CS212282B2 - Herbicide means - Google Patents

Abstract

The invention relates to a herbicidal composition herbicidally effective combination thiocarbamate, chlorinated Ν, Ν -substituted acetamide, as an antidote for thiocarbamate and a particular organophosphorothioate of which is used to prevent degradation thiocarbamate in soil. Influence of organophosphorothioate lifetime is significantly increased herbicide in soil.

Description

(54) Herbicidal product

The invention relates to a herbicidal composition comprising a combination of a herbicidally active thiocarbamate, chlorinated Ν, Ν-substituted acetamide, as an antidote for thiocarbamate, and certain organophosphorothioate, which is used to prevent thiocarbamate degradation in the soil. Due to the organophosphorothioate, the life of the herbicide in the soil is substantially prolonged.

The present invention relates to herbicidal compositions and their use, and in particular to herbicidal compositions comprising a herbicidally active thiocarbamate in combination with a specific oetamide as an antidote and an organic phosphorus compound which serves to prolong the efficacy and effectiveness of a single application of the thiocarbamate herbicide in controlling unwanted plant growth.

Thiocarbamates are well known in agricultural practice as herbicides useful for controlling weeds in crops such as corn, potatoes, beans, beets, spinach, tobacco, tomatoes, alfalfa, etc. Thiocarbamates are predominantly applied pre-emergence. They have been found to be particularly effective when introduced into the soil before sowing crops. The concentration of thiocarbamate herbicide in the soil is highest immediately after application. The time to maintain the original concentration depends largely on the soil treated. The rate at which the concentration of thiocarbamate herbicide decreases after application varies depending on the type of soil.

This is evident both from the observable extent of true weed control and the detectable presence of undegraded thiocarbamate that remains in the soil after a significant period of time.

It has now been found that the persistence of certain herbicidally active thiocarbamates combined with antidote-active acetamides in the soil is substantially prolonged by introducing into the herbicidal composition certain organophosphorus compounds which have no intrinsic herbicidal activity. Improved persistence of thiocarbamates in the soil is manifested in various ways.

For example, it can be shown that the rate of decrease of the thiocarbamate content in the soil is substantially reduced using an organophosphorus compound. This can be demonstrated by analyzing soil samples taken at regular intervals after application of the thiocarbamate herbicide.

Improved soil persistence is also evident from herbicidal activity tests in which the degree of weed damage is determined after some time after application of the herbicide. These tests demonstrate that organophosphorus compounds having no intrinsic herbicidal effect enhance the herbicidal activity of thiocarbamates by increasing their persistence in the soil and thereby extending their effective shelf life. Other manifestations of increased persistence of thiocarbamate herbicides are apparent from the following description.

The present invention relates to a novel herbicidal composition comprising

a) a herbicidally effective amount of a thiocarbamate of the formula r'-s-c-n wherein.

ni each of R ² and R ³ is C -C alkyl, C ^ -Cg alkenyl, phenylalkyl or phenyl and each of these groups optionally substituted with one, two or three halogens, and is independently C, -Cg alkyl or C ^ -C? cycloalkyl or both together represent an alkylene together with a non-phytotoxic antidotally effective amount of a compound of the formula ^{R 1 C} n ^GH (3-n) - ^C - ^{N 4} _Q wherein n

represents 1 or 2 and each of the symbols

R ⁸ and R ⁸ independently represent O, -C, ₂ alkyl or C ₂ -C ₁₂ alkenyl or a group

-N

represents a group of the general formula

R ¹ 'wherein each of β'θ and r' ¹ independently represents hydrogen or methyl;

R is hydrogen, O, -C 1-4 alkyl or phenyl

b) an organophosphorus compound of the formula

R

WITH

II

P-X-R where

R ⁴ represents C 1 -C 8 alkyl, C 1 -C 8 alkenyl, C 8 -C 8 alkynyl or C 8 -C 8 alkyl; cycloalkyl, each of which is optionally substituted with up to three substituents selected from the group consisting of halogen, cyano,

C 1 -C 8 alkoxy and C 1 -C ₃ alkylthio,

R 6 represents C 1 -C 4 alkyl O, -O 4 alkoxy or C 1 -C 4 alkylthio,

R ⁸ is C, -C _J0 alkyl, _Cg-I0 alkenyl or C ^ Cg-alkynyl, each of those groups being optionally substituted with up to three substituents selected from halo, nitro, cyano, Cj-C ^ alkoxy and C C 1 -C 6 alkylthio, C 1 -C 6 alkylthio cycloalkyl or a radical of formula

- <R ⁷ ) _m -0 where

R represents 0, -C ^ alkyl, Cg-C ^ ^{a: Lk} phenyl or C ^ Cg-alkynyl, each of those groups being optionally substituted with up to three substituents selected from halo and cyano, m is 0 or 1 and represents phenyl optionally substituted with up to three substituents selected from the group consisting of halogens, trifluoromethyl, nitro, cyano, C 1 -C 6 alkoxy, C 1 -C 6 carbalkoxy and C 1 -C 6 alkylsulfinyl,

X represents oxygen or sulfur; and

Y represents oxygen or sulfur, wherein the weight ratio of thiocarbamate to organophosphorus compound is 1: 1 to 15: 1.

