DE2634278A1 - WEED REPRODUCTORS CONTAINING DIBROME-SUBSTITUTED PROPIONAMIDES AS ANTIDOTS - Google Patents

Description

PATENT LAWYERS

DR. WALTER KRAUS DIPLOMA CHEMIST. DR.-ING. ANNEKÄTE WEl SERT DIPL.-ING. SPECIALIZATION CHEMISTRY IRMGARDSTRASSE 15 D-8OOO MÜNCHEN 71 -TELEPHONE 089 / 797077-797078 TELEX O5-212156 kpatd

TELEGRAM CRAUS PATENT

PR-3880A V 1278 AW / MY

STAUFFER CHEMICAL COMPANY, Westport, Conn. / UNITED STATES

Weedkillers, the dibromo-substituted propionamides included as antidotes

The invention relates to weedkillers that contain dibromo-substituted propionamides as active antidotes for herbicides for small-grain, beneficial plants,

The herbicides according to the invention contain the active thiocarbamates and a compound of formula

BrCH ₂ BrCH - C - ^

wherein

'R ₁ denotes hydrogen, alkenyl or lower-alkyl and

R _{2 is} alkyl, alkenyl, alkynyl, dimethoxyethyl or 1-ethynylcyclohexyl, in an amount sufficient for the compounds to be effective as antidotes.

Many herbicides are directly toxic to a large number of different types of weeds. However, it is known

that the effect of many herbicides on important plant varieties is either not selective or not sufficiently selective is. Many herbicides not only damage the weeds to be controlled, but also, to a large extent or to a lesser extent, the desired crops. This is true of many herbicidal compounds that are widely used and are technically available. These herbicides are e.g. triazines, urea derivatives, halogenated acetanilides, Carbamates, thiocarbamates and similar compounds. Some examples of these compounds are given in U.S. Patents

2 913 327, 3 037 853, 3 175 897, 3 185 720, 3 198 786 and

3,582,314.

The side effect that a cultivated useful plant or harvesting plant is damaged by various herbicides is very unpleasant and undesirable. Used to control broad-leaved weeds and soil Grasses treated with the recommended amount of herbicide can sometimes cause serious malformations or Growth inhibitions occur in the useful plants. Abnormal growth in the crops results in loss in harvest yield. There is therefore a great need for good, elective herbicides.

Many attempts have been made to overcome these difficulties. The treatment of useful ^{plant seeds with certain M} hormonal "antagonistic agents before planting is described, for example, in US Patents 3,131,509 and 3,564,768. These protective agents, as well as the herbicides, in the known processes are specific for certain cultivated plant species. The antagonistic agents have not been very successful until now Other examples of known methods are described in BE-PS 782 120 and in South African patent specification 72: 6259. In the patents previously described, the treatment of seeds is described

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«= 3 -

and the use of other herbicides and crops. Different types of chemical compounds are described

The present invention is based on the object to be created ^ herbicides s ₈ have no adverse effect on the crops ₀ In addition to a Verfan '= ren to protect crops from certain herbicides are created.

The present invention thus relates to active thiocarbamate herbicides and compounds of the class of 2,3-dibromo-substituted propionamides as antidotes. for these thiocarbamate herbicides to protect crops with small grains, such as wheat, barley ^ rice ₅ oats ^ rye and triticale, from damage. (Triticale is a hybrid = cross between rye and wheat) _o

It was found that certain ^ cultured Nutzpflan = zen with small grains, such as wheat barley ^ ,, rice _{9 9} oats rye and triticale, from damage by = ein'aktives thiocarbamate Herbieid either alone or mixed together or mixed with other herbicidal compounds , can be protected. Furthermore, the tolerance of certain specific plants to these herbicides is significantly increased if the seeds are treated before planting, the furrows are treated before or after sowing or setting the seeds or seeds and / or in the soil. either alone or with another herbicide there is an antidote compound of the following formula

0 R ₁

BrCH ₂ BrCH - δ - N \

R ₂

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R ₁ denotes hydrogen, alkenyl or lower-alkyl and

1 * 2 alkyl, alkenyl, alkynyl, dimethoxyethyl or 1-ethynylcyclohexyl means

In the present description and in the claims, the various substituent groups are intended to mean: R ,. and Rp alkenyl, preferably those alkenyl groups the 3 or 4 carbon atoms and at least one olefinic Contain double bond; lower alkyl, preferably those alkyl groups containing 1 to 4 carbon atoms inclusive straight and branched chain alkyl groups; Alkyl, preferably those alkyl groups which have 1 to 6 carbon atoms including straight and branched chain alkyl groups; Alkynyl, preferably such alkynyl groups with a triple or acetylenic bond and with 3 to 8 carbon atoms.

The compounds according to the invention act with the normal herbicidal action of the herbicides of the thiocarbamate type and other herbicides together and cause these are selective in their effect. Surprisingly, the herbicidal action of the thiocarbamates is not affected; at the same time, however, the herbicidal effect on the desired useful plant species is reduced. The useful plant species, for the herbicidal antidotes and the thiocarbamate herbicides are particularly effective and useful referred to as small-grain crops. Collectively, the term includes various types of cereal grass. Examples for crops with small grains are barley, wheat, rice, oats, rye and triticale.

