JPS6244547B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel compounds exhibiting activity as plant growth regulators, particularly as chemical hybridization agents, growth regulator compositions containing these compounds, and methods for inducing selective male sterility using these compounds and compositions. Concerning how to regulate plant growth. Cereals such as corn, wheat, rice, wheat, barley, millet, corn, and teff are major food crops throughout the world.
This importance has led to extensive research to improve both the productivity and food value of these crops. One of the most important solutions taken to improve grain quality and yield has been hybridization. Although hybridization has been an effective technique for several crops, most notably corn, there are several problems with the current technology. For example, hybridization of corn requires time-consuming manual detasseling or inefficient mechanical detasseling that may possibly damage the corn plant. Crossing of corn, barley, and wheat with cytoplasmic male sterile varieties is possible only with limited genetic criteria requiring conservation and restorer lines. Furthermore, the technology of cytoplasmic male sterility for barley and wheat requires highly sophisticated methods to handle the genetic complexities of these crops, and there has yet to be much success in developing suitable solutions. I've never done it before.
Inducing selective male sterility by chemical means would eliminate many of the problems faced by current hybridization techniques, so new compounds that selectively produce the desired sterility would be able to eliminate the male sterility required for mating. It would be highly desirable to provide fertile plants reliably and economically. A new class of compounds has now been discovered that can be used to induce selective male sterility in cereals. The compound of the present invention has the formula [Here, R ¹ is a carboxy group (-COOH), or a crop-acceptable salt thereof (as this term is commonly used, it means a salt suitable for use in crop cultivation, and the specific examples are given below), or a carbalkoxy group (-COOR, where R is an alkyl group, preferably having up to 12 carbon atoms, most preferably up to 4 carbon atoms), and R ² is phenyl or a substituted phenyl group, preferably with up to 3 substituents with a total of up to 6 carbon atoms, or a chloro-substituted naphthyl group, where R ³ is an alkyl group, preferably with up to 4 carbon atoms and R ⁴ is a hydrogen atom, an alkyl group, preferably one having up to 4 carbon atoms, or a halogen atom,
preferably a bromine or chlorine atom]. In a particularly suitable embodiment of the invention, R ¹ is a carboxy group or a salt thereof, R ³ is a methyl group, R ⁴
is a hydrogen atom or a halogen atom, and R ² is a substituted phenyl group. When R ¹ is a salt of a carboxy group, an alkali metal, an alkaline earth metal, or a transition metal may supply the cation. A cation can also be an ammonium or substituted ammonium group. Typical metal salt cations include alkali metal cations (which are particularly good), such as sodium,
potassium, lithium, etc., alkaline earth metal cations, such as calcium, magnesium, barium, strontium, etc., or heavy metal cations, such as zinc, manganese, cupric, cuprous, etc.
Includes ferric iron, ferrous iron, titanium, aluminum, etc. Ammonium salts have ammonium cations with the formula NZ ¹ Z ² Z ³ Z ⁴ [where Z ¹ , Z ² ,
