A cinnoline derivative having the formula (I): ##STR1## in which X is --OH, --O- M+, --OR1 or ##STR2## wherein M+ is an alkali metal cation, an alkaline earth metal cation or ##STR3## in which R4, R5 and R6 are the same or different and each is a hydrogen atom, a C1 -C6 alkyl group, a C3 -C4 alkenyl group, a C3 -C4 alkynyl group, a C3 -C8 cycloalkyl group, a benzyl group or a phenyl group; R1 is a C1 -C9 alkyl group, a C3 -C6 alkenyl group, a C3 -C4 alkynyl group, a C1 -C3 alkoxy(C1 -C4) alkyl group, a C1 -C3 haloalkyl group, a C3 -C8 cycloalkyl group, a benzyl group or a phenyl group; and R2 and R3 are the same or different and each is a hydrogen atom, a C1 -C6 alkyl group, a C3 -C4 alkenyl group, a C3 -C4 alkynyl group, a C3 -C8 cycloalkyl group, a benzyl group in which at most two of hydrogen atoms at the α-position thereof may be substituted by methyl group, a C2 -C3 hydroxyalkyl group or a phenyl group in which at most three of hydrogen atoms thereof may be substituted by the same or different C1 -C2 alkyl group or halogen atom;
Y is a C1 -C4 haloalkyl group; A1 and A2 are the same or different and each is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a trihalomethyl group, a C1 -C2 alkylthio group or a C1 -C2 haloalkoxy group, a process for preparing the same, and a herbicidal composition containing the same as an acitve ingredient, a method for controlling undesired weeds using the same, and use of the same as a herbicide.
|
1. A cinnoline derivative having the formula (I): ##STR30## in which X is --OH, --O- M+, or --OR1 or ##STR31## wherein M+ is an alkali metal cation, an alkaline earth metal cation or ##STR32## in which R4, R5 and R6 are the same or different and each is hydrogen, C1 -C6 alkyl, C3 -C4 alkenyl, C3 -C4 alkynyl, C3 -C8 cycloalkyl, benzyl or phenyl; R1 is C1 -C9 alkyl, C3 -C6 alkenyl, C3 -C4 alkynyl, C1 -C3 alkoxy-(C1 -C4) alkyl, C3 -C8 cycloalkyl, benzyl or phenyl; and R2 and R3 are the same or different and each is hydrogen, C1 -C6 alkyl, C3 -C4 alkenyl, C3 -C4 alkynyl, C3 -C8 cycloalkyl, benzyl in which at most two hydrogen at the α-position thereof may be substituted by methyl, C2 -C3 hydroxyalkyl or phenyl in which at most three hydrogen thereof may be substituted by the same or different C1 -C2 alkyl or halogen;
Y is C1 -C4 fluoroalkyl, C1 -C4 chloroalkyl, C1 -C4 bromoalkyl, C1 -C4 fluoro-bromoalkyl or C1 -C4 fluoro-chloroalkyl; A1 and A2 are the same or different and each is hydrogen, fluorine, chlorine, bromine, trifluoromethyl, C1 -C2 alkylthio or OCF3, OCHF2, OCF2 Br or OCF2 CHCl2.
3. The cinnoline derivative according to
8. A method for controlling undesired weeds, which comprises applying a herbicidally effective amount of the compound according to
|
|||||||||||||||||||||||||||||||||||||||||||||||||||||||
The present invention relates to novel cinnoline derivatives, processes for preparing the cinnoline derivatives and herbicidal compositions containing the cinnoline derivatives as an active ingredient. The present invention further relates to a method for controlling undesired weeds using the cinnoline derivatives and use of the cinnoline derivatives as a herbicide.
Some 1-aryl-1,4-dihydro-4-oxocinnoline-3-carboxylic acid derivatives have been hitherto reported in literatures such as Zh. Obshch. Khim., vol. 37, p. 2487 (1967), J. Chem. Soc. Chem., Comm., p. 752 (1974), Synthesis, p. 52 (1983), U.S. Pat. No. 4,604,134 and European Patent Publication No. 197226 Al. However, there has not been reported that cinnoline derivatives in the present invention have herbicidal activity.
As a result of the eager study for providing a novel herbicide, it has now been found that cinnoline derivatives having the formula (I): ##STR4## in which X is --OH, --O- M+, --OR1 or ##STR5## wherein M+ is an alkali metal cation, an alkaline earth metal cation or ##STR6## in which R4, R5 and R6 are the same or different and each is a hydrogen atom, a C1 -C6 alkyl group, a C3 -C4 alkenyl group, a C3 -C4 alkynyl group, a C3 -C8 cycloalkyl group, a benzyl group or a phenyl group; R1 is a C1 -C9 alkyl group, a C3 -C6 alkenyl group, a C3 -C4 alkynyl group, a C1 -C3 alkoxy(C1 -C4) alkyl group, a C1 -C3 haloalkyl group, a C3 -C8 cycloalkyl group, a benzyl group or a phenyl group; and R2 and R3 are the same or different and each is a hydrogen atom, a C1 -C6 alkyl group, a C3 -C4 alkenyl group, a C3 -C4 alkynyl group, a C3 -C8 cycloalkyl group, a benzyl group in which at most two of hydrogen atoms at the α-position thereof may be substituted by methyl group, a C2 -C3 hydroxyalkyl group or a phenyl group in which at most three of hydrogen atoms thereof may be substituted by the same or different C1 -C2 alkyl group or halogen atom;
Y is a C1 -C4 haloalkyl group; A1 and A2 are the same or different and each is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a trihalomethyl group, a C1 -C2 alkylthio group or a C1 -C2 haloalkoxy group exhibit both excellent herbicidal activity and selectivity between crops and weeds, and thus the present invention has been accomplished.
In accordance with the present invention, there are provided a cinnoline derivative having the formula (I), a process for preparing it, a herbicidal composition containing it as an active ingredient, a method for controlling undesired weeds using it and use of it as a herbicide.
