JPH0260656B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to biologically active organic compounds (particularly herbicidal organic compounds) and methods for synthesizing such compounds. We have discovered a new class of diphenylamines that exhibit biological activity, especially herbicidal activity. Therefore, the present invention provides a compound represented by the general formula () K0085. In the above formula (), A is selected from the group consisting of hydrogen, halogen, nitro, cyano, amino, trifluoromethyl, sulfo, sulfamoyl, methoxycarbonyl and methoxysulfonyl, and D is hydrogen, halogen, nitro, cyano, Methyl, trifluoromethyl, C _1-3 alkoxy, C _1-2
haloalkoxy, fluoromethylsulfinyl,
Fluoromethylsulfonyl, sulfamoyl,
N,N-dimethylsulfamoyl, carboxy,
(C _1-2 alkoxy)carbonyl, N,N-dimethylcarbamoyl, methylsulfonyl and formyl, E is selected from the group consisting of hydrogen and halogen, and T consists of hydrogen, halogen and nitro. wherein at least one of A, D, E and T is not hydrogen, U and V are each independently selected from the group consisting of hydrogen, halogen and nitro, and R ¹ is Hydrogen, C _1-4 alkyl, C _2-3 alkynyl,
is selected from the group consisting of acetyl and benzyl, R ² and R ³ are each independently selected from the group consisting of hydrogen and methyl, W is [Formula] [wherein G is hydroxy, C _1-6 Alkoxy, C _1-2 bromoalkoxy, C _2-3 alkenyloxy, C _2-3 alkynyloxy, C _1-4 alkylthio, cyclohexyloxy, benzyloxy; morpholino, methylthio, 2-pyridyl,
C _1-2 alkoxy group substituted with one substituent selected from the group consisting of N,N-dimethylamino and N,N,N-trimethylammonio; phenyl ring substituted with two halogens phenoxy; selected from the group consisting of methanesulfonamide group and dimethylamino group] and -CH ₂ Z [in the formula, Z is
selected from the group consisting of halogen, hydroxy, methoxycarbonylmethyl and C _1-2 alkoxy]
selected from the group consisting of. Compounds of general formula () in which R ² and R ³ are not the same have optical activity. The present invention also includes individual stereoisomers of such compounds and mixtures of such stereoisomers, including racemic mixtures of such stereoisomers. Suitable A, D, E, T, U and V include hydrogen, halogen, nitro, cyano, amino, methyl, trifluoromethyl and C _1-3 alkoxy. Suitable R ¹ include hydrogen, C _1-4 alkyl, C _2-3 alkenyl and benzyl. Suitable R ² and R ³ include hydrogen and methyl. Suitable W includes: and -CH ₂ Z. Suitable G is hydroxy, C _1-6 alkoxy,
C _1-2 bromoalkoxy, C _2-3 alkenyloxy,
C _1-2 alkoxy group substituted with a substituent selected from the group _consisting of C 2-3 alkynyloxy, C _1-4 alkylthio, benzyloxy: and N,N-dimethylamino and N,N,N-trimethylamino including. Suitable Z includes C _1-2 alkoxy. Preferred A, D, E and T include hydrogen, halogen, nitro, cyano, amino, formyl, methyl, C _1-3 alkoxy and trifluoromethyl. Preferred U and V include hydrogen and halogen. Preferred R ¹ includes hydrogen, C _1-4 alkyl, C _2-3 alkynyl and benzyl. Preferred R ² and R ³ include hydrogen and methyl. Preferable W is (a) a group [formula] [wherein G is hydroxy, C _1-6 alkoxy, C _1-2 bromoalkoxy, C _2-3
alkenyloxy, C _2-3 alkynyloxy,
C _1-4 alkylthio, benzyloxy; and N,
substituted with a substituent selected from N-dimethylamino and N,N,N-trimethylammonio
_C1-2 alkoxy; and (b) the group _-CH2Z , where Z is selected from _C1-2 alkoxy. A preferred compound of the present invention is a compound of general formula () K0089. More preferred compounds of the invention are divided into several subgroups and include the following compounds. (a) A is nitro, D is selected from the group consisting of trifluoromethyl and halogen, R ¹ is selected from the group consisting of hydrogen, C _1-4 alkyl and benzyl, and R ² is hydrogen and selected from the group consisting of methyl, E, T, U, V and R ³ are hydrogen, W is a [formula] group [wherein G is hydroxy, C _1-6 alkoxy and C _1-4 alkylthio] chosen from the group consisting of]. (b) A is nitro and D is hydrogen, nitro, cyano, methyl and
R 1 is selected from the group consisting of C _1-3 alkoxy, R ¹ is selected from the group consisting of hydrogen, C _1-4 alkyl, C _2-3 alkynyl and benzyl, and R ² is selected from the group consisting of hydrogen and methyl. , E, T, U, V and R ³ are hydrogen, and W is a [formula] group [in the formula, G is hydroxy, C _1-6 alkoxy, C _2-3 alkenyloxy,
C ₁ substituted with one substituent selected from the group consisting of C _2-3 alkynyloxy, C _1-4 alkylthio, benzyloxy; and N,N-dimethylamino and N,N,N-trimethylammonio _-2 alkoxy group] and -
CH ₂ Z group [Z in the formula is selected from the group consisting of C _1-2 alkoxy]. (c) A is selected from the group consisting of hydrogen, halogen and amino; D is selected from the group consisting of hydrogen, nitro, cyano, halogen, methyl, trifluoromethyl and C _1-3 alkoxy; and R ¹ is , hydrogen, C _1-4 alkyl, C _2-3 alkynyl and benzyl, R ² is selected from the group consisting of hydrogen and methyl, E, T, U, V and R ³ are hydrogen and W is a [formula] group [in the formula, G is hydroxy, C _1-6 alkoxy, C _2-3 alkenyloxy,
C _1-4 alkylthio, benzyloxy; and N,
selected from the group consisting of a C _1-2 alkoxy group substituted with one substituent selected from the group consisting of N-dimethylamino and N,N,N-trimethylammonio] and a -CH ₂ Z group [formula The Z inside is
selected from the group consisting of C _1-2 alkoxy]. (d) A is nitro, D is selected from the group consisting of trifluoromethyl and halogen, R ¹ is selected from the group consisting of hydrogen, C _1-4 alkyl and benzyl, and R ² is hydrogen and methyl, E, T, U, V and R ³ are hydrogen, W is [Formula] group [In the formula, G is C _2-3 alkenyloxy, C _2-3 Alkynyloxy, benzyloxy; and C _1-2 alkoxy substituted with one substituent selected from the group consisting of N,N-dimethylamino and N,N,N-trimethylammonio. ] and -
A group selected from the group consisting of CH ₂ Z groups, where Z is selected from the group consisting of C _1-2 alkoxy. (e) A is nitro, D is selected from the group consisting of trifluoromethyl and halogen, R ¹ is C _2-3 alkynyl, and R ² is selected from the group consisting of hydrogen and methyl; , E, T, U, V and R ³ are hydrogen, W is a [formula] group [in the formula, G is hydroxy, C _1-6 alkoxy, C _2-3 alkenyloxy,
C ₁ substituted with one substituent selected from the group consisting of C _2-3 alkynyloxy, C _1-4 alkylthio, benzyloxy; and N,N-dimethylamino and N,N,N-trimethylammonio _-2 alkoxy group] and -
A group selected from the group consisting of CH ₂ Z groups, where Z is selected from the group consisting of C _1-2 alkoxy. (f) A is nitro, D is selected from the group consisting of trifluoromethyl, fluoro, chloro and bromo, and R ¹ consists of hydrogen, methyl, ethyl, n-propyl, n-butyl and benzyl. R ² is selected from the group consisting of hydrogen and methyl, E, T, U, V and R ³ are hydrogen, and W is a group [formula, where G is hydroxy, selected from the group consisting of C _1-6 alkoxy and C _1-4 alkylthio]. (g) A is nitro, D is selected from the group consisting of nitro, cyano, methyl, methoxy and ethoxy, and R ¹ is hydrogen, methyl, ethyl, n-propyl, n-butyl, allyl, propargyl; and benzyl, R ² is methyl, E, T, U, V and R ³ are hydrogen, W is [Formula] group [where G is hydroxy, C _{1 -6} alkoxy, allyloxy, propargyloxy, C _1-4 alkylthio, benzyloxy, 2-(N,N-dimethylamino)ethoxy and 2-(N,N,N-trimethylammonio)
[selected from the group consisting of ethoxy] and -
A group selected from the group consisting of CH ₂ Z groups, where Z is selected from the group consisting of C _1-2 alkoxy. (h) A is selected from the group consisting of hydrogen, fluoro, chloro, bromo and amino, D is selected from the group consisting of fluoro, chloro, bromo, nitro and trifluoromethyl, and R ¹ is hydrogen, methyl , ethyl, n-propyl, n-butyl, allyl, propargyl and benzyl, R ² is methyl, E, T, U, V and R ³ are hydrogen, W is [ Formula] Group [In the formula, G is hydroxy, C _1-6 alkoxy, allyloxy, propargyloxy, benzyloxy, 2-(N,N-
dimethylamino)ethoxy and 2-(N,N,
N-trimethylammonio)ethoxy] and -CH ₂ Z group [where Z
is selected from the group consisting of C _1-2 alkoxy]
selected from the group consisting of. (i) A is nitro, D is selected from the group consisting of fluoro, chloro, bromo and trifluoromethyl, and R ¹ consists of hydrogen, methyl, ethyl, n-propyl, n-butyl and benzyl. selected from the group, R ² is methyl, E, T, U, V and R ³ are hydrogen, W is [formula] group [wherein G is allyloxy, propargyloxy, benzyloxy,
2-(N,N-dimethylamino)ethoxy and 2-(N,N,N-trimethylammonio)ethoxy] and -CH ₂ Z
A group selected from the group consisting of [Z in the formula is selected from the group consisting of C _1-2 alkoxy]. (j) A is nitro, D is selected from the group consisting of fluoro, chloro, bromo and trifluoromethyl, R ¹ is propargyl, R ² is methyl, E, T, U , _V and R ³ are hydrogen;
dimethylamino)ethoxy and 2-(N,N,
N-trimethylammonio)ethoxy] and -CH ₂ Z group [where Z
is selected from the group consisting of C _1-2 alkoxy]
selected from the group consisting of. (k) A is nitro, D is selected from the group consisting of chloro and trifluoromethyl, R ¹ is selected from the group consisting of hydrogen and methyl, R ² is methyl, E, T , U, V and R ³ are hydrogen, and W is a [formula] group [wherein G represents allyloxy, propargyloxy and 2-(N,N-
