JPH0415227B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides biologically active organic compounds,
In particular, it relates to organic compounds having herbicidal activity, methods for producing such compounds, intermediates useful for producing such compounds, herbicidal compositions utilizing such compounds, and methods of use. The inventors have discovered a new class of benzotriazines that have biological activity, in particular herbicidal activity. The compound according to the present invention is a compound represented by the formula or a salt thereof. In the formula, A, B, D, E, U and V independently represent a hydrogen atom, a halogen atom, a nitro group, a _C1 - _C6 alkyl group, a _C1 - _C6 haloalkyl group, and a C1- _C6 haloalkyl group.
A group selected from the group consisting of C ₆ alkoxy groups, and R ¹ is a hydrogen atom, a C ₁ to C 10 alkyl group, and a C ₂ to C ₁₀ alkyl group.
A group selected from the group consisting of a C ₁₀ alkynyl group and a benzyl group, and R ² is a hydrogen atom, a C ₁ to C ₆ alkyl group, and
is a group selected from the group consisting of a C ₂ - C ₆ alkoxyalkyl group, R ³ is a group selected from the group consisting of a hydrogen atom and a C ₁ - _{C 6} alkyl group, and W is a group

[Formula] [In the formula, G is a hydroxy group, a C ₁ to _{C 10} alkoxy group, a C ₁ to _{C 10} haloalkoxy group, a C ₂ to C ₁₀ alkenyloxy group, a C ₂ to
a _C10 alkynyloxy group, a _C1 - _C10 alkylthio group, a C1- _C6 alkoxy group substituted _with N,N-di( _C1 - _C6 alkyl)amino, a group -OM (in the formula, M is a cation of an inorganic or organic base),
Group -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are independently a hydrogen atom, a C ₁ to C ₆ hydroxyalkyl group, and a C ₁ to
is a group selected from the group consisting of C ₆ haloalkyl groups) and the group -O-N=R ¹⁰ (wherein R ¹⁰ is a C ₁
~ _C10 alkylidene group), k and l are independently 0 or 1 (however, k+l is 0 or 1) 1). Compounds in which R ² and R ³ are not the same are optically active, and the invention also includes individual stereoisomers of such compounds as well as mixtures of those stereoisomers, as well as additions. It also includes racemic mixtures of stereoisomers. Suitably, A, B, D, E, U and V independently represent a hydrogen atom, a halogen atom, a nitro group, C ₁ -C ₆
alkyl groups, C ₁ -C ₆ haloalkyl groups and
A group selected from the group consisting of _C1 to _C6 alkoxy groups, ^R1 is a group selected from the group consisting of a hydrogen atom, a _C1 to _C10 alkyl group, and a benzyl group, ^R2 is a hydrogen atom, a _C1 - _C6 alkyl group, and
is a group selected from the group consisting of C ₂ to C ₆₀ alkoxyalkyl groups, R ³ is a group selected from the group consisting of a hydrogen atom and a C ₁ to _{C 6} alkyl group, and W is a group

[Formula] [In the formula, G is a hydroxy group, a C ₁ to _{C 10} alkoxy group, a C ₁ to _{C 10} haloalkoxy group, a C ₂ to C ₁₀ alkenyloxy group, a C ₂ to
a _C10 alkynyloxy group, a _C1 - _C10 alkylthio group, a group -OM (wherein M is a cation ^of an inorganic or inorganic base), a group ^-NR5R6 (wherein ^R5 and ^R6 are independently a group selected from the group consisting of a hydrogen atom, a C ₁ -C ₆ haloalkyl group, and a C ₁ -C ₆ hydroxyalkyl group, and k and l and m are independently 0 or 1 (k+l is 0 or 1). Preferably, A, B, D and E each represent a hydrogen atom, a halogen atom, a nitro group, C ₁ - C ₆ alkyl groups of C ₁ -C ₆ haloalkyl groups and C ₁ -
A group selected from the group consisting of C ₆ alkoxy groups, and U and V are hydrogen atoms, halogen atoms, nitro groups, C ₁ to C ₆ alkyl groups, and C ₁ to
A group selected from the group consisting of C ₆ haloalkyl groups, and R ¹ is a hydrogen atom, a C ₁ to C 6 alkyl group, and a C ₂ to C ₆ alkyl group.
A group selected from the group consisting of a C ₆ alkynyl group and a benzyl group, and R ² is a group selected from a hydrogen atom, a C ₂ to _{C 6} alkoxyalkyl group, and a C ₁ to _{C 6} alkyl group. , R ³ is a group selected from a hydrogen atom and a C ₁ to C ₁₀ alkyl group, and W is a group

[Formula] [In the formula, G is a hydroxy group, a C ₁ to _{C 10} alkoxy group, a C ₁ to _{C 10} haloalkoxy group, a C ₂ to C ₁₀ alkenyloxy group, a C ₂ to
a _C10 alkynyloxy group, a _C1 -C10 alkylthio group, a _C1 - _C10 alkoxy group substituted with N,N-di( _C1 - _{C10 alkyl} )amino, a group -OM (in the formula, M is an alkali metal ion) and the group -
A group selected from the group consisting of O-N=R ¹⁰ (wherein R ¹⁰ is a C ₁ to C ₁₀ acylidene group), and k and l are Each is 0 or 1 (however, k+l is 0 or 1). More preferably, A, B, D and E each represent a group selected from a hydrogen atom, a halogen atom, a _C1 - _C6 alkyl group, a _C1 - _C6 haloalkyl group, and a _C1 - _C6 alkoxy group. , U and V are atoms selected from hydrogen atoms and halogen atoms, respectively, and R ¹ is a hydrogen atom, a C ₁ to C ₆ alkyl group, and a C ₂ to C ₆ alkyl group.
is a group selected from an alkynyl group and a benzyl group, and R ² is a hydrogen atom, a C ₁ to C ₆ alkyl group, and a C ₂
A group selected from the group consisting of ~ _C6 alkoxyalkyl groups, ^R3 is a hydrogen atom and a group selected from _C1 to _C6 alkyl groups, and W is a group

[Formula] [In the formula, G is a hydroxy group, a C ₁ to C ₁₀ alkoxy group, a C ₂ to _{C 10} alkenyloxy group, a C ₂ to _{C 10} alkynyloxy group, a C ₁ to C ₁₀
alkylthio group, C ₁ - C ₁₀ haloalkoxy group,
_C1 - _C6 alkoxy group substituted with N,N-di( _C1 - _C10 alkyl)amino, group -O-N= ^R10
(wherein R ¹⁰ is a C ₁ to C ₁₀ alkylidene group),
group -OM (wherein M is an alkali metal ion)
and ^-NR5R6 , where ^R5 and ^R6 are a hydrogen atom, ^a _C1 - _C10 alkyl group, and a _C1 - _C10 haloalkyl group, respectively. ], k and l are 0 and 1, respectively, and k+l is 0 or 1. Preferred compounds of the formula have a phenyl group of 1,
This is a compound substituted at the 4-position and is represented by the formula. Specific examples of compounds of the present invention are described below in Section 1:
Details are given in Tables 2, 3 and 4.

【table】

【table】

【table】

【table】

TABLE The compounds of the invention can be made by a variety of methods and in a further aspect, the invention provides a method of making a compound of formula. Compound of formula a (:W=

[Formula]), in which G is not a hydroxy group, the formula b
(:W=-CO ₂ H), for example, by neutralizing the acid with a base to obtain an acid salt, and then esterifying the acid with alcohols or phenols. It can be produced by obtaining an acid ester or by reacting the acid (or its acid halide derivative) with an amine to obtain an amide [Method A]. Known methods for preparing acid salts, acid esters, acid halides and acid amides may be adapted without undue experimentation to prepare compounds of formula a of the invention from compounds of formula b of the invention. I can do it. The nitriles represented by the formula c (:W=-C≡N) of the present invention are, for example, the nitriles represented by the formula d (:W=
_-CONH2 ) [Method B]. The alcohol of the formula e (:W=CH ₂ OH) of the present invention has the formula f [I:W=

It can be produced by reducing an acid or acid ester represented by the formula: [Method C] (wherein G=OH or O-alkyl group). Known methods for reducing acids or acid esters to alcohols, such as lithium aluminum hydride reduction, do not require extensive experimentation to prepare alcohols of formula e of the invention from esters of formula f of the invention. It can be adapted without any problem. Formula g of the present invention (:W= _-CH2 -halogen)
The alkyl halide has the formula e(:W=-
It can be obtained by halogenating CH ₂ OH). Known methods of converting alcohols to alkyl halides, such as halogenation methods with thionyl chloride, require considerable experimentation to prepare alkyl halides of formula g of the invention from alcohols of formula e of the invention. It can be adapted without any problem. The ethers of the formula h (:W=CH ₂ OR) of the present invention can be obtained by alkylating the alcohols of the formula e (:W=-CH ₂ OH). Known methods for converting alcohols into ethers, such as reaction with alkyl halides using Williamson's ether synthesis, can be used to prepare ethers of formula h of the invention from alcohols of formula e of the invention. can be adapted without much experimentation. The formula h(i) of the present invention [:W=-CH ₂ OR(-
CH ₂ SR)] ethers (thioethers) are
It can be obtained by alkoxylating (thioalkylating) an alkyl halide of formula g (: W=CH ₂ -halogen). Known methods for converting alkyl halides into ethers (thioethers), such as alcohols (thiols)
The method of reacting using Williamson's ether synthesis method is a method for obtaining the ethers (thioethers) of the formula h(i) of the present invention from the alkyl halide of the formula g of the present invention without making extensive experiments. can be adapted. The amines of formula j (:W= _CH2NR4R5 ) of the present invention can be obtained by aminating an alkyl halide of formula g (:W= _-CH2 -halogen ⁾ or by aminating the alkyl halide of formula k ⁽ :W=-CH2-halogen).
(:W=

