CS226040B2 - Herbicide - Google Patents

Abstract

Compounds of general formula XCH2CONRCH2A wherein X is chloro, bromo or iodo; R is an acyclic 1-alken- 1-yl radical having up to 8 carbon atoms, a C5-7 1-cycloalken-1-yl radical or one of said radicals substituted with one or more C1-4 alkyl radicals and A is an unsubstituted or C1-4 alkyl-substituted pyrazolyl, imidazolyl, triazolyl or tetrazolyl radical are useful as herbicides exhibiting both pre- and post-emergence activity.

Description

BACKGROUND OF THE INVENTION The present invention relates to a herbal composition which is effective both before and after emergence and which contains 2-haloacetamides as the active ingredient.

It is already known in the art to use various 2-haloacetamides as herbicidal compositions of cells alone or in admixture with other herbicides.

Herbicidally active compounds known from the prior art include 2-haloacetamides having, in different configurations and combinations, substituents on a nitrogen atom selected from the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkoxy, atom halogen, a haloalkyl group, an eryl group, an aralkyl group, a nitrogen-containing heterocyclyl group, an oxygen atom and / or a sulfur atom, and the like, all of which may be substituted by other groups.

Examples of prior art compounds similar to those of the present invention include compounds having an azolylmethyl group on an acetamide nitrogen atom; however, such known compounds must satisfy the requirement that aromatic groups are also substituted on a nitrogen atom. Examples of such N-azolylmethyl substituted 2-haloacetanild compounds are those described in DE Patent Applications Nos. 2,704,281, 2,648,008 and 2,744,396. Other prior art compounds having 1-cycloelken-1-yl groups on a nitrogen atom they must also fulfill the condition that they contain otherwise non-heterocyclyl groups, see U.S. Patent Nos. 3,574,746 and 3,586,496.

Other similar compounds known in the art are 2-haloacetamides which have a 1-alken-1-yl group nitrogen atom, such compounds of the formula I. however, on the nitrogen atom, as substituents, contain groups from the group. comprising an alkoxyethyl group, an alkoxypropyl group, an alkyl group or an alkenyl group. Such compounds are disclosed in Southern Patent Specification No. 753,918.

They are probably effective in the prior art. According to the invention, the most closely related 2-halo-etamides, inter alia at the same time, the substituents of the ecetamide nitrogen atom

A 1-cycloalken-1-yl or acyclic 1-elken-1-yl moiety and a nitrogen-containing heterocyclyl moiety. Thus, U.S. Pat. No. 4,155,744 protects such 2-haloecetemides containing esophageal 1-cycloelken-1-yl and N-heterocyclyl groups. The 2-urogeno-acetyl containing acyclic 1-el-C 1 -yl-1 and N-heterocyclyl groups are required when the Ueterocyclyl group is bound by an unspecified nitrogen atom, the 1-elken-1-yl group has a salt. Other than a hydrogen atom, an alkyl group or an alkenyl group.

And, according to the aforementioned U.S. Pat

The 2-haloacetate contains a nitrogen-containing heterocyclylocyl group, which nitrogen must be substituted by a non-ring member selected from the group consisting of hydrogen, cycloalken-1-yl or cyclocyclenylphenyl having from 5 to 7 carbon atoms or a saturated or unsaturated UeterocyClcelCylooc group.

Therefore, the most related compounds of the state of the art are different from the novel 2-helogeectectides of the invention. *

The subnets of the herbicidal composition according to the invention are characterized in that they contain, as active ingredient, a compound of the formula I.

C1CH-C.

CH ₂ -A (I), where is

R acyclic 1-p-p-1-yl or 1-yl-p-hex-1-yl, these groups being optionally substituted with one or more C 1 -C 2 alkyl groups, and

And optionally a pyrazolyl group, an imidazolyl group or a triazolyl group substituted with two methyl groups.

Preferred active compounds of the invention are those compounds of formula I wherein A is p-methyl-1-yl and R is 1-methyl-1-yl-1-yl, which may be substituted with 1 to 2 carbon atoms.

Jeko ^through HP jediotlivé OY ^h o n ^{e d e} la ^EFFECTIVE them ^ y ^ i is given: N - ^ - ^{methyl-Acetyl-1} - / ^ rnotyleji / '- ¹ - ^P ro ~ pen- 1-yl] JN- (1H-pyrazoo-1-yl-ethyl) -2-chloromethyl, N- (1,2-ethyl-1-piperidyl) -N-11H-plrezce-1-yl-ethyl] -2-chloroacetate, N- (2-chloro-1-ylmethyl) -N- 6-Dimethyl-4- (4-Chloro-hexen-1-yl) -N- (1H-pylezol-1-yl-ethyl) -2-trifluoromethyl-N- (2,6-diethyl-1-chloro-1-yl) -1- N - (1H-1,2,4-triazol-1-yl-ethyl) -2-trifluoromethyl-N- (2,6-ethyl-1-chlorophen-11-yl) -N- (1H) -azole- 1-chloroethyl-2-chloroethyl and N- (2,5-diethyl-1-chloro-1-yl) -N- (1H-pyrazol-1-ylethyl) -2-chloroacetate. Other active compounds according to the invention will be described below. ^!

