CS262435B2 - Herbicide - Google Patents

Abstract

A controlled release herbicidal composition comprises 0.5 to 95% by weight of one or more alpha - chloroacetanilide derivatives of the formula I <IMAGE> as active ingredients, optionally with further herbicidally active ingredients, in admixture with 1 to 80% by weight of extenders selected form the group of (1) a N,N-diallylacetamide derivative of the formula II <IMAGE> or (2) a N-allyl-N',N'-disubstituted glycinamide derivative of the formula III <IMAGE> or (3) a 2,6-dinitroaniline derivative of the formula IV <IMAGE> or (4) a dithiocarbamate derivative of the formula V <IMAGE> in admixture with usual additives, wherein the weight ratio of the herbicidal active agent(s) and the extender(s) is 200:1 to 1:10.

Description

The invention relates to a prolonged-acting herbicidal composition comprising, as active ingredient, 0.5 to 95% by weight of α-chloroacetanilide derivatives, as well as 11 to 80% by weight of N, N-dlallylacetamide or N-allyl-N ', N' derivatives. disubstituted glycinamide or 2,6-dinitroaniline derivatives or dithiocarbamate derivatives as a delaying agent.

The α-chloroacetanilide derivatives are used extensively in agriculture as active ingredients in weed control products. The active compounds and their use are described, for example, in U.S. Pat. Nos. 2,863,752, 2,864,683, 3,442,945 and 3,547,620, as well as in German Laid-Open Publication No. 2,320,340.

N-lsopropyl-α-chloroacetanilide (propachlor), 2-methyl-6-ethyl-N- (ethoxymethyl) -achloroacetanilide (acetochlor), 2,6-diethyl-N- (methoxymethyl) -α-chloroacetanilide are the most widely used in agriculture (alachlor), 2,6-diethyl-N- (butoxymethyl) -α-chloroacetanilide (butachlor), and 2-methyl-6-ethyl-N- (2-methoxy-1-methylethyl) -α-chloroacetanilide (metholachlor).

The α-chloroacetanilide derivatives are used in combination with other herbicides, such as triazine derivatives, carbamide derivatives or thiolcarbamate derivatives, to increase the effect and selectivity (Hungarian patents 178 892, 178 895, 179 092, 179 093, 181 621 and 181 849).

In addition to the high potency and the corresponding selectivity, the weed control compositions should have an optimal duration of action.

It is known that the concentration of herbicides immediately after application is considerably high and decreases due to metabolism of the active ingredient over a longer or shorter time. The metabolism of the active substance is influenced by soil and other circumstances. The decrease in concentration is apparent from the decrease in effect as well as from the content of active substance found in the soil.

It is also known that the degradation time of the active ingredient decreases when used repeatedly at the same site. The effect is always less and after a certain number of applications, the rapid decomposition of the active substance causes weed to overwhelm and damage crop plants. Against this, graded amounts of herbicides are used, which is economically inappropriate and at the same time harmful to the landscape.

This problem can be solved by prolonging the duration of action of the herbicidal composition. Research has shown that the action of thiolcarbamate derivatives can be maintained in soil by the addition of carbamate derivatives (Hungarian T-30317), 4-phenyl-1,2,3-thiazoles (Hungarian T-28322), amines or amine salts (Hungarian T-26610) or organic phosphorus compounds (Hungarian patent specification 185 612) for a longer period of time. These additives themselves have very little or no herbicidal effects and do not additionally affect the action of the thiolcarbamate derivatives.

By preventing the degradation of the active ingredient, the effectiveness of the active ingredient is increased by the application of said excipients.

The present inventors have conducted investigations to prolong the effect of α-chloroacetanilide derivatives. In doing so, they observed that the duration of action and, in many cases, even selectivity can be increased considerably by the simultaneous use of aminal derivatives (Hungarian patent application no. 3,856/84). These agents make it possible to establish an optimum duration of action as well as to reduce the amount of active ingredient used and to increase selectivity.

Surprisingly, however, it has been found that the duration of action and the selectivity of the N-chloroacetanilide derivatives can be substantially increased by the addition of the dial, dial-diallylacetamide derivatives of the formula II (Table I) or N-allyl-N ', N'-disubstituted glycinamide derivatives. II (Table II) or 2,6-dinitroaniline derivatives of formula IV (Table III) or dithiocarbamate derivatives of formula V (Table IV).

The sustained-release herbicidal composition according to the invention contains, as active ingredient, 0.5 to 95% by weight of α-chloroacetanilide derivatives of the general formula I ^{R 0} (I) in which

R ( ¹⁾ is hydrogen, methyl or ethyl,

R ² is hydrogen or ethyl and

R3 1-propyl, methoxymethyl, ethoxymethyl, butoxymethyl or 2-methoxy-1-methyl-ethyl as well as 1-80% by weight of the Ν, Ν-dlallylacetamide derivatives of the formula II

CH2-CH = CH2 /

R4_C — N

II \

O CH 2 — CH = C ‰.

