JPS6214522B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has the general formula: The present invention relates to a protective agent containing an oxime derivative having the effect of protecting cultivated plants from pesticide damage represented by: In the above general formula, R ₁ is - OR ₂ (in the formula, R ₂ represents an alkyl group having 1 to 4 carbon atoms), or - N(R ₃ ) (R ₄ ) (in the formula, R ₃ is represents a hydrogen atom or a lower alkyl group, R ₄ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aminocarbonyl group), X represents a cyano group, and Q is substituted by a cyano group. lower alkyl group, -alkoxycarbonylalkyl group (however, the alkyl moiety has 1 to 4 carbon atoms), or -ammonium cation or mono- or dialkylammonium cation (however, the alkyl moiety has 1 to 4 carbon atoms). 4). The term "lower alkyl" by itself or as part of a substituent refers to a branched or unbranched alkyl group having 1 to 4 carbon atoms. For example, methyl, ethyl, propyl, isopropyl, butyl,
These are isobutyl, sec-butyl, and tert-butyl. The quaternary ammonium salts contain C1 -C4 alkyl groups as similar or different substituents. Oximes of the general formula () are suitable for the protection of cultivated plants, such as rice, maize, cereals (cultivated millet, wheat, rye, barley, oats), against the attack of phytotoxic pesticides, in particular various herbicides. These are the cases in which the pesticide is not at all or not very selective, i.e., in addition to the weeds to be controlled,
It is suitable for protecting cultivated plants when the cultivated plants are also damaged to some extent. Various substances have already been proposed as antagonists or antidotes that specifically antagonize the damaging effects of herbicides on cultivated plants, ie are able to protect cultivated plants without affecting the herbicidal action on the weeds to be controlled. There is. Depending on their nature, antagonists (also called safeners) of this type can be used in the pretreatment of seeds of cultivated plants (soaking of seeds or cuttings) or before sowing in the sowing furrow, or in tanks alone or together with herbicides. It can be used as a mixture before or after plant emergence. Pre-emergence treatment includes treatment of cultivated surfaces before sowing (ppi = "pre-planting formulation") as well as treatment of cultivated surfaces that have been sown but have not yet flourished. British Patent No. 1277557 discloses the treatment of wheat and sorghum seeds or shoots with certain oxamic acid esters and amides for infringement by N-methoxymethyl-2',6'-diethyl-chloroacetanilide (Alachlor). This is disclosed.
Also, other documents (German Patent Application Publication No. 1952910
No. 2245471, French Patent No.
2021611) proposes an antidote for treating grain, corn and rice seeds to protect against herbicidal thiol carbamate attack. In German Patent No. 1576676 and US Pat. No. 3,131,509 hydroxy-amino-acetanilides and hydantoins are proposed for the protection of cereal seeds against carbamates such as IPC, CIPC. However, previous studies have shown that all these drugs are not satisfactory. Compounds that have remarkable antidote effects are those represented by the above formula. Further preferred compound groups for their detoxifying action are those in which R ₁ represents -OR ₂ (R ₂ in the group represents an alkyl group having up to 4 carbon atoms), and X and Q are defined in the formula It has meaning. These active ingredient types are referred to as compound groups Ie.
Among these groups, those in which Q has the meaning of a cyanoalkyl group are referred to as functional compound groups If. The oximes of the general formula () are surprisingly useful in phytotoxic pesticides, especially herbicides of various substance systems, especially 1,
3,5-triazines, 1,2,4-triazinones, phenylamin derivatives, carbamates, thiol carbamates, phenoxyacetic acid esters, phenoxypropionic acid esters, halogenacetanilides, halogenphenoxyacetic acid Esters, substituted phenoxy phenoxy acetic acid esters, substituted phenoxy phenoxy propionic acid esters, substituted pyridineoxyphenoxy acetic acid esters, substituted pyridine oxyphenoxy propionic acid esters, benzoic acid derivatives, etc. It has the property of protecting cultivated plants against the encroachments of plants which are not at all or poorly tolerated in cultivation. This type of antagonist or antidote of the general formula () is:
Depending on the intended use, it can be used for pre-treatment of seeds of cultivated plants (soaking of seeds or cuttings), mixed into the soil before or after sowing, or alone or together with herbicides before the germination of plants. Alternatively, it can be applied after germination. Treatment of plants or seeds with antidotes can therefore in principle be carried out independently of the time of application of the phytotoxic chemical. However, it is also possible to carry out the treatments simultaneously (tank mixing). Pre-emergence treatment includes treatment of cultivated surfaces before sowing (ppi = "pre-planting formulation") and treatment of cultivated surfaces that have been sown but have not yet flourished. . The amount of antidote applied to herbicides depends primarily on the method of use. When carrying out arable treatment, the ratio of the amount of antidote of the general formula () to the phytotoxic chemical is from 1:100 to 5:1, in particular from 1:20 to 1:1. However, in the case of seed treatments and similar protective measures, small amounts of antidote are required compared to the amount of herbicide subsequently applied per hectare of cultivated area (e.g. approximately 1:3000-1 :1000).