Each of Z ³ and Z ⁴ is a hydrogen atom, a hydroxy group, a (C ₁ -C ₄ ) alkoxy group, a (C ₁ -C ₂₀ ) alkyl group, a (C ₃ -C ₈ ) alkenyl group, or a (C ₃ - C ₈ ) alkynyl group, (C ₂ -C ₈ ) hydroxyalkyl group, (C _2
-C8 ) alkoxyalkyl group, ( _C2 - _C6 ) aminoalkyl group, ( _C2 - _C6 ) haloalkyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted phenylalkyl group (4 carbons in the alkyl part) atoms), amino or alkyl-substituted amino groups, or any two of Z ¹ , Z ² , Z ³ , or Z ⁴ together with the nitrogen atom form a 5- or 6-membered heterocycle. (optionally having up to one additional heterooxygen, nitrogen, or sulfur atom in the ring),
(preferably saturated), for example, can be considered to form a piperidine, morpholine, pyrrolidine, or piperazine ring, or Z ¹ ,
Any three of Z ² , Z ³ or Z ⁴ together with the nitrogen atom is a 5- or 6-membered aromatic heterocycle,
For example, it may be considered to form a pyrrole or pyridine ring. When the ammonium group contains a substituted alkyl, substituted phenyl, or substituted phenylalkyl group, the substituents generally include a halogen atom, a (C ₁ -C 8 )alkyl group, a ( _C 1 -C ₈ )alkyl group,
_-C4 ) alkoxy group, hydroxy group, nitro group,
trifluoromethyl group, cyano group, amino group,
It may be selected from (C ₁ -C ₄ )alkylthio groups, etc. Such substituted phenyl groups may have up to two such substituents. Representative ammonium cations include ammonium, dimethylammonium, 2-ethylhexylammonium, bis(2-hydroxyethyl)ammonium, tris(2-hydroxyethyl)ammonium, dicyclohexylammonium, t -octylammonium, 2-hydroxyethylammonium, and morpholinium. , piperidinium, 2-phenethylammonium, 2-methylbenzylammonium,
n -hexylammonium, triethylammonium, trimethylammonium, tri( n -butyl)ammonium, methoxyethylammonium, diisopropylammonium, pyridinium, diallylammonium, pyrazolium, propargylammonium, dimethylhydrazinium, hydroxyammonium, methoxyammonium, dodecylammonium, Octadecylammonium, 4-dichlorophenylammonium,
These include 4-nitrobenzylammonium, benzyltrimethylammonium, 2-hydroxyethyldimethyloctadecylammonium, 2-hydroxyethyldiethyloctylammonium, decyltrimethylammonium, hexyltriethylammonium, 4-methylbenzyltrimethylammonium, and the like. The more commonly used salts are the alkali metal salts such as sodium, potassium, and lithium;
and ammonium salts, especially ammonium. Typical examples of R ² include alkyl groups, aryl groups, preferably phenyl or substituted phenyl groups, preferably alkoxy groups, phenoxy or substituted phenoxy groups, preferably having up to 4 carbon atoms, halogen atoms. , such as fluorine, chlorine, bromine and iodine atoms, nitro groups, perhaloalkyl groups, such as trifluoromethyl groups, alkoxyalkyl groups preferably having up to 6 carbon atoms, alkoxyalkoxy groups preferably having up to 6 carbon atoms, an amino group, preferably an alkyl or dialkylamino group with up to 4 carbon atoms in each alkyl substituent, a cyano group, a carbalkoxy group, preferably with up to 4 carbon atoms in the alkoxy moiety, a carbamoyl group, in each alkyl substituent an alkyl or dialkylcarbamoyl group, preferably with up to 4 carbon atoms, a sulfo group, a sulfonamido group, an alkylcarbonyl or carboxyalkyl group, preferably with up to 4 carbon atoms in the alkyl part, an alkanoyloxy group, preferably with up to 4 carbon atoms; , haloalkyl group, alkanoylamide group,
preferably those having up to 4 carbon atoms, alkylthio groups, preferably those having up to 4 carbon atoms, alkylsulfinyl groups, preferably having up to 4 carbon atoms, alkylsulfonyl groups,
