CS208671B2 - Herbicide mixture - Google Patents

Description

The invention relates to the field of crop protection. It relates to novel compositions and methods for reducing or eliminating damage to young crop plants by selective herbicides. More specifically, it relates to novel compositions and methods of reducing deterioration of young grassy plants, e.g., corn, rice, barley, sorghum and wheat, with thiolcarbamate herbicides such as diallate and triallate, characterized in that the location of the crop plant or crop seeds grown, processed before growing with an antibody (antidote) of a selective herbicide.

Thiolcarbamate herbicides such as diallate and triallate are very useful in controlling certain weeds alongside other growing plants. However, these herbicides sometimes damage certain crops, retard the growth and development of these plants when used at the application rates necessary to stun or kill weeds.

As a result, it is sometimes disadvantageous to use thiolcarbamate herbicides to control weeds in the presence of certain crops, some of which are important for the world's food supply.

There is a clear need for a method to reduce or eliminate crop damage by selective herbicides without affecting the herbicidal action on the weeds to be controlled.

It is known to those skilled in the art that to reduce damage to various crops by herbicides, antibody-acting agents or protecting compounds are used which have an antagonistic or nullifying effect on the active ingredients of the herbicides by one or another mechanism.

By way of illustration, the use of carbamate or thiolcarbamate herbicide antibodies may be mentioned in the prior art from U.S. Pat. No. 3,131,509 and South African Patent Publication no.

72/2519. U.S. Patent No. 3,131,509 discloses the use of various hormone-type plant growth regulators, e.g., a bromoalkyl compound, as antagonists of certain carbamates.

The South African patent describes the use of various acetamides and carbamate compounds. as thiolcarbamate herbicide antagonists. U.S. Patent No. 4,036,628 discloses the use of certain phosphate, phosphonate and phosphinate compounds as antibodies to certain thiolcarbamate herbicides.

However, it is not in the literature that the organothiophosphorous compounds have the effect of antibodies on thiolcarbamate compounds (herbicides).

However, many other compounds have been described in the literature as being useful as antibodies to carbamate and acetaniliric herbicides. However, organophosphorus compounds do not appear to be widely used as antibodies to thiolcarbamate herbicides.

Mostly, the organophosphorus compounds according to the literature are used in agriculture as insecticides, defoliants, herbicides, weed growth inhibitors or as fruit abscess agents.

See, for example, U.S. Patent Nos. 3,879,189, 3,907,540, 3,861,899 and 3,826,640 to illustrate the use of organophosphorus compounds in crop protection.

The present invention relates to the use of certain organophosphorus compounds as antibody-acting, antagonist or preservative agents for reducing post-cropping by thiolcarbamate herbicides. More particularly, the present invention relates primarily to reducing the damage to grassy crops such as barley, rice, sorghum and wheat by thiolcarbamate herbicides by diallate or triallate.

SUMMARY OF THE INVENTION The present invention provides a thiolcarbamate herbicide preservative composition comprising 5 to 95% by weight of a thiolcarbamate herbicide, 5 to 95% by weight of a compound of formula I,

WITH

R- / X / _b -P- / Z / _O- B ² / W / (I) wherein a, b, c are integers zero or one, but all cannot simultaneously represent zero,

W, X and Z are each independently O or S,

R, R and R are each independently hydrogen, C 1 -C 13 alkyl, 1-methyl-2-nitroethyl, allyl, haloallyl, propynyl, chloromethylcarbonyl, (3-chloro-2-butenylsulfonyl) methyl, dichlorallylthiomethyl , halophenylthio, p-aminosulfonyl, p-nitrobenzyl, chlorophenyl, thiomethyl, phenyl, benzyl, naphthyl, naphthyl substituted with one or two methyl or halogen, alpha-nitromethylbenzyl, alpha-methylbenzyl, phenyl substituted up to three alkyl groups having 1 to 12 carbon atoms, an allyl group, a halogen atom, and the NO, -, CN-, IJ- or CH 3 S- radicals; with that p

If A is zero, c is one and Z is sulfur then R can not be hydrogen or a halogenophenyl group, a phenyl group may simultaneously be substituted, -N0 ₂ and -CF ^ if X and W are oxygen and Z is a sulfur atom, then E, E * and E ² cannot simultaneously represent a methyl group, and if W, X and Z are oxygen, then E, E ¹ and E ² cannot simultaneously represent a phenyl group, and 1-94% by weight of the agricultural adjuvant and / or solvents, wherein in said mixture the ratio of thiolcarbamate herbicide to protecting compound is 1: 5 to 5: 1 parts by weight.

Preferred alkyl groups in the above formula are those having 1 to 6 carbon atoms. The term halogen group ^'1 or halogen is chlorine, bromine or iodine. The term carbonyl group refers to radical O.

As described in further detail below, certain subgroups of organophosphorus compounds exhibit a general feature of activity as antibodies to thiolcarbamate herbicides.

Other aspects of the present invention pertain to preservatives of thiolcarbamate herbicides, in particular diallate and triallate, an effective amount of an organophosphorus antibody, and methods of reducing damage to young plant crops, especially grass crops such as barley, rice, sorghum and wheat by using the above. securing means. The preferred crop to be protected is wheat.