The usefulness of the herbicidal compositions of the invention is exemplified in Table II and Table III.

The novel 2-haloethers of the present invention can be prepared by reacting a suitable azole compound with the corresponding N-haloethyl-N- (11-cyclohexen-1-yl) -2-chloroethyl ether or with the appropriate N-hydroxymethyl-N- (1-cyclollken-1-yl). (2-Chloroethyl ether) to replace the halogen atom on the halomethyl group with a suitable ezolyl group. The starting N-halo-ethyl-2-helogenecetemides can be prepared in a novel manner involving the reaction of concentrated hydrogen halide with N-Zelkoxyethyl / -2-hioogence etemide to replace the alkoxy moiety with a halogen atom. Such β-β-β-β-β-α may be conveniently prepared by the N-alkylation process described in U.S. Patent 4,258,196 (Mar. 24, 1981).

Example 1

This example describes a process for preparing one active ingredient according to the invention. Paragraph a) describes a process for preparing N- (alkoxyethyl) -2-haloacetamide used to prepare the corresponding N-halomethyl-2-haloacetamide. B) describes the reaction of the amide prepared according to a) with halogen to prepare the N-halomethyl compound, and c) describes the reaction of the N-halomethyl amide with a suitable ezole to obtain the active compound of the invention.

a) Describing a multi-phase system for preparing the anion of the desired secondary 2-haloacetamide and alkylating the anion, preferably in the presence of a phase transfer catalyst for the preparation of the desired tertiary 2-haloacetate.

A mixture of 400 g of the secondary amide, N- (2,6-diethyl-1-cyclohexyl-11) -2-hydroxyacetate, m.p. 114 DEG-115 DEG C. in 760 ml of methylene chloride and 300 ml of chloroethyl ether, is mixed with 2 g of benzyltriethyllevone bromide. The mixture is cooled to 10 ° C and then added in a thin stream over a period of half an hour to a vigorously stirred salt of 1,100 ml of 50% sodium hydroxide solution, 300 ml of ethyl chlorochloride and 9 g of benzyltrethelium nitride in a 5 liter four-necked rounded flask. day.

Outdoor cooling in an ice / acetone bath is required to keep the temperature below 25 ° C. The mixture was stirred for one additional hour. The gas-liquid chromatography showed 78% of the tertiary amide and 22% of the corresponding non-oxygenated product of the alkylated by-product. O-ethyl-N- (2,6-chloro-1-chlorophen-1-yl) -2-chloroacetate. The reaction mixture was separated and the organic layer was washed with 5% hydrochloric acid solution to convert the imidate to the starting secondary am.d.

An additional 120 ml of chloromethyl methyl ether and 5.0 g of quaternary ammonium phase transfer catalyst were added to the washed ethyl acetate salt, followed by the addition of 350 ml of 50% sodium hydroxide solution with stirring. After separation of the layers and additional washing with water, the product is filtered off with clay. The solvent was evaporated and the residue was heated to 85 DEG C. under 50 mm Hg and filtered through clay to purify the product. The product is obtained in a yield of approximately 99% and has a boiling point of 127 ° C at 20 Pa.

For C ₂ H ₂₀ Cl 2 NO ₂

H, 8.20; N, 5.70; Found: C 58.48, H 8.22, N 5.62%.

The product was identified as N- (2,6-diethyl-1-chloro-1-ene) -N- (ethyl) -2-chloro-acetamide.

The above process can be carried out without imidate formation, bypassing acidic acid reformation of the sec. Amide when using less emo, i.e. up to 50 g sec. Amide, the catalyst concentration is increased to up to 20-50%. with respect to the secondary amide used and the base, sodium hydroxide, is added at once.

The structure of the product obtained by the procedure described in this example and the longer examples is verified by mass spectrometry, gas-cepalin-based chemistry, nuclear resonance analysis and / or elemental analysis.

(b) One granule of the product prepared according to (a) is added to 10 µl of carbon tetrachloride and mixed with 10 µl of 37% hydrochloric acid for two hours. After completion of the reaction by nucleation resonance, the layers were separated, 5 ml of fresh hydrochloric acid were added and the mixture was stirred for one hour. After separation of the layers, the organic layer was stripped to a temperature of 75 ° C / 26 Pa to yield 0.8 g of an oil, which is a 934 yield.

For Сц Hi ₈ NO ₂ Cl calculated: 52.60% C, 7.22% H, 5.58% N; found: 51.87 C, 6.79% H, 5.27% N.