Included are phenyl groups substituted, preferably with up to 4 carbon atoms, and the like. Preferably the substituted phenyl group will have up to 3 of the above substituents and the substituents will have a total of up to 6 carbon atoms. The most preferred substituents on the phenyl group are one or two halogen atoms, (C ₁ -C ₄ )alkyl, preferably a methyl group, (C ₁ -C ₄ )alkoxy, preferably a methoxy group, or trifluoromethyl. It is the basis. Typical compounds falling within the scope of this invention include: 1-(4-chlorophenyl) 1-phenyl-1,4-dihydro-4-oxo-6-methylpyridazine-3-carboxylate -1,4-dihydro-4-oxo-6-methylpyridazine-3-
Carboxylic acid 1-(4-fluorophenyl)-1,4-dihydro-4-oxo-6-methylpyridazine-3
-Carboxylic acid 1-(4-bromophenyl)-1,4-dihydro-4-oxo-6-methylpyridazine-3-
Carboxylic acid 1-(4-iodophenyl)-1,4-dihydro-4-oxo-6-methylpyridazine-3-
Carboxylic acid 1-(3-fluorophenyl)-1,4-dihydro-4-oxo-6-methylpyridazine-3
-Carboxylic acid 1-(3-chlorophenyl)-1,4-dihydro-4-oxo-6-methylpyridazine-3-
Carboxylic acid 1-(3-bromophenyl)-1,4-dihydro-4-oxo-6-methylpyridazine-3-
Carboxylic acid 1-(3,4-dichlorophenyl)-1,4-
Dihydro-4-oxo-6-methylpyridazine-3-carboxylic acid 1-(2-fluorophenyl)-1,4-dihydro-4-oxo-6-methylpyridazine-3
-Carboxylic acid 1-(2-chlorophenyl)-1,4-dihydro-4-oxo-6-methylpyridazine-3-
Carboxylic acid 1-(4-trifluoromethylphenyl)-
1,4-dihydro-4-oxo-6-methylpyridazine-3-carboxylic acid 1-(3-trifluoromethylphenyl)-
1-phenyl 1,4-dihydro-4-oxo-6-methylpyridazine-3-carboxylate-1-(4-chlorophenyl)-1,4-dihydro-4-oxo-6-ethylpyridazine-3-carboxylate 1,4-dihydro-4-oxo-6-ethylpyridazine-3-
Carboxylic acid 1-(4-fluorophenyl)-1,4-dihydro-4-oxo-6-ethylpyridazine-3
-Carboxylic acid 1-(3,4-dichlorophenyl)-1,4-
1-phenyl-1,4-dihydro-4-oxo-6-propylpyridazine-3-carboxylate 1-phenyl-1,4-dihydro-4-dihydro-4-oxo-6-ethylpyridazine-3-carboxylate Oxo-5,6-dimethylpyridazine-3-carboxylic acid 1-(4-chlorophenyl)-1,4-dihydro-4-oxo-5,6-dimethylpyridazine-3-carboxylic acid 1-phenyl-1,4- 1-phenyl-1,4-dihydro-4-oxo-5,6-diethylpyridazine-3-carboxylate 1-(4-methylphenyl dihydro-4-oxo-5-ethyl-6-methylpyridazine-3-carboxylate) )-1,4-dihydro-4-oxo-6-methylpyridazine-3-
Carboxylic acid 1-(2-chloro-4-methyl)-1,4-dihydro-4-oxo-6-methylpyridazine-
3-carboxylic acid 1-(2,4,6-trichlorophenyl)-
1,4-dihydro-4-oxo-6-methylpyridazine-3-carboxylic acid 1-(3-ethoxyphenyl)-1,4-dihydro-4-oxo-6-ethylpyridazine-3
-Carboxylic acid 1-(4-methylthiophenyl)-1,4-dihydro-4-oxo-6-methylpyridazine-
3-carboxylic acid 1-(3-cyanophenyl)-5-bromo-
1,4-dihydro-4-oxo-6-ethylpyridazine-3-carboxylic acid 1-phenyl-5-bromo-1,4-dihydro-4-oxo-6-methylpyridazine-3-carboxylic acid 1-(3 -chlorophenyl)-5-chloro-
1,4-dihydro-4-oxo-6-methylpyridazine-3-carboxylic acid 1-(4-chlorophenyl)-5-bromo-
1,4-dihydro-4-oxo-6-ethylpyridazine-3-carboxylic acid, etc., and salts and esters of the above acids. Compounds of the invention may be made by several convenient manufacturing routes. In the first method, the formula 4-hydroxy-2-pyrone (wherein R ⁶ is a hydrogen atom or an alkyl group and R ³ is defined above), or pyrone of the formula, with an equivalent amount of potassium or sodium hydroxide, acetic acid salt,
or a salt of the pyrone prepared from an amine of the formula R ² −NH ₂ ( ), where R ² is as previously defined, by treatment with an aqueous solution of a suitable base such as a carbonate. Diazonium salts, such as diazonium chloride, prepared by common diazotization techniques in polar solvents such as water, methanol, ethanol, glyme, dimethylformamide, etc.
