DD142275A5 - Weed killer - Google Patents

Abstract

The invention relates to a weed killer, consisting of herbicidally active compounds, such as thiolcarbamate, triazine, - Chloroacetanilide, carbamide or phenoxyacetic acid derivatives or their mixtures and based on the mass of these compounds 0.1 to 50% of compounds of general formula I, wherein X is is oxygen, sulfur, SO or SO 2, n is 0 or 1 and R, and R 2 are hydrogen, alkyl group, for Halogen, hydroxyl or nitro substituted phenyl group. - Formula I -

Description

211 475 - "-

Field of application of the invention;

The invention relates to herbicidal agents suitable for the

protective crops are phytotoxic. The herbicidal compositions according to the invention contain as herbicidally active compound thiolcarbamate derivatives or triazine derivatives or chloroacetanilide derivatives or carbamide derivatives or phenoxyacetic acid derivatives or mixtures of these compounds, they also contain, based on the amount of the active compounds, in an amount of 0.1- 50 % of a dichloroaoetaraid derivative of general formula I.

a » « ff 8

NC-CHCl ₂

•; ; Λ ^R 2

X represents oxygen or sulfur, furthermore represents SO or SO ₂ group,

η is 0 or 1, and

R ^ and R ₂ independently of one another represent hydrogen, alkyl group, phenyl group substituted by halogen, hydroxyl or nitro or together denote a butylene, pentyXene or hexylene group which is optionally substituted by one or two methyl groups, with the proviso that for the pail η = > 0 R. and R_ have a meaning other than hydrogen, Alky! Group or substituted phenyl group.

The invention further relates to the application of the above

Compounds for the Protection of Cultivated Plants Characteristics of the Known Technical Solutions It is known from the specialist literature and the practice of plant protection that a significant group of the herbicidal active compounds also damage the cultivated plants to be protected. This phytotoxic effect depends in part on the dose used and is also influenced by the circumstances of the treatment (weather, soil, etc.). Also known herbicidal active ingredients, which are indeed selective for the crops, their selectivity jedooh necessary for effective weed control

Λ _ Λ Λ Λ

-3- Zl1 475

Winding and the growth of crops have a damaging effect »

In the German Pat. No. 3,131,509, in order to reduce the damaging effect of herbicidally active substances, it is proposed to add these 1,8-naphthalic acid or its derivatives (anhydride, solvents, etaides, etc.)

According to the Hungarian patent Hr. No. 165,736, to reduce the damaging effect of thiolearbamates, it is proposed to add to the weight of the herbicidal active ingredient 0.0001-30 % of N, N-disubstituted dichloroacetamides.

The two groups of compounds mentioned - which have so far found the most widespread use in practice "are only partially suitable for solving the multi-faceted task, since the group of herbicidal active substances whose harmful effect must be reduced is extremely large, and you the phytotoxic Furthermore, there is no doubt that the crop plants react in different ways to the damaging effect of the individual herbicidally active substances, and for this very reason the reduction of the damaging effect by means of the compounds developed for this purpose can only be achieved in loading

be reached to a limited extent.

Object of the invention .

~~ The goal of their own, in the field of reduction

The Phytotoxicity of herbicidally active compounds has been to develop a formerly new group of compounds, which are used for. Reduction of this damaging effect, no environmental problems are

it

gentle and more economical use of the herbicides

remedial action enables «

DaJlegang the essence of the invention

It has now surprisingly been found "that the

Dichloroacetamide derivatives of general formula I are suitable for reducing the sohdigende effect of thlolcarbamate, triazine, carbamide, chloroacetanilide and Ehenoxyesaigsäure derivatives used as herbicidal 'active ingredients'. If one of the compounds of the general formula I is added to the herbicidally active compounds listed above, based on their amount in an amount of 0.-1-50 %, and the crops are protected by treatment with the resulting agent, the damaging effect becomes the herbicidal active ingredients practically avoided, the desired weed-vemient end effect is retained. It has also been found that the phytotoxicity can also be avoided by treating (treating) the seed of the crop with a compound of general formula I prior to sowing and weed-killing after sowing with the known herbicides

A list of compounds of the general formula I according to the invention is given in Table 1 "

Connections ITr ·

R-, Table 1 Name of the compound

phys. constant _ (melting point 0, calculation index) _

1 2

5 t 7 8

10 11 12

13

14 15

16

0 0 pentylene

0 0 1 »-methylpentylene

0 0

3 »-Methylpentylen

0 0 1.5 * -Dimethylpentylen

0 0 butyl

0 0 hexylene

S 0 pentylene

S 0 l'methylpentylene- ¹

0 3'-methylpentylene

S S

so ο

SO ₂

Butylene hexylene pentylene

pentylene

1 H 1 CH-

0 1 CH 2 N-dichloroacetyl-1-oxa-4-aza-spiro (4,5) -decane

N-dichloroacetyl-lO-methyl-l-oxa-4-aza-spiro- (4,5) -decane

lT-dichloro-8-methyl-l-oxa-4-aza-spiro- (4,5) -decane

N-dichloroacetyl-6, lO-dimethyl-l-oxa-4-azaspiro- (4,5) -decane

H-dichloroacetyl-1-oxa-4-aza-spiro (4,5) -nonane N-dichloroacetyl-1-oxa-4-aza-spiro (4,6) -undecane H-dichloroacetyl-1-thia- 4-aza-spiro (4,5) -decane N-dichloroacetyl-10-methyl-1-thia-4-aza-spiro (4,5) -decane