The expression "herbicidal antidote" or "antidote-effective amount" is intended to describe the effect which consists in that the normal, harmful herbicidal response that the

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Herbicid would otherwise cause, is counteracted »Whether The antidote is referred to as a cure, antidote, or protective agent or similar, depends on the exact type of the Effect from. The type of action or application is varied. However, the desired effect is the result of the treatment of the soil in which the crop is planted or «is sown * Up to now no systems» are known fulfill this purpose «,

The compounds of the present invention represented by the above formula can be prepared by various methods depending on the raw materials. In a general process for the preparation of 2,3-dibromopropionamide compounds according to the invention, 2,3-dibromopropionyl chloride and the suitable amine are reacted in the presence of a suitable solvent. Suitable solvents are toluene, methylene chloride and Freon-113, methylene fluoride and others a solvent facilitates the progress of the reaction and the stirring of the reaction mixture, since this creates a suitable volume. The reagents will continue to solubilize. After addition of the acid chloride and the amine, the solution is cooled to a temperature between about "■ 20 and O ⁰ C. After completion of the addition of the reagents, the reaction mixture to a temperature between about room temperature and about 50 to 6O ⁰ C to complete The use of excess amine allows the amine to act as an acid acceptor, ie as a catalyst, during the reaction When the reaction is terminated, the desired compound is obtained by customary work-up processes, such as crystallization, sublimation or distillation.

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The following examples illustrate the invention. The connections have been numbered, and these will be used for identification in the present application.

example 1

Preparation of N, N-diallyl-2,3-dibromopropionamide

3.0 g of diallylamine are mixed with 3.5 g of triethylamine in 25 ml of methylene chloride. 7.5 g of 2,3-dibromopropionyl chloride in a mixture of Freon-113 and methylene chloride are added dropwise with stirring in a water bath. The mixture is washed with water, dried and stripped in vacuo. The yield is 6.6 g of the title compound; this is an oil; n ^ 1.5308.

Example 2

Preparation of N-methyl-N-3-butynyl-2,3-dibromopropionamide

5.1 g of 3-methylamino-1-butyne are dissolved in 25 ml of methylene chloride. 7.5 g of 2,3-dibromopropionyl dissolved in a Mixture of Freon-113 and methylene chloride, are added dropwise added with stirring in a water bath. The mixture is washed with water, dried and stripped in vacuo. The. Yield is 7.5 g of the title compound; this is an oil, n ^ ° 1.5548.

Example 5

Preparation of N-tert-amyl-2,3-dibromopropionamide

A solution of 21.6 g (0.248 mol) of tert-amylamine in 80 ml of toluene at -10 to -15 ° C. is added to a solution of 30 g (0.12 mol) of 2,3-dibromopropionyl chloride in 160 ml of toluene . The mixture is stirred at room temperature for 1 hour and at 40 to 45 ^° C. for 1 hour. . It is filtered and the bodice becomes

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washed well with water. The insoluble part is dried; 11.6 g (32 %) of product are obtained, mp ₀ 174 Ms 175 ^° C. The structure is determined by IR-. ₉ NMR »and mass spectroscopy determined. - ■ -. ■■; "

Example 4

Preparation of N- (1-ethynylcyclohexyl) ~ 2 _P 3 ~ dibromopropionamide

To a solution of 6 ₉ 49 g (O ₉₀₅₂ mole) of I-Äthinyleyelohexylamin in 60 ml of toluene there was added a solution of _6} 3 g (0.025 mol) of acid chloride in 20 ml of toluene at ° -5 to 0 ⁰ C. The mixture is Stirred for 3 hours at room temperature and filtered »The filter cake is washed with water and the insoluble part is dried _? Mp ₈ 135 to 137 ⁰ C ₀ The yield is 3.3 g (39%) «The structure is confirmed by IR»

The compound listed in the table below genes are prepared according to the procedures and examples described above. The compound numbers are for the identifier used in the present application

Connect 1 H manure no, H 1 H 2 H 3 ethyl 4th H 5 Allyl 6th H 7th H 8th H 9 methyl 10 H 11 H 12th 13th

Table I.

BrCH ₂ BrCH - C »

Mp. C or E °

tert-butyl
2-methyl-2-butyl 1-ethynylcyclohexyl 4-methyl-2-pentyl isopropyl
3-methyl-2 = p entyl allyl

2,2-dimethoxyethyl Allyl

3-methyl-3- = butynyl 3-methyl-3-butynyl *> -C = C-CH ₃

(C (CH

179 to 180 174 to 175 134 to 137 103 to 106 (yellow oil) 100 to 103 1.5308
73 to 74 99 to 101 118 to 119 1.5548
111 to 112 103 to 107

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The herbicides given in the table and the others Herbicides are used at such rates that the unwanted vegetation is effectively controlled. The range of amounts used is exemplary Results within the supplier's recommended quantities. In any event, weed control is technically acceptable within the desired or recommended amount.