The product was identified as N- (2,6-diethyl-1-cyclohexen-1-yl) -N- (chloomethyl) -2-chloroacetenide.

c) 4.9 g (0.072 mol) of pyrazole are added to 8.9 g (0.036 mol) of the anide prepared as described in (b) above dissolved in toluene; this is maintained at a temperature of ° C of stirring for 7 hours. The next day, the toluene solution is decanted, washed twice with water, and distilled under vacuum to remove the solvent and the residue from moisture. The residue, which is 9.0 g of oil, is allowed to crystallize. A sample of the product is recrystallized from hpptee / methylcyilohexene to give a solid, m.p. 83-84 ° C, yield 89 °.

For ^C 14 ^H 20 ^ClN 3 ^O : calculated: 59.67% C, 7.15% H, 14.91% N; Found:% C, 59.64;% H, 7.17;% N, 14.96.

The product was identified as N- (2,6-dimethyl-1-cyanohexee-1-yl) -N-1H-pyrrolidin-1-ylmethyl-1H-dioromethyl-1H-pyrrolidine.

EXAMPLE 2 ^{2.0 g of} N- / no toxqrne the l / N - ^ - t ^y not D - / ^ - butyl RNE nape / - ¹ - propen-1-yl ^-2-ij du chloreceeen ^{and dissolved} in 20 % of carbon tetrachloride, was contacted with 20 µl of 37% hydrochloric acid and shaken in a large funnel. If not poinooí ^g geticié nuclear resonance detects the completion of the reaction, the lower layer was vacuum stripped product at a temperature of about 50 ° C / 6.7 Pa rent give 1.6 g of product.

For C ^ HH ^ d ^NO NO requires: C, 50.43; H, 7.19; N, 5.88; Found: C 51.17, H 7.39, N 6.07.

The product, whose structure was confirmed by nuclear naagetickou Rezon ^ i, was identified as N - / - hloonetyl / N £ 2 metyll1- / -netyletyl ¹ / - ^{1 p} -prc ^ee-1-yl-7 -2-chlooa etariLd . The magnetic resonance magnetic resonance products of the product are as follows: (CDCl 3, 0.95, 1.1 CH / CH 3/2 (2 dubbets, 3H each, J = 7Hz); δ 2.7, 2.84 (2 singlets, 3H each) = C / CH _3/2; 5 5.95 / CH _3/2 CH- / heptet 1H, J = 7Hz /, δ 4.02, Cl CHgCO (s, 2H); 5 = 5.38 N-CHgCb (AB q _e meta position, 2H, J = 8.5 Hz).

To 1.4 g (0.0059 mol) of N - [(2-chloroeyl) -2-chloroaneate] prepared above, was added 0.8 g (0.012 mol) of pretreatment and kept in approximately 20 µl of toluene. at a temperature of 80 to 90 ° C for about 6 to 7 hours. Decant, wash with 10% saline and then water, strip and recrystallize from nseylcyclohexane to give 1.0 g (634 yield) of a white solid, mp 101.0-101, Low: 14 ° C.

For C ₁₃ H ₂₀ CIN ₃ on calculated: 57.88% C, 7.47% H, 15.58% N; Found: C, 57.41; H, 7.59; N, 16.25.

The product, confirmed by nuclear magnetic resonance, identified as N - [(2-methyl-1- (1-methylmethyl) -1-propenyl) -N- (1H-pyrazol-1-ylmethyl) -2-chloroacetamide.

Example 3

Using the general procedure described in Example 2, dissolve 2.0 g of N- (methoxymethyl) -N- (1,2-dimethyl-1-propenyl) -2-chloroacetamide in 20 ml of carbon tetrachloride and shake in a small separating funnel with 25 ml of 37% hydrochloric acid. The lower organic layer was drawn off and the reaction was found to be complete by nuclear magnetic resonance; the solvent was stripped on a water bath (60 ° C under vacuum pump) to give 1.2 g (57% yield) of the product.

For C ₈ H ₁₃ Cl ₂ NO: calculated: 45.73% C, 6.24% H, 6.67% N; Found: C, 45.24; H, 6.21; N, 6.35.

The product was identified as N- (chloromethyl / N- / 1,2-dimethyl-1-propen-1-yl / -2-chloroacetamide. Nuclear magnetic resonance characteristics of this product are: (CDC1 ₃₎ δ 1.65, 1 , 8, 1.95 (3 · C-CH ₃ , 9 protons, each wide singlet with partial multiplicity): δ = 4.0, C1CH ₂ CO (singlet, 2H); δ = 5.35, CICHgN ( AB quartet, 2H, J = 9 Hz).

The pyrazole, 0.54 g (0.008 mol) and 0.8 g (0.0038 mol) of the N-chloromethyl-2-chloroacetamide prepared above were stirred in toluene and heated to 90 ° C. After working up as in Example 1, 0.6 g (67% yield) of amber oil was obtained, having an N-value of 1.5607.

H, 6.67; N, 17.38. Found: C 54.71, H 6.80, N 17.51.