Preferred specific embodiments of the invention include protecting or reducing wheat damage by the trilate herbicide by using the compound 0,0-di-, ethyl-O- (m-tolyl) phosphorothioeth as the antibody.

The invention can be more clearly understood by the following detailed description of its specific arrangement.

Compounds useful for reducing or eliminating crop damage are commonly referred to by those skilled in the art as herbicidal antibodies (antidotes), preservatives and antagonists.

These compounds act in the opposite direction to the herbicides, reducing damage to the crop. In many cases, weed damage is also reduced, but to a tolerable level given by economic factors.

In practice, according to the present invention, the organophosphorus compounds of the above formula are used as antibodies to thiolcarbamate herbicides.

In the examples, thiolcarbamates are represented by triallate and diallate. Triallet is the trivial name for the compound S- (2,3,3-trichlorallyl) -diisopropylthiolcarbamate, diallate is the trivial name for S- (2,3-dichlorallyl) diisopropylthiolcarbamate.

Triallate and diallate, respectively, are active ingredients in the herbicides Avadex BW ^R , FAE-GO® and Avadex ^K (trademarks of Monsanto Company).

Analysis of the test results in the study of a large number and species of organophosphorus compounds tested, with particular regard to the applicability of the triallate, shows the following general feature of antibody efficacy of different species of organophosphorus compounds:

SSS ⁰ 2 \ ¹¹ 2

R0-P-0R ² > RP-OR ² J> RP-OR ² = ¹¹ 2 \ ¹¹ 2 ro-p-sr ² ^> rp-sr ²

OR ¹

STEED'

OR ¹

OR '(I) (II) (III) (IV) (V)

The compounds of the structures of the formulas I to V are known as: I = phosphorothioates or thiophosphonates, II = phosphonothioates, III = phosphinothioates, IV = phosphonothioates and V = phosphonodithioates.

The amount of antibody used in the methods and compositions of this invention varies. It depends on the herbicide used and the application rate of the herbicide.

In any case, the amount of antibody used is an effective protective amount. By effective protective amount is meant an amount that reduces crop damage by herbicides.

In the tests used to illustrate the invention, crop damage was reduced by up to 100%.

The compounds used herein as thiolcarbamate herbicide antibodies are either known or are readily obtainable from known compounds by known and / or conventional methods of manufacture.

The methods and compositions of this invention are exemplified by the following examples.

Examples 1 to 75

The protective effects of representative triallate herbicide antibodies against wheat are shown in the test results shown in Table 1. For each antibody, the protective effect of the antibody is shown as a percent reduction in crop damage. The percent protection effect is determined by the following calculation: [% inhibition of plant which is caused by herbicide alone +% inhibition of plant which is caused by antibody] -% inhibition of plant which is caused by combination of herbicide with antibody. These results are obtained as follows.

The aluminum bowl is filled with good topsoil. The soil is treated so that its surface is 0.95 to 1.27 from the top of the dish. A predetermined amount of seed from each plant species tested was placed on the soil in the dishes.

The amount of soil sufficient to substantially fill the dish is measured and placed in a suitable container. The measured amount of antibody is dispersed or dissolved in a suitable carrier and the soil in the vessel is sprayed with it.

The soil already treated with the preservative is then sprayed with a measured amount of the triallate herbicide which is dispersed or dissolved in a suitable carrier. The amounts of triallate herbicide and antibody used are then expressed in kilograms per hectare.

The soil containing the antibody and the triallate herbicide is mixed thoroughly. Mixing is sometimes referred to as introducing the herbicide and antibody into the soil. Mixing or loading results in a substantially uniform distribution of the antibody and herbicide in the soil.

The seeds are covered with soil containing the antagonist and triallate herbicide, and the dishes are leveled. The dishes were then placed in a sandbed in a greenhouse and watered from below as needed. Plants are observed at the end of day 21.

Results in% inhibition of each crop species are recorded. For all series tested, dishes containing plants containing no herbicide or anti-substance are prepared as a control.

To ensure that the antibody as such has no herbicidal effect, a bowl of plants is prepared for each test where the seeds are covered with soil that does not contain a triallate herbicide but only a measured amount of antibody.

For each series of tests, the herbicidal effect of the triallate was observed on the dishes with plants treated with the same amount of herbicide alone.

