JPH0566921B2 - - Google Patents

Description

The scope of the claims 1 Formula () of the effective amount as a herbicide

2-[1-(3-trans-chloroallyloxyimino)propyl]-5-(2-ethylthiopropyl)-cyclohexane represented by the formula: (wherein R ¹ is 3-trans-chloroallyl) -1,3-
A herbicidal composition comprising a dione or a compatible salt thereof and a compatible carrier. 2. The herbicidal composition according to claim 1, wherein the carrier comprises cereal oil. 3 0.02-0.6% by weight of the compound of formula (); 0.001
The herbicidal composition of claim 1, comprising -0.15% by weight emulsifier; 0.08-2.5% by weight organic solvent and about 95-99% by weight water. 4. The herbicidal composition of claim 3 comprising about 0.25 to 2% by weight of cereal oil. 5. Herbicidal composition according to claim 1, comprising a concentrated composition comprising 23-27% by weight of a compound of formula (); 2-4% by weight of an emulsifier and about 70-75% by weight of an organic solvent. . BACKGROUND OF THE INVENTION The present invention relates to trans-2-[1-(3-chloroallyloxyimino)propyl]-5-(2-ethylthiopropyl)cyclohexane-1,3-dione and salts thereof and such compounds. Regarding its use as a herbicide. Inventor's USP No. issued April 3, 1984.
The inventor of 4440566 formula:

[Formula] (wherein R is most preferably alkyl of 1 to 3 carbon atoms, most preferably ethyl or propyl; R ¹ is most preferably 3-trans-chloroallyl or 4-chlorobenzyl; ² and R ³ are each alkyl of 1 to 3 carbon atoms or one of R ² or R ³ is hydrogen;
the other is alkylthioalkyl having 2 to 8 carbon atoms, most preferably each of R ² and R ³ is methyl or one of R ² or R ³ is hydrogen and the other is 2-ethylthiopyrropyro. discloses a compound having a pill). The inventor's patent teaches that these compounds exhibit herbicidal activity on grasses and are safe on broadleaf crops. SUMMARY OF THE INVENTION One of the compounds encompassed within USP No. 4440566 (i.e., see the formula below where R is ethyl) has surprising properties compared to other compounds including its congeners where R is propyl. It was found that it exhibits excellent herbicidal activity. This is particularly surprising since such analogs where R is propyl are very good herbicides. In addition to exhibiting pre-emergence activity, the compounds of the present invention are useful for Bermudagrass, foxtail, crabgrass, volunteer corn, native sorghum, barnyardgrass, and broadleaf signalgrass. (broad leaf Signalgrass), Goosegrass, red rice
rice), Sprangletop, seedling Johnson grass and Rhizone Johnson grass.
It exhibits excellent post-emergence herbicide activity against grasses. The compounds of the formula exhibit excellent phytotoxicity to grasses even at very low application rates, yet can be safely applied to broadleaf crops at such application rates. Accordingly, the compounds of the present invention are particularly useful for controlling grass weeds in broadleaf crops, and are especially useful for controlling grass weeds in soybean crops. The compound of the present invention has the following formula:

It can be represented by the formula: where R ¹ is 3-transchloroallyl. The present invention also includes compatible salts of compounds of formula. As is well recognized, compounds of the type formula () exist as tautomers. This compound also has two asymmetric carbon atoms and can also exist as optical isomers. The above formula is intended to include the respective tautomers as well as the individual optical isomers and mixtures thereof and the respective tautomers and optical isomers and mixtures thereof. In another aspect of the invention, there is provided a herbicidal composition comprising a compatible carrier and a herbicidally effective amount of a compound of the invention or a mixture thereof. According to the present invention, there is provided a method for interfering with or suppressing the growth of undesirable herbaceous vegetation, the growth environment and/or foliage of such vegetation being treated with a compound of the present invention or a mixture thereof as a herbicide. A method is provided comprising treating with an effective amount. In accordance with the present invention, the growth environment and/or foliage of such vegetation is treated with an amount of a compound of the present invention or a mixture thereof effective to control plant growth, Also provided is a method of controlling plant growth characterized by changing the growth pattern. The present invention also provides intermediates for the compounds of the present invention and methods for making the compounds of the present invention. The invention is further described below. DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS THEREOF Compounds of formula () may be conveniently prepared by the following schematically illustrated method: (wherein R ¹ is 3-trans-chloroallyl). The process may be conveniently carried out by contacting compound (A) and 3-trans-chloroallyloxyamine (B), preferably in an inert organic solvent. Typically, the process uses 1 to 2, preferably 1.05 to 1.2, moles of 3-trans-chloroallyloxyamine (B) per mole of compound (A) at a temperature of about 0 to 80°C, preferably It is carried out at a temperature in the range of about 20-40°C for about 1-48 hours, preferably about 4-12 hours. Suitable inert organic solvents that can be used include, for example, lower alkanols such as methanol, ethanol, ethers such as ethyl ether; methylene chloride. Two phases of water and immiscible organic solvents (eg hexane), etc. and compatible mixtures can also be used. Trans-chloroallyloxyamine is a known compound, for example, the inventor's USP No. 4440566
It can be produced by a known method such as that described in . The hydrochloride salt of trans-chloroallyloxyamine can be conveniently used by neutralizing it in situ with an alkali metal alkoxide. The starting materials of formula (A) are listed under inventor's USP No.