N-dichloroacetyl-S-methyl-l-thia-4-aza-spiro - (4,5) -decane

N-Dichloroacetyl-1-thia-4-aza-spiro (4,4) -nonane J \! - dichloroacetyl-1-thia-4-aza-spiro (4, t>) -undecane-1-dichloro-acetyl -l-thia-4-aza-spiro- (4,5) -decane-1-oxide

N-dichloroacetyl-l-thia-4-aza-spiro- (4,5) -decane-1,1-dioxide

N-dichloroacetyl-tetrahydro-1,3-2H-oxazine, 1-dichloro-acetyl-2,2-dimethyl-tetrahydro-1,3-2H-oxazine

H-dichloro-2-methyl-2-ethyl-tetrahydrol, 3 (2H) -oxazine

105.5 to 107

100-102 119-120

79-80

81-82

149-151

106-109

127-129 83-85 96-99

188 180-181

n ^ ^b: 1.5070 n £ ^b: 1.4919

It can be seen from the table that most 'ae.i · new derivatives are solid, crystalline compounds and only a few are in a liquid state at room temperature.'

The compounds of general formula I are acid

amido. For their production, the specialist literature

various methods known.

Among them, the acylation of cyclic amides or their salts with dichloroacetyl chloride in the presence of an acid acceptor and an inert solvent medium is most common (DT Patent Nos. 2,350,547 and 2,350,900 * WR Vaughan et al., J. Org. Chem. 2 §_ 145-148 / 1961 /) »Suitable inert solvents may be, for example, ketones (acetone, methyl ethyl ketone) or aliphatic hydrocarbons (for example hexane) or aromatic hydrocarbons (benzene, toluene, xylene, chlorobenzene, nitrobenzene), furthermore diethyl ether, Dimethyl sulfoxide or chlorinated aliphatic hydrocarbons (methylene chloride, carbon tetrachloride) can be used * However, the acylation can also be carried out without a solvent.

As the acid acceptor, organic bases (for example triethylamine, triethylamine, eyridine, N, H-dimethylaniline) or else inorganic bases (alkali metal carbonates, alkali metal hydrogencarbonate alkali metal hydroxides or their aqueous solutions) can be used. The acylation is carried out at temperatures between 50 and 160.degree. preferably »20 and 40 ⁰ C, executed.

The starting amines are five "or six-membered heterocyclic compounds that contain in the ring one nitrogen atom and one oxygen or sulfur atom" The preparation of these compounds is from the F _a loading chlitoratur

Porting Table 1

fertilizer. Σ η 'E ₁ R ₂ Name of the compound

(Melting p.oC calculation index)

17 0 1 Pentylene N-dichloroacetyl-1-oxa-5-aza-spiro - (5,5) - undecane 111-112

18.0 l of 1''-methylp deolefin N-dichloroacetyl: 1-il-methyl-1-oxa-5-aza-spiro

(5,5) -undecane 135-138

19 0 1 3 ¹ -M.eihy I ¹ P deplete IT-pDicJiloracet ^ / l-9-methyl-l-oxa-5-aza-spiro

(5,5) -uno: ecan · 115-118

20 O 1 Butylene-N-dichloroacetyl-1-oxa-5-aza-spiro (5,4) -decane 62-64

21 0 1 hexyls N-dichloroacetyl-1-oxa-5-aza-spiro (5,6) -dodecane n ^: 1.5012

Su 9 Λ

(See, for example, D.Bergman et al., J.Am.Chera.Soc. 75, 358-361 / 1953 / j JB Dougough et al .: J. Am. Chem. Soc., 72, 2866-7 / 1979/1 VY .H * Watansboj _{e e} «Chem.Soc · 7 £ 2833-6 / 1957 /). Both the five- and the mono-membered ring-shaped amines can be prepared by reacting the corresponding hydroxyalkylamines or mercaptoalkylamines or their hydrochlorides with the corresponding carboxylic compounds with or without solvent, with or without catalyst at room temperature or elevated temperature using or without dehydrating agent be "As the catalyst, basic catalysts, for example alkali carbonate · = nate ₉ or acidic catalysts, for example, hydrogen chloride, hydrogen bromide, p-Toluolsulfonssure used" As the solvent, aliphatic hydrocarbons (sum as hexane _s petroleum ether), halogenated derivatives thereof, (Ziirn example Methylene chloride, carbon tetrachloride) ₉ aromatic hydrocarbons (for example, benzene, toluene, xylene) or their derivatives (for example, chlorobenzene ₀ j-nitrobenzene), further

It "

8ber ether or an excess of the carbonyl reagent used as! Connection in erage _e Reaktionsteiapera The door is 20-200 Co ⁰ In this V / else may be cyclic amines having 5 members by reacting aziridine. be prepared with the corresponding carbonyl compound or hydrogen sulfide

Another possibility for the preparation of the compounds of the general formula I is that the N ~ dichloro »acetylated hydroxyalkylamine or mercaptoalkylamine or their hydrochlorides under the reaction conditions already explained a with the corresponding CarboEylverbindung where ·! tare Herstellunßsmöglichkeit is the with

-9- 211 47S

Dichloroacetyl chloride implementation of the N-nitroso derivatives of the corresponding heterocyclic amines (DT-PS Nr ♦ 2 035 796 | KLHebenbrock et al. »Justus Liebig * Ann.Chem · 1972 765. 78-93).