Table 1

example and. amount triallate antibody amount antibodies (kg / ha) percent protective effect ! 0.14 O, O-diethyl-S- (methyl-2,6-xylylcarbamoylmethyl) rosfordithioate 8.96 55 2 0.28 O- (2-chloro-4-nitrophenyl) -O, O-diethylphosphorothioate 4.48 20 May 3 0.28 O- (3-cyanophenyl) -O, O-diethylphosphorothioate 8.96 70 4 0.28 3- (3,3-dichloroethyl) -0,0-dimethylphosphorothioate 8.96 40 5 0.28 O- (3,3-dichlorallyl) -O, O-diethylphosphorothioate 4.48 35 6 0.2e S- (1,3-Dichlorallyl) -0, O-diethylphosphonite oate 8.96 50 7 0.28 O, O-diethyl S- (1-methyl-2-nitroethyl) phosphorothioate 8.96 30 8 0.28 S- (2,3-dibromallyl) -0, O-diethylphosphorothioate 4.48 30 9 0.28 O, O-dimethyl-O- (4-sulfamylphenyl) phosphorothioate 8.96 80 10 0,2β S- (3,3-dichloroallylthiomethyl) -O, O-diethylphosphorothioate 8.96 60 1! 0.28 O, O-diethyl-O-p-nitrophenylphosphorothioate 8.96 50 12 0.28 O, O-diethyl-O-p-nitrophenylphosphorothioate 8.96 60 13 0.28 S - {[(p-chlorophenyl) thio] methyl} -O, O-diethyl- fosfordithicát 8.96 45 14 0.28 O, O-dimethyl 1-O- [4- (methylthio) -m-tolyl] phosphorothioate 4.48 85 15 Dec 0.28 O, O-dimethyl-O- (4-nitro-m-tolyl) phosphorus- thVaát 4.48 20 May 16 0.28 O, 3-dimethyl-O- (2,4,5-trichlorophenyl) phosphorothioate 4.48 35 17 0.28 S [(3-chloro-2-butenylsulfonyl) methyl] -0,0-diethylphosphorothioate 8.96 30 18 0.56 S- (2-bromoallyl) -0.0-diethylphosphorothioate 8.96 80 19 Dec 0.56 S- (alpha-methylbenzyl-O, O-diethylphosphorothioeth) 8.96 90 20 May 0.56 O, O-diethyl O- (p-trifluoromethylphenyl) phosphorothioate 8.96 95 21 0.28 O, O-diethyl-S- (1-n-phenylmethyl) phosphorodithioeth 8.96 20 May 22nd 0.28 O, O-diethyl S-2-propynylphosphorothioate 8.96 45 23 0.28 0,0,0-tributylphosphorthioeth 8.96 55 24 0.28 S- (chloroacetyl) -0,0-diisopropylphosphorothioate 8.96 20 May 25 0.28 S, S- (p-chlorophenyl) -0,0-diisopropylperoxyphosphoric triothioate 4.48 30 26 0.28 O, O-diisopropyl-S, S- (o-nitrophenyl) peroxylphosphoric thioeth 8.96 25

example E. amount triallate antibody amount antibodies (kg / ha) percent protective effect

27 Mar: 0.28 Mixed diethyldithiolcarbamic acid anhydride and O, O-diisapiyl-S-hydrogen phosphorothiothioate 4.48 50 28 0.28 - Ο, Ο-diisopropyl-S- [2- (2-pyridyl) ethyl] - phosphorothioate 8.96 40 29 0.28 S- [1- (ethoxycarbonyl) ethyl] O, O-diisopropylphosphorothioate 8.96 40 30 0.42 S- (5-Chloro-2-thienyl) -0,0-diisopropyl- » fosfordithioót 8.96 43 31 0.42 O, O-dipropyl-S-hydrogenphosphorodithioate 4.48 23 32 0.42 S- (3,3-dihlorallyl) -0, O-diisopropylphosphorothioate 4.48 97 33 0.42 S- (3,3-dichloroallyl) -0,0-dipropylphosphorothioate 8.96 92 34 0.42 O, O-dibutyl-S- (3,3-dichloroallyl) phosphorothioate 8.96 22nd 35 0.42 O, O-dibutyl-S- [alpha- (nitromethyl) benzyl] phosphoronithioate 8.96 32 36 0.42 O, O-bis (2,4-dichlorophenyl) -S- [alpha- (nitromethyl) benzyl] phosphorothioate 8.96 18 37 0.42 0,0-ditrideeyl-S-hydrogenphosphorothioate (branched C,.,) 8.96 23 33 0.42 0,0-bia (p-dodecylphenyl) -S-hydrogenphosphorothioate (branched C _{) 2} ) 8.96 23 39 0.42 mixed O, O-bis (2,4-dichlorophenyl) -5-hydrogenphosphorothioeth anhydride 8.96 and p-nitrothiolbenzoic acid 23 40 0.42 S- [alpha- (nitromethyl) benzyl] O, O-diphenylphosphorothioethate 8.96 18 41 0.42 O-methyl-S-hydrogenphenylphosphonodithioate 4.48 35 42 0.28 O-phenyl-N-isopropyl-p-methoxyphosphono- amidothioate 4.48 40 43 0.28 O- (p-chlorophenyl) -N-isopropyl-p-methylphosphonoamidothioate 4.48 20 May 44 0.28 S-Benzyl-O-ethylmethylphosphonodithioate 8.96 65 45 0.28 O- (m-isopropylphenyl) -N-methylmethylphosphonoamidothioate 4.48 45 46 0.28 Ο, Ο-Diethyl-O-m-tolylphosphorothioate 8.96 80 47 0.28 O- (3,3-dihlorallyl) -O-ethylmethylphosphonothioate 8.96 50 48 0.28 O-ethyl-O- (2,3,3-trichlorallyl) methylphosphonothioeth 8.96 35 49 6.28 O- (2,3,3 * trichlorallyl) -S-hydrogenmethylphosphonodithioate 1.12 50 50 0.28 O-butyl-O- (3-trifluoromethylphenyl) methylphosphonothioate 8.96 80 3 « 0.28 O- (4-cyano-3-trifluoromethylphenyl) -O-propylmethylphosphonothioeth 8.96 30 52 o, as S- (H-methylcarhamoylmethyl) -O-ethylphenylphosphonodithioate 8.96 23 53 0.28 S. S-diallylmethylphosphonotrithloate 4.48 30 54 0.28 O- (2,6-dibromophenyl-5-O-ethylmethylphosphonothioate). 8.96 45 55 0.28 O- (2-chloroethyl) -O- (4-cyanophenyl) isopropylfoaphonothioate 8.96 45 56 0.56 O- (4-chloro-m-tolyl) -O-ethylmethylphosphonothioate 4.48 45 57 0.56 O- (o-chlorophenyl) -O-ethylmethylphosphonothioate 8.96 95 58 0.56 O-ethyl-H, K-diethyl-β-methylphosphonoamidothioate 8.96 30 59 0.28 O-ethyl-S-2-propynylmethylphosphonodithioate 8.96 20 May