The class of herbicides described in the present application are effective herbicides that exhibit such activity. The level of herbicidal activity varies with the various compounds and in the case of mixtures of specific mixtures within the classes. The level of activity continues to vary somewhat Extent depends on the plant species treated with the specific herbicidal compound or mixture will. A selection of the specific herbicidal compounds or mixtures can help control undesirable Plant species are made easy. According to the invention, damage to desired useful plant species, in particular of small-grain crops, most preferably rye and wheat, in the presence of more specific herbicidal compound or herbicidal mixtures are prevented.

Active thiocarbamate herbicides of the general class are used as herbicides in the present invention. Thiocarbamatherbicides are herbicidally active compounds that are active against a wide variety of plant species can be used without distinguishing between desirable and undesirable species. The procedure for control the vegetation consists in that one herbicidally effective amount of the herbicidal compound described above applies to the area or plant location where a control is to be carried out. The agents according to the invention include those that have the antidote described above and are preferred

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active herbicidal compound contain a compound from the class of thiocarbamate herbicides! Examples are the • following compounds: S-ethyldipropylthiocarbamate S- = ethyldiisobutylthiocarbamate, S-propyl-di-n-propylthio carbamate, S-ethylcyclohexylethyl-thiocarbamate, S-ethylhexahydro ~ 1H ~ azepioin-1-carbamate, Trichlorallyl-N;, N ~ diisopropyl ~ thiocarbamate, S-isopropyl-1- (S-ethyl-Z-methylpiperidine) ° carbothioate, either alone or as different mixtures and optionally together with other classes of herbicidal compounds, such as .triazines, e.g. 2-chloro-4- ° ethylamino-S-'isopropylamino-s-triazine-2-chloro, 6-bis- (ethylamino) -3-triazine, 2- (4-chloro-β-ethylamine-s-triazine-2- yl- 'amino) -2-methylpropionitrile _s 2-chloro-4-cyclopropylamino-6-isopropylamino-s-triazine.

The term "herbicide" as used in the present application is used means any compound that controls vegetation growth or plant growth or modified. Such controlling or modifying effects are all deviations from natural development, e.g. killing, delaying, defoliation, dehydration or drying out, regulation, a growth inhibition, an influence on the root saplings, a stimulation, a dwarfism, etc. The expression "Plants" includes germinating seeds, emerging seedlings and existing vegetation including the roots and the parts above the earth. '

Investigation procedure

Flat boxes used for growing the useful Plants and the weed species used are filled with loamy sandy soil. There will be different application methods used. Thus (1) the herbicide and the antidote are separated and (2) a tank mix of herbicide and antidote applied together before planting. The application

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training takes place through training. Then the seeds are planted or sown in the ground, which is effective with a herbicidal composition of thiocarbamate and antidote was treated. The application is carried out by in-furrow treatment of the seeds and the surrounding soil, the soil having been previously treated with the herbicide, and by treating the useful plant seeds or the seeds with the antidote to be tested before planting in the with Herbicide treated soil.

Stock solutions of the corresponding thiocarbamate herbicides and the antidote compounds to be tested are as follows manufactured:

Herbicide

(A) S-propyl di-n-propyl thiocarbamate - VERNAM ^ '6E 130 mg are dissolved in 125 ml of distilled water, leaving 5 ml applied to the bottom of a plant box 1.12 kg / ha (1 Ib / A) and in 749 1 (80 gal) water / ha (acre) are applied.

(B) S-propyl di-n-propyl thioearbamate - VERNAM ^ 6E 550 mg of VERNAM 6E are dissolved in 400 ml of distilled water, leaving 4 ml to be applied to the bottom of a plant box , 1.12 kg / ha of active ingredient is equivalent or 5 ml is 1.4 kg / ha (1.25 lb / A) equivalent.

(C) S-ethyl di-n-propyl thiocarbamate - EPTC - EPTAM ^ 6E 130 mg dissolved in '.' 125 ml of distilled water, so that 5 ml, with which the soil of a plant box is treated, are equivalent to 1.12 kg / ha that applied in 749 1 water / ha will.

(D) S-Isopropyl-1- (5-ethyl-2-methylpiperidine) -carbothioate (R-12001) - 78 mg are dissolved in 50 ml of acetone with Λ% Tween 20 ^v ', so that 5 ml of solution that on A plant box can be used, equivalent to 2.25 kg / ha (2 lb / A) of pre-planting treatment.

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(E) S-ethyl-disobutylthiocarbamate -SUTAN ^ 6E or S-ethylcyclohexylethyl-thiocarbamate - ROIEET ^ ^R ? 6E - 54mg or 108 mg are dissolved in 50 ml of distilled water ₈ so that 5 ml, with which the bottom of a plant box " is treated * are equivalent to 1, 12 or 2 ₉ 25 kg / ha, which are applied in 749 1 water / ha _o

(F) 2,3r3-Trichlorallyl-N ₉ N = diisopropylthiocarbamate AVADEX B ¥ ^ ^R He - 509 mg are dissolved in 100 ml of distilled water, so that 5 ml is equivalent to 3 ₉ 37 kg / ha (3 lb / A) when the bottom of a plant box is treated with it before planting.