(II), or N-allyl-N ‘, N‘-disubstituted glycinamide derivatives of formula III

R 5 ON-CH 2 -CH = CH ₂ \ III

N — C — CH2 — C = O / I

R ⁶ R or the 2,6-dinitroaniline derivatives of the general formula IV

(IV) or dithiocarbamate derivatives of the general formula V

R12 \ N —O — S — R14 / II

R ¹³ S (V) as a sustaining agent in addition to the usual excipients. The weight ratio of herbicide to extenders is

200: 1 to 1:10. In the general formulas, R ^{4 is} -CHCl 2 or -CH 2 Cl, R ⁵ and R ⁶ are equally or differently hydrogen, straight or branched alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 5 carbon atoms or feinyl,

R ^{7 is} straight or branched alkyl of 1 to 5 carbon atoms or alkenyl of 2 to 5 carbon atoms,

R ^{8 is} C 1 -C 4 alkyl, C 2 -C 5 alkenyl or O-methylallyl,

R ^{9 is} C 1 -C 5 alkyl, C 2 -C 5 alkenyl or β-methylallyl,

R ¹⁰ is - CF 3,. R ^u is hydrogen,

R ^{12 is} C 1 -C 3 alkyl or C 2 -C 5 alkenyl,

R ^{13 is} C 2 -C 5 alkenyl or phenyl or R ¹² and R ¹³ together form a hexamethyleneimine group,

R ¹⁴ is C 1 -C 5 alkyl or C 2 -C 5 alkenyl.

TABLE I

Useful Ν, Ν-diallylacetamide derivatives of the general formula II

Compound R ⁴ no.

Compound R ⁴ no.

II-1 —СНз П-2 —C? H5 П-25 II-3 —CHC12 И-4 —CH2Cl II-5 —CC13 П-26 II-6 —СН (СНз) Вг П-7 —С (СНз) 2Вг II-8 —CC12 — СНз П-9 —C1 = CC12 11-10 CF2-C2F5 П-27 11-11 —СО — OC2H5 П-12 —С '(СНз) 2 — C3H7 П-13 —СН (СНз) —СзН7 П-28 11-14 - C & H19 11-15 —СбН13 11-16 - СзН7 П-17 —СН = СН — СНз П-29 11-18 —СН = СН — СН = СН — СНз

П-19 -см 1 П-30 П-20 -о П-31 П-32 П-21 П-ЗЗ П-22 П-34 П-35 П-23 —СВгз П-24 - (СН2) 4 — СН2 — Вг

—CH2 — CH2 — Cl

-CH2-J

R ⁴

C.

Compound

R ⁴

C.

Compound

П-59

-CH = CH- / OY'CH ₃

-ch, -ch., -Q

П-60 — СО — N— (СНг — СН = СН2) 2 — СНг — СНг — СО — N (CH2 — СН = СН2):

- (СН2) з — СО — N (СНг — СН = СНг) г - (СН2) 4 — СО — N (CH2 — СН = СН2) 2 —СНг — О — СНг — СО — N (CH2 — сн = с

СО

AND

CHsCHl them ^) _of

о —С (СНз) г — СО — N (СН ₂ —СН = СНг) г.

П-61

П-62

П-63

П-64

П-65

П-66

I.I-67

-СН = СН

-сн = сн

—СН2 — SO ₂ —КЦСНг — СН = СНг) —CH (S — СгН5) 2 —СНг — О — СО — СНС12

-CH = CH'XP2;

F

СО-М (СНрСН = С / _-и г

CO-NCHCH 2 -CH 2

П-68

co-ch = ch ₁ ) _2>

П-69

CO-NH-C (CH _{3) Z} C = CH

- <θ) OxC-OH 11-70 (си _г си-сн _г ; _г «со - ^ S — 1 / ^сн 3 -Cl 11-71 —0 — СНг — C = C — СНз _S _J —OCaHiCl 11-72 —CH2—0 — CO — CC1 = CC1 — CC1 = —ОСНг — CHC12 o - <0> - c * П-73 11-74 —СНг— 0 — С (СНС12) г— ОН —СНг — 0 — С (СНС12) (СС1з) —01 —СНг — S — CN —СНг — N (CH2 — СН = СНг) г. 11-75 —СНг — СО — СНз F П-76 -СН ^ -СН 11-77 -O-СН (СНз) 2

В 2 4 3 5

Ί

The abovementioned compounds and their preparation are known for their applicability to prolongation (see, for example, the Hungarian patents of the active ingredient not previously known, 165 165). These compounds are used as antidotes.

TABLE II

Useful N-allyl-N ‘, N‘-disubstituted glycinamide derivatives of the general formula III

