HU191288B - Herbicide preparates consisting 2-/2-substituated-benzoil/-1,3-cyclohexan-dion-derivatives - Google Patents

Abstract

The present invention relates to herbicidal compositions comprising 2- (2-substituted-benzoyl) -1,3-cyclohexane-dione derivatives of formula I wherein R and R 1 are hydrogen or C 1-4 alkyl; R2 is chloro, bromo or iodo; R3 is hydrogen, iodo or chloro; and R 4 is hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, nitro or trifluoromethyl. Rs -1-

Description

The present invention relates to herbicidal compositions containing 2- (2-substituted-benzoyl) -1,3-cyclohexanedione derivatives.

Japanese Patent 84632-1974 discloses compounds of formula A wherein X is alkyl, n is 0.1 or 2, and R is phenyl or substituted phenyl. These compounds are intermediates in the preparation of herbicides of the formula (B) compounds of the formula wherein R, X and n are as defined above and R ₂ alkyl, alkenyl or alkynyl. , Compounds this latter group are particularly good herbicidal activity, in which n is 2, X is 5,5-diinetilcsoport, R ₂ alkyl, and R is phenyl, 4-chloro-phenyl, or

4-methoxy-phenyl.

The precursor intermediates have no or little herbicidal activity.

U.S. Patent Nos. 4,202,840 and 4,227,919 disclose herbicidal compositions containing substituted 3,5-cyclohexanedione derivatives.

The effect of the herbicidal compositions of the present invention is superior to the known compositions. Formulations in which the active compounds are substituted with a halogen at the 2-position of the phenyl group show particularly favorable herbicidal activity. The reason for the excellent herbicidal action of these preparations is still unknown to us.

The present invention therefore relates to a herbicidal composition comprising as active ingredient a novel 2- (2-substituted-benzoyl) -cyclohexane-1,3-dione derivative of the formula (I). In this formula R and R ^{1 are} hydrogen or C 1-4 alkyl, preferably methyl, especially R and R ¹ are hydrogen, R ^{2 is} chlorine, bromine or iodine, R ^{3 is} hydrogen or halogen, preferably iodine or chlorine, especially is hydrogen and R ⁴ is hydrogen, chlorine, bromine or iodine, C1-4 alkyl, preferably methyl, C1-4 alkoxy, preferably methoxy, and nitro, or trifluoromethyl group, ^R4 represents in particular a hydrogen atom or 4-chloro.

The compounds of formula (I) may exist in the forms corresponding to the tautomeric formulas (Ia), (Ib) and (Ic). In these formulas, R, R ¹ , R ² , R ³ and R ⁴ are as defined above.

The compounds of formula (I) can be alkyl or alkoxy substituents, both linear and branched. Examples include methyl, ethyl, n-propyl, isopropyl, η-butyl, sec-butyl, isobutyl and tert-butyl.

Herbicidal compositions containing the compounds of formula (I) as active ingredients are active against a general type of agent and a wide variety of plant species. The unwanted plants are controlled with the compositions of the invention by applying them in an effective amount to the areas in which the unwanted plants are to be controlled.

Compounds of formula (I) are prepared according to the general method outlined in Scheme A.

Generally, diol and substituted benzoyl cyanide are used in molar equivalents, while zinc chloride is used in small amounts. The two reagents and the zinc chloride are reacted with one another in a solvent such as methylene chloride. A small excess of triethylamine was slowly added to the reaction mixture under cooling. The mixture was stirred at room temperature for 5 hours.

The reaction product is worked up by conventional methods.

substituted benzoyl cyanide starting material according to T. S. Oakwocd and C. A. Weisgerbcr according to the method of Organic Synthesis Collected, Vol.

III. pp. 122 (1955).

The following examples further illustrate the preparation of compounds of formula (I).