The product, whose structure was confirmed by nuclear magnetic resonance, identified as N- (1,2-dimethyl-1-propen-1-yl) -N- (1H-pyrazol-1-ylmethyl) -2-chloroacetemide.

The N- (methoxymethyl) -N- (acyclic 1-alken-1-yl) -2-chloro-acetamides used for the preparation of the corresponding N- (chloromethyl) -2-chloro-acetamides used as starting materials in the process of Examples 2 and 3 were prepared as analogous to N- (methoxymethyl) -N- (1-cycloelken-1-yl) 2-chloroacetemides as exemplified in Example 1a). The N- (alkoxymethyl) amide precursor used in Example 3 is thus prepared as follows:

To 200 ml of dichloromethane was added 16.0 g (0.1 mol) of N- (1,2-dimethyl-1-propen-1-yl) -2-chloroacetamide, 4.0 g of benzyltriethylemonium chloride and 16 ml of bromomethyl methyl ether. The mixture is cooled to. 10 ° C and all 100 ml of 50% sodium hydroxide solution are added in one portion. After treatment with water, 4.0 g (19.5% yield) of the corresponding N- (methoxymethyl) -2-chloroacetamide product are obtained, b.p. 110-120 ° C / 6.7 Pa.

For C ₉ H ₁₆ CNO ₂ calculated: 52.56% C, 7.84% H, 6.81% N; Found: C, 50.65; H, 7.56; N, 6.38.

Product Identified as N- (methoxymethyl) -N- (1,2-dimethyl-1-propen-1-yl) -2-chloroacetamide.

Examples 4 to 10

In the same manner as described in Examples 1 to 3, but using the appropriate starting materials and reaction conditions, the 2-halo-logoacetate compound of formula (I) was prepared using the same equivalent solvents, catalysts and the like. , together with an appropriate reaction time and temperature at an equivalent temperature. Typical additional compounds of Formula I, prepared by the shore methods, are listed in Table I, along with some of their physical properties.

Tabulkel

Example number Compound Physical property Element Calculated Found 4 N- (6-ethyl-2H-ethyl-1-cyclohexanol) colorless oil C 60.90 60.84 -1-yl) -N- (1H-pyrezol-1-yl) methyl- N‘3 1,5 300 H 7.50 7 5-1 tlU-2-chlorobacaoid in the mixture N 14.21 14.20 with its 4-methyl-1-methyl-1-cyclohexen-1-yl) isomer 5 N- (2,6-dimethyl-1-cyclohexene-1- oraniový olej C 62.02 7.81 13.56 62.60 -YD-N - (-) - dimethyl-1H-pyrazole- Nj ⁵ 1 .5312 H 7.86 -1- (11) -ethyl-2-chloroacetate N 14.04 6 N- (2,1-dimethyl-1-cyclohexen-1-yl) -N- (1H-1,2,4-triteul-1-11-) yellow oil N2 ⁵ 1 ^, 5377 C H 55.22 6.77 54.90 6.90 (ethyl) -2-chloroacetate N 19.81 18.87 7 N- (2,6-Dimethyl-1-cyclohexen-1-yl) -N- (1H-imidazol-1-yl-ethyl) - C 59.67 59.60 mp 81-183 ° C H 7.15 7.19 14.85 -2-chloroacetamide N 14.91 8 N- (2,6-Diethyl-1-cyclohexene-1- yellow oil C 62.02 62.13 -yl) -N- (1H-pyrazol-1-ylmethyl) - N ^{25 ,} 5287 H 7.81 7.84 -2-chloroacetate N 13.56 13.46 9 N- (2-ethyl-1-ciclohexen-1-yl) - C 58.31 57.50 -N- (1H-Pylae-1-ylethyl) -2- yellow oil H 6.78 15.69 6.67 -chlurt-! ttθíid N 15.46 10 N- (2,6-Dimethyl-1,1-ciclohexene-1- mp 106-110 ° C C 60.91 60.79 -ll) -N- (1H-2-methylieldazoo-1- H 7.50 7.74 (1-methyl) -2-chloraceaamide N 14.20 14.08

The compounds of formula (I) prepared by the process of the invention have herbicidal activity before emergence and post-emergence and are therefore suitable for both uses. Preferably, however, they are used before emergence, as will be described in further detail below.

The herbicidal activity before emergence of representative compounds of formula I is determined. in this manner:

A good type of potted soil is placed in aluminum bowls and suffocated at a height of 9.5 and 12.7 mm from the top of the bowl. Different seeds or vege-shoots of different plant species are applied to the soil surface. The trays are weighed with the soil needed to fill the trays after sowing or after vegetative shoots have been planted. The soil and the known amount of active ingredient, taken up in a solvent or in the form of a wettable powder suspension, are thoroughly mixed and used to cover the prepared bowls. After treatment, the bowls are placed on shelves in a greenhouse, then watered from below as needed to provide enough moisture for germination and growth. Observations are made 2 to 3 weeks after sowing and treatment.