Compound No. R ⁵ RS R ⁷ III-1 phenyl ethyl methyl III-2 phenyl ethyl. ethyl II1-3 phenyl ethyl n-propyl III-4 phenyl ethyl i-propyl III-5 phenyl ethyl allyl III-6 phenyl ethyl n-butyl III-7 phenyl ethyl sek.butyl III-8 phenyl ethyl i-butyl III-9 phenyl ethyl tert-butyl Ш-10 allyl allyl .... methyl III-II allyl allyl; , ethyl III-12 dllyl allyl allyl III-13 ethyl ethyl. allyl III-14 i-butyl i-butyl. ethyl ΠΙ-15 methyl methyl n-propyl III-16 methyl methyl,. i-propyl III-17 methyl methyl, < .allyl III-18 methyl methyl,. ethyl. III-19 ethyl ethyl n-propyl III-20 ethyl ethyl i-propyl III-21 ethyl ethyl. ·· .. '. ethyl III-22 cyclobexyl ethyl. ethyl ΠΙ-23 phenyl H ethyl III-24 allyl H allyl III-25 n-propyl n-propyl allyl III-26 cyclobexyl H allyl UI-27 phenyl H allyl III-28 2,6-dimethylphenyl H ethyl. ΙΠ-29 2,6-diethylphenyl H ethyl III-30 hexamethylene H ethyl. 31Π-31 3-chlorophenyl ethyl ethyl Ш-32 ethyl ethyl n-butyl -Π-33 ethyl ethyl i-butyl III-34 ethyl ethyl sec.-butyl III-35 ethyl methylL tert-butyl ΠΙ-36 phenyl methyl ethyl III-37 phenyl methyl n-propyl III-38 phenyl i-propyl allyl Ш-39 phenyl i-propyl ethyl III-40 phenyl H allyl III-41 methyl H methyl III-42 ethyl H ethyl III-43 n-propyl H n-propyl III-44 i-propyl H i-propyl Ш-45 n-butyl H n-butyl Ш-46 1-butyl H I-butyl .111-47 sec.-butyl H sec.-butyl III-48 benzyl H benzyl III-49 n-propyl n-propyl allyl III-50 phenyl methyl methyl III-51 phenyl methyl i-propyl 111-52 2,6-dimethylphenyl H methyl III-53 2,6-dimethylphenyl H allyl III-54 2,6-diethylphenyl H methyl III-55 2,6-diethylphenyl H allyl III-56 allyl H n-butyl

10

Compound R ⁵ R ⁶ R ⁷

C.

III-57 allyl H i-butyl III-58 allyl H i-propyl III-59 allyl H n-propyl III-60 allyl H ethyl

The abovementioned compounds, their preparation and their usefulness for prolonging the time to be used as an antidote are known (maquette was not previously known, Danish Patent Application No. 2,565/83).

TABLE lil

Useful dinitroaniline derivatives of formula IV

Compound No. R ⁸ R® R10 R ¹¹ IV-1 ethyl butyl CFs H IV-2 n-propyl n-propyl CF3 H IV-3 n-propyl β-chloroethyl CFs H IV-4 allyl 3-chloroethyl CF3 H IV-5 allyl allyl CF3 H IV-6 ethyl 3-chloroethyl CFs H IV-7 ethyl 3-Bromoethyl CF3 H IV-8 N-methyl-allyl ethyl CFs H IV-9 n-propyl 3-Bromoethyl CFs H IV-10 O-methoxy-ethyl S-chloroethyl CFs H IV-U i-propyl propargyl CFs H IV-12 n-propyl allyl CFs H IV-13 n-propyl propargyl CFs H IV-14 3-chloroethyl 3-chloroethyl CFs H IV-15 (i-Methoxy-ethyl) (S-methoxy-ethyl) CFs H IV-16 n-propyl cyclopropyl CFs H IV-17 n-propyl tetrahydrofuranamide CFs H IV-18 ethyl tetrahydrofuryl CF3 H 1V-19 n-propyl cyclopropylmethyl CFs H IV-20 n-propyl allyl methylsulfonyl H Apr-21 n-propyl n-propyl methylsulfonyl H 1V-22 n-propyl n-propyl aminosulfonyl H Apr-23 n-propyl n-propyl methyl H IV-24 sec.-butyl check-butyl tert-butyl H IV-25 n-propyl n-propyl i-propyl H IV-26 ethyl ethyl CFs amino IV-27 methyl 3-chloroethyl methyl H IV-28 n-propyl n-propyl methoxy H Apr-29 3-chlorophenyl 3-chloroethyl methyl H

The aforementioned compounds are known, for example, from U.S. Pat. No. 3,257,190, German Offenlegungsschrift 1,643,719 or Hungarian Pat. No. 169,820.

Their herbicidal action is known from Hungarian Unloading Document T / 30 851.

Their applicability for prolonging the duration of action has not been previously known.

292435

TABLE IV

Useful dithiocarbamate derivatives of formula (V).

Compound No. R ¹² R ¹³ . R ¹⁴ V-l methyl methyl methyl V-2 methyl methyl ethyl V-3 allyl allyl methyl V-4 methyl ethyl i-propyl V-5 hexamethylenimino ethyl V-6 ethyl ' ethyl 2-chlorallyl V-7 methyl benzyl ¹ n-butyl V-8 ethyl ethyl p-chlorobenzyl V-9 allyl allyl allyl V-10 bicyclo (2,2,1 Jheptyl ethyl ethyl V-II i-propyl 1-propyl 2 ₎ 3,3-Trichloro-al V-12 ethyl cyclohexyl ethyl V-13 n-propyl n-propyl 2,3-dichlorallyl V-14 methyl phenyl allyl AT 15 n-butyl n-butyl 2-chloro-4-ethylene V-16 i-propyl propargyl n-propyl

The adjuvants of formulas (II) to (V) may be used to extend the duration of action of herbicidal compositions containing propachlor, acetochlor, ala-chlorine, butachlor or metholachlor. Optionally other active substances and / or antidotes can be used.

The adjuvants of the invention and α-chloroacetamide derivatives may be introduced into the soil in their formulations simultaneously in the form of final formulations or tank mixes, or separately before or after planting, or before or after emergence of the plants at an early stage, or for plants. In separate use, a short time lag between application of the active agent formulation and the adjuvant formulations should preferably be maintained.

