JPS637534B2 - - Google Patents

Description

[Detailed description of the invention] Structural formula (wherein X is alkyl, n is 0, 1 or 2, and R ₁ is phenyl or substituted phenyl). (wherein R ₁ , X and n are as defined above and R ₂ is alkyl, alkenyl or alkynyl) as an intermediate for the production of herbicidal compounds,
It is described in Japanese Patent Application No. 84632-1974.
Especially for the latter herbicidal compound, n is 2, X is 5,
5-dimethyl, _R2 is allyl and _R1 is phenyl, 4-chlorophenyl or 4-methoxyphenyl is taught. Intermediates for the three compounds taught have no or little herbicidal activity. In contrast, the compounds of the present invention have exceptional herbicidal activity. In order for Applicant's compounds to have exceptional herbicidal activity, they must have a halogen as a substituent in the 2-position of the phenyl moiety of the compound. The exact reasons why such substitutions confer exceptional herbicidal activity are not clear. This invention relates to certain novel 2-(2-substituted benzoyl)-cyclohexane-1,3-dione herbicides. The compound of this invention has the following structural formula. (wherein R and R ¹ are hydrogen or C ₁ - C ₄ alkyl,
Preferably methyl, most preferably R and R ¹ are hydrogen and R ² is chlorine, bromine or iodine;
^R3 is hydrogen, or halogen, preferably iodine or chlorine, most preferably ^R3 is hydrogen, and ^R4 is hydrogen, chlorine, bromine, iodine, _C1 - _C4 alkyl, preferably methyl, _{C1- C4} alkoxy,
Preferably methoxy, nitro, trifluoromethyl, most preferably ^R4 is hydrogen and 4-chlorine. The compound of this invention has the following three formulas due to tautomerism. (wherein R, R ¹ , R ² , R ³ and R ⁴ are as defined above). In the above description of the compounds of this invention, alkyl and alkoxy refer to straight-chain and branched structures, such as methyl, ethyl, n-propyl, isopropyl, n-
Includes butyl, sec-butyl, isobutyl and tert-butyl. The compounds of this invention are active herbicides of the common type. That is, it has a herbicidal effect on a wide variety of plants. The method for suppressing undesirable plants according to the present invention consists of applying the above-mentioned compound to an area where the herbicidal effect is desired to be suppressed. The compounds of this invention can be prepared by the following general method. Generally, molar amounts of iodine and substituted benzoyl cyanide are used with a slight molar excess of zinc chloride. Both reagents and zinc chloride are combined in a solvent such as methylene chloride. While cooling, a slight molar excess of triethylamine is slowly added into the reaction mixture. This mixture is stirred at room temperature for 5 hours. The reaction products are removed in the usual manner. The above-mentioned substituted benzoyl cyanides are available from T.S. Oakwood and CAWeisgerber;
Organic Synthesis Collected, Vol. 122 (1955). It can be manufactured by the following method. The synthesis of representative compounds of this invention is illustrated in the following examples. Example 1 2-(2,4-dichlorobenzoyl)-cyclohexane-1,3-dione 1,3-cyclohexanedione 11.2g (0.1 mol), 2,4-dichlorobenzoyl cyanide 20.0
g (0.1 mol), and 13.6 g of anhydrous powdered zinc chloride
(0.11 mol) were combined in 100 ml of methylene chloride. While cooling, add 10.1 g (0.12 g) of toluethylamine.
mol) was added slowly. The reaction mixture was stirred at room temperature for 5 hours and then poured into 2N hydrochloric acid. Separate the aqueous phase and combine the organic phase with 150 ml of 5% Na ₂ CO ₃ aqueous solution.