Tables II and III show the results of the tests carried out to determine the herbicidal activity before emergence of the active compounds according to the invention. The herbicidal effect is assessed by a fixed scale based on the percentage damage of each plant species. Grades are defined as follows:

% damage stamp 0 to 24 0 25 to 49 1 50 to 74 2 75 to 100 3 not specified 5

The plant species used in a series of tests, the results of which are given in Table II, are marked with the letters having the following meaning:

And thistle

В řepeň

C abutllon

D povíjnice

E white aerik

F ferns pepper

G šáchor *

H creeping grass

Even sorghum sorghum

J roof brome

К hedgehog corns * from vegetative shoots

Table II

Before emerging

Example compound kg / ha

11.2

5.6

11.2

5.6

11.2

5.6.

11.2

5.6

11.2

5.6

11.2

5.6

11.2

5.6

11.2

5.6

11.2

5.6

Type of plant

ABCDEFGHIJK

2 2 33

2 2 23

13 33

2 2 33

2 2 33

2 2 33

2 2 23

2 2 23

13 33

112 23

11213

0113

0 0 02

5 0 01

2 3 33

2 2 33

2 2 32

1133

2 3 3 1 3 3 2 3 3 0 3 3 3 3 3 2 3 3 3 0 3 0 3 3 3 3 3 0 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 2 3 2 3 3 3 3 3 3 3 3 3 3 3 3 3 3 2 1 0 0 3 3 1 0 3 0 3 3 2 0 2 0 0 2 1 0 0 0 0 1 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 2 3 3 2 3 3

The active substances ее further test chore in the above manner with regard to the action of these plants

L soya beans

M sugar beet

N wheat

About rice

P čřok

В řepeň.

Q buckwheat

D povíjnice

R hemp

E. White soap

F rdesno pepper

C abutilon

J roof brome

S millet

К hedgehog corns leg

T rosacea bloody.

The results are shown in Table III.

Table III

Pre-emergence ^The number% Example 8 ^{eq / ha} LMNOPBQDREFCJSKT

5.63

1,123

0.280

0,060

0.010

5.63

1,123

0.283

0,062

0.012

5.63

1,122

0.281

0,063

0.011

5.62

1,121

0.280

0,061

0.010

0.0060

3 3 32

2 2 31

112 0

0 0 01

1110

3 3 32

3 3 32

3 3 30

1110

110 00

3 3 33

3 3 12

1100

2 * 0 0 01

0 0 00

3 3 31

3 3 35

3 3 35

113 00

105

100 ALIGN!

3 o

1o o

3 o 3

3 2 3

2

3 2 3 o o o o o o o

33

33

33

31

11

33

33

33

33

21

33

33

33

21

1o

33

33

33

23

22nd

2

3 3 33

2 3 33

2 133

0 0 23

3 3 33

3 3 33

3 3 33

2 3 32

1123

3 3 33

3 3 33

2 3 33

2 3 33

0 123

3 3'33

3 3 33

3 3 33

3 2 33

0 133

0 0 12

Continuation of Table III

Compound according to example no kg / ha L M N 0 P (B) Q D Ή E F C J with TO T 5 5.6 3 3 3 3 3 2 2 3 3 3 3 3 3 3 3 3 1.12 1 3 3 3 3 0 3 3 2 2 2 0 3 3 3 3 0.28 0 2 2 3 1 5 0 0 0 . 2 3 0 3 3 3 3 0.06 0 1 0 1 0 0 0 0 0 2 3 0 0 2 3 3 0.01 0 0 0 1 0 0 0 0 5 0 0 0 0 1 3 3 6 5.6 1 3 3 3 3 3 2 3 3 3 3 2 3 3 3 3 1.12 0 2 3 3 1 0 2 0 2 3 3 0 3 3 3 3 0.28 0 1 2 2 0 0 0 0 2 1 3 0 2 2 3 3 0.06 0 1 0 1 0 0 0 0 3 2 2 0 0 1 3 3 8 5.6 1 2 3 3 3 3 1 3 3 3 3 2 3 3 3 3 1.12 2 2 2 3 3 3 1 1 3 3 1 0 3 3 3 3 0.28 0 3 2 3 2 0 1 0 2 3 3 0 3 3 3 3 0.06 0 1 1 1 1 0 0 0 0 1 1 0 0 2 2 3 0.02 0 0 0 0 0 5 0 0 0 0 0 0 0 0 1 2 0.006 0 0 0 0 0 5 0 0 5 0 0 0 0 0 1 1 9 5.6 3 2 2 3 0 1 3 3 2 3 3 0 3 3 3 3 1.12 2 2 0 3 0 1 2 2 1 1 1 0 3 3 3 3 0.28 1 2 0 1 0 0 1 2 1 1 1 0 3 3 3 3 0.06 0 0 0 0 0 0 0 0 0 0 0 0 1 2 2 3 0.01 0 0 1 0 0 0 0 0 0 1 1 0 0 0 2 3

The herbicidal compositions according to the invention include concentrates which must be diluted before use and contain at least one active ingredient and an excipient; such compositions are liquid or solid. The compositions of the present invention are prepared by mixing the active ingredient with an excipient, including diluents, non-sequencers, carriers and conditioning agents for the preparation of the composition in the form of finely divided solids, granules, pellets, solutions, dispersions or erythers. The active ingredients can therefore be used with excipients such as finely divided solid, liquid of organic origin, water, wetting agent, dispersing agent. an emulsifying agent or any suitable mixture thereof.