Example 1

2- (2,4-Dichlorobenzoyl) -cyclohexane-1,3-dione Compound (1)

11.2 g (0.1 mol) of 1,3-cyclohexanedione, 20.0 g (0.1 mol) of 2,4-dichlorobenzoyl cyanide and 13.6 g (0.11 mol) of anhydrous powdered zinc chloride is added to 100 ml of methylene chloride. Triethylamine (10.1 g, 0.12 mol) was added slowly while cooling. The reaction mixture was stirred for 5 hours and then poured into 2N hydrochloric acid. The aqueous phase is discarded and the organic phase is washed with 150-150 mL of 5% sodium carbonate solution. The aqueous washings were combined and acidified with HCl, m.p. extracted with ethylene chloride, dried and concentrated to give 25.3 g of crude product. The crude product was dissolved in ether and the solution was mixed with 250 ml of 5% copper (II) acetate. The resulting copper salt was collected by filtration, washed with ether and mixed with 6N hydrochloric acid to decompose the salt. The extract is washed with ether to give 22.15 g of the desired tea.

138-140 ° C. Yield 77.7%.

The structure is confirmed by instrumental analysis.

The following table lists some of the compounds prepared as described in the previous example. Each compound is numbered.

191,288

Table I Compounds of Formula I

Dry. song R R ¹ R ² R ³ R ⁴ n ³ , ^0, or m.p. I -cn ₃ CH, 2-Cl H H 1.5613 Second -ch ₃ -ch ₃ 2-Cl H 4-0 1.5655 Third -ch ₃ -ch ₃ 2-C1 H 6-0 103-108 * 4 H H 2-Cl H 4-0 138-140 5th -ch ₃ -ch ₃ 2-Br H H 6th -ch ₃ -ch ₃ 2-Cl H 5-0 74-77 7th H H 2-Cl H 5-0 104-107 8th H H 2-Br H H 93-96 9th H H 2-Cl H H 79-87 10th H H 2-J H H 66-70 11th H H 2-0 H 4 — N0 ₂ 118-122 12th H H 2-Cl H 6-0 143-148 13th H H 2-Cl H 5-Br 109-115 14th H H 2-J 3-J 5-J 164-167 15th H H 2-0 H 5-CH ₃ 60-65 16th H H 2-0 H 4-0CH ₃ 79-86 17, H H 2-0 H 4 — CH ₃ 60-63 18th H H 2-0 3-0 6-0 19th H H 2-0 H 5-0CH ₃ 77-80 20th H H 2-0 H 3-0 80-90 21st H H 2-0 H 5 — CF ₃ 74-75 22nd H H 2-0 H 5-NO ₂ 140-143 23rd H H 2-0 3-0 4-0 152-154 24th H H 2-0 3-C1 4-0CH ₃ 169-170 25th H H 2-0 H 4-Br 104-107

* Compound prepared according to the example.

Herbicide impact studies

As mentioned above, the compounds thus prepared are phytotoxic and therefore useful in the control of various unwanted plant species in the form of compositions. The effects of herbicidal formulations containing such agents were investigated as follows.

Investigation of pre-emergence herbicide effect

One day before treatment, seeds of eight different weed species were sown in clayey-sandy soil. One row of each variety was sown along the entire width of the plot. The following weeds were used for the study: green marigold (FT) (Setaria viridis), cockroach (WG) (Echinochloa crusgalli), wild oat (WO) (Avena fatua), perennial yarrow (Ipomea lacunosa), silkworm (VL) (Abutilon theophrasti), Indian Mustard (MD) (Brassica juncea), Red Pigwort (PW) (Amaranthus retroflexus), and Yellow Mud (YNG) (Cyperus esculentus). Large seeds were sown with about 20-40 seedlings per row after emergence, depending on the size of the plants.

