HU203026B - Selective herbicide composition of wide spectrum of activity and process for producing the active component - Google Patents

Abstract

The herbicidal composition of the present invention comprises from 1 to 50% by weight of (- 3-isopropyl- (1H) -2,1,3-benzothiadiazine-4 (3H) -one-2,2-dioxide) of formula (I) - (II) a substituted phenoxyalkanoic acid or benzoic acid and a derivative thereof with 1,2-ethylenediamine or 1,3-propylene diamine, wherein R1 is chloro, methyl or methoxy, R2 is hydrogen or chloro, R3 is hydrogen or hydrogen; chlorine, R4 is hydrogen or chloro, n is 0 or 1, m is 0.1 or 2 or 3, and z is 2 or 3 to 50 to 99% by weight of a carrier, dispersant, and wetting agent. Scope of the description: page 6, figure 1 EN 203 026 A -1-

Description

FIELD OF THE INVENTION The present invention relates to a compound of formula (I), a 3-isopropyl- (1H) -2,1,3-benzothiadiazin4- (3H) -one-2,2-dioxide and a substituted phenoxyalkanoic acid benzoic acid derivative of a compound having two amino groups. wherein R1 is chloro, methyl or methoxy, R2 is hydrogen or chloro, R3 is hydrogen or chloro, R4 is hydrogen or chloro, n is 0 or 1, m is 0.1 or 2 or 3, and z is 2 or 3 - a herbicidal composition containing from 1 to 50% by weight of a compound, and a process for the preparation of compounds of the formula I.

As it is known, Basagran (containing the sodium salt of 3-isopropyl- (1H) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide) as active ingredient kills dicotyledone weeds. , however, monocotyledon plants (grasses) are not damaged. The disadvantage of the composition, however, is that it can be used in relatively high doses (1.1-2.2 kg active ingredient / ha) and only on small weeds of 3-4 leaves. Due to the short application time and the high cost per hectare, the product was not widely distributed. Because of its "bad" properties described above, it was therefore combined with cheaper herbicides with the same spectrum of activity as bentazone. This is how BAS 35801H / 250 g bentazone + 350 g dichloropropylethylammonium (1) Basagran MCPA / 250 g bentazone + 125 g MCPA (1) etc. were marketed. (The Pesticide Manual 8th Edition, 170 pp. 63-64).

In this combination, bentazone is used in combination with various auxin herbicides. Such an auxin-acting herbicide is (2,4-dichlorophenoxy) -acetic acid (The Pesticide Manual 8th Edition, 3780, pp. 220-222), which is commercially available as Dikamin-D, Dikonirt-D. Similar herbicides are (4-chloro-2-methylphenoxy) acetic acid, 4- (4-chloro-2-methylphenoxy) butyric acid and 2- (4-chloro-2-methylphenoxy) propionic acid (The Pesticide Manual 8th Edition, 7790 pp. 514: 518, 7810 pp. 519, 7860 pp. 522523). The above compounds are marketed, respectively, as SYS 67 ME 80 or dicotex 40 and SYS 67 MB (Pesticides, Fertilizers, Agricultural Publication, 1988).

This group of compounds is characterized by monocot (grass) benefits and does not damage weeds. However, they are also ineffective against certain dicotyledonous (broadleaf) weeds. against Galium spp., Veronica sp., Matricaria sp.

The second class of auxin herbicides effective against broadleaf weeds is represented by 3,6-dichloro-2-methoxybenzoic acid (The Pesticide Manual 8 th Edition, 4100 pp. 251-252). The sodium salt of the compound is known as the Banvel 480 formulation (Pesticides and Fertilizers, Agricultural Publisher, 1988). It is a more aggressive herbicide with a broader spectrum of action than the hormone herbicides described above. It also has good control over the resistant weeds listed. It has the disadvantage of damaging monocotyledonous crops, such as. root of corn, sorghum, cereals. As a result, they are less able to absorb nutrients and water from the soil. In addition, wind causes plants to fall down easily, making it more difficult to harvest.

Despite their disadvantageous properties, agriculture cannot afford to use them due to their cheap production and wide spectrum of effects. Among their various combinations, in which besides the hormonal preparations, bentazone, which is selective for contact, scorching, monocot (grass) and certain dicot (broad-leaved) crop plants (broad beans, peas, soy), is particularly preferred.