The reaction is carried out at a temperature of 50°C to about 50°C. formula (wherein R ² , R ³ , and R ⁶ are as previously defined) is then treated with an acid such as hydrochloric acid, trifluoroacetic acid, sulfuric acid, methanesulfonic acid, nitric acid, etc. or an aqueous solution of a base such as sodium carbonate or sodium hydroxide at a temperature of about 20 to about 150°C, preferably about 40 to about 100°C, the formula (where R ² , R ³ , and R ⁶ are as previously defined). Esters of the formula pyridazine are prepared by esterification with a suitable alcohol, preferably a (C ₁ -C ₄ )alkanol. One convenient technique is Fischer esterification using anhydrous hydrochloric acid or sulfuric acid as the catalyst and the alcohol as the solvent. This esterification generally ranges from about 35 to about
It is carried out at 150° C., optionally using an inert co-solvent such as methylene chloride, ethylene chloride, diethyl ether, toluene, xylene and the like. Salts of the formula pyridazines or their 5-halo analogs may be made by conventional techniques, eg, by neutralization with a suitable inorganic or organic base in a solvent such as water or methanol. The compound of the present invention in which R ⁴ is a halogen atom has R ⁴
is a hydrogen atom in a suitable inert solvent such as hexane, benzene, ethylene dichloride, methanol, etc. from about 0 to 50
C., preferably at room temperature, by reaction with one equivalent of a halogenating agent such as bromine, chlorine, sulfuryl bromide, sulfuryl chloride, etc. The following examples illustrate the compounds of the invention and their preparation in more detail, but are not intended to limit the invention in any way. Unless otherwise indicated, all temperatures are in degrees Celsius and parts and percentages are by weight. Example 10,
Special preparation examples for compounds 12, 14 and 16 are shown. The table lists typical compounds of the invention, their melting points and elemental analysis values.

【table】

[Table] Example 10 1-(4-fluorophenyl)-1,4-dihydro-4-oxo-6-methylpyridazine-3
-Production of carboxylic acid 4-hydroxy-6-methyl-2-pyrone (7.88 g) is suspended in 250 ml of water, and 6.63 g of anhydrous sodium carbonate is added to this suspension to dissolve the pyrone. In a separate flask, 4-fluoroaniline 7.22
g is mixed with 25 ml of concentrated hydrochloric acid and 31 ml of water. The resulting solution is maintained at approximately 5-10° and a solution of 4.75 g of sodium nitrate in 16 ml of water is added. The obtained chloride 4-
A solution of fluorophenyldiazonium is added dropwise to the stirred pyrone solution, while maintaining the temperature at about 5-10° and the pH at about 8-9° by addition of a small amount of aqueous sodium hydroxide. The resulting hydrazone is refluxed with 500 ml of concentrated hydrochloric acid for about 2 hours. When cooled and filtered, 10.2g of 1-(4-
Fluorophenyl)-1,4-dihydro-4-oxo-6-methylpyridazine-3-carboxylic acid is obtained which is recrystallized from chloroform/ether (melting point 185-7°). Example 12 Production of 1-(4-chlorophenyl)-1,4-dihydro-4-oxo-6-methylpyridazine-carboxylic acid and its sodium salt P-chloroaniline (12.75 g) was dissolved in 40 ml of concentrated hydrochloric acid.
and cooled to 0°. sodium nitrite
7.6g solution temperature 0-5°. Diazotized aniline in 500 ml of water with 12.6 g of 4-hydroxy-6-methyl-2-pyrone and 55 g of sodium carbonate.
Add to the previously prepared solution under ice cooling. Heat the resulting slurry to reflux overnight. When complete reaction is not observed, adjust the pH to 12 and continue refluxing. The dark solution is neutralized to pH 6-7 with acetic acid and treated with activated carbon. When the liquid is acidified to pH2 with concentrated hydrochloric acid while cooling on ice, the product precipitates. Recrystallizing this acid from acetone/hexane yields 10.5
g (39%) of 1-(4-chlorophenyl)-1,
4-dihydro-4-oxo-6-methylpyridazine-3-carboxylic acid (melting point 229-230°C) is obtained. The sodium salt is obtained by treating this acid (5.0 g) with 0.76 g of sodium hydroxide in 200 ml of anhydrous methanol. Remove the solvent, wash the solid with ether, and dry under vacuum at 90 °C. Analysis.
Calculated value for C ₁₂ H ₈ ClN ₂ ONa・1/2H ₂ O: C,
48.75; H, 3.07; N, 9.48; Cl, 11.99, Na,
7.78. Actual value: C, 48.11; H, 2.80; N, 9.24;
Cl, 12.37; Na, 7.62. Example 14 1-Phenyl-1,4-dihydro-4-oxo-6-methylpyridazine-3-carboxylic acid 4-hydroxy-6-methyl-2 in 375 ml of water
-Suspend 11.8g of pyrone and add anhydrous sodium carbonate.
Add 9.95g to dissolve pyrone. In a separate flask, add 9.08 g of aniline to concentrated hydrochloric acid.
Mix with 37.5ml and 47ml water. Keep the resulting solution at about 5 to 10° and add sodium nitrite in 24 ml of water.