The individual substituents in the above compounds preferably have the following meaning:

R

R

R

R j

are as defined above, represents a Cj-C ^ alkyl, CpC represents alkyl, _Cj-C4 alkoxy or C ^ C ^ alkylthio, represents phenyl, chlorophenyl, nitrophenyl, C ^ -rCg alkylsulfinylfenyl Cy-Cg phenylalkyl, or Cg- C 8 alkylthioalkyl, represents oxygen or sulfur and represents oxygen.

More preferably, the individual symbols in the above compounds have the following meanings:

R ² and R ³ have the abovementioned meaning, represents alkyl, CpC represents alkyl, C -C alkoxy or C -C alkylthio, represents phenyl, chlorophenyl, nitrophenyl, Ογ alkylsulfinylfenyl-Cg or _C2-Cg alkyl thiophenyl, represents oxygen or sulfur and represents oxygen.

The most preferred compounds are those in which

R ¹ represents C 1 -C 6 alkyl,

3 °

R and R are independently C 1 -C 6 alkyl, r 4 is C 1 -C 6 alkyl,

S ³ represents C 1 -C 4 alkyl, C ₍ -C 4 alkoxy or ¢) -04 alkylthio,

R 6 represents phenyl, chlorophenyl, nitrophenyl, C 1 -C 8 alkylsulfinylphenyl, or C 1 -C 8 alkylthiophenyl,

X represents oxygen or sulfur; and

Y represents oxygen.

Alkyl, alkenyl, alkynyl and alkylene are understood to mean both straight and branched chain radicals. All ranges of number of carbon atoms include both upper and lower limits.

The term halogen atom refers to a fluorine, chlorine, bromine or iodine atom and combinations thereof.

By herbicide is meant a compound that suppresses or modifies plant growth. By herbicidally effective amount is meant an amount of a compound which has a modifying effect on plant growth. The term plant refers to germinated seeds, emerging seedlings and mature vegetation, both roots and above-ground parts of plants. The suppression or modification effects include any deviations from natural development such as killing, retardation, defoliation, desiccation, regulation, stunting, offshooting, stimulation, leaf burning, dwarf forms, and the like.

By extending the lifetime of said thiocarbamate in soil is meant the effect of maintaining the molecular structure and / or herbicidal activity of thiocarbamate substantially the same as after the first application to the site. Prolonged soil shelf life results in a lower rate of decline in weed killing ability or an increase in half life of effective thiocarbamate concentration in soil. Other methods for determining the viability of soil compounds are apparent to those skilled in the art.

Thus, according to the invention, the above-described organophosphorus compound is added to the thiocarbamates in order to prolong their molecular integrity and herbicidal activity.

As the examples below show, there is no critical range of ratio between the two components. The soil prolongation effect occurs in a wide range of ratios. However, it is most preferred to apply the compounds in a ratio of thiocarbamate to organophosphoric compound of from about 0.1: 1 to about 50: 1 relative to each other. The preferred range for this ratio is about 1: 1 to about 25: 1 and most preferred is about 1: 1 to about 15: 1.

Thiocarbamates suitable for use in the compositions of the present invention include S-ethyldi-n-propylthiocarbamate, S-ethylhexahydro-1H-azepine-1-carbothioate, S-ethyldiisobutylthiocarbamate, Sn-propyldi-n-propylthiocarbamate, S-ethylethyl ethyl acetate. propylethyl n-butylthiocarbamate, S-chlorobenzyldiethylthiocarbamate, S-2,3,3-trichlorallyl5 diisopropylthiocarbamate, S-2,3-dichlorallyldxisopropylthiocarbamate, and S-benzyldis-butylthiocarbamate.

Organophosphorous compounds suitable for use in the compositions of the present invention include O-ethyl-S-phenylethylphosphonodithioate, O-ethyl-S-chlorophenylethylphosphonodithioate, O, O-diethyl-S-ethylthioethylphosphorodithioate, O, O-diethyl-O-p-methylsulfinylphenyl phosphorodithioate, O, O-diethyl-S-ethylthiomethylphosphorothioate, O, O-dimethyl-O-p-nitrophenylphosphorothioate, O, O-diethyl-O-p-nitrophenylphosphorothioate, O-dimethyl-O-phenylphosphorothioate, O, O-diethyl- O-phenylphosphorothioate, O, O-dimethyl-O-benzylphosphorothioate, O, O-dimethyl-O- (2-phenylethyl) phosphorothioate, Q, O-di-n-propyl-O -phenylphosphorothioate, O-ethyl-S-ethyl-O-phenylphosphorothioate, O, O-di-n-propyl-O-phenylphosphorothioate and O-methyl-S-phenylmethylphosphonodithioate. Further examples are provided in the tests below.

The usefulness of many thiocarbamates as herbicides can be substantially extended to a wider range of crop species by adding an antidote to the herbicidal composition. The antidote protects the crop from damage by the herbicide and increases crop tolerance to the herbicide. This increases the selectivity of the herbicide, i.e. maintains activity against unwanted weeds, while reducing the herbicidal activity against the desired crop species.

