JPS6127366B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a plant growth regulator composition containing a novel N,N-disubstituted alanine derivative as an active ingredient and a method for producing the same. That is, the present invention is based on the following general formula: [Wherein, X is a chlorine atom or a fluorine atom,
and n is 1 or 2; Y represents a phenyl group; R is an azide group or a general formula -
NHNR ¹ represents a group of R ² , and each of R ¹ and R ² is
Each independently represents a hydrogen atom, methyl group, ethoxycarbonyl group, 1,2,4-triazol-4-yl group, phenyl group or chlorophenyl group, or R ¹ and R ² together represent ethylene oxa-ethylene. or a salt thereof which is an iodide or methosulfate of a hydrazinium compound thereof,
The present invention relates to a plant growth regulator composition characterized by containing it as an active ingredient, and a method for producing the same. Preferred compounds according to the invention are of the formula ()
A compound of the formula, wherein X is chlorine or fluorine as described above; n is 1 or 2; Y is a phenyl group; R is an azide group or a compound of the formula -
NHNR ¹ R ² (where R ¹ and R ² each independently represent a hydrogen atom, a methyl group, an ethoxycarbonyl group,
1,2,4-triazol-4-yl group, phenyl group, chlorophenyl group, or R ¹
and R ² together represent an ethyleneoxa-ethylene group), and salts of the derivative when the derivative can form a salt. Particularly preferred among these compounds are those in the general formula () in which X is fluorine or chlorine;
n is 1 or 2; Y is a phenyl group; R is an azide group or the formula -NHNR ¹ R ² (wherein
R ¹ and R ² each independently represent a hydrogen atom, a methyl group or a chlorophenyl group, and a salt of the derivative. It will be appreciated that the N·N-disubstituted alanine derivatives according to the invention may exhibit geometric and/or optical isomerism. Individual isomers and mixtures thereof fall within the scope of the invention. The compound of formula () can be produced by the following production method. Formula () in which R is a substituted hydrazino group
The derivative of is the formula (): The formula for the compound is: (wherein X, n, Y, R ¹ and R ² have the meanings defined above). The reaction is a condensation process with substantial elimination of water, e.g.
This is carried out in the presence of a suitable dehydrating agent such as N'-dicyclo-hexylcarbodi-imide. The reaction takes place at room temperature and is carried out in an inert reaction medium such as methylene chloride. The dehydrating agent is converted to dicyclohexyl urea during the reaction and removed by filtration, and the remaining reaction mixture is
processed by conventional methods. Compounds of formula () in which R is an unsubstituted hydrazino group, R is alkoxycarbonyl, preferably
A compound of formula (), which is tert-butoxycarbonyl, can be prepared by treating with dry hydrogen chloride, the reaction being carried out in a suitable solvent such as ethyl acetate. Salts of N.N-disubstituted alanine derivatives of formula () are prepared by preparing compounds of formula () in which R is a group of formula -NHNR ¹ R ² with inorganic acids such as hydrochloric acid or sulfuric acid or with alkyl halides such as methyl or ethyl Obtained by reaction with bromides or iodides or with alkyl sulfates such as dimethyl sulfate. Derivatives of formula () in which R is an azido group can be obtained by reacting sodium azide with the corresponding mixed carboxylic acid anhydride, preferably obtained by reacting a compound of formula () in situ with ethyl chloroformate. obtained by. The reaction solvent is conveniently aqueous acetone. The composition of the invention comprises a carrier and/or a surfactant and at least one active ingredient.
Generally preferred are compositions comprising compounds of the above general formula () of species. An appropriate amount of this composition can be applied to a desired growing site of a plant. As used herein, the term "carrier" means
It may be an organic or inorganic, synthetic or natural substance, with which it is mixed or formulated with the active compound and used for its application to plants, seeds, soil or other objects to be treated, or for its storage, transport or means said substance that facilitates handling. The carrier may be solid or liquid. Substances commonly used in formulating insecticides, herbicides or fungicides can be used as carriers. Suitable solid carriers are natural and synthetic clays and silicates, such as natural silica, such as diatomaceous earth; magnesium silicates, such as talc; magnesium aluminum silicates, such as attapulgite and vermiculite; aluminum silicates, such as kaolinite, montmorillonite and mica. ; calcium carbonate; calcium sulfate; synthetic hydrated silicon oxides and synthetic calcium or