It can be produced by the general method described in No. 4440566. Compatible salts of formula () can be prepared by conventional methods, eg, by reacting a compound of formula with a base having the desired cation, such as sodium hydroxide, potassium hydroxide, and the like. Subsequent modification of the cations of the salts mentioned above can be carried out by ion exchange through the use of ion exchange resins with the desired cations. General Process Conditions The reaction products can be recovered from the reaction product mixture by any suitable separation and purification method, such as chromatography. For example, suitable separation and purification methods are illustrated in the Examples provided below. The above reaction is generally carried out in a liquid phase, meaning that the reaction is carried out at reflux and the pressure is equal to the temperature (boiling point).
Pressure is generally not important except in influencing the Therefore, these reactions generally require 300 to
It is carried out at a pressure of 3000 mm Hg, conveniently at about atmospheric or ambient pressure. Although typical or preferred process conditions (eg, reaction temperature, time, molar ratios of reactants, solvents, etc.) are given, it should be recognized that other process conditions can also be used. Optimal reaction conditions (eg, temperature, reaction time, molar ratio, solvent, etc.) may vary depending on the particular drug or organic solvent used, but can be determined by routine optimization methods. When a mixture of optical isomers is obtained, each optical isomer can be obtained by a conventional resolution method. Geometric isomers can be separated by conventional separation methods that depend on the differences in physical properties between the isomers. However, it is generally preferred to use the desired isomeric starting material in the reaction. DEFINITIONS As used herein, unless otherwise specified, the following terms have the following meanings:
Refers to salts that do not significantly adversely alter the herbicidal properties of the parent compound. Suitable salts include, for example, lithium, sodium, potassium, alkaline earth metal, copper, zinc, ammonia cation salts, quaternary ammonium salts, and the like. The term "room temperature" or "ambient temperature" refers to approximately 20 to
Indicates 25℃. Practicality The compounds of formula () and their salts exhibit both pre- and post-emergent herbicidal activity and particularly good herbicidal activity against grasses. This compound has particularly good phytotoxicity (herbicidal properties, herbicidal effect) against weed species that are generally very difficult to control: hoxtail, vermewgrass, crabgrass, rhizonium grass, and native corn.