Washed 4 times with The combined aqueous washings were acidified with HCl, extracted with methylene chloride, dried, and concentrated to yield 25.3 g of crude product. The crude product was dissolved in ether, and 250 ml of 5% copper acetate () was added and stirred. The produced copper salt was filtered, washed with ether, and then stirred with 6N hydrochloric acid to decompose the salt. The extract was washed with ether to give a melting point of 138~
22.15 g of the desired product was obtained at 140°C. (yield 77.7
%). Its structure was confirmed by nuclear magnetic resonance analysis. A table of compounds obtained by the above method is given below. The numbers assigned to each compound are used throughout this specification. [Table] [Table] Herbicidal Screening Test As mentioned above, the compounds described herein produced by the above method are effective and useful in controlling various plant species. The compound according to the present invention was tested as a herbicide by the following method. Pre-emergence weed control test On the day before the treatment date, one seed of eight types of weeds were sown in each box made in loamy sandy soil across the width of the box. The seeds used are as follows. green foxtail
(FT) ( Setaria viridis ), watergrass (WG) ( Echinochloa
crusgalli), wild oat (WO) ( Avena
fatua ), Anual Morning Glory (annal)
morningglory) (AMG) ( Ipomocalacunosa ), velvetleaf (VL)
( Abutilon theophrasti ), Indian mustard
(MD) ( Brassica juncea ), yellow nutsedge
(YNG) ( Cypcrus esculentus ). Enough seeds were sown to produce about 20 to 40 seedlings per row, depending on the size of the plants after germination. Using an analytical balance, 600 mg of the test compound was weighed onto glass weighing paper. The paper and compound were placed in a 60 ml wide-mouth clear bottle and dissolved in 45 ml of acetone or an alternative solvent. Transfer 18 ml of this solution to a 60 ml wide-mouth transparent bottle and dilute with 22 ml of a water-acetone mixture (19:1) containing sufficient amount of polyethylene sorbitan monolaurate emulsifier to make a final solution.
A 0.5% (V/V) solution was prepared. Apply this solution to a linear spray table.
The seeded flats placed above were sprayed at a rate of 80 gallons per acre (748/ha). The application rate is 4 pounds/acre (4.48 Kg/ha). After processing, this flat box(s) is 70~80〓(21.1~
Water was supplied by sprinkling in a greenhouse at a temperature of 26.6°C. Two weeks after treatment, the degree of damage, ie, the degree of inhibition, was determined in comparison with untreated control plants of the same age. For each type, the degree of damage was rated between 0 and 100%. Note that 0% represents no damage and 100% represents complete suppression. The test results are shown in the table. [Table] Post-emergence weeding test It was conducted in the same manner as the pre-emergence weeding test.
However, seeds of eight weed species were sown 10 to 12 days before treatment. Of course, the water supply to the treated flats was limited to the soil surface and not to the leaves of the germinated plants. The results of the post-emergence weed control test are shown in the table. TABLE TABLE The compounds of this invention are useful as herbicides, particularly as pre-emergence herbicides, used at various concentrations and in a variety of ways. In practice, the compounds mentioned herein can be made into herbicidal compositions by mixing their herbicidally effective amounts with auxiliaries and carriers commonly used to suspend the active ingredient for agricultural purposes. Ru. It is recognized that the method of preparation and the method of application of the poison can influence its activity in the application. Therefore, depending on the desired application method, these herbicidal active compounds can be prepared in the form of relatively large granules.
It may be formulated into a wettable powder, an emulsifiable concentrate, a powder, a solution, or several other known types of formulation.
Preferred formulations for pre-emergence herbicidal applications are wettable powders, emulsifiable concentrates and granules. These formulations contain as little as about 0.5% to as much as 95% or more active ingredient. The herbicidal amount is determined by the nature of the seeds or plants to be controlled and the application rate, but from 0.05 pounds (0.0227Kg) to about 25 pounds (11.33Kg), preferably about 0.1 pounds (0.0453Kg) per acre (0.4 hectare). Approximately 10 pounds (4.53Kg). Wettable powders are finely divided particles that are easily dispersed in water or other dispersion media. Wettable powders are applied to soil as dry powders or dispersed in water or other liquids. Typical carriers for wettable powders include clay, kaolin clay, silica and other wettable organic or inorganic diluents. Wettable powders usually contain from about 5% to about 95% active ingredient and small amounts of wetting agents, dispersing agents, or emulsifying agents and are readily wetted and dispersed. An emulsifiable concentrate is a homogeneous liquid composition,
They are readily dispersible in water or other dispersion media and consist only of the active compound and a liquid or solid emulsifier, or contain a liquid carrier such as xylene, heavy aromatic naphthals, isophorone, and other non-volatile organic solvents. For application as herbicides, these concentrates are dispersed in water or other liquid carrier and usually applied by spraying to the area to be treated. Weight % of active ingredient in the composition
will vary depending on the method of application of the composition, but is typically about 0.5% by weight of the herbicidal composition.