dimethylamino)ethoxy] and _-CH2Z groups, in which Z is ethoxy. Examples of compounds encompassed by the present invention include the following. K0101 K0102 K0103 K0104 K0105 K0106 K0107 K0108 K0109 K0110 K0111 Representative examples of the compounds of the present invention include compounds of general formula () detailed in Table 1 below. In addition, compound numbers 40 and 123 in Table 1 are listed as reference examples. K0112 [Table] [Table] [Table] In the above table, K0116 b HF ₂ C-ClFCO- c (CH ₃ ) ₂ NSO ₂ - d (CH ₃ ) ₂ NCO- e CO ₂ CH ₂ CH ₂ N (CH ₃ ) ₃ I K0117 g CO ₂ CH ₂ CH ₂ N (C ₂ H ₅ ) ₂ K0118 K0119 K0120. [Table] [Table] The compounds of the present invention can be prepared by various methods. In another aspect, the present invention provides a method for producing a compound of general formula (). Compounds of general formula (a) [; [formula] (wherein G is not hydroxy)] can be prepared by any of the known conventional methods for converting carboxylic acids into acid salts, acid esters or acid amides. , can be produced from the acid of the general formula (b) [;W=-CO ₂ H] (reaction formula A). K0132 K0133 The compound of general formula (c) [;W=-C≡N] can be produced by any of the known conventional methods for converting acid amides into nitrile derivatives of acids (reaction formula B). K0134 K0135 The compound of the general formula (e) [;W=-CH ₂ OH] is an acid or acid ester of the general formula (f) [;[formula] (in the formula, G=OH or O-alkyl). Alternatively, it can be produced by any of the known conventional methods for converting acid esters into alcohols (for example, LiAlH ₄ reduction) (reaction formula C). K0137 K0138 General formula (e) [; W=-CH ₂ OH ] alcohol can be prepared by any known conventional method from an alkyl halide [;W=-CH ₂ -halogen) and an ether or thioether (;W=-
CH ₂ OR or −CH ₂ SR). Amines of general formula (g) [; W=-CH ₂ NR ⁵ R ⁶ ] can be prepared according to two known conventional methods, namely:
From an alkyl halide (;W= _-CH2 -halogen) or from an amide (;
It can be produced by reduction of [Formula]). Compounds of general formula () in which R ¹ is not hydrogen can be prepared by any of the conventional methods known for preparing derivatives of secondary amines (e.g., alkylation and acylation). It can be produced from a compound of formula () in which R ¹ is hydrogen. General formula () [wherein, A, D, E, T, U, V,
R ¹ , R ² , R ³ and W are as described above],
It can be produced by condensing a phenol or thiophenol of the general formula () with a compound of the general formula () [in the formula, hal is chlorine, bromine or iodine], preferably in the presence of an alkaline material ( Reaction formula D). K0140 K0141 The compound of general formula () can also be produced by the following method. (a) General formula () [wherein L is a leaving group (for example,
(usually an alkylsulfonyl, chlorine, bromine or iodine activated for substitution) with a suitable aniline of the general formula (Scheme E) K0142 K0143 or (b) Sequence of steps of: (i) general formula ( ) [where L is a leaving group (e.g. alkylsulfonyl, usually activated for substitution, chlorine, bromine or iodine)
] and a suitable benzene derivative of the general formula () [wherein Q is hydroxy, mercapto,
C _1-6 alkoxy or C _1-6 alkylthio] by condensation with a suitable aniline of the general formula () [wherein Q is hydroxy, mercapto, C _1-6 alkoxy or C _1-6 alkylthio] (ii) by dealkylation of the compound of general formula ( ) [wherein Q is C _1-6 alkoxy or C _1-6 alkylthio] prepared in step (i) above; (iii) condensation of the product of general formula () obtained in step (i) or (ii) with the compound of general formula () (reaction formula D) [step ( i) and (ii) are shown in reaction scheme F]; or (c) the following sequence of steps: (i) a suitable aniline derivative of general formula (XI) and general formula (XII) [wherein L is groups (for example,
Q is hydroxy, mercapto, C _1-6 alkoxy or C _1-6 alkylthio] by condensation with a suitable benzene derivative of the general formula () [where Q As mentioned above]
(ii) by dealkylation of the compound of general formula ( ) [wherein Q is C _1-6 alkoxy or C _1-6 alkylthio] prepared in step (i) above; () [Step (ii) of Reaction Formula F]; and (iii) Combination of the product of general formula () obtained in the above step (i) or (ii) with the compound of general formula (). Condensation (reaction formula D above) [Step (i) is shown in reaction formula G]. K0144 K0145 K0146 The condensation reaction shown in reaction formula D is preferably carried out in the presence of an alkaline material and preferably in the presence of a solvent. Suitable alkaline materials include, for example, alkali and alkaline earth metal hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. Suitable solvents include, for example, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone and dipneutral solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, hexamethylphosphoamide and sulfolane. Examples include solvents. The condensation reactions shown in Reaction Schemes E and F are preferably carried out in the presence of a solvent. The reaction conditions necessary to carry out the condensation reactions shown in Reaction Schemes D, E, F and G will vary depending on the type of reactants and solvents used. Generally, the reaction is accelerated by heating, and reaction temperatures ranging from 40 to 150°C and reaction times from 0.5 to 20 hours are usually satisfactory. However, higher or lower reaction temperatures and/or shorter or longer reaction times can be used if desired. As shown in Reaction Equations F and G above, and as shown in (b) above.
The dealkylation reactions outlined in (ii) and (c)(ii) can be carried out using a variety of known reagents. For example, aryl-alkyl ethers are pyridine hydrochloride, hydroiodic acid, hydrobromic acid, sodium thioethoxide in dimethylformamide, acetyl-p-toluene-sulfonate, sodium or potassium iodide in formic acid or acetic acid. , lithium iodide in 2,4,6-collidine as well as boron tribromide. Reaction times and conditions vary widely depending on the dealkylating agent used and the ether to be cleaved. Reaction conditions commonly used when using the above "ether-cleavage" reagents are known to those skilled in the art and are shown in Schemes F and G above and described without undue experimentation. (b)(ii) and
It can be adapted to carry out the "ether-cleavage" reaction outlined in (c)(ii). The compounds of the invention have activity as herbicides. Accordingly, in another aspect, the present invention provides a method for causing severe damage to plants, characterized in that an effective amount of the compound of general formula () as defined above is applied to the plants themselves or to their growing environment unnecessarily. or a method for killing the plant. Generally speaking, the compounds of the present invention are effective as herbicides against a variety of plants. however,
Some of the compounds of the present invention are selectively active against monocotyledonous plants, and dicots may be affected by compounds of the present invention that severely damage or kill other species of plants. is relatively unaffected by the amount applied. Therefore, in yet another aspect, the present invention comprises:
A method of selectively controlling the growth of weeds in a crop, such that the amount is sufficient to severely damage the weeds or to kill the weeds but does not substantially damage the crop. provides a method characterized in that the compound of the general formula () described above is applied to the crop itself or its growth environment. The compounds of the invention can be applied directly to the plants (post-emergent application) or to the soil before the plants germinate (pre-emergent use). However, the compounds are generally more effective when applied to plants after germination. Although the compounds of general formula () can be used alone to inhibit the growth of plants, cause severe damage to plants, or kill plants, carriers containing solid or liquid diluents may be added to the compounds of the present invention. It is preferable to use the composition in the form of a blended composition.
Accordingly, in yet another aspect, the present invention provides a compound comprising a compound of general formula () as defined above and a carrier inert thereto, which suppresses the growth of plants, damages plants, or inhibits plants. A composition for killing is provided. Compositions according to the invention include both dilute compositions, which are ready for use as is, and concentrated compositions, which usually require dilution with water before use. Preferably, these compositions contain from 0.01 to 90% by weight of active ingredient. Preferably, the ready-to-use diluted compositions contain 0.01 to 2% by weight of active ingredient.
Concentrate compositions, on the other hand, can contain from 20 to 90% by weight of the active ingredient, but preferably from 20 to 70% by weight. Solid compositions include, for example, granules or dustings in which the active ingredient is mixed with finely divided solid diluents such as kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talc, powdered magnesium oxide, Fuller's earth and gypsum. Any form of agent (powder) is acceptable. They may also be in the form of dispersible powders or grits containing wetting agents to facilitate dispersion of the powder or grits in liquids. Solid compositions in powder form can be applied as foliar sprays. The liquid composition may be an aqueous solution or dispersion of the active ingredient, optionally including a surfactant, or dispersed as droplets in water.
