JPS60239484A - Dioxacyclohexylanilide herbicide, preparation, composition and use for stopping growth of undesirable plants - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to specific dioxacyclohexylanilide herbicides, the preparation of such compounds, herbicidal compositions containing them, and their use in inhibiting undesirable plant growth. Concerning the use of.

(Prior art) For example, US Pat.
Otsu! ! As described in No. 7, certain substituted phenylurea derivatives are known to be effective herbicides. Dioxacyclohexyl-phenylurea is described as a herbicide in the applicant's European Patent Application No. 00975PgO. It has been discovered that dioxacyclohexylanilide has useful herbicidal activity.

(Structure and operation of the invention) Therefore, the present invention provides the general formula R2 is combined with an alkylene group, thereby forming a cycloalkylidene group together with the adjacent internal carbon atoms; Rs represents an alkyl.haloalkyl or cycloalkyl group; and X is hydrogen or a hydrogen atom or an alkyl group. dioxacyclohexylanilide herbicide characterized by having the following: - If any of these substituents R, , R2, R or Contains atoms, methyl.

Ethyl, cyclozoropyl or l-methylcyclozorobyl are preferred, and the halogen atom in the cycloalkyl group is suitably fluorine or chlorine, with fluoromethyl, trifluoromethyl and chloromethyl groups being preferred. . When R1 and 82 are combined to represent an alkylene group, it is suitably of ≠ or 5 carbon atoms and is preferably unbranched so that adjacent internal carbon atoms are Together they form a cycloyntyl or cyclohexyl ring system. The substituent X preferably occupies a meta position with respect to the amide group < i7 ie an ortho position with respect to the dioxane ring, and is suitably a chlorine atom or a methyl group.

The present invention also provides an aniline of the formula (■): a nologonated acyl of the formula R5C0Hat (in the formula, Hat represents a norogon atom, preferably a chlorine atom), and 7'C is derived from this acyl group R,Co-. Provided is a method for producing the anilide, which comprises reacting the anilide with an acylic anhydride.

This reaction is preferably carried out in the presence of a base such as triethylamine to remove the hydrogen halide;
and is conveniently carried out in an organic solvent such as toluene and the like.

The starting aniline of formula (1) can be prepared by reaction of the λ-phenyl 43 diol of formula (1) with a haloketone of formula (1), using appropriate established synthetic routes, followed by reduction of the resulting dioxacyclohexylnitrobenzene (11C). Properly prepared. This diol-ketone reaction is conveniently carried out in the presence of p-toluenesulfonic acid and in an organic solvent such as benzene, and the reduction of the product is carried out in the presence of a platinum catalyst in an organic solvent such as alcohol, etc. Herbicidal compositions containing a compound of general formula (1) which also has significant herbicide activity, and combining the compound of formula (2) with at least one carrier, which is conveniently carried out by reaction with gaseous hydrogen at Also provided are methods of making such compositions.

The invention also provides the use of such compounds or compositions according to the invention. Further in accordance with the invention there is provided a method of inhibiting undesirable plant growth in a location by treating the location with a compound or composition of the invention. Application to this location may be pre- or post-emergence.

The amount of active ingredient used is, for example, 0.0! ;-4'
kll/ha. The carrier in the composition according to the invention is used to facilitate the application of the active ingredient to the site to be treated, for example to plants, seeds or soil, or to facilitate storage, transport or handling. The material contained in the material is either a material or a liquid, usually gaseous, but contains a material that has been compressed into a liquid, and any carrier commonly used in the formulation of herbicidal compositions is present. used.

The compositions of the invention preferably contain 5% by weight of active ingredient.

Suitable solid supports include natural and synthetic clays and silicates, such as natural silicas such as diatomaceous earth; magnesium silicates, such as talc; magnesium aluminum silicates, such as attapulgite and vermiculite; e.g. kaolin, montmorillonite. and aluminum silicates such as mica; calcium carbonate, calcium sulfate; ammonium sulfate; synthetic aqueous silicon oxides and synthetic calcium or aluminum silicates; elements such as carbon and sulfur; such as coumaron resins, polyvinyl chloride and styrene polymers and copolymers natural and synthetic resins such as; solid polychlorophenols; bitumen; waxes; and solid fertilizers such as superphosphates.

Suitable liquid carriers include water; alcohols such as isozolopanol and glycols; ketones such as acetone, methyl ethyl ketone, methyl imbutyl ketone and cyclohexanone; ethers;
c (!: , t iL' Aromatic or araliphatic hydrocarbons such as benzene, toluene and xylene; petroleum distillates such as kerosene and light mineral oils; e.g. carbon tetrachloride, chloroethylene and trichloroethylene Mixtures of a variety of different liquids are often suitable.