(G) S-Ethylhexahydro ° 1H = -azepine ° 1- = carbothioate-ORDRA 6E- 303 mg are dissolved in 50 ml of distilled water ^ so that 5 ml is equivalent to 8g98 kg / ha (8 lb / A) and 3p75 ml are equivalent to 6.74 kg / ha (6 lb / A) _ΰ if the soil of a plant _{box is treated with it before planting or similar}

Antidotes /

(H) For each compound to be tested - that is used, 250 mg of active ingredient are dissolved in 2 ₅ 5 ml of acetone _s with V / a Tween 20 / · '(polyoxyethylene sorbitan monolaurate) _p so that 0.5 ml of the solution / 10 g of seeds or _o seeds are equal to 1/2% wt. / wt. For the seed or, seed treatment of 1/4% 0.25 ml 0.25 ml with acetone diluted so that 0.5 ml _s of the solution to 10 g of seed and seed are equal to. 1/4% w / w This solution is used for the seed treatment process.

(I) For each compound to be tested which is used in the "InFurchen method" ₉ , 95 mg of active ingredient are dissolved in 15 ml of acetone with V / o Tween 20 ^ ^R ', so that 1.5 ml with which the Seed and the soil in the furrow treated in half the box are equivalent to 5,62 kg / ha (5 lb / A).

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(J) For each compound to be tested, which is used in the pre-plant treatment trial of a "tank mix", 58 mg of active ingredient is dissolved in 15 ml of acetone with Λ% Tween 20 ^ 'so that 5 ml if the soil of a box is treated with it is equivalent to 5f62 kg / ha. In addition, the following stock solutions are used: 11 mg / 20 ml acetone plus Λ% Tween 20, so that 5 ml are equivalent to 1.12 kg / ha and 2.5 ml are equivalent to 0.56 kg / ha (0, 5 lb / A).

The above stock solutions are used in the in-furrow application of the antidote used. As a preliminary step, a 0.5 liter (1 pint) soil sample is taken from each box and retained and later used to cover the seeds after treatment with the stock solutions. The floor is leveled before planting. The various boxes and pre-plantings that are in the ground from the planted Boxes that have been planted become more active with the herbicidal stock solution at an equivalent rate of 1.12 kg / ha Component or treated in the specified rate or amount.

1/4 inch deep rows are made lengthways in each treated box prior to sowing. After sowing, the boxes are divided into two equal parts using a wooden border. 1 1/2 ml Additive Stock I is sprayed directly onto the exposed seeds and onto the furrows in half of the box. The untreated part of the box serves as a herbicide control and also allows observation of a lateral movement of the antidote through the ground. The seeds are mixed with the 1/2 1 sample of untreated soil was previously removed, covered.

For the tank mixes that are treated with prior to planting:; ... use the following solutions and procedures used. 5 ml of Herbicide Vorroatslösung A or C will be

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mixed with 5 ml each of the antidote stock solution J to be tested in such a way that the soil of each box was treated with the equivalent of 1., 12 kg / ha and 5.62 kg / ha herbicide or antidote and the corresponding amount was incorporated _o For pre-planting treatment or incorporation, the mixed stock solutions are placed in the soil by mixing in a 19 liter (5 gal) rotary mixer. Other stock solutions are used at the rates indicated in the tank mix process

For the seed treatment, 10 g of the seed are mixed in a suitable container with 0.5 ml of antidote stock solution H or other stock solutions, as indicated ^, so that the seed treatment is equivalent to 0.1% w / w, 0.25 % W / w or 0.125% w _e / w "is shaken until the seeds are uniformly covered. The antidote compounds can be used as liquid slurries and powders or as a pollinant »The treated seed is planted in a soil, in which the herbicide stock solution B before planting the soil at a rate equivalent to 1.12. kg / ha (1 lb / A) was incorporated.

All the boxes are placed in greenhouses, where the temperature of 21-32 ° C is maintained (70 to 90 ⁰ F). The soil is watered by sprinkling, so that good plant growth is ensured. The damage assessments are carried out 2 and 4 weeks after application. Individual control boxes treated with the herbicide alone are also scored so that there is a basis on which to assess the reduction in damage caused by the herbicide antidotes. The results of these tests are shown in Table II.

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Application method:

Useful plant species; Weed species!

+ = % Damage ++ = % protection

Table II Antidote Activity

Seed treatment - ST
In-The-Furrow Treatment - IF
Pre-Planting Incorporation - PPI

(Tank mix)

Barley - BA [Hordeum vulgare (L.)] Wheat - WT LTriticum aestivum (L.)]

Paspalum - WG [Echinochloa crusgalli] Green Foxtail - FT [Setaria viridis] Wild Oats - WO [Avena fatua (L.)]

link χι IF FT FT ST ) 5 _f b PPI PPI PPI lb / A) FT BA 50 0.5 ^ B ¹ A (5.5 kg / ha) kg / ha (5th (5, b k FT , 12kg /
ha 80 I2 + 5, e> kg / ha (
+ 5 lb / A) ST BA 95
70 VERNAM Wg ¹ 50
50 + VERNAM ^W 1,
+ EPTAM ^ IF Flat share (0.5SS) 100 Flat share FT 80
70 Connect , 12 + 5.6 80 VERNAM s / ha) duns no. TJ BA EPTAM kg / ha BA WG BA VEKNAM BA Flat share