It may also be a solution or dispersion of the active ingredient in a water-immiscible organic solvent. Surfactants may be cationic, anionic or nonionic. Cationic surfactants are, for example, quaternary ammonium compounds (eg, cetyltrimethylammonium bromide). Suitable anionic surfactants are soaps; aliphatic monoester salts of sulfuric acid, such as sodium lauryl sulfate; and salts of sulfonated aromatic compounds, such as sodium dodecylbenzenesulfonate, sodium lignosulfonate, A mixture of calcium and ammonium, butylnaphthalene sulfonate, and the sodium salt of diisopropyl- and triisopropylnaphthalene sulfonic acid. Suitable nonionic surfactants are the condensation products of fatty alcohols such as oleyl alcohol and cetyl alcohol with ethylene oxide, or the condensation products of ethylene oxide with alkylphenols such as octylphenol, nonylphenol or octylcresol. It is a thing. Other nonionic surfactants include partial esters derived from long chain fatty acids and hexitol anhydrides, such as sorbitan monolaurate; condensation products of ethylene oxide and partial esters; and lecithins. Aqueous solutions or dispersions are obtained by dissolving the active ingredient in an organic solvent or in water, with or without wetting agents or dispersing agents, and then, when an organic solvent is used, with or without wetting agents or dispersing agents. It can be prepared by adding the mixture thus obtained to free water. Suitable organic solvents include, for example, ethylene dichloride,
Mention may be made of isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylene and trichloroethylene. Compositions used in the form of aqueous solutions or dispersions are generally supplied in the form of a concentrate containing a high concentration of the active ingredient, and this concentrate is diluted with water before use. Typically, these concentrates must be able to withstand long-term storage and, by dilution with water after such storage, can be applied uniformly over time and with conventional spray equipment. It must be possible to form an aqueous formulation that can Preferably, the concentrates contain from 20 to 90% by weight of active ingredient, especially from 20 to 70% by weight. The ready-to-use dilute formulations can contain varying amounts of active ingredient depending on the intended use. Usually 0.01
From 10% to 10% by weight of active ingredient is used, preferably from 0.1 to 2% by weight. A preferred form of concentrated composition comprises the active ingredient micronized and dispersed in water in the presence of a surfactant and a suspending agent. Suitable suspending agents are hydrophilic colloids and
Examples include polyvinylpyrrolidone and sodium carboxymethylcellulose and vegetable gums such as gum acacia and tragacanth. Preferred suspending agents are those that impart thixotropic properties to the concentrate and increase the viscosity of the concentrate. Examples of preferred suspending agents include colloidal hydrated inorganic silicates such as montmorillonite, banderite, nontronite, hectorite, saponite and sorcolite. Among these, bentonite is particularly preferred. Other suspending agents include cellulose derivatives and polyvinyl alcohol. The dosage of the compounds of the invention depends on a number of factors, including, for example, the compound used, the plant whose growth is to be inhibited, the dosage form used, and the site of application of the compound (whether taken foliar or root). Varies depending on factors. However, in general, the appropriate application amount is 0.005 to 20 kg per hectare, with 0.05 to 5 kg per hectare being preferred. In addition to one or more compounds of the invention, the compositions of the invention can contain one or more biologically active compounds other than the invention. For example, as mentioned above, the compounds of the present invention are generally found in dicotyledonous or broad-leaved species.
It is substantially more effective against monocot or grass species plants than against other plants. As a result, the use of compounds of the invention alone as herbicides may be insufficient to protect crops. Accordingly, in yet another embodiment, the present invention provides a herbicidal composition comprising a mixture of at least one herbicidal compound of general formula () as defined above and at least one other herbicide. do. The other herbicides may be any herbicides that do not have the general formula () and are generally herbicides with complementary action. For example, one preferred herbicide is a mixture comprising herbicides that are active against broadleaf weeds. A second preferred herbicide is a mixture comprising a contact herbicide, a herbicide that is active when applied to the leaves (i.e. post-emergence) and acts quickly on a wide range of plants. Examples of useful supplemental herbicides 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 [common name bentazone (bentazon)]; B Hormone 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 [common name MCPB], 2,4-dichlorophenoxyacetic acid [common name 2,4-D], 4-
(2,4-dichlorophenoxy)butyric acid [common name 2,4-DB], 2-(4-chloro-2-methylphenoxy)propionic acid [common name mecoprop], and their derivatives (e.g. salts, esters, amides, etc.); C 3-[4-(4-halofenoxy)phenyl]
-1,1-dialkylureas, e.g. 3
-[4-(4-chlorophenoxy)phenyl]-
1,1-dimethylurea (common name chloroxuron); D Dinitrophenols and their derivatives (e.g. acetates), such as 2-methyl-4,6-dinitrophenol (common name
DNOC), 2-tert-butyl-4,6-dinitrophenol (common name dinoterb), 2-sec-butyl-4,6-dinitrophenol (common name dinoseb)
and its esters, 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 (common name trifluralin) and 4-methylsulfonyl-
2,6-dinitro-N,N-dipropylaniline (common name nitralin); F phenylurea herbicides, such as N'-
(3,4-dichlorophenyl)-N,N-dimethylurea [common name diuron] and N,
N-Dimethyl-N'-[3-(trifluoromethyl)phenyl]urea (common name fluometuron); G Phenylcarbamoyloxyphenyl carbamates, such as 3-[(methoxycarbonyl)amino]phenyl (3 -methylphenyl)
Carbamates [common name phenmedipham] and 3-[(ethoxycarbonyl)amino]phenyl phenyl carbamate [common name desmedipham]; H 2-phenylpyridazin-3-ones, e.g. 5-amino -4-chloro-2-phenylpyridazin-3-one (common name pyrazon); I uracil herbicides, such as 3-cyclohexyl-5,6-trimethyleneuracil (common name lenacil); 5-bromo-3-sec-
Butyl-6-methyluracil (common name bromacil) and 3-tert-butyl-5-
Chloro-6-methyluracil (common name terbacil); J triazine herbicides, such as 2-chloro-
4-ethylamino-6-(iso-propylamino)-1,3,5-triazine [common name atrazine], 2-chloro-4,6-di(ethylamino)-1,3,5- Triazine (common name simazine and 2-azide)
4-(iso-propylamino)-6-methylthio-1,3,5-triazine (common name aziprotryne; K 1-alkoxy-1-alkyl-3-phenylurea herbicides, e.g. 3-(3 , 4-dichlorophenyl) 1-methoxy-1-methylurea (common name linuron), 3-(4-
(chlorophenyl)-1-methoxy-1-methylurea (common name monolinuron)
and 3-(4-bromo-4-chlorophenyl)-
1-Methoxy-1-methylurea (common name chlorobromuron); L thiocarbamate herbicides, such as S-propyldipropyl-thiocarbamate (common name vernolate); M 1,2,4 - triazin-5-one herbicide,
For example, 4-amino-4,5-dihydro-3
-Methyl-6-phenyl-1,2,4-triazin-5-one (common name metamitron) 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) , its corresponding N-methoxy compound [common name alachlor], its corresponding N-iso-propyl compound [common name propachlor] and 3',4'-dichloropropionanilide [common name propanil]. )]; P dihalobenzonitrile herbicides, e.g.
2,6-dichlorobenzonitrile [common name dichlobenil], 3,5-dibromo-4-hydroxybenzonitrile [common name bromoxynil] and 3,5-diiodo-4-hydroxybenzonitrile [common name ioxynil]; Q haloalkanoic acid herbicides, such as 2,2-
Dichloropropionic acid (common name: dalapon), trichloroacetic acid (common name: TCA)
and salts thereof; R diphenyl ether herbicides, such as 4-
Nitrophenyl 2-nitro-4-trifluoromethylphenyl ether (common name fluorodifen), methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate (common name bifenox) , 2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoic acid and 2-chloro-4-
Trifluoromethylphenyl 3-ethoxy-4
-nitro-phenyl ether; S N,N-dimethyldiphenylacetamide [common name diphenamide], N
-(1-naphthyl)phthalamic acid (common name naphtalam) and 3-amino-1,
Various herbicides containing 2,4-triazole. Examples of effective contact herbicides include: T bipyridylium herbicides, such as those whose active substance is 1,1'-dimethyl-4,4'-dipyridylium ion (common name paraquat) and those whose active substance is 1,1'-dimethyl-4,4'-dipyridylium ion (common name paraquat); 2,2'-dipyridylium ions (common name diquat); U organic arsenic herbicides, such as monosodium methanarsonate (common name MSMA); and V amino acid herbicides, such as N -phosphonomethyl)glycine (common name: glyphosate) and its salts and esters. The present invention will be explained with reference to the following examples, but these are not intended to limit the invention in any way. Example 1 Methyl-22-[4-(4-chloroanilino)phenoxy]propionate (12) (a) 4-chloro-4'-methoxydiphenylamine [3.0 g: EANodiff kept at a temperature of -78°C
and M.Hausmann, J.Org.Chem., 29, 2453.