Pesticide compositions are often formulated and transported in concentrated form and then diluted by the user prior to application. The presence of a small amount of carrier, a surfactant, facilitates this dilution process. Thus, at least one carrier in the composition of the invention is a surfactant. For example, the composition may contain at least two carriers, at least one of which is a surfactant.

The surfactant may be an emulsifier 1 dispersant or wetting agent, and it may be nonionic or ionic. Examples of suitable surfactants are sodium or calcium salts of I-lyacrylic acid and ligninsulfonic acid; condensation of ethylene oxide and/or propylene oxide with fatty acids or aliphatic amines or amides containing at least 72 carbon atoms in the molecule; fatty acid esters of glycerol, sorbitan, sucrose or intererythritol; condensates of these with ethylene oxide and/or zolopyrene oxide; fatty alcohols or alkylphenols such as p-octylphenol or p-
Condensation products of octyl cresol and ethylene oxide and/or propylene oxide; sulfates or sulfonates of these condensation products; at least 10
Alkali or alkaline earth metal salts, preferably sodium salts, of sulfuric acid or sulfonic acid esters containing 5 carbon atoms, such as sodium lauryl sulfate, sodium secondary alkyl sulfate, sodium salt of sulfonated castor oil and dodecylbenzene sulfonate. alkylaryl sulfonates such as; as well as ethylene oxide? Includes lima and copolymers of ethylene oxide with propylene oxide.

The composition of the present invention can be used, for example, as an aquarium, a powder, or a granule.

It is formulated as solutions, concentrates, emulsions, concentrates, suspensions, and aerosols. Irrigation agents are usually xs,! ;0 or 7
of active ingredient and usually contains 3-10% by weight of a dispersant in addition to a solid inert carrier and optionally 0% by weight of a dispersing agent.
Contains ~10w% stabilizers and/or other additives such as penetrants or fixing agents. Powders usually have a similar composition to irrigation agents, but are formulated as concentrated powders without dispersants, and are further diluted with solid carriers in the field to give compositions that usually contain from 10% to 10% by weight of active ingredient.

Granules are usually 10 to 100BS mesh (/, 7 to 0
, / j 2 vm) and manufactured by agglomeration or impregnation techniques. Generally, granules contain //2-7jv% active ingredient and 0-10v
% stabilizers, surfactants, release modifiers and binders etc. So-called 6 Dry Fluid Powder”
consists of relatively small granules with a relatively high concentration of active ingredient. Concentrated emulsions usually contain, in addition to the solvent, co-solvents, 10-jOw/v% of active ingredients, 2-20w/v% of emulsifiers, and 0-20w/v% of stabilizers, penetrants, preservatives, etc. Contains other additives such as. Concentrated suspension agents are usually formulated to provide stable, non-settling, flowable products and contain 10 to 7 J"w% active ingredient, O
, S~/jW% dispersants, 0.7~10W% protective colloids, and suspending agents such as thixotropic agents, 0~
Contains 10w% of other additives such as defoamers, preservatives, stabilizers, penetrants and fixing agents, etc., as well as water or an organic liquid in which the active ingredient is substantially insoluble. Certain organic solids or inorganic salts may be dissolved in the formulation to aid in preventing precipitation or as antifreeze agents for the water.

Also within the scope of the invention are aqueous suspensions and emulsions, such as compositions obtained by diluting the aqueous agents or concentrates of the invention with water. The emulsion may be in the form of water-in-oil or oil-in-water, and may have a thick "mayonnaise" consistency.

The composition of the present invention may also contain other ingredients such as herbicidal,
It may also contain other compounds with insecticidal or fungicidal properties.

(Example) The invention is illustrated in the following examples.

Example/ ≠-(J-methyl-nochloromethyl-43
-Dioxacyclohex-3-yl)-3-methyl-/'-methyl-cyclopropanilide (A) 3-Methyl-≠-(43-dioxy-zolopy2
-yl) nitrobenzene (zi) to pensoba (10O1
nl) and chloroacetone (2,lIl).

l) and p~toluenesulfonic acid (o, sy) were added and the reaction mixture was refluxed overnight. The bath solution was removed, the product was diluted with methylene dichloride and the product was washed with sodium bicarbonate solution, dried, purified by chromatography and recrystallized to give 11-(2-methyl-λ-chloromethyl-43- Dioxacyclohex-5-yl)-J-methylnitrobenzene was produced. m, p, /θj~
70℃.

(B) The product of (A) above (440 g) was dissolved in ethanol, j-% platinum/carbon was added and hydrogen was fed at 3 atmospheres. After λ hours, the anilide product was chromatographed and used directly in the final step.

(C) The product (θ, RI) of (B) above was dissolved in toluene, triethylamine (0,339) and /-methyl-cyclozoronoyl chloride (O, tl, 2 g
) was added. The reaction mixture was stirred at room temperature for 7 hours, the toluene was removed and the product was diluted with methylene dichloride, washed,
Silica by drying and chromatography (200~Hiroj
Purification by separation on O mesh gave the desired title product.

m, p, / 2 j-1:≠℃.