In our studies, it has been found that the formation of compositions in which a properly selected diamine derivative forms a link between bentazone and hormonal herbicides results in an unexpected increase in biological efficacy. As a result, the dose may be reduced. This reduces the pesticide load on the environment, reduces the cost and reduces the risk of crop damage without compromising efficiency.

The diamine compounds of the present invention are not currently used in plant protection. The compounds are known primarily in medicine (Knoll J. Pharmacology, Medicina Publishing House, Budapest, 1983, pp. 713-725). They are also known in nature where they are formed by the decomposition of organic wastes (Szekeres L. Organic Chemistry, Agricultural Publisher, Budapest, 1967, p. 210), or some of their derivatives are used to form metal complexes (p.213).

In our studies, it was found that 3-isopropyl- (1H) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxid was dissolved in a solvent with a compound of formula (Π) and a compound of formula ((). Reaction with a base of formula (I), such as 1,2-ethylenediamine or 1,3-propylene diamine, provides herbicides of formula (I) which have a broad spectrum of activity and are better than conventional combinations.

This discovery has led to the present invention for a herbicidal composition comprising from 1 to 50% by weight of a compound of formula (I) wherein R1, R2, R3, R4, n, m and z are as defined above. A process for preparing the active ingredient by reacting 3-isopropyl- (1H) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide in a solvent, preferably aqueous or alcoholic medium, with phenoxyalkanoic acid or benzoic acid and diamine compound (ΠΙ), wherein the substituents have the meanings given above, are blended in an equivalent amount, and the active compound thus obtained is isolated by conventional procedures such as cooling, washing, drying. Further details of the invention are illustrated by the following examples:

Example 1

0.05 mol of 3-isopropyl- (1H) -2,1,3-benzothiadiazin4 (3H) -one-2,2-dioxide and 0.05 mol of 2,4-dichlorophenoxyacetic acid are mixed with 30 ml of water. and dropwise addition of 0.05 mole of 1,2-ethylenediamine. The mixture is boiled and water (about 15 mL) is added to obtain a homogeneous solution and then cooled. The

The solution is kept at 0 'C for 3 hours, the precipitated crystals are filtered off, washed with water and dried. 1,2-Ethylenediamine (2 ', 4 "-dichlorophenoxyacetate) - (3-propyl- (1'H) -2", 1 ", 3" benzothiadiazine-4) is obtained in good yield. '(3' H) -on-2 ', 2' dioxide). 5

Example 2

0.05 mol of 3-isopropyl- (1H) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide and 0.05 mol of 4-chloro-2-methylphenoxyacetic acid are added as described above. 0.05 mol of 10-1,3-propylene diamine and the product was isolated in a similar manner. Yield 1,3-propylene diamine (4'-chloro-2'-methylphenoxy) acetate (3 "-isopropyl- (1" H) -2 ", 1", 3 ") in good yield. benzothiadiazine-4 "(3" H) -one-2 ", 2" dioxide salt, m.p. 96-99 ° C.

Example 3

0.05 mol of 3-isopropyl- (1H) -2,1,3-benzothiadiazin4 (3H) -one-2,2-dioxide and 0.05 mol of 4- (4-chloro-2-methylphenoxy) -butyric acid and 0.05 mol of 1,3-propylene diamine are dissolved in 50 ml of methanol. After complete dissolution, diethyl ether is added until it becomes cloudy (about 30 mL). Subsequently, the reaction mixture is maintained at 0-10 ° C for 24 hours. The precipitated crystals were filtered off, washed with methanol-1: 1 and dried. With good yield, 1,3-propylene diamine (4'4'-chloro-2'-methylphenoxy) butylate) (3 "-isopropyl- (l" H) -2 ", l") is obtained. 3 "Benzothiadiazine-4" (3 "H) -one-2", 2 "Dioxide Salt, 105-108 ° C.

Example 4

0.05 mol of 3-isopropyl- (1H) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide and 0.05 mol of 3,6-dichloro-2-methoxybenzoic acid and 0 05 Mole of 1,2-ethylenediamine was mixed and worked up in analogy to Example 1. 3,5-Ethylenediamine (3 ', 6'-dichloro-2'-methoxybenzoate) - (3 "-isopropyl- (1" H) -2 ", 1", 3 "- is obtained in good yield. benzothiadiazine-4 "(3" H) -on-2 ", 2 ^", dioxide salt, m.p. 135-139'C.