Among the cinnoline derivatives having the formula (I) of the present invention, cinnoline derivatives having --OH, --O- M+ or --OR1 as X are preferable because of the highly herbicidal activity against weeds. Further, among them, cinnoline derivatives having a fluorine atom, a chlorine atom, a bromine atom, a trifluoromethyl group, a difluoromethoxy group or a trifluoromethoxy group as A1 and a hydrogen atom or a fluorine atom as A2 are more preferable. Moreover, among them, cinnoline derivatives having a C1 -C2 polyfluoroalkyl group (especially a difluoromethyl group, a trifluoromethyl group or a 2,2,2-trifluoroethyl group) as Y are still more preferable.
Hereinafter, processes for preparing the cinnoline derivatives of the present invention are explained.
In the compounds of the present invention, a cinnoline derivative having the formula (I-a): ##STR7## in which R1, Y, A1 and A2 are as defined above can be prepared by subjecting a hydrazone having the formula (II): ##STR8## in which R1, Y, A1 and A2 are as defined above and Z is a fluorine atom, chlorine atom or bromine atom to ring closure with a dehydrohalogenating agent.
The above reaction is usually carried out without any solvent or in a solvent, at a temperature of 0° to 150°C, for a period of 10 minutes to 20 hours. The dehydrohalogenating agent may be used in an amount of 1 to 10 equivalents to one equivalent of the hydrazone (II).
Examples of the solvent are, for instance, aliphatic hydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene), ethers (e.g. diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone), esters (e.g. ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate), nitro compounds (e.g. nitroethane, nitrobenzene), nitriles (e.g. acetonitrile, isobutylnitrile), tertiary amines (e.g. pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine), acid amides (e.g. formamide, N,N-dimethylformamide, acetamide), sulfur compounds (e.g. dimethyl sulfoxide, sulfolane), water, and the like. Their mixtures are also usable.
Examples of the dehydrohalogenating agent are, for instance, organic bases (e.g. pyridine, triethyl amine, N,N-diethylaniline), inorganic bases (e.g. sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride), alkali metal alkoxide (e.g. sodium methoxide, sodium ethoxide), and the like.
For the purpose of conducting the reaction more efficiently, quaternary ammonium salts and crown ethers can be added. Examples of the quaternary ammonium salts are, for instance, benzyltriethylammonium chloride, tetrabutylammonium chloride, and the like. Examples of the crown ethers are, for instance, dibenzo-18-crown-6, and the like.
After completion of the reaction, the reaction mixture is subjected to ordinary post-treatment such as addition of water followed by collection of precipitated crystals, extraction with an organic solvent, or concentration. If necessary, a purification procedure such as chromatography or recrystallization may be adopted. Thus the cinnoline derivative (I-a) of the present invention can be obtained.
In the compounds of the present invention, a cinnoline derivative having the formula (I-b): ##STR9## in which Y, A1 and A2 are as defined above can be prepared by hydrolyzing the cinnoline derivative (I-a).
The above reaction is carried out in water or a mixed solvent of water and an alcohol (e.g. methanol, ethanol, isopropanol, diethylene glycol, glycerin), an ether (e.g. tetrahydrofuran, dioxane), a nitrile (e.g. acetonitrile), an acid amide (e.g. formamide, N,N-dimethylformamide) or a sulfur compound (e.g. dimethyl sulfoxide). Usually the acid or the alkali is added in an amount of 1 to 100 equivalents to one equivalent of the cinnoline derivative (I-a). The reaction temperature is 20° to 100°C The reaction period is 30 minutes to 10 hours.
Examples of the acid are, for instance, hydrochloric acid, sulfuric acid, nitric acid, and the like. Examples of the alkali are, for instance, sodium hydroxide, potassium hydroxide, and the like. When the alkali is used, the reaction mixture is neutralized with hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, or the like after completion of the reaction.
After completion of the reaction, the reaction mixture is subjected to ordinary post-treatment such as collection of precipitated crystals, extraction with an organic solvent, or concentration. If necessary, a purification procedure such as chromatography or recrystallization may be adopted. Thus the cinnoline derivative (I-b) of the present invention can be obtained.
In the compounds of the present invention, a cinnoline derivative having the formula (I-c): ##STR10## wherein Y, A1 and A2 are as defined above, and M'+ is an alkali metal cation or an alkaline earth metal cation can be prepared by reacting the cinnoline derivative (I-b) with a hydroxide having the formula (III): ##STR11## wherein M'+ is as defined above.
The above reaction is usually carried out in water at a temperature of 0° to 50°C for a period of 5 minutes to 5 hours. The hydroxide (III) may be used in an amount of 0.7 to 1 equivalent to one equivalent of the cinnoline derivative (I-b).
Examples of the hydroxide (III) are, for instance, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and the like.
After completion of the reaction, if necessary, the water layer is washed with an organic solvent, and then concentrated. Thus the cinnoline derivative (I-c) of the present invention can be obtained.
In the compounds of the present invention, a cinnoline derivative having the formula (I-d): ##STR12## wherein R4, R5, R6, Y, A1 and A2 are as defined above can be prepared by reacting the cinnoline derivative (I-b) with an amine having the formula (IV): ##STR13## wherein R4, R5 and R6 are as defined above.
The above reaction is usually carried out without any solvent or in a solvent, at a temperature of 0° to 100°C, for a period of 5 minutes to 3 hours. The amine (IV) may be used in an amount of 1 to 10 equivalents to one equivalent of the cinnioline derivative (I-b).
Examples of the solvent are, for instance, aromatic hydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene), ethers (e.g. diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), alcohols (e.g. methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol, methyl cellosolve, diethylene glycol, glycerin), esters (e.g. ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate), nitro compounds (e.g. nitroethane, nitrobenzene), nitriles (e.g. acetonitrile, isobutylnitrile), water, and the like. Their mixtures are also usuable.