The compositions according to the invention, in particular wettable powders and liquids, preferably contain as one or more surfactants in a sufficient amount such that the compositions are readily dispersible in water or oil. The incorporation of a surfactant into the compositions of the invention greatly enhances their effectiveness. By surfactant is meant herein surfactants, dispersants, suspending agents, and the like. means. Annontal, cationic and nonionic compositions have the same efficacy.

Preferred wetting agents include alkyliensensulfonates and alkylnaphthaltsulfotates, sulfated fatty alcohols, amines or acid amides, long-chain esters of sodium isothionate, esters of sodium salt of sodium, petroleum sulfonates of sulfated sulfonates or sulfonates, polyoxyethylene derivatives of alkylphenols, especially isooctylphenol and non-phenol, and polyoxyethylene derivatives of mono-higher fatty acid esters of hexitol anhydrides, for example sorbitan.

Preferred dispersing agents are methyl cellulose, polyvinyl alcohol, sodium lignite sulfonate, polymeric alkyl sulfonyl phosphates, sodium naphthalene sulfonates and polymatylene sulfaphthalenesulfonates.

Compatible powders are aqueous dispersible mixtures containing one or more active ingredients, an inert solid extender and one or more wetting agents and dispersing agents. Inert solid extenders are generally of mineral origin, such as natural clays, diatomaceous earth and synthetic minerals derived from silica and the like. Examples of extenders include kaolinity, attapulgite clay and synthetic magnesium silicate. The wettable powders according to the invention generally contain about 0.5 to 95 parts, preferably 5 to 20 parts of active ingredient, about 0.25 to 25 parts, preferably 1 to 15 parts of a surfactant, about 0.25 to 25 parts, preferably 8 to 1 part. 0 to 15 parts of a dispersant and about 5 to 95 parts, preferably 5 to 50 parts of an inert solid extender, all parts being by weight with respect to the composition as a whole. Optionally, 0.1 to 2.0 parts of the solid inert extender may be non-credited by a corrosion inhibitor or antifoam or mixtures thereof.

Other compositions are powdered concentrates containing 0.1 to 60% by weight of active ingredient on a suitable extender; these powders are to be diluted for use at a concentration of 0.1 to 10% by weight.

Aqueous suspensions or emulsions may be prepared by mixing an aqueous mixture of the water-insoluble active ingredient and the emulsifying agent until uniform, and then homogenizing until a stable emulsion of the finely divided particles is obtained. The resulting concentrated aqueous suspension is characterized by extremely small particles, so that after dilution and spraying, the coating is very uniform. Suitable concentrations of these compositions contain from about 0.1% to about 60%, preferably from about 5% to about 50%, by weight of the active agent, the upper limit being determined by the solubility limit of the active agent in the solvent.

In another form of the aqueous suspension, the water-immiscible herbicidal composition is encapsulated in the form of a microencapsulated phase dispersed in the aqueous phase. In one embodiment, the tiny capsules are formed by contacting an aqueous phase comprising a lignin sulfonate emulsifier and a water-immiscible chemical and polymethylene polyphenylisocyanate, dispersing the water-immiscible phase in the aqueous phase, and adding a polyfunctional amine. The isocyanate and amine compound react to form a solid urea wall around the particles of the water-immiscible chemical, thereby forming microparticles of the chemical. Generally, the concentration of the microencapsulated material is about 480 to 700 g / l of the composition as a whole, preferably 480 to 600 g / l. The microencapsulation process disclosed herein is described in detail in U.S. Patent 4,280,833 (Jul 28, 1981).

Concentrates are generally solutions of the active ingredient in water-immiscible or partially water-immiscible solvents and also contain a surfactant. Suitable solvents for the active ingredient of the present invention include diethylformamide, dimethylsulfoxide, N-methylpyrrolidone, hydrocarbons and water-immiscible ethers, esters or ketones. However, other highly concentrated liquid concentrates may be formulated by dissolving the active ingredient in a solvent and then diluting, for example, kerosene, not a concentration suitable for spraying the herbicidal composition.

The concentrate compositions generally comprise about 0.1 to 95 parts, preferably 5 to 60 parts active ingredient, about 0.25 to 50 parts, preferably 1 to 25 parts surfactant and optionally 4 to 94 parts solvent, all parts being are by weight and refer to the weight of the emulsifiable oil as a whole.