Add 7.13g of solution. The resulting phenyldiazonium chloride solution is added dropwise to the stirred pyrone solution while maintaining a temperature of about 5 to 10°. The PH is kept at about 8 to 9 by adding a small amount of sodium hydroxide solution. After the addition is complete, the resulting hydrazone (18 g) is separated and resuspended in 500 ml of concentrated hydrochloric acid. Mixture 2 1/
Reflux for 2 hours and then cool. 1-Phenyl-
1,4-dihydro-4-oxo-6-methylpyridazine-3-carboxylic acid precipitates as brownish crystals, which are recrystallized from water. yield
7.0g; melting point 173°. Example 16 1-(4-fluorophenyl)-5-bromo-
1,4-dihydro-4-oxo-methylpyridazine-3-carboxylic acid 1-(4-fluorophenyl)-1,4-dihydro-4-oxo-6-methylpyridazine-3-
Carboxylic acid (1.5 g) suspended in 100 ml of dry methanol and 1.038 g of bromine dissolved in 50 ml of methanol.
Add dropwise. Removal of the solvent leaves a white solid, which is taken up in dilute base and the solution acidified with hydrochloric acid. The resulting precipitate was filtered and recrystallized from chloroform/ether to give 1.4 g of 1-(4
-fluorophenyl)-5-bromo-1,4-dihydro-4-oxo-6-methylpyridazine-3
-Carboxylic acid (melting point 219-20°) is obtained. Example 20 1-(4-methylsulfonylphenyl)1,4
-Dihydro-4-oxo-6-methylpyridazine-3-carboxylate Add methyl 1- to 50 ml of glacial acetic acid cooled to 5°C.
(4-Methylthiophenyl)-1,4-dihydro-4-oxo-6-methylpyridazine-3-carboxylate (2.9 g (0.01 mol)) is suspended in a solution containing 3.4 g of 30% peroxide aqueous solution. (0.02 mol) dropwise. The mixture is stirred at 5° C. for 1 hour and at room temperature for 2 days. Then add water to this mixture.
Add 200ml and stir for 1 hour at room temperature. The resulting suspension was filtered under reduced pressure, and the filter cake was recrystallized with methyl cellosolve to obtain 1.15 g (30 g) of the product.
% yield) was obtained. It decomposed with a melting point of 253°-257°. The compounds of the invention are suitable for cereal crops such as wheat, barley,
It is particularly useful as a chemical hybridization agent for corn, rice, corn, millet, mullet, rhinoceros, etc. When used as a chemical hybridization agent,
These compounds effectively induce a high degree of selective male sterility. That is, it does not induce significant female sterility in treated plants, nor does it cause significant growth inhibition in treated plants. As used herein, the term male sterility includes both actual male sterility, evidenced by the absence of male floral parts or by sterile pollen, and functional male sterility, in which the male floral parts are unable to undergo pollination. The compounds of the invention also cause other plant growth regulating reactions, such as inhibition of flowering, inhibition of fruiting and prevention of seed formation in non-cereal species, and other related growth regulating reactions. When used as plant growth regulators, the compounds of the present invention are applied in amounts sufficient to effect the desired plant response without causing undesirable or toxic reactions. For example, when the compounds of this invention are used as chemical breeding agents, they are generally applied to the crop to be treated at a rate of about 1/32 to about 20 pounds/acre, preferably about 1/8 to about 10 pounds/acre. Ru. This application rate will vary depending on the crop being treated, the compound used in the treatment, and related factors. The following procedure is generally used to obtain hybrid (hybrid) seeds. Plant the two parents you want to cross in alternating rows. The female parent is treated with a compound of the invention. The male sterile female parent thus produced will be pollinated with pollen from another male fertile male parent, and the seeds produced by the female parent will become hybrid seeds. This material can then be harvested by normal means. A particularly suitable method of applying the compounds of the invention as chemical breeding agents is foliar application. Using this method, selective male sterility is most effectively induced when the compound is applied between the onset of flowering and meiosis. The compounds of the invention can also be used as seed treatments by soaking the seeds in a liquid preparation containing the active compound or by coating the seeds with the compound. In seed treatment applications, the compounds of this invention are generally applied at a rate of about 1/4 to 10 pounds per 100 weight seeds. The compounds of the present invention are also effective when applied to soil or water in rice crops. The compounds of the invention can be used alone or in mixtures as plant growth regulators. For example, they may contain other plant growth regulators such as auxins, gibberellins, ethylene-releasing agents such as ethephon, pyridone, cytokinin, maleic hydrazide, 2,2-dimethyl succinate hydrazide, choline and its salts, chloride (2- (chloroethyl)trimethylammonium, triiodobenzoic acid, tributyl-2,4-dichlorobenzylphosphonium chloride, polymeric N-vinyl-2-oxazolidinone, tri(dimethylaminoethyl)phosphate and its salts, and N-dimethylamino-1, 2,