Example 5

20 g of the active compound of Example 3 are dissolved in 50 ml of 20% w / w isopropyl alcohol. 10 g of poly (ethylene oxide) sorbitan monooleate was added and the latter solvent was added to 45 ml (100 ml) to give a composition of 200 g / l.

Example 6

40 g of the active ingredient prepared according to Example 1 are mixed in a laboratory powder mixer with 25 g of Sipemate 50 (synthetic silicate), 2 g of Netzer IS aliphatic sulfonic acid-Na-wetting agent and 3 g of Dispergiermitt 1494 (cresol formaldehyde condensate). and 5 g of sulfite lye powder dispersants and 25 g of kaolin carrier.

The whole is homogenized by stirring and finely ground in an Alpine 63 G laboratory hammer mill. A wettable powder composition containing 40% by weight of active ingredient is thus obtained.

Example 7

In the apparatus of Example 6, 2.5 g of Ca lignin sulfonic acid salt, 2.5 g of fatty alcohol sulfonate, 5 g of the active ingredient of Example 4, 40 g of silica and 50 g of kaolin are mixed. The mixture is finely ground to give a wettable powder formulation containing 5% by weight of active ingredient.

Example 8

30 g of the active compound prepared according to Example 2 are dissolved in 40 ml of dimethyl sulfoxide. 10 g of isopropyl naphthol sulfonic acid Caso are added and the solution is made up to 100 ml to give a composition containing 300 g / l of active ingredient.

Example 9

In winter wheat we tested the effectiveness of the combinations according to the invention on plots of 10 m ² . At the time of spraying, the wheat had finished shrubbing. The dominant weeds in the area, which had different levels of development, were the hen string (Stellaria spp. STEME), the prey (Galium spp. GALAP) and the common weed (Matriceria spp. ΜΑΊΊΝ). Their development ranged from 4-8 leaves. Spraying was carried out using 3001 / ha water. The effect of the treatments was evaluated on the 14th day after spraying. For weeds, the percent mortality, and for the crop, the phytotoxicity score on the EWRC scale, where 1 denotes immunity and 9 denotes total mortality.

Evaluating the results of the study, it can be concluded that the active ingredient according to the invention had a better effect than when its ingredients were used in a tank mix. In the conventional combination, the active ingredients are merely complementary. In contrast, an unexpected positive interaction between the active compounds of the invention is observed (Table 1). BASAGRAN 480 WSC Liquid herbicide containing 480 g / l bentazone (BASF AG, Germany) DICAMIN-D 40% liquid herbicide containing 2,4-dichlorophenoxyacetic acid (Nitrochemical Industrial Plant).

No. 1 spreadsheet

treatments Dose preparation 1 / ha Dose agent kg / ha Winter wheat EWRC- FIDE rating STEME GALAP death MaiiRa % control - 1 0.0 0.0 0.0 Example 6 Preparation 40 WP 0.25 0.1 1 29.0 11.0 7.0 ♦ " 0.5 0.2 1 46.0 17.0 11.0 1.0 0.4 1 100.0 49.0 68.0 2.0 0.8 1 100.0 100.0 100.0

-3EN 203026 A

No. 1 Continue Table

treatments Dose preparation 1 / ha Dose agent kg / ha Winter wheat EWRC- FIDE rating STEME GALAP death MaiiRa % Basagran 480 WSC + Dikamin-D 0.052 + 0.12 0.1 1 0.0 0.0 0.0 n 0.104 + 0.25 0.2 1 0.0 0.0 0.0 M 0.208 + 0.50 0.4 1 30.0 20.0 21.0 ♦ » 0.832 + 1.00 0.8 1 65.0 49.0 43.0 Basagran 480 WS 0.208 0.1 1 0.0 0.0 0.0 »» 0.416 0.2 1 0.0 0.0 0.0 0.832 0.4 1 16.0 11.0 13.0 1 » 1,664 0.8 1 47.0 31.0 41.0 Dikamin D 0.25 0.1 1 0.0 0.0 0.0 ♦ » 0.50 0.2 1 0.0 0.0 0.0 1.0 0.4 1 36.0 0.0 0.0 "♦ 2.0 0.8 1 70.0 0.0 0.0

Example 10

In maize, the efficacy of the active compounds of the invention was tested on 40 m plots. After sowing, the soil was treated with 7 kg / ha Niticid 65 WP (active ingredient: 651% 2-chloro-N-isopropylacetanilide) to prevent emergence of monocotyledonous weeds. The dominant dicotyledonous (broadleaf) weeds in the area were as follows:

- Hairy swine (Amaranthus spp. AMARE)

- White goose top (Chenopodium spp. CHEAL)

- Apricot bitter grass (Polygonum spp. POLPE) 35

- Duct tape (Datura spp. DATST)

No. 2, table

The formulations were sprayed at a height of 20-25 cm of corn in 2201 / ha water. The weeds were 4-8 leafy. Evaluation was performed as described in Example 9.