example C. amount triallate antibody amount antibodies (kg / ha) percent protective effect 60 0.28 S- (p-chlorophenylthiomethyl) -O-isopropyl- raethylphosphonodithioate 8.96 55 61 0.28 O- (2-allyl-6-chlorophenyl) -O-ethylmethyl- phosphonothioate 8.96 70 62 0.28 O- (4,6-Chloro-m-tolyl) -O-ethylmethyl- phosphonothioate 8.96 45 63 0.14 O-ethyl-O- (ρ-tolyl) methylphosphonothioate 8.96 -43 0.28 8.96 80 64 0.28 methylphenylphosphinodithioic acid 4.48 35 65 0.28 O-Phenyldimethylphosphinothioate 8.96 40 0.14 8.96 55 66 1.12 O- (2,6-xylyl) diethylphosphinothioate 8.96 23 0.56 8.96 65 0.28 8.96 70 0.14 8.96 50 67 0.28 S- (2,4-xylyl) dimethylphosphinodithioate 8.96 30 68 0.28 O- (2-isopropyl-6-methyl-4-pyrimidinyl) dimethylphosphinothioate 8.96 15 Dec 69 0.28 O- (2,3,3-tri chlorosllyl Mimethylphosphinothioate) 8.96 30 70 0.28 O- (2 _with 4-dichloro-1-naphthyl) dimethylphosphino thioate 8.96 40 71 0.28 S- (2-chloroallyl) -0.0-diethylphosphorothioate 8.96 50 72 0.28 S- (4-chlorophenyl) -S-phenylmethylphosphono- trithioate 8.96 15 Dec 73 0.56 S-hydrogen-O, O-diethylphosphorothioate 8.96 25 74 0.28 Ο, Ο, Ο-triethylphosphorothioate 8.96 25 75 0.28 O, Ο-dibutyl-O- (p-nitrephenyl) phosphorothioate 8.96 15 Dec

Further examples of the use of representative organophosphorus compounds as antibodies to thiolcarbamate herbicides are given in Tables 2 and 3.

The tables show the effect of various organophosphorus compounds as triallet antibodies in grass crops - barley, rice, slave and / or wheat. In these tests, the herbicide / antibody mixture is applied by inclusion in soil.

The plot, A inhibition (%) in Table 2 above plants, refers to the change in inhibition (in percent) of plant growth by treating the plant with a preservative containing the herbicide and antibody relative to inhibition (in percent) of plant growth caused by itself herbicide.

Said change in inhibition (in percent) is expressed in plus (+) and minus (-) values respectively, which is an increase or decrease in inhibition (in percent), respectively, due to the presence of antibody.

Table 2

Hibinhibice ())

herbicide kg / ha antibody dose kg / ha plant barley rice sorghum wheat triallate 0.28 ϋ, Ο-Diethyl-Q-phenyl 'phosphorothioate 4.48 0 +15 -55 -55 triallate 0.28 O- (2,6-xylyl) dimethylphosphinothioate 8.96 0 +10 '-55 -65

% Herbicide kg / ha antibody dose δ inhibition (% plant)

js & aen rice sorghum wheat tríallát 0.28 O-m-tolyldimethyl- řosřinothioát 8.96 § -55 -40 -10 triallate 0.28 O-methyl-S-hydrogenphenylphosphonodithioate 4.43 +15 -35 triallate o,.? e S-benzyl-O-ethylmethylphosphonodithioate 8.96 +10 -55 -65 -65

NWhich effects <which arise from differences in the concentration of the trlelllate herbicide at a constant antibody concentration, are shown for representative organophosphorus antibodies in Table 3 <

The herbicide composition of the antibody is applied by inclusion in the soil. Note that it is interesting to observe from the data of these tests that the majority of antibodies have a herbicidal effect of triallate in barley with increasing concentrations of triallate, while in sorghum and Wheat was observed with certain exceptions the opposite effect.