aluminum silicates; elements such as carbon and sulfur; natural and synthetic resins such as coumaron resins, polyvinyl chloride and styrene polymers and copolymers; solid polychlorophenols. waxes such as beeswax, paraffin wax, and chlorinated mineral waxes; and solid fertilizers such as lime superphosphate. Suitable liquid carriers are: water, alcohols such as isopropanol and glycols; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers, aromatic hydrocarbons such as benzene, toluene and xylene; petroleum distillates. , such as kerosene and light mineral oils; chlorinated hydrocarbons such as carbon tetrachloride, perchlorethylene and trichloroethane; and liquefied perchlorethylene and trichloroethane, which are usually gaseous; and liquefied gas compounds, which are usually gaseous. Mixtures of different liquids are often suitable. Surfactants can be emulsifiers or dispersants or wetting agents, and they can be nonionic or ionic. Surfactants commonly applied when formulating insecticides, herbicides or fungicides may be used. Examples of suitable surfactants are sodium or calcium salts of polyacrylic acids and ligninsulfonic acids; condensates of fatty acids or aliphatic amines or amides having at least 12 carbon atoms in the molecule with ethylene oxide and/or polypropylene oxide. fatty acid esters of glycerol, sorbitol, sucrose or pentaerythritol; condensates of glycerol, sorbitol, sucrose or pentaerythritide with ethylene oxide and/or propylene oxide; for example p-octylphenol or p-
- condensates of alkylphenols or fatty alcohols, such as octylgresol, with ethylene oxide and/or propylene oxide; sulfates or sulfonates of these condensates; sulfonic acids or sulfuric esters containing at least 10 carbon atoms in the molecule; alkali or alkaline earth metal salts, preferably sodium salts such as sodium lauryl sulfate, sodium secondary alkyl sulfate
sulphates), sodium salts of sulfonated castor oil, and sodium alkylarylsulfonic acids, such as dodecylbenzenesulfonic acid sodium salt; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide. The compositions of the invention may be formulated as wettable powders, powders, granules, solutions, emulsions, emulsions, suspension concentrates and aerosols. Wettable powders are usually formulated to contain 25, 50 or 75% W of the toxic agent, plus 3-10% W of a dispersant and optionally a stabilizer 0-10% W and/or a penetrating agent or It is usually formulated to include other additives such as binding agents. Powders are usually formulated as powder concentrates with a composition similar to wettable powders except for the absence of dispersants, and are further diluted with a solid carrier in the field, usually to remove toxic substances.
The composition contains 1/2 to 10% W. Granules are usually 10 to 100 BS mesh (1.676 to 0.152
mm) and can be manufactured by agglomeration or impregnation methods.
Typically, granules will contain 1/2 to 25% W of the poison and 0 to 10% W of additives (eg stabilizers, slow-release enhancers and binders). Emulsions are usually
Solvent plus co-solvent if desired, poison 10-50%
W/V, emulsifier 2-20% W/V and suitable additives (e.g. penetrants, stabilizers and corrosion inhibitors) 0
Contains ~20%W/V. Suspension concentrates are formulated to obtain a stable, non-settling, flowable product and typically contain 10-75% W of toxicant, 0.5-15% dispersant.
W, suspending agents (e.g. protective colloids and thixotropic agents) 0.1-10% W, suitable additives (e.g. defoamers, corrosion inhibitors, stabilizers, penetrants and fixing agents) 0-10% W, and carrier. including water or organic liquids (in which the poison is not substantially soluble); certain organic solids or inorganic salts may be dissolved in the carrier to aid in anti-settling, or as antifreeze agents for water. May be used. Aqueous dispersions and emulsions, which are compositions obtainable, for example, by diluting the wettable powders or concentrates according to the invention with water, also fall within the scope of the invention. The emulsion may be water-in-oil or oil-in-water and will have a thick mayonnaise-like consistency. The compositions of the invention may also contain other ingredients, such as other compounds with insecticidal, herbicidal or fungicidal properties. The invention will now be explained in more detail with reference to examples. Example 1 2-(N-benzoyl-N-(3-chloro-4-
Production of amino-N'-(4-chlorophenyl)-propionohydrazide N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine (6.4 g) was mixed with triethylalanine (2.8 ml). ) was added to a stirred suspension of 4-chlorophenylhydrazine hydrochloride (3.6 g) in methylene chloride (50 ml). The mixture was stirred for an additional 30 minutes at room temperature. Dicyclohexylcarbodi-imide (5g) in methylene chloride (20ml) was added and stirring continued for 1 hour. The precipitated N·N-dicyclohexylurea was separated and the liquid was evaporated. The residue was triturated with ether to give the desired product as a white solid (product melting point 88-89