The weight ratio of adjuvants to α-chloroacetamide derivatives may vary to a large extent depending on the physical and chemical properties of both compounds, on crop plants, on pleivels, on soil properties and other circumstances.

The formulations contain from 0.5 to 95% by weight of active ingredient and from 1 to 80% by weight of excipient, the weight ratio of active ingredient to excipient being 200: 1 to 1: 10, preferably 60: 1 to 3: 1, in particular 12: 1. : 1 to 1.5: 1.

The amount of adjuvant used essentially depends on the degradability of the soil. Usually, an amount of between 0.2 and 10 kg of adjuvant per hectare of soil area is used, preferably 0.5 to 5 kg / ha, in particular 1 to 2 kg / ha.

According to the present invention, formulations in the form of concentrates as well as dosage forms prepared therefrom by dilution are protected. The present invention further provides dosage forms which are prepared immediately prior to application in a tank or sprayer by mixing the active ingredient formulations, the adjuvant formulations containing optionally an antidote, and the delaying agent, and optionally diluting. The adjuvant formulation usually contains from 0% to 85% by weight; preferably 1 to 80% by weight of the delaying agent.

The formulations which may be used are the known solid or liquid formulations which are used in agriculture and contain, in addition to the active ingredient and the delaying agent, 1 to 96% by weight of a solid or liquid extender and optionally 0.1 to 25% by weight of a surfactant.

As carriers, natural or synthetic, organic or inorganic carriers can be used. of substances usable in agriculture. Suitable solid carriers are, for example, clays, natural or synthetic silicates, silicic acid, dolomite, kaolin, plant granules and starch. Suitable liquid carriers are, for example, water, alcohols, esters, ketones, mineral oil fractions, aromatic, aliphatic or cyclic hydrocarbons, halogenated hydrocarbons, dimethylformamide, dimethylsulfoxide and N-methylpyrrolidone.

They come as surfactants; contemplated ioinogenic and / or non-ionic emulsifying, dispersing or wetting agents, for example salts of ligninsulfonic acids; salts of phenolsulfonic or naphthalenesulfonic acid, ethyloxide as well as polycoindensates of fatty alcohols; fatty acids or amides thereof, arylalkylsulfonates, substituted phenols, alkylphenols, arylphenols and polyoxyethylated phenols, and finally cresol formaldehyde condensates, sulfite waste liquors and the like.

The compositions of the invention may be in the form of solid formulations in the form of powders,

2 (12436 dusts or granules, optionally as liquid formulations in the form of solutions, emulsifiable concentrates, emulsions, concentrates, emulsions, concentrated suspensions, wettable powders, dusts or pastes. The concentrated formulations may be appropriately diluted.

The compositions of the invention may also be used in mixtures with known plant protection agents. For such mixtures, suitable are herbicidal, pest control, fungicidal, bactericidal, and growth-regulating agents which are compatible with α-chloroacetanilide derivatives.

The use of the formulations optionally after dilution is carried out in a conventional manner, for example by misting, spraying, sprinkling or spraying.

The composition and manufacture of the herbicidal compositions of the present invention will be apparent from the following examples, without being limited thereto.

Example 1

The wettable powder of Ν, Ν-diallyldichloroacetamide (Compound No. II-3) is admixed with 3 g of dichloromethane and sprayed as a fog in a powder mixer onto a 10 g silicate material capable of adsorption. The solvent was evaporated at 40-50 ° C under reduced pressure. 60 g of propachlor as active substance and 2 g of Netzer IS (sodium salt of aliphatic sulphonic acid), 3 g of cresol formaldehyde condensate and 5 g of sulphite lyes are added as well as 19 g of diatomaceous earth as extender. The powder mixture is homogenized and finely ground in an Alpine 100 LV mill (Ultraplex).

A wettable powder is thus obtained having an active ingredient content of 61% by weight, the ratio of propachlor to prolonging agent being 60: 1.

Example 2

A wettable powder of Ν, Ν-diallylchloroacetamide (Compound No. II-4) is sprayed in a powder mixer onto 15 g of a synthetic silicate carrier (Wessalon 50). 60 g of propachlor as active substance, 2 g of sodium aliphatic sulfonic acid as a wetting agent, 3 g of cresol formaldehyde condensate as dispersant and 5 g of sulphite waste liquors and 10 g of kaolin as extender are added. The powder mixture is homogenized and finely ground in an Alpine 63 C mill (Kontraplex). A wettable powder with an active substance content of 65% by weight is obtained, the ratio of propachlor to the extender being 12: 1,

Example 3

The emulsifiable propachlor concentrate g was dissolved in 50 g of xylene and 20 g of dimethylformamide. To this solution are added 5 g of N, N-dlallyldichloroacetamide (Compound No. II-3) and 10 g of a mixture of emulsifiers (a mixture of calcium dodecylbenzosulfonic acid and an alkylaryl polyglycol ether). The mixture was homogenized by stirring and filtered.

An emulsifiable concentrate with an active substance content of 20% w / w is thus obtained, the ratio of propachlor to the delaying agent being 3: 1.