In general, protective measures such as seed treatment with antidotes of the general formula () and subsequent field treatment with pesticides are of little relevance. The pretreated seeds and plants can then be contacted with various chemicals in agriculture, horticulture and forestry. The present invention therefore relates to a cultivated plant protection agent containing as an active ingredient an antidote of the general formula () together with customary excipients. Such protective agents can optionally also be mixed with pesticides, such as herbicides, from which the cultivated plants are to be protected. In the present invention, cultivated plants are cultivated plants that produce some form of harvest (seeds, roots, stems, tubers, leaves, flowers, contents such as oil, sugar, starch, protein, etc.), and are cultivated for that purpose. All cultivated plants. These plants include, for example, all cereals, corn, rice, millet, soybeans, beans,
Peas, potato, vegetables, cotton, sugar beet,
There are cane, peanut, tobacco, hops, as well as ornamental plants, fruit trees and banana, cocoa and natural rubber plants. It is not limited to those listed here. In principle, antidotes can be used wherever cultivated plants are to be protected from the phytotoxicity of chemicals. The invention also relates to a method for protecting cultivated plants from the attack of (phytotoxic) pesticides, in which the oxime derivatives of the general formula () as antidotes are applied before or after application of the pesticide, or simultaneously with the pesticide. used. The invention further relates to the propagation of such cultivated plants treated and protected with oxime derivatives of the formula. "Propagation body" means all productive parts of a plant that can be taken into account for the propagation of a cultivated plant. These parts include grain seeds, roots, fruits, tubers, rhizomes, stems, twigs (cuttings) and other plant parts. However, it also includes germinated plants and young plants which are to be further transplanted after germination or growth. The purpose of protection is achieved by soaking such young plants in whole or in part before further transplantation. Compounds of the formula are prepared in a manner known per se, i.e. an oxime-like compound of the following formula: R ₁ --CO-CH ₂ --X (), in which R ₁ has the same meaning as in the formula, is added to nitric acid ( HNO ₃ ) or an organic or inorganic nitrite, converting the resulting free oxime into a salt, e.g. with a base;
by acylation with acids or acid halides or other forms with halogen separating groups;
It turns into an oxime ether with Q. These cited documents include German Published Patent Applications Nos. 2312956 and 2350910 and "Deutsche Chemistry Gesellschaft" 42, S. 738ff. [1909]. Oximes exist in two stereoisomeric forms, the syn-form and the anti-form. Therefore, both stereoisomers are to be considered herein as such and as a mixture in any proportion of intermixing. Below are two production examples showing the production of oxime,
The present invention will be explained in more detail. Temperatures are in degrees Celsius. Manufacturing example 1 Formula: Production of α-cyano-α-hydroxyimino-acetylurea represented by: Add cyanacetylurea to a solution of 50 g of sodium nitrate dissolved in 250 ml of water over 5 minutes with stirring at 80°C, then heat to 100°C. do.
After everything has dissolved, stir for an additional hour at room temperature and cool to 10°C. The sodium salt of the final product formed is filtered and dissolved in 200 ml of water under heating. This solution is then mixed with 70 ml of concentrated hydrochloric acid, cooled and filtered. Melting point (decomposition) α of 210° to 212°C
-Cyano-α-hydroxyimino-acetylurea is obtained. Manufacturing example 2nd formula: α-cyano-α-allyloxyimino-acetamide represented by α-cyano-α in 100 ml of acetonitrile
10.1 g (0.1 mol) of triethylamine was added to a solution containing 11.3 g (0.1 mol) of oximino-acetamide, and 12.1 g (0.1 mol) of allyl bromide was added thereto.
mol) dropwise. Subsequently, heated under reflux for 4 hours,
The solution is concentrated under reduced pressure and the residue is taken up in methylene chloride. The organic phase is washed several times with water, stirred with activated carbon while drying over sodium sulphate and filtered until clear. Concentration of the filtrate gives 12.7 g (83% of theory) of the final product, melting point 79-80°C. A compound represented by the following formula is prepared by this method or according to the above method.