(1964)] of dichloromethane (20
Boron tribromide (2.5 ml) was added dropwise to the stirred solution. After the addition was complete, the solution was stirred at −78° C. for 1 hour and then warmed to room temperature for 2 hours. After stirring for 4 hours at room temperature,
The solution was cooled and water (10ml) was carefully added to it to destroy the excess boron tribromide. Sodium bicarbonate was added to the mixture until no carbon dioxide evolved, the organic layer was separated and the aqueous layer was extracted with chloroform (2 x 50ml). The organic layer and extract were combined, dried over anhydrous magnesium carbonate, and the solvent was evaporated. As a result, 4-(4-chloroanilino)phenol (2.8 g) was obtained as a light gray solid. (b) 4-(4-chloroanilino)phenol (2.8
g), methyl 2-bromopropionate (2.4
g), anhydrous potassium carbonate (2.0 g) and methyl ethyl ketone (50 ml) was heated with stirring and under reflux for 5 hours. The reaction mixture was poured into water (200ml) and the aqueous mixture was extracted with chloroform (2x100ml). The combined extracts were dried over anhydrous magnesium sulfate and the solvent was evaporated. As a result, methyl 2-[4-(4-chloroanilino)phenoxy]propionate (2.5 g) was obtained as a light gray solid (melting point 103°C). Example 2 Methyl 2-[4-(4-chloro-N-methylanilino)phenoxy]propionate (13) (a) A solution of 4-chloro-4'-methoxydiphenylamine (3.0 g) in toluene (30 ml) treated with sodium hydride (1.0 g) and the mixture
Heat at reflux for 18 hours. Methyl iodide (3ml) was added to this and the reaction mixture was heated for a further 5 hours under gentle reflux. The cooled solution was washed with water, the organic layer was separated and it was dried over anhydrous magnesium sulfate.
The solvent was distilled off under reduced pressure to give a brown oil (2.6
g) was obtained. This was subjected to column chromatography on silica gel [eluent: n-hexane/
chloroform (4:1)].
As a result, the product, 4-chloro-4'-methoxy-N-methyldiphenylamine (1.4 g), was obtained as a pale cream solid (melting point 69°C). (b) 4-chloro-4'-methoxy-N according to substantially the same procedure as described in Example 1(a).
-4-(4-chloro-N-methylanilino)phenol was prepared from methyldiphenylamine. (c) From 4-(4-chloro-N-methylanilino)phenol and methyl 2-bromopropionate to methyl 2-[ 4-(4-chloro-N-methylanilino)phenoxy]propionate was prepared. The product was a colorless oil with a characteristic PMR spectrum.
Details are recorded in Example 29, Table 2. Example 3 Methyl 2-[4-(4-trifluoromethyl-N
-methylanilino)phenoxy]propionate (14) (a) 4-bromobenzotrifluoride (18g),
p-anisidine (5g), potassium carbonate (5.4
g) and cuprous iodide (1.2 g).
Heat at reflux for an hour. After cooling, the mixture was diluted with chloroform (200ml) and passed through Celite. The excess 4-bromobenzotrifluoride was distilled off under reduced pressure and the residue was chromatographed on silica gel (eluent: dichloromethane). the result,
The product, 4-trifluoromethyl-4'-methoxydiphenylamine, was obtained as a red oil. By leaving it alone, it crystallizes,
A low melting solid was obtained (2.0 g). (b) 4-trifluoromethyl-4'- according to substantially the same procedure as described in Example 2(a).
4-trifluoromethyl-4'-methoxy-N from methoxydiphenylamine and methyl iodide
-Methyl diphenylamine was prepared. (c) 4-(4-Trifluoromethyl-N-methylanilino)phenol was prepared following substantially the same procedure as described in Example 1 (a). (d) from 4-(N-methyl-4-trifluoromethylanilino)phenol and methyl 2-bromopropionate following substantially the same procedure as described in Example 1(b). , methyl 2-
[4-(4-trifluoromethyl-N-methylanilino)phenoxy]propionate was prepared. The product is a pale orange oil whose pm
r.The spectrum was characteristic. Details are examples
29, recorded in Table 2. Example 4 Compound No. 12 was prepared following substantially the same procedure as described in Example 1 for preparing Compound No. 12.
15, 16, 19, 20 and 22 were manufactured. Example 3
Compound No. 49 was prepared according to substantially the same procedure as described in (a), (c), and (d). These compounds had distinctive pmr spectra. Details are recorded in Table 2 of Example 29. Example 5 Methyl 2-[4-(N-methylanilino)phenoxy]propionate (17) A solution of methyl 2-[4-anilinophenoxy]propionate (3.5 g) in anhydrous toluene (30 ml) was added with sodium hydride (0.5 g) was gradually added.
The mixture was stirred for 1 hour and then methyl iodide (3ml) was added to it. The mixture was heated to 60° C. under an inert atmosphere and stirred at room temperature overnight. After cooling, the mixture was carefully treated with water and then washed with water. The organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The crude product was purified by chromatography on silica gel (eluent: chloroform) to give a brown oil (1.9 g).
This product had a characteristic pmr spectrum. Details are recorded in Example 29, Table 2. Example 6 Compound No. 17 was prepared following substantially the same procedure as described in Example 5 for preparing Compound No. 17.
18, 23, 27, 30, 35, 37, 38, 56, 64, 66, 71,
Compounds 81, 92, 93, 94, 102, 105, 109 and 118 were prepared. These compounds had distinctive pmr spectra. Details of the spectra of the compounds or, if solid, the melting points of the compounds, are recorded in Example 29, Table 2. Example 7 Methyl 2-[4-(2,4-dichloro-N-methylanilino)phenoxy]propionate (1) (a) 2,4-dichloro-N-methylaniline (12.0 g), 4-bromoanisole (40.0 g),
A mixture of bronze (0.1 g), cuprous bromide (0.1 g) and anhydrous potassium carbonate (9.42 g) was heated at 200° C. for 30 hours. After cooling, unreacted 4-bromoanisole was distilled from the reaction mixture under reduced pressure and dichloromethane was added to the residue. The mixture was washed with dilute aqueous hydrochloric acid and then water, the organic layer was separated and it was dried over anhydrous magnesium sulfate. Evaporation of the solvent and purification by chromatography on silica gel (eluent: chloroform) gave 2,4-dichloro-4'-methoxy-N-methyldiphenylamine (3.6 g). Ta. (b) 2,4-dichloro-4'-methoxy-N-methyldiphenylamine to 4-(2,
4-Dichloro-N-methylanilino)phenol was prepared. (c) 4-(2,4-dichloro-N-
From methylanilino)phenol and methyl 2-bromopropionate, methyl 2-[4-
(2,4-dichloro-N-methylanilino)phenoxy]propionate was prepared. The product was a light brown oil with a characteristic PMR spectrum. Details are recorded in Example 29, Table 2. Example 8 Methyl 2-[4-(2-nitro-4-trifluoromethylanilino)phenoxy]-propionate (21) (a) J.Soc.Dyers Colour. by Day and Peters,
83, 137 (1967).
-Aminophenol to 4-(2-nitro-4
-trifluoromethylanilino)phenol was prepared. (b) from 4-(2-nitro-4-trifluoromethylanilino)phenol and methyl 2-bromopropionate following substantially the same procedure as described in Example 1(b). Methyl 2-[4
-(2-nitro-4-trifluoromethylanilino)phenoxy]propionate was prepared. The product is a red oil whose pmr
The spectrum is characteristic. For details, see Example 29.
It is listed in Table 2. Example 9 Following substantially the same procedure as described in Example 8(b) for producing Compound No. 21, the compound
No.24, 25, 26, 28, 29, 31, 33, 34, 36, 39,
40, 41, 42, 43, 44, 45, 58, 60, 67, 68, 69,
70, 72, 73, 74, 75, 76, 77, 82, 101, 103,
110, 114, 115, 117, 119, 122 and 124 were prepared. These compounds had distinctive pmr spectra. Details of the spectra of the compounds or, if solid, the melting points of the compounds, are recorded in Example 29, Table 2. Example 10 Methyl 2-[4-(2-amino-4-bromoanilino)phenoxy]propionate (32) (a) 4-(4-bromo-2-nitroanilino)phenol (7.7 g) in acetic acid (8 ml) and ethanol (80 ml) was treated with reduced iron (7.7 g) while stirring. While adding iron,
The temperature of the solution increased and after 2 hours the reduction was complete (as indicated by thin layer chromatography). The solvent was evaporated under reduced pressure, the residue was triturated with ethyl acetate and it was passed through diatomaceous earth. The liquid was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure to yield 4-(2-amino-4-bromoanilino)phenol (6.9 g). (b) From 4-(2-amino-4-bromoanilino)phenol and methyl 2-bromopropionate to methyl 2-[ 4-(2-amino-4-bromoanilino)phenoxy]propionate was prepared. This product had a characteristic pmr spectrum. Details are recorded in Example 29, Table 2. Example 11 2-[4-(2-nitro-4-trifluoromethylanilino)phenoxy]propionic acid (46) Methyl 2[4-(2-nitro-4-trifluoromethylanilino)phenoxy]propionate ( A mixture of 10 g (Example 8), potassium hydroxide (1.5 g) and methanol (50 ml) was stirred at a temperature of 20° C. for 24 hours. The solution was acidified with dilute hydrochloric acid and then extracted with chloroform (500ml).