Granules are physically stable particulate compositions containing the active ingredient adhered or distributed on a matrix of an inert, finely divided particulate carrier. In order to prevent leaching of the active agent from the particles, the composition may comprise a surfactant, for example the above. Examples of suitable classes of fixed extenders are natural clays, pyrophyllites, illite and vermiculite. Preferred extenders are porous, absorbent spun particles, such as preformed and sorted particles of attapulgite or heat expanded ortho-lithium in the form of particles and finely divided clays such as kaolin clay, hydrated attapulgite or bentordtic clays. These are not sprayed with the active ingredient or mixed with the active ingredient to form herbicidal granules.

The granular compositions of the invention may contain 0.1 to about 30 parts, preferably about 3 to 20 parts by weight of active ingredient per 100 parts by weight of clay and 0 to about 5 parts by weight of surfactant per 100 parts by weight of particulate clay.

The compositions of the invention may also contain ingredients such as fertilizers, other herbicidal compositions, other pesticidal compositions, safe-use compositions and the like used as adjuvants or in admixture with any of the aforementioned compositions. Chemicals used in admixture with the active compounds of the present invention include, for example, triazines, carbamates, ecetamines, acetainilides, uracils, acetic acid or phenolic derivatives, thiolcobbeates, thiazolobenzoic acids, nitriles, biphenyl ethers and similar substances such as:

heterocyclic derivatives containing sulfur

2-chloro-4-ethylamino-6-isopropylamine amino-triazine, 2-chloro-4,6-bis / isopropylspinin-8-yne-trrazine,

2-chloro-4,6-bis (ethylsilyl) -yl-triazio, i-yytyl-carbo-phenynyl-3 (2H) -pyrrolidine,

3-isopropyl: -1,1,2,1-benzoShadiazio-4 H- sn-3,2-dihydro-1-methyl---InniOs - pheno-1 0,4-triisio-5-so, 1-amino-1'-amino-1'-d, 7-dirsdro.ipiprid-31,2зe: 2 *, 1 * ypapidioidium salt, Узoproyyl-6-tylylerccl a

1,1'ydethyl-4,4'-bipyridine salt.

M ^ o ^ č ^^^ yny *

N '- / ^4-cUlsl'> fensxy / phenyl-N-NydУi tylioδovУne, N-0N dУityУ-; N- / 1-chlspy4- * ietylf-phenyl / iSčsvУne 1- / 1,4ydicUltгfenyУ / Y1) 1 -dУtietylio -ovine,, 1-di-yl-1--3yb-nzsthУizslyl / isCsvУ109,

1- / p-chУsrfenoУ / -1J-dietary io δ v У a a

- tbllyУ-1- / 1,4-dУccUlsгf -! OyУ / -1-i-thyisis.

Kaг1temittУthУslkaгbaiéty

2- chloreУlyldУetyУdУUhSokaгbiiát,

S- / 4-chlorobenzyl 1 / -Ν, N-dl-ty 1 thi o-t ba m t,

УssprspyУyN- / 1-cUlsrfeoyУ / kirbaiit

S-2,1-di-L, N-N, N-di-propyl polycarbamethyl, N, N-dipropyltisylcipyl, S-proppyropropylpyrrolidone.

AcetamУddУβictt-01Уny / ioil0nyeaiУdy

3- chУsryN, N-УdεllyУic-t8iLd,

N, N-ddimethyl-3,2-dyph-4-ynyl-c-t-E-m, emino / phenyl-ecetemide,

N- (3,4-diethyl) 5- (7-trifluoromethyl / sulphonino) phenyl-ec N-УisprospУ-У-УhreetreetanOid,

2 ', 6'ydL eУy - N-ietsxymityУ-УзyhUoorceete01id, * yietyУ-6 * yetyУ-Ny / 3-ietsxyyprs-2-yУ / -2-chULt · aietenOУid,

229040 slfe, EFSE, llae _tflUlroг-2) 6-eLt0lro-N, N-DO] 0'o0l1-0 toluidie-and N- / 1,1 - &. MeeylpoopJrtn ¹ / '3,5-dlchOoгbenz · шld.

»

K ^y 8sliey / eeteoy / eliohlly '

2,2-dichloro-epoic acid,

2-yleyl-4-chloro-hexylacetic acid,

2,6-dihydroxyacetic acid, 2,4-di-phenyl-2,4-di-phenoxy-propionate,

3-anino-2,5-dichlorobenzoic acid, α-neto-1,6-dichlorobenzoic acid,

2.3.6- ^ Ι ^ Ιμ ^ Dreams! acetic acid,

N-1-eefelyl: teaililic acid,

52 - l-100 --- Уo / tuiflnorme / yleOeølς,

4.6-dinieгtrc-o-a-iutylphenoe,

N- (Phospholithityl) glycine and its oonosicylanine with 1 to 6 centimeters of carbon and alkali metal salts and their sharing.

Ethers

2,4-di-hlcгfsnl ’-—- nLtoofsnylether,

2-hlocraefa, alpha, elf-rifrifluoro-β-tolyl-setsetozyl-4-eltoodifeylérs.