℃, yield was 72%). Analysis Calculated value for C ₂₂ H ₁₈ Cl ₂ FN ₃ O ₂ : C59.2; H4.0; N9.4% Experimental value: C59.5; H4.1; N9.3% Example 2 2-(N- Benzoyl-N-(3-chloro-4-
fluorophenyl))amino-N′-(methyl)
Preparation of propionohydrazide N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine (6.4 g) was dissolved in methylene chloride (70 ml) and then N-methyl-hydrazine (1 ml) was dissolved. added. The mixture was stirred for 1/4 hour to obtain a clear solution. Dicyclohexylcarbodi-imide (5g) was added and then the precipitated urea was separated off. The desired product was obtained by evaporating the methylene chloride solution and then trituring the residue with ether (the melting point of the product was 135-138 °C, the yield was 20%
). Analysis Calculated value for C ₁₇ H ₁₇ ClFN ₃ O ₂ : C58.4; H4.9; N12.0% Experimental value: C58.7; H4.9; N12.1% Example 3 2-(N-benzoyl- N-(3-chloro-4-
fluorophenyl))) Production of amino-N'-(tert.butoxycarbonyl)-propionohydrazide N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine (6.4 g) Zate (tert.butylcarbazate) (2.7g)
of methylene chloride (70ml). Dicyclohexylcarbodi-imide (5 g) dissolved in methylene chloride (20 ml) was added at room temperature,
Stirring gave a clear solution. almost immediately,
N.N'-dicyclohexylurea precipitated. The reaction mixture was stirred for an additional hour. After separating the solids and evaporating the liquid, the residue was recrystallized with petroleum ether (60-80 °C) to obtain the desired product (melting point of the product was 78-80 °C, yield was 84 °C). %). Analysis Calculated value for C ₂₁ H ₂₃ ClFN ₃ O ₄ : C58.0; H5.5; N9.6% Experimental value: C58.9; H5.9; N9.5% Example 4 2-(N-benzoyl- N-(3-chloro-4-
Production of fluorophenyl)) aminopropionohydrazide 2-(N-benzoyl-N-(3-chloro-4-
fluorophenyl))amino-N′-(tert.butoxycarbonyl)propionohydrazide (11g)
was dissolved in ethyl acetate (110ml) and dry hydrogen chloride was passed into the ice-cooled solution. The solution was allowed to stand overnight and then evaporated to give a resinous product. After treatment with ether, the solid was washed with sodium bicarbonate solution, extracted with ether and distilled to give the desired product (melting point 135-137 °C, yield 64%)
I got it. Analysis Calculated value for C ₁₆ H ₁₅ ClFN ₃ O ₂ : C57.5; H4.5; N8.3% Experimental value: C57.5; H4.3; N8.2% Example 5 2-(N-benzoyl- N-(3-chloro-4-
Preparation of amino-N-morpholinopropionamide (fluorophenyl)) N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine (6.4 g) was dissolved in methylene chloride (100 ml) and further diluted with N- Aminomorpholine (2 ml) was added. This mixture was mixed for 1/4 hour to obtain a clear solution. Methylene chloride (20ml)
Dicyclohexylcarbodiimide (5 g) dissolved in the mixture was added and stirring continued for 12 hours. The precipitated urea was separated, the liquid was evaporated to half its volume, and then left overnight at 0°C. The precipitated solid was filtered, dried and recrystallized from ethanol to give the desired product (mp 205-207°C, 93% yield). Analysis Calculated value for C ₂₀ H ₂₁ ClFN ₃ O ₃ : C58.9; H5.1; N10.3% Experimental value: C58.7; H5.3; N10.1% Example 6 2-(N-benzoyl- N-(3-chloro-4-
2-(N-benzoyl-N-(3-chloro-4-
fluorophenyl))amino-N′-(dimethyl)
Propionohydrazide (1.1g) was dissolved in ether/acetone (50ml) and then sequential methyl iodide was added. The mixture was refluxed for 6 hours, then
The solvent was evaporated. The residue was treated with ether/acetone (20ml) to give the desired product as pale yellow crystals (60% yield). Analysis Calculated value for C ₁₉ H ₂₂ ClFN ₃ O ₂ : C45.1; H4.3; N8.3% Experimental value: C45.1; H4.5; N8.1% Example 7 2-(N-benzoyl- N-(3-chloro-4-
Production of aminopropionyl azide (fluorophenyl)) N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine (16.0 g) was dissolved in water (7
ml) and stirred, and enough acetone (30 ml) was added to this solution. The solution was cooled to 0°C and then triethylamine (7ml) in acetone (90ml)
was added while maintaining the temperature at 0°C; acetone, (20
Ethyl chloroformate (6 ml) in ml) was slowly added and the mixture was stirred at 0°C for 40 minutes. Water (15ml)
Sodium azide (4.3 g) was then added and the mixture was stirred at 0° C. for 1 hour and then at room temperature for 5 hours. The reaction mixture was poured into ice-water (1) and extracted with ether (2x250ml). Evaporate the ether solution to give the desired product (mp 88-91
°C, yield 22%). Analysis Calculated values for C ₁₆ H ₁₂ ClFN ₄ O ₂ : C55.4; H3.5; N16.1% Experimental values: C55.1; H3.5; N15.8% Examples 8-18 Examples 1-7 Various compounds were further produced in the same manner as the above procedure. Table 1 shows its physical properties and analysis.
Shown below.

