CS258135B2 - Herbicide - Google Patents

Abstract

The herbicidal composition contains as herbicide 5 to 65 wt. chlorocethanilide of formula IV wherein R7 and R8 are each C 1-8 alkyl, R 9 C 1-5 alkyl or C 2-5 alkenyl, and 0.2 to 32 wt. antidote agents of formula I wherein R1 and R2 are hydrogen, C1-10- alkyl, C 2-10 alkenyl, Cy or C 6 cycloalkyl, phenyl, optionally substituted with C 1-3 alkyl or halogen, or together hexamethylene, and when R 1 is hydrogen, R 2 has another than substituted phenyl, R 3 is C 1-5 alkyl or C 2-5 alkenyl. Herbicidal the composition has reduced phytotoxic effects on crop plants.

Description

The present invention relates to a herbicidal composition comprising chloroacetanilide as the herbicidally active agent together with an anti-toxic agent represented by N- (dichloroacetyl) glycine amides.

The novel N- (dichloroacetyl) glycinamides have the general formula I

R ¹ Cl \ /

N - C - CH 2 - N - C - CH

From II I II \ r ² o R ³ o Cl (I) where

R ¹ and R ² are each independently hydrogen, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 5 or C 6 cycloalkyl, phenyl, phenyl mono- or di-substituted alkyl having 1 to 3 carbon atoms, a halophenyl group or together a hexamethylene group, and when R ¹ is a hydrogen atom, R ^{2 has} a meaning other than phenyl or substituted phenyl,

R ³ is C 1 -C 5 alkyl or C 2 -C 5 alkenyl.

Chloroacetanilide derivatives of general formula IV have long been used in plant protection against unwanted weeds, in particular against weed weeds.

X.

/

6 '

R ⁹

N ' ^c ~ I want

II 2 o

dV) where

R ⁷ and R ^s is independently alkyl of 1-5 carbon atoms and

R ⁹ is C 1 -C 5 alkyl or C 2 -C 5 alkenyl.

Particularly known representatives of these chloroacetanilides of formula IV are 2-chloro-N-isopropylacetanilide (Propachlor), 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) acetanilide (Alachlor), 2-chloro-2'-methyl 6'-ethyl-N- (ethoxymethyl) acetanilide (AcetochlorJ and 2-chloro-2 ', 6'-diethyl-N-butoxymethyl) acetanilide (ButachlorJ.

The chloroacetanilides of the general formula (IV), when used in an amount necessary for the control of monocotyledonous weeds, also damage protected crop plants. These phototoxic properties limit the possibilities of use or allow use only in doses which do not harm the crop plants and thus reduce the effectiveness of these herbicidal substances.

About 20 years ago, Hoffmann discovered that there are compounds (1,8-naphthoic acid anhydride derivatives) that reduce this phytotoxic effect and, when used together with herbicidally active substances, compensate for their toxic effects on crop plants. or counteracting substances, or antidotes, i.e., antidote agents.

Since then, numerous other such antidote compounds have been discovered and patented. Hungarian Patent No. 168,977 discloses oxazolidine and thiazolldine derivatives as antidotes; Hungarian Patent Application No. 170 214 recommends thiazolidine sulfoxide and thiazolidine sulfone based substances as antidotes. Sulfides are used as antidotes in accordance with Hungarian Patent Specification 173 755. Also oxazolidine derivatives are recommended as antidotes in Hungarian Patent Specification 176 867. Hungarian Patent Specification 179 643 describes N- (benzoylsulfonylcarbamates) and Hungarian Patent Specification 180 069 N - (benzoylsulfonyl) thiocarbamate and in Hungarian patent specification 180 068 2,3-dibromopropionamide derivatives as antidotes.

Dichloroacetamide compounds are described in Hungarian patents 176 458 and 176 784. Hungarian patents 176 669, 176 796, 178 883, 178 892, 178 985, 179 092 and 179 093 disclose the action of dicarboxylic acid derivatives as antidotes.

However, the large number of antidotes known from the prior art shows that, despite diligent research, it has not yet been found that a compound could be protected from the harmful effects of individual herbicidally active compounds. Relative evidence of not solving this problem is also that there is no consistent view of the biochemical processes occurring in the addition of antidotes and the mechanism of action of such compounds in the plant organism. The harmful effects of herbicidal active substances are also influenced in a variety of ways by parallel-acting factors (such as temperature, soil moisture, soil pH) and the physical properties of the herbicidal compositions (e.g. vapor pressure, water solubility).