On an analytical balance, 600 mg of the test compound was weighed on a batch paper, and the ve45 compound was then placed in a 60 mL wide mouth clear flask, dissolved in 45 mL of acetone or equivalent. 18 ml of this solution were then transferred to another 60 ml wide mouth slit, with 22 ml (19: 1) of water / accton, which was an emulsifier in 0.5% polyoxyethylene sorbitan monolaurate. was diluted. Hy gave a 0.5% (v / v) solution. The solution was then sprayed onto the sown area at a rate of 748 liters / hectare. In this way the application rate was 4.48 kg / ha gg.

After treatment, the pots were placed in a greenhouse and kept at 21-27 ° C while the pots were watered with water. Two weeks after treatment, the extent of damage or eradication was determined by comparing two untreated plants of the same age. The degree of damage is given on a 0-100% scale, where 0% means no damage, while 100% indicates complete destruction.

The results obtained are shown in Table II. table.

191,288

II. spreadsheet

Pre-emergence herbicidal effect

The application rate is 4.48 kg / ha

Dry. song FT WG WO AMG VL MD PW YNG First 100 90 20 40 65 50 35 80 Second 80 90 0 30 80 90 20 90 Third 0 0 0 40 40 40 0 0 4th 100 100 50 35 100 100 90 95 5th 100 95 65 35 90 85 50 95 6th 50 25 0 25 100 100 35 80 7th 80 90 10 60 100 100 100 80 8th 95 95 45 40 100 80 95 95 9th 95 100 55 30 100 90 100 95 10th 100 100 60 20 85 100 100 95 11th 85 100 30 40 100 100 100 95 12th 85 85 90 75 80 95 90 90 13th 85 75 10 10 85 65 95 90 14th 40 10 80 0 65 40 65 100 15th 40 60 20 30 100 30 75 95 16th 80 80 20 55 75 90 40 95 17th 20 - 10 25 100 95 85 90 18th 65 - 30 70 100 100 85 90 19th 45 60 0 30 40 0 20 60 20th • 30 85 20 40 95 85 40 45 21st 80 100 0 80 100 100 95 95 22nd 20 10 0 20 75 30 45 10 23rd 45 45 10 0 100 85 100 95 24th - 100 0 25 70 90 - 100 25th - 100 25 80 100 100 - 100 active ingredient of the comparator THE. 20 25 25 20 20 25 25 20 B 25 20 20 25 20 20 25 25 C. 25 25 25 25 20 25 20 25 D. 20 25 25 25 20 25 20 25

The active ingredients of the comparators are those disclosed in U.S. Patent Nos. 4,202,840 and 4,227,919.

A: 1-Hydroxy-2-acetyl-4,4,6,6-tetramethyl-cyclohexane-3,5-dione,

B; 1-hydroxy-2-isovaleryl-4,4,6,6-tetramethylcyclicolxane-3,5-dione,

C: 1-hydroxy-2-propionyl-4,4,6,6-tetramethylcyclohexane-3,5-dione,

D: 1-Hydroxy-2-butynyl-4,4,6,6-tetramethylcyclalexane-3,5-dione.

- - The breed did not germinate for unknown reasons.

Investigation of the post-emergence herbicidal effect

This test was carried out in a similar manner to the pre-emergence test, except that seeds of eight different weed species were sown 10-12 days prior to treatment. We also watered the treated pots so that the water asks you to sit on the soil surface and not on the germinated plants.

The results of the post-emergence herbicide test are shown in Table III. table.

-4 ,. 191,288

III. spreadsheet

Post-emergence herbicide heat:

The application rate is 4.48 kg / ha

Dry. No. FT WG WO AMG VL MD PW YNG

First 60 70 20 40 60 60 35 60 Second 30 70 0 50 90 85 30 80 Third 0 30 0 70 100 90 55 70 4th 95 98 20 98 100 100 30 95 5th 80 80 75 50 60 80 0 95 6th 40 40 10 60 100 100 75 65 7th 60 75 40 60 100 75 100 75 8th 85 80 75 70 95 80 90 90 9th 85 80 75 70 95 80 90 90 10th 95 85 90 60 95 95 80 95 11th 50 80 35 55 3 100 100 95 80 12th 45 75 50 55 75 60 50 80 13th 30 60 20 60 80 50  60 70 14th 20 10 20 50 45 40 40 0 15th 65 95 0 65 95 30 100 80 16th 65 80 20 85 85 30 30 80 17th 75 80 30 70 100 100 85 90 18th 100 95 10 100 100 100 100 90 19th 60 80 40 70 100 75 80 90 20th 65 · 80 10 85 95 95 100 70 21st 30 55 0 80 100 80 65 80 22nd 0 30 0 20 45 0 30 20 23rd 85 90 40 85 100 95 100 90 24th 0 80 0 70 90 74 - 100 25th 100 100 75 90 100 100 - 100

- = The breed did not germinate for unknown reasons.

active ingredient of the comparator THE. 25 25 25 25 20 25 25 25 B 25 20 25 25 25 20 25 25 C. 25 25 25 20 25 25 25 25 D. 20 25 25 25 25 25 25 25

The compounds of the formula I have a herbicidal activity and are used primarily as active ingredients of pre-emergence herbicides. The method of application of the gas and the concentration of the active ingredient may vary. The herbicidal compositions of the present invention contain an effective amount of the active ingredient in admixture with excipients and carriers. These excipients and carriers are intended to: · facilitate the dispersion of the active ingredients and make them suitable for agricultural use. The formulation and mode of administration will affect its effect in a given application. The active compounds of Formula I may be formulated in the form of granules of relatively large particle size, and may be formulated as wettable powders, emulsifiable concentrates, spray powders, solutions, or formulations of any known type depending on the intended use. Preferred pre-emergence herbicidal formulations are wettable powders, emulsifiable concentrates and granules.

The compositions of the present invention may contain the active ingredient in very low concentrations to high concentrations. The amount of active ingredient in these formulations may range from about 0.5% to about 95% by weight, or more.

The effective amount of herbicide depends on the nature of the crop to be controlled and the type of seed. The amount of active ingredient used ranges from about 0.056 to about 28 kg / ha, preferably about 0.14 to about 14 kg / ha.

191,288

Wettable powders are formulations of finely divided particles which are readily dispersible in water or other dispersants. Wettable powders may be applied to the soil in the form of a dry powder or a dispersion in water or other liquid. Typical lubricants for wettable powders include fuller earth, kaolin chalk, silica, or other readily wettable organic or inorganic diluents. Wettable powders are generally formulated to contain from about 5% to about 95% by weight of the active ingredient and will usually include a small amount of wetting, dispersing or emulsifying agent to assist in wetting or dispersing.

Emulsifiable concentrates are liquid homogeneous compositions which are dispersible in water or other dispersants and contain, in addition to the active ingredient, a liquid or solid dispersant, or may include a liquid carrier such as xylene, heavy aromatic hydrocarbons, isophorone and other volatile organic solvents. For herbicidal application, these concentrates are dispersed in water or other liquid vehicle and usually applied as a spray on the surface to be treated. The percentage of active ingredient will vary depending on the composition employed and the route of administration. Usually the amount used is from about 0.5% to about 96% by weight of the active ingredient in the herbicidal composition.

Granules are formulations in which the active ingredient is contained in relatively coarse granules and which are usually applied undiluted to the surface on which the growth of undesired plants is desired. Typical carriers for granules are sand, fuller earth, bentonite chalk, vermiculite, perlite and other organic or organically absorbent substances which can be absorbed or coated with the active ingredient. Granules generally contain from about 5% to about 25% by weight of the active ingredient and include surfactants such as heavy aromatic hydrocarbons, kerosene or other mineral oil fractions or vegetable oils; and / or adhesives such as dextrin, glue or synthetic resins.