The chloroform extract was dried (anhydrous MgSO ₄ ) and the solvent was evaporated. As a result, 2-[4-
(2-nitro-4-trifluoromethylanilino)
Phenoxy]propionic acid as an orange solid (8.4g)
(melting point: 160°C). Example 12 2-[4-(N-methyl-2-nitro-4-trifluoromethylanilino)phenoxy]propionic acid (96) Method and substance described in Example 11 for producing compound No. 46 Following the same procedure, methyl 2-
The target compound was prepared from [4-(N-methyl-2-nitro-4-trifluoromethylanilino)phenoxy]propionate. The melting point of this product is
It was 110℃. Example 13 Sodium 2-[4-(2-nitro-4-trifluoromethylanilino)phenoxy]propionate (65) 2-[4-(2-nitro-4-trifluoromethylanilino)phenoxy]propion Acid (2.0g)
and sodium hydroxide (0.2g) were dissolved in water (10ml) and the solution was concentrated. The result is an orange powder (2.14g) of the sodium salt of the acid.
(melting point: 259°C). Example 14 n-Butyl 2-[4-(2-nitro-4-trifluoromethylanilino)phenoxy]propionate (48) Thionyl chloride (15 ml) and 2-[4-(2-nitro-4-trifluoro) methylanilino)phenoxy]propionic acid (2.0 g) for 2 hours.
It was boiled under reflux. Excess thionyl chloride was distilled off and n-butanol (2 ml) was added to the residue with stirring. After stirring for 1 hour at 20°C, excess butanol was distilled off under reduced pressure. The residue was chromatographed on silica gel (eluting with dichloromethane) to give n-
Butyl 2-[4-(2-nitro-4-trifluoromethylanilino)phenoxy]propionate was obtained as an orange solid (2.04 g) (melting point: 67°C). Example 15 Compound No. 50 was prepared following substantially the same procedure as described in Example 14 for preparing Compound No. 48.
51, 52, 53, 54, 55, 57, 59, 61, 62, 63, 79,
80, 88, 89, 95, 97, 98, 104, 106, 107, 108 and 113 were prepared. These compounds had characteristic PMR spectra. For details, see Example 29, 2nd
Recorded in the table. Example 16 2-(N,N,N-trimethylammonio)ethyl 2-[4-(2-nitro-4-chloroanilino)phenoxy]propionate iodide salt (90) 2-(N,N-dimethyl amino)ethyl 2-[4
A mixture of -(2-nitro-4-chloroanilino)phenoxy]propionate (1.0 g, Example 15), methyl iodide (1 ml) and dichloromethane (10 ml) was stirred at 20°C for 2 hours. The solvent was distilled off under reduced pressure to obtain the target compound as an orange solid (1.3 g) (melting point: 138-140°C). Example 17 2-(N,N,N-trimethylammonio)ethyl 2-[4-(2-nitro-4-trifluoromethylanilino)phenoxy]propionate iodide salt (91) Compound No. 90 2-(N,
The target compound was prepared from N-dimethylamino)ethyl 2-[4-(2-nitro-4-trifluoromethylanilino)phenoxy]propionate.
The melting point of the product was 156°C. Example 18 Methyl 2-[4-(N-methyl-2-nitro-4
-Sulfonamidoanilino)phenoxy]propionate (47) (a) 4-chloro-3-nitrobenzenesulfonamide (2.3g), sodium acetate (1.6g), 4-
A mixture of (N-methylamino)phenolsulfate (1.7 g) and water (50 ml) was boiled under reflux for 20 hours. After cooling, the mixture was extracted with ethyl acetate (2x150ml), the organic layer was separated and extracted with 1M sodium hydroxide solution. The aqueous layer was separated, acidified and extracted with ethyl acetate (2x200ml). The extract was dried (anhydrous MgSO ₄ ) and the solvent was evaporated.
4-(2-nitro-4-sulfonamide-N-
Methyanilino)phenol (2.9 g) was obtained. (c) 4-(2-nitro-4-sulfonamide-
N-methylanilino)phenol and methyl 2
- from bromopropionate, methyl 2-[4
-(2-nitro-4-sulfonamido-N-methylanilino)phenoxy]propionate was prepared. The product is an oil whose pmr
The spectrum was characteristic. Details are examples
29, recorded in Table 2. Example 19 Ethyl 2-[6-nitro-3-(2-nitro-4
-trifluoromethylanilino)phenoxy]
Propionate (120) (a) A solution of 3-(2-nitro-4-trifluoromethylanilino)phenol (8.0 g) in diethyl ether (100 ml) was added dropwise to fuming nitric acid (3.4 g) at 20°C. processed by
The formed mixture was then kept at 20°C for 20 hours. The precipitated solid was collected by filtration and recrystallized first from ethanol and then from ethyl acetate. As a result, 6-nitro-3-
(2-Nitro-4-trifluoromethylanilino)phenol (1.6 g) was obtained as yellow needle-like crystals. (c) 6-nitro-3-(2-nitro-4-trifluoromethylanilino)phenol and ethyl 2-bromo, following substantially the same procedure as described in Example 1(b). From propionate,
Ethyl 2-[6-nitro-3-(2-nitro-4
-trifluoromethylanilino)phenoxy]
Propionate was prepared. The product was a solid (melting point: 66-68°C). Example 20 Methyl 2-[2-chloro-4-(2-nitro-4
-trifluoromethylanilino)phenoxy]
Propionate (116) A mixture of methyl 2-[4-(2-nitro-4-trifluoromethylanilino)phenoxy]propionate (5.0 g, Example 8), N-chlorosuccinimide (1.9 g) and chlorobenzene (50 ml) of
Heated under reflux for 24 hours. The chlorobenzene solvent was distilled off under reduced pressure, the residue was dissolved in dichloromethane, and the solution was washed with water. Dry the dichloromethane solution (anhydrous
MgSO ₄ ) and the solvent was removed by evaporation under reduced pressure. The residue was chromatographed on silica gel (eluting with dichloromethane) to give the desired compound (3.5 g) as a red oil.
This compound had a characteristic pmr spectrum. Details are recorded in Example 29, Table 2. Example 21 2-[4-(2-nitro-4-trifluoromethylanilino)phenoxy]propanol (83) Powdered lithium aluminum hydride (2.0 g)
Anhydrous diethyl ether of methyl 2-[4-(2-nitro-4-trifluoromethylanilino)phenoxy]propionate (25 g, Example 8) was added to a stirred mixture of anhydrous diethyl ether and anhydrous diethyl ether (40 ml). (100 ml) was added dropwise. After the addition was complete, the mixture was heated at reflux for 1 hour. This mixture was mixed with ethyl acetate (3 ml) and 5M
Excess lithium aluminum hydride was destroyed by successive treatments with aqueous hydrochloric acid (3 ml). The mixture was subsequently extracted with diethyl ether to separate the organics. The solvent was evaporated and the residue was chromatographed on silica gel to give the desired compound (15 g) as a red oil. This compound had a characteristic pmr spectrum. Details are recorded in Example 29, Table 2. Example 22 2-[4-(N-Methyl-2-nitro-4-trifluoromethylanilino)phenoxy]propanol (84) Following substantially the same procedure as described in Example 21, methyl The target compound was prepared from 2-[4-(N-methyl-2-nitro-4-trifluoromethylanilino)phenoxy]propionate (Example 6). The product is an oil whose pmr
The spectrum was characteristic. For details, see Example 29.
Recorded in Table 2. Example 23 2-[4-(2-nitro-4-trifluoromethylanilino)phenoxy]propyl chloride (87) 2-[4-(2-nitro-4-trifluoromethylanilino)phenoxy]propanol ( 1.5g,
To a solution of Example 21) in chloroform (5 ml) was added dropwise a solution of thionyl chloride (0.6 g) in chloroform (5 ml). The mixture was stirred at room temperature for 2 hours and then heated at reflux for 10 minutes. The solvent and excess thionyl chloride were distilled off under reduced pressure and the residue was chromatographed on silica gel to give the target compound (0.8 g). The product is an oil whose p.
The mr spectrum was characteristic. Details are examples
29, recorded in Table 2. Example 24 Ethyl 2-[4-(2-nitro-4-trifluoromethylanilino)phenoxy]propyl ether (85) 2-[4-(2-nitro-4-trifluoromethylanilino)phenoxy]propanol (1.0g,
Example 21), ethyl iodide (1.0g), potassium carbonate (0.5g) and dimethylformamide (20ml)
The mixture was heated at a temperature of 67°C for 24 hours.