Table 3 antibody dose (kg / ha)

O-Phenyldimethylorefincthioate 8.96

O- (2,6-aryl) dimethylfoafinothioate 8.96

O-methyl-S-hydrogenphenylphosphonodithioate 4.48

O-phenyl-1-isopropyl-β-methylphosphonoamidothioeth 4,48

S-benzyl-O-ethylmethylphosphonodithioate 9.96

O, O-diethyl-S- (methyl-2,6-xylylkerbemoylmethyl) phaferdithioate 8.96

Hibinhibiee (%)

triallate (kg / ha) plant barley sorghum wheat 1.12 0 δ 0 0.56 +5 -3 0 0.28 +10 -8 -40 0.14 +10 -65 -55 1.12 +15 -38 -23 0.56 -5 -63 -65 0.28 -10 -68 -70 0.14 +10 -65 -50 1.12 -10 0 0 0.56 0 0 0 0.28 0 0 -50 0.14 +25 -65 -45 1.12 -30 -53 -3 0.56 +15 -88 -50 0.28 +10 -38 -60 0.14 +20 -90 -65 1.12 -25 -63 0.56 +10 -73 -85 0.28 +20 -73 -90 0.14 +10 -70 -65 1.12 -49 0 0 0.56 ~ 5 0 -5 0.28 0 -8 -20 0.14 +10 -70 -55

In a preferred embodiment of the invention, the antibody is applied to the seeds of the crop to reduce, mature or even eliminate crop damage by herbicides.

In order to prevent this herbicide damage, crop seeds need only be treated with a small amount of antibody. For example, about 1,100 g to about 1.5 g of antibody can be used per 36 liters of seed. A preferred application rate is in the range of about 1.5 g to about 550 g of agent per 36 liters. The seeds are treated with the antibody by conventional seed processing machines well known to those skilled in the art. The seeds are mixed with the antibody in a seed processing machine to produce seeds that are coated with the agent.

Since only a very small amount of antibody is required for seed processing, the compound can be formulated as a wettable powder or as an emulsifiable concentrate, which is diluted for use in a seed processing machine with water.

Alternatively, the antibody can be dissolved or suspended in an organic solvent and thus used in seed processing. Alternatively, the pure compound may be used alone and under appropriately controlled conditions.

Accordingly, novel compositions useful in seed processing are provided according to the present invention which comprise one or more of the disclosed active antibodies in an inert carrier or diluent. These carriers are either solids such as talc, clay, diatomaceous earth, sawdust, calcium carbonate and the like, or liquids such as water, kerosene, acetone, benzene, toluene, xylene, chlorinated hydrocarbons and the like in which the antibody can dissolve or disperse.

If two immiscible liquids are used as the carrier, it is wise to use emulsifying agents to produce a suitable emulsion.

If a liquid is used as the carrier in which the active antagonist is not completely soluble, a wetting agent may be used for dispersion. Emulsifying and wetting agents, also known as surfactants, are sold under numerous trade names and can be either pure compounds or mixtures of compounds of the same kind, or they can be mixtures of completely different compounds.

Typical satisfactory surfactants which may be used are higher alkali metal alkylarylsulfonates such as sodium dodeeylbenzenesulfonate, sodium alkylnaphthalenesulfonic acid sodium salts, fatty alcohol sulfates such as sodium monoesters of sulfuric acid β aliphatic alcohols having 8 to 18 carbon atoms, quaternary long chain compounds, sodium salts of naphthyl-derived alkylsulfonic acids, polyethylene sorbitan monooleate, alkylaryl polyether alcohols, water-soluble lignin sulfonate salts, alkaline casein compositions, long chain alcohols having usually 10 to 18 carbon atoms, and ethylene oxide fatty acid condensation products, alkylphenols and mercury .

Example 76

This example illustrates the protective effect of various organophosphorus compounds in wheat when thiolcarbamate herbicides are used as antibodies that are applied by seed processing at various concentrations.

The procedure used for testing in this case is as follows:

Toluene solutions or antibody suspensions are applied to wheat seeds to obtain the desired concentration. Unprocessed seeds, such as deaf oats (WO), pubescens (DB), foxtail (BG) and rind (ET), together with processed and unprocessed wheat seeds, are grown in a container filled with sedimentary sandy loam soil.

A soil cover layer is placed on the planted soil of the containers. In an assay in which a thiolcarbamate herbicide, e.g., a triallate, is used, the herbicide is applied with a belt sprayer to the cryogenic soil layer and included in the soil. The treated soil layers are then placed on pre-planted containers. The containers are transferred to a greenhouse and irrigated from below as needed.

The results obtained after 4 weeks from the start of the test are shown in Table 4. Tacitly (-) in the table indicates that the species has not been tested.

