch ₂ ) ₅ - CN -COOT ₃ viscos 161 -CH ₂ CH ₂ -O-CH ₂ CH ₂ - CN OT ₃ viscos 162 -CH ₂ CH ₂ -O-CH ₂ CH ₂ - -COOT ₃ C ₂ H ₅ viscos 163 -CH ₂ CH ₂ -O-CH ₂ CH ₂ - -COCH ₃ -OT ₂ -OT = CH ₂ Oei 164 - (CH ₂ ) ₅ - -COOT ₃ -OT ₂ -CONH ₂ resin 165 - (ch ₂ ) ₅ - -COOOT ₃ -OT ₂ -COOC ₃ H ₇ (n) resin 166 - (ch ₂ ) ₄ - CN C ₂ H ₅ resin 167 - (ch ₂ ) ₄ - CN -OT (CH ₃ ) COOC ₂ H ₅ resin 168 - (ch ₂ ) ₄ - -COOC ₂ H ₅ C ₂ H ₅ Oei 169 - (ch ₂ ) ₄ - -COOC ₂ H ₅ -OT ₂ -C = OT resin 170 - <ch ₂ ) ₅ - H -CH (CH ₃ ) COSC ₂ H ₅ Oei 171 - (ch ₂ ) ₄ - H H Oei 172 -CH ₂ CH ₂ -O-CH ₂ CH ₂ - H -OToCO-NH ₉ resin 173 - (CH ₂ ) ₅ - OT ₃ -SO ₂ NH ₂ Oei 174 - (CH ₂ ) ₄ - CH ₃ cyclopropyl Oei 175 -CH ₂ OT ₂ -O-CH ₂ CH ₂ - OT ₃ 176 -CH ₂ OT ₂ -O-CH ₂ CH ₂ - OT ₃

-21- 23.1.1979

AP A 01 N / 207 605 (54 148/11)

Implementation Example

The invention will be explained in more detail below with reference to some embodiments.

As already mentioned, various methods and techniques are suitable for the use of the compounds of the formula I for the protection of crop plants from agrochemicals:

1 · seed dressing

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

b) dressing the seeds with an emulsion concentrate of the active ingredient of the formula I according to the method a) (wet pickling).

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

The seed dressing or the treatment of the germinated seedling are by nature the preferred methods of administration because the treatment of the active ingredient is completely directed to the target crop. It usually verv / ends 10g to 500 g, preferably 50 to 250 g AS per 100 kg of seed, which, depending on the methodology, which also allows the addition of other active ingredients or Kikronährstoffe differ from the specified limit concentrations up or down can (repeat pickle) ·

2 * Application of tank mix

A liquid work-up of a mixture of counterparts

agent and herbicide (reciprocal ratio of between 1:20 and 5: 1) is used, wherein the application rate of herbicide from 0.1 to 6 kg per hectare. Such tank mixture 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.

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 (coating granules) which allows dispensed dosed over a certain period of time.

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

The compounds of the formula I can be used alone or 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 e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

The content of active substance in marketable agents is between 0.1 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 working-up forms: Dusts and scattering agents (up to 10 7o) granules, coating granules, impregnating granules and homogeneous granules, pellets (grains) 1 to 80%);

Liquid reprocessing forms:

a) water-dispersible active substance concentrates:

Wettable powders and pastes (25-90 % in hands 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 %) ; aerosols

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

I? "23.1.1979

AP A 01 N / 207 (54 148/11)

Granules11 The following substances are used to prepare a 5% granulate: 5 parts of active ingredient 0.25 part of epichlorohydrin 0.25 part of cetyl glycol glycol ether, 3.50 parts of polyethylene glycol 91 parts of kaolin (particle size 0.3-0.8 mm)

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and polyglycol ether are added thereto. The solution thus obtained is sprayed onto kaolin and then the acetone is evaporated in vacuo.

Injection powder t For the preparation of a) follow 70 and b) 10% wettable powder v / the following constituents used:

a) 70 parts of active ingredient

5 parts of sodium dibutylnaphthylsulfonate, 3 parts of naphthalenesulfonic acid-phenolsulfonic acid-formaldehyde condensate 3: 2: 1,

10 parts kaolin,

12 parts Champagne chalk;

b) 10 parts of active ingredient

3 parts mixture of sodium salts of saturated

Fatty alcohol sulfates 5 parts naphthalenesulfonic acid / formaldehyde

Condensate, 82 parts kaolin;

The active ingredients are intimately mixed in appropriate mixers with the aggregates and ground on appropriate mills and rollers. This gives wettable powders of excellent wettability and suspension, which can be diluted with water to give suspensions of the desired concentration and can be used in particular for foliar application.