Examples of antidote agents and methods for their use are disclosed in U.S. Patent No. 3,959,304, issued to EG Teach 25, 5, 976, U.S. Patent No. 3,989,503, to FM Pallos et al., Nov. 2, 1976, U.S. Pat. U.S. Patent No. 4,021,224 issued to FM Pallos et al. on May 3, 1977, U.S. Patent No. 3,113,509 to OL Hoffmen on May 5, 1964, and U.S. Patent No. 3,564,768 issued to L. L. Hoffman 3 2. 1971.

Examples of antidotes falling within the above general formula include Ν, Ν-diallyldichloroacetamide and Ν, Ν-diallylchloroacetamide. Examples of substances not falling within the scope of this formula are 1,8-naphthalic anhydride.

The antidote is administered in conjunction with the thiocarbamate and the organophosphorus compound in a non-phytotoxic amount in which the antidote is present. A non-phytoxic amount is an amount of antidote that causes at most only minor damage to the desired crop. The amount in which an antidote effect occurs is an amount of antidote that substantially reduces the extent of thiocarbamate damage to the desired crop species.

A preferred herbicide to antidote ratio is from about 0.1: 1 to about 30: 1. A particularly preferred amount is from about 3: 1 to about 20: 1.

The following examples further illustrate the means, methods, and effect of the invention. The examples are illustrative only and do not limit the scope of the invention in any way.

Example 1

Persistence tests in soil

This example shows, not based on periodic chemical analyzes of the soil composition, the efficacy of the organophosphorus compounds of the invention to prolong the life of thiocarbamate herbicides in the soil.

A half-liter glass can containing 250 g of soil (dry matter) is used for each test. Three types of soil with different structures of clayey soil, alluvial soil and clay soil are used. The relative amounts of sand, alluvium and clay in these soils are determined mechanically and the amount of organic matter and acidity (pH) are determined chemically. The results of the analyzes are shown below.

Table I

Soil analysis

Soil Composition (% by weight) Organic matter sand naplevenina clay hm ·) pH clayey sand soil 64 29 7 4 6.8 alluvial soil 32 56 12 3 7.2 clay soil 50 30 20 May 4.7 6.1

Test compounds or combinations thereof are dissolved in water at concentrations such that 5 ml of the sample contains an amount of active ingredient that is equivalent to the desired degree of treatment when added to the jars. Thiocarbamates are used in these tests in the form of emulsifiable liquid concentrates containing an antidote to prevent crop damage. The concentrates are diluted accordingly to a degree of treatment of 6.72 kg / ha of active ingredient. Of the test organophosphorus compounds, O-ethyl-O-phenylphosphorodithioate is applied as a technical liquid diluted to an application concentration of 0.56 kg / ha or 1.12 kg / ha and O-ethyl-S-phenylethylphosphonodithioate is applied as an emulsifiable liquid concentrate diluted to an application concentration of 4.48 kg / ha of active ingredient.

An aliquot of the aqueous mixture containing thiocarbamate, antidote and organophosphorus additive at the appropriate concentration (5 ml) is pipetted into a canister and mixed with a spatula into the soil. The bottle is then capped and shaken by hand for about 30 seconds.

After this treatment, about 50 seeds of Echinochloa crusgalli and two seeds of D-Kalb XL-45A maize are sown in the soil. The soil is then moistened to a level corresponding to field conditions and the unclosed bottle is placed in a greenhouse where the temperature is maintained at about 21-27 ° C. Water is regularly introduced into the soil.

The tests are carried out twice and a separate bottle is used for each test. After a specified period of time, two bottles are removed from the greenhouse, the above-ground parts of the plants are removed, the bottles are sealed and frozen until chemical analysis is performed. After the next interval, another pair of bottles is removed and subjected to the same treatment. For each stage of application, 6 preservative bottles are prepared for analysis (2 of these 6 bottles are control bottles, ie bottles processed immediately after treatment with test chemicals).

Each of the prepared samples was macerated with 2 liters of water in a Waring Blender and transferred to a 4 L vessel. About 10.0 ml of antifoam is added and the mixture is distilled rapidly. About 400 ml of distillate are collected. 5 drops of concentrated hydrochloric acid were added to the distillate to prevent emulsion formation. The thiocarbamate is extracted from the distillate with two 2.0 ml portions of isooctane. The extracts are then combined. Analysis for thiocarbamate content is performed by gas chromatography.

In Tables II and III, the chromatographic analysis data are converted to equivalent soil concentrations in weight ppm of thiocarbamates. These tables show the results as the average of each pair of duplicate samples.

The tables clearly show that the thiocarbamate content decreases with time for each soil type. It is further apparent that this decrease is substantially slower in the presence of the organophosphorus compound. The effect of the organophosphorous compound on clayey soil is particularly evident from data corresponding to 21 days in Table II and three weeks in Table III. compared to experimental data obtained with control samples. The higher values obtained from the experimental data are a clear confirmation of the tone that the rate of decrease will substantially decrease due to the presence of organophosphorus compounds. A similar effect on alluvial soil is evident from data corresponding to 3 days in Table 1 and one week in Table XII. A similar effect is finally evident in clay soil and from data corresponding to 7 days in Table II and two weeks in Table III.