shows. Generally, for post-emergence applications, the herbicide compound is applied directly to the foliage or other plant parts. For pre-emergence applications, the herbicide compound is applied to the growing environment or anticipated growing environment for the crop. The optimal amount of herbicide compound or composition will depend on the particular plant species and extent of plant growth (if growing) and the site and extent of contact on the plant. Optimal dosages may also vary depending on the general location or environment (eg, a covered area such as a greenhouse compared to an exposed area such as the field) and the type and degree of control desired. Generally, for both pre-emergence and post-emergence control, the compounds of the invention are applied at a rate of about 0.02 to 60 Kg/ha, preferably about 0.02 to 10 Kg/ha. Also, while in theory the compounds could be applied undiluted, in practice they are generally applied as compositions or formulations consisting of an effective amount of the compound and a suitable carrier. A suitable or compatible carrier (agronomically suitable carrier) is a carrier that serves for the dilution of the active compound without significantly adversely affecting the desired biological effect achieved by the active compound. Typically, the composition contains about 0.05-95% by weight of a compound of formula () or mixtures thereof. Concentrates with high concentrations designed to be diluted before application can also be produced. The carrier may be solid, liquid or aerosol. The actual composition may take the form of granules, powders, dusts, solutions, emulsions, slurries, aerosols, and the like. Suitable solid carriers that can be used include, for example, natural clays (kaolin, attapulgite,
montmorillonite, etc.), talc, pyrophyllite, diatomaceous silica, synthetic fine silica, calcium aluminosilicate, tricalcium phosphate, etc. For example, walnut shell powder, cottonseed shell,
Organic materials such as flour, wood flour, bark flour, etc. can also be used as carriers. Suitable liquid diluents that can be used include, for example, water, organic solvents such as benzene, toluene, dimethyl sulfoxide,
(kerosene, diesel fuel, fuel oil, petroleum naphtha, etc.). Suitable aerosol carriers that can be used include conventional aerosol carriers such as halogenated alkanes. The compositions of the invention can also contain various accelerators and surfactants that accelerate the rate of transfer of active compounds into plant tissues, such as organic solvents, wetting agents and oils, and are designed for pre-emergence applications. In the case of prepared compositions, agents that reduce the leaching properties of the compound or promote soil stability can be included. Cereal oils such as soybean oil, paraffinic oils, and olefinic oils are also particularly advantageous as carriers or additives because they promote phytotoxicity. The compositions may also contain various compatible adjuvants, stabilizers, conditioners, insecticides, fungicides and, if desired, other herbicidally active compounds. One type of convenient concentrated formulation that can be used is
27% by weight of the active herbicide of the invention, 2-4% by weight
of emulsifiers, such as calcium alkylbenzenesulfonates, octylphenol ethoxylates, etc. or mixtures thereof, and about 70 to 75
% of xylene, etc.
The concentrate is mixed with water and preferably grain oil before application and is applied as a water emulsion containing about 0.5 to 2% of grain oil, such as soybean oil, and paraffinic and olefinic oils. . This herbicide contains approximately 0.02-0.6% by weight,
Preferably from 0.07 to 0.15% by weight of the herbicide of the invention;
It is conveniently applied as a water emulsion containing about 0.001-0.01% by weight emulsifier; about 0.08-2.5% by weight organic solvent and about 95-99% by weight water. Preferably, the composition contains about 0.25-2% by weight of grain oil. Application compositions can be conveniently prepared by mixing the concentrated formulation described above with about 1/4 to 1/2 the desired amount of water. Then mix with the grain oil and then add the remaining amount of water. If grain oil is not used, simply mix the water and concentrate formulation. To further understand the invention, the following non-limiting Preparations and Examples are provided. In this case, unless otherwise noted, all temperatures and temperature ranges are expressed in degrees Celsius and the terms "ambient" or "room temperature" refer to approx.
Indicates 20-25℃. The term "percent" or "%" indicates weight percent; "mole" or "mols"
The term indicates g moles. The term "equivalent" refers to a molar amount of drug that is equal to the moles of reactants cited before or after that example by constant mole or by constant weight or volume. Where a proton-magnetic resonance spectrum (PMR or NMR) is shown, this was measured at 60 mHz and the signal is singlet (s), broad-
doublet (bs), doublet (d), double doublet (dd),
Triplet (t), double triplet (dt), quartet (q)
and multiplets (m), and cps indicates cycles/second. If necessary, the example is repeated to provide additional starting material for the next example. Examples Example 1 Trans-2-[1-(3-chloroallyloxyimino)propyl]-5-(2-ethylthiopropyl)-cyclohexane-1,3-dione In this example, 17.2 g (0.0636 mole)
2-propionyl-5-(2-ethylthiopropyl)cyclohexane-1,3-dione; 0.9g
(0.0153 mol) of acetic acid, and 10.9 in 35 ml of water
g (0.0757 mol) of 3-trans-chloroallyloxyamine was added to 20 ml of hexane and stirred. Aqueous 5% by weight sodium hydroxide was gradually added over about 15 minutes until 3.0 g (0.0757 m + 100% excess) of sodium hydroxide was added to a reaction mixture with a pH of about 6. The reaction mixture was heated to 40°C, maintained at the same temperature for 21/2 hours, and then cooled to room temperature. Separate the organic (i.e. hexane) phase and incubate for 10
ml of aqueous 5% by weight hydrochloric acid and then 6.25% by weight aqueous sodium hydroxide was added to Hz12. Separate the aqueous phase and mix with 25 ml hexane;
Adjust the pH by adding aqueous 36 wt% hydrochloric acid dropwise on an ice bath.