Emulsifiable Concentrates: The following materials are used to prepare a 25% emulsifiable concentrate:

25 parts of active ingredient

2.5 parts epoxidized vegetable oil,

10 parts of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture,

5 parts of dimethylformamide, 57.5 parts of xylene.

From such concentrates emulsions of the desired concentration can be prepared by dilution with water.

- H -tt-

Pre-emergence antidote test in nutrient solution

A Hewitt broth is prepared containing the following amount of herbicide and 10 ppm of the antidote to be tested.

One uses culture seeds, which should be expected to be damaged by the herbicide used in the specified test concentration and sow it in granulated zonolith (= expanded vermiculite), which is located in a perforated at the bottom plastic flower pot (upper 0 6 cm). This is placed in a second transparent plastic flower pot (upper 0 7 cm), in which there are about 50 ml of prepared with herbicide and antidote nutrient solution, which now rises capillary in the filler of the smaller pot and wetted seeds and germinating plant. The fluid loss is supplemented daily with pure Hewitt nutrient solution to 50 ml. 3 weeks after the start of the test is evaluated on a linear scale from 1 to 9, where 1 means total damage to the plant and 9 unimpaired health. The control solution used in parallel contains no antidote additive.

One uses:

1) 4 ppm Prometryn = 2,4-bis (isopropylamino) -6-methylthios-triazine in Sorghum millet of the variety "Funk G-522".

2) 4 ppm of 4-ethylamino-6-tert-butylamino-2-chloro-s-triazine in wheat of the variety "Farnese".

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

4) 5 ppm of metolachloro-N- (1-methyl-2-methoxyethyl) -N-chloroacetyl-ethyl-δ-methylaniline in Sorghum millet of the variety "Funk G-522".

5) 1 ppm of 2-methoxy-4,6- (ν-methoxy-propylamino) -s-triazine in sugar beets of the variety "Kleinwanzleben"

Compounds of the formula I achieve good antidote activity in these experiments.

-28 -13-

Post-emergence antidote test in nutrient solution General methodology:

One fills small plastic flower pots (upper 0 6 cm), which are perforated at the bottom, with granulated Zonolith and sow the culture names. The pot is then placed in a second transparent plastic flower pot (upper 0 7 cm) containing 50 ml of water, which rises capillary and wets the seed. From the 5th day, the ongoing water loss is compensated with Hewitt nutrient solution. From the 15th day, when the crop is in the lh - to 2-leaf stage, the nutrient solution supplemented with 50 ml is optionally available.

&) 10 ppm of the antidote to be tested + the

b) 1 ppm of the antidote to be tested + the

amount of herbicide given below

added. From the 16th day, the fluid loss is compensated by pure Hewitt nutrient solution again. During the entire test period, the temperature is 20-23 ° C at a relative humidity of 60-70%. 3 weeks after addition of the herbicide and the antidote, the evaluation is carried out according to a linear scale of up to 9, wherein 1 means total plant damage and 9 undamaged state of health.

Test versions:

1) 15 ppm of a [4- (3,5-dichloropyridyl-2-oxy) phenoxy] propionyl-propargylthioloester in wheat of the variety "Zenith".

2) 4ppm of A-ethylamino-O-tert-butylamino-Z-chloro-s-triazine in wheat of the variety "Zenith".

3) 2 ppm a- [4- (prTrifluoromethylphenoxy) phenoxy] -propionic acid n-butoxyethyl ester in maize of the variety "Orla".

A) 8 ppm of α- [4- (p-trifluoromethylphenoxy) phenoxy] -propionic acid n-butoxyethyl ester in Sorghum millet of the variety "Funk G-522".

5) 4 ppm Prometryn = 2,4-bis (isopropylamino) -6-methylthio-s-triazine in sorghum millet of the variety "Funk G-522".

6) 8 ppm al4- (3,5-dichloropyrid-2-oxy) -phenoxy] -propionic acid methyl ester in wheat of the variety "Zenith".

Compounds of the formula I achieve good antidote activity in these experiments, for example compound no. 1.