The N-aoylated heterocyclic amines can also be prepared by reacting the Schiff base formed from the corresponding aminoalcohol and the carbonyl compound under the reaction conditions already described with dichloroacetyl chloride (M.Businollit Il Farmaco / Pavia / Ed. 127-134

/ 1955 /).

Exemplary embodiments

The preparation of the compounds of the general

Formula I is illustrated by the following Preparation Examples. Example 1

N "Dichloraoetyl-l-p3;. A.-4-aza-api ro- _(! 4 _{i p T} 5) ~ decane (comp.", Hr 1) 64 g (0.645 mol) of cyclohexanone and 30 g (0.491 mol Ethanolamine are boiled in 100 ml of Benaol with continued distilling off of the resulting water until 8.8 ml of water are added, and the reaction mixture is cooled and treated with 55 g of 40% sodium hydroxide solution (0.55 mol). Under external cooling with an ice-salt refrigeration mixture, 74 g (0 _y 5 mol) of dichloroacetyl chloride are added dropwise to the reaction mixture After completion of the addition, the mixture is stirred at room temperature for two hours, then with hydrochloric acid and then with water until neutral The benzene is distilled off in vacuo, giving 10 g (0 _s 4 mol) of a greenish-white crystalline substance at room temperature.

crystallize from absolute ethanol white crystal © © gives · The substance melts at 105.5 to 107 ⁰ C, its structural "· door is evidenced by the IR spectrum ~" analysis "

Calculated j C 47.63 % N 5.50 % Cl 28.12 % found «. C 47.12 % N 5.70 % Cl 28.56 % _o

Example 2

H ^ MchJiprace ^ ffi ^ (verb «, Nr / 7)

9.8 g ₍₉ I O mole) of cyclohexanone and && 7 _ä 7 g (O ₅ I mol) of 2 »Meroaptoäthylamin be gekooht in 100 ml Benaol under continuous removal of the water formed as long as ₉ to 1.8 ml of water are distilled off" to 11.7 g (0.1 mol) of dioxoryl chloride are added dropwise to the cooled ethereal solution. 11 g of 40% aqueous solution are added dropwise with external cooling with an ice-salt mixture. After completion of the addition, the reaction mixture is still at room temperature Stirred for 2 hours, then washed first with hydrochloric acid, then with water, and finally the benzene distilled off in a vacuum. 17.2 g (0.064 mol) of the above compound are obtained in the form of a white, sweet Sabstan Ethanol are obtained white crystals, which at 149-151 ⁰ O sohEtelzefto The structure of the compound is proved by the IR spectrum * · Analyzes

Calculated? C 44.77 % N 5.22 % S 11.98 % Cl 26 _S 23 % found «C 44 _e 51 f> N 5.31 % S 12 _S 15 % Cl 26.25 $>. Example 3

ίΛ »Β«

- "- · - £. II 4 AD

11.2 g (0.1 KoI) of 4-methyl-oyclohexanone and 6.1 g (0.1 ί, ίοΐ)

♦ t: "

Athanolamine be boiled in 100 ml of benzene while distilling off the water formed until 1.8 ml of water have passed. Then the reaction mixture is cooled and treated with 8g (0.1 mol) of pyridine. With external cooling with an ice-sals-Kültegemisch 14.7 g (0.1 mol) DiohloracetylChlorid are zugotropft. The mixture is worked up in the manner described in Example 2. 20.7 g (0.070 mol) of the above compound are dissolved in a pink, ointment-like substance.

Recrystallization from absolute ethanol gives a white, crystalline substance at 119-120 ° C. The structure of the compound is proved by the IR spectrum

 Analysis:

reputed: C 49.63 % N 5.26 % Cl 26.64 % found «C 49.45 % N 5.35 % Cl 26.92 <$>. Example 4

^^% ^^ ^^ 9 9 ^ 3 ^^^^^^^^^^^ ~ ^ - ^^ "^^ ^ 9 (verb · Hr. 19) 17.5 g (0.18 mol) cyclohexanone and 11.2 g (0.15 mol) of 3-aminopropanol in 50 ml benzene are boiled under continuous Eatzug the water formed until 2.7 ml of water are distilled off. Then the reaction mixture is cooled and follow with 16 g 40 ? aqueous sodium hydroxide solution (0.165 mol) set before · Under external cooling with an ice-salt "mixture is 22.1 g (0.15 mol) was added dropwise Dichloraoetylchiorid" the reaction mixture is worked up as described in the game If '2 way "15 , 7 g (0.059 mol) of the above compound are in Porm a greenish white »crystalline

- • la

from absolute ethanol, white crystals are obtained which melt at xl-112 0. The structure of the compound is proved by the IR ~ & pektrum

 Analysis:

Calculated ü 49.63% N 5.2b% Cl 26.64% found: - G 49.52% U 5.32% C i 26.45%.