It can be obtained by reducing the amides of [Formula]). Known methods for converting alkyl halides to amines, such as reduction with reagents such as lithium aluminum hydride, convert amines of formula j of the invention from each of the alkyl halides of formula g and amides of formula k of the invention. can be adapted without extensive experimentation to produce . The N-oxides of the present invention of the formula (one or more of k, l and m are 1) include compounds of the formula (k and/or l and/or m are 1). It can be obtained by oxidation. Known methods for converting benzotriazines to benzotriazine N-oxides, such as oxidation methods using persulfates, peroxides, peracids or peresters, include:
It can be adapted without undue experimentation to produce the novel N-oxides of the present invention. A compound of the present invention represented by the formula, in which R ¹ is not a hydrogen atom, is a compound of the present invention represented by the formula, in which R ¹ is a hydrogen atom, for example, It can be obtained by alkylation or acylation.
Known methods for producing derivatives of secondary amines, such as the alkylation method with alkyl halides and the acylation method with acyl halides, can be used to prepare the novel compounds of the invention in which R ¹ is not a hydrogen atom. It can be adapted without much experimentation. In the formula, A, B, D, E, U, V, X,
Compounds in which R ¹ , R ² , R ³ , W, k and l have the same definitions as above, preferably combine the phenols of the formula with compounds in which hal is a chlorine atom, a bromine atom or an iodine atom. It can be obtained by condensation according to method D in the presence of alkaline substances. Compounds of formula can also be prepared by the following method. (a) Suitable benzotriazines of the formula in which L is a dissociable group (e.g. an alkylsulfonyl group, chlorine, bromine or iodine) are condensed with suitable anilines of the formula by method E. Method. or (b) carrying out the following steps in sequence: () a suitable benzotriazine derivative of the formula in which L is a dissociable group (for example alkylsulfonyl, chlorine, bromine or iodine), in which Q is hydroxy or a _C1 - _C6 alkoxy group to obtain a compound in which Q is a hydroxy group or a _C1 - _C6 alkoxy group, () the above step ( ), in which Q is a C ₁ -C ₆ alkoxy group, is dealkylated to obtain a compound of the formula, and () obtained in the above step () or step (). or (c) a condensation reaction of a product of formula with a compound of formula according to the method described for step D above (steps () and () are shown in method F); or (c) Carrying out the steps in sequence: () A suitable benzotriazine derivative of formula , or a C ₁ -C ₆ alkoxy group, with a suitable benzene derivative to obtain a compound of formula (wherein Q has the same definition as above), () obtained in the above step () dealkylation of a compound of the formula in which Q is a C ₁ -C ₆ alkoxy group to obtain a compound of formula according to the method described in step () above of Method F, and () above Condensing the product obtained in step () or () with a compound of formula according to the method described in method D above (step () is described in method G). The condensation reaction shown in Method D and outlined above is preferably carried out in the presence of an alkaline substance and preferably in the presence of a solvent. Suitable alkaline substances include alkali metal and alkaline earth metal hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Suitable solvents include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and dipolar intermediate solvents such as dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, N-methylpyrrolidone, hexamethylphosphoramide and Includes sulfolane. The condensation reactions shown in Methods E and F and outlined above are preferably carried out in the presence of a solvent. The reaction conditions necessary to carry out the condensations illustrated in Methods D, E, F and G and outlined above will vary depending on the nature of the reactants and solvents used. Generally, the reaction is accelerated by heating, and reaction temperatures in the range of 40°C to 150°C and reaction times of 0.5 to 20 hours are usually sufficient. However, higher or lower reaction temperatures and/or shorter or longer reaction times can also be used if desired. The dealkylation reactions illustrated in Methods F and G and outlined in sections (b)() and (c)() can be carried out by using a variety of known reagents. For example, aryl-alkyl ethers include pyridine hydrochloride, hydroiodic acid, hydrobromic acid, sodium thioethoxide in dimethylformamide, acetyl p-toluenesulfonate, sodium or potassium iodide in formic or acetic acid, , 4,6-collidine and lithium iodide in boron tribromide. Reaction times and conditions vary widely depending on the dealkylating agent used and the ethers to be cleaved.
The reaction conditions commonly employed when using the above "ether cleavage" reagents are known to those skilled in the art and are illustrated in Methods F and G and (b)() and (c) above. ) It can be adapted without extensive experimentation to carry out the "ether cleavage" reaction outlined in section (). formula: The compound represented by is a novel compound and a useful intermediate in the preparation of compounds of formula. Therefore, in another aspect, the invention provides that in the formula: A, B, D, E,
Compounds are provided in which k, l, R ¹ , U, V and Q have the same definitions as above. The compounds of the formula are active as herbicides and therefore, in a further aspect, the present invention provides for the application of an effective amount of a compound of the formula as described above to a plant or to the growth medium of the plant. The present invention provides a method of severely damaging or killing undesirable plants. Generally speaking, the compounds of the formula have herbicidal effects on a variety of plants. However, certain of the compounds of the invention have selective activity against monocots, while others are severely damaging or lethal to other plant species. It is relatively unaffected by the application rate of the compound according to the invention. Additionally, certain of the compounds of the formula have selective activity against certain monocot groups and cause severe damage to monocot weeds in monocot cereal crops. or at a rate sufficient to cause death. Therefore, in a further aspect, the present invention comprises:
A method comprising applying to a crop or the growing medium of the crop a compound of the formula as hereinbefore defined in an amount sufficient to seriously damage or kill the weeds, but not substantially damage the crop; The present invention provides a method for selectively suppressing the growth of weeds within crops. The compound of formula can be applied directly to the plant (post-emergent application) or to the soil before the plant germinates (pre-emergent application). However, the compounds of the invention are generally more effective when applied after plant emergence. The compounds of the formula can be used by themselves to inhibit plant growth, cause severe damage to plants or kill plants;
Preference is given to using the compounds according to the invention in the form of compositions consisting of mixtures with solid or liquid diluents. Accordingly, in a further aspect, the present invention provides a composition for inhibiting plant growth, damaging or killing plants, comprising a compound of the formula as defined above and an inert carrier therefor. Compositions according to the invention include both diluted compositions for ready-to-use and concentrated compositions that usually require dilution with water before use. Preferably, the composition contains from 0.01% to 90% by weight of the active ingredient.
Contains weight%. Dilute, ready-to-use compositions preferably contain 0.01% to 2% active ingredient, whereas concentrated compositions contain 20 to 90%.
can contain active ingredients, but from 20%
Up to 70% is usually preferred. Solid compositions may be in the form of granules or powders, in which the active ingredient is present in a finely divided solid diluent;
For example, it is mixed with kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth and lime.