The mixture was poured into water (30ml) and the aqueous mixture was extracted with diethyl ether. The ether extract was dried (anhydrous MgSO ₄ ) and the solvent was evaporated under reduced pressure. The residue was chromatographed on silica gel to give the desired compound (0.7 g).
was obtained as a red oil. This compound had a characteristic pmr spectrum. Details are recorded in Example 29, Table 2. Example 25 Ethyl 2-[4-(N-methyl-2-nitro-4
-trifluoromethylanilino)phenoxy]
Propyl ether (86) 2-[4-(N-methyl-2-nitro-4
The target compound was prepared from -trifluoromethylanilino)phenoxy]propanol (Example 22). Example 26 Ethyl 2-[4-(4-chloro-2-methoxycarbonylanilino)phenoxy]propionate (99) (a) Method of Ledochosski et al. [Chem.Abstract,
59, 570 (1963)], 5-chloro-N-
(4-Methoxyphenyl)anthranilic acid was prepared. 5-chloro-N-(4-methoxyphenyl)
A mixture of anthranilic acid (2g), anhydrous potassium carbonate (1g) and dimethyl sulfate (1ml) in acetone (20ml) was boiled under reflux for 3 hours. Acetone was removed under reduced pressure and the residue was partitioned between chloroform and water. Dry and concentrate the chloroform layer;
Methyl 5-chloro-N-(4-methoxyphenyl)anthranilate (1.8 g) was obtained as a pale yellow crystalline solid (melting point 87°C). (b) From methyl 5-chloro-N-(4-methoxyphenyl)anthranilate, 5-
Methyl chloro-N-(4-hydroxyphenyl)anthranilate was prepared. (c) Methyl 5-chloro-N-(4-hydroxyphenyl)anthranilate and 2-
Ethyl bromopropionate to ethyl 2-[4
-(4-chloro-2-methoxycarbonylphenylamino)phenoxy]propionate was prepared. The product is a pale yellow oil;
The pmr spectrum was characteristic. Details are recorded in Example 29, Table 2. Example 27 Propyl 2-[4-(4-cyano-2-nitroanilino)phenoxy]propionate (100) Methyl 2-[4-(4-cyano-2-nitroanilino)phenoxy]propionate (1.2 g) and p-toluene A solution of sulfonic acid (40 mg) in propanol (90 ml) was boiled at reflux for 48 hours. The propanol was removed under reduced pressure and the residue was partitioned between chloroform and dilute aqueous sodium bicarbonate solution. Drying and evaporating the chloroform layer gave propyl 2-[4-(4-cyano-2-nitroanilino)phenoxy]propionate as a red oil. This product had a characteristic pmr spectrum. Details are recorded in Example 29, Table 2. Example 28 2-[4-(2-nitro-4-trifluoromethylanilino)phenylthio]acetic acid (123) 4-chloro-3-nitrobenzotrifluoride (4.5 g), 4-aminophenylthioacetic acid ( 3.6g)
and anhydrous potassium carbonate (5.6 g) in n-butanol (100 ml) was refluxed for 24 hours. The butanol was removed under reduced pressure and the residue was partitioned between chloroform and 1M sodium hydroxide solution. The aqueous layer was acidified with 1M hydrochloric acid and then extracted with chloroform. As a result, 2-[4-(2-nitro-4-
Trifluoromethylanilino)phenylthio]acetic acid (1.5g) was obtained as a dark red oil. This compound had a characteristic pmr spectrum. This is recorded in Example 29, Table 2. Example 29 Most of the compounds of the present invention are oils and have a characteristic PMR spectrum and can be identified by the PMR spectrum. For your convenience, pm
r.Spectral analysis data, mass spectrometry data,
Melting points and boiling points are recorded in Table 2 below as appropriate. [Table] [Table], [Table] [Table] [Table] “Teric” N13 [“Teric” is a registered trademark; “Teric” N13 is an ethoxylation product of nonylphenol and is a product of ICI Australia Limited (ICI Australia Limited)
Australia Limited] and 3
%v/v “Kemmat” SC15B
(“Kemmat” is a registered trademark; “Kemmat”
(SC15B is a brand name for calcium dodecylbenzenesulfonate); To 94 parts by weight of an aqueous solution containing N8 (ethoxylation product of nonylphenol), 5 parts by weight of the compound of the present invention and "Dyapol"
PT (“Dyapol” is a registered trademark; “Dyapol”
PT is an anionic suspending agent) and ball milling the mixture to produce a stable suspension. Thereafter, by diluting the emulsifiable concentrates and suspensions with water, aqueous compositions of desired concentrations suitable for evaluating the pre- and post-emergence herbicide activity of the compounds of the invention are prepared. produced something. Example 31 The pre-emergence herbicide activity of compounds of the invention formulated as described in Example 30 was evaluated by the following procedure. Seeds of plants of the species to be tested were sown in rows in the soil 2 cm deep in seed boxes. Monocots and dicots were sprayed with the required amount of the composition of the invention. Two duplicate seed boxes were prepared in a similar manner. However, these were used for comparison without being sprayed with the composition of the invention. All boxes were placed in a greenhouse and the seeds were germinated with a small amount of water by spraying from above, followed by subsurface irrigation as required for optimal plant growth. After 3 weeks, the boxes were removed from the greenhouse and the treatment effects were visually evaluated. The results are shown in Table 3. In the table, damage to plants was rated on a scale of 0 to 3. 0 represents 0 to 25% damage; 3 represents 75 to 25% damage;
It represents 99% wilting, and 3+ means 100% wilting. A dash (-) means that the experiment was not performed. The names of the test plants are as follows. Wh Wheat Ot Wild crow wheat Rg Japanese millet P Pea Ip Ipomea Ms Mustard Sf Sunflower [Table] [Table] Example 32 Formulated as described in Example 30 The post-germination herbicide activity of the compound of the present invention was evaluated by the following method. Seeds of plants of the species to be tested were sown in seed boxes in rows in the soil 2 cm deep. Monocots and dicots were sown in separate seed boxes in duplicate. Four seed boxes were placed in a greenhouse and allowed to germinate by watering lightly by spraying from above, followed by subsurface irrigation as required for optimal plant growth. After the plants had grown to a height of about 10 to 12.5 cm, each box of monocots and dicots was removed from the greenhouse and sprayed with the required amount of the composition of the invention. After spraying, the boxes were returned to the greenhouse for an additional 3 weeks, and treatment efficacy was visually evaluated in comparison to an untreated control group. The results are shown in Table 4. In the table, damage to plants was rated on a scale of 0 to 3. 0 represents 0-25% damage, 3 represents 75-99% wilting and 3+ represents 100% wilting. A dash (-) means that the experiment was not performed. The names of the test plants are as follows. Wh Wheat Ot Wild crow wheat Rg Japanese millet P Pea Ip Ipomea Ms Mustard Sf Sunflower [Table] [Table] Example 33 "Span" 80 in methylcyclohexanone An appropriate amount of the compound of the present invention is mixed with 5 ml of an emulsion prepared by diluting 160 ml of a solution containing 21.8 g/Tween 20 and 78.2 g/Tween 20 to 500 ml. In particular, compounds of the invention were formulated for testing. "Span" 80 is a registered trademark for surfactants containing sorbitan monolaurate. "Tween" 20 is a registered trademark for a surfactant containing a condensate of sorbitan monolaurate and ethylene oxide in a 20 molar ratio. 5 ml each of the emulsion containing the test compound was then diluted to 40 ml with water and sprayed on seedlings of bee plants of the species named in Table 5 below (post-emergence test). After 14 days, damage to the test plants was rated on a scale of 0 to 5. 0 represents 0-20% damage and 5 represents complete wilting. In the pre-emergence test for herbicide activity, seeds of test plants were sown in shallow slits formed in the soil surface in fiber dishes. The surface was then leveled and sprayed with the test composition. A thin layer of new soil was then spread on the sprayed surface. Herbicide damage assessment is 21
Days later, the same scale from 0 to 5 was used as in the post-emergence test. In each case, the degree of herbicide damage was evaluated in comparison to untreated control plants. The results obtained are shown in Table 5 below. A dash (-) means that the experiment was not performed. The names of the test plants are as follows. Sb Sugar beet Rp Western oil Ct Cotton Sy Soybean Mz Corn Ww Autumn wheat Rc Rice Sn Senecio vulgaris Ip Ipomea purpurea Am Amaranthus retroflexus Pi Polygonum aviculare Ca Pigweed (Chenopodium album) Po Portulaca oleracea (Chenopodium album)
oleracea) Xa Xanthium pensylvanicum Ab Abutilon
theophrasti) Cv Convolvulus arvensis Ot Cultivated and wild oat (Avena
fatua) Wild oats were used for post-emergence tests, and cultivated oats were used for pre-emergence tests. Dg Digitalia sanguinalis
sanguinalis) Pu Poa annua St Setaria viridis Ec Echinochloa
crus-galli) Sh Sorghum Heilpens (Sorghum
Example 34 This example illustrates the selective herbicide activity of compounds of the invention. Seeds of plants of the species to be tested were scattered on the soil surface in seed boxes and covered with a thin layer of sand. The box is sprayed with a small amount of water by spraying from above and placed in the greenhouse for one week to germinate the seeds and plant the plants 4 to 5 inches (10.2 to 12.7 cm).