Example 5

IJ '' _{i i} Dichl Orace tyl _i - L _'i thio --4 ~ aza-spiro-- _(i 4> 4) - no nan (comp. No. iO) 8.4 g (0.1 7.7 g (X, X mol) of 2-mercaptoethylamine are boiled in 100 ml of benzene with continuous removal of the resulting water until 1.8 ml of water are distilled off 8 g (0.1 mol) of pyridine are added. Under external cooling with an ice-salt Kältemiscnung 14.7 g (0.1 mol) of dicloroacetyl chloride are added dropwise. The reaction mixture is worked up in the manner described in Example 2. 21.6 g (0.085 mol) of the above compound are obtained in the form of a yellowish, pasty substance. The white crystalline product obtained after recrystallization from hexane melts at 83-85 η-C ⁰ ₀ The structure of the compound by the IR Spektrum.bewiesen. Analysis:

Calculated: C 42.52% Ή 5.51% S 12.61% Cl 27.89% Found: C 42.35% N 5.45 % S 12.80% Cl 27.56 %.

Example 6

N-dichloroacetyl 1-1-thia-4-azaspiro (4 ». 5) decan-1-yl-cyxl (Compound Ir. 12).

13.41 g (0.05 mol) of N-dichloroacetyl-1-thia-4-azaspiro (4,5) -decgn are dissolved in 100 ml of methylene chloride. At -25 to -15 C, a solution of 9.15 g (0.053 mol) of m-chloro

perbenzoic acid in 100 ml of methylene chloride added dropwise. Then, the reaction mixture is stirred at room temperature for two hours, then cooled to 10 ⁰ C and freed by nitriding from undissolved. The filtrate is washed first with 2x30 ml of saturated sodium carbonate solution, then with water, dried over anhydrous sodium sulfate and then evaporated to dryness. 13 »23 g (93 %) of a white, crystalline substance are obtained, which, after recrystallization from absolute ethanol, melts with decomposition at 188C. Analysisί Calculated found

Chlorine 24.95 % 24.90 %

Sulfur 11.28 % 11.30 %

Carbon 42.26 % 42.18 %

Oxygen 11.26 % 11.35 %

Nitrogen 4.93 # 4.98 %

Hydrogen 5.32 % 5.30 %,

The structure of the compound is demonstrated by the IR spectrum »

Example 7

³ ~ (fLsJOr ^ ecan-l _% 1-dioxyd

(Connection lir «13)

13 »4l g (0.05 mol) of dichlorosiloxy ~ l-thia-4-asaspiro- (4,5) -decane were dissolved in 150 ml of methylon chloride. To the solution is added dropwise at 0-3 ⁰ C, the solution of 18.12 g (0.105 mol) of m ~ chloroperbenzoic acid in 200 ml of methylene chloride. The reaction mixture is stirred at room temperature for one hour and boiled for one hour. Eaan the mixture is cooled to 5 ⁰ C, the precipitated precipitate is

β ·. -Sr β

filtered off and washed with 50 ral methylene chloride. The filtrate is combined with the solution of Yfloso's liquid, washed with 2 x 50 ml of saturated sodium carbonate solution, then with water, dried over water * free sodium sulfate, and finally evaporated to dryness. 13.7 g (91 %) of a yellowish-brown, crystalline substance are obtained. This is dissolved in acetone, the solution is clarified with activated charcoal and the substance crystallizes. The resulting white, crystalline product melts with decomposition at 180 ° -181 ° C.

Analye chlorine sulfur carbon hydrogen oxygen nitrogen

The structure of the compound is proved by the IR spectrum «

The other compounds listed in Table 1 are prepared in a similar manner. The physical constants used for their identification (melting point information) are given in Table 1.

The compounds of general formula I can be used, for example, to prevent the ifeytotoxicity of the following herbal active substances

calculates j found: 23.66 % 23 * 60 % 10.68 % 10.72% 40.00% 40.10 % 5.12 % 5,08 % 15.09 % 16 ₆ % 3 % 4.67 % 4.70 % *

S »ethyl ~ N, K" = dipropylthiolcarbamate, S-propyl-dipropylthiolcarbamate,

SA thyl-diisobutylthiolcarbamet, S "2ρ 3 _s 3 T ^ ichlorallyl-diisopropylthiolcarbama1 ₁ S-ethyl-oyolohexyläthylthiooarbamat,

lid.

211 475

9-ethylhexahydro-1H-azepine-1-carbothiate, 2-chloro-rN-isopropylacetanilide, N, N-diallyl-chloroacetamide,

S-4-chlorobenzyl diethylthiolcarbamate, 2-chloro-4-ethylamino-6-io-isopropyl-amino-s-triazine, 2-chloro-4,6-bis (ethylamino) -s-triazine, 2- (4-chloro-6-ethyl-amino -s-triazin-2-yl-ajnino) -2-methylpropionitrile,

2-chloro-4-cyclopropylamino-6-isopropylaJnino-s-triazine, 3- (3 *, 4 ^l -Mchlorphenyl) -l-methyl-l- (n-butyl) -carbamid, 2-Ghlor-2 ^I -ättiyl -b ^l mettiyl-N- (1-methyl-2-niethoxyethyl) -

acetanilide,

2-chloro-2 ', 6'-diethyl-N- (l, 3-dioxolan-2-yl-methyl -) - acetaldehyde

anilide,

2-chloro-2 ', 6'-diethyl-N- (ethoxycarbonyl-methyl) -acetanilide, 2-chloro-1-ethoxymethyl-2'-methyl-6 ^! ethyl acetanilide, 2-chloro-N- (2'-methoxyethyl) -2 ", b" -dimethyl-acetanilide,