After completion of the reaction, the reaction mixture is subjected to ordinary post-treatment such as concentration. If necessary, a purification procedure such as recrystallization may be adopted. Thus the cinnoline derivative (I-d) can be obtained.
In the compounds of the present invention, a cinnoline derivative (I-e): ##STR14## wherein R2, R3, Y, A1 and A2 are as defined above can be prepared by reacting a halide having the formula (V): ##STR15## wherein Y, A1 and A2 are as defined above and W is a halogen atom
with an amine having the formula (VI): ##STR16## wherein R2 and R3 are as defined above.
The above reaction is usually carried out without any solvent or in a solvent, in the presence of a dehydrohalogenating agent, at a temperature of 0° to 50°C, for a period of 10 minutes to 3 hours. The amine (VI) and the dehydrohalogenating agent are used in an amount of 1 to 5 equivalents and 1 to 2 equivalents respectively, to one equivalent of the halide (V).
Examples of the solvents are, for instance, aliphatic hydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene), ethers (e.g. diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), esters (e.g. ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate), nitro compounds (e.g. nitroethane, nitrobenzene), nitriles (e.g. acetonitrile, isobutylnitrile), tertiary amines (e.g. pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine), acid amides (e.g. formamide, N,N-dimethylformamide, acetamide), sulfur compound (e.g. dimethyl sulfoxide, sulfolane), water, and the like. Their mixtures are also usable.
Examples of the dehydrohalogenating agent are, for instance, organic bases (e.g. pyridine, triethyl amine, N,N-diethyl aniline), and the like.
After completion of the reaction, the reaction mixture is subjected to ordinary post-treatment such as extraction with an organic solvent or concentration. If necessary, a purification procedure such as chromatography or recrystallization may be adopted. Thus the cinnoline derivative (I-e) can be obtained.
The halide (V) is easily prepared by usual acid halogenation of the cinnoline derivative (I-b).
Typical examples of the cinnoline derivatives which can be prepared according to the above procedures are shown in Table 1.
| TABLE 1 |
| ______________________________________ |
| ##STR17## |
| A1 A2 X Y |
| ______________________________________ |
| H H OH CHF2 |
| " " OK " |
| " " OC2 H5 |
| " |
| 2-Cl " " " |
| 4-Cl " " " |
| " " OH " |
| " " OK " |
| " " ONH4 " |
| " " N(CH3)2 |
| " |
| 2-F 4-Cl OC4 H9 -n |
| " |
| " " OC2 H5 |
| " |
| 3-Cl 4-F " " |
| 2-Cl 4-Cl " " |
| 4-Br H OH " |
| " " |
| ##STR18## " |
| 2-F 4-Br OC3 H7 -i |
| " |
| 4-CF3 H OH " |
| " " ONa " |
| " " OCH3 " |
| 4-SCH3 |
| " OH " |
| " " OK " |
| 4-SCH3 |
| " OC2 H5 |
| " |
| 4-OCHF2 |
| H OCH3 CHF2 |
| 2-F 4-OCHF2 |
| OK " |
| 3-OCF3 |
| H OC2 H5 |
| " |
| 4-OCF3 |
| " " " |
| " " OH " |
| " " ONa " |
| " " O(1/2Ca) " |
| " " ONH(C2 H5)3 |
| " |
| 4-OCF2 Br |
| " OC2 H5 |
| " |
| 4-OCF2 CHCl2 |
| " " " |
| H " OH CF3 |
| " " ONa " |
| " " OC2 H5 |
| " |
| 4-F " " " |
| 4-Cl " OH " |
| " " OK " |
| " " OC2 H5 |
| " |
| " " |
| ##STR19## " |
| 3-F 4-Cl OH " |
| " " OK " |
| " " OCH3 " |
| " " OC4 H9 -n |
| " |
| 2-Cl " OC2 H5 |
| " |
| 4-Br H OCH3 " |
| 2-F 4-Br OC2 H5 |
| " |
| 3-CF3 H OCH3 " |
| 4-CF3 " OC3 H7 -i |
| " |
| 4-SCH3 |
| " OH " |
| " " ONa " |
| " " OC2 H5 |
| " |
| 4-OCHF2 |
| H OC2 H5 |
| CF3 |
| 2-OCHF2 |
| 4-F OCH3 " |
| 4-OCF3 |
| H OH " |
| " " OK " |
| " " OC2 H5 |
| " |
| 4-OCF2 Br |
| " OK " |
| H " OC2 H5 |
| CF2 Br |
| 4-Cl " OK " |
| 2-F 4-Cl OC3 H7 -i |
| " |
| 4-SCH3 |
| H OC3 H7 -n |
| " |
| 4-OCHF2 |
| " OH " |
| 4-OCF3 |
| " OC2 H5 |
| " |
| H " OH CF2 CF2 H |
| " " ONa " |
| " " OC2 H5 |
| " |
| 2-Cl " OCH3 " |
| 4-Cl " OC2 H5 |
| " |
| 2-F 4-Cl OCH3 " |
| 3-F " OC2 H5 |
| " |
| 3-Cl 4-F OK " |
| 4-Br H OH " |
| 4-CF3 " " " |
| 4-SCH3 |
| " OK " |
| " " OCH3 " |
| 4-OCF3 |
| " OC2 H5 |
| " |
| 4-CF2 Br |
| " OH " |
| 4-F " OC2 H5 |
| CH2 CF3 |
| 4-Cl " " " |
| 4-Br " OH " |
| 4-CF3 " OK " |
| 4-SCH3 |
| " OH " |
| 2-F 4-OCHF2 |
| OC2 H5 |
| " |
| 2-Cl 4-F OC3 H7 -n |
| CF2 CHCl2 |
| 3-Cl " OCH3 " |
| 4-SCH3 |
| H OC2 H5 |
| " |
| 4-OCF3 |
| " OK " |
| H " OC2 H5 |
| CF2 CHFCl |
| 4-F " " " |
| " " OH " |
| " " OK " |
| 4-Br " OCH3 " |
| 2-F 4-Br OH " |
| 4-OCF3 |
| H OC2 H5 |
| " |
| 4-Cl " OK CFClCHFCl |
| 3-Cl 4-Cl OC2 H5 |
| " |
| 4-CF3 H OC3 H7 -n |
| " |
| 4-SCH3 |
| " OH " |
| 4-OCHF2 |
| " " " |
| H " " CF2 CHFCF3 |
| 4-F " OC2 H5 |
| " |
| 4-Cl " OK " |
| 2-F 4-Cl OCH3 " |
| 4-CF3 H OC2 H5 |
| " |
| 4-SC2 H5 |
| " OH " |
| 4-OCF3 |
| " ONa " |
| ______________________________________ |
In preparing the compound of the present invention, the hydrazone derivative (II), which is the starting material, can be prepared by reacting a ketoester having the formula (VII): ##STR20## in which R1, Y and Z are as defined above with a diazonium salt having the formula (VIII): ##STR21## in which A1 and A2 are as defined above.