++ 1 2

3 4th 6th

7th 8th

10 11

70 70 50 42 70

75 72 38 88 63 80
70

0 0 0

0 0 0

58

79

68

90

90

47

47

37.5 0

0

0

O 70

57

86

86

70

57

O 70

O 47

73

60

0 0 0 0 0 0 0 0 0 0

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Table II (continued) barley BA wheat Flat share Flat share FT - Herbicide 95 85 80 50 - + VERNAM ^W 1.12 kg / ha (1 lb / A) 70 70 80 - 70 50 - + EPTAM ^ 1.12 kg / ha 20th 58 20th 0 - - - + 0RDRAM ^ ^R ^ 9.0 kg / ha (8 lb / A)
+ RO-NEET ( ^R ) 2.25 kg / ha (2 lb / A) 80 71 90 0 80 100 - 1.12 kg / ha (1 lb / A) - 57 70 0 - - - + SUTAN ( ^R ) 2.25 kg / ha (2 lb / A) 75 - - - 90 100 - 1.12 kg / ha (1 lb / A) - 67 40 - - - 0 + R-12001 2.25 kg / ha (2 lb / A) 85 - 100 0 95 100 0 + AVADEX BW ^ 3.4 kg / ha (3 lb / A) - £ g / fea4i 80 0 0 100 0 Combination Herbicide Application Rate - 0 0 manure no. (kg / ha) - 0 - avail. 50 0 - ++ 1 VERNAM IF 1.12 + 5.6 80 0 - PPI ditto 70 - 0 EPTAM PPI ditto 80 - - 2 EPTAM PPI ditto 73 0 0 IF ditto - - 0 R-12001 PPI 2.25 + 5.6 - - 0 . IF ditto - - - ST 0.25 ^ + 2.251 - - RO-NEET PPI 2.25 + 5.6 86 56 Protection 0 IF ditto WT ST 0.25 ^ + 2.25 FT V / 0 VERNAM PPI 1.12 + 5.6 - IF ditto - ST 0.2596 + 1.12 - SUTAN ST 0.25% + 5.6 37.5 0.25 ^ + 1.12 62.5 AVADEX BW PPI 3.4 + 5.6 58 IF ditto 71 ST 0.56 + 5.6 22nd 3 EPTAM PPI 1.12 + 5.6 30th IF ditto 33 43 30th 30th - - 75 50 50 37.5 44 50 - 0 0 0 - - 0 - - - - 0 - - mm - - - 0

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- 15 - 2.25 + 5.6 BA - 2 Flat share 634 278 0.25 ^ + 2.25 - - 0 Table II (continued) Application rate 2.25 + 5.6 71 - % Protection 0 Verbin- Herbicide manure (kg / ha)
avail. dito - 71 WT 0 FT Where application no. IF 0.25 # + 2.25 - - 14th 0 0 - 3 R-12001 ST 0.2556 + 1.12 58 - 40 0 - 0 PPI 0.2550 + 2.25 - - 33 - - 0 RO-NEET IF 0.15% + 1.12 47 87 33 0 - 0 ST 1.12 + 5.6 - 71 - - - 0 ST dito 68 60 43 0 - mm ST 0.556 + 1.12 50 - - - 0 SUTAN ST 3.4 + 5.6 70 50 - - - PPI dito - 41 - 40 - VERNAM IF 1.12 + 5.6 - 41 - - - ST dito 86 - 0 "- - PPI 0.25% + 6.8 - 37.5 - - 0 AVADEX BW " IF 2.25 + 5.6 100 50 - mm 0 PPI dito - 37.5 0 0 - 4 EPTAM IF dito - 62.5 0 - - ST 1.12 + 5.6 - 100 0 - - ORDRAM IF dito 89 57 0 0 - R-12001 IF dito 43 22nd - - 0 RO-NEET PPI dito - 22nd - - 0 PPI dito 41 - 0 - VERNAM IF dito 29 - - - PPI dito 31 - - - 5 EPTAM IF dito 50 0 - - PPI 2.25 + 5.6 35 - - - VERNAM IF dito 23.5 0 - - PPI 1.12 + 5.6 37.5 0 0 - EPTAM IF dito 50 0 - - PPI 0.25 ^ + 1.12 22nd - - 0 RO-NEET IF 11 - 0 PPI 29 0 - VERNAM IF 29 - - ST - -