Typical wetting, dispersing or emulsifying agents for use in agricultural formulations include alkyl and alkylaryl sulfonates and sulfates, and their sodium salts; polyhydroxyalkolols, but other types of surfactants that are commercially available may also be used. The amount of surfactant in the herbicidal compositions is generally 0.1 to 15% by weight.

Powders which are free-flowing mixtures of the active ingredient with finely divided solids such as talc, chalk, flour and other organic or organic substances which serve as dispersants and carriers, are admixed with the soil. '. Pastes are homogeneous suspensions of a finely divided solid active ingredient in a liquid carrier such as water or oil. These pastes are used for appropriate purposes. Pastes typically contain from about 5% to about 95% by weight of active ingredient, together with a small amount of a wetting, dispersing or emulsifying agent, to facilitate dispersion. For use, the pastes are usually diluted and sprayed onto the surface to be protected.

Other useful formulations suitable for herbicidal use are solutions of the active ingredient in a dispersant in which it is completely soluble in the desired concentration. These include acetone, alkyl naphthalenes, xylene and other organic solvents. Further formulations are pressurized sprays, typical aerosols, in which the active ingredient is in finely divided form! is dispersed in a low boiling solvent carrier. Freon can be used for this purpose.

The herbicidal compositions of the invention are applied to the plants in a conventional manner. Thus, the powders and liquid formulations are sprayed or sprayed on the plants using a spray gun, hand or machine sprayers. The formulations can also be sprayed or sprayed on aircraft to be treated, as they are effective in very small doses. In order to modify or suppress the growth of germinating seeds or emerged plants, for example, dusts and liquid compositions are applied to the soil in conventional manner or mixed into the soil at a depth of at least 12.5 mm. It is also not necessary to mix these formulations with the soil particles, since they are effective even when sprayed or sprayed on the soil surface. In addition, the compositions of the invention may be incorporated into the soil to be treated together with the irrigation water. This mode of application allows the formulation to be absorbed into the soil when irrigation water enters. Dusts, granules or liquid formulations which are applied to the soil can be applied to the soil in the usual manner, such as dialing, brushing or mixing operations.

The herbicidal compositions of the invention may also be mixed with other additives, such as fertilizers, other pesticides, in addition to the aforementioned excipients. In addition to the active compounds of formula (I), the compositions of the present invention may be formulated with, for example, the following active compounds: 2,4-dichlorophenoxyacetic acids,

2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid and their salts, esters or amides; and triazine derivatives such as 2,4-bis (3-methoxypropylamino) -6-methyl thio-s-triazine, 2-chloro-4- (ethylamino) -6 (bopropylamino) -s-triazine and 2- (ethylamino) -4- (isopropylamino) -6- (methylthio) ) -s-triazine; urea derivatives such as 3- (3,5-dichlorophenyl) -1,1-dimethylurea and 3- (p-chlorophenyl) -1,1-dimethylurea; acetamides such as Ν, Ν-diallyl-α-chloroacetamide; benzoic acid such as 3-amino-2,5-dichlorobenzoic acid; thiocarbamates such as S-propyl-N, N-dipropylthiocarbamate, Set 1-NN-dipropylthiocarbamate, S-ethylcyclohexylethylthiocarbamate, S-ethylhexahydro-1H-azepine-1-carbothioate; anilines such as 4- (methylsulfonyl) -2,6-dinitroN-N-substituted-aniline, 4- (trifluoromethyl) -2,6-dinitro-N / N-di (n-propyl) aniline and - (trifluoromethyl) -2,6'dini ro-N-ethyl-N, N-di (n-butyl) aniline. SUMMARY OF THE INVENTION

Fertilizers suitable for use in formulations of 191,288 include ammonium nitrate, urea and superphosphate. Other useful materials are those in which the plants shed or grow roots, such as compost, farmyard manure, humus and sand.

The composition of the compositions of the present invention is illustrated by the following examples.