The above reaction is usually carried out in a solvent at a temperature of 0° to 50°C for a period of 10 minutes to 5 hours. The diazonium salt (VIII) may be used in an amount of 0.7 to 1.5 equivalents to one equivalent of ketoester (VII).
Examples of the solvent are, for instance, ethers (e.g. diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), alcohols (e.g. methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol, methyl cellosolve, diethylene glycol, glycerin), tertiary amines (e.g. pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine), acid amides (e.g. formamide, N,N-dimethylformamide, acetamide), water, and the like. Their mixture are also usable.
For the purpose of conducting the reaction more efficiently, inorganic bases (e.g. sodium carbonate, potassium carbonate, sodium acetate, potassium acetate) can be added to the reaction system.
After completion of the reaction, the reaction mixture is subjected to ordinary post-treatment such as extraction with an organic solvent or concentration. If necessary, a purification procedure such as chromatography or recrystallization may be adopted. Thus the desired starting material (II) can be obtained.
The diazonium salt (VIII) is prepared according to an ordinary process from an aniline having the formula (IX): ##STR22## in which A1 and A2 are as defined above.
Moreover, the ketoester having the formula (VII) can be prepared in accordance with the following steps. ##STR23## In the above schema, R1, Y and Z are as defined above, Y' is a polyhalogenated hydrocarbon, which is capable of being added to a phenol and Y" is a C1 -C4 haloalkyl group except --CF3 and --CH2 CF3.
The compounds of the present invention show an excellent herbicidal activity and an excellent selectivity between crops and weeds. That is, in upland fields, by soil treatment or foliage treatment, the cinnoline derivatives of the present invention exhibit a herbicidal activity against undesired weeds, for instance, broad-leaved weeds such as wild buckwheat (Polygonum convolvulus), pale smartweed (Polygonum lapathifolium), common purslane (Portulaca oleracea), common chickweed (Stellaria media), common lambsquarters (Chenopodium album), redroot pigweed (Amaranthus retroflexus), radish (Raphanus sativus), wild mustard (Sinapis arvensis), shepherdspurse (Capsella bursapastoris), velvetleaf (Abutilon theophrasti), prickly sida (Sida spinosa), field pansy (Viola arvensis), cleavers (Galium aparine), field bindweed (Convolvulus arvensis), purple deadnettle (Lamium purpureum), henbit (Lamium amplexicaure), jimsonweed (Datura stramonium), black nightshade (Solanum nigrum), persian speedwell (Veronica persica), scentless chamomile (Matricaria perforata) and corn marigold (Chrysanthemum segetum); graminaceous weeds such as Japanese millet (Echinochloa frumentacea), barnyardgrass (Echinochloa crus-galli), green foxtail (Setaria virides), large crabgrass (Digitaria sanguinalis), annual bluegrass (Poa annua), blackgrass (Alopecurus myosuroides), oats (Avena sativa), wild oat (Avena fatua), johnsongrass (Sorghum halepense), quackgrass (Agropyron repens), downy brome (Bromus tectorum) and bermudagrass (Cynodon dactylon); commelinaceous weeds such as asiatic dayflower (Commelina communis); cyperaceous weeds such as purple nutsedge (Cyperus rotundus) and rice flatsedge (Cyperus iria); and the like. The cinnoline derivatives of the present invention do not exert any material phytotoxicity to main crops such as corn, wheat, rice, soybean, cotton and sugar beat.
The cinnoline derivatives of the present invention also exhibit a herbicidal activity on various lowland weeds in question, for instance, graminaceous weeds such as barnyardgrass (Echinochloa oryzicola); broad-leaved weeds such as common falsepimpernel (Lindernia procumbens), indian toothcup (Rotala indica) and waterwort (Elatine triandra); cyperaceous weeds such as smallflower umbrellaplant (Cyperus difformis), hardstem bulrush (Scirpus juncoides), needle spikerush (Eleocharis acicularis) and water nutsedge (Cyperus serotinus); and the like without exerting any material phytotoxicity to rice plants in treatment under flooded condition.
When the cinnoline derivatives are employed as an active ingredient in a herbicidal composition of the present invention, they are usually formulated in the form of emulsifiable concentrates, wettable powders, suspensions, granules and the like in combination with auxiliary agents such as a solid carrier, liquid carrier and surface active agent. The content of the cinnoline derivatives of the present invention as the active ingredient in such formulations is within a range of 0.1 to 90% by weight, preferably 0.2 to 80% by weight.