Such compositions may also be dispersible powders or granules consisting of a wetting agent that facilitates dispersion of the powder or granules into a liquid. Powdered compositions can also be applied as foliar dusts. Liquid compositions consist of a solution or dispersion of the active ingredient in water, optionally containing a surfactant, or the active ingredient and a non-aqueous solution dispersed as droplets in water. It consists of a solution or a diffusion liquid with a sterile organic solvent. Surfactants may be cationic, anionic, or nonionic. Examples of cationic surfactants include quaternary ammonium compounds (eg, cetyltrimethylammonium bromide). Suitable anionic agents are soaps; salts of aliphatic monoesters of sulfuric acid, such as sodium lauryl sulfate; and salts of sulfonated aromatic compounds, such as sodium dodecylbenzenesulfonate, sodium salt of lignosulfonic acid, calcium. salts and ammonium salts, butylnaphthalene sulfonate and mixtures of sodium diisopropylnaphthalene sulfonate and sodium triisopropylnaphthalene sulfonate. Suitable nonionic surfactants include condensation products of ethylene oxide with fatty alcohols, such as oleyl alcohol and cetyl alcohol, or alkylphenols, such as octylphenol or nonylphenol or octylcresol. can be mentioned. Other nonionic surfactants include partial esters derived from long-chain aliphatic and hexitol anhydrides, such as sorbitan monolaurate; condensation products of partial esters with ethylene oxide; and lecithins. There is. Aqueous solutions or diffusion solutions are obtained by dissolving the active ingredient in water or an organic solvent, optionally containing a wetting agent or a dispersing agent, and then, when an organic solvent is used, the active ingredient so obtained. The mixture can be obtained by adding to water, which may optionally contain wetting or spreading agents. Suitable organic solvents include, for example, ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene,
Examples include xylenes and trichloroethylene. Compositions used in the form of aqueous solutions or diffusion solutions are
Generally, they are supplied in the form of a concentrate containing a high proportion of the active ingredient, which concentrate is then diluted with water before use. Concentrates usually withstand long periods of storage and are subject to the requirement that after storage they must remain homogeneous long enough to be diluted with water to form an aqueous preparation and applied by conventional atomization equipment. Is pleased. The concentrates conveniently contain from 20 to 90% by weight of active ingredient, preferably from 20 to 70%. In dilute formulations, the concentration of the active ingredient can vary depending on the intended purpose, and amounts of active ingredient of 0.01 to 10.0% by weight, preferably 0.1 to 2% by weight, are usually used. A preferred form of concentrated composition is one consisting of the active ingredient finely divided and dispersed in water in the presence of a surfactant and a suspending agent. Suitable suspending agents are hydrophilic colloids, examples of which include, for example, polyvinylpyrrolidone and sodium carboxymethyl cellulose, and vegetable gums,
Examples include gum acacia and gum tragacanth. Preferred suspending agents are those that impart thixotropic properties to the concentrate and increase its viscosity. Examples of preferred suspending agents include hydrated colloidal mineral silicates such as montmorillonite, beidellite, nontronite, hectorite, sapoite and sauconite. Bentonite is particularly preferred. Other suspending agents include cellulose derivatives and polyvinyl alcohol. The application rate of the compound according to the invention is determined by various factors, such as the type of compound used, the type of plant whose growth is to be inhibited, the formulation used and whether the compound should be applied to the leaves. ,
It is decided based on factors such as whether it should be applied for uptake from the roots. However, as a general guide, application rates of 0.005 to 20 kg/ha are suitable;
Preferred rates are from 0.01 to 5 kg per hectare. In addition to one or more of the compounds of the invention, the composition of the invention may also consist of one or more biologically active compounds that are not compounds according to the invention. For example, as mentioned above, the compounds of the present invention are generally substantially more effective against monocotyledonous or grass species than against dicotyledonous or broad-leaved species. As a result, in certain applications the use of compounds according to the invention alone may not be sufficient for crop protection. Accordingly, in another further aspect, the invention provides a herbicidal composition comprising a mixture of at least one compound of the above-mentioned formula and at least one other herbicide. be. The other herbicide may be any herbicide not shown in the formula. In general, it is better to use herbicides that have complementary actions. For example, one preferred class includes mixtures with herbicides that are active against broadleaf weeds. A second preferred category includes mixtures with contact herbicides. Examples of useful herbicides with complementary actions include: A benzo-2,1,3-thiadiazin-4-one-2,2-dioxides, such as 3-
Isopropylbenzo-2,1,3-thiadiazin-4-one-2,2-dioxide (generic name: bentazone); B Hormonal herbicides, especially phenoxyalkanoic acids, such as 4-chloro-2-methylphenoxyacetic acid (Common name: MCPA), 2-(2,4-
dichlorophenoxy)propionic acid (common name:
dichlorprop), 2,4,5-
Trichlorophenoxyacetic acid (common name: 2,4,
5-T), 4-(4-chloro-2-methylphenoxy)butyric acid (generic name: MCPB), 2,4-dichlorophenoxyacetic acid (generic name: 2,4-D),
4-(2,4-dichlorophenoxy)butyric acid (common name: 2,4-DB), 2-(4-chloro-2-
Methylphenoxy)propionic acid (generic name: mecoprop) and derivatives thereof (e.g., salts, esters, amides, etc.); C 3-[4-(4-halofenoxy)phenyl]
-1,1-dialkyl ureas, such as 3-
[4-(4-chlorophenoxy)phenyl]-1,
1-dimethylurea (generic name: chloroxuron)
chloroxuron); D dinitrophenols and their derivatives (e.g. acetate), e.g. 2-methyl-4,6
-Dinitrophenol (generic name: DNOC), 2
-Tertiary butyl-4,6-dinitrophenol (generic name: dinoterb), 2-secondary butyl-4,6-dinitrophenol (generic name: dinoseb) and its ester dinoceb acetate; E Dinitroaniline herbicides, such as N′,
N'-diethyl-2,6-dinitro-4-trifluoromethyl-m-phenylenediamine (common name: dinitramine), 2,6-
Dinitro-N,N-dipropyl-4-trifluoromethylaniline (generic name: trifluralin) and 4-methylsulfonyl-2,6-dinitro-N,N-dipropylaniline (generic name: nitraline); F Phenyl urea type Herbicides, such as N′-(3,
4-dichlorophenyl)-N,N-dimethylurea (common name: diuron) and N,N
-dimethyl-N'-[3-(trifluoromethyl)
phenyl]urea (generic name: fluometuron =
G phenylcarbamoyloxyphenyl carbamates, such as 3-[(methoxycarbonyl)amino]phenyl (3-methylphenyl)
Carbamates (common name: fuemmedefam) and 3-[(ethoxycarbonyl)amino]phenyl phenyl carbamate (common name: desmedefam); H 2-phenylpyridazin-3-ones, e.g. 5-amino-4-chloro- 2-phenylpyridazin-3-one (generic name: pyrazone); I uracil herbicides, such as 3-cyclohexyl-5,6-trimethyleneuracil (generic name: renacil), 5-bromo-3-secondary Butyl-6-methyluracil (generic name: bromacil) and 3-tert-butyl-5-chloro-6
-Methyluracil (generic name: Terbacil); J Triazine herbicides, such as 2-chloro-4-ethylamino-6-(isopropylamino)-1,3,5-triazine (generic name: atrazine), 2- Chloro-4,6-di(ethylamino)-1,3,5-triazine (common name: simazine) and 2-azido-4-(isopropylamino)-6-methylthio-1,3,6-triazine (common name: simazine) Name: Aziprotoline=
K 1-alkoxy-1-alkyl-3-phenylurea herbicides, such as 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (generic name: Linyuron), 3 -(4-chlorophenyl)-1-methoxy-1-methylurea (common name: monolinuron) and 3-(4-bromo-4-chlorophenyl)-1-methoxy-
1-methylurea (generic name: chlorobromyuron); L Thiol carbamate herbicides, such as S
-Propyl dipropylthiocarbamate (common name: Berorate); M 1,2,4-triazin-5-one herbicide, such as 4-amino-4,5-dihydro-3-methyl-6-phenyl-1 ,2,4-triazin-5-one (generic name: metamitrone)
and 4-amino-6-tert-butyl-4,5
-dihydro-3-methylthio-1,3,4-triazin-5-one (common name: metribuzin); N Benzoic acid herbicides, such as 2,3,6 trichlorobenzoic acid (common name: 2,3, 6-
TBA), 3,6-dichloro-2-methoxybenzoic acid (common name: dicamba) and 3-amino-
2,5-dichlorobenzoic acid (common name: chloramben); O Anilide herbicides, such as N-butoxymethyl-α-chloro-2',6'-diethylacetanilide (common name: butachlor), the corresponding N -Methoxy compound (generic name: alachlor), corresponding N-isopropyl compound (generic name: propachlor) and 3',4'-dichloropropionanilide (generic name: propanil); P dihalobenzonitrile herbicide, For example, 2,6-dichlorobenzonitrile (common name: dichlobenil), 3,5-dibromo-4-hydroxybenzonitrile (common name: bromoxynil) and 3,5-diiodo-4-hydroxybenzonitrile (common name: isoxynil) ; Q Haloalkanoic acid herbicides, such as 2,2
-dichloropropionic acid (generic name: Darapon),
Trichloroacetic acid (common name: TCA) and salts thereof; R diphenyl ether herbicides, e.g. 4
-Nitrophenyl 2-nitro-4-trifluoromethyl phenyl ether (generic name: fluorodiphen), methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate (generic name: bifuenox), 2- Nitro-5-(2-
chloro-4-trifluoromethylphenoxy)
benzoic acid, 2-chloro-4-trifluoromethylphenyl 3-ethoxy-4-nitrophenyl ether and the compounds described in European Patent Publication No. 3416; and S other herbicides, such as N,N-dimethyldiphenyl ether; enylacetamide (generic name: diphenamide), N-(1-naphthyl)phthalamic acid (generic name: naptalam) and 3-amino-1,
2,4-triazole. Examples of useful contact herbicides include: T dipyridylium herbicides, for example those whose active substance is 1,1'-dimethyl-4,4'-dipyridylium ion (common name: paraquat);
and the active substance is 1,1'-ethylene-2,