Table II

Results of persistence tests in soil

Herbicide: S-ethyldi-n-propylthiocarbamate (active ingredient) mixed in a 12: 1 weight ratio with N, N-diallyldichloroacetamide (antidote)

Application rate: 6.72 kg / ha

Amount of herbicide present in soil (ppm of active ingredient)

Degree Number of days after application

Organophosphorus additive application 0 3 7 14 21 283

Clay-sandy soil

- (control experiment) - 11.71 9.97 7.88 6.12 0.76 0.71 O, O-diethyl-O-phenylphosphorothioate 0.56 11.43 10.25 8.41 6.88 5.38 2.28 O, O-diethyl O-phenylphosphorothioate 1,121 12.10 13.23 10.91 6.79 5.74 3.95 O-ethyl-S-phenylethylphosphonodithioate 4.48 10.36 11.70 8.05 5.17 3.18 1.04

Alluvial saw

- (control experiment) - 10.59 2.58 0.24 0.12 0.00 - ^(b) O, Q-diethyl-O-phenylphosphorothioate 0.56 12.05 9.05 7.26 0.82 0.41 O, O-diethyl-O-phenylphosphorothioate 1,121 12.02 10,04 7.58 1,23 0,38 - O-ethyl-S-phenylethylphosphonodithioate 4.48 10.24 9.54 1.48 0.30 0.00 Clay soil - (control experiment) - 15.79 8.75 0.40 0.27 0,22 - O, O-diethyl-O-phenylphosphorothioate 0.56 12.24 9.38 5.87 0.51 0,43 - O, O-diethyl-O-phenylphosphorothioate 1,121 12.68 10.88 9.26 0.55 0,39 - O-ethyl-S-phenylethylphosphonodithioate 4.48 1-1,47 8.88 4.29 0.24 0,18 - (a! each number represents an average value of two samples.

(b) - indicates that the sample has not been analyzed.

Table III

Results of persistence tests in soil

Herbicide: 3-ethyldiisobutylthiocarbamate (active ingredient) mixed in a weight ratio of 24: 1 with Ν, dial-diallyldichloroacetjunide (antidote)

Application rate: 6.72 kg / ha

Degree Amount of herbicide present in soil (ppm of active ingredient) Number of weeks after application Organophosphorus additive application (kg / ha) 0 1 2 3 4 5

Clay-sandy soil

- (control experiment) - 9.00 7.30 6.15 3.35 0.68 0.30 O, O-diethyl-O-phenylphosphorothioate 1,121 9.40 9.14 6.55 5.25 5.18 3.65 Soil from alluvia - (control experiment) - 8.05 1,25 0.13 0.17 0.07 0.03 O, O-diethyl-O-phenylphosphorothioate 1,121 7.95 7.45 6.05 5.65 4.84 0.66 Clay soil - (control experiment) - 8.35 7.00 0.16 0.11 0.07 0.07 O, Q-diethyl-O-phenylphosphorothioate 1,121 8.35 7.10 4.90 2.11 1.18 0.37 (a) Each number is an average value of two measurement.

Example 2

Tests for improving herbicidal activity

This example provides herbicidal activity data showing that organophosphorus additives improve the herbicidal activity of thiocarbamates. The effect is monitored by comparing the extent of weed control in thiocarbamate-treated test plates compared to similar dishes treated with both thiocarbamate and organophosphorus compound.

As in Example 1, the thiocarbamates are used in the form of an emulsifiable liquid concentrate containing 0.72 kg / l of active ingredient. As shown below, in several tests, an antidote will also be included in the formulation to prevent crop damage. Organophosphorus compounds are used primarily in technical form, although in some cases, as indicated, they are used in the form of emulsifiable liquids, granules, and microcapsules.

Stock solutions are prepared by adding appropriate quantities of test chemicals to 100 ml of a mixture containing equal volumes of water and acetone by volume. 5 ml of the stock solution is then added to 13.62 kg of soil containing about 5% moisture in a rotary mixer and a volume of 18.9 L. In the mixer, the soil is mixed with the stock solution for 10 to 20 seconds.

The soil is then placed in 6.4 cm deep, 8.9 cm wide and 19.0 cm long aluminum dishes. The soil is compacted and six furrows are marked along the length. Different weeds were used as test weeds in each test. Overall, the following plants are used:

shark hedgehog corns the leg of sorghum

Setaria lutescens (Wigel) Houbb, Echinochloa crus-galli (L.) Beauv, Sorghum bicolor (L.) Moench (milo), barley Hordeum vulgare (L.), giant foxtail Setaria faberi Herrm gi _ro] t Sorghum bieolor (L.) Moench (wild cane )

Corn is also sown in some of these tests. Zea mays CL ·.) De Kelb XL-45A is used.

Sufficient seeds are sown to produce several 2.5 cm seedlings in each row. The trays were placed in a greenhouse where the temperature was maintained at 21-29.5 ° C. The dishes are watered daily.