Antidote Test Seed Soaking

Rice seeds of the type IR 8 are soaked for 48 hours with solutions of the test substances of 10 or 100 ppm. Subsequently, the seeds are allowed to dry for about 2 hours until they no longer stick. Rectangular plastic pots (8x8 cm, 10 cm high) are filled up to 2 cm below the edge with sandy loam. 4 g of seeds are sown per pot and covered only slightly (about the diameter of the seed). The earth is kept in a damp (not swampy) state. Then, optionally, the herbicide N- (1-methyl-2-methoxyethyl) -N-chloroacetyl-2-ethyl-6-methylaniline or N-propoxyethyl-N-chloroacetyl-2,6-diethylaniline in dilute solution and Ln in an amount applied, the equivalent of 1.5 kg AS / ha

equivalent. 18 days after transplantation is evaluated on a linear scale of 1 to 9, where 1 is total plant damage and 9 is undamaged state of health.

Compounds of the formula I show good antidote activity in this experiment.

Claims (33)

invention claim in / in R-. optionally - a radical -OR ~, wherein Rp is an aliphatic group having a maximum of 8 carbon atoms or araliphatic group having a maximum of 15 carbon atoms or a cycloaliphatic or aromatic group having a maximum of 10 carbon atoms, wherein this as a substituent of the aromatic Radicals or of the cycloaliphatic radical halogen, -CN, -NOp, lower alkyl, lower alkoxy, haloalkyl come into question, a radical -NH-CO-NH-R ₄ or - a radical -N (R ..) (R ₄ ), v / orin R ^ is hydrogen or lower alkyl and R _{4 is} hydrogen or an aliphatic group having a maximum of 8 carbon atoms or araliphatic group having a maximum of 15 carbon atoms or a cycloaliphatic or aromatic group each having a maximum of 10 carbon atoms, suitable halogen, -CN, NO ₂ , lower alkyl, lower alkoxy, haloalkyl being possible substituents of the aromatic groups or the cycloaliphatic radical, -33 - AP A 01 N / 207 605 54 148 11 - a radical -N (R ^) (R,), where R-. and R. together form a 5- or 6-membered heterocyclic ring which may still contain oxygen as a possible further heteroatom, X represents hydrogen, -CN, halogen, lower alkyl, lower alkanoyl, -COOH, a carboxylic ester residue, a carboxylic acid amide residue, Q - hydrogen, lower alkyl which may be interrupted by heteroatoms or substituted by halogen or cyano, lower alkenyl or haloalkenyl, lower alkynyl, optionally substituted by halogen 0 -, - C ₇ cycloalkyl, lower alkane carboxylic acid ester group, lower alkanecarbonoethio-thioester group, lower alkanecarboxamide group, alipahtic acyl radical, aralipahtic, cycloaliphatic or optionally substituted aromatic or heterocyclic acyl radical, - Alkylsulfonyl - Sulfonsäureamidrest - a metal salt a quaternized ammonium salt, with the proviso that at least one substituent X, Q or Ro is different from hydrogen, if R, a meta and / or para-halogen-substituted phenyl radical. - 3H- AP А 01 N / 207 54 148 11 ² Ii is used ² Il W is used. ² II N-OH and its alkali metal salt and its quaternary ammonium salt containing 1, 2 or 3 alkyl and / or hydroxyalkyl groups, which together have at most 6 C atoms, is used. 2. The method according to item 1, characterized in that an oxiin derivative of the formula I is used, wherein R .. a radical -NH-R. in which R is hydrogen or a lower alkyl group, X has the meaning mentioned in point 1 and Q is hydrogen, lower alkyl, lower cyanoalkyl, CU-CL alkenyl, propargyl, acetamide, -CH ₂ C00-lower alkyl or -CH (CH ,) Represents COO-lower alkyl. ³ Il NO-CH ₂ CN is used. 3. The method according to item 1, characterized in that an oxime derivative of the formula I is used, wherein R _{1 is} a radical -NH-CO-NH-R. in which R represents hydrogen or a lower alkyl group and in which X and Q have the meaning given in point 1. Method according to item 3, characterized in that an oxime derivative of the formula I is used, in which Q has the meaning given in point 2. 5. The method according to item 1, characterized in that an oxime derivative of the formula I is used, wherein R _{1 represents} a radical -OR ₂ , wherein Rp is an alkyl, alkenyl or alkynyl group having a maximum of 6 C Atoms and in which X and Q have the meaning given in point 1. 6. The method according to item 5, characterized in that an oxime derivative of the formula I is used, wherein Q has the meaning given in point 2. 