Different

2.6- dL-hlootbseooitr01, monosodium salt of acidic tenor, tu salt

Suitable formulations with the active compound according to the invention include, for example, ammonium nitrate, potassium nitrate, potash and suppefoate. Other useful ingredients include those in which plants have rooted and grow, such as koanoot, manure, burnus, and the like.

The herbicidal composition of the rows of the types described above will illustrate the following.

I. Polyolefins

AND. Compound of Example 1 Kelvin-11bsezneuUlfoet / polyolyl ether ethers (e.g., Atlox 3437F and Atlox 33438F) Monochloo benzene Canon nasal pro-seta 50.0 5.0 45.0 100.0 B, Example 2 compound 85.0 ielcluiiolecyl8uU: lolnt / alkl- * ryloolyetheretherilcl 4.0 C8 and non-hydrocarbon hydrocarbon solvent 11.0 C. 100.0 Example 3 compound 5.0 Stoes, kel-iododes-1-benzene-ureate, and p ' of ether (for example, Atlox 3437F) 1.0 Xlen 94.0

100,0 t3

II. Liquid concentrates

AND.

Example 4 compound

Xrlen

B. Compound of Example 5

Dimethyleulfoxid

C. Compound of Example 6 N-methylpyrrolidinone

D. Compound of Example 7

Ethoxylated castor oil RhodeimLn B

Dmeeylf ormamid

HmoOnootní percent

10.0

90.0

100.0

85.0

15.0

100.0

50.0

50.0

100.0

5.0

20.0

0.5

74.5

100.0

III. Wettable powders

A. Compound of Example 825.0

Sodium lignosulfonate 3.0

Sodium N-methyl-N-benzytalate 1.0

Anionic silica 71.0

100.0

B. Compound of Example 1080 0

Sodium diotylsulfosuccinate1,25

Calcium lignosulfonate2,75

Arnoophilic silica 16.0

100.00

C. Example compound 210.0

Sodium gnosulfonate 3.0

Sodium methyl-10-oleate ether 1.0

Keeoinite clay86,0

100.0

IV. Pills

AND. The compound of Example 3 2,0 Attaoulgit 98.0

100.0

B. Example 4 compound 60.0 Mootmomoilonite 40.0

100.0

C

Example 5 Bmtonite

D. Compound of Example 6

Kieselguhr

Valve valued 30,0 7 °? 0 100,0

1.0 99.0 100.0

V. Granule

A. Compound of Example β

Genulate Attapulgite (0.84 / 0,

B. The compound of Example 1

Quartz (0.84 / 0.42 mm)

C. Compound of Example 2

Bentonite (0.84 / 0.42 mm)

D. Compound according to 3

Pyrooylite (0, 440O, 4e mm)

15.0 mm) 85.0

100.0

30.0

70.0

100.0

0.5

99.5 100.0

5.0

95.0

100.0

The herbicidal composition according to the invention, containing the active compound of the formula I, is applied to the soil containing the plants or introduced into the aqueous medium by any known means. The application of liquid and particulate solid compositions to the soil is possible in any known manner, for example by a powder sprayer, a boom or hand mower or by powder misting. The herbicidal compositions containing the active ingredient according to the invention can also be applied from the aircraft in the form of powder or spray, since they are effective in small doses. When using the herbicidal compositions according to the invention for aqueous. In plants, the composition is generally added to water in the area where the plant is to be destroyed.

Pouužtí effective IOZIA ^^ ^{^,} ^ :( compound of formula I, effective according to the invention, the place where is to destroy unwanted weeds is essential and rozhodduící pouužtí importance for the inventive compositions. Exact mnnožtví active ingredient to be pouuít , depends on various factors such as the type of plant, the stage of development of the plant, the type and condition of the soil, the amount of rainfall and the rcetenilia used. / ha, preferably about 0.04 to about 5.60 kg / ha, or suitably 1.12 to 5.6 kg / ha of acetenilide In some cases, lower or higher doses may be required. This will readily determine the optimum dose of the herbal agent for each purpose.

The term soil is used in its broadest sense, so that it includes all common soil types as defined in Heters Newewritioial Dctionery, Second Edition, Unebrlded (1961). Soil refers not to any environment or to any substance in which the plant can be ingrown and grow and includes not only soil but also kommpot, rot, ο ^ ^μ, humus, sand and similar substances that are suitable tuberculosis plant growth.

Claims (1)

A herbicidal composition, characterized in that it contains, in addition to the auxiliaries, herbicidally effective amounts of the active compounds of the formula (I): O C1CH.-C. ch ₂ -a (I) wherein is R is an acyclic 1-propen-1-yl group or a 1-cyclohexen-1-yl group, these groups being optionally substituted by one or more C 1 -C 2 alkyl groups, and And, optionally, two methyl groups are a stistituent pyrazolyl group, an imidezolyl group or a triazolyl group.