2-chloro-N-butoxymethyl-2 ', 6'-diethyl-acetanilide,

2-Chloro-N- (2 "-methoxy-1" -methylethyl) -2 ^l -methyl-6 ^l -äthLyl-

acetanilide,

2-chloro-N-isopropoxy: ymethyl-2 ^l , 6'-dimethylacetanilide,

Ν, Ν-hexamethylene-S-ethyl-thiocarbamate, N- (3-chlorophenyl) -LT ^t -methyl-N ^! -methoxy.carbamid,

N- (3,4-dichlorophenyl) -N'-methyl-N'-me thoxy-carbamide, N- (3-chloro-4-bromo-phenyl) -N ^t -methyl-N ^< -methoxy-carbamide,

2-butylamino-4-chloro-b-ethylamino-s-tiaziazine, 2-fluoro-4,6-bis-isopropylamino-s-triazine, 2-methylmercapto-4,6-bis-isopropylamino-s-triazine,

2-MethylmeΓcapto-4-ethylamino-6-teΓt _u -butylamino-s-triazine, 2-terto _w -i3utylamino-4 -äth5zlamino-6-methoxy-l, 3,5-triazine, 4-amino-6-tert .-butyl-3-methylthio-4,5-dihydro-l, 2,4-

triazine-i? -one

2,4-dichlorophenoxyacetic acid,

2.4 ~ dichlorophenoxypropionic acid,

2,4-dichlorophenoxybutyric acid _f

2 "methyl" 4 ~ chlorophenoxyacetic acid, 2,4 »5-trichlorophenoxyacetic acid and the mixtures of listed herbicidal active ingredients.

The dichloroacetamides of the general formula I can be formulated both in themselves and externally together with the abovementioned herbicidal active compounds or mixtures thereof with the methods customary in the preparation of crop protection agents into pulverulent or liquid preparations. The crystalline compounds of the general formula I can be formulated, for example, according to the following recipe into wettable pulverulent preparations;

7O ₄ O % active ingredient of the general formula I 17.0 % kaolin 8.0 % active silicic acid 2.5 % fatty alcohol sulfonate 2.5 % sodium lignosulfonate *,

The components blended together in the above ratio are ground in an Alpine mill to give a ready-to-use wettable powder preparation. If the compounds of general formula I are to be formulated together with a herbicidal active ingredient, the indicated composition should be modified in such a way in that, for example, 50 % herbicidal active ingredient and 20 % compound of formula I were mixed with the additives

• When dor already .erwähnten method Phytotoxisität the known Herbiside by pickling of the S _a raens of the crop plant with compounds of the general formula I shown below verxdngörBß is-es appropriate the compound of general $ o: formulated with talc su rael I, with about 20 -30 % this

Substance can be used.

Some of the compounds of general formula I at room temperature is in the liquid state before _e These compounds are primarily formulated into emulsifiable concentrates, for example according to the following recipe: 20-50% compound of the general formula I 74 to 45% solvent (for example xylene),

9 % polyoxyethylene alkyl ether (emulsifier) "An emulsifiable concentrate can also be prepared according to the following recipe»

7 % compound no. 1

5δ EPTC (AthjifNjN-dipropylthiocarbamate) SS xylene

5 % polyoxyethylene alkyl ether (emulsifier)

 Of course, crystalline compounds can also be formulated into emulsifiable concentrates. This is particularly advantageous darm when the herbicidal active ingredient whose harmful effect is to be reduced by the compound of general formula I, in the liquid state (for example, EPTC).

Emulsifiable concentrate III 50 % 2 "Chloro-N" (methoxymethyl) -2 ', 6 * -diäthylaoetanilid _i

8 % N ~ D ± chloroacetyl-l-thia-4-aza-spiro »(4 ₉ 5)" decane, 5 % Polyo3cyalkylacyl-Emul>2; ator ₉ .

37 % xylene · granules »

5.0 % S-propyl-H, N-aiidobutyl-thioloarbamate, 0.5 % N-dichloroacetyl-1-oxo-5-aza-spiro-5 (5 ₅ 5) uadecane _i

94 »5 % pumice *

..- te- 211

The heterocyclic Diohloracetamide the general formula I exert their phytotoxicity reducing effect both then ₉ they Wonn with the known herbicidal active ingredients applied together are (regardless of whether to-'with these together formulated or before spraying as Tankmisohung in place with the herbicides mixed), as well as to whom they are applied prior to application of the weedcurifying agent, an economically advantageous and expedient method © for the latter. Possibility is the treatment of the seed with the formulated compounds of general formula I before sowing. The herbicidal agent is then sprayed on the ground immediately before or after sowing. "

The following examples show the phytotoxicity decreasing effect of the compounds of general formula I for the herbicides Afalon (N ^^ dichlorophenyl / ^ - methyl-lj ·· "metho3cycarbam ± d) j Eptom (lI _s N <" Mpropyl-S »ethyl thioloarbamate),

; Sencor (4-amino ~ 5 ^s;> tert _e "butyl-4S5 ™ dihydro ~ 3» methylthioünd Lasso / 2-chloro-K ~ (methoxymethyl) -2 ', o'-diethyl-acetanilide / l _i 2 _4? tria25in-5-one) ^/ e the reduction in the phytotoxicity was diallyl-2 _i, 2-dichloroacetamide and 1 ₉ 8 ° -Naphthalsäureanhydrid compared the extent of phytotoxicity with the action of the known antidotes N, K ^e 'by determining the green weight of the treated Plants scored · The green weight of mechanically vegetated plants is used as control ©, this was assumed to be 100 % «. '.