Analysis result Calculated value “C”, H7, /: NIA
/Actual yield value C3. B: H7, /: Net, /CH Example No.// Further examples of the compounds of the present invention were prepared according to procedures similar to those described in the previous examples, and their melting points and chemical analysis results were are shown in Table 1 below.

In the table, compounds were identified by checking the substituents in the following formula.

Example/2 Herbicidal Activity Zeamays (M
Z) ) :Rice (Oryza 5ativa(R)
): Golden millet (Eehinochloa crusg)
alli (BG)): Oat (Avsna 5a)
tiva (0)): Linum usita
tiasium (L): White mustard (5inapsi)
s alba (M)): Sugar beet (Beta v
ulgaris (SB)) and soybean (Gly
The test was conducted using cine max (S) 1.

These tests are divided into two categories: pre-emergence and post-emergence. The pre-emergence test involved spraying a liquid formulation of the compound onto Bakashi soil where seeds of the plant species were sown. Post-emergence tests included two types of tests: soil irrigation and foliar spray tests. In soil irrigation tests, the soil in which seedling plants of the species described above are growing is irrigated with a liquid formulation containing a compound of the invention, and in foliar spray tests, seedling plants are sprayed with such a formulation.

The soil used in these tests was a prepared horticultural loam.

The formulation used in the test was manufactured under the trade name Triton (T) for the test compound.
RITON)
, ≠g% by weight of an alkylphenol/ethylene oxide condensate in acetone. These acetone solutions were diluted with water and the resulting formulations were tested in spray tests and at doses corresponding to 7 kg of active substance per hectare, and in soil drench tests with gills equal to 001 per hectare. 1 Okl/ha? of active substance was applied in an amount equal to approximately 300,011 kg/hectare.

In the pre-emergence test, untreated seeded soil was used as a total control, and in the post-emergence test, untreated soil with seedling plants was used as a total control.

The herbicidal effect of the test compound was evaluated visually after 2 days after spraying on leaves and soil and 73 days after soil irrigation.
It was recorded on a scale of 1. A degree of "0" indicates growth as an untreated control, and a degree of "1" indicates death. A unit increase on a linear scale is equivalent to a 70% increase in effect level.

The test results are listed in Table 2 below.Continued from page 10 Inventor: Andrew Frew, United Kingdom
-Do 69

Claims (9)

[Claims] (1) General formula I: (wherein R1 and R2 may be the same or different and each independently represents an alkyl or haloalkyl group, or R1 and R2 combine to represent an alkylene group, thereby dioxacyclohexylani IJ F, which together with internal adjacent carbon atoms represents a cycloalkylidene group; R3 represents an alkyl, haloalkyl or cycloalkyl group; and X represents a hydrogen or halodane atom or an alkyl group) . (2) R and R2 each independently represent an alkyl group containing up to 6 carbon atoms optionally having a fluorine or chlorine substituent, or R4 and R2 are combined to form an alkyl group containing up to 6 or 5 carbon atoms; Table alkylene group containing a carbon atom (wash;
A patent characterized in that R3 represents an alkyl, haloalkyl or cycloalkyl group up to the carbon atom side, and X is...Dan atom 4fc represents an alkyl group having up to 5 carbon atoms (3) R and R2 each independently and uniquely represent a methyl or ethyl group having a fluorine or chlorine substituent, or R and R2 combine to represent a tedramethylene group; R is methyl or ethyl; , trifluoromethyl, cyclozorobyl, or /-methylcyclozorobyl group; and X represents a chlorine atom or a methyl group occupying the meta position relative to the amide group. Compounds described. (4) The aniline of the formula ■: is reacted with an acyl anhydride derived from an acyl halide of the formula R5C0HaL (in the formula, Hat represents a haof/atom) or an acyl group of the tag A process for preparing a compound of general formula I according to claim 1, characterized in that it comprises: (5) The method according to claim 1, wherein the reaction is carried out in an organic solvent in the presence of a base. (6) The aniline of formula (2) is prepared by reacting the diol of (2) with the haloketo/ of (2) and then reducing the product. Method. (7) The diol-ketone reaction is carried out in an organic solvent in the presence of tosyl alcohol, and the reduction is carried out with gaseous hydrogen in the presence of a platinum catalyst. Method. (8) A compound according to claim 1, which is prepared by the method according to any one of claims 1 to 7. (9) A herbicidal composition comprising the compound described in any one of claims 7 to µ and g together with a carrier. Ring Claims 7 to ψ and g
A method for inhibiting the growth of undesirable plants, characterized in that it comprises treating a site with a compound according to any one of the preceding paragraphs or a composition according to paragraph 2. αρ Use of a compound according to any one of claims 7 to ≠ and g as a herbicide.