It can be used in combination with, for example, 3,6-tetrahydrophthalamic acid and its salts, and under certain conditions can be used advantageously with other agricultural chemicals such as herbicides, fungicides, insecticides, and plant fungicides. . The compounds of the invention may be applied to the cultivation medium to be treated or to the plants, either by themselves or as part of a growth regulator composition or formulation (which also includes an agronomically acceptable carrier) as is commonly practiced. Can be applied as a component. A “crop-acceptable carrier” is one that can be used to dissolve, disperse, or diffuse a compound without impairing its effectiveness and that is itself compatible with soil, equipment, crops, or the agronomic environment. means a substance that does not have a significant harmful effect on Mixtures of the compounds of the invention can also be used in any of these formulations. The compositions of the present invention may be either solid or liquid formulations or solutions. For example, the compounds may be formulated as wettable powders, emulsifiable concentrates, powders, granular formulations, aerosols, or flowable emulsion concentrates. In such formulations, the compound can be diluted with a liquid or solid carrier and a suitable surfactant added if desired. Particularly for foliar applications, it is usually desirable to include adjuvants such as wetting agents, spreading agents, dispersants, stickers, adhesives, etc. in accordance with agricultural practices. Examples of adjuvants commonly used in this field are
Can be found in the publication "Detergents and Emulsifiers Annual Report" by John W. McCutcheon, Inc. Compounds of the invention may be dissolved in any suitable solvent. Examples of solvents useful in the practice of this invention include water, alcohols, ketones, aromatic hydrocarbons, halogenated hydrocarbons, dimethylformamide, dioxane, dimethyl sulfoxide, and the like. Mixtures of these solvents can also be used. The concentration of the solution is approximately 2
% to about 98% by weight, a particularly suitable range is about 20% to about 75%. For the preparation of emulsifiable concentrates, organic solvents such as benzene, toluene, xylene, methylated naphthalenes, corn oil, pine oil, It can be dissolved in chlorobenzene, isophorone, cyclohexanone, methyl oleate, etc., or a mixture of these solvents. Suitable emulsifiers include, for example, ethylene oxide derivatives of alkylphenols or long-chain alcohols, mercaptans, carboxylic acids and reactive amines and partially esterified polyhydric alcohols.
Solvent-soluble sulfates or sulfonates, such as alkaline earth or amine salts of surface-active alkylbenzenesulfonic acids and sodium sulfate fatty alcohols, can be used as emulsifiers, alone or together with the ethylene oxide reaction product. Flowable emulsion concentrates are formulated similarly to emulsifiable concentrates and contain, in addition to the above ingredients, water and stabilizers, such as water-soluble cellulose derivatives or water-soluble salts of polyacrylic acid. The concentration of active ingredient is usually about 10% to 60% by weight in emulsifiable concentrates and about 10% in flowable emulsion concentrates.
and 60% by weight, and in flowable emulsion concentrates this can be as high as about 75%. Wettable powders suitable for spraying mix the compound with finely divided solids, such as clays, inorganic silicates and carbonates, and silica, and add wetting agents, adhesives, and/or dispersants to such mixtures. It can be manufactured by The concentration of active ingredient in such formulations will normally range from about 20% to 98% by weight, preferably from about 40% to 75%. The dispersant generally comprises about 0.5% to about 3% of the composition.