Example 4

Emulsifiable concentrate

Under stirring, 24 g of acetochlor as active ingredient are dissolved in a mixture of 26 g of o-xylene, 12 g of chlorobenzene and 12 g of ethylene chlorohydrin. To this solution were added 16 g of Ν, Ν-diallylchloroacetamide (compound number II-4) and 10 g of a mixture of emulsifiers (analogously to Example 3). The mixture was homogenized by stirring and filtered.

An emulsifiable concentrate with an active substance content of 40% by weight is thus obtained, the ratio of acetochlor to the delaying agent being 3: 2.

Example 5

Wettable powder

Dissolve 5 g of alachlor and 0.8 g of the N-allyl-N ‘, N‘-disubstituted glycinamide derivative (Compound No. III-9, hereinafter referred to as DKA-9) in 10 g of dichloromethane. This solution was sprayed with stirring to 24.2 g of amorphous diatomaceous earth. The solvent was evaporated at 30-40 ° C in a fluidized bed jet dryer. 60 g of diatomaceous earth as carrier, 3 g of sodium sulfonic acid sodium salt as wetting agent, 3 g of cresol formaldehyde condensate and 4 g of sulphite waste liquors as dispersants are added to the powder mixture. The mixture is finely ground in an Alpine 63 C mill (Kontraplex).

A wettable powder is obtained having an active compound content of 5.8% by weight, the ratio of alachlor to DKA-9 being 6.25: 1.

Example 6

An emulsifiable concentrate of alachlor and 0.25 g of an N-allyl-N ', N'-disubstituted glycinamide derivative (Compound No. III-24, hereinafter referred to as DKA-24) is dissolved in a mixture of 22 g of xylene and 21.7.5 g of dichloromethane. . 6 g of a mixture of emulsifying agents composed of lime are added

1S salts of alkylarylsulfonic acid and fatty acid polyglycol ester. The mixture was homogenized by stirring and filtered.

Thus obtained emulsifiable concentrate with an active ingredient content of 50 _y 25% by weight, the ratio of alachlor к DKA-24 is 200: first

Example 7

The emulsifiable concentrate of g butachlor and 20 DKA-24 was dissolved in a mixture of 16 g of xylene, 16 g of dichloromethane and 8 g of dimethylformamide. The solution is mixed with 10 g of a mixture of emulsifying agents consisting of a calcium salt of alkylarylsulfonic acid and a polyglycol fatty acid ester under stirring. The mixture is homogenized by stirring for 15-20 minutes and filtered.

An emulsifiable concentrate with an active substance content of 50% by weight is obtained, the ratio of butachlor to DKA-24 being: 2.

Example 8

The active ingredient is mixed with 32 g of DKA-46 (Compound No. III-46) and dissolved in a mixture of 25 g of xylene, 20 g of dichloromethane and 15 g of dimethylformamide. Add 6.5 g of Emulsogen IP (alkylphenolpolyethylene glycol ether) and 1.5 g of Emulsogen EL (oxyethylated castor oil) with stirring, homogenize and filter.

An emulsifiable concentrate is obtained with an active substance content of 37% by weight, the ratio of alachlor to DKA-46 being 1: 6.4.

Example 9

The emulsifiable concentrate of alachlor and 5 g of DKA-57 (Compound No. ΠΙ-57) was dissolved in a mixture of 12 g of xylene and 1.1 g of dimethylformamide. A mixture of emulsifying agents consisting of g Emulsogen is added. IP and 3 g Emulsogen EL, homogenize for 15 minutes, and filter.

An emulsifiable concentrate is thus obtained having an active ingredient content of 70% by weight, the ratio of alachlord to DKA-57 being 13: 1.

Example .10

Emulsifiable concentrate

Combine 5 g of acetochlor with 32 g of DKA-33 (Compound No. III-33) and dissolve in a mixture of 20 g of xylene, 15 g of dichloromethane and 10 g of dimethylformamide. A mixture of emulsifying agents consisting of 6 g Emulsogen IP and 2 g Emulsogen EL is added to the solution with stirring. After homogenization, the solution is filtered.

An emulsifiable concentrate is obtained with an active substance content of 37% by weight, the ratio of acetochlor to DKA-33 being: 6.4.

Example 1 a d 11

Wettable powder

In a ball mill, 60 g of propachlor are homogenized for one hour, 1 g of all-liluralyn- (2,6-dimmitro-N, N-di-phenyl-4-trifluoromethyl) aniline (Compound No. 1V-5), 2 g of surfactant based sodium salts of aliphatic sulfonic acid, 3 g of cresol-formaldehyde condensate as dispersant and 5 g of waste silane liquors, as well as 11 g of synthetic silicates as carrier and kieselguhr. The mixture is finely ground in an Alpine 100 LV mill (Ultraplex).

So it comes off ^; A wettable powder having an active ingredient content of 61% by weight, the ratio of propachlor to allylfluralyne being 60: 1.

Example 12

Wettable powder

60 g of propachlor, 5 g of allylfluralyne, g of sodium aliphatic sulfonic acid wetting agent, 3 g of cresol formaldehyde condensate as dispersant, 5 g of sulphite waste liquors, 10 g of synthetic silicate as carrier and g of kieselguhr are homogenized in a ball mill for one hour. The mixture is finely ground in an Alpine 100 LV mill (Ultraplex). A wettable powder is obtained having an active ingredient content of 65% by weight, the propachlor to allylfluralyne ratio being 12: 1.