2′-dipyridylium ion (common name: diquat); U organoarsenic herbicides, such as monosodium methanarsonate (common name: MSMA); and V amino acid herbicides, such as N-( (phosphonomethyl)glycine (common name: glyphosphate) and its salts and esters. Hereinafter, the present invention will be explained with reference to examples, but the present invention is not limited by the examples. Example 1 2-{4-[N-methyl-N-(7-chloro-1
-Oxide-1,2,4-benzotriazine-
3-yl)amino]phenoxy}propionic acid methyl ester (1) (a) 3,7-dichloro-1,2,4-benzotriazine 1-oxide ^{* (} 3.5g)
J.JuiS and G.P.
GPMueller): Journal of Organic Chemistry (J.Org.Chem.), Volume 24,
Produced according to the method on pages 813-818 (1959).
F.G.A. Wolf, R.M. Wilson, K.P. Filter and M.
Teishuller (FJWolf, RMWilson, KP
Fister and M.Tishler): Journal of
American Chemical Society (J.
Amer. Heat to reflux. The solvent was partially removed by evaporation and a precipitated red solid (3.0 g) was obtained by filtration. Chromatography on silica gel (80 g) was performed using chloroform as the eluent.
4-[methyl-(7-chloro-1-oxide-
1,2,4-benzotriazin-3-yl)amino]phenol (2.1 g) was obtained as a red solid. Mass spectrometry: _Measurement M (molecular ions ₎ m/ _e = 302; _C14H11ClN4O2 required 302. (b) 4-[methyl-(7-chloro-1-oxide-
A mixture of 1,2,4-benzotriazin-3-yl)amino]phenol (2.1 g), 2-bromopropionic acid methyl ester (1.9 g), anhydrous calcium carbonate (1.6 g) and methyl ethyl ketone (30 ml) was heated for 20 hours. Heat to reflux. The reaction solution was filtered and the solvent was removed by vacuum distillation to obtain an orange solid (3.0 g). Chromatography on silica gel (70 g) using chloroform/methanol as eluent yielded 2-
{4-[methyl(7-chloro-1-oxide-
1,2,4-benzotriazin-3-yl)amino]phenoxy}propionic acid methyl ester (2.7 g) was obtained as orange crystals. Mass spectrum analysis: Measurement M at m/e386
(molecular ion); C ₁₈ H ₁₇ ClN ₄ O ₄ requires 386. Example 2 2-{4-[N-methyl-N-(7-chloro-1
-Oxide-1,2,4-benzotriazine-
3-yl)amino]phenoxy}propionic acid methyl ester (1) (a) 3,7-dichloro-1,2,4-benzotriazine-1-oxide (30.0g), 4-(N-
Methylamino)phenol sulfate (48.0
g), water (400ml) and acetonitrile (400ml)
ml) was heated under reflux with stirring for 24 hours. The resulting solution was concentrated and cooled to obtain red crystals. When this product was recrystallized from acetonitrile-water, 4-[N-methyl-N
-(7-chloro-1-oxide-1,2,4-
Benzotriazin-3-yl)amino]phenol (36.5 g) was obtained as a red crystalline solid. Melting point 228-230℃. (b) 4-[N-methyl-N-(7-chloro-1-oxide-1,2,4-benzotriazine-3-
yl)amino]phenol (20.8g), 2-bromopropionic acid methyl ester (13.8g),
A mixture of anhydrous potassium carbonate (11.4g) and anhydrous dimethylformamide (100ml) was heated at 100°C for 2 hours with stirring. The solution was cooled and dichloromethane was added, then the mixture was washed repeatedly with water. The organic phase was dried over anhydrous magnesium sulfate and the solvent was removed by vacuum distillation. The obtained product was recrystallized from methanol to give the title product (16.8 g) as orange crystals (melting point 132°C). The structure of the above compound was confirmed by proton magnetic resonance spectrum and mass spectrum. Example 3 Compound numbers 5, 6, 7, 8, detailed in Table 1
9, 10, 11, 14 and 54 are appropriate 1, 2, 4-
Obtained by substantially the same method as described in Example 1 or Example 2 using benzotriazine, 4-(N-methylamino)phenol sulfate and the appropriate 2-halopropionic acid alkyl ester. Ta. The structure of each compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Appropriate physical data are recorded in Example 24, Table 5. Example 4 2-{4-[N-(7-chloro-1-oxide-
1,2,4-benzotriazin-3-yl)amino]phenoxy}propionic acid methyl ester (2) (a) 3,7-dichloro-1,2,4-benzotriazin-1-oxide ^* (3.5g) , 4-aminophenol (3.53g) and aqueous ethanol (30ml) was heated to reflux for 18 hours. When the solvent was removed by vacuum distillation, 4-[(7-chloro-1-oxide-1,2,4-benzotriazin-3-yl)amino]phenol (4.0 g)
was gotten. (b) 4-[(7-chloro-1-oxide-1,2,
4-benzotriazin-3-yl)amino]phenol (4.0 g; obtained in step a) above,
2-bromopropionic acid methyl ester (3.7
g), anhydrous potassium carbonate (3.0 g) and methyl ethyl ketone (40 ml) was heated under reflux for 18 hours. The solvent was removed by distillation under reduced pressure and the residue was partitioned between water and chloroform. The chloroform layer was dried and the chloroform was evaporated to give a deep red solid (3.0 g). Washing the solid with boiling methanol gives 2-{4-
[(7-chloro-1-oxide-1,2,4-benzotriazin-3-yl)amino]phenoxy}propionic acid methyl ester (2.0 g) was obtained as a red solid. Mass spectrum analysis: Measurement M at m/e374
(molecular ion); C ₁₇ H ₁₅ ClN ₄ N ₄ requires 374. Example 5 Compound No. 4 detailed in Tables 1, 2 and 3,
46, 48, 57, 59, 66 and 77 are appropriate 1, 2,
Obtained in substantially the same manner as described in Example 4 using 4-benzotriazine, 4-aminophenol and the appropriate 2-halopropionic acid alkyl ester. The structure of each compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Appropriate physical data can be found in Example 24, No. 5
recorded in the table. Example 6 2-{4-[N-methyl-N-(7-chloro-1,
2,4-benzotriazin-3-yl)amino]phenoxy]propionic acid methyl ester
(3) (a) 4-[N-methyl-N-(7-chloro-1-oxide-1,2,4-benzotriazine-3-
yl)amino]phenol (10.0 g; obtained in Example 1, step a)) and zinc powder (4.3 g) were added to acetic acid (100 ml) and water (10 ml).
was added to the mixture. The resulting mixture was heated at 100° C. for 30 minutes with vigorous stirring. Furthermore,
Zinc dust (4.3g) was added and heating and stirring continued for an additional 30 minutes. The cooled mixture was filtered and the filtrate was diluted with hydrogen peroxide (30% v/v 5
ml) and water (100 ml) and the aqueous mixture was stirred for 1 hour at room temperature. The solid is filtered off, washed with water and dried to give 4-
[N-methyl-N-(7-chloro-1,2,4-
Benzotriazin-3-yl)amino]phenol (8.2 g) was a red crystalline solid (melting point 224-
226°C). (b) 4-[N-methyl-N-(7-chloro-1,
Reacting 2,4-benzotriazin-3-yl)amino]phenol with 2-bromopropionic acid methyl ester in substantially the same manner as described in step b) of Example 1 gives the title compound ( A melting point of 120°C was obtained. The structure of this compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Example 7 Compound numbers 12, 13, 15, 19, detailed in Table 1
21, 40 and 55 are appropriate 4-[N-methyl-N
-(1-oxide-1,2,4-benzotriazin-3-yl)amino]phenol and then reduce the appropriate 4-[N-methyl-N-(1,2,4-
benzotriazin-3-yl)amino]phenol with the appropriate 2-halopropionic acid alkyl ester in substantially the same manner as described in Example 6. The structure of each compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Appropriate physical data are recorded in Example 24, Table 5. Example 8 2-{4-[N-ethyl-N-(7-chloro-1
-Oxide-1,2,4-benzotriazine-
3-yl)amino]phenoxy}propionic acid ethyl ester (50) 2-{4-[N-(7-chloro-1-oxide-
1,2,4-benzotriazin-3-yl)amino]phenoxy}propionic acid ethyl ester (1.5 g; compound no. 77, see Example 5), sodium hydride (0.19 g of 50% dispersion in mineral oil) , ethyl iodide (0.60 g) and dimethylformamide were stirred at room temperature for 15 minutes. The resulting mixture was poured into dichloromethane and washed repeatedly with water. The organic phase was dried over anhydrous magnesium sulfate and the solvent was removed by vacuum distillation to yield a red oil. The crude product was purified by chromatography on silica gel using dichloromethane as eluent to give the title compound as a red oil. The structure of this compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Proton magnetic resonance spectrum (δppm,
CDCl ₃ ): 1.30, t, 3H; 1.65, d, 3H; 4.20,
m, 4H; 4.80, q, 1H; 7.20, m, 4H; 7.60,
d, 2H; 8.20, s, 1H Example 9 Compound No. 16 detailed in Tables 1, 2 and 3;
17, 18, 22, 23, 24, 47, 49, 60, 65 and 67
Example ⁸
It can be obtained by alkylation by substantially the same means as described in . (Compound number 57 is
Compound numbers 46, 48, 49, 77 and 66 were used to produce compound numbers 47, 49, 60, 65 and 67, respectively. was used for. ) The structure of each compound was confirmed by proton nuclear magnetic resonance spectroscopy and mass spectrometry. Appropriate physical data are recorded in Example 24, Table 5. Example 10 2-{4-[N-methyl-N-(7-chloro-1,
2,4-benzotriazin-3-yl)amino]phenoxy}propionic acid (20) 2-{4-[N-methyl-N-(7-chloro-1,
2,4-benzotriazin-3-yl)amino]
Phenoxy} propionic acid ethyl ester (5.0
g; Compound No. 13, Example 7) was suspended in isopropyl alcohol (25 ml), and a solution of sodium hydroxide (0.56 g) and water (25 ml) was added over 45 minutes. Additionally, isopropyl alcohol (30
ml) was added and the resulting mixture was stirred at room temperature for 48 hours. The aluere was removed by vacuum distillation, the residue was dissolved in water and the aqueous solution was acidified to PH4 by addition of aqueous 2M hydrochloric acid. The precipitate was collected by filtration and then dried to give the title compound, melting point 125°C. The structure of this compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Example 11 Compounds Nos. 36, 61 and 74 detailed in Tables 1 and 4 were prepared by hydrolyzing the corresponding esters (10, 51 and 76, respectively) in substantially the same manner as described in Example 10. It was obtained by The given structure of each compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Appropriate physical data are recorded in Example 24, Table 5. Example 12 2-{4-[N-methyl-N-(7-chloro-1,