Examples of the solid carrier are, for instance, fine powders or granules of kaolin clay, attapulgite clay, bentonite, terra alba, pyrophyllite, talc, diatomaceous earth, calcite, walnut powders, urea, ammonium sulfate, synthetic hydrous silicate, and the like. Examples of the liquid carrier are, for instance, aromatic hydrocarbons (e.g. xylene, methylnaphthalene), alcohols (e.g. isopropanol, ethylene glycol, cellosolve), ketones (e.g. acetone, cyclohexanone, isophorone), vegetable oils (e.g. soybean oil, cotton seed oil), dimethylsulfoxide, N,N-dimethylformamide, acetonitrile, water, and the like.
Examples of the surface active agent used for emulsification, dispersion or wetting are, for instance, anionic surface active agents such as alkylsulfates, alkylsulfonates, alkylarylsulfonates, dialkylsulfosuccinates and polyoxyethylenealkylaryl ether phosphates; non-ionic surface active agents such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters; and the like.
Examples of the auxiliary agents other than above are, for instance, ligninsulfonates, alginates, polyvinyl alcohols, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate), and the like.
As the method for controlling undesired weeds of the present invention, the cinnoline derivatives of the present invention are usually formualted and used in soil treatment, foliage treatment or treatment under flooded condition before the emergence of weeds or within about one month after the emergence of weeds to the area where undesired weeds grow or will grow. Soil treatment includes soil surface treatment, soil incorporation treatment, and the like. The foliage treatment includes, in addition to the treatment of the plant over the top, directed application wherein herbicides are applied only to weeds so as not to attach to crops, and the like.
The cinnoline derivatives of the present invention may be used together with other herbicides to improve their activity as herbicides.
Further, they may applied in combination with insecticides, acaricides, nematocides, fungicides, plant growth regulators, fertilizers, soil improvers, and the like.
Furthermore, the cinnoline derivatives of the present invention can be used as an active ingredient of a herbicide for paddy field, upland field, orchard, pasture land, lawn, forest, non-agricultural field, and the like.
The dosage rate of the cinnoline derivatives of the present invention varies depending on weather conditions, preparation form, prevailing season, mode of application, soil involved, crop and weed species aimed at, and the like. Generally, however, the dosage rate is from 0.5 to 500 grams, preferably from 1 to 300 grams of the active ingredient per are. The herbicidal composition of the invention formulated into emulsifiable concentrate, a wettable powder, a suspension, or the like is ordinarily employed by diluting a designed amount of it with water, if necessary with addition of an auxiliary agent such as a spreading agent, at a volume of 1 to 10 liters per are. The herbicidal composition formulated into granule and the like is usually applied without any dilution.
Examples of the wetting agent are, in addition to the surface active agents as noted above, for instance, polyoxyethylene resin acid (ester), ligninsulfonate, abiethylenic acid salt, dinaphthylmethanedisulfonate, paraffin, and the like.
The present invention is more specifically described and explained by means of the following Examples, Reference Example, Formulation Examples and Test Examples, wherein the compound Nos. of the active ingredient corresponds to those in Table 2. It is to be understood that the present invention is not limited to the Examples, Formulation Examples, and Test Examples and various changes and modifications may be made in the invention without departing from the spirit and scope thereof.
PAC [Preparation of the compound No. 33]Ethyl 2-[(4-trifluoromethoxyphenyl)-1,1-diazanediyl]-(2-fluoro-6-difluoromethoxy benzoyl)acetate (530 mg), and potassium carbonate (157 mg) were added to N,N-dimethylformamide (10 ml), and the resultant mixture was heated at 100°C for 1 hour. The mixture was cooled to room temperature, and was poured into ice-water (about 50 ml). After allowing it to stand for 2 hours, the precipitated crystals were collected by filtration. The crystals were washed with water (5 ml) two times and were dried under reduced pressure to give 478 mg of desired ethyl 1-(4-trifluoromethoxyphenyl)-1,4-dihydro-4-oxo-5-difluoromethoxycinnoline- 3-carboxylate (yield: 94.3%). m.p., 145°C
PAC [Preparation of the compound No. 15]Ethyl 2-[(2-fluoro-4-chlorophenyl)-1,1-diazanediyl]-(2-fluoro-6-difluoromethoxyb enzoyl)acetate (460 mg) and potassium carbonate (137 mg) were added to N,N-dimethylformamide (10 ml), and the resultant mixture was heated at 100°C for 1 hour. The mixture was cooled to room temperature, and was poured into ice-water (about 50 ml). After allowing it to stand overnight, the precipitated crystals were collected by filtration, washed with water (5 ml) two times and were dried under reduced pressure to give 410 mg of desired ethyl 1-(2-fluoro-4-chlorophenyl)-1,4-dihydro-4-oxo-5-difluoromethoxycinnoline-3 -carboxylate (yield: 93.8%). m.p., 140°-142°C
PAC [Preparation of the compound No. 30]Ethyl 1-(4-trifluoromethoxyphenyl)-1,4-dihydro-4-oxo-5-difluoromethoxycinnoline- 3-carboxylate (200 mg) and a 1N aqueous solution of sodium hydroxide (0.93 ml) were added to a mixed solvent of ethanol (5.5 ml) and water (1.5 ml), and the resultant mixture was stirred at 70° to 80°C for 3 hours. After being allowed to cool to room temperature, the mixture was diluted with water (50 ml), and washed with ethyl acetate (20 ml). The pH of the water layer was adjusted to pH 2 with concentrated hydrochloric acid to precipitate crystals. The precipitated crystals were collected by filtration, washed with water (5 ml) two times, and dried under reduced pressure to give 120 mg of desired 1-(4-trifluoromethoxyphenyl)-1,4-dihydro-4-oxo-5-difluoromethoxycinnoline- 3-carboxylic acid (yield: 64.2%). m.p., 236.5°C
PAC [Preparation of the compound No. 31]1-(4-Trifluoromethoxyphenyl)-1,4-dihydro-4-oxo-5-difluoromethoxycinnoline-3 -carboxylic acid (120 mg) and a 1N aqueous solution of sodium hydroxide (0.265 ml) were added to water (5 ml), and the mixture was stirred at room temperature for 1 hour. The resultant mixture was washed with ethyl acetate (10 ml). After removing the water, the obtained crystals were dried to give 91 mg of desired sodium 1-(4-trifluoromethoxyphenyl)-1,4-dihydro-4-oxo-5-difluoromethoxycinnoline- 3-carboxylate (yield: 78.4%). m.p., 165°-169°C
Some of the cinnoline derivatives of the present invention obtained according to these process as above are shown in Table 2.