Example β

In this experiment, the harmful effect of Afalons in Sonnenblumeukulturon was examined and determined to what extent this effect is reduced by the compounds of general formula I.

Zl 1 475

The experiments were carried out on plots of size 20 m

made in quadruple repetition. The Afalon was used in each case in the form of 50 WP at a dose of 5 kg of active ingredient per hectare. The antidote was applied in the form of an aqueous suspension simultaneously with the spraying of the Afalon. The results obtained are summarized in Table 2.

Table 2

Used pesticides Greenweight in % of

Control at an antidotum dose of 0.5 1.0 2.0 kg / ha

Afalon 41 41 41

Afalon. + 1,8-naphthalic anhydride 58 69 75 Afalon + N, N-diallyl-2,2-dichloro

acetamide 48 51 67

Afalon + Compound No. ₀ 2

Afalon + compound ETr. 7

Afalon + Compound No. 15

Afalon m compound no. 17

mechanically controlled control 100 100 100

The measurement of the green weight of the sunflower shows that the heterocyclic dichloroacetamides according to the invention reduce the phytotoxicity of the afalo much better than the known antidotes 1,8-naphthalic anhydride and N, N-diallyl-2,2-dichloroacetamide. The compound No. 17 completely removes the damaging effect.

Example 9

The aim of this experiment was to investigate the extent to which the sunflower seed can be reduced by adding the antidotum to the sunflower seed before sowing and spraying the afalon at a dose of 5 kg of active substance per hectare after sowing, conditions and conditions Evaluation of the experiments were similar to those in the

78 92 95 67 89 90 75 93 102 81 95 99

-αο- 2 1 1 47

Example 8 ,, The results are shown in Table 3 °

Table 3

Substances used Green weight in % of

Control at an antidotum dose of

· 0.25 0.50 1.00 kg / 100 kg

Afalon 41 41 41 Afalon + 1,8-naphthalic anhydride 57 69 75 Afalon. + N, N-diallyl-2,2-dichloroacetamide 62 71 75 Afalon + compound Hr. 2 89 95 98 Afalon + Compound No. ₀ 7 78 86 90 Afalon + Compound No. ₀ 15 90 94 96 Afalon + compound ETr ₀ 17 92 98 100 mechanically controlled control 100 100 100

As the table shows, the results do not differ materially from the results of example 8, except for the limits of measurement errors. Compounds Nos. 2, 7, 15 and 17 may have the phytotoxic effect of the afaloon on the sunflower be cheaply reduced »

Example 10

In this experiment, the damaging effect of the eptam on maize cultures was investigated and the extent to which this effect is reduced by the compounds of the general formula I _o

The tests were carried out on 20-m cells with Beke 270 maize hybrids. The active substances were applied before sowing in the form of tank mixes containing different amounts of antidotum and the liquid weed killer Eptam 6 E in an amount of 13 liters / ha.

The results are summarized in Table 4 »

ZIt 47

table

Used active ingredients

Green weight % of control at an antidotum dose of 0.5 1.0 2.0 kg / ha

Eptam

48

48

48

Eptam + 1,8-naphthalic anhydride

Eptam + N, N-dialyl-2,2-dichloroacetamide

60

84

70

Eptam + Compound No. 1 Eptam + Compound No. ₀ 2 Eptam + Compound No. ₀ 3 Eptam + Compound No. 7 Eptam -t- Compound No. 9 Eptam - Compound No. 17 Eptam + Compound No. 19

98 90 94 97 92 98 96

102 93 97

100 97

100 98

105

95

100

100

98

100

102

mechanically controlled control

100

100

From the table it can be seen that of the 7 heterocyclic dichloroacetamides studied, five completely eliminate the damaging effect of the eptam, and the other two are at least as effective as the N, N-dialyl-1,2-dichloroacetamide (Eradioane ).

Example 11

In parallel with the experiments described in Example 10, the same active ingredients were tested by pickling the seeds with the antidote and treating them with the herbicidal agent eptam 6E at a dose of 13 liters / ha before sowing the soil. As in the experiments already described, the green weight of the plants was rated.

The results are shown in Table 5.

-Ä «*, - & i i

Table 5

Active ingredients used Green weight % of control at an antidotum dose of (kg / 100 kg seed) 0.25 0.50 1.00

Eptam 48 48 48

Eptam + 1,8-naphthalic anhydride 68 70 72 eptam +]! T, N-diallyl-2,2-dichloro

acetamide 65 75 80

Eptam + Compound No. 1

Eptam + Compound No. 2

Eptam + compound no. 3

Eptam + Compound No. 7

Eptam + compound no. 9

Eptam + compound no. 17

Eptam + compound no. 19

mechanically controlled control 100 100 100

The data show well that although the doses of the compounds of general formula I used are lower, the harmful effects of thiolcarbamate on compounds Nos. 1, 3, 7 and 19 have been completely eliminated.