Example 13

Wettable powder

In a ball mill, 45 g propachlor, 15 g allylfluralyne, 2 g aliphatic sulphonic acid sodium wetting agent, g cresol formaldehyde condensate as dispersant, 5 g sulphite waste liquors, 15 g synthetic silicate as carrier are homogenized in a ball mill. and 15 g of diatomaceous earth.

Z ^r twisted in a wettable powder containing the active substance 60% by weight, the ratio of propachlor к allylfluraline is 3: 1st

Example 14

Wettable powder

The following amount of substances was homogenized in a ball mill logically according to Example 12: 36 g of propachlord, 24 g of ethalfluralyne [2,6-dinitro-N- (p-methylallyl) -N-ethyl-4- (trifluoromethyl) aniline, compound no. IV-8], 2 grams of sodium aliphatic sulfonic acid surfactant, 3 g cresol formaldehyde condensate as dispersant, 5 g sulfite waste liquor, 15 g synthetic silicate and 15 grams kieselguhr.

A wettable powder is obtained having an active ingredient content of 60% by weight, the propachlor to ethalfluralyne ratio being 3: 2.

Example 15

Emulsifiable concentrate

While stirring, 20 g of acetochlor and 6 g of allylfluralyne are dissolved in a mixture of 40 g of xylene and 24 g of dimethylformamide. A 10 g mixture of emulsifying agents (dodecylbenzenesulfonic acid calcium salt and alkylaryl polyglycol ether) was added to the solution. The mixture was homogenized and filtered.

An emulsifiable concentrate with an active compound content of 26% by weight is obtained, the ratio of acetochlor to allylfluralyne being 10: 3.

Example 16

Wettable powder

Analogously to Example 12, the following amounts were homogenized in a ball mill: 60 g of alachlor and 5 g of allylfluralyne, and the excipients of Example 12.

A wettable powder is obtained having an active ingredient content of 65% by weight, with an alachlor ratio of 1k to allylfluralyne of 12: 1.

Example 17

Wettable powder

In a ball mill, propachlor is homogenized analogously to Example 12 in amounts of 45 g and 15 g of DKA-24, as well as the excipients mentioned in Example 13.

A wettable powder is thus obtained having an active substance content of 60% by weight, the ratio of propachlor to DKA-24 being 3: 1.

Example 18

Emulsifiable concentrate

1.5 g of alachlor as active substance are mixed with 8.5 g of ethalfluralyne and dissolved in a mixture of 45 g of xylene, 20 g of dichloromethane and 17 g of dimethylformamide. A mixture of emulsifiers consisting of 6 grams of Emulsogen IP and 2 g of Emulsogen EL is added, homogenized and filtered.

An emulsifiable concentrate is obtained with an active substance content of 10% by weight, the ratio of alachlor to ethalfluralyne being 1.5 to 8.5.

Example 19

The emulsifiable concentrate of acetochlor active ingredient was dissolved in a mixture of 13 g of o-xylene, 6 g of chlorobenzene and 6 g of ethylene chlorohydrin with stirring. To the solution are added 40 g of trifluralyne [2,6-dinitro-N, N-di- (n-propyl) -4- (trifluoromethyl janiline, compound No. IV-2) and 5 g of a mixture of emulsifying agents (analogously to the example). (3) The mixture is homogenized by stirring.

An emulsifiable concentrate with an active ingredient content of 80% by weight is obtained, the ratio of acetochlor to trifluralyne being 1: 1.

Example 20

The emulsifiable concentrate g of butachlor and 8 g of trifluralyne was dissolved in a mixture of 20 g of xylene, 20 g of dichloromethane and 10 g of dimethylformamide. 10 g of a mixture of emulsifying agents consisting of a calcium salt of alkylarylsulfonic acid and a polyglycol ester of a fatty acid are added to the solution with stirring. The solution is homogenized by stirring for 15-20 minutes and filtered. 1

An emulsifiable concentrate is obtained with an active substance content of 40% by weight, the ratio of butachlor to trifluralyne being 4: 1.

Example 21

Aqueous dispersion of g propachlor and 1 g of dithiocarbamate derivatives (Compound No. V-3) is dissolved in a mixture of 8 g of xylene, 8 g of ethylene oxide and 1 g of N-monoethanolamide oleic acid, followed by 3 g of from the calcium salt of dodecylbenzenesulfonic acid, ethylene oxide and castor oil. Pour the solution into 60 g of water and distribute it evenly.

An aqueous dispersion having an active compound content of 20% by weight is obtained, the ratio of propachlor to dithiocarbamate derivative being 19: 1.

Example 22

An aqueous dispersion of alachlor and 10 g of the dithiocarbamate derivative (Compound No. V-9) is dissolved in a mixture of 15 g of cyclohexanol, 5 g of ethylene oxide and 15 g of a mineral oil fraction (boiling point 210-250 ^° C). Pour the solution into 35 g of water and distribute it evenly.

An aqueous dispersion having an active compound content of 30% by weight is thus obtained, the ratio of alachlor to the dithiocarbamate derivative being 2: 1.

Example 23

Aqueous dispersion

In a ball mill, 0.5 g of acetochlor and 0.5 g of dithiocarbamate derivative (Compound No. V-5) are mixed with 17 g of sodium lignin sulphonic acid, 60 g of silica gel and 3 g of diisobutylnaphthalene-a in a ball mill. -sulfonic acids. The powder mixture obtained is made up to 1000 g with water and distributed evenly.