| TABLE 2 |
| ______________________________________ |
| ##STR24## (I) |
| Melting |
| Compound point |
| No. A1 A2 |
| X Y (°C.) |
| ______________________________________ |
| 1 H H OH CHF2 |
| 261-263 |
| 2 " " OK " 277-279 |
| 3 " " OC2 H5 |
| " 159-161 |
| 4 4-F " ONa " 248-255 |
| 5 " " OC2 H5 |
| " 185.5 |
| 6 2-Cl " " " 191.7 |
| 7 4-Cl " OH " 256.8 |
| 8 " " OK " 270-275 |
| 9 " " OC2 H5 |
| " 198.3 |
| 10 4-Br " OH " 260-263 |
| 11 " " ONa " 211-215 |
| 12 " " OC2 H5 |
| " 192-194 |
| 13 2-F 4-Cl OH " 206.5 |
| 14 " " ONa " 240-246 |
| 15 " " OC2 H5 |
| " 140-142 |
| 16 " 4-Br OH " 208-210 |
| 17 " " OC2 H5 |
| " 137-140 |
| 18 2-Cl 4-F " " 142-146 |
| 19 " 4-Cl " " 176 |
| 20 3-Cl 4-F OH " 266-268 |
| 21 " " ONa " 260-265 |
| 22 " " OC2 H5 |
| " 138-144 |
| 23 4-CF3 H OH " 260-263 |
| 24 " " ONa " 240-250 |
| 25 " " OK " >300 |
| 26 " " OC2 H5 |
| " 192.8 |
| 27 4-OCHF2 |
| " OH " 237-241 |
| 28 " " ONa " 183-187 |
| 29 " " OC2 H5 |
| " 141.7 |
| 30 4-OCF3 |
| " OH " 236.5 |
| 31 " " ONa " 165-169 |
| 32 4-OCF3 |
| H OK CHF2 |
| 267-270 |
| 33 " " OC2 H5 |
| " 145 |
| 34 4-SCH3 |
| " OH " 253-256 |
| 35 " " OC2 H5 |
| " 152-156 |
| 36 4-OCF2 CHF2 |
| " " " 162.1 |
| 37 4-Cl " OH CF3 |
| 264-268 |
| 38 " " OK " 270-274 |
| 39 " " OC2 H5 |
| " 207-209 |
| 40 4-OCF3 |
| " OH " 269-270 |
| 41 " " OK " 205-210 |
| 42 " " OC2 H5 |
| " 145-148 |
| 43 4-Cl " " CH2 CF3 |
| 172.9 |
| 44 4-Br " " " 176.6 |
| 45 4-Cl " OH CF2 CHF2 |
| 197-200 |
| 46 " " OK " 265-272 |
| 47 " " OC2 H5 |
| " 127-130 |
| 48 4-OCF3 |
| " OH " 254-261 |
| 49 " " OK " 290-300 |
| 50 " " OC2 H5 |
| " 147-149 |
| ______________________________________ |
An example of process for preparing the hydrazone derivative (II), which is the starting material of the compound of the present invention is shown in the following Reference Example.
To 4-trifluoromethoxyaniline (289 mg) were added water (3 ml) and concentrated hydrochloric acid (1 ml) to give a solution. To the solution was added dropwise a solution of sodium nitrite (124 mg) in water (2 ml) over about 5 minutes while cooling with ice to give a solution of a diazonium salt. The obtained solution was added dropwise to a solution of ethyl 2-fluoro-6-difluoromethoxybenzoyl acetate (500 mg, purity 90%) in a mixed solvent of 70% methanol (8 ml) and pridine (0.8 ml) at 10° to 20°C over about 10 minutes. After the reaction mixture was stirred at room temperature for 1 hour, the resultant mixture was added to ice-water (30 ml) containing a 1N hydrochloric acid (2 ml), the resultant mixture was extracted with ethyl acetate (30 ml) two times. The extract was washed with water (20 ml) and a saturated saline solution (20 ml) successively, and was dried over anhydrous magnesium sulfate. The solid obtained by removing ethyl acetate under reduced pressure was washed with a mixed solvent of hexane and ethanol to give 530 mg of desired ethyl 2-[(4-trifluoromethoxyphenyl)-1,1-diazanediyl]-(2-fluoro-6-difluoromethoxy benzoyl)acetate (yield: 70%). m.p., 80.5°C
Formulation Examples are shown below. In the Formulation Examples, all parts are by weight.
Fifty parts of any one of Compound Nos. 5, 6, 7, 8, 9, 12, 15, 19, 26, 27, 29, 32, 33, 43 and 44, 3 parts of calcium ligninsulfonate, 2 parts of sodium laurylsulfate and 45 parts of synthetic hydrous silicate are well mixed to obtain a wettable powder.
Ten parts of any one of Compound Nos. 5, 6, 7, 9, 12, 15, 19, 26, 27, 29, 33, 43 and 44, 14 parts of polyoxyethylenestyrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 30 parts of xylene and 40 parts of cyclohexanone are well mixed to obtain an emulsifiable concentrate.
Two parts of any one of Compound Nos. 5, 6, 8, 9, 12, 15, 26, 29, 32 and 43, 1 part of synthetic hydrous silicate, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 65 parts of kaolin clay are well pulverized and mixed together. The mixture is then kneaded with water, granulated and dried to obtain a granule.