It was grown to a height of cm). Thereafter, the boxes were removed from the greenhouse and sprayed with a composition of the invention prepared as described in Example 30. For comparison, 1
At least one box containing week-old seedlings was lightly sprayed with water only. After spraying, the boxes were returned to the greenhouse and kept there for an additional 29 days, after which time treatment effects were visually evaluated. The test was performed in triplicate. The results are expressed as % damage and are recorded in Table 6. To assess the safety of the test compounds to the crops of the species tested, the crops were tested at 10 times the application rate used for the weeds. The names of the test plants are as follows. Ct Cotton Sb Soybean Ot Wild Crow Wheat Rg Annual Barley Jm Japanese millet St Setaria aviceps Sh Sorghum
halepense) EXAMPLE 35 This example illustrates the selective herbicide activity of compounds of the invention. 5 ml of an emulsion prepared by diluting 160 ml of a solution containing 21.8 g of Span 80 and 78.2 g of Tween 20 with water to 500 ml in methylcyclohexanone. Compounds of the invention were formulated for testing by mixing with appropriate amounts of compounds of the invention. "Span" 80 is a registered trademark for surfactants containing sorbitan monolaurate. "Tween" 20 is a registered trademark for a surfactant containing a condensate of sorbitan monolaurate and ethylene oxide in a 20 molar ratio. 5 ml each of the emulsion containing the test compound was then diluted to 40 ml with water and sprayed with this on seedlings of bee plants of the species named in Table 7 below (post-emergence test). After 20 days, damage to the test plants was rated on a scale of 0 to 9. 0 is 0 to 10
% damage, with 9 indicating 90 to 100% wilting. The test was performed in triplicate. The average results are recorded in Table 7 below. The names of the test plants are as follows. Sy Soybean (Amsoy) Ct Cotton (Deltapine) Ec Echinochloa class Gari (Echinochloa
clus-galli) Sh Sorghum Heilpens (Sorghum
halepense) St Setaria viridis Dg Digitalia sanguinalis
sanguinalis) [Table]

Claims (1)

[Claims] 1. A compound represented by the general formula () K0054. In the above formula (), A is selected from the group consisting of hydrogen, halogen, nitro, cyano, amino, trifluoromethyl, sulfo, sulfamoyl, methoxycarbonyl and methoxysulfonyl, and D is hydrogen, halogen, nitro, cyano, Methyl, trifluoromethyl, C _1-3 alkoxy, C _1-2
haloalkoxy, fluoromethylsulfinyl,
Fluoromethylsulfonyl, sulfamoyl,
N,N-dimethylsulfamoyl, carboxy,
(C _1-2 alkoxy)carbonyl, N,N-dimethylcarbamoyl, methylsulfonyl and formyl, E is selected from the group consisting of hydrogen and halogen, and T consists of hydrogen, halogen and nitro. wherein at least one of A, D, E and T is not hydrogen, U and V are each independently selected from the group consisting of hydrogen, halogen and nitro, and R ¹ is Hydrogen, C _1-4 alkyl, C _2-3 alkynyl,
is selected from the group consisting of acetyl and benzyl, R ² and R ³ are each independently selected from the group consisting of hydrogen and methyl, W is [formula] [wherein G is hydroxy, C _1-6 Alkoxy, C _1-2 bromoalkoxy, C _2-3 alkenyloxy, C _2-3 alkynyloxy, C _1-4 alkylthio, cyclohexyloxy, benzyloxy; morpholino, methylthio, 2-pyridyl,
C _1-2 alkoxy group substituted with one substituent selected from the group consisting of N,N-dimethylamino and N,N,N-trimethylammonio; phenyl ring substituted with two halogens phenoxy; selected from the group consisting of methanesulfonamide group and dimethylamino group] and -CH ₂ Z [in the formula, Z is
selected from the group consisting of halogen, hydroxy, methoxycarbonylmethyl and C _1-2 alkoxy]
selected from the group consisting of. 2 In the above formula, A is selected from the group consisting of hydrogen, halogen, nitro, and amino, and D is selected from the group consisting of hydrogen, halogen, nitro, cyano, methyl, trifluoromethyl, and C _1-3 alkoxy. , in that case, at least one of A and D is not hydrogen, E and T are hydrogen, U and V are each independently selected from the group consisting of hydrogen and halogen, and R ¹ is hydrogen, is selected from the group consisting of C _1-4 alkyl, C _2-3 alkynyl and benzyl, R ² and R ³ are each independently selected from the group consisting of hydrogen and methyl, and W is G is hydroxy, C _1-6 alkoxy, C _1-2 bromoalkoxy, C _{2-3 alkenyloxy, C 2-3 alkynyloxy} , benzyloxy, C _1-4 alkylthio; and N,N-dimethylamino and _-CH2Z [wherein Z _is , C _1-2 alkoxy]. 3. A compound according to claim 1 or 2, which is represented by the following formula (): K0057. 4 In the above formula, A is nitro, D is selected from the group consisting of trifluoromethyl and halogen, R ¹ is selected from the group consisting of hydrogen, C _1-4 alkyl and benzyl, and R ² is , hydrogen and methyl, E, T, U, V and R ³ are hydrogen, and W is a [Formula] group [where G is hydroxy, C _1-6 alkoxy and C ₁ The compound according to any one of claims 1 to 3, which is selected from the group consisting of _-4 alkylthio. 5 A in the above formula is nitro, D is hydrogen, nitro, cyano, methyl and C _1-3
selected from the group consisting of alkoxy, R ¹ is selected from the group consisting of hydrogen, C _1-4 alkyl, C _2-3 alkynyl and benzyl, R ² is selected from the group consisting of hydrogen and methyl, E, T, U, V and R ³ are hydrogen, W is a [formula] group [in the formula, G is hydroxy, C _1-6 alkoxy, C _2-3 alkenyloxy,
C substituted with one substituent selected from the group consisting of C _2-3 alkynyloxy, C _1-4 alkylthio, benzyloxy; and N,N-dimethylamino and N,N,N-trimethylammonio _1-2 alkoxy] and -CH ₂ Z group [wherein Z is selected from the group consisting of C _1-2 alkoxy] The compound according to any one of Items 1 to 3. 6 A in the above formula is selected from the group consisting of hydrogen, halogen and amino, D is selected from the group consisting of hydrogen, nitro, cyano, halogen, methyl, trifluoromethyl and C _1-3 alkoxy, R ¹ is selected from the group consisting of hydrogen, C _1-4 alkyl, C _2-3 alkynyl and benzyl, R ² is selected from the group consisting of hydrogen and methyl, and E, T, U, V and R ³ are , hydrogen, and W is a [formula] group [in the formula, G is hydroxy, C _1-6 alkoxy, C _2-3 alkenyloxy,
C _1-4 alkylthio, benzyloxy; and N,N
-dimethylamino and a C _1-2 alkoxy group substituted with one substituent selected from the group consisting of N,N,N-trimethylammonio] and a -CH ₂ Z group [formula The compound according to any one of claims 1 to 3, wherein Z is selected from the group consisting of C _1-2 alkoxy. 7 In the above formula, A is nitro, D is selected from the group consisting of trifluoromethyl and halogen, R ¹ is selected from the group consisting of hydrogen, C _1-4 alkyl and benzyl, and R ² is , hydrogen and methyl, E, T, U, V and R ³ are hydrogen, and W is a [formula] group [where G is C _2-3 alkenyloxy, C _{2- 3} alkynyloxy, benzyloxy; and N,N-dimethylamino and N,N,
selected from the group consisting of C _1-2 alkoxy substituted with one substituent selected from the group consisting of N-trimethylammonio] and -CH ₂ Z group [in the formula Z
is selected from the group consisting of C _1-2 alkoxy. 8 In the above formula, A is nitro, D is selected from the group consisting of trifluoromethyl and halogen, R ¹ is C _2-3 alkynyl, and R ² is selected from the group consisting of hydrogen and methyl. selected, E, T, U, V and R ³ are hydrogen, W is a [formula] group [in the formula, G is hydroxy, C _1-6 alkoxy, C _2-3 alkenyloxy,
C substituted with one substituent selected from the group consisting of C _2-3 alkynyloxy, C _1-4 alkylthio, benzyloxy; and N,N-dimethylamino and N,N,N-trimethylammonio _1-2 alkoxy group] and -CH ₂ Z group [wherein Z is selected from the group consisting of C _1-2 alkoxy], Claim 1 The compound according to any one of Items 1 to 3. 9 In the above formula, A is nitro, D is selected from the group consisting of trifluoromethyl, fluoro, chloro and bromo, and R ¹ is hydrogen, methyl, ethyl, n-propyl,
selected from the group consisting of n-butyl and benzyl, R ² is selected from the group consisting of hydrogen and methyl, E, T, U, V and R ³ are hydrogen, W is a group [formula] The compound according to any one of claims 1 to 4, wherein G is selected from the group consisting of hydroxy, C _1-6 alkoxy, and C _1-4 alkylthio. 10 In the above formula, A is nitro, D is selected from the group consisting of nitro, cyano, methyl, methoxy and ethoxy, and R ¹ is hydrogen, methyl, ethyl, n-propyl,
selected from the group consisting of n-butyl, allyl, propargyl and benzyl, R ² is methyl, E, T, U, V and R ³ are hydrogen, W is G is hydroxy, C _1-6 alkoxy, allyloxy, propargyloxy, C _1-4 alkylthio, benzyloxy,
2-(N,N-dimethylamino)ethoxy and 2
-(N,N,N-trimethylammonio)ethoxy] and -CH ₂ Z group [wherein Z is selected from the group consisting of C _1-2 alkoxy] A compound according to any one of claims 1, 2, 3, or 5. 11 In the above formula, A is selected from the group consisting of hydrogen, fluoro, chloro, bromo and amino, D is selected from the group consisting of fluoro, chloro, bromo, nitro and trifluoromethyl, and R ¹ is hydrogen , methyl, ethyl, n-propyl,
selected from the group consisting of n-butyl, allyl, propargyl and benzyl, R ² is methyl, E, T, U, V and R ³ are hydrogen, W is G is selected from the group consisting of hydroxy, C _1-6 alkoxy, allyloxy, propargyloxy, benzyloxy, 2-(N,N-dimethylamino)ethoxy and 2-(N,N,N-trimethylammonio)ethoxy ] and -CH ₂ Z group [wherein Z is selected from the group consisting of C _1-2 alkoxy]; A compound according to any of paragraph 6. 12 In the above formula, A is nitro, D is selected from the group consisting of fluoro, chloro, bromo and trifluoromethyl, and R ¹ is hydrogen, methyl, ethyl, n-propyl,
selected from the group consisting of n-butyl and benzyl, R ² is methyl, E, T, U, V and R ³ are hydrogen, W is [formula] group [wherein G is allyloxy , propargyloxy, benzyloxy, 2-
(N,N-dimethylamino)ethoxy and 2-
(N,N,N-trimethylammonio)ethoxy] and -CH ₂ Z group [wherein Z is selected from the group consisting of C _1-2 alkoxy] , a compound according to claim 1, 2, 3 or 7. 13 In the above formula, A is nitro, D is selected from the group consisting of fluoro, chloro, bromo and trifluoromethyl, R ¹ is propargyl, R ² is methyl, E, T , U, _V and R ³ are hydrogen; amino)ethoxy and 2-(N,N,N-trimethylammonio)ethoxy] and _-CH2Z group [wherein Z is selected from the group consisting of _C1-2 alkoxy] A compound according to any one of claims 1, 2, 3, or 8, selected from the group consisting of: 14 In the above formula, A is nitro, D is trifluoromethyl or chloro, R ² is methyl, E, T, U, V, R ¹ and R ³ are hydrogen, Claims 1 to 4 or 9, wherein W is a group [formula], wherein G is selected from the group consisting of methoxy, ethoxy, and n-propoxy.