Table 4 the antibody of Example no. % inhibition of wheat antibody concentration in g / kg seed % inhibition of grass weeds herbicide amount herbicide DB FT BG VO 0 0,031 0.125 0.5 triallate 0 46 0 10 10 15 Dec 0 0 0 0,035 0 00 00 15 Dec 60 - 20 May 90 0.07 10 0 10 15 Dec 100 ALIGN! - 80 95 0.14 45 0 0 10 100 ALIGN! - 90 , 00 0.28 65 0 0 10 100 ALIGN! - 98 95 0.56 98 70 0 10 100 ALIGN! - 98 , 00 1.12 98 80 15 Dec 15 Dec 100 ALIGN! - 100 ALIGN! 100 ALIGN! 2.24 98 98 60 25 100 ALIGN! - , 00 100 ALIGN! triallate 0 3 0 0 10 15 Dec 0 - 0 0 0,035 0 0 10 40 40 - 25 45 0.07 40 0 0 30 , 00 - 45 98 0.14 50 0 0 15 Dec 100 ALIGN! - 70 98 0.28 80 0 0 15 Dec , 00 - 98 100 ALIGN! 0.56 95 10 10 15 Dec 100 ALIGN! - 100 ALIGN! 100 ALIGN! 1.12 98 30 15 Dec 40 100 ALIGN! - , 00 100 ALIGN! 2.24 100 ALIGN! 25 0 35 100 ALIGN! - 100 ALIGN! 100 ALIGN! triallate 0 , 0 0 0 20 May 0 0 - 0 0 0,035 0 0 10 20 May 20 May - 10 90 0.07 0 0 0 20 May 80 - 75 98 0.14 20 May 0 , 0 15 Dec 98 - 80 95 0.28 80 10 10 30 100 ALIGN! - 98 95 80 25 25 30 , 00 - 98 100 ALIGN! 1.12 95 80 70 40 100 ALIGN! - 100 ALIGN! , 00 2.24 100 ALIGN! 90 85 70 100 ALIGN! - , 00 100 ALIGN! triallate 0 48 0 0 0 15 Dec 0 j 0 0 * »T * 0 0 0 25 40 - 40 75 C, 07 25 0 0 45 80 - 80 98 0.14 45 15 Dec 0 25 95 - 90 100 ALIGN! _? <55 60 30 0 25 98 - 98 95 0 5 $ 6 90 30 25 45 , 00 - 100 ALIGN! , 00 1,1; · 98 50 60 35 100 ALIGN! - 98 100 ALIGN! 2.24 100 ALIGN! 90 90 40 100 ALIGN! - 100 ALIGN! 100 ALIGN! triallate 0 50 0 10 , 0 30 0 - 0 0 0,035 0 0 0 60 20 May - 30 50 0.07 10 0 0 45 75 - 75 98 0.14 30 10 0 10 98 70 95 0.28 75 10 20 May 10 100 ALIGN! - 98 98 0.56 95 50 20 May 30 100 ALIGN! - 98 90 1.12 98 80 75 45 100 ALIGN! - 100 ALIGN! 98 z, z 4 100 ALIGN! 90 80 65 100 ALIGN! • 100 100 ALIGN!

herbicide amount herbicide the antibody of Example no. % inhibition of wheat antibody concentration in g / kg seed % inhibition of grass weeds DB FT BG Sat 0 0,031 0.125 0.5 triallate 0. 54 00 0 0 10 0 0 - 0 0,035 0 0 0 15 Dec 60 0 - 85 0.07 0 0 0 15 Dec 80 30 - 95 0.14 35 0 0 15 Dec 95 20 May - 1O0 0.28 60 0 0 20 May 100 ALIGN! 40 - 100 ALIGN! 0.56 50 45 10 30 100 ALIGN! 60 - 100 ALIGN! 1.12 §8 75 25 20 May 100 ALIGN! 80 - 160 2.24 100 ALIGN! 80 70 55 100 ALIGN! 85 - 100 ALIGN! triallate 0 56 0 0 5 45 0 0 - 0 0.35 0 15 Dec 35 60 60 0 - 65 0.07 0 0 5 20 May 80 0 - 90 0.14 15 Dec 0 30 60 98 15 Dec - 100 ALIGN! 0.28 60 15 Dec 25 50 100 ALIGN! 25 - 100 ALIGN! 0.56 85 20 May 15 Dec 55 100 ALIGN! 35 - 100 ALIGN! 1.12 98 60 25 40 100 ALIGN! 50 - 100 ALIGN! 2.24 100 ALIGN! 80 50 55 100 ALIGN! 70 - 100 ALIGN! triallate 0 57 0 0 0 55 0 0 - 0 0,035 0 0 0 50 80 0 - 95 0.07 0 0 0 65 95 0 - 100 ALIGN! 0.14 0 15 Dec 0 65 100 ALIGN! 10 - 100 ALIGN! 0.28 60 0 0 60 10Θ 25 - 100 ALIGN! 0.56 70 20 May 15 Dec 70 100 ALIGN! 35 - 160 1.12 90 30 30 75 106 45 100 ALIGN! 2.24 95 55 40 60 106 70 - 100 ALIGN! triallate 0 63 0 0 25 30 0 E - 0 0,035 0 0 25 30 70 O - 75 0.07 0 0 25 55 90 0 - 95 0.14 23 0 20 May 60 98 20 May - 100 ALIGN! 0.28 65 16 15 Dec 35 100 ALIGN! 35 - 100 ALIGN! 0.56 80 35 15 Dec 90 100 ALIGN! 40 - 100 ALIGN! 1.12 95 50 10 30 100 ALIGN! 55 ' 100 ALIGN! 2.24 100 ALIGN! 75 43 55 100 ALIGN! 70 - 100 ALIGN!