【table】 and a compound represented by the following formula:

【table】 and a compound represented by the following formula

【table】 and a compound represented by the following formula

[Table] There are various methods and techniques for using compounds of formula (). (1) Seed soaking (a) Soaking the seeds with the active ingredient prepared as a wettable powder by shaking in a container until it is evenly distributed over the seed surface (dry soaking). seed
Approximately 10-500g of active ingredient of formula () per 100Kg
(Use 40g to 2kg of hydrating agent). (b) Seeds are soaked in a concentrated emulsion of the active ingredient of formula () according to method (a) (wet soaking). (c) Seeds are impregnated with a solution containing 50 to 3200 ppm of the active ingredient of formula () for 1 to 72 hours, and the seeds are optionally dried (impregnated). Soaking of seeds or treatment of germinated seedlings are of course advantageous application methods. This is because the active ingredients have a complete effect on the target cultivated plants. Generally, 10g of active ingredient per 100kg of seeds
- 500 g, in particular 50 to 250 g, which may be biased above or below the above-mentioned limit concentration depending on the method, which also allows the addition of other active ingredients or trace ingredients (repeated immersion ). (2) Application from tank mixture Mixture of antagonist and herbicide (relative ratio 1:
20-5:1) liquid formulations are used, the application rate of herbicide being 0.1-6 kg/ha. Advantageously, such tank mixtures are applied immediately after sowing or mixed into the unsown soil at a depth of 5 to 10 cm. (3) Application in the seeding furrow The antagonist is released as a concentrated emulsion, wettable powder, or granule. The herbicide is applied into the seeding furrow where the seeds have been sown, and then the herbicide is applied using the pre-emergence method after the sowing furrow is coated in a conventional manner. In principle, antagonists can be applied before, simultaneously with or after the application of the pest control agent, and can also be applied on the seeds or on the land before or after sowing or, in some cases, after the germination of the seeds. can. (4) Controlled release of the active ingredient The active ingredient is dissolved and coated onto a mineral granule carrier or polymeric granules (urea/formaldehyde) and dried. Optionally, a coating can be applied which allows release of the active ingredient over a period of time (coated granules). Of course, all other active ingredient application methods can also be used. Examples are listed below. The compounds of formula may be used alone or with suitable carriers and/or with other additives. Suitable carriers and additives may be solid or liquid and are those customary in pharmaceutical formulations, such as natural or recycled mineral substances, solvents, dispersants, wetting agents, fixing agents, thickeners, binders or fertilizers. The active ingredient content in commercially available drugs ranges from 0.1 to 90%.
It is between. For application, the compounds of the formula are presented in the following formulations (the figures in % by weight in brackets indicate the advantageous amounts of active ingredient): Solid preparations: powders and dusting powders (up to 10%), granules, [coated granules, impregnated granules and homogeneous granules] pellets (granules) (1 to 80%) Liquid preparations: (a) Water-dispersible active ingredient concentrates: Water Japanese additives and pastes (25-90 in commercially available fillers)
%, 0.01 to 15% in ready-to-use solution);
Emulsifiable and solvent-based concentrates (10 to 50%; 0.01 to 15% in ready-to-use solutions); (b) solutions (0.1 to 20%); active ingredients in aerosol formulations, e.g. Can be blended with: Granules Make 5% granules using each of the following ingredients: Active ingredients 5 parts Epichlorohydrin 0.25 parts Cetyl polyglycol ether 0.25 parts Polyethylene glycol 3.50 parts Kaolin (particle size 0.3-0.8 mm) 91 parts Active ingredients is mixed with epichlorohydrin and dissolved in 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. This solution is sprayed onto the kaolin and the acetone is then distilled off under reduced pressure. Wettable powders Prepare (a) 70% and (b) 10% wettable powders using the following ingredients: (a) Active ingredient 70 parts Sodium dibutylnaphthylsulfonate Naphthalenesulfonic acid - Phenolsulfonic acid -
Formaldehyde-condensate 5 parts 3:2:1 3 parts Kaolin 10 parts Cyanpentyoke 12 parts (b) Active ingredient 10 parts Mixture of sodium salts of saturated sulfated fatty alcohols 3 parts Naphthalene sulfonic acid/formaldehyde condensate 5 parts Kaolin 82 parts The active ingredient is intimately mixed with the additives in a suitable mixer and the mixture is ground in a suitable grinder, rollers. A wettable powder with excellent wetting and suspending properties is obtained which can be diluted with water to a suspension of the desired concentration and can be applied in particular to leaves. Emulsifiable concentrate A 25% emulsifiable concentrate is prepared using each of the following ingredients: Active ingredients 25 parts Epoxidized vegetable oil 2.5 parts Alkylaryl sulfonate/fatty alcohol polyglycol ether mixture 10 parts Dimethylformamide 5 parts Xylene 57.5 parts Above By diluting the concentrate with water, a concentrate of the desired concentration, which is particularly suitable as a seed soaking agent, is produced. Pre-emergence in Nutrient Solution - Antidote/Test A Hewitt nutrient solution containing the following amounts of herbicide and 10 ppm of the antidote to be tested is prepared. Cultivated seeds considered to be harmed by the herbicides used at the test concentrations were used and granulated zonorites (expanded vermiculite) were placed in plastic flowerpots (6 cm diameter at the top) with holes in the bottom. ). Place this pot in a second transparent plastic flowerpot (top diameter 7cm).
Add approximately 50 ml of the nutrient solution prepared using the herbicide and antidote to this second pot. This solution rises through the filling material of the smaller pot by capillary action and moistens the seeds and germinated plants. Replenish solution losses daily to 50 ml with pure Hewitt nutrient solution. Three weeks after the start of the study, evaluation is made on a linear scale of 1 to 9. 1 represents total damage to the plant, 9
represents a state of undamaged health. A control solution used in parallel does not contain antidote additive. Use the following; (1) promethrin = 2,4 bis(isopropylamino)-
6-Methylthio-S-triazine 4ppm (2) “Farnese” wheat,
4-ethylamino-6-tert-butylamino-
2-Chlor-S-triazine 4ppm (3) “Mazurka” barley with α-
[4-(p-trifluoromethylphenoxy)
-Phenoxy]-propionic acid-n-butoxyethyl ester 4ppm (4) Metolachlor = N-(1-methyl-2-methoxy-ethyl)-N-chloroacetyl-2 in “Funk Gi-522” millet -Ethyl-6
-Methylaniline 5ppm (5) 2-methoxy-4,6-(γ-methoxy-propylamino)-s-triazine 1ppm in sugar beet of the “Kleinwanzleben” variety (6) “Hark” variety 4-ethylamino-6-tert-butylamino-2-methoxy-s triazine 3 ppm on soybean The compound of general formula () achieves good detoxification effects in these tests.