A compound according to any of the paragraphs. 15 Methyl 2-[4-(2,4-dinitroanilino)phenoxy]propionate, 2-[4-(4-
Methoxy-2-nitroanilino)phenoxy]propionate, 2-[4-(4-cyano-2-
Methyl nitroanilino)phenoxy]propionate and 2-[4-(4-cyano-N-methyl-2-
Claim 1 selected from the group consisting of nitroanilino)phenoxy]ethyl propionate.
The compound according to any one of Items 1, 2, 3, 5, and 10. 16 Methyl 2-[4-(2,4-dichloro-N-methylanilino)phenoxy]propionate, 2
- methyl [4-(2,4-dichloroanilino)phenoxy]propionate and methyl 2-[4-(4-nitroanilino)phenoxy]propionate,
A compound according to any one of Items 2, 3, 6, or 11. 17 In the above formula, A is nitro, D is selected from the group consisting of chloro and trifluoromethyl, R ¹ is selected from the group consisting of hydrogen and methyl, R ² is methyl, and E , T, U, V and R ³ are hydrogen, W is a group [formula] [wherein G is selected from the group consisting of allyloxy, propargyloxy and 2-(N,N-dimethylamino)ethoxy] ]
and _-CH2Z group [Z in the formula is ethoxy]
A compound according to any one of claims 1, 2, 3, 7, or 12, selected from the group consisting of: 18 Claims 1, 3, 4, and 9, which are methyl 2-[4-(2-nitro-N-propargyl-4-trifluoromethylanilino)phenoxy]propionate or a compound according to any of paragraph 14. 19 General formula (): K0070 {In the above formula (), A is selected from the group consisting of hydrogen, halogen, nitro, cyano, amino, trifluoromethyl, sulfo, sulfamoyl, methoxycarbonyl and methoxysulfonyl, and D is Hydrogen, halogen, nitro, cyano, methyl, trifluoromethyl, C _1-3 alkoxy, C _1-2
haloalkoxy, fluoromethylsulfinyl,
Fluoromethylsulfonyl, sulfamoyl,
N,N-dimethylsulfamoyl, carboxy,
(C _1-2 alkoxy)carbonyl, N,N-dimethylcarbamoyl, methylsulfonyl and formyl, E is selected from the group consisting of hydrogen and halogen, and T consists of hydrogen, halogen and nitro. wherein at least one of A, D, E and T is not hydrogen, U and V are each independently selected from the group consisting of hydrogen, halogen and nitro, and R ¹ is Hydrogen, C _1-4 alkyl, C _2-3 alkynyl,
is selected from the group consisting of acetyl and benzyl, R ² and R ³ are each independently selected from the group consisting of hydrogen and methyl, W is [formula] [wherein G is hydroxy, C _1-6 Alkoxy, C _1-2 bromoalkoxy, C _2-3 alkenyloxy, C _2-3 alkynyloxy, C _1-4 alkylthio, cyclohexyloxy, benzyloxy; morpholino, methylthio, 2-pyridyl,
C _1-2 alkoxy group substituted with one substituent selected from the group consisting of N,N-dimethylamino and N,N,N-trimethylammonio; phenyl ring substituted with two halogens phenoxy; selected from the group consisting of methanesulfonamide group and dimethylamino group] and -CH ₂ Z [in the formula, Z is
selected from the group consisting of halogen, hydroxy, methoxycarbonylmethyl and C _1-2 alkoxy]
A method for synthesizing a compound represented by the general formula (): K0072 [wherein A, D, E, T, U, V and R ¹ are selected from the group consisting of] in the presence of an alkaline material. phenol or thiophenol of the general formula (): K0073 [wherein R ² , R ³ and W are as described above; hal
is chlorine, bromine or iodine. 20 General formula (): K0074 {In the above formula (), A is selected from the group consisting of hydrogen, halogen, nitro, cyano, amino, trifluoromethyl, sulfo, sulfamoyl, methoxycarbonyl and methoxysulfonyl, and D is Hydrogen, halogen, nitro, cyano, methyl, trifluoromethyl, C _1-3 alkoxy, C _1-2
haloalkoxy, fluoromethylsulfinyl,
Fluoromethylsulfonyl, sulfamoyl,
N,N-dimethylsulfamoyl, carboxy,
(C _1-2 alkoxy)carbonyl, N,N-dimethylcarbamoyl, methylsulfonyl and formyl, E is selected from the group consisting of hydrogen and halogen, and T consists of hydrogen, halogen and nitro. wherein at least one of A, D, E and T is not hydrogen, U and V are each independently selected from the group consisting of hydrogen, halogen and nitro, and R ¹ is Hydrogen, C _1-4 alkyl, C _2-3 alkynyl,
is selected from the group consisting of acetyl and benzyl, R ² and R ³ are each independently selected from the group consisting of hydrogen and methyl, W is [Formula] [wherein G is hydroxy, C _1-6 Alkoxy, C _1-2 bromoalkoxy, C _2-3 alkenyloxy, C _2-3 alkynyloxy, C _1-4 alkylthio, cyclohexyloxy, benzyloxy; morpholino, methylthio, 2-pyridyl,
C _1-2 alkoxy group substituted with one substituent selected from the group consisting of N,N-dimethylamino and N,N,N-trimethylammonio; phenyl ring substituted with two halogens phenoxy; selected from the group consisting of methanesulfonamide group and dimethylamino group] and -CH ₂ Z [in the formula, Z is
selected from the group consisting of halogen, hydroxy, methoxycarbonylmethyl and C _1-2 alkoxy]
A method for synthesizing a compound represented by the general formula (): K0076 [wherein A, D, E and T are as described above;
L is a leaving group] and aniline of the general formula (): K0077 [wherein U, V, W, R ¹ , R ² and R ³ are as described above] are condensed. A synthesis method consisting of 21 General formula (): K0078 {In the above formula (), A is selected from the group consisting of hydrogen, halogen, nitro, cyano, amino, trifluoromethyl, sulfo, sulfamoyl, methoxycarbonyl and methoxysulfonyl, and D is Hydrogen, halogen, nitro, cyano, methyl, trifluoromethyl, C _1-3 alkoxy, C _1-2
haloalkoxy, fluoromethylsulfinyl,
Fluoromethylsulfonyl, sulfamoyl,
N,N-dimethylsulfamoyl, carboxy,
(C _1-2 alkoxy)carbonyl, N,N-dimethylcarbamoyl, methylsulfonyl and formyl, E is selected from the group consisting of hydrogen and halogen, and T consists of hydrogen, halogen and nitro. wherein at least one of A, D, E and T is not hydrogen, U and V are each independently selected from the group consisting of hydrogen, halogen and nitro, and R ¹ is Hydrogen, C _1-4 alkyl, C _2-3 alkynyl,
is selected from the group consisting of acetyl and benzyl, R ² and R ³ are each independently selected from the group consisting of hydrogen and methyl, W is [Formula] [wherein G is hydroxy, C _1-6 Alkoxy, C _1-2 bromoalkoxy, C _2-3 alkenyloxy, C _2-3 alkynyloxy, C _1-4 alkylthio, cyclohexyloxy, benzyloxy; morpholino, methylthio, 2-pyridyl,
C _1-2 alkoxy group substituted with one substituent selected from the group consisting of N,N-dimethylamino and N,N,N-trimethylammonio; phenyl ring substituted with two halogens phenoxy; selected from the group consisting of methanesulfonamide group and dimethylamino group] and -CH ₂ Z [in the formula, Z is
selected from the group consisting of halogen, hydroxy, methoxycarbonylmethyl and C _1-2 alkoxy]
A method for synthesizing a compound represented by the following steps (a) to (c); (a) General formula (): K0080 [wherein A, D, E and T is as mentioned above;
L is a leaving group] and the compound of the general formula (): K0081 [wherein R ¹ , U and V are as described above; Q
is hydroxy, mercapto, C _1-6 alkoxy or C _1-6 alkylthio] and condensed with aniline of the general formula (): K0082 [wherein A, D, E, Q, T, U, V and R ¹ are as described above; (b) producing a compound of the general formula () [wherein Q is C _1-6 alkoxy or C _1-6 alkylthio]; alkylation to produce a compound of the general formula (): K0083, in which A, D, E, T, U, V and R ¹ are as described above; and (c) as described in (a) above. The compound of the general formula () obtained in step and (b) is prepared in the presence of an alkaline material to form a compound of the general formula (): K0084 [wherein R ² , R ³ and W are as described above; hal
is chlorine, bromine or iodine].