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II (continued) To whom- - 17 - BA 2634278 % Protection V / G FT Where Tabel Herbicide manic
avail. - WI - - 0 Connect PPI rate - 25th - - 0 application no. AVADEX BW IF (kg / ha) 47 37.5 0 0 - '5 PPI 3.4 + 5.6 62, - 0 0 - EPTAM PPI dito 75 5 - - - - 7th VERNAM IF 1.12 + 5.6 71 - 0 0 - PPI dito - 37.5 - - - EPTAM IF dito 100 12.5 - - - 8th ST dito 67 100 - - - ORDRAM PPI dito - 58 0 0 - R-12001 IF 0.25% + 6.8 - 29 0 - 0 PPI 2.25 + 5.6 47 22nd 0 0 - RO-NEET • ppi dito 79 29 - - - VERNAM IF due to 50 24 - - - ST 1.12 + 5.6 - - - - 0 PPI dito - 25th - - 0. AVADEX BW IF 0.14 +1.12 47 25th 0 0 - PPI 3.4 + 5.6 37, - 0 0 - EPTAM PPI dito 37, 5 - - - 9 VERNAM IF 1.12 + 5.6 73 5 - 0 0 - PPI dito 100 - - EPTAM ST dito - 100 O 0 - 10 ORDRAM IF dito 53 57 0 - 0 R-12001 ST 0.25% + 6.8 - 30th 0 - 0 PPI 2.25 + 5.6 - 67 0 0 RO-NEET IF 0.25 ^ + 2.25 50 67 0 - 0 ST 2.25 + 5.6 - - - - - ST dito 73 29 0 - 0 ST dito 88 - O 0 - SUTAN PPI 1.12 + 5.6 88 - - - - VERNAM IF 2.25 + 5.6 - - - - 0 PPI 1.12 + 5.6 37.5 0 AVADEX BW IF dito 50 3.4 + 5.6 dito

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II (continued) To whom- - 18 - Jba WT 2634278 ' FT V / 0 Tabel Herbicide manic Connect avail. rate 60 - % Protection 0 application no. PPI (kg / ha) - 43 Flat share 0 EPTAM IF 75 - 0 11 R-12001 PPI 1.12 + 5.6 62, 5 - 0 ot mm VERNAM IF 2.25 + 5.6 - 57 O 0 IF 1.12 + 5.6 86 - 0 0 R-12001 PPI 1 dito 50 50 - - 12th VERNAM IF 1 2.25 + 5.6 - 43 0 0 IF , 25 +1.12 71 - 0 0 R-12001 PPI 1 , 25 + 5.6 75 78 0 - - 13th VERNAM IF 1 2.25 + 5.6 O , 25 +1.12 O , 25 +5.6 O

The compounds and agents according to the invention are used as effective herbicides containing the antidote and a thiocarbamate herbicide as described. The herbicides are tested in the following ways.

The weedkillers according to the invention for Protection of cultivated crops contain an active herbicidal compound and an antidote for it, that of the above connections described is selected. The herbicide and antidote compositions can be produced by known processes by mixing the active herbicides and antidotes with suitable carriers and / or other distribution media, optionally with the addition of dispersants or solvents, well mixed and ground.

The antidote compounds and the agents or compositions according to the invention can be in any suitable form Form. The antidote compounds and the compositions containing the thiocarbamate herbicide can as emulsifiable liquids, emulsifiable concentrates,

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Liquids, wettable powders, atomizers, granules, or any other suitable form. In a preferred form, a non-phytotoxic amount of the herbicidal antidote compound is added to the selected Herbicide mixed and added to the soil before or after the seeds are planted. However, the herbicide can also can be incorporated into the soil beforehand, and then the antidote compound can be incorporated into the soil. Farther the seed of the useful plant can itself be treated with a non-phyto-toxic amount of the compound and in the soil that has been treated with the herbicide or that has not been treated with an herbicide is planted and is then treated with the herbicide. The addition of the antidote compound affects the herbicide activity of the herbicide.

The amount of antidote compound present can be in the range from about 0.001 to about 30 parts by weight of the antidote compound according to the invention / part by weight of herbicide. The exact amount of the antidote compound will usually be determined by economic considerations for the most effective amount useful. In the novel herbicides a non-phytotoxic _s but effective amount of antidote compound.

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Claims (66)