Three weeks after treatment, the degree of weed control and maize damage was estimated and recorded as a percent control compared to the growth of the same species of the same age in the control untreated dish. A scale of 0 to 100% is used, where 0% means no effect, i.e. plant growth is the same as that of control plants in untreated dishes and 100% means complete killing.

The test results are summarized in the following tables. Each table contains a control comparison experiment. It is apparent from all the tables that, at all stages of application of the organophosphorus additive, the average percentage of weed control is significantly improved compared to the control. All experiments listed in each individual table are performed at the same time under the same conditions. However, there are variations between tables because it is difficult to reproduce the same ambient conditions at different times of the year. Variations also occur because different combinations of weeds and / or soils have been used. Overall, however, it is clear that the herbicidal effect of thiocarbamates three weeks after application is considerably better when using an additive of organophosphorus compounds.

Table IV

Herbicidal effect on Hordeum Vulgare, Echinochloa orusgalli, Sorghum bieolor (milo) and others. «:,! ··· ria faberi

Herbicide: S-ethyldi-n-propylthiocarbamate in the form of an emulsifiable liquid at a concentration of 0.72 kg / l containing, where indicated, Ν, dial-diallyldichloroacetamide (p.nti · ´ 'in a weight ratio of 12: 1

Application rate: 3.36 kg / ha

Soil: clay

Evaluation time: 3 weeks after treatment Degree No antidote Organophosphorus application Average grade Damage Average grade Damage ingredient (kg / ha) suppression of pleve- maize skin suppression kuku? and. O large (%) (%) large (%) («)

- (control experiment) O-ethyl-S-phenylethyl- 0.56 65 92 0 60 58 95 0 0 phosphonodithioate 1.12 100 ALIGN! 100 ALIGN! 1 00 20 May (4E) ^ís) 2.24 100 ALIGN! 80 100 ALIGN! 0 4.48 100 ALIGN! i 00 99 0 O-ethyl-S-phenylethyl- 0.56 97 90 78 0 phosphonodithioate 1.12 100 ALIGN! 80 81 0 ( ^B) 2.24 100 ALIGN! 30 88 0 4.48 100 ALIGN! 90 99 10

continuation of Table IV

Organophosphorus Degree application No antidote Average grade Damage Average grade Damage ingredient (kg / ha) skin suppression maize skin suppression maize large (%) (%) large (%) (%)

O-ethyl-S-p-chloro- 0.56 8, 0 phenylethylphosphonodi- 1.12 90 20 May thioate (4E) 2.24 100 ALIGN! 75 4.48 100 ALIGN! 80 O-Ethyl-S-p-chloro- 0.56 66 0 nylelthylphosphonodi- 1.12 84 0 thioate (10G) 2.24 82 30 4.48 96 60 O, O-diethyl-S-ethyl- 1.12 80 20 May thioethylphosphorodi- 2.24 85 40 thioate (technical) 4.48 87 50 O, O-diethyl-O-p-me- ’.12 96 60 thylsulflnylfepylfo s- 2.24 100 ALIGN! 95 forodithioate (those- 4.48 100 ALIGN! 90 nický) 0,0-Diethyl-S-ethyl- 1.12 97 75 thioMethylphosphorus- 2.24 98 90 thioate (technical) 4.48 98 80 O, O-dimethyl-O-p-ni- 1.12 98 70 trophenylphosphorodi- 2.24 95 70 thioate (technical) 4.48 100 ALIGN! 90

(a) 4E: emulsifiable liquid containing 0.48 kg / l of active ingredient (b) 10G: granular composition containing 10% by weight of active ingredient.

Methods of application

The herbicidal compositions according to the invention are suitable for controlling the growth of undesirable vegetation and are applied pre-emergence or post-emergence to the place where the control is to be achieved. Application can be carried out before sowing, after sowing to the soil or to the surface. The compositions typically have similar, conventional standard compositions that are well handled. Typical standard compositions include adjuvants or diluents and a carrier that are either inert or active. Examples of such additives or carriers include water, organic solvents, dusting carriers, granulate carriers, surfactants, olefin / water mixture, water-oil emulsions, wetting agents, dispersing agents and emulsifying agents. The herbicidal compositions usually take the form of dusts, emulsifiable concentrates, granules, pellets or microcapsules.

A. Popraěe

In addition, they are heavy, pulverulent compositions which are used in dry form. They are loose and quickly settle so that they are not blown by the wind where they are not desired. They contain, in particular, the active ingredient and a heavy particulate powder carrier.

Their effect is sometimes increased by adding wetting agents and, for ease of manufacture, inert absorbent grinding aids are also added. For dusts according to the invention, inert carriers of either vegetable or mineral origin can be used. Preferred wetting agents are anionic or nonionic substances. Suitable absorbent grinding aids are those of mineral origin.

Suitable inert solid carriers which are suitable for dusting are organic or inorganic powders which have a high bulk density and are very free-flowing. They are also characterized by having a small specific surface and a low liquid absorption capacity. Suitable grinding aids are natural clays, diatomaceous earth and synthetic mineral fillers derived from silica or silicates. Among the ionic and nonionic surfactants, those which are commonly referred to as surfactants or emulsifiers are most suitable.