Twenty-five parts of any one of Compound Nos. 5, 6, 7, 8, 9, 12, 15, 19, 26, 27, 29, 32, 33, 43 and 44, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 69 parts of water are mixed and pulverized until the particle size of the mixture becomes not more than 5 microns to obtain a suspension.
Three parts of any one of Compound Nos. 2, 8, 25, 32, 38 and 41, 1 part of polyoxyethylenestyrylphenyl ether and 96 parts of water are well mixed to obtain a liquid formulation.
The herbicidal activity of the compounds are illustratively shown in the following Test Examples wherein the degree of germination and the degree of growth inhibition are observed with the naked eye and herbicidal activity is rated with an index 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, in which the numeral "0" indicates no material difference is seen in comparison with the untreated plant and the numeral "10" indicates the complete inhibition or death of the test plants. Compounds A, B, C, D and E used for comparison are shown in Table 3.
| TABLE 3 |
| ______________________________________ |
| Com- |
| pound |
| No. Formula Remarks |
| ______________________________________ |
| ##STR25## coumarin |
| B |
| ##STR26## the compound disclosed in European Patent |
| Publication No. 197226 Al |
| C |
| ##STR27## the compound disclosed in European Patent |
| Publication No. 197226 Al |
| D |
| ##STR28## the compound disclosed in European Patent |
| Publication No. 197226 Al |
| E |
| ##STR29## fluometuron |
| ______________________________________ |
Plow-field soil was filled in a cylindrical plastic pot (diameter: 10 cm, height: 10 cm), and the seeds of Japanese millet and oats were sowed and covered with the soil. A prescribed amount of the test compound formulated into emulsifiable concentrate or liquid formulation according to Formulation Example 2 or 5 was diluted with water of an amount corresponding to 10 liters/are, and applied to the soil surface by means of a small-sized sprayer. After treatment, the test plants were cultivated for 20 days in a greenhouse to examine the herbicidal activity. The results are shown in Table 4.
| TABLE 4 |
| ______________________________________ |
| Compound Dosage Herbicidal activity |
| No. (g/are) Japanese millet |
| Oats |
| ______________________________________ |
| 5 40 10 10 |
| 6 40 10 10 |
| 8 40 10 10 |
| 9 40 10 10 |
| 12 40 10 10 |
| 15 40 10 10 |
| l9 40 10 10 |
| 26 40 10 10 |
| 27 40 10 10 |
| 29 40 10 10 |
| 33 40 10 10 |
| 43 40 10 10 |
| 44 40 10 10 |
| ______________________________________ |
The seeds of Japanese millet, oats and radish were sowed in cylindrical plastic pots (diameter: 10 cm, height: 10 cm) filled with plow-field soil, and cultivated in a greenhouse for 10 days. A prescribed amount of the test compound formulated into emulsifiable concentrate or liquid formulation according to Formulation Example 2 or 5 was diluted with water containing a spreading agent, and the dilution was sprayed over the foliage of the test plants by means of a small-sized sprayer at a spray volume of 10 liters/are. The test plants were further grown in a greenhouse for 20 days, and the herbicidal activity was rated. The results are shown in Table 5.
| TABLE 5 |
| ______________________________________ |
| Herbicidal activity |
| Compound Dosage Japanese |
| No. (g/are) millet Oats Radish |
| ______________________________________ |
| 5 40 9 9 10 |
| 10 7 9 10 |
| 6 40 9 9 9 |
| 10 -- -- 9 |
| 7 40 10 10 10 |
| 10 10 9 10 |
| 8 40 10 10 10 |
| 10 10 10 10 |
| 9 40 9 9 9 |
| 10 7 8 7 |
| 12 40 9 9 9 |
| 10 8 8 8 |
| 15 40 9 9 9 |
| 10 7 8 8 |
| 19 40 9 8 9 |
| 10 -- -- 8 |
| 26 40 9 9 10 |
| 10 -- 7 10 |
| 27 40 10 9 9 |
| 10 7 9 8 |
| 29 40 9 8 9 |
| 10 -- 7 7 |
| 32 40 9 9 9 |
| 10 8 8 8 |
| 33 40 9 8 10 |
| 10 9 7 10 |
| 43 40 9 9 9 |
| 10 8 7 -- |
| 44 40 9 9 9 |
| 10 8 8 -- |
| ______________________________________ |
The seeds of velvetleaf were sowed in cylindrical plastic pots (diameter: 10 cm, height: 10 cm) filled with plow-field soil, and cultivated in a greenhouse for 10 days. A prescribed amount of the test compound formulated into emulsifiable concentrate or liquid formulation according to Formulation Example 2 or 5 was diluted with water containing a spreading agent, and the dilution was sprayed over the foliage of the test plants by means of a small-sized sprayer at a spray volume of 10 liters/are. The test plants were further grown in a greenhouse for 20 days, and the herbicidal activity was rated. The results are shown in Table 6.
| TABLE 6 |
| ______________________________________ |
| Compound Dosage Herbicidal activity |
| No. (g/are) Velvetleaf |
| ______________________________________ |
| 5 40 10 |
| 10 7 |
| 6 40 7 |
| 7 40 7 |
| 9 40 7 |
| 26 40 7 |
| ______________________________________ |
Cylindrical plastic pots (diameter: 8 cm, height: 12 cm) were filled with paddy field soil, and the seeds of barnyardgrass were sowed in 1 to 2 cm depth. Water was poured therein to make a flooded condition. The test plants were grown in a greenhouse. Six days (at that time weeds began to germinate) thereafter, a prescribed amount of the test compound formulated into emulsifiable concentrate or liquid formulation according to Formulation Example 2 or 5 was diluted with water (5 ml) and applied to the water surface. The test plants were grown for further 20 days in the greenhouse, and the herbicidal activity was rated. The results are shown in Table 7.