It has now been found that the novel N-substituted or N‘-substituted N- (dichloroacetyl) glycinamides of the formula I compensate for the phytotoxic action of the herbicidally active compounds of the formula IV.

The present invention relates to a herbicidal composition comprising 5 to 65% by weight of the chloroacetanilides of the above formula (IV), wherein R ⁷ , R ⁸ and R ⁹ are as defined above and 0.2 to 32% by weight of the antioxidant formula I wherein ^R! R ² and R ³ are as defined above.

Method for producing antidote active substances, i.e. N-substituted or N'-substltuo a substituted N- (dichloro oracetyl j glycinamide of formula I wherein R ^1, R ² and R ³ are as defined above, consists in reacting N-substituted or N'-substituted glycinamide of formula II

R \ l ~~ C-CH-NH-R ³ / II

R ² O (II) wherein ^R! R ² and R ³ are as defined above, in the presence of an acid acceptor and optionally in the presence of a solvent, with dichloroacetyl chloride.

The process for the production of an antidote active ingredient is the subject of our Czechoslovak patent No. 258,781. This patent also provides details of the conditions used in the manufacture of such an antidote active ingredient, as well as illustrating a number of specific embodiments of the method.

The herbicidal compositions according to the invention are preferably in the form of emulsion concentrates, wettable powders, granules, aqueous or oily suspensions. The following non-limiting examples illustrate the preparation of the herbicidal compositions containing the antidote of the present invention.

Example 1

Dissolve 5 parts by weight of Alachlor [2 ', 6'-diethyl-N- (methoxyethyl) chloroacetanilide] and 0.8 parts by weight of the active ingredient, a compound of formula I wherein R ¹ is phenyl], R ² is ethyl and R ³ is tert-butyl (mp 100-101 ° C), in 10 parts by weight of dichloromethane. The solution is sprayed on with stirring. 24.2 parts by weight of amorphous silica. The solvent was then removed at 30-40 ° C in a liquid evaporator. 60 parts by weight of diatomaceous earth, 3 parts by weight of sodium sulfonic acid sodium salt as wetting agent, 3 parts by weight of cresol formaldehyde condensate and 6 parts by weight of sulphite lye powder are added to the powder mixture as dispersant. The mixture is finely ground in a mill (Kontraplex Alpina 63 C). A wettable powder is obtained having a content of 5.8% by weight of active ingredient. The buoyancy retention (at a concentration in water with a hardness of 19.4 ° DH 1% after half an hour) is 81.6%. The residue on the sieve (in the case of a mechanical sieve 325) is 0.82% by weight.

Example 2 and 0.25 parts by weight of the active compound, a compound of formula I, wherein R ¹ and R ³ denote ailyl and R ² is hydrogen (n _D ²⁰ = 1.5250) (hereinafter referred to as active substance A), in a mixture consisting of 22 parts by weight of xylene and 21.75 parts by weight of dichloromethane. An emulsifier containing a mixture of alkylarylsulfonic acid calcium salt and fatty acid polyglycol esters is added to the solution in an amount of 6 parts by weight. The solution is homogenized by stirring and filtered. The emulsion concentrate contains 50.25% by weight of the active ingredients.

Example 3

In a mixture consisting of 21.75 parts by weight of xylene and 21.75 parts by weight of dichloromethane, 50 parts by weight of Alachlor and 0.5 parts by weight of active substance A are dissolved. While stirring, 6 parts by weight of the emulsifier mixture consisting of calcium salt are added. alkylarylsulfonic acids and polyglycol esters of fatty acids. The emulsion concentrate obtained contains 50.5% by weight of active ingredients.

Example 4 parts by weight of Alachlor and 1 part by weight of active ingredient A are dissolved in a mixture consisting of 21.5 parts by weight of xylene and 21.5 parts by weight of dichloromethane. 6 parts by weight of the same emulsifier mixture as in Example 3 are added to the solution. % by weight of active substances.

Example 5

50 parts by weight of Alachlor and 2 parts by weight of active substance A are mixed together and dissolved in a solvent mixture consisting of 20 parts by weight of xylene and 20 parts by weight of dichloromethane. The same emulsifier as in the example was added to the solution in an amount of 8 parts by weight

3. After homogenization, the solution is filtered. The emulsion concentrate contains 52% by weight of active ingredients.

Example 6

46.3 parts by weight of Alachlor and 3.7 parts by weight of active substance A are dissolved in a solvent mixture consisting of 19 parts by weight of xylene, 19 parts by weight of dichloromethane and 4 parts by weight of dimethylformamide. 8 parts by weight of the same emulsifier mixture as in Example 3 were added to the solution with stirring. The solution was filtered. The emulsion concentrate contains 50% by weight of the active ingredients.