Seeing skilled js-jTOs AE applications besides protecting Síníbla containing herbicide and antidote and the ee _with Ranma Reads the soil may be used with any alternative conventional způaob application * ?,

For example, the herbicide with the antibody is applied to the ecuSeaoS, for example, as a mixture in a pot, or gradually to the surface of the soil in which the seeds are grown, before the seeds are germinated. Alternatively, the herbicide and antibody can only be applied after seed germination. These alternative methods are conventional methods of crop protection.

The organophosphorus compounds referred to herein as antibodies, as mentioned above, are generally known and / or readily obtainable by conventional procedures, as is apparent to those skilled in the art.

For example, typical processes for the production of phosphates, phosphite (phosphorothioates (thionophosphates) or dithioates, phosphonates, phosphonothioates and dithioates, phosphinates and their sulfur analogues and various phosphorus compounds such as aipids, amines, etc. are produced as described by GM Kosolaporf: Organophosphorus Compounds, John Wiley &amp; Sons, Inc., New York, 1950, and further as described in En-? Cyclopedia of Chemical Technology, red. R. E. Kirk and D. F. Othmer, vol. 10, 594 (1953),

The Interseience of Eneyclopedia, Xnc., New York.

The above example illustrates that the organophosphorus derivatives of the invention are useful in reducing herbicidal damage to crops such as sorghum, rice and wheat. The preservatives may be applied to the plants as a mixture, i.e., a sier of a herbicidally effective amount of a thiolcarbamate herbicide and an effective preservative, or sequentially, i.e., the plants may be treated with an effective amount of herbicide followed by treatment with the preservative or vice versa.

The ratio of herbicide to preservative may vary depending on the crop to be protected, the weed to be eradicated and the herbicide used, and so on, but normally the ratio of herbicide to preservative is between 1:25 and 25: 1 (preferably 1: 5 to 5: 1) parts by weight.

The herbicide, preservative or mixture thereof may be applied to the plants alone or the herbicide, preservative or mixture thereof may be applied in conjunction with materials referred to by the skilled person as adjuvants and which may be in liquid or solid form.

Compositions containing the respective herbicide and preservative are always prepared by mixing the herbicide and the preservative with an adjuvant including diluents, fillers, carriers and conditioning agents to form the mixture as finely divided powders, granules, pellets, wetting dusts, dusts, solutions and aqueous. dispersions or emulsions. Thus, the composition may include an adjuvant, which may be a finely divided solid, a liquid solvent of organic origin, water, a wetting agent, a dispersing or emulsifying agent, or any suitable combination thereof.

When the herbicide, preservative or mixture thereof is applied to plants, finely pulverized solid carriers and fillers are, for example, talc, clays, silica, diatomaceous earth, quartz sand, fuller's earth, sulfur, ground cork, wood meal, nut shell meal, chalk, tobacco dust, coal and similar substances.

Typical liquid diluents include, for example, petroleum distillates, acetone, alcohols, glycols, ethyl acetate, benzene, and the like. Such compositions, in particular in the form of liquids and wettable dusts, usually contain as the conditioning agent one or more surfactants in an amount necessary to allow easy dispersion of the composition in water or oil.

The term surfactant as used herein refers to wetting, dispersing, suspending and emulsifying agents. Such surfactants are well known to those skilled in the art and detailed examples thereof are disclosed in U.S. Patent No. 2,547,724, columns 3 and 4.

The composition of the invention generally comprises 5 to 95 parts by weight of the herbicide and the preservative, 1 to 50 parts by weight of the surfactant and 4 to 94 parts by weight of the solvent, all parts by weight based on the total weight of the composition.

The application of the herbicide, preservative or mixture thereof in liquid or powdered solid form can be accomplished by conventional techniques, for example, using spreaders, dusters, hand and frame sprayers, sprayers and grain applications.

The compositions may also be applied in the form of dusts or sprays from aircraft. Application of the composition of the invention may optionally be achieved by incorporating the composition into soil or other environment.

The above examples also illustrate that crops can be protected by treating crop seeds before sowing with an effective amount of a preservative. Generally, a small amount of preservative is required to remove such seeds.

Even as low a weight ratio as 0.031 parts by weight of preservative to 1000 parts by weight of seeds is effective. The amount of preservative used in seed treatment may be increased if desired. In general, however, the weight ratio of preservative to seed may range from 0.1 to 1.0-0.0% by weight of preservative per 1000 parts by weight of seed. Determination of the required effective amount of a preservative is well known to those skilled in the art. ‘'

Only a very small amount of an effective preservative is required for seed treatment, and therefore the compound is preferably formulated as a powder or emulsifiable concentrate which can be diluted with water by a seed processor for use in a seed treatment device.

Under certain conditions, it may be appropriate to dissolve the preservative in an organic solvent for use as seed treatment, or the pure compound itself may be used under suitably controlled conditions.