Claims 1. Weedkillers, characterized in that it is essentially a thiocarbamate herbicide and an antidote for it of the formula BrCH ₂ BrCH - R ₁ R ₂ R ₁ denotes hydrogen, alkenyl or lower-alkyl and R ₂ denotes alkyl, alkenyl, alkynyl, dimethoxyethyl or 1-ethynylcyclohexyl,
in such an amount as to be effective as an antidote. 2. Antidote-containing weedkiller according to claim 1, characterized in that the amount of antidote between about 0.001 and about 30 parts by weight / part by weight thiocarbamate herbicide lies. 3. Weedkiller according to claim 1 or 2, characterized in that R _{1 is} hydrogen and R _{2 is} alkyl. 4. Weedkiller according to at least one of claims 1 to 3, characterized in that R _{2 is} t-butyl. 5. Weedkillers according to at least one of claims 1 to 3, characterized in that R _{2 is} 2-methyl-2-butyl. 6. Weedkiller according to at least one of claims 1 to 3 »characterized in that R _{2 is} 4-methyl-2-pentyl. 709808/1154 7. Weedkiller according to at least one of claims 1 to 3, characterized in that R _{2 is} 3-methyl-2-pentyl. 8. Weedkiller according to at least one of claims 1 or 2, characterized in that R _{1 is} hydrogen and R _{2 is} 1-ethynylcyclohexyl. 9. Weedkiller according to at least one of claims 1 or 2, characterized in that R _{1 is} alkenyl and R _{2 is} alkenyl. 10. Weedkillers according to at least one of claims 1, 2 or 9, characterized in that R _{1 is} allyl and R _{2 is} allyl. 11. Weedkillers according to at least one of claims 1 or 2, characterized in that R _{1 is} hydrogen and R _{2 is} 2,2-dimethoxyethyl. 12. Weedkillers according to at least one of claims 1 or 2, characterized in that R _{1 is} hydrogen and R _{2 is} alkenyl. 13. Weedkiller according to at least one of claims 1, 2 or 12, characterized in that R _{2 is} allyl. 14. Weed-forming agent according to at least one of claims 1 or 2, characterized in that R _{1 is} hydrogen and R _{2 is} alkynyl. 15. Weedkiller according to at least one of claims 1, 2 or 14, characterized in that R _{2 is} 3-methyl-3-butynyl. 709 808/1154 16. Weedkiller according to at least one of claims _{1, 2 or 14, characterized in that R 2 is} 1,1-dimethy 1-2 butynyl. 17. Weedkiller according to at least one of claims 1, 2 or 14, characterized in that Rp 1,1-dime means ethyl-2-pentinyl. 18. Weedkillers according to at least one of the claims * 1 or 2, characterized in that R-, lower-alkyl and Rp are alkynyl. 19. Weedkillers according to at least one of Claims 1, 2 or 18, characterized in that R _{1 is} methyl and R _{2 is} 3-methyl-3-butynyl. 20. Method of protecting small-grain crops from damage by a thiocarbamate herbicide is caused, characterized in that the soil in which the useful plant is planted and in which it grows, with a non-phytotoxic, antidote-effective amount of a compound of the formula BrCH ₂ BrCH - R ₂ R ₁ denotes hydrogen, alkenyl or lower-alkyl and R ₂ denotes alkyl, alkenyl, alkynyl, dimethoxyethyl or 1-ethynylcyclohexyl,
is treated. 21. The method according to claim 20, characterized in that R ^ is hydrogen and R _{2 is} alkyl. 709808/1154 22. The method according to claim 20 or 21, characterized in that R _{2 is} t-butyl. 23. The method according to claim 20 or 21, characterized in that R _{2 is} 2-methyl-2-butyl. 24. The method according to claim 20 or 21, characterized in that R _{2 is} 4-methyl-2-pentyl. 25. The method according to claim 20 or 21, characterized in that R _{2 is} 3-methyl-2-pentyl. 26. The method according to claim 20, characterized in that R _{1 is} hydrogen and R _{2 is} 1-ethynylcyclohexyl. 27. The method according to claim 20, characterized in that R _{1 is} alkenyl and R _{2 is} alkenyl. 28. The method according to claim 20 or 27, characterized in that R _{1 is} allyl and R _{2 is} allyl. 29. The method according to claim 20, characterized in that R _{1 is} hydrogen and R _{2 is} 2,2-dimethoxyethyl. 30. The method according to claim 20, characterized in that R _{1 is} hydrogen and R _{2 is} alkenyl. 31. The method according to claim 20 or 30, characterized in that R _{2 is} allyl. 32. The method according to claim 20, characterized in that R _{1 is} hydrogen and R _{2 is} alkynyl. 33. The method according to claim 20 or 32, characterized in that R _{2 is} 1,1-dimethyl-2-butynyl. 709808/1 1 54 34. The method according to claim 20 or 32, characterized in that R _{2 is} 1, i-dimethyl-2-pentinyl. 35. The method according to claim 20 or 32, characterized in that R _{2 is} 3-methyl-3-butynyl. 36. The method according to claim 20, characterized in that R ^ is lower-alkyl and R _{2 is} alkynyl. 37. The method according to claim 20 or 36, characterized in that R _{1 is} methyl and R _{2 is} 3-methyl-3-butynyl. 38. A method for controlling weeds in the presence of small-grain crops, characterized in that one the soil before planting or sowing with an herbicide treated according to at least one of claims 1 to 19. 39. Methods for protecting small grain crops from damage caused by thiocarbamate herbicides is, characterized in that the seeds of the small-grain crops before planting or sowing with a non-phytotoxic, antidote effective amount of a compound the formula 0 R ₁ BrCH ₂ BrCH - C - N ^ R ₂ R ₁ denotes hydrogen, alkenyl or lower-alkyl and R ₂ denotes alkyl, alkenyl, alkynyl, dimethoxyethyl or 1-ethynylcyclohexyl,