Although solid surfactants are preferred, for ease of handling, some liquid nonionic agents can also be used in the manufacture of dusts.

Preferred dust carriers are mica talc, pyrophyllite, heavy kaolin clays, tobacco powder and ground calcium phosphate (mineral).

Preferred grinding aids are attapulgite, diatomaceous earth, synthetic fine silica and synthetic calcium and magnesium silicates.

The most preferred wetting agents are alkylbenzene and alkylnaphthalenesulfonates, sulfated fatty alcohols, amines or acid amides, long chain sodium isothionate acid esters, sodium sulfosuccinate esters, sulfated or sulfonated fatty acid esters, petroleum product sulfonates, sulfonated vegetable oils and di-tertiary acetylates. Preferred dispersants are methylcellulose, polyvinyl alcohol, lignin sulfonates, polymeric alkyl naphthalenesulfonates, sodium naphthalenesulfonate, polymethylene naphthalenesulfonate, and long-chain alkanoyl N-methyl-N-alkanoyl taurate sodium.

The inert solid carriers in the dusts of the present invention are usually present in concentrations of from about 30 to 90% by weight of the total composition. The grinding aid usually constitutes 5 to 50% by weight of the composition and the wetting agent is about 0 to 1.0% by weight of the composition. Dusts can also contain other surfactants, such as dispersants in concentrations up to about 0.5% by weight, and minor amounts of anti-agglomeration and antistatic agents. The particle size of the carrier is usually in the range of from 30 to 50 µm.

B. Emulsifiable concentrates

Emulsifiable concentrates are usually solutions of the active ingredients in water-immiscible solvents mixed with an emulsifying agent. Before use, the concentrate is diluted with water to form an emulsion of solvent droplets.

Typical solvents for use in emulsifiable concentrates are oils, chlorinated hydrocarbons and ethers, esters and ketones immiscible with water.

Typical emulsifiers are anionic or nonionic surfactants or mixtures of the two. Examples include alkyl (long chain) or mercaptopolyethoxyalcohols, alkylarylpolyethoxyalcohols, sorbitan fatty acid esters, sorbitan polyoxyethylene ethers of fatty acid esters, polyoxyethylene glycol esters of fatty or resin acids, condensates of fatty alkyloamides, calcium and petroleum sulfates of fatty products oils or preferably mixtures of these emulsifiers. These emulsifiers make up about 1 to 10% by weight of the total composition.

The emulsifiable concentrates of the invention contain about 15 to about 50% by weight of the active ingredient, about 40 to about 50% by weight. 82% by weight of a solvent and about 1 to 10% by weight of an emulsifier. Other additives may also be present, such as leveling agents and sticking agents.

C. Granules and pellets

Granules and pellets are physically stable, particulate formulations containing the active ingredients that adhere to or are distributed within the matrix. The basic matrix is a coherent inert carrier of macroscopic dimensions. Typical particles have a diameter of about 1 to 2 mm. Granules and pellets also often contain surfactants to facilitate leaching of the active ingredients from the granules or pellets.

The carrier is preferably of mineral origin and carriers of either of the following two types are usually present. The carriers of the first type are porous overflow granules of high absorbency, such as preformed attapulgite, from which a suitable fraction or thermally expanded granular vermiculite has been separated from the sieves, from which a suitable fraction has been separated on the sieves. Each of these substances can be sprayed with a solution of the active ingredient and the solution is absorbed in the carrier up to 25% by weight of the total weight.

A second type of carrier which is also suitable for pellets are initially pulverized kaolin clays, hydrated attapulgite or bentonite clays in the form of sodium, calcium or magnesium bentonites. Water-soluble salts, such as sodium salts, which facilitate the disintegration of granules or pellets in the presence of moisture may also be present. These ingredients are mixed with the active ingredients to form a mixture which is granulated or pelletized and dried. The compositions obtained contain the active ingredient uniformly distributed throughout the composition. Such granules and pellets can also be produced with up to 25-30% by weight of active ingredient, but more often a concentration of about 10% by weight is required for optimal distribution. Most preferred granulates of the invention have a particle size in the range of 15 to 30 mesh.

The surfactant is usually a conventional anionic or nonionic surfactant. Which surfactant is most suitable depends on the type of granules used. When the granulate is produced by spraying the active ingredient in liquid form onto the preformed granules, the most suitable wetting agents are nonionic liquid wetting agents which are miscible with the solvent.

Such materials are commonly known as emulsifiers and include, but are not limited to, alkyl aryl polyether alcohols, alkyl polyether alcohols, polyoxyethylene sorbitan fatty acid esters, fatty acid or polyethylene glycol esters of fatty acids, fatty alcohol condensates, petroleum fraction sulfonates or vegetable oils that are soluble in oil or mixtures thereof. These substances generally comprise up to about 5% by weight of the total composition.