Example 12

In this experiment it was determined to what extent the harmful effect of Sencor on soybean is reduced by the compounds of general formula I.

can.

The experiments were carried out on 20 m cells.

After sowing the soybeans, the plots were treated simultaneously with the antidotum applied in different concentrations and in the form of an aqueous suspension and Sencor, the dose of which in each case being 1.5 kg of active ingredient per hectare.

98 100 100 95 97 97 97 99 102 98 102 105 90 05 95 95 98 98 97 100 108

d \ 1

The results are recorded in Table 6.

Table 6

Substances used Green weight % of control at an antidotum dose of 0.5-1.0. 2.0 kg / ha

Sencor 17 17 17 Sencor + 1,8-naphthalic anhydride 30 41 52 Sencor + N, N-dial; yl ~ 272-dichloroacetamide 20 21 26 Sencor + connection no. 1 42 65 72 Sencor + connection no. 7 48 70 76 Sencor + connection no. ₀ 8 45 68 76 Sencor + connection no. ₀ 17 48 71 82 mechanically controlled control 100 10Ö 100

The results demonstrate that the compounds of general formula I in each case significantly reduce the damaging effect of Sencor significantly better than the known antidotes 1,8-naphthalic anhydride and N, N-diallyl-2,2-dichloroacetamide.

Example 13

Also in the case of Sencor, the phytotoxicity-reducing effect of the compounds of general formula I was also determined in pickling. The soybean seeds were pickled, and after sowing, the herbicidal agent was sprayed on the soil, also at a rate of 1.5 per hectare. The results are shown in Table 7o

Table 7

Substances used Green weight % of control at an antidotum dose of • . 0.25 0.50 1.00 kg / 100 kp;

Sencor ·. 17 17 17

Used active ingredients

Green weight in % of the control at an antidotum dose of 0.25 0.50 l, 00kg / 100 kg

Sencor + 1,8-naphthanic anhydride 51 64 70 Sencor + N, N-dialkyl-yl-2,2-dichloro-acetamide 26 28 31 Sencor + connection no. 1 52 75 80 Sencor + connection no. 7 58 79 87 Sencor + connection no. 8 55 75 82 Sencor + connection no. ₀ 17 61 82 92 mechanically controlled control 100 100 100

It will be readily apparent from the table that when the compounds of general formula I, especially compound No. 17, are used, the herbicidal agent Sencor exerts practically no significant injurious effect, while the known antidotes 1,8-naphthalic anhydride and N, N Diallyl-2,2-dichloro-acetamide reduce the phytotoxic effect much less.

Example 14

In this experiment, the harmful effect of the active ingredient 2-chloro-N- (methoxymethyl) ~ 2 ', 6'-diethylacetanilide herbicidal agent Lasso on the sorghum was examined and determined to what extent this effect by the compounds of the general Formula I

can be reduced.

The experiments were carried out in quadruplicate on 20-m cells

In each case, Lasso 48 EC was applied at a rate of 4.5 liters per hectare as Herbic, and only the control was mowed in the Arabian way

From the active compounds of the general formula I containing wettable powder preparations, an aqueous suspension was prepared. This was in the apparent from Table 8 doses of the aqueous emulsion of Lasso 48 EC

- «- 211 475

and the mixture obtained after sowing, but before emergence (i.e., pre emergence) of the black sorghum. After 4 weeks, the green weight of the plants was determined and compared with the green weight of the mechanically-hatched control.

Table 8

Substances used Green weight % of control at an antidotum dose of 0.5 1.0 2.0 kg / ha

Lasso 48 EC 37 37 37

Lasso 48 EC + 1,8-naphthalic acid

anhydride 6l

Lasso 48 EC + N, N-Diallyl-2,2 ~

dichloroacetanilide 72

Lasso 48 EC + connection No. ₀ 1 95

Lasso 48 EC + connection No. 2 80

Lasso 48 EC + connection No. 7 90.-:

Lasso 48 EC + connection No. 12 75

Lasso 48 EC + connection no. 12 92

Jaasso 48 EC + connection No. 14 90

mechanically controlled control 100 100 SOO

Example 15

The experiment described in Example 14 was repeated with the difference that, prior to sowing, the seed was stained with compounds of general formula I applied in different dose. This seed was then sown, the soil was then treated with Lasso 48 EC at a rate of 4.5 liters / ha. Evaluation was carried out similarly as already described by determining the green weight of the 4-week-old plants. The baseline here again was the green weight of mechanically controlled control. "The results are shown in Table 9.

65 70 78 82 97 102 87 92 95 98 78 83 98 100 96 98

-afc- 211 47

table

Active ingredients used Green weight % of control at an antidotum dose (kg / 100 kg seed) of 0.25 0.50 1.0

Lasso 48 EC 37 37 37

Lasso 48 EG + 1,8-naphthaic acid anhydride

Lasso 48 EG + N, N-dialkyl-2,2-dichloro-acetamide

Lasso 48 EC + connection no. 1

Lasso 48 EC + connection no. 2 Lasso + connection no. 7 Lasso 48 EC + connection no.