7. Method according to item 1, characterized in that an oxime derivative of the formula I described herein is used. -Ч - 3S-AP А 01 F / 207 605 54 148 11 8. The method according to any one of items 1 to 7 and 21 to 29 »characterized in that the cultivation area of the crops is treated independently before or after application of the agricultural chemical with the antidote of formula I. 9. The method according to any one of items 1 to 7 and 21 to 29, characterized in that the cultivation area of the crops is treated simultaneously with the agricultural chemical and the antidote of formula I. 10. The method according to any of items 1 to 7 and 21 to 29 »characterized in that the crops or parts thereof are treated before cultivation with the oxime derivatives. 11. The method according to item 11, characterized in that the propagation of the plant is treated. 12. A means for protecting crops from aggressive agrochemicals, characterized in that it contains as antidotes an oxime derivative of the formula I of item 1, together with a suitable carrier material. 13. Composition according to item 12, characterized in that it contains as antidote an oxime derivative of the formula I according to one of the items 1 to 7 and 21 to 29. 14. Composition according to item 12, characterized in that it contains as antidote an oxime derivative of the formula I described herein. 15. A composition according to item 12, characterized in that it contains an agricultural chemical and an Охідг derivative of the formula I acting as an antidote for crops, together with a suitable carrier material. AP A 01 N207 605
54 148 11 16. Composition according to item 15, characterized in that the agrochemical is a herbicide. 17 · Means according to item 16, characterized in that the agricultural herbicide is a herbicide belonging to the class of
1,2,4-triazines, 18. Means according to item 16, characterized in that the agrochemical is a herbicide belonging to the class of
Chloroacetanilides is. 19 · Means according to item 16, characterized in that the aromatic chemical is a herbicide from the class of 4- (phenoxy) phenoxy-propionic acid esters. 20. Composition according to item 16, characterized in that the agricultural chemical is a herbicide from the class of
4- (pyridyloxy) phenoxy-propionic acid ester. 21. The method according to item 1, characterized in that
an oxime derivative of the Pormel N-CO-C-CN
Il N-OH in which Ro and R, independently of one another, denote hydrogen or methyl, and their alkali metal salt and its quaternary ammonium salt which contains 1, 2 or 3 alkyl and / or hydroxyalkyl groups, which together are at most
Possess 6 C-atoms, verv / ends. - & - h AP A 01 N / 207 605 54 H8 11 22. The method according to item 2, characterized in that an oxime derivative of the formula H ₀ N-CO-KH-CO-C-CT Process according to item 5, characterized in that an oxime derivative of the formula H ₀ CO-CO-C-CN 24 · Method according to item 1, characterized in that the compound of the formula
H ₀ N-CO-C-CN Method according to item 1, characterized in that the compound of the formula H ₂ N-CO-C-CN is used. AP A 01 N / 207 605 54 148 11 26. The method according to item 1, characterized in that the compound of formula H ₀ N-CO-NH-CO-C-CIi Il is used. 27- · Method according to item 1, characterized in that the compound of the formula HoN-CO-NH-CO-C-CN N- wifh 0 (CH _{3) 2} CH ₂ CH ₂ ОН 28. The method according to item 1, characterized in that the compound of formula CH ₀ -NH-CO-C-CN CH ₀ CH ₀ OH 3 "j 2 2 N-000 NH CH ₂ CH ₂ OH Process according to item 1, characterized in that the compound of the formula (CHJ ₀ N-CO-C-CN 30. The method according to any one of items 21 to 29, characterized in that the plant culture with the antidote of formula I either before or after application of a herbicide from the class of 1,3 »5-triazines or chloroacetanilides is treated. -S ₄ -SS * AP A 01 N / 207 605 54 H8 11 31. The method according to any of items 21 to 29, characterized in that the plant culture is treated simultaneously with a herbicide from the class of 1,3,5-triazines or chloroacetanilides. 32. The method according to any of items 21 to 29, characterized in that the crops or their generative parts are treated before cultivation with the oxime derivative. ³² II. -O (-χ +) NH ₃ - is used · 33. Composition according to item 12, characterized in that it contains as antidote an oxime derivative according to one of the items to 29.