An aqueous dispersion having an active compound content of 0.1% by weight is obtained, wherein the ratio of acetochlor to dithiocarbamate derivative is 1: 1.

Example 24

Powder spray

2.7 g of butachlor and 0.3 g of the dithiocarbamate derivative (Compound No. V-14) are mixed with 97 g of powdered kaolin. A dusting agent having an active compound content of 3% by weight is obtained, the ratio of butachlor to the dithiocarbamate derivative being 9: 1.

Example 25

The emulsifiable concentrate of Ν, Ν-diallyl dichloroacetamide (compound number II 3) was dissolved with stirring in a mixture of 10 g of o-xylene, 5 g of chlorobenzene and 4.5 g of ethylene chlorohydrin.

Add 0.5 g of a mixture of emulsifiers (dodecylbenzenesulfonic acid calcium and alkylaryl polyglycol ether). After homogenization, an emulsifiable concentrate having an 80% by weight prolonging agent content is obtained.

Example 26

The emulsifiable concentrate g of DKA-24 (Compound No. III-24) was dissolved in a mixture of 5 g of xylene, 5 g of dichloromethane and 4 g of dimethylformamide. Add 1 g of a mixture of emulsifiers (alkylarylsulfonic acid in the form of a calcium salt and a polyglycol ester of a fatty acid). After homogenization, an emulsifiable concentrate is obtained having an additive of 85% by weight.

Example 27

The emulsifiable concentrate g of allylfiuralyne was dissolved in a mixture of 10 g of xylene, 8 g of dimethylformamide and 2 g of a mixture of emulsifiers (calcium dodecylbenzenesulfonic acid calcium and alkylaryl polyglycol ester) were added. After homogenization, an emulsifiable concentrate is obtained having an effect-producing agent content of 80% by weight.

Example 28

The emulsifiable concentrate g of the dithiocarbamate derivative (Compound No. V-3) was dissolved in a mixture of 10 g of xylene, 4 g of dichloromethane and 10 g of cyclohexane, and 1 g of an emulsifying agent (diisobutyl-naphthalene-phth-sulfonic acid sodium salt) was added. homogenizing to obtain an emulsifiable concentrate having a 75% weight-prolonging agent content.

Example 29

Testing of delaying agents

Investigations have shown that the effect of a propellant that has been sprayed at 6 kg / ha on potted soil can be substantially prolonged by the addition of a delaying agent.

400 g of soil was placed in pots capable of holding 1,000 g of soil. The soil used was moderately bound (Arany binding: 60), pH | & lt _{; Cl} = 5.88, humus content: 1.87% / NO, NO: &gt; + NO2 = 9.2 ppm, P2O5 ^ 81 ppm and K2O = 300 ppm. Four maize seeds of the NKPX-20 type, MVSC 484 and JX 97 SC, as well as 0.5 g of Panic millium, were sown in this soil and covered with 100 g of soil. 6 kg / ha of the aftercooler were applied to the treatment, as well as a delaying agent in an amount of 0.1 to 0.5 to 2.0 to 4.0 kg / ha separately or in combination. The active substance propachlor was applied in the form of a herbicidal composition, which is usually commercially available, brand SATECID ^R 65 WP, after dilution in water. For treatment with the delaying agent, the emulsifiable concentrate of Examples 25-28 was poured onto the soil, which had been diluted beforehand. For the treatment of the combination of the dessicant with the delaying agents, either the above two agents were used immediately one after the other, or the agents of Examples 1 to 22 were used. The biological effect is not influenced in any way by any treatment method. The soil is then irrigated with water at 60% of its water-collection capacity and loss of 262435 days and evaluated on day 23. The data are summarized in Table V.

the water is replaced daily. The first planting was evaluated on the 13th day by measuring green matter. The second planting was carried out 15.

Herbicide Dose (kg / ha)

TABLE V

Weed weight (%)

X

Means for prolonging the effect

Compound Dose Mass C. (kg / ha) weeds q [%] У

Herbicidal -b effect prolonging agents (P 4- q kg / ha) Weed weight Calculates- Found no Ei (%)

Proipachlor 6 70 25 Propachlor 6 70 26 Propachlor 6 70 27 Mar: Propachlor 6 70 28

0.1 102 71.4 34 0.5 99 69.3 0 2,0 95 66.5 15 Dec 4.0 85 59.5 10 o.i 108 75.6 75 0.5 105 73.5 15 Dec 2,0 102 71.4 36 4.0 90 63.0 42 0.1 72 50.4 31 0.5 36 25.2 15 Dec 2,0 19 Dec 13.3 0 4.0 8 5.6 0 0.1 95 66.5 63 0.5 84 58.8 42 2,0 72 50.4 33 4.0 59 41.3 8

In the evaluation / result, it was found that with the use of propachlor alone it was possible to completely control the weeds of the first planting (0% by weight of the weeds), but the weeds of the second planting had no effect (70 weed weights). The corn was not damaged, its green matter was the same or even higher than in the control experiment.

The effect of propachlor can be substantially prolonged by the use of the delaying agent of the present invention. From this it can be concluded that the second planting resulted in complete weed control (last paragraph, lines 2, 11, 12 and 16 in Table V), or the effect was much higher than previously anticipated.