50 parts by weight of Alachlo7 are dissolved

Example 7 parts by weight of Alachlor, 7 parts by weight of active substance A are homogenized with 18 parts by weight of xylene, 18 parts by weight of dichloromethane and 5 parts by weight of dimethylformamide together with 8 parts by weight of emulsifier mixture according to Example 3. The solution is then filtered. The emulsion concentrate contains 51% by weight of the active ingredient.

Example 8

In a solvent mixture consisting of 18 parts by weight of xylene, 18 parts by weight of dichloromethane and 6 parts by weight of dimethylformamide, 38 parts by weight of Alachlor and 12 parts by weight of active substance A are dissolved. active ingredient content of 50% by weight. Example 9

30.5 parts by weight of Alachlor and 19.5 parts by weight of active substance A are dissolved in a solvent mixture consisting of 16 parts by weight of xylene, 16 parts by weight of dichloromethane and 8 parts by weight of dimethylformamide. 10 parts by weight of the emulsifier mixture of Example 3 are added to the solution. The solution is homogenized for 15-20 minutes and then filtered. The emulsion concentrate contains 50% by weight of the active ingredients.

Example 10 parts by weight of Alachlor and 32 parts by weight of the active compound, a compound of formula I, wherein R ¹ and R ³ are isobutyl and R ² is hydrogen (n _D ²⁰ = 1.4880), are dissolved in a solvent mixture consisting of 25 parts by weight xylene, 20 parts by weight of dichloromethane and 15 parts by weight of dimethylformamide. 6.5 parts by weight of Emulsogen IP and 1.5 parts by weight of Emulsogen EL are added to the solution. The mixture is homogenized and then filtered. The emulsion concentrate contains 37% by weight of active ingredient.

Example 11 parts by weight of Acetochlor [2-chloro-2-methyl-6'-ethyl-N- (ethoxymethyl) acetanilide] and 0.2 parts by weight of the active compound, a compound of formula I wherein R ¹ is allyl, R ² is hydrogen R ³ isobutyl (mp 60-60)

6.3 ⁽ C), is dissolved in a solvent mixture consisting of 22 parts by weight of xylene and 11 parts by weight of dimethylformamide. After adding 4.5 parts by weight of Emulsogen IP and 3.5 parts by weight of Emulsogen EL, the mixture is homogenized for 15 minutes and then filtered. The emulsion concentrate obtained contains 65.2% by weight of active ingredient.

Example 12 parts by weight of Alcetochlor and 32 parts by weight of the active compound, a compound of formula I, wherein R ¹ and R ² are ethyl and R ³ is isobutyl (mp 59.5 to 62.5 ° C) are dissolved in a solvent mixture consisting of 20 parts by weight of xylene, 15 parts by weight of dichloromethane and 10 parts by weight of dimethylformamide, 6 parts by weight of Emulsogen IP and 2 parts by weight of Emulsogen EL were added to the solution with stirring, and the mixture was homogenized and filtered.

In the above examples, the following emulsifiers are used:

-Emulsogen EL is oxethylated castor oil,

Emulsogen IP is an alkylphenoylpolyethylene glycol ether.

(In both cases, Hoechst AG is the manufacturer.)

It has now been found that the compounds of the formula I protect, in particular, maize from the harmful action of the acetanilides of the formula IV. In order to elucidate the relationship between the dose size and the effect of the tests carried out, the compounds of the formula I have a significant effect on the improvement of 0.5 to 64% (with respect to the herbicidally active substance considered to be 100%). The following examples describe biological action.

Example 13

Dose and action

Using the active compound A, the action of the compound of the formula I was investigated at various doses. The tests were carried out as follows:

The test series are carried out in cultivation containers with an area of 1.13 dm ² each time four times. The boxes are filled with 400 g of dried air, a 2 mm sieve of sieved meadow soil with a humus content of 1.4% and a pH of 7.5. (Arana soil: 61.) Test crops are sown in these crates: MVTC 596 maize (Zea maysj, 15 grains per crate; green shear (Setaria viritus) 0.5 g per crate. Then the seeds are covered with 200 g of soil and finally The amount of chemical spray applied is calculated per hectare and 20 ml of water is used to prepare the spray suspension.

After chemical treatment, 100 g of soil was added to the crates and poured up to 65 ° / o 23

IQ city water intake. During the cultivation period, constant watering is maintained by daily watering.

It is irradiated daily for 14 hours by means of a high-pressure mercury lamp (µgMI / D 400 W). The mean daily temperature is maintained at 25 ^° C (minimum 23 ° C, maximum 27 ° C). Untreated controls are used to evaluate the tests.