[Table] After germination in nutrient solution - antidote test General method Small plastic pots with holes in the bottom (top diameter 6 cm) are filled with granular Zonolith and the cultivated seeds are sown. . Next, place this flower pot into a second transparent flower pot (7 cm in diameter at the top), and pour 50 ml of water into this second pot. This water rises by capillarity and wets the seeds 3. Starting from day 5, continuous water losses are replenished with Hewitt nutrient solution. From the 15th day (when the cultivated plants reach the 11/2-2 leaf stage), add (a) 10 ppm of the antidote to be tested plus the following amount of herbicide into the nutrient solution supplemented to 50 ml. (b) 1 ppm of the antidote to be tested + the following amount of herbicide. Add. From the 16th day, fluid losses are again replenished with pure Hewitt nutrient solution. During the whole test period, the temperature was 20-23℃ with relative humidity of 60-70%
It is. Three weeks after addition of the herbicide and antidote, the plants were evaluated on a linear scale from 1 to 9, with 1 representing overall damage to the plant and 9 representing undamaged health. Test item (1) α-
[4-(3,4-dichloropyridyl-2-oxy)-phenoxy]-propionic acid-propargylthiol ester 15ppm (2) 4-ethylamino-6-tert-butylamino -2-chlor-s
-Triazine 4ppm (3) “Orla” corn
-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionic acid-n-butoxyethyl ester 2ppm (4) “Funk G-522” type millet (Sorghun-Hirse) ), α-[4-
(p-trifluoromethylphenoxy)-phenoxy]-propionic acid-n-butoxyethyl ester 8ppm (5) Promethrin (=2,4-bis(isopropylamino) -6-methylthio-s-triazine)
4ppm (6) α-[4-
(3,5-dichlorpyridyl-2-oxy)-
Phenoxy]-propionic acid methyl ester
8ppm Compounds of general formula (), especially compound No. 1, achieve good detoxification effects in these tests. Antidote test by seed swelling Rice seeds of IR8 variety are impregnated with a solution of the test substance at 10 ppm or 100 ppm for 48 hours. The seeds are then dried for about 2 hours until they are no longer sticky.
Square plastic pot (8 x 8 cm, height 10
cm) and fill it up to 2 cm below the green with mixed sand and clay. 1
Sow 4 g of seeds per pot, covering very little (approximately the diameter of the seed grain). Keep the soil moist (not swampy). Next, the herbicide N-(1-methyl-2-methoxyethyl)-N
- Chloracetyl-2-ethyl-6-methylaniline or N-propoxyethyl-N-chloroacetyl-2,6-diethylaniline in a dilute solution,
Apply in an amount equivalent to 1.5 kg of active ingredient per hectare. The effects of herbicides without and with antidotes after transplanting
On day 18, rate on a linear scale of 1-9. At that time 1
represents overall damage to the plant, and 9 represents undamaged health. Compounds of general formula () show good detoxifying activity in this test.