Lasso 48 EO + connection no.

Lasso 48 EC + connection no.

mechanically controlled control 100 100 100

It can be seen that each one of the tested compounds of general formula I reduced or eliminated the deleterious effect of lasso 48 EC on the sorghum. In some cases (see compounds Nos. 1, 7 and 13), there was a pronounced growth-promoting effect »

68 71 73 75 80 85 98 105 110 95 98 96 97 102 105 93 96 96 94 98 107 87 91 85

Claims (4)

1. tfokrautvijrnichtungsmittel, characterized geke η η records that they herbicidally active compounds, preferably ihioloarbamat-, triazine, Chloraoetanilid-, carbamide or phenoxyacetic acid derivatives or their aemic and based on the weight of these compounds 0.1-50 % compounds of general formula I CHp CHp ι Γ X N-C-CHOI, Λ «a wherein Z stands for oxygen or sulfur, furthermore for SO or SO «group,. " η is 0 or 1, and R and Rp are independently hydrogen or _f alkyl group are substituted by halogen, hydroxyl or nitro phenyl group together form a optionally substituted by one or two iäethy! Groups substituted butylene · _»t pentylene» ⁷ or hexylene mean with one ore Hnkung ,, that for the pail η = O R, and R _{g have} a meaning other than hydrogen ₉ alkylgruppa or substituted phenylgroup ©, contained »2-Batylaffiino-4 'c} ilor" = 6-ethylamino ™ s "trlaziji, 2» Chlorine ~' s _triaziri> 2 ~ Methyliaeroapto-4 _{t 6-bis-iso?} 2 "methylmeroap1; o-4-ethylamino-6-tert.-butylaraino-s-tria- inen, 2" tert-butylamino "4" ethylamino ~ 6-metb.oxy-1 »3,5" tria2in _s 4-araino- _{6-tert-butyl-3-e-4 s} tnethylthio 5-dihydrol _t ', 4-triazin-5-one 2, 2 ^ Bichlorphenoxyessigsäure, 2 _t 4 "D3, chlorphen oxypropionic acid _f 2 _s 4 ~ Dicb.lorphsaoxybuttersäure, 2 contains "methyl-4-chlorpbeaöxyessi ^ Akure, 2948 5-Srichlorphenoxyessigsäure * 2-lfotbyl-4 · chlorpheno x $ acetic acid" or their Gendsohe. · 2. Weedkiller according to item I ₉ thereby characterized in that it is one of the compounds of the general formula X and as herbicidal active substance S = * Athyl « S-ethyl-diisobutylthiolcarbamate> S-2,3,3-trichloroallyl-di-i-di-propylthiolcarbamate, S-ethylcyclohexyl-ethylthiolcarbamate "2 ~ chloro ~ 2 * _s 6 * -diethyl-K- (methoxymethyl) ~ acetanilide, 9 ~ ethylhexahydro ~ lH- azepine-1-carbothoate _$ 2-chloro-isopropylacetanilide, N, N-diallyl-2-chloroacetamide _t S-4-chlorobenzyldiethylthiolcarbamate, 2-chloro-4-ethylamino-6-isopropylamino-3-triazine ₈ 2-Chloro -4 ₉ 6-bis- (ethylamino) "D-" triazine _} 2- (4-chloro-6-ethylamino-s-triazin-2-yl-amino.) "2"methyl-> propionitrile-S-chloro ^ - oyolopropylamino-G-isopropylamino-striaain, 3- (3 *, 4 * -dichlorophenyl) - ' 1-methyl-1- (n-butyl) -oarbamide _t 2-chloro-2-ethyl-6-o-ethyl-N- (1-taethyl-2-methoxyethyl) aoetanilide, 2-chloro-2 *, 6'-diethyl-li- (l _f 3-dioxolan-2 "yl-methyl) -acotaiiilid, 2-chloro-2 ^J, 6» -diäthyl ~ H '(ethoxycarbonyl ~ raethyl) ^"> _i acetaailid 2- Chlorine "N"^> ethoxyniethyl-2 * '- taethyl-6 * -ethyl-acetanilide "2" Chloro-li- (2 * -methyltoxyethyl) -2 ^t1 , 6' ^t dimethyl »acetaiiilide ₈ 2-Chloro-E '» butoxymethyl-2 ', 6 * -diäthyl-acet · "enilid 2" chlorine _"H?" - (2 "-raethoxy-l ^K» methylethyl) »2 * methyl-6" -äthyl- ecetanilid, 2 ". chlorine '''l'i"isopropo2yme-fchyl''2 ^i, 6'-dimethyl ™ aoetanilid" methyl (K) metiioxyoarbamide N-, (3 ', 4-dichlorophenyl) -N * -methyl-K * - 3. A method for the destruction of weeds _f, characterized in that one expresses compounds of ellgo "my formula I and known herbicidal active ingredients separately at the same time or sequentially on the au treating soil surface ο. 4 »Process for the destruction of weeds, characterized in that the seeds are treated prior to sowing with compounds of the general formula I or their Po3? Mulaulations and the confessed herbicidal active ingredients on d © r zn treating soil surface ·