% by weight, and wetting agents generally account for about 0.1% of the composition.
and about 5% by weight. Powders may be prepared by mixing the compound of the invention with a finely divided inert solid, which may be organic or inorganic. Materials useful for this purpose include, for example, vegetable flours, silicas, silicates, carbonates and clays. One convenient method of preparing powders is to dilute the wettable powder with a micronized carrier. about
Dust concentrates containing 20% to 80% active ingredient are conventionally prepared and then diluted to a working concentration of about 1% to 10% by weight. Granular formulations can be made by impregnating solids, such as granulated Fuller's earth, vermiculite, ground corncobs, seed hulls (including bran or other grain hulls), or similar materials. A solution of one or more compounds in a volatile organic solvent is sprayed onto or mixed with the particulate solid, and the solvent is then removed by evaporation. The particulate material can be of any suitable size, with a particularly suitable size range being 16 to 60 mesh. The active compound is usually about 2% of the granular formulation.
or 15% by weight. The salts of the compounds of the invention are prepared and applied as aqueous solutions. Salts typically make up about 0.05 to about
50% by weight, preferably from about 0.1% to about 10%. These compositions can also be further diluted with water if desired prior to actual application. In some applications, the activity of these compositions can be enhanced by incorporating adjuvants into the composition.
For example, it can be further increased by adding glycerin, methyl ethyl cellulose, hydroxyethyl cellulose, polyoxyethylene sorbitan monooleate, polypropylene glycol, polyacrylic acid, polyethylene sodium maleate, polyethylene oxide, and the like. Adjuvants generally comprise from about 0.1 to about 5% by weight of the composition, preferably from about 0.5 to about 2%. Such compositions may also optionally include an agronomically acceptable surfactant. The compounds of the invention are applied as sprays by commonly used methods, such as common hydraulic sprays, air sprays, and dusts. Solutions of the compounds are commonly used for small volume applications. The dilution and volume of application will normally depend on factors such as the type of equipment used, the method of application, the area to be treated, and the type and developmental stage of the crop being treated. The following examples further illustrate the growth regulating activity of the compounds of the invention, but are not intended to limit the invention. Example 21 Chemical Crossing Activity The following method is used to evaluate the activity of compounds of the invention for inducing male sterility in cereals. Spring wheat varieties Fielder and Mayo-64 are sown at a rate of 6 to 8 seeds per 6" pot containing a sterile medium of 3 parts soil and 1 part humus. Plants are grown for the first 4 weeks under short day (9 hours) conditions to obtain good vegetative development before the onset of flowering.The plants are then grown under long day (16 hours) conditions (this is done in a greenhouse with high intensity lighting). Fertilize the plants 2, 4, and 8 weeks after sowing with a water-soluble fertilizer (16% nitrogen - 25% phosphorus - 16% potassium) at a rate of 1 teaspoon per gallon of water;
Often sprayed with suitable insecticides, such as Isotox, to control ticks, and with sulfur to control powdery mildew. The test compound is applied foliarly to female plants when they reach the flag leaf stage (stage 8 on the Feeke scale). All compounds are applied at a carrier volume of 50 gallons/acre with a surfactant such as Triton x-100 at a rate of 2 ounces/50 gallons. After the emergence of the spikes, but before flowering, bag the 4 to 6 spikes/pots to prevent external cross-pollination. At the first sign of flowering, two spikes per pot are cross-pollinated using the present method with a viable male parent. As soon as the seeds are set and visible, measure the length of the spike and count the number of seeds per spikelet in both the bagged and crossed spikes. Male sterility can then be calculated as the percent inhibition of seeds that set on bagged spikes of treated plants, and female fertility of cross-pollinated spikes can be calculated as the percent of control seeds that set. After maturity, seeds on cross-pollinated spikes are sown for determination of hybridization percentage. Percent sterility, percent fertility, and percent spike length inhibition are calculated from the following formulas: a % sterility = Sc - St / Sc x 100 Sc = spikelet in bagged spike of control plant Number of seeds per hit. St = number of seeds per spikelet in bagged spikes of treated plants. b Fertility % = Ft/Fc x 100 Ft = Number of seeds per spikelet in study cross-pollinated panicles of treated plants. Fc = number of seeds per spikelet in unbagged spikes of control plants. c % spike inhibition = Hc - Ht/Hc x 100 Hc = spike length of control plants. Ht = spike length of treated plants. The table is a summary of typical results obtained in the evaluation of compounds of the invention. Datsushi indicates that no evaluation was performed.

【table】

TABLE It is to be understood that changes and modifications may be made without departing from the spirit and scope of the invention as defined by the claims.