The effect was calculated based on the following equation by S. R. Colby (Weeds, 15, 20-22, 1967):

In equation X, the weed weight is the percentage of control experiments using the herbicidal active ingredient at pkg / ha, Yi is the weight of the weed percentage of the control experiments using q kg / ha, and Ej is the expected weed weight at percent of control experiments using a herbicidally active agent and a delaying agent in an amount of (p 44 q) kg / ha.

Example 30

Testing of the prolonging agent

Biological experiments according to Example 29 were performed on Poa pratensis weeds. The results are shown in Table VI.

Xi. Yi

100 ALIGN!

TABLE VI

Herbicide Dose (kg / ha) P P Weed weight (%) X ‘Means of prolonging the effect Herbicidal + prolonged effect, composition (p-Hi kg / ha) Weed weight Calculated Found Merge. C. Dose (kg / ha) q Weed weight (%) У Ei (%) Propachlor 6 93 25 0.1 113 105 62 0.5 125 118 0 2,0 109 101 25 4.0 92 86 13 Propachlor 6 93 26 0.1 96 89 51 0.5 78 73 0 2,0 74 69 19 Dec 4.0 69 64 7 Propachlor 6 93 27 Mar: 0.1 74 69 31 0.5 62 58 17 2,0 34 32 0 4.0 17 16 0 Propachlor 6 93 28 0.1 83 77 49 0.5 71 66 31 2,0 42 39 12 4.0 23 21 0 When evaluating the result was found- noticeably increase by combining with resources well that when using propachlor it was possible prolonging effect because i also pleve- completely destroy weeds first planting (0%) ly second planting out completely destroy (last weight of weeds), but the active ingredient was column, Line 2, 6 8, 11, 12 and Table 16 ineffective for weeds of second planting (93% Or the effect is distinctly higher than that weed weights). Herbicidal effect can be was to be expected.

I will invent the object

Claims (5)

A sustained-action herbicidal composition comprising, as active ingredient, 0.5 to 95% by weight of an alpha-chloroacetanilide derivative of the formula I or an N-allyl-N ', N‘-disubstituted glycinamide of the formula III R ⁵ O \ II N - C - CH 2 - N - CH 2 - CH = CH 2 / 1 R ⁶ C = O 1 R ⁷ (III), or 2,6-dinitroaniline derivatives common of formula IV in which it means R ( ¹⁾ is hydrogen, methyl or ethyl, R ² is hydrogen or ethyl and R ^{3 is} i-propyl, methoxymethyl, ethoxymethyl, butoxymethyl or 2-methoxy-1-methyl-ethyl as well as 1-80% by weight of the Ν, Ν-diallylacetamide derivatives of the general formula II NO0 (IV) II \ CH 2 -CH = CH 2 or the dithlocarbamate derivatives of formula V (II), 2В R ¹² N - C - S - R ¹⁴ / II R ¹³ S (V) as a sustaining agent in addition to the usual excipients, wherein the weight ratio of herbicide to extenders is 200: 1 to 1: 10, and in the general formulas R ⁴ is -CH 2 Cl or -CHCl2. R ⁵ and R ⁶ represent the same or different hydrogen atom, straight or branched alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 5 carbon atoms or phenyl, R ⁷ represents straight or branched alkyl of 1 to 5 carbon atoms or alkenyl of 2 to 5 carbon atoms, R ⁹ is C 1 -C 5 alkyl, C 2 -C 5 alkenyl or β-methylallyl, R ¹⁰ means - CF 3, R ^J1 is a hydrogen atom, R ¹² represents alkyl of 1 to 3 carbon atoms or alkenyl of 2 to 5 carbon atoms, ^R13 is alkenyl having 2 to 5 carbon atoms or phenyl, or _{and R} i3 RJ2 together form hexamethylene imine group, R ¹⁴ is C 1 -C 5 alkyl or C 2 -C 5 alkenyl, R ³ is C 1 -C 4 alkyl, C 2 -C 5 alkenyl or β-methylallyl. 2. A composition according to claim 1, characterized in that it comprises as active ingredient α-chloroacetanilide derivatives of formula I wherein R ^1, R ² and R ³ are as defined above, as well as derivatives of N, N-diallylacetamidu formula II as a delaying agent, wherein R ⁴ is as defined above. 3. A composition according to claim 1, characterized in that it comprises as active ingredient α-chloroacetanilide derivatives of formula I wherein R ^1, R ² and R ³ are as defined above, as well as derivatives of N-allyl-N ', N '-disubstituovaného glycinamide of formula III, as a means of prolonging effect, wherein R ^5, R ⁶ and R ⁷ are as defined above. Fourth herbicidal composition according to claim 1, characterized in that it comprises as active ingredient α-chloroacetanilide derivatives of formula I wherein R ^1, R ² and R ³ are as defined above, as well as derivatives of 2,6-dinitroaniline of the formula IV as a means of prolonging effect, wherein R ^8, R ^9, R ¹⁰ and R ¹¹ are as defined above. Fifth herbicidal composition according to claim 1, characterized in that the active ingredient is a derivative of α-chloroacetanilide · formula I wherein R ^1, R ² and R ³ are as defined above, and also derivatives of the dithiocarbamate of general formula V, as a means of where R ¹² , R ¹³ and R ¹⁴ are as defined above.