When the active ingredient is first admixed with a powdered carrier and only then granulated or pelletized, liquid nonionic surfactants may also be used, but usually some of the solid powdered anionic surfactants, such as those mentioned above in connection with wettable materials, are preferably added at the time of mixing. pills. These comprise about 0 to 2% by weight of the total composition.

Preferred granules or pellets according to the invention thus contain 5 to 30% by weight of active ingredient, about 0 to 5% by weight of wetting agent and about 65 to 95% by weight of inert carrier.

D. Microcapsules

The microcapsules consist of completely enclosed droplets or granules containing the active ingredients. The capsule shell material forms an inert porous membrane that allows the encapsulated material to be released into the environment at a controlled rate for a predetermined period of time. Microcapsules are particularly suitable compositions of the present invention since the orgenophosphorous compounds which form part of the compositions of the present invention are liquid.

Encapsulated droplets typically have a diameter of about 1 to 50 µm. Encapsulated liquid typically

2J2282 constitutes about 50 to 95% by weight of the entire capsule and may contain a small amount of solvent in addition to the active ingredients.

Encapsulated granules are characterized in that the porous membrane closes the pore openings of the granule carrier and thus closes the liquid containing the active ingredients inside the capsule. It is then released in a controlled manner. Typical encapsulated granule sizes range from 1 mm to 1 cm. In agricultural practice, a granule of about 1 to 2 mm is usually used.

As granules, granules produced by extrusion, agglomeration or granular materials in natural form may be used. Examples of carriers include vermiculite, sintered clay granules, kaolin, attapulgite, sawdust and granulated charcoal.

Suitable encapsulants are natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyurethanes and starch xanthates.

E. General

Each of the compositions can be manufactured as a pack containing both a thiocarbamate herbicide and an antidote, as well as an organophosphorus additive together with other ingredients (diluents, emulsifiers, surfactants, etc.). The compositions can also be prepared on site. The components are transported to the application site in separate tanks. The herbicide, the antidote and the organophosphorus component may be in the form of compositions of the same or different types prior to the final mixing. For example, the herbicide and antidote may be in the form of microcapsules and the organophosphorus component in the form of an emulsifiable concentrate or vice versa.

As a further alternative, it is contemplated that the herbicide, the antidote, and the organophosphorus component are applied sequentially, any of which may be applied first. This method is less suitable because better results are obtained when applied simultaneously.

In general, any conventional method of administration may be used. The site of application may be soil, seeds, seedlings or mature plants, as well as irrigation fields. Application to soil is preferred. Dusts and liquid compositions can be applied using dusting devices, hand sprayers and aerosol generating devices. The compositions can also be applied from aircraft such as dusts or sprays as they are effective at very low doses. To modify or suppress the growth of germinating seeds or emerging seedlings, dusts and liquid compositions are typically applied to the soil.

After application by conventional methods, the compositions are distributed in the soil to a depth of at least 1.25 µm below the surface. Pytotoxic agents need not be pre-mixed with soil particles. Instead, the compositions may be applied directly to the soil surface by spraying or sprinkling. The phytotoxic compositions of the invention may also be applied by admixing the irrigation water supplied to the field to be treated. This method permits the penetration of the compositions into the soil along with the absorbed water. Dusts, granules or liquid formulations applied to the soil surface can be introduced below the soil surface by conventional means such as disking, shearing or mixing.

The herbicide-based compositions, antidotes, and organophosphorus additives can be applied to the soil through irrigation systems. In this method, the compositions are directly added to the irrigation water immediately prior to irrigation of the field. This method can be used in all geographic areas irrespective of rain, as it allows for the replenishment of natural precipitation during a critical period of plant growth. Typically, the concentration of the herbicide / additive system composition in the irrigation water is in the range of about 10 to about 150 ppm by weight. The irrigation water can be supplied by sprinkling systems, furrows or flooding. Such application is most effectively performed before weed germination is early in the spring before germination or within two days of field cultivation.

The compositions of the invention may also contain other ingredients such as fertilizers, insecticides or other herbicides. Suitable pesticides are 2,4-dihlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid and their salts, esters and amides, triazine derivatives such as 2,4-bis- (3-methoxypropylamino) 6-methylthio-s-triazine, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine-2-ethylamino-4-isopropylamino-6-methylmercapto-s-triazine, urea derivatives such as 3- ( 3,4-dichlorophenyl) -1,1-dimethylurea, acetamides such as Ν, Ν-diallyl-alpha-chloroacetaniid, N- (slfB-o, chloroacetyl) hexamethylenimine and Ν, Ν-diethyl-alpha-bromoacetamide, and benzoic acids such as 3-amino-2,5-dichlorobenzoic acid.

Suitable fertilizers which can be used in conjunction with the active ingredients of the invention are ammonium nitrate, urea and superphosphate. Other useful ingredients are substances in which plant organisms are rooted and grown, such as compost, manure, humus, sand, and the like.

The amount of the composition according to the invention which forms a herbicidally effective amount depends on the type of seeds or plants to be controlled. The rate of application of the active ingredient varies from about 0.01 to about 56 kg / ha, preferably from about 0.11 to about 28 kg / ha, the amount actually used depends on the total cost and the desired results. It will be appreciated by those skilled in the art that compositions which exhibit a lower herbicidal effect must be used at higher doses to achieve the same degree of control.