Adjusted to 5.4. The organic phase is separated, dried over magnesium sulphate and then concentrated by evaporation,
18.0 g of crude product was obtained. The crude product was purified by column chromatography on silica gel, eluting with hexane:methylene chloride to give the title compound as an oil. Elemental analysis, carbon calculation value 56.73%, analysis value 56.63%; hydrogen calculation value 7.28%, analysis value 7.55%; nitrogen calculation value
The analysis value was 3.89%, and the analytical value was 3.55%. Example 2 Sodium 2-[1-(3-trans-chloroallyloxyimino)propyl-3-oxo-
5-(2-Ethylthiopropyl)-cyclohex-1-en-1-oleate This example describes a method that can be used to prepare the named compound. A solution containing 0.01 mol of sodium hydroxide dissolved in 2 ml of water was added at room temperature to 0.01 mol of 2-
[1-(3-trans-chloroallyloxyimino)propyl-5-(2-ethylthiopropyl)-
Add to the solution containing cyclohexane-1,3-dione. After the reaction is completed, the solvent is evaporated off under vacuum to give 2-[1-(3-trans-chloroallyloxyimino)propyl-3-oxo-5-
(2-ethylthiopropyl)-cyclohexe-1-
The 1-hydroxy sodium salt of en-1-ol is obtained. Example 3 In this example, the compound described in Example 1, namely 2-[1-(3-trans-chloroallyloximino)propyl]-5-(2-ethylthiopropyl)-cyclohexane-1, 3-dione,
Pre- and post-emergence phytotoxic activity against various grasses and broad-leaved plants, including one cereal crop and one broad-leaved crop, was tested by the method described below. Pre-emergence Herbicide Test Pre-emergence herbicide activity was determined by the following method: Test solutions of each compound were prepared as follows: 355.5 mg of the test compound was dissolved in 15 ml of acetone. 2 ml of acetone containing 110 mg of nonionic surfactant was added to the above solution. 12 ml of this stock solution was then added to 47.7 ml of water containing the same nonionic surfactant at a concentration of 625 mg/ml. Seeds of test plants were sown in pots of soil and sprayed uniformly onto the soil surface at a dose of test compound of 27.5 r/cm ² unless otherwise specified in the table below. The water was drained into this pot and placed in the greenhouse. Water was intermittently drained from the pot, and the germination of the seeds and the health status of the seeds during germination were observed for 3 weeks. At the end of this period, the herbicidal efficacy of the compounds was graded based on physiological findings. A scale of 0 to 100 was used, with 0 representing zero phytotoxicity and 100 representing complete death. These results are summarized in Table 1. Post-emergence Herbicide Testing Test compounds were formulated in the same manner as described above for pre-emergence testing. This formulation was applied to two pots (each containing plants 2 to 3 inches tall, except for wild oats, soybeans, and watergrass, which were 3 to 4 inches tall). Pots (containing approximately 15-25 plants) were uniformly sprayed with a dose of test compound of 27.5 r/cm ² unless otherwise specified in the table below. After the plants were dry, they were placed in the greenhouse and their roots were watered intermittently as needed. Plants were observed periodically for phytotoxic effects and physiological and morphological responses to this treatment. After three weeks, the herbicidal efficacy of the compounds was graded based on these findings. 0～
A scale of 100 was used. 0 represents phytotoxicity 0;
100 represents complete death. The results of these tests are summarized in Table 2.

[Table] Compound White Kara Red Large
dog club wild o
number the shina the bean
Bier Grass Wheat Rice