Claims (1)

[Claims] 1 formula [Here, R ¹ is a carboxy group, a salt thereof acceptable for crop cultivation, or a carboxy group (C ₁ -
_C4 ) alkoxy group, ^R2 is an unsubstituted phenyl group, or ( _C1 - _C4 ) alkyl group, ( _C1 - _C4 ) alkoxy group, halogen, nitro group, trifluoromethyl group, cyano group, and a substituted phenyl group having up to three substituents independently selected from a (C ₁ -C ₄ )alkylsulfonyl group, or a chloro-substituted naphthyl group, and R ³ is a (C ₁ -C ₄ )alkyl group. group, and R ⁴ is a (C ₁ -C ₄ ) alkyl group or a halogen atom. 2 R ² is an unsubstituted phenyl group, a (C ₁ - C ₄ ) alkyl group, a (C ₁ - _{C 4} ) alkoxy group, a halogen,
The compound according to item 1 above, which is a substituted phenyl group having up to three substituents independently selected from a nitro group and a trifluoromethyl group. 3 R ¹ is a carboxyl group or a salt thereof acceptable for crop cultivation, and R ² is a phenyl group or two substituents each independently selected from halogen, methyl group, methoxy group, and trifluoromethyl group. The compound according to item 2 above, which is a substituted phenyl group substituted with , R ³ is a (C ₁ -C ₄ ) alkyl group, and R ⁴ is a (C ₁ -C ₄ ) alkyl group or a halogen. 4. The compound according to item 3 above, wherein R ⁴ is chloro, bromo, methyl or propyl group. 5 A plant before meiosis is expressed by the formula [Here, R ¹ is a carboxy group, a salt thereof acceptable for crop cultivation, or a carboxy group (C ₁ -
_C4 ) alkoxy group, ^R2 is an unsubstituted phenyl group, or ( _C1 - _C4 ) alkyl group, ( _C1 - _C4 ) alkoxy group, halogen, nitro group, trifluoromethyl group, cyano group, and a substituted phenyl group having up to three substituents independently selected from a (C ₁ -C ₄ )alkylsulfonyl group, and R ³ is a (C ₁ -C ₄ )alkyl group or a chloro-substituted naphthyl group. and R ⁴ is a hydrogen atom, a (C ₁ -C ₄ ) alkyl group, or a halogen atom. A method of inducing male sterility in plants. 6. The method according to item 5 above, wherein R ¹ is a carboxy group or a crop cultivation-acceptable salt thereof. 7 ^R2 is an unsubstituted phenyl group, or one or two halogen atoms, a methyl group, a methoxy group,
or the method of the above item 6, which is a phenyl group substituted with a trifluoromethyl group. 8. The method of item 7 above, wherein R ⁴ is a hydrogen atom. 9. The method of item 8 above, wherein R ³ is a methyl group. 10. The method of item 9 above, wherein R ² is a halophenyl group. 11. The method of item 10 above, wherein R ² is a 4-halophenyl group. 12. The method of item 10 above, wherein R ² is a 3-halophenyl group. 13. The method of item 9 above, wherein R ² is a trifluoromethylphenyl group. 14. The method of item 7 above, wherein R ³ is a methyl group and R ⁴ is a halogen atom. 15. The method according to item 14 above, wherein R ² is a halophenyl group and R ⁴ is a bromine atom. 16. The method of item 6 above, wherein the grain is wheat. 17. The method of item 6 above, wherein the grain is barley. 18. The method of item 6 above, wherein the grain is corn. 19 formula [Here, R ¹ is a carboxy group, a salt thereof acceptable for crop cultivation, or a carboxy group (C ₁ -
_C4 ) alkoxy group, ^R2 is an unsubstituted phenyl group, or ( _C1 - _C4 ) alkyl group, ( _C1 - _C4 ) alkoxy group, halogen, nitro group, trifluoromethyl group, cyano group, (C ₁
-A substituted phenyl group having up to three substituents each independently selected from a C4) alkylthio group, a ( _C1 - _C4 ) alkylsulfinyl group _, and a ( _C1 - _C4 ) alkylsulfonyl group, or A chloro-substituted naphthyl group, R ³ is a (C ₁ - C ₄ ) alkyl group, and R ⁴ is a hydrogen atom, a (C ₁ - _{C 4} ) alkyl group, or a halogen atom] and crop cultivation A composition for inducing male sterility for cereal plants, comprising a carrier acceptable as above. 20 R ¹ is a carboxyl group or a salt thereof acceptable for crop cultivation, and R ² is an unsubstituted phenyl group or substituted with one or two halogen atoms, methyl group, methoxy group, or trifluoromethyl group The composition according to item 25 above, wherein R ³ is a methyl group and R ⁴ is a hydrogen atom or a halogen atom.