Claims (7)

SUBJECT OF THE INVENTION What is claimed is: 1. A herbicidal composition comprising a) a herbicidally effective amount of a thiokerbamate of the formula O ¹¹ rscn; Where R ¹ represents C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 1 -C 6 phenylalkyl, or phenyl, and each of these groups is optionally substituted with one, two or three halogen atoms and each of the symbols oi R 1 and R 2 are independently C 1 -C 6 alkyl or C 1 -C 6 cycloalkyl, or both together represent C 1 -C 6 alkyl; alkylene together with a non-phytotoxic antidotally effective amount of a compound of formula ^{G 1} n ^CH (3-n) O-R ° -ft-A where χχ represents 1 or 2 and each of the symbols R ⁸ and R ⁸ independently represent alkyl or C ₂ -C ₁₂ alkenyl or a group R ⁸ represents a group of the general formula R 1 1 wherein each of R ^G and R ¹ 'independently represent hydrogen or methyl and R ¹² represents hydrogen, C, -C ₄ alkyl or phenyl and (b) an organophosphoric compound of the general formula wherein R ⁴ represents C 8 -C 8 alkyl, C 8 -C 8 alkenyl, C 8 -C 8 alkynyl or C 8 -C 8 alkyl; cycloalkyl, each of which is optionally substituted with up to three substituents selected from the group consisting of halogens, cyano, C 1 -C 8 alkoxy and C 1 -C 8 alkylthio, R 1 represents C 1 -C ₄ alkyl, C 1 -C ₄ alkoxy or C 1 -C ₄ alkylthio, R 6 represents C 1 ^-C 6 alkyl, C 1 ^-C 6 or ^C 2 ^-C 4, each of which is optionally substituted with up to three substituents selected from the group consisting of halogens, nitro, cyano, Ο, -C 8 alkoxy and C 1-6 alkyl; -C 8 alkylthio, C 8 -C 8 alkylthio; cycloalkyl or a radical of formula - (R ⁷ ) _ffl -0 where R ⁷ represents a C, -C 4 alkyl, C 2 ^-C 4 ^{ell £ en-yl} or _C2-C4 alkynyl, each of those groups being optionally substituted with up to three substituents selected from halo and cyano, m. represents 0 or 1; and O represents phenyl optionally substituted with up to three substituents selected from the group consisting of halogens, trifluoromethyl, nitro, cyano, C 1 -C 8 alkoxy, C 1 -C 8 carbaloxy and C 1 -C 8 alkylsulfinyl, X represents oxygen or sulfur; and Y represents oxygen or sulfur, wherein the weight ratio of thiocarbamate to organophosphorus compound is 1: 1 to 15: 1. 2. A composition according to claim 1, characterized in that the thiocarbamate containing a thiocarbamate of the formula R · ^ ³ where R 'is a C, -Cg alkyl, Cg-Cg alkenyl, Cy-Cg phenylalkyl, or phenyl, each of these groups are optionally substituted with one, two or three halogen atoms and each of the symbols R ² and R ³ are independently C 1 -C 8 alkyl and C 8 -C 8 alkyl; cycloalkyl, or both together form a C 1-6 alkyl alkylene, and as organophosphorus compound it contains an organophosphorus compound of formula. R ⁴ C> S ^{x L 2} → ⁶ where R ⁴ represents C 1 -C 4 alkyl, R ^ is C ^ -C ^ alkyl, O, alkoxy or C -C alkylthio, R6 is phenyl, chlorophenyl, nitrophenyl, C ^ Cy-alkylsulfinylfenyl, Cy-C ^ Cg-phenylalkyl or -C ^{ell £ £} yl ^thioall .yl ^a X represents oxygen or sulfur. 3. The herbicidal composition of claim 1, wherein the thiocarhamate comprises a thiocarbamate of the formula R ¹ represents C 1 -C 8 alkyl, C 1 -C 8 alkenyl, C 1 -C 6 phenylalkyl, or phenyl, each of which is optionally substituted with one, two or three halogen atoms and each of the symbols 2 3 R and R independently represent C 1 -C 8 alkyl or C 8 -C 8 alkyl; cycloalkyl, or both together form C 1 -C 6 alkyl; alkylene and contains as organophosphorous compound O, O-diethyl O-phenylphosphorothioate. 4. The herbicidal composition of claim 1, wherein the thiocarbamate is S-ethyldi-n-propylthiocarbamate and the organophosphoric compound is O, O-phenylphosphorothioate. and 5. The herbicidal composition of claim 1, wherein the thiocarbamate is 5-ethyldiisobutylthiocarbamate and the organophosphorus compound is O, O-phenylphosphorothioate. 6. The herbicidal composition of claim 1, 2, 3, 4 or 5 wherein the weight ratio of thiocarbamate to organophosphoric compound is from 1: 1 to 15: 1. ' 7. The herbicidal composition of claims 1 to 6, wherein the antidote is N, N-diallyldiehlorecetamide.