Contains 95% of active ingredients. In granular formulations, the poison is in relatively coarse particles and is usually applied undiluted to an area of the plant that is desired to be controlled. As carriers for granular preparations,
There are sand, clay, bentonite clay, vermiculite, perlite and other organic and inorganic materials that absorb or are coated with poisonous agents. Granular formulations are usually about 5% to about 25%
active ingredients such as heavy aromatic naphtha, kerosene or other petroleum distillates, surfactants such as vegetable oils, and/or adhesives such as dextrins, glues or synthetic resins. Include. Typical wetting agents, emulsifying agents, and dispersing agents used in agricultural formulations include, for example, alkyl and alkylaryl sulfonates and sulfates and their sodium salts; polyhydrogenated alcohols; although other types of surfactants , these are commercially available. When using surfactants, the herbicide usually contains 0.1% to 15%. Powders are free-flowing mixtures of the active ingredient and finely divided talc, clay, flour and other organic and inorganic solids that act as dispersants and carriers for poisonous agents and are used for incorporation into soil. Ru. Pastes are homogeneous suspensions of finely divided poisonous agents in a liquid carrier such as water or oil and are used for special purposes. These preparations are usually
They contain about 5% to 95% active ingredient by weight and small amounts of wetting agents, dispersing agents, and emulsifying agents to facilitate dispersion. When applied, the paste is usually diluted and applied as a spray to the required area. Other formulations used for herbicide applications include simply dissolving the active ingredient in a dispersion medium, which
Completely soluble in acetone, alkylated naphthalenes, xylene and other organic solvents to the desired concentration.
Pressure sprays, typically aerosols, are used in which the active ingredient is divided into fine powders by evaporation of a low boiling solvent carrier such as Freon. The phytotoxin compositions of this invention are applied to plants in any convenient manner. That is, powder and liquid compositions are applied to plants by power dusters, boom and manual sprayers, and powder sprayers. This composition is effective at very low doses and is therefore applied as a powder or spray from aircraft. For the purpose of regulating seed germination, inhibiting germination growth, for example, powder and liquid compositions are conveniently applied to the soil to reach at least 1/2 inch (1.25 cm) below the soil surface. The toxicant compositions do not need to be mixed with the soil particles, so these compositions can be simply sprayed onto the surface of the soil or
Can be applied by simply sprinkling water. The poison compositions of this invention can also be applied as added to irrigation water to fields to be treated. In this application method, water is absorbed into the soil as well as seeped into the soil. Powder, granular compositions or liquid formulations applied to the soil surface can be distributed below the soil surface by conventional methods such as discing, dragging or mixing. Other additives may be included in the phytotoxin compositions of this invention. For example, fertilizers, pesticides and the like can be used as auxiliaries or in combination with any of the auxiliaries mentioned above. Other phytotoxic compounds that may be used with the above compounds include, for example: 2,4-dichlorophenoxyacetic acid, 2,
4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid, and salts thereof,
their esters and amides, 2,4-bis(3-methoxypropylamino)-6-methylthio-S-triazine, 2-chloro-4-ethylamino-6-isopropylamino-S-triazine,
and triazine derivatives such as 2-ethylamino-4-isopropyl-amino-6-methyl-mercapto-S-triazine, 3-(3,5-dichlorophenyl)-1,1-dimethylurea and 3-(para urea derivatives such as -chlorophenyl)-1,1-dimethylurea, acetamides such as N,N-allyl-α-chloroacetamide and its analogues, 3
-benzoic acids such as amino-2,5-dichlorobenzoic acid, S-propyl N,N-dipropylthiocarbamate, S-ethyl N,N-dipropylthiocarbamate, S-ethyl cyclohexyl thiocarbamate, S-ethyl Thiocarbamates such as hexahydro-1H-azepine-1-carbothioate and its analogs, 4-(methylsulfonyl)-2,6-dinitro-N,N-
Substituted aniline, 4-trifluoromethyl-2,6
Anilines such as -dinitro-N,N-di-n-propyl aniline and 4-tri-fluoromethyl-2,6-dinitro-N-ethyl-N,N-di-n-butylaniline. Fertilizers used with active ingredients include, for example, ammonium nitrate, urea and superphosphates. Other useful additives include compost, mulch, humus, sand, and other substances in which plants can root and grow.