When applied to broadleaf weeds in maize, the active compound according to the invention can be found to have suffered significant damage (at 0.2 kg / ha) even at relatively low doses. The efficacy of the conventional combination (Basagran 480 WSC + Banvel 480 WSC) did not achieve this (Table 2).

BANVEL 480 480 g of herbicide containing the salt of 12-methoxy-3,6-dichlorobenzoic acid (Chemie Linz, Ag, Austria).

treatments Dose preparation kg / ha Dose agent kg / ha Maize EWRC- FIDE rating AMARE CHEAL merely POLPE ul% DATS control - - 1 0.0 0.0 0.0 0.0 The composition of Example 7 is 5 WP 1.0 0.0 1 27.0 21.0 17.0 34.0 »» 2.0 0.10 1 53.0 49.0 43.0 65.0 ♦ » 4.0 0.20 1 79.0 68.0 70.0 91.0 »» 8.0 0.40 1 100.0 100.0 100.0 100.0 Basagran 480 WSC + BANVEL 480 WSC 0.05 + 0.05 0.05 1 7.0 0.0 0.0 10.0 »» 0.104 + 0.104 0.10 1 31.0 12.0 0.0 21.0 ♦♦ 0.208 + 0.208 0.20 1 56.0 47.0 16.0 53.0 »» 0.416 + 0.416 0.40 1 87.0 61.0 63.0 100.0 Basagran 470 WSC 0,104 0.5 1 0.0 0.0 0.0 0.208 0.1 1 0.0 0.0 0.0 0.0 »» 0.416 0.2 1 0.0 0.0 0.0 0.0 »» 0.032 0.4 1 16.0 11.0 0.0 24.0 Banvel480WSC 0,104 0.05 1 0.0 0.0 0.0 0.0 »» 0.208 0.1 1 12.0 11.0 16.0 41.0 ♦♦ 0.416 0.2 1 39.0 16.0 53.0 69.0 "♦ 0.832 0.4 5 100.0 100.0 100.0 100.0

-4EN 203026 A

Example 11

The efficacy of the combinations according to the invention against dicotyledonous (broadleaf) weeds was investigated in peas on 10 m ² plots.

At the time of treatment, 2-3 true autumn leaves developed on the soy, 4-8 leaves on the weeds. The most abundant weeds in the area were as follows

- Wild hemp (Cannabis spp. CANSA)

white goose (Chenopodium spp. CHEAL) 10

- hairy swine (Amaranthus spp. AMARE)

- sticky fin (Gallium spp. GALAP)

The formulations were sprayed with 300 L / ha water and evaluated for efficacy as described in Example 9.

According to the evaluation data (Table 3), the tested weeds were more effective in killing the tested weeds than when the two formulations were used as a tank mix. A high efficiency improvement was also observed when comparing the active ingredient of the invention with its ingredients.

SYS 67 MB Powdered Herbicide with 80% 4- (2-Methyl-4-chlorophenoxy) -butyric acid (VEB Synthesewerk, Schwanheide, Germany)

No. 3 spreadsheet

treatments Dose preparation kg / ha Dose agent s / ha Pea EWRC value song Canson CHEAL Busan AMARE ulási% GALAP control - 1 0.0 0.0 0.0 0.0 Example 5 Preparation 20 EC 1.0 0.2 1 0.0 0.0 0.0 0.0 »» 2.0 0.4 1 39.0 46.0 60.0 30.0 4.0 0.8 1 87.0 89.0 97.0 63.0 8.0 1.6 1 100.0 100.0 100.0 100.0 Basagran 480 WSC + SYS 67 80 WP 0.208 + 0.125 0.2 1 0.0 0.0 0.0 0.0 ♦ " 0.416 + 0.25 0.4 1 11.0 10.0 20.0 0.0 »» 0.832 + 0.50 0.8 1 40.0 47.0 50.0 31.0 »í 1.664 + 1.00 1.6 1 61.0 66.0 79.0 58.1 Basagran 480 WSC 0.416 0.2 1 0.0 0.0 0.0 0.0 > » 0.832 0.4 1 13.0 0.0 29.0 0.0 ♦ t 1,664 0.8 1 46.0 34.0 50.0 17.0 »1 3,328 1.6 1 69.0 72.0 82.0 43.0 SYS 67 MB 80 WP 0.25 0.2 1 0.0 0.0 0.0 0.0 »» 0.5 0.4 1 17.0 25.0 21.0 0.0 1.0 0.8 1 39.0 34.0 36.0 0.0 »» 2.0 1.6 3 81.0 74.0 76.0 0.0