2,4-benzotriazin-3-yl)amino]phenoxy}propionic acid n-propyl ester (28) 2-{4-[N-methyl-N-(7-chloro-1,
2,4-benzotriazin-3-yl)amino]
Phenoxy} propionic acid ethyl ester (80
6 g, Compound No. 13, Example 7), a mixture of n-propanol (800 ml) and concentrated sulfuric acid (3 ml).
Heated at reflux for an hour. A small amount of water was added and the resulting mixture was concentrated. Dichloromethane was added and the mixture was washed first with dilute aqueous potassium carbonate solution and then with water. The organic phase was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure to give the title compound (80 g) as a red oil. The structure of this compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Proton magnetic resonance spectrum (ppm, _CDCl3 ):
0.90, t, 3H; 1.65, m, 5H; 3.65, s,
3H; 4.20, t, 2H; 4.80, q, 1H; 7.20, m,
4H; 7.65, s, 2H; 8.25, s, 1H Example 13 Compound No. 25 detailed in Tables 1 and 4,
26, 27, 32, 33, 34, 35 and 70 were obtained by transesterifying the corresponding ethyl esters in substantially the same manner as described in Example 12 (compound no. 25, 26 and 27 are obtained from compound no. 13; compound no. 32, 33, 34 and 35
was obtained from compound no. 10; compound no. 70 was obtained from compound no. 68). The structure of each compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Appropriate physical data are recorded in Example 24, Table 5. Example 14 2-{4-[N-methyl-N-(7-chloro-1,
2,4-benzotriazin-3-yl)amino]
Sodium phenoxy}propionate (29) (melting point 178°C) and 2-{4-[N-methyl-N-(7
Sodium -chloro-1-oxide-1,2,4-benzotriazin-3-yl)amino]phenoxy}propionate (37) (melting point 184°C) was added to the corresponding acids (Compound 20, Example 10 and Compound 36) , Example 11) by neutralizing with aqueous sodium hydroxide and evaporating the solvent under reduced pressure. Example 15 2-{4-[N-methyl-N-(7-chloro-1
-Oxide-1,2,4-benzotriazine-
3-yl)amino]phenoxy}propionic acid 2-(dimethylamino)ethyl ester (43) (a) 2-{4-[N-methyl-N-(7-chloro-
A mixture of 2-oxide-1,2,4-benzotriazin-3-yl)amino]phenoxy}propionic acid (1.5 g; Compound No. 36, Example 11) and excess thionyl chloride was heated to reflux for 5 hours. Excess thionyl chloride was distilled off under reduced pressure to give 2-{4-[N-methyl-N-(7-chloro-1-oxide-1,2,
4-benzotriazin-3-yl)amino]phenoxypropionyl}chloride was obtained. (b) A mixture of the acid chloride obtained in (a) above, 2-(dimethylamino)ethanol (0.41 g) and dichloromethane (20 ml) was stirred at room temperature overnight. The solvent was removed by vacuum distillation to give a red oil. The crude product was purified by silica gel chromatography using dichloromethane as the eluent to give the title compound (1.0 g) as a red oil. The structure of this compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Proton magnetic resonance spectrum (δppm, _CDCl3 ):
1.65, d, 3H; 2.00, s, 6H; 2.40, t,
2H; 3.65, s, 3H; 4.15, t, 2H; 4.80, q,
1H; 7.20, m, 4H; 7.60, s, 2H; 8.20, s,
1H Example 16 Compound numbers 30, 31, detailed in Tables 1 and 4
41, 42, 44, 45, 52, 62, 63, 64 and 75 were obtained from the corresponding acids via acid chlorides by substantially the same means as described in Example 15. Compound Nos. 30, 31 and 63 are obtained from the acid (Compound No. 20, Example 10); Compound No. 41,
42, 44, 45, 52, and 64 are acids (compound number 36,
Compound No. 62 was obtained from the acid (Compound No. 61, Example 11); and Compound No. 75 was obtained from the acid (Compound No. 74, Example 11). The structure of each compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Appropriate physical data are recorded in Example 24, Table 5. Example 17 2-{4-[N-methyl-N-(7-chloro-1
-Oxide-1,2,4-benzotriazine-
3-yl)amino]phenoxy}propionic acid propargyl ester (39) 2-{4-[N-methyl-N-(7-chloro-1
-oxide-1,2,4-benzotriazine-3
A mixture of -yl)amino]phenoxy}propionic acid (2.1 g; Compound No. 36, Example 11), p-toluenesulfonic acid (0.5 g) and excess propargyl alcohol was stirred at 100°C for 4 hours.
The cooled solution was poured into ethyl acetate and the resulting mixture was washed with water. The organic phase was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure to give an oil. The crude product was purified by silica gel chromatography using dichloromethane as eluent to give the title compound (1.26
g) was obtained as an orange crystalline solid. melting point 101
℃. The structure of this compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Example 18 2-{4-[4-methyl-N-(7-chloro-1
-oxide-1,2,4-benzotriazine-3
-yl)amino]phenoxy}propionic acid allyl ester (38) is 2-{4-[N-methyl-N
-(7-chloro-1-oxide-1,2,4-benzotriazin-3-yl)amino]phenoxy}propionic acid and allyl alcohol,
Obtained by substantially the same procedure as described in Example 17. 2-{4-[N-methyl-N-(7-chloro-2
-oxide-1,2,4-benzotriazine-3
-yl)amino]phenoxy}propionic acid n-
Propyl ester (58) is 2-{4-[N-methyl-N-(7-chloro-2-oxide-1,2,
It was obtained in a similar manner from 4-benzotriazin-3-yl)amino]phenoxy}propionic acid and n-propanol. The structure of each compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Appropriate physical data can be found in Example 24, Section 5.
recorded in the table. Example 19 2-{4-[N-methyl-N-(7-chloro-1,
2,4-benzotriazin-3-yl)amino]phenoxy}-2-methylpropionic acid ethyl ester (73) 4-[N-methyl-N-(7-chloro-1,2,
4-Benzotriazin-3-yl)amino]phenol [1.5 g; Example 6, step a], 2-bromo-2-methylpropionate ethyl alcohol (1.23 g), anhydrous potassium carbonate (0.87 g) and dimethylformamide The mixture (15 ml) was heated at 100° C. for 3 days with stirring. The cooled solution was poured into dichloromethane and the mixture was washed with water, the aqueous phase was dried over anhydrous magnesium sulfate and
The solvent was then distilled off under reduced pressure to obtain an oily substance. The crude product was purified by chromatography on silica gel using dichloromethane as eluent to yield the title compound (0.9 g).
was obtained as a red oil. The structure of this compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Proton magnetic resonance spectrum (δppm, _CDCl3 ):
1.30, t, 3H; 1.70, s, 6H; 3.65, s,
3H; 4.30, q, 2H; 7.20, m, 4H; 7.60, s,
2H; 8.20, s, 1H Example 20 Compound numbers 68, 69, 71, 72 and 36 are the appropriate 4-[N-methyl-N-(1,2,4-benzotriazin-3-yl)amino] Obtained in substantially the same manner as described in Example 19 from phenol and the appropriate 2-haloalkanecarboxylic acid alkyl ester. The structure of each compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Appropriate physical data are recorded in Example 24, Table 5. Example 21 2-{4-[N-methyl-N-(7-chloro-2
-Oxide-1,2,4-benzotriazine-
3-yl)amino]phenoxy}propionic acid methyl ester (51) 2-{4-[N-methyl-N-(7-chloro-1,
2,4-benzotriazin-3-yl)amino]
Phenoxy}propionic acid methyl ester (6.1
A mixture of Compound No. 3, Example 6), acetic acid (110 ml) and hydrogen peroxide (44 ml of 30% v/v) was stirred at room temperature for 5 days. The precipitated yellow solid was collected by filtration and recrystallized from acetic acid to yield the title compound (5.0 g).
was obtained as a yellow crystalline solid. Melting point: 130℃. The structure of this compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Example 22 2-{4-[N-(7-chloro-2-oxide-
1,2,4-benzotriazin-3-yl)amino]phenoxy}propionic acid ethyl ester (56) The title compound is 2-{4-[N-(7-chloro-
Oxidizing 1,2,4-benzotriazin-3-yl)amino]phenoxy}propionic acid ethyl ester (Compound No. 57, Example 5) by substantially the same means as described in Example 21. Obtained by. The structure of this compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Appropriate physical data can be found in Example 24, Section 5.
recorded in the table. Example 23 2-{3-chloro-4-[N-(7-chloro-1
-Oxide-1,2,4-benzotriazine-
3-yl)amino]phenoxy}propionic acid ethyl ester (53) 2-{4-[N-(7-chloro-1-oxide-
A mixture of 1,2,4-benzotriazin-3-yl)amino]phenoxy}propionic acid ethyl ester (1.5g; Compound No. 77, Example 5), N-chlorosuccinimide (0.57g) and dichloromethane (20ml) was stirred at room temperature for 3 days. This mixture was washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a red oily substance. The crude product was purified by chromatography on silica gel using dichloromethane as eluent to give the title compound (0.81 g) as an orange crystalline solid (mp 169°C). The structure of this compound was confirmed by proton magnetic resonance spectroscopy and mass spectrometry. Example 24 A number of the compounds according to the invention detailed in Tables 1 to 4 are solids and can be identified by their melting points. Many of the compounds according to the invention detailed in Tables 1 to 4 can be characterized and identified by their proton magnetic resonance (PMR) spectra. For convenience, the PMR spectroscopy data is recorded in Table 5b below.