Claims (13)

CLAIMS 1. A herbicidal composition comprising ^: 0.01 to 95% by weight, as an active ingredient, of a 2- (2-substituted-benzoyl) -1,3-cyclohexane dione derivative of formula (I): R and R ^{1 are} hydrogen or C 1-4 alkyl; R ^{2 is} chloro, bromo or iodo; R ^{3 is} hydrogen, iodine or chlorine and R ^{4 is} hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro or trifluoromethyl - one or more additives such as a liquid or solid carrier or diluent, preferably petroleum. water, acetone, attapulgite or calcium carbonate and optionally a mixture of surfactants, preferably oil soluble sulfonates and polyoxyethylene ethers, sodium dialkylnaphthalene sulfonate, polyoxyethylene ether and / or sodium lignin sulfonate. The herbicidal composition according to claim 4z, wherein the active ingredient is a compound of formula (I) wherein: R and R ^! hydrogen or methyl; R ^{2 is} chloro, bromo or iodo; R ^{3 is} hydrogen; R ^{4 is} hydrogen, chlorine, nitro or trifluoromethyl. The herbicidal composition according to claim 2, wherein the active ingredient is a compound of formula (I) wherein R ^{4 is in the} 4-position or in the f-position. The herbicidal composition according to claim 2, characterized in that it contains as an active ingredient a compound of the formula (I) in which R and R ^{1 are} hydrogen; R ^{2 is} chloro, bromo or iodo; R ^{3 is} hydrogen; and R ^{4 is} chloro at the 4-position, chloro at the 5-position, nitro at the 4-position, trifluoromethyl at the 5-position or hydrogen. 5. The herbicidal composition according to claim 4, wherein the active ingredient is a compound of formula (I) wherein R ² is chlorine. 6. The herbicidal composition according to claim 1, wherein the active ingredient is a compound of formula (I) wherein R is methyl, R ^{1 is} methyl, R ^{2 is} chloro, R ^{3 is} hydrogen and R ^{4 is} hydrogen. chlorine atom. 7. The herbicidal composition according to claim 1, wherein the active ingredient is a compound of formula (I) wherein R is hydrogen, R ^{1 is} hydrogen, R ^{2 is} chloro, R ^{3 is} hydrogen, and R ^{4 is} hydrogen. · chlorine idle. 8 A herbicidal composition according to claim 1, characterized in that it contains the active substance (I) compound wherein R is hydrogen, ^R¹ is hydrogen, R ² 2-position is a chlorine atom, R ³ is hydrogen and R ⁴ 6 is chloro; . 9. The herbicidal composition according to claim 1, wherein the active ingredient is a compound of formula I wherein R is hydrogen, R ^{1 is} hydrogen, R ^{2 is} chloro, R ^{3 is} chloro and R ⁴ Chlorine ltom 6 position. 10. The herbicidal composition according to claim 1, wherein the active ingredient is a compound of formula (I) wherein R is hydrogen, R ^{1 is} hydrogen, R ^{2 is} chloro, R ^{3 is} hydrogen, and R ^{4 is} 5. trifluorinetl group. 11. The herbicidal composition according to claim 1, wherein the active ingredient is (I) -713 It contains a compound of Formula 191,288 wherein R is hydrogen, R ^{1 is} hydrogen, R ^{2 is} chloro, R ^{3 is} chloro and R ^{4 is} chloro. 12. A herbicidal composition according to claim 1, wherein the active ingredient comprises (1) a compound of the formula wherein R is hydrogen, ^R1 is hydrogen, ^R2 in position 2 klórrtoin, R ^{in the} 3-position chlorine atom and R ⁴ Methoxy group 4. 13. A herbicidal composition according to claim 1, characterized izzal that contains the active substance (I) álta5 Compound general, where R is hydrogen, ^R1 is hydrogen, ^R2 in position 2 klórltom, R ³ is hydrogen, and R ⁴ 4- of bromine.