treated. 709808/1154 -25- 263A278 40. The method according to claim 39, characterized in that wheat, barley, rice, oats, Rye and / or triticale can be treated. 41. The method according to claim 39, characterized in that barley is treated as a small-grain crop plant and that the thiocarbamate herbicide S-ethyldipropyl-thiocarbamate, S-ethyldiisobutyl-thiocarbamate, S-propyl-di-n-propyl-thiocarbamate, S-ethylcyclohexylethyl-thiocarbamate, S-ethylhexahydro-1H-azepine-1-carbothioate, 2,3,3-Trichloroallyl-N, N-diisopropylthiocarbamate and / or S-isopropyl-1- (5-ethyl-2-methylpiperidine) -carbothioate be used. 42. The method according to claim 39, characterized in that barley is treated as a small-grain crop plant and that S-propyl-di-n-propyl-thiocarbamate is used as the thiocarbamate will. 43. The method according to claim 39, characterized in that that barley is treated as a small-grain crop and that S-ethyl-di-n-propyl-thiocarbamate is used as thiocarbamate will. 44. The method according to claim 39, characterized in that the antidote is N- (1-ethynylcyclohexyl) -2,3-dibromopropionamide is used. 45 · Process according to claim 39, characterized in that N-t-butyl-2,3-dibromopropionamide is used as the antidote will. 46. The method according to claim 39, characterized in that the antidote is N- (3-methyl-3-butynyl) -2,3-dibromopropionamide is used. 709808/1154 47. The method according to claim 39, characterized in that N-t-pentyl-2,3-dibromopropionamide is used as the antidote will. 48. The method according to claim 39, characterized in that the antidote is N- (1,3-dimethylbutyl) -2,3-dibromopropionamide is used. 49. The method according to claim 39, characterized in that the antidote is 2- (2,3-dibromopropionamido) -3-methylpentane is used. 50. The method according to claim 39, characterized in that the antidote is N- (dimethyl-2-butynyl) -2,3-dibromopropionamide is used. 51. The method according to claim 39, characterized in that the antidote is N- (1,1-Dimethy1-2-pentinyl) -2,3-dibromopropionamide is used. 52. Methods for protecting small grain crops from damage caused by thiocarbamate herbicides is, characterized in that the seeds for the small-grain crops in the furrow and / or the soil, containing the thiocarbamate herbicide, before covering and, if necessary, before planting the seeds for small grains Crop plants with a non-phytotoxic, antidoteic amount of a compound of the formula 0 R ₁ BrCH ₂ BrCH - C - R ₂ R ₁ denotes hydrogen, alkenyl or lower-alkyl and R ₂ denotes alkyl, alkenyl, alkynyl, dimethoxyethyl or 1-ethynylcyclohexyl,
treated. 709808/1 1 54 53 · The method according to claim 52, characterized in that wheat, barley, rice, oats, Rye and / or triticale can be treated. 54. The method according to claim 52, characterized in that barley is treated as a small-grain crop plant and that the thiocarbamate herbicide S-ethyldipropyl-thiocarbamate, S-ethyldiisobutyl-thiocarbamate, S-propyl-di-n-propyl-thiocarbamate, S-ethyl cyclohexyl ethyl thiocarbamate, S-ethylhexahydro-1H-azepine-1-carbothioate, 2,3,3-Trichloroallyl-N, N-diisopropylthiocarbamate and / or S-isopropyl-1- (5-ethyl-2-methylpiperidine) -carbothioate be used. 55. The method according to claim 52, characterized in that that barley is treated as a small-grain crop and that S-propyl-di-n-propyl-thiocarbamate is used as thiocarbamate will. 56. The method according to claim 52, characterized in that that barley is treated as a small-grain crop and that S-ethyl-di-n-propyl-thiocarbamate is used as the thiocarbamate will. 57 · The method according to claim 52, characterized in, that as an antidote N- (1-ethynylcyclohexyl) -2,3-dibromopropionamide is used. 58. The method according to claim 52, characterized in that that N-t-butyl-2,3-dibromopropionamide is used as the antidote. 59 · The method according to claim 52, characterized in that N- (3-methyl-3-butynyl) -2,3-dibromopropionamide as the antidote is used. 709808/1154 60. The method according to claim 52, characterized in that N-t-pentyl-2,3-dibromopropionamide is used as the antidote will. 61. The method according to claim 52, characterized in that the antidote is N- (1,3-dimethylbutyl) -2,3-dibromopropionamide is used. 62. The method according to claim 52, characterized in that 2- (2 ₉ 3-dibromopropionamido) -3-methylpentane is used as the antidote. 63. The method according to claim 52, characterized in that N- (dimethyl-2-butynyl) -2 _s 3-dibromopropionamide is used as the antidote. 64. The method according to claim 52, characterized in that the antidote is N- (1,1-dimethyl-2-pentinyl) -2,3-dibromopropionamide is used. 65. Weedkiller according to at least one of claims 1 to 19, characterized in that it is used as a thiocarbamate herbicide S-ethyld'ipropyl-thiocarbamate, S-ethyldiisobutyl-thiocarbamate, S-propyl-di-n-propyl-thiocarbamate, S-ethylcyclohexylethyl-thiocarbamate, S-Ä "ethylhexahydro-1H-azepine-1-carbothioate, 2,3 »3-Trichloroallyl-N, N-diisopropylthiocarbamate and / or S-isopropyl-1- (5-ethyl-2-methylpiperidine) -carbothioate contains. 66. A method for controlling weeds in the presence of small-grain crops, characterized in that one treated the soil with the herbicide according to claim 65 before planting. 70 9 808/1154 263-278 Process according to claim 2O _8, characterized in that the thiocarbamate herbicide is S-ethyldipropyl-thiocarbamate, S-ethyldiisobutyl-thiocarbamate, S-propyl-di-n-propyl-thiocarbamate, S-ethylcyclohexylethyl-thiocarbamate, 1H-azo-azo-ethyl-thiocarbamate, 1-carbothioate, 2,3,3-trichlorally1-N, N-diisopropyl-thiocarbamate and / or S-isopropyl-1- (5-ethyl-2-methylpiperidine) -carbothioate can be used « 709808 / 115.4