【table】

【table】

【table】

Table Example 25 A concentrated formulation of the compound according to the invention is obtained as follows: (a) If the compound according to the invention is an oily substance and a waxy solid, the compound is added at 7% v/v.
v “Teric N13” (“Teric” is a trade name and “Teric” N13 is a product obtained by ethoxylating nonyl alcohol) manufactured by ICI Australia Limited ) and “Kemmat”
(b) if the compound according to the invention is a crystalline solid; 5 parts by weight of the compound and 1 part by weight of "Dyapol" PT ("Dyapol"
is a trade name and “Dyapol” PT is an anionic suspending agent) in an aqueous solution containing 0.25% v/v “Teric” N8 (product of ethoxylation of nonyl alcohol). and ball mill the mixture to produce a stable suspension. The suspending concentrate and the suspension are then diluted with water to prepare an aqueous composition of a predetermined concentration suitable for use in evaluating the pre- and post-emergent herbicidal activity of the compounds according to the invention. do. Example 26 The pre-emergence herbicidal activity of compounds according to the invention formulated as described in Example 25 was evaluated by the following procedure. Seeds of the test plant species were sown in several rows at a depth of 2 cm in soil placed in seed boxes. Monocots and dicots were sown in separate boxes, and the two boxes after sowing were sprayed with a predetermined amount of the composition according to the invention. Two pairs of seed boxes were prepared similarly, but one was not sprayed with the composition of the invention and was used for comparative purposes. All boxes were placed in a greenhouse and lightly watered with overhead spray to initiate germination. After three weeks, the boxes were removed from the greenhouse and the effects of the treatment were visually assessed. The rest is shown in Table 6. In the table, damage to plants is graded on a scale from 0 to 3, where 0 represents 0 to 35% damage and 3 represents damage of 0 to 35%.
75 to 99% mortality, and 3+ represents 100% mortality. A dash (-) means that the experiment was not conducted. The names of the test plants are as follows: Wh Wheat Ot Wild Crow Wheat Rg Rye Jm Millet (Japanese millet) P Pea Ip Morning Gourd Ms Mustard SF Sunflower

【table】

【table】

[Table] Example 27 The post-emergence herbicidal activity of compounds according to the invention formulated as described in Example 25 was evaluated using the following procedure. Seeds of the test plant species were sown in several rows at a depth of 2 cm in soil placed in seed boxes. Monocots and dicots were sown in pairs in separate seed boxes. Four seed boxes were placed in the greenhouse and lightly watered with an overhead spray to initiate germination, then watered as necessary for optimal plant growth.
After the plant has grown to a height of about 10 to 12.5 cm,
One box each of monocots and dicots was removed from the greenhouse and sprayed with a predetermined amount of the composition according to the invention. After spraying, the boxes were returned to the greenhouse and left for an additional 3 weeks, and the effects of the treatment were visually evaluated in comparison to untreated controls. The results are shown in Table 7, in which damage to plants is graded on a scale of 0 to 3. On that scale, 0 indicates damage from 0 to 25%, 3 indicates a fatality rate of 75 to 99%, and 3+ indicates a fatality rate of 75 to 99%.
Shows 100% mortality. A dash (-) means that the experiment was not conducted. The test plant names are as follows: Wh Wheat Ot Wild Crow Wheat Rg Rye Jm Millet P Pea Ms Mustard Sf Sunflower

【table】

[Table] Example 28 “Span” 80 of 21.8g per 1 liter
and the compound by mixing the appropriate amount of the compound with 5 ml of an emulsion prepared by diluting 160 ml of a methylcyclohexanone solution containing 78.2 g of "Tween" 20 per liter to 500 ml with water. was formulated for testing. "Span" 80 is a trade name and is a surfactant consisting of sorbitan monolaurate. "Tween" 20 is a trade name and is a surfactant consisting of a condensate of sorbitan monolaurate and 20 molar percentages of ethylene oxide. Each of 5 ml of emulsion containing the test compound was then diluted to 40 ml with water and sprayed on young pot plants (post-emergence test) of the plant species listed in Table 8 below. Damage to the test plants was evaluated after 14 days and graded on a scale of 0 to 5. Scale 0 indicates damage from 0 to 20%, and 5
represents complete lethality. In tests for pre-emergence herbicidal activity, seeds of test plants were sown into small slits formed in the surface of the soil in fibrous dishes. The surface was then leveled, sprayed, and a thin layer of fresh soil was sprinkled over the sprayed surface. twenty one
After a day, the weeding damage was evaluated and graded using a scale from 0 to 5 as in the post-emergence evaluation test. In both cases, the extent of herbicidal damage was evaluated in comparison to untreated control plants. The results are shown in Table 8 below. A dash (-) means that the experiment was not performed. The names of the test plants are as follows. SB Tenssei RP Soya CT SY Soy Soy Mz MZ MZ MZ Winter Wheat RC RC rice SN Novorogik (IPomea Purpurea) IPomea Purpure AM AMA AMARANTHUS RETROFLEXUS (Polygonum Aviculare) CA Hosoba ANBUM PO Tachi Portulaca oleracea Ga Gallium aparine Xa Xanthium pensylvanicum Ab Abutilon
theophrasti) Cv Convolvulus arvensis Co Cassia obtusifolia
obtusifolia) Av Avena fatua Dg Digitaria sanguinalis
sanguinalis) Pu Poa annua Al Alopecurus myosuroides St Setaria viridis Ec Echinochloa crus-galli Sh Sorghum
halepense) Ag Agropyron repens
repens) Cn Cyperus rotundus

【table】

Table: Example 29 This example demonstrates the selective herbicidal activity of compounds of the invention when applied in the field. The test compounds were formulated by substantially the same means as described in Example 28. Seeds of test plants were sown using a Stanhay Precision Seeder in flat-topped furrows spaced 1 meter apart. Two plant species were sown in each row. The flat-topped ridges were divided into subsections based on the application rate of the test agent. Plant species were sown at different times so that they reached approximately the same growing season at the same time. Separate each flat-topped ridge to be sprayed with the formulated test compound by striking it with a 1.25 meter center rod, and then mark it with two numbers “0”.
Oxford Precision Sprayer with T-Jet
was used to spray a 1 meter wide area. In the pre-emergence test, flat-topped furrows were sprayed with the test compound after sowing and damage to the test plants was measured at 14, 21, 35 and 63 days after spraying.
Visual evaluation was performed on the following day. The results expressed as mortality percentage are shown in Table 9, Part A. In the post-emergence test, the test compound is sprayed on flat-topped ridges after the test plants have reached the 2-3 leaf stage, and the degree of damage is measured 7 days after spraying.
Visual evaluation was performed on days 1, 14, 28, and 56.
The results were expressed as a mortality percentage and are shown in Table 9, Part B. The names of the test plants are as follows. Sy Soybean (Bethal) Ct Cotton (Delta Pine 16) Pn Peanut (Red Spanish) Mz Corn (XL 45) Ss Setaria anceps Dg Digitaria sanguinalis
sanguinalis) Ec Echinochloa crus-galli Sg Sorghum (gold raspberry species) Sh Sorghum herepense
helepense)