Thus, according to the invention, the novel seed treatment composition comprises one or more of the disclosed effective preservatives, intimately dispersed in an inert carrier or solvent for the intended use. Such carriers may be either solids such as talc, clay, diatomaceous earth, piliyum, calcium carbonate and the like, or liquids such as science, kerosene, acetone, benzene, toluene, xylene and the like in which it may be the active agent either dissolved or dispersed.

Suitably, the emulsifying agents are used to achieve a suitable emulsion when two immiscible liquids are used as the carrier. Wetting agents may also be used to promote dispersion of the effective preservative agent in liquids used as the carrier in which the preservative is not completely soluble.

Emulsifying and wetting agents are sold under numerous trade names and can be either pure compounds, mixtures of compounds of the same kind, or mixtures of completely different compounds. Typical satisfactory surfactants which may be used are the higher alkali metal alkylarylsulfonates, such as sodium dodecylbenzenesulfonate and sodium salts of alkylnaphthalenesulfonic acids, fatty alcohol sulfates, such as sodium salts of monoesters of sulfuric acid with C8-C10 aliphatic alcohols, long-chain quaternary ammonium compounds, sodium salts of naphtha-derived alkylsulfonic acids, polyethylene sorbitan monooleate, alkylaryl polyalcohol alcohols, water soluble lignin sulfonate salts, alkaline casein compositions, long chain alcohols containing usually 10 to 18 carbon atoms and ethylene oxide fatty acid condensation products, alkylphenols and mercaptans.

Although the invention is described with respect to certain arrangements, it is to be understood that it is not limited thereto and that various variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims (7)

OBJECT OF THE INVENTION i A herbicidal mixture comprising a protective thiolcarbamate herbicide, comprising 5 to 95% by weight of a thiolcarbamate herbicide, 5 to 95% by weight of a protecting compound of the general formula X, (I) R- / X / _b -P- / Z, _c -ir / »/" in which a, b, c are integers zero or one, but inhale at the same time cannot mean zero, W, X and Z are each independently O or S, 12 'i - ¹ J 1, R 2 and R 3 are each independently hydrogen, C 1 -C 13 alkyl, 1-methyl-2-nitroethyl, allyl, haloallyl, proplynyl, chloromethylcarbonyl, (3-chloro-2-butenylsulfonyl) methyl, dichlorallylthlomethyl , halophenylthio, p-aminosulfonyl, p-nitrobenzyl, chlorophenyl, thiomethyl, phenyl, benzyl, naphthyl, naphthyl substituted with one or two methyl or halogen, alpha-nitromethylbenzyl, alpha-methylbenzyl, phenyl one to three C 1 -C 12 alkyl, allyl, halogen and -NO ₂ , -CM, -CF, or -SCH ₃ radicals; provided that when a is zero, c is one and Z is sulfur, then R ² can not represent. a hydrogen atom or a halophenyl group, fsnylově group may simultaneously be substituted, and -CF ^ -NOg if X and W are oxygen and Z is sulfur then R, R ¹ and R ² can not simultaneously represent a methyl group and "p if W, X and Z are oxygen, then R, R and R cannot simultaneously represent a phenyl group, and 1-94% by weight of the agricultural adjuvant and / or solvent, wherein said mixture is a 1: 5 to thiolcarbamate herbicide to protecting compound ratio 5: 1 parts by weight. 2. The herbicidal mixture of claim 1, wherein the thiolcarbamate herbicide is a triallase. 3. The herbicidal mixture of claim 1, wherein in formula I, a, b are one and c is zero. <1. The herbicidal mixture of claim 1, wherein in formula I, ft, e is one and b is zero. 5. The herbicidal mixture of claim 1, wherein in formula (I), c, b are the number one a and the number zero. F 6. The herbicidal mixture of claim 1, wherein in formula (I), R &lt; 1 &gt; and R ^{2 is} C 1 -C 13 alkyl, allyl, halogenallyl, propynyl, phenyl, benzyl, naphthyl, alpha-nitromethylbenzyl, alpha-methylbenzyl or phenyl substituted with one to three C 1 -C 12 alkyl, allyl, a halogen atom, the radicals -NOg, -CN and -CF4 and the methylthio radical. 7. The herbicidal mixture of claim 1, wherein the compound of formula I is O, O-diethyl O- (4-sulfamylphenyl) xO-phosphorothioate, O, O-dimethyl O- [4- (methylthio) -m-. tolyl] phosphorothioeth, S- (2-bromoalkyl) -0,0-diethylphosphorothioate, O, O-diethyl-O '(p-trifluoromethylphenylphosphorothioate, S- (3,3-dichloroalkyl) -0,0-diisopropylphosphorothioeth, O, O -diethyl-O- (N-tolyl) phosphorothioate, O, O-diethyl-O- (m-tolyl) phosphorothioate, O- (o-chlorophenyl) -O-ethylmethylphosphonothioate or O-ethyl-O- (p (tolyl) methylphosphonothioate. 8. The herbicidal mixture of claim 1, wherein the compound of formula I is O, O-diethyl-O- (.alpha.-tolyl) phosphorothioate.