[Table] Pre-emergence antidote test (basic test) General method Fill a small flowerpot (top diameter 6 cm) with horticultural soil, sow cultivated seeds, cover with soil, and press lightly. The substance to be tested as an antidote is then sprayed as a dilute solution (obtained from a wettable powder) in an amount corresponding to 4 kg of active ingredient per hectare. The herbicide is then sprayed in the same manner. Approximately 20-23℃, relative humidity
After 18 days at 60-70%, it is evaluated on a linear scale from 1 to 9, where 1 represents total plant loss and 9 represents undamaged health of the cultivated plants. Plants not protected with antidote were used as controls. Use the following: 1 “Orla 264” corn with α[4-p-trifluoromethylphenoxy]
-Phenoxy]-Propionic acid n-butoxyethyl ester, 1.5 kg per hetar; 2 Metolachlor = N- to “Funk G-522” type Sorghum-millet
(1-Methyl-2-methoxyethyl)-N-chloroacetyl-2-ethyl-6-methylaniline at 1.5 kg per hectare; -2.0Kg/ha of s-triazine; 4 for “Farnese” wheat variety
-ethylamino-6-tert-butylamino-2-
Chloro-s-triazine per hectare
2.0Kg; 5 “Funk G-522” millet with promethrin 2,4-bis-(isopropylamino)-6-methylthio-s-triazine at 4.0Kg per hectare; 6 “Mazurka” ``α- to seed barley
[4-(p-trifluoromethylphenoxy)
-Phenoxy]-Propionic acid n-butoxyethyl ester at 2.0 kg per hectare; 1.0Kg per. Compounds of the formula show good detoxifying activity in these tests. The following results are shown as an example.

【table】

Claims (1)

[Claims] 1. With a suitable carrier, as an antidote, the following formula: {In the formula, R ₁ is - OR ₂ (In the formula, R ₂ represents an alkyl group having 1 to 4 carbon atoms), or - N(R ₃ )(R ₄ ) (In the formula, R ₃ is hydrogen atom or lower alkyl group, R ₄ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aminocarbonyl group), X represents a cyano group, and Q is substituted by a cyano group. lower alkyl group, - alkoxycarbonylalkyl group (however,
The alkyl moiety has 1 to 4 carbon atoms. ), or - represents an ammonium cation or a mono- or dialkylammonium cation (provided that the alkyl moiety has 1 to 4 carbon atoms). } An agent for protecting cultivated plants from pesticide attack, characterized by containing an oxime derivative represented by the following. 2. The protective agent according to claim 1, which contains, together with a suitable carrier, a pesticide and an oxime derivative of the formula as an antidote for cultivated plants. 3. The protective agent according to claim 2, wherein the agricultural chemical is a herbicide. 4. The protective agent according to claim 3, wherein the agricultural chemical is a herbicide comprising 1,2,4-triazines. 5 As an antidote, the following formula: The protective agent according to claim 4, which contains an oxime represented by: 6. The protective agent according to claim 3, wherein the agricultural chemical is a herbicide comprising a chloroacetanilide type herbicide. 7 Pesticides are 4-(phenoxy)-phenoxy-
The protective agent according to claim 3, which is a propionic acid ester herbicide. 8. The protective agent according to claim 3, wherein the agricultural chemical is a herbicide of 4-(pyridyloxy)-phenoxy-propionic acid esters. 9. The protective agent according to claim 1 for treating propagated plants of cultivated plants.