In order to allow comparison with known antidotes, the widely used compound R-25 788 (N, N-diallyl-2,2-dichloroacetamide) is used in practice.

Evaluation is performed on the 10th day after treatment by measuring the length of the shoots and evaluating the morphological changes.

The following scale is used to assess morphological changes:

100% healthy corn,% slight leaf curl, slight deformation,% perfect deformation, cessation of plant growth and cessation of plant development.

The green scar used as a single-crop sucked weed is always destroyed by the action of the herbicidal agent in the presence of an antidote, i.e. the protective action of the herbicidal agent of the general formula on it.

I does not work.

In the tests, sprayable emulsions of Examples 1 to 12 are used. For comparison, tests are also carried out with Alachlor and Acetochlor as active ingredients of an antidote-free herbicidal composition and with herbicidal compositions containing said herbicidal active ingredients and the known antidote R 25 788. shoots length measured and morphological changes evaluated. The test results are shown in the tables below.

The symbols "a" and "b" in the tables always have the following meaning:

and active ingredient A, b antidote R 25 788.

The maize was treated with Alacholren used at 1.5 L / ha, optionally with the antidote R 25 788. The results in percent, with respect to the untreated control, are shown in Table 1.

TABLE I

Antidote 1 / ha % Length of corn sprout Appearance b A a — b and b A a — b and 0.008 0.5 91 81 + 10 97 87 + 10 0.015 1.0 98 87 + 11 98 84 + 14 0.030 2,0 104 105 - 1 98 97 + 1 0,060 4.0 97 107 - 10 99 94 + 5 0.120 8.0 97 114 - 17 99 100 ALIGN! - 1 0.240 16.0 96 100 ALIGN! - 4 100 ALIGN! 97 + 3 0.480 32.0 93 97 - 4 100 ALIGN! 100 ALIGN! 0 0,960 64.0 86 97 - 11 100 ALIGN! 99 + 1 sd ₅ % = 9.9% among any SDs% = 9.6% among any combinations combinations shoots length (without antidote) appearance (without antidote) 81% 80% The same test repeated p Acetochlor, used in an amount of 1.5 I / liu. Results in percent, you collapse quarry on untreated control, are given in Table II. TABLE II Antidote % Length of corn sprout Appearance 1 / ha and b A a — b and b A a — b 0.008 0.015 0.5 73 54 + 19 82 66 + 16 1.0 73 57 + 16 86 68 + 18 0.030 2,0 76 71 + 5 72 81 - 9 0,060 4.0 75 83 - 8 75 88 - 13 0.120 8.0 98 78 + 20 84 80 + 4 0.240 16.0 80 85 . - 5 91 84 + 7 0.480 32.0 78 89 - 11 94 98 - 4 0,960 64.0 88 87 + 1 93 98 - 5

SD ^5% = 9% between any combinations

SD ₅ ° / "= 14% between any combinations Shoot length (no antidote) 44% appearance (no antidote)%

258

The values in the tables show that the active compounds of the formula I are in particular in the dosage range 0.5 to 2.0% more advantageous than the known and widely used formulations of R 25 788. the difference between the two antidotes. When used in an amount of 4 to 16%, maize remained healthy without any symptoms.

The active compounds of the formula I promote the selectivity of chloroacetanilides. The phytotoxic activity of these compounds is not manifested, while the herbicidal activity of these herbicidal compounds remains.

Claims (1)

Subject A herbicidal composition comprising chloroacetanilides and an antidote as herbicidal active ingredient, characterized in that it contains 5 to 65% by weight of chloroacetanilide of the general formula IV v. · - i: Z 'C-CuCp ii Z o (where R ⁷ and R ³ are independently C 1 -C 5 alkyl and R ⁹ represents a C 1 -C 5 alkyl group or a C 2 -C 5 alkenyl group, and 0.2 to 32% by weight of an antioxidant of formula I OF THE INVENTION R ¹ Cl \ Z N - C - CH 2 -N ------ C - CH / ^z II! \ R ² O R 3 O Cl (I) wherein R ¹ and R ² are each independently hydrogen, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 5 -C 6 cycloalkyl, phenyl, phenyl mono- or di-substituted alkyl having 1 to 3 carbon atoms, a halophenyl group or together a hexamethylene group, and when R ¹ is a hydrogen atom, R ^{2 has} a meaning other than phenyl or substituted phenyl, R ³ is C 1 -C 5 alkyl or C 2 -C 5 alkenyl.