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1. A compound represented by the following general formula or a salt thereof. In the formula, A, B, D, E, U and V independently represent a hydrogen atom, a halogen atom, a nitro group, a _C1 - _C6 alkyl group, a _C1 - _C6 haloalkyl group, and a C1- _C6 haloalkyl group.
A group selected from the group consisting of C ₆ alkoxy groups, and R ¹ is a hydrogen atom, a C ₁ to C 10 alkyl group, and a C ₂ to C ₁₀ alkyl group.
A group selected from the group consisting of a C ₁₀ alkynyl group and a benzyl group, and R ² is a hydrogen atom, a C ₁ to C ₆ alkyl group, and
is a group selected from the group consisting of a C ₂ - C ₆ alkoxyalkyl group, R ³ is a group selected from the group consisting of a hydrogen atom and a C ₁ - _{C 6} alkyl group, and W is a group [Formula] [In the formula, G is a hydroxy group, a C ₁ to _{C 10} alkoxy group, a C ₁ to _{C 10} haloalkoxy group, a C ₂ to C ₁₀ alkenyloxy group, a C ₂ to
a _C10 alkynyloxy group, a _C1 - _C10 alkylthio group, a C1- _C6 alkoxy group substituted _with N,N-di( _C1 - _C6 alkyl)amino, a group -OM (in the formula, M is a cation of an inorganic or organic base),
Group -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are independently a hydrogen atom, a C ₁ to C ₆ hydroxyalkyl group, and a C ₁ to
is a group selected from the group consisting of C ₆ haloalkyl groups) and the group -O-N=R ¹⁰ (wherein R ¹⁰ is a C ₁
~ _C10 alkylidene group), k and l are independently 0 or 1 (however, k+l is 0 or 1) 1). 2 A, B, D, E, U and V independently represent a hydrogen atom, a halogen atom, a nitro group, a _C1 - _C6 alkyl group, a _C1 - _C6 haloalkyl group, and a _C1 - _C6
is a group selected from the group consisting of an alkoxy group, R ¹ is a group selected from the group consisting of a hydrogen atom, a C ₁ to C ₁₀ alkyl group, and a benzyl group, R ² is a hydrogen atom, _C1 - _C6 alkyl groups and
is a group selected from the group consisting of a C ₂ - C ₆ alkoxyalkyl group, R ³ is a group selected from the group consisting of a hydrogen atom and a C ₁ - _{C 6} alkyl group, and W is a group [Formula] [In the formula, G is a hydroxy group, a C ₁ to _{C 10} alkoxy group, a C ₁ to _{C 10} haloalkoxy group, a C ₂ to C ₁₀ alkenyloxy group, a C ₂ to
a _C10 alkynyloxy group, a _C1 - _C10 alkylthio group, a group -OM (wherein M is a cation ^of an organic or inorganic base), a group ^-NR5R6 (wherein ^R5 and ^R6 are independently a group selected from the group consisting of a hydrogen atom, a C ₁ -C ₆ haloalkyl group, and a C ₁ -C ₆ hydroxyalkyl group, and k and The compound according to claim 1, wherein l is independently 0 or 1 (k+l is 0 or 1). 3 A, B, D and E each represent a hydrogen atom, a halogen atom, a nitro group, _C1 - _C6 alkyl group,
A group selected from the group consisting of a C ₁ to C ₆ haloalkyl group and a C ₁ to _{C 6} alkoxy group, and U and V are each a hydrogen atom, a halogen atom, a nitro group, and a C ₁ to C ₆ alkyl group. and C ₁ ~
A group selected from the group consisting of C ₆ haloalkyl groups, and R ¹ is a hydrogen atom, a C ₁ to C 6 alkyl group, and a C ₂ to C ₆ alkyl group.
A group selected from the group consisting of a C ₆ alkynyl group and a benzyl group, and R ² is a group selected from a hydrogen atom, a C ₁ to _{C 6} alkoxyalkyl group, and a C ₁ to _{C 6} alkyl group. , R ³ is a group selected from a hydrogen atom and a C ₁ to C ₆ alkyl group, W is a group [formula] [wherein G is a hydroxy group, a C ₁ to _{C 10} alkoxy group , _C1 - _C10 haloalkoxy group, C2 _{- C10} alkenyloxy group, C2 _- C10
a _C10 alkynyloxy group, a _C1 - _C10 alkylthio group, a _C1 - _C6 alkoxy group substituted with N,N-di( _C1 - _C6 alkyl)amino, a group -OM (in the formula,
M is an alkali metal ion) and the group -O-
N = a group selected from the group consisting of R ¹⁰ (wherein R ¹⁰ is a C ₁ to C ₁₀ alkylidene group), and k and l are each 0 or 1 (however, k+l is 0 or 1), the compound according to claim 1. 4 A, B, D and E are each a group selected from a hydrogen atom, a halogen atom, a _C1 - _C6 alkyl group, a _C1 - _C6 haloalkyl group, and a _C1 - _C6 alkoxy group, U and V are atoms selected from hydrogen atoms and halogen atoms, respectively, and R ¹ is a hydrogen atom, a C ₁ to C ₆ alkyl group, and a C ₂ to C ₆ alkyl group.
is a group selected from an alkynyl group and a benzyl group, and R ² is a hydrogen atom, a C ₁ to C ₆ alkyl group, and a C _2
-C6 alkoxyalkyl group, ^R3 is a hydrogen atom and a _C1 - _C6 alkyl group, W is a group [formula] [wherein, G is a hydroxy group, a _C1 - _C10 alkoxy group, a _C2 - _C10 alkenyloxy group, a _C2 - _C10 alkynyloxy group, _C1
-C10 alkylthio group, _C1 - _C10 haloalkoxy group, _C1 - _C6 alkoxy group substituted with N,N-di( _C1 - _C6 alkyl)amino, group -O-N
= R ¹⁰ (wherein R ¹⁰ is a C ₁ -C ₁₀ alkylidene group), the group -OM (wherein M is an alkali metal ion) and the group -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are a hydrogen atom, a C ₁ to C ₆ alkyl group, and
a _C1 - _C6 haloalkyl group], k and l are 0 and 1, respectively, and k+l is 0 or 1, A compound according to item 1 or item 3. 5 Formula: The compound according to any one of claims 1 to 4, which is represented by: 6 A, E and V are each hydrogen atoms,
B is a group selected from the group consisting of a hydrogen atom, a halogen atom, a _C1 - _C6 alkyl group, a _C1 - _C6 alkoxy group, and a _C1 - _C6 haloalkyl group, and D and U are each A group selected from a hydrogen atom and a halogen atom, and R ¹ , R ² and R ³ are each a hydrogen atom or a C ₁
A group selected from ~ _C6 alkyl groups, W is a group [formula] [wherein G is a hydroxy group, a _C1-C10 alkoxy group, a _C2 - _C10 alkenyloxy group, a C2- _C10 alkenyloxy group, ₂ - _C10 alkynyloxy group, _C1
-C10 alkylthio group, _C1 - _C10 haloalkoxy group, _C1 - _C6 alkoxy group substituted with N,N-di( _C1 - _C6 alkyl)amino group, group -O-
N=R ¹⁰ (wherein R ¹⁰ is a C ₁ -C ₁₀ alkylidene group) and the group -OM (wherein M is an alkali metal ion); The compound according to claim 1 or any one of claims 3 to 5, wherein k and l are 0 and 1, respectively, and k+l is 0 or 1. 7 A, D, E, U, V and R ³ are each a hydrogen atom, B is a group selected from a halogen atom and a C ₁ to C ₆ haloalkyl group, and R ¹ and R ² are both a methyl group , W is a group [formula] [wherein G is a hydroxy group, a C ₁ to C ₆ alkoxy group, a C ₂ to C ₆ alkenyloxy group, a C ₂ to _{C 6} alkynyloxy group, a C ₁ to C ₆
alkylthio group, _C1 - _C6 haloalkoxy group, and group -OM (wherein M is an alkali metal ion), k and l are each 0 or 1, and , and k+l is 0 or 1. The compound according to any one of claims 1 to 6. 8 A, D, E, U, V and R ³ are each a hydrogen atom, B is a bromine atom or a chlorine atom, R ¹ and R ² are both a methyl group, and W is a group [Formula] [Formula Among them, G is a hydroxy group, a C ₁ to C ₆ alkoxy group, an allyloxy group, a C ₂ to
C ₆ alkynyloxy group, C ₁ to C ₆ alkylthio group, C ₁ to _{C 6} chloroalkoxy group and group -
OM (wherein M is sodium or potassium), k and l are each 0 or 1, and k+l is 0 or 1, Claim 1 A compound according to any one of Items 1 to 7. 9 2-{4-[N-methyl-N-(7-chloro-
1,2,4-benzotriazin-3-yl)amino]phenoxy}propionic acid, 2-{4-[N-
Methyl-N-(7-bromo-1,2,4-benzotriazin-3-yl)amino]phenoxy}propionic acid, 2-{4-[N-methyl-N-(7-
Chloro-1-oxide-1,2,4-benzotriazin-3-yl)amino]phenoxy}propionic acid, 2-{4-[N-methyl-N-(7-bromo-1-oxide-1,2) ,4-benzotriazin-3-yl)amino]phenoxy}propionic acid, 2-{4-[N-methyl-N-(7-chloro-
2-oxide-1,2,4-benzotriazine-
3-yl)amino]phenoxy}propionic acid and 2-{4-[N-methyl-N-(7-bromo-
2-oxide-1,2,4-benzotriazine-