Example 72

In winter barley, the efficacy of the combinations according to the invention against seedling dicotyledonous (broadleaf) weeds was examined on 5 m ² plots. At the time of treatment, the barley was at the end of shrubbery. The highest proportion in the area is

-fume (Fumaria spp. FUMSC) 50

- Veronica (Veronica spp. VERHE)

- Chickweed (Stellaria spp. STEME) weeds with 4-8 leaf stage development.

The effect of the treatments was evaluated as described in Example 9.

The formulations were sprayed with 400 l / ha water. When tested in barley (Table 4), a positive interaction between the components of the active compound of the invention was also confirmed. The herbicidal activity of the active ingredient according to the invention was significantly better than when the ingredients of the active ingredient were used alone or in a tank mix. Dikotex 40 Liquid herbicide containing 32% 2-methyl-4j-chlorophenoxyacetic acid (J. Dimitrov Chemical Works, Czechoslovakia)

No. 4 spreadsheet

treatments Dose preparation 1 / ha Dose agent kg / ha Autumn barley EWRCvalue number FUMSC CERHE% mortality SEME control - - 1 0.0 0.0 0.0

Example 8

-5HU 203026 A

No. 4 Continue Table

treatments Dose preparation 1 / ha Dose agent kg / ha Autumn barley EWRCvalue number FUMSC Cerha death SEME % preparation 20 EC 1.0 0.2 1 14.0 23.0 0.0 2.0 0.4 1 60.0 82.0 67.0 Basagran 480WSC + 4.0 0.8 1 100.0 100.0 98.0 Dikotex 40 0.208 + 0.294 0.2 1 0.0 0.0 0.0 "♦ 0.416 + 0.588 0.4 1 11.0 13.0 10.0 »> 0.832 + 1.176 0.8 1 53.0 61.0 50.0 Basagran 480 WSC 0.416 0.2 1 0.0 0.0 0.0 »» 0.832 0.4 1 0.0 0.0 7.0 »» 1,654 0.8 1 39.0 46.0 51.0 Dikotex 40 .588 0.2 1 0.0 0.0 0.0 ♦ " 1,176 0.4 1 19.0 16.0 0.0 2,532 0.8 1 56.0 30.0 19.0

PATENT CLAIMS

Claims (2)

CLAIMS 1. A herbicidal composition comprising as active ingredient 1-50% by weight of an active ingredient of the formula I - 3-isopropyl- (1H) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide A derivative of a substituted phenoxyalkanoic acid of formula (vagy) or benzoic acid and 1,2-ethylenediamine or 1,3-propylene diamine, wherein R 1 is chloro, methyl or methoxy, R _{2 is} hydrogen or chloro; , R1 is hydrogen or chlorine, R4 is hydrogen or chlorine, n is 0 or 1, m is 0,1,2 or 3 and z is 2 or 3 - contains 99-50% by weight of a solid or liquid carrier - preferably silicate such as diatomaceous earth, kaolin, water-alcohol mixture, dimethyl sulfoxide, optionally in the presence of an emulsifier such as sodium salt of aliphatic sulfonic acid. (Priority: September 23, 1988) 2. A process for the preparation of the 3-isopropyl (1Η) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide substituted phenoxyalkanoic acid or benzoic diamine salt derivative of formula I wherein Rt, _R2, R3, R4. n, m and z as defined in claim 1, characterized in that the 3-isopropyl- (1H) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide The mixture is stirred at reflux with an equivalent amount of a compound of formula (Π) and a diamine compound of formula (ΠΙ), and the resulting compound of formula (I) is isolated from the reaction mixture by conventional procedures. (Priority: September 23, 1988)