【table】

[Table] Example 19 Plant growth regulation effect evaluation test 25 seeds of cultivated glass wheat were placed in a pot with a diameter of 7 cm in a pot [John Innes No. 1 Compost (John Innes No. 1 Compost)]
Innes No.1 Compost)]. Seedlings are 11/2
When the ~21/2 leaf stage was reached, a solution of the compound to be tested in a 1:1 acetone/water mixture (also containing wetting agent/fixing agent) was sprayed. The application rate of each compound was 1Kg/ha and 5Kg/ha. The pots were kept in a greenhouse at about 21° C. with a daily light exposure time of 16 hours. The evaluation was carried out 7 days after the day of the spray operation. The degree of suppression of growth of barley was visually examined,
The inhibition rate (%) was recorded. An inhibition rate of 0% means "normal growth", and 100% means "no growth after treatment". The results obtained are shown in the table below.

[Table] Example 20 Plant growth regulating effect evaluation test In order to evaluate the plant growth regulating effect in more detail, the compounds of the present invention were tested using the following plants as representatives: Corn [Zea mays]
(MZ)]; Rice (Oryza sativa (R)); Echinochloa crusgalli (BG); Pea (Pisum sativum (P)); Flax (Linum)
usitatissimum (L); mustard greens [Sinapis alba
(M)] and sugar beet [Bata vulgaris (SB)]. The test was divided into two types: before germination and after germination. In the pre-germination test, a compound-containing liquid composition was sprayed onto soil that had been previously sown with seeds of the plants described above. In the post-emergence test, a liquid composition containing a compound of the invention was sprayed onto the leaves of the seedlings. The soil used in the test was a steam sterilized modified John-Ines compost mix in which half of the peat was replaced with bulky vermiculite. The composition used in the test was an acetone solution of the test compound [alkylphenol/ethylene oxide condensate (commercial product; trade name "Triton-X-155")]
0.4% by weight] by diluting with water. That is, this acetone solution was diluted with an equal volume of water and the resulting composition was applied, with an application rate of 5 kg of active compound/
ha or 1 Kg/ha (expressed in volume units, it was an amount equivalent to 400/ha). Evaluation of the plant growth regulating effect of the test compound was performed by visual observation 7 days after the foliar spray and 11 days after the soil spray, and was recorded on a scale of 0 to 9. A rating of 0 means “no effect on plant growth regulation”, a rating of 1 means “approximately 15% reduction in fresh weight of plant stems and leaves”, and a rating of 2 means “approximately 15% reduction in fresh weight of plant stems and leaves”. A rating of 5 means "a reduction of about 25% of the weight," a rating of 9 means "a reduction of about 95% of the weight." The test results are shown in the table.

[Table] Example 21 Test A A test for evaluating the plant growth regulating effect of the compounds described in Examples 5, 6, 10, 11, and 18, respectively, was conducted in Example 21.
The test was conducted according to the test method described in 20. The results of this test are shown in the table below.

[Table] Test B A test for evaluating the plant growth effect of the compounds described in Examples 10 and 14, respectively, was conducted according to the test method described in Example 19. The results are shown in the table below.

【table】

Claims (1)

[Claims] 1. The following general formula: (wherein, X is a chlorine atom or a fluorine atom,
and n is 1 or 2; Y represents a phenyl group; R is an azide group or a general formula -
NHNR ¹ represents a group of R ² , and each of R ¹ and R ² is
Each independently represents a hydrogen atom, methyl group, ethoxycarbonyl group, 1,2,4-triazol-4-yl group, phenyl group or chlorophenyl group, or R ¹ and R ² together represent ethylene oxa-ethylene. A plant growth regulator composition comprising, as an active ingredient, an N,N-disubstituted alanine derivative having the group (representing a group), or a salt of a hydrazinium compound thereof, which is an iodide or a methosulfate. 2 (a) In the case of the preparation of compounds of formula () in which R is a substituted hydrazino group, formula (): The formula for the compound is: or (b) in the case of producing a compound of formula () in which R is an unsubstituted hydrazino group, drying a compound of formula () in which R is alkoxycarbonyl; (c) for the preparation of salts of compounds of formula (), reacting the compound in which R is -NHNR ¹ R ² with an inorganic acid or with an alkyl halide or an alkyl sulfur or (d) in the case of the preparation of compounds of formula () in which R is an azide group, reacting the sodium azide with the corresponding mixed carboxylic acid anhydride. The first claim characterized in
A method for producing a plant growth regulator composition as described in 2.