| TABLE 7 |
| ______________________________________ |
| Compound Dosage Herbicidal activity |
| No. (g/are) Barnyardgrass |
| ______________________________________ |
| 1 40 10 |
| 2 40 10 |
| 3 40 10 |
| 5 40 10 |
| 6 40 10 |
| 7 40 10 |
| 8 40 10 |
| 9 40 10 |
| 10 40 10 |
| 12 40 10 |
| 15 40 10 |
| 19 40 10 |
| 23 40 10 |
| 25 40 10 |
| 26 40 10 |
| 27 40 10 |
| 29 40 10 |
| 30 40 10 |
| 32 40 10 |
| 33 40 10 |
| 34 40 10 |
| 35 40 10 |
| 39 40 10 |
| 42 40 10 |
| 43 40 10 |
| 44 40 10 |
| ______________________________________ |
Paddy field soil was filled in 1/5000 ares Wagner's pots, and the seeds of barnyardgrass were sowed in 1 to 2 cm depth in the soil. After creating the state of paddy field by flooding, rice seedlings in a 3-leaf stage were transplanted and cultivated in a greenhouse. After 5 days, a prescribed amount of the test compound formulated into emulsifiable concentrate or liquid formulation according to Formulation Example 2 or 5 was diluted with 10 ml of water and applied to the water surface, and the depth of water was made 4 cm. After treatment, the test plants were cultivated for 20 days in a greenhouse to examine the herbicidal activity. The results are shown in Table 8. In this test, water leakage corresponding to a water level of 3 cm/day was carried out for 2 days from the day subsequent to the treatment.
| TABLE 8 |
| ______________________________________ |
| Compound Dosage Herbicidal activity |
| No. (g/are) Rice Barnyardgrass |
| ______________________________________ |
| 5 2.5 3 10 |
| 0.63 0 10 |
| 6 2.5 1 10 |
| 0.63 0 10 |
| 9 2.5 0 10 |
| 0.63 0 8 |
| 12 2.5 0 10 |
| 0.63 0 10 |
| 15 2.5 0 10 |
| 0.63 0 10 |
| 26 2.5 0 10 |
| 0.63 0 10 |
| 29 2.5 2 10 |
| 0.63 0 10 |
| 32 2.5 3 10 |
| 0.63 2 10 |
| 43 2.5 2 10 |
| 0.63 0 10 |
| A 40 0 0 |
| 10 0 0 |
| B 40 6 9 |
| 10 4 5 |
| C 10 0 8 |
| 2.5 0 0 |
| D 40 0 4 |
| 10 0 0 |
| ______________________________________ |
Plow-field soil was filled in a vat (area: 33×23 cm2, height: 11 cm) and the seeds of cotton, morning glories, common cocklebur, barnyardgrass and Johnsongrass were sowed and cultivated for 18 days. Thereafter, a prescribed amount of the test compound formulated into emulsifiable concentrate or liquid formulation according to Formulation Example 2 or 5 was diluted with a spreading agent-containing water of an amount corresponding to 5 liters/are, and uniformly applied to the entire foliage of the test plants over the top by means of a small-sized sprayer. The state of growth of the weeds and crops at that time varied with the kind thereof, but they were in a cotyledonous stage and from 5 to 19 cm in height. Twenty days after treatment, the herbicidal activity was examined. The results are shown in Table 9.
These tests were carried out in a greenhouse through the entire period of test.
| TABLE 9 |
| ______________________________________ |
| Herbicidal activity |
| Com- Barn- |
| pound Dosage Cot- Morning- |
| Common yard- Johnson- |
| No. (g/are) ton glories |
| cocklebur |
| grass grass |
| ______________________________________ |
| 7 20 0 8 7 8 7 |
| 5 0 8 -- 7 -- |
| 8 20 0 8 8 9 10 |
| 5 0 7 8 8 9 |
| 10 20 0 8 8 7 8 |
| 5 0 8 7 -- -- |
| 32 20 0 8 9 9 9 |
| 5 0 8 8 9 9 |
| E 20 2 8 5 5 5 |
| 5 0 8 0 0 0 |
| ______________________________________ |
In addition to ingredients used in the Examples, Reference Example, Formulation Examples and Test Examples, other ingredients can be used in the Examples as set forth in the specification to obtain substantially the same results.
Mito, Nobuaki, Sakaki, Masaharu, Shiroshita, Masao, Mizutani, Masato, Okuda, Hiroki
| Patent | Priority | Assignee | Title |
| Patent | Priority | Assignee | Title |
| 4604134, | Sep 14 1983 | E I DU PONT DE NEMOURS AND COMPANY | Pollen suppressant comprising a fused pyridazine |
| 4729782, | Sep 14 1983 | E I DU PONT DE NEMOURS AND COMPANY | Pollen suppressant comprising a fused pyridazinone |
| 4875924, | Dec 25 1986 | Sumitomo Chemical Company, Limited | Cinnoline derivative, process for preparing the same and herbicidal composition containing the same |
| EP197226, | |||
| JP62228067, |
| Executed on | Assignor | Assignee | Conveyance | Frame | Reel | Doc |
| Dec 09 1988 | Sumitomo Chemical Company, Limited | (assignment on the face of the patent) | / |
| Date | Maintenance Fee Events |
| Date | Maintenance Schedule |
| Jul 03 1993 | 4 years fee payment window open |
| Jan 03 1994 | 6 months grace period start (w surcharge) |
| Jul 03 1994 | patent expiry (for year 4) |
| Jul 03 1996 | 2 years to revive unintentionally abandoned end. (for year 4) |
| Jul 03 1997 | 8 years fee payment window open |
| Jan 03 1998 | 6 months grace period start (w surcharge) |
| Jul 03 1998 | patent expiry (for year 8) |
| Jul 03 2000 | 2 years to revive unintentionally abandoned end. (for year 8) |
| Jul 03 2001 | 12 years fee payment window open |
| Jan 03 2002 | 6 months grace period start (w surcharge) |
| Jul 03 2002 | patent expiry (for year 12) |
| Jul 03 2004 | 2 years to revive unintentionally abandoned end. (for year 12) |