Claims (1)

[Claims] 1. A compound having the following general formula, (wherein R and R ¹ are hydrogen or C ₁ -C ₄ alkyl; R ² is chlorine, bromine or iodine; 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. ). 2. A compound according to claim 1, wherein R and R ¹ are hydrogen or methyl; R ² is chlorine, bromine or iodine; R ³ is hydrogen; and R ⁴ is hydrogen, chlorine, nitro or trifluoromethyl. . 3. The compound according to claim 2, wherein ^R4 is a substituent at the 4- or 5-position. 4 R and R ¹ are hydrogen; R ² is chlorine, bromine or iodine; R ³ is hydrogen; and R ⁴ is 4-chlorine, 5-chlorine, 4-nitro, 5-
A compound according to claim 2 which is CF ₃ or hydrogen. 5. The compound according to claim 4, wherein R ² is chlorine. 6 R is methyl, R ¹ is methyl, R ² is 2-chlorine,
A compound according to claim 1, wherein R ³ is hydrogen and R ⁴ is 6-chlorine. 7. A compound according to claim 1, wherein R is hydrogen, R ¹ is hydrogen, R ² is 2-chlorine, R ³ is hydrogen, and R ⁴ is 4-chlorine. 8. A compound according to claim 1, wherein R is hydrogen, ^R1 is hydrogen, ^R2 is 2-chlorine, ^R3 is hydrogen, and ^R4 is 6-chlorine. A compound according to claim 1, wherein 9 R is hydrogen, R ¹ is hydrogen, R ² is 2-chlorine, R ³ is 3-chlorine, and R ⁴ is 6-chlorine. 10 R is hydrogen, R ¹ is hydrogen, R ² is 2-chlorine, R ³
A compound according to claim 1, wherein is hydrogen and ^R4 is 5-trifluoromethyl. 11 R is hydrogen, R ¹ is hydrogen, R ² is 2-chlorine, R ³
A compound according to claim 1, wherein is 3-chlorine and ^R4 is 4-chlorine. 12 R is hydrogen, R ¹ is hydrogen, R ² is 2-chlorine, R ³
A compound according to claim 1, wherein is 3-chlorine and ^R4 is 4-methoxy. 13 R is hydrogen, R ¹ is hydrogen, R ² is 2-chlorine, R ³
2. A compound according to claim 1, wherein is hydrogen and ^R4 is 4-bromine. 14. A method for controlling undesirable plants, which comprises applying a herbicidally effective amount of a compound of the following formula to an area where suppression is desired: (wherein R and R ¹ are hydrogen or C ₁ -C ₄ alkyl; R ² is chlorine, bromine or iodine; 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. ). 15. The method of claim 14, wherein R and R ¹ are hydrogen or methyl; R ₂ is chlorine, bromine or iodine; R ³ is hydrogen; and R ⁴ is hydrogen, chlorine, nitro or trifluoromethyl. . 16. The method according to claim 15, wherein 16 R ⁴ is a 4- or 5-position substituent. 17 Claims in which R and R ¹ are hydrogen; R ² is chlorine, bromine or iodine; R ³ is hydrogen; and R ⁴ is 4-chlorine, 5-chlorine, 4-nitro, 5-CF ₃ or hydrogen The method according to paragraph 15. 16. The method of claim 15, wherein 18R is chlorine. 19 R is methyl, R ¹ is methyl, R ² is 2-chlorine,
15. The method of claim 14, wherein ^R3 is hydrogen and ^R4 is 6-chlorine. 20 R is hydrogen, R ¹ is hydrogen, R ² is 2-chlorine, R ³
15. The method of claim 14, wherein is hydrogen and ^R4 is 4-chlorine. 21 R is hydrogen, R ¹ is hydrogen, R ² is 2-chlorine, R ³
15. The method of claim 14, wherein is hydrogen and ^R4 is 6-chlorine. 22 R is hydrogen, R ¹ is hydrogen, R ² is 2-chlorine, R ³
15. The method of claim 14, wherein is 3-chlorine and ^R4 is 6-chlorine. 23 R is hydrogen, R ¹ is hydrogen, R ² is 2-chlorine, R ³
15. The method of claim 14, wherein is hydrogen and ^R4 is 5-trifluoromethyl. 24 R is hydrogen, R ¹ is hydrogen, R ² is 2-chlorine, R ³
15. The method of claim 14, wherein is 3-chlorine and ^R4 is 4-chlorine. 25 R is hydrogen, R ¹ is hydrogen, R ² is 2-chlorine, R ³
15. The method of claim 14, wherein is 3-chlorine and ^R4 is 4-methoxy. 26 R is hydrogen, R ¹ is hydrogen, R ² is 2-chlorine, R ³
15. The method of claim 14, wherein is hydrogen and ^R4 is 4-bromine.