3-yl)amino]phenoxy}propionic acid selected from the group consisting of methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, isobutyl ester and secondary butyl ester A compound according to any one of Items 1 to 8. 10 The following general formula, [In the formula, A, B, D, E, U and V independently represent a hydrogen atom, a halogen atom, a nitro group, a _C1 - _C6 alkyl group, a _C1 - _C6 haloalkyl group, and a C1- _C6 haloalkyl group.
A group selected from the group consisting of C ₆ alkoxy groups, and R ¹ is a hydrogen atom, a C ₁ to C ₆ alkyl group, and
A group selected from the group consisting of C ₂ - C ₆ alkynyl groups, R ² is a hydrogen atom, a C ₁ - C ₆ alkyl group, a C ₂ -
A group selected from the group consisting of a C ₆ alkoxyalkyl group and a benzyl group, R ³ is a group selected from the group consisting of a hydrogen atom and a C ₁ to C ₆ alkyl group, and W is a group [Formula] [In the formula, G is a hydroxy group, a C ₁ to _{C 10} alkoxy group, a C ₁ to _{C 10} haloalkoxy group, a C ₂ to C ₁₀ alkenyloxy group, a C ₂ to
a _C10 alkynyloxy group, a _C1 - _C10 alkylthio group, a _C1 - _C6 alkoxy group substituted with N,N-di( _C1 - _C10 alkyl)amino, a group -OM (in the formula, M is a cation of an inorganic or organic base),
Group -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are independently a hydrogen atom, a C ₁ to C ₆ hydroxyalkyl group, and a C ₁ to
is a group selected from the group consisting of C ₆ haloalkyl groups) and the group -O-N=R ¹⁰ (wherein R ¹⁰ is a C ₁
~ _C10 alkylidene group), k and l are independently 0 or 1 (however, k+l is 0 or 1) 1)] A method for severely damaging or killing an undesired plant, which comprises applying an effective amount of a compound represented by the formula (1) or a salt thereof to the undesired plant or to the growth medium of the plant. 11 from 0.005 to 20 per hectare of the above compounds.
11. A method according to claim 10, comprising applying at a rate in the kilogram range. 12 The following general formula, [In the formula, A, B, D, E, U and V independently represent a hydrogen atom, a halogen atom, a nitro group, a _C1 - _C6 alkyl group, a _C1 - _C6 haloalkyl group, and a C1- _C6 haloalkyl group.
A group selected from the group consisting of C ₆ alkoxy groups, and R ¹ is a hydrogen atom, a C ₁ to C 10 alkyl group, and a C ₂ to C ₁₀ alkyl group.
A group selected from the group consisting of a C ₁₀ alkynyl group and a benzyl group, and R ² is a hydrogen atom, a C ₁ to C ₆ alkyl group, and
is a group selected from the group consisting of a C ₂ - C ₆ alkoxyalkyl group, R ³ is a group selected from the group consisting of a hydrogen atom and a C ₁ - _{C 6} alkyl group, and W is a group [Formula] [In the formula, G is a hydroxy group, a C ₁ to _{C 10} alkoxy group, a C ₁ to _{C 10} haloalkoxy group, a C ₂ to C ₁₀ alkenyloxy group, a C ₂ to
a _C10 alkynyloxy group, a _C1 - _C10 alkylthio group, a C1- _C6 alkoxy group substituted _with N,N-di( _C1 - _C6 alkyl)amino, a group -OM (in the formula, M is a cation of an inorganic or organic base),
Group -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are independently a hydrogen atom, a C ₁ to C ₆ hydroxyalkyl group, and a C ₁ to
is a group selected from the group consisting of C ₆ haloalkyl groups) and the group -O-N=R ¹⁰ (wherein R ¹⁰ is C ₁
~ _C10 alkylidene group), k and l are independently 0 or 1 (however, k+l is 0 or 1) 1)] or a salt thereof is applied to the crop or to the growth medium of the crop in an amount that severely damages or dies the weeds but does not substantially damage the crop. A method for selectively suppressing the growth of monocotyledonous weeds in dicotyledonous crops. 13 The above compound at a rate of 0.005 to 20 per hectare
13. A method according to claim 12, comprising applying at a rate in the kilogram range. 14 The following general formula, [In the formula, A, B, D, E, U and V independently represent a hydrogen atom, a halogen atom, a nitro group, a _C1 - _C6 alkyl group, a _C1 - _C6 haloalkyl group, and a C1- _C6 haloalkyl group.
A group selected from the group consisting of C ₆ alkoxy groups, and R ¹ is a hydrogen atom, a C ₁ to C 10 alkyl group, and a C ₂ to C ₁₀ alkyl group.
A group selected from the group consisting of a C ₁₀ alkynyl group and a benzyl group, and R ² is a hydrogen atom, a C ₁ to C ₆ alkyl group, and
is a group selected from the group consisting of a C ₂ - C ₆ alkoxyalkyl group, R ³ is a group selected from the group consisting of a hydrogen atom and a C ₁ - _{C 6} alkyl group, and W is a group [Formula] [In the formula, G is a hydroxy group, a C ₁ to _{C 10} alkoxy group, a C ₁ to _{C 10} haloalkoxy group, a C ₂ to C ₁₀ alkenyloxy group, a C ₂ to
a _C10 alkynyloxy group, a _C1 -C10 alkylthio group, a _C1 - _C10 alkoxy group substituted with N,N-di( _C1 - _{C10 alkyl} )amino, a group -OM (in the formula, M is a cation of an inorganic or organic base),
Group -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are independently a hydrogen atom, a C ₁ to C ₆ hydroxyalkyl group, and a C ₁ to
is a group selected from the group consisting of C ₆ haloalkyl groups) and the group -O-N=R ¹⁰ (wherein R ¹⁰ is a C ₁
~ _C10 alkylidene group), k and l are independently 0 or 1 (however, k+l is 0 or 1) 1)] When producing a compound represented by the formula or a salt thereof, the formula: A benzotriazine derivative represented by ^the formula: (wherein R ¹ , R ² and W have the above definitions,
and hal is a chlorine atom, a bromine atom or an iodine atom). 15 A benzotriazine compound of formula: (In the formula, L is a dissociative group, and A, B,
D, E, k and l have the above definitions), a benzotriazine derivative represented by the formula: (wherein Q is a hydroxy group or a _C1 - _C6 alkoxy group, and U, V and ^R1 have the above definitions) by reacting with an aniline derivative of the formula: (In the formula, A, B, D, E, U, V, Q, R ¹ , k
and l have the same definition as above) and when Q is a C ₁ -C ₆ alkoxy group, by dealkylation of a compound of formula to obtain a compound of formula 15. A method of manufacturing according to claim 14. 16 The following general formula, [In the formula, A, B, D, E, U and V independently represent a hydrogen atom, a halogen atom, a nitro group, a _C1 - _C6 alkyl group, a _C1 - _C6 haloalkyl group, and a C1- _C6 haloalkyl group.
A group selected from the group consisting of C ₆ alkoxy groups, and R ¹ is a hydrogen atom, a C ₁ to C 10 alkyl group, and a C ₂ to C ₁₀ alkyl group.
A group selected from the group consisting of a C ₁₀ alkynyl group and a benzyl group, and R ² is a hydrogen atom, a C ₁ to C ₆ alkyl group, and
is a group selected from the group consisting of a C ₂ - C ₆ alkoxyalkyl group, R ³ is a group selected from the group consisting of a hydrogen atom and a C ₁ - _{C 6} alkyl group, and W is a group [Formula] [In the formula, G is a hydroxy group, a C ₁ to _{C 10} alkoxy group, a C ₁ to _{C 10} haloalkoxy group, a C ₂ to C ₁₀ alkenyloxy group, a C ₂ to
a _C10 alkynyloxy group, a _C1 - _C10 alkylthio group, a C1- _C6 alkoxy group substituted _with N,N-di( _C1 - _C6 alkyl)amino, a group -OM (in the formula, M is a cation of an inorganic or organic base),
Group -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are independently a hydrogen atom, a C ₁ to C ₆ hydroxyalkyl group, and a C ₁ to
is a group selected from the group consisting of C ₆ haloalkyl groups) and the group -O-N=R ¹⁰ (wherein R ¹⁰ is C ₁
~ _C10 alkylidene group), k and l are independently 0 or 1 (however, k+l is 0 or 1) 1)] When producing a compound represented by the formula or a salt thereof, the formula: (In the formula, L means a dissociable group, and A,
B, D, E, k and l have the above definitions)
The benzotriazine derivative represented by the formula: (wherein U, V, W, R ¹ , R ² and R ³ have the above definitions).