JP2001354637A - 2-fluoropropionic acid anilide derivative and antimicrobial/insecticidal agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antimicrobial/insecticidal agent characterized by comprising a 2-fluoropropionic acid anilide derivative as an active iggredient. SOLUTION: This antimicrobial/insecticidal agent comprises a 2- fluoropropionic acid anilide derivative of formula (1) (X is an oxygen atom or a sulfur atom; R is a halogen atom, a 1-8C alkyl group, a 1-4C haloalkyl group, a nitro group, a phenoxy group, a phenyl group or the like; n is an integer of 1-5) as an active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a 2-fluoropropionic anilide derivative and a fungicide / insecticide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art 2-halopropionic anilide derivatives and
Therefore, compounds as shown in the following (1) to (4) are known.
You. (1) Appl. Microbiol. ,18(3), 3
69 (1969) 2-chloropropionic anilide derivative shows herbicidal activity
However, it is noted that the bactericidal and insecticidal activities
Not listed. (2) J.I. Chem. Soc. C,4, 319 (196)
7) 2-Fluoropropionic anilide is described
Describes whether the compound has pesticidal activity
Not at all. (3) Appl. Radiat. lost. ,45
(6), 715 (1994) 4'-Methyl-2-fluoropropionic acid anilide is described.
Whether or not this compound has pesticidal activity
There is no description about this. (4) Org. Magn. Resonance. ,5
(9), 413 (1973) 4'-methoxy-2-fluoropropionic anilide is
Whether or not this compound has pesticidal activity
Is not described at all.

[0003]

SUMMARY OF THE INVENTION The present invention provides a novel 2-fluoropropionic anilide derivative having a bactericidal and insecticidal activity.

[0004]

The present inventors synthesized a 2-fluoropropionic anilide derivative and examined its physiological activity. As a result, the 2-fluoropropionic anilide derivative showed excellent bactericidal and insecticidal activities. Was found to have. That is, the present invention is as follows. According to a first aspect, the following formula (1):

[0005]

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The present invention relates to a 2-fluoropropionic anilide derivative represented by the formula: However, 2-fluoropropionic anilide, 4'-methyl-2-fluoropropionic anilide and 4'-methoxy-2-fluoropropionic anilide are excluded. X, R and n in the formula
Is as follows. X represents an oxygen atom or a sulfur atom. R represents a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a nitro group, a carbonyl group having an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or phenyl. Group, a condensed ring formed by a benzene ring and (R) _n , CH ₂ PO
(R ¹ ) ₂ represents an alkoxy group having 1 to 4 carbon atoms. n represents an integer of 1 to 5. R ¹ represents an alkoxy group having 1 to 4 carbon atoms. A second invention provides the following formula (1 ′):

[0007]

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The present invention relates to a fungicidal and insecticide comprising a 2-fluoropropionic anilide derivative represented by the formula (1) as an active ingredient. X and R in the formula have the same meanings as described above. n ′ represents an integer of 0 to 5.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The various substituents represented by the above compounds are as follows. In the description of the present invention, parenthesized numbers, symbols, and the like attached to chemical formulas are also referred to as "compounds (numerals, symbols, and the like)." For example, a compound represented by the formula (1) is also referred to as a compound (1). ]. [X] X includes an oxygen atom and a sulfur atom. [R] R is a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms,
Nitro group, carbonyl group having 1 to 4 carbon atom alkoxy group, phenoxy group, phenyl group, condensed ring formed with benzene ring and (R) _n , CH ₂ PO
(R ¹ ) ₂ and an alkoxy group having 1 to 4 carbon atoms.

(1) As the halogen atom, a fluorine atom,
Examples thereof include a chlorine atom, a bromine atom and an iodine atom; preferred are a fluorine atom, a chlorine atom and a bromine atom. And the substitution position of the halogen atom is not particularly limited. (2) Examples of the alkyl group having 1 to 8 carbon atoms include linear or branched ones; preferably 1 to 6 carbon atoms; more preferably Having 1 to 4 carbon atoms. And although the substitution position of an alkyl group is not specifically limited, Preferably it is 2-position and / or 4-position. (3) Examples of the haloalkyl group having 1 to 4 carbon atoms include a linear or branched haloalkyl group; a trifluoromethyl group is preferred. The substitution position of the haloalkyl group is not particularly limited, but is preferably 3
-And / or 4-position. (4) The substitution position of the nitro group is not particularly limited, but is preferably at the 4-position.

(5) Examples of the carbonyl group having an alkoxy group having 1 to 4 carbon atoms include a carbonyl group having a linear or branched alkoxy group; preferably a methoxycarbonyl group. is there. The substitution position of the carbonyl group having an alkoxy group is not particularly limited, but is preferably the 4-position. (6) Examples of the phenoxy group include an unsubstituted or substituted group. The substitution position of the phenoxy group is not particularly limited, but is preferably the 3-position or the 4-position.

(7) Examples of the phenyl group include unsubstituted or substituted ones. The substitution position of the phenyl group is not particularly limited.
-Place. (8) Examples of the condensed ring formed by the benzene ring and (R) _n include those in which a condensed ring is formed with an unsubstituted or substituted benzene ring; As, for example, "2,3-CH = CH-C
H = CH- "," 3,4-CH = CH-CH = CH
- "," _{3,4-CH 2 CH 2 CH 2} CH 2 - ", and the like. _{(9) CH 2 PO (R} 1) R 1 in the ₂ is a linear or branched 1 to 4 carbon atoms alkoxy group; preferably an ethoxy group. And CH ₂ PO (R ¹ )
The substitution position of ₂ is not particularly limited, but is preferably 4-position
Rank. (10) Examples of the alkoxy group having 1 to 4 carbon atoms include a linear or branched alkoxy group;
Preferably, it is a methoxy group. The substitution position of the carbonyl group having an alkoxy group is not particularly limited, but is preferably at the 3- or 4-position. [N] n is an integer of 1 to 5, preferably 1 or 2. [N ′] n ′ is an integer from 0 to 5, preferably
It is an integer of 0 to 2.

As the compound (1), compounds obtained by combining the above-mentioned various substituents can be mentioned, and preferred ones are as follows. (1) X is an oxygen atom, R is a halogen atom, n
Is the compound of 1 or 2. For example, there can be mentioned compounds 1, 3, 5, 7, 9, 11, 13, 15 and the like described in Tables 1 and 2 described below. (2) X is a sulfur atom, R is a halogen atom, n
Is the compound of 2. For example, there can be mentioned Compound 14 described in Tables 1 and 2 described below. (3) The compound wherein X is an oxygen atom, R is an alkyl group having 1 to 8 carbon atoms and / or a halogen atom, and n is 2. For example, compounds 17 described in Tables 1 and 2 below can be mentioned.

(4) A compound wherein X is an oxygen atom, R is an alkyl group having 1 to 8 carbon atoms, and n is 1. For example, compounds 39, 41, and 4 described in Tables 1 and 2 below
3, 45, 47 and the like. (5) The compound wherein X is an oxygen atom, R is a haloalkyl group having 1 to 4 carbon atoms and / or a halogen atom, and n is 1 or 2. For example, compounds 19 and 21 described in Tables 1 and 2 below can be mentioned. (6) X is an oxygen atom, R is a nitro group, and n is 1
Compound. For example, compounds 23 described in Tables 1 and 2 described below can be mentioned. (7) The compound wherein X is an oxygen atom, R is a carbonyl group having an alkoxy group having 1 to 4 carbon atoms, and n is 1. For example, there may be mentioned Compound 25 described in Tables 1 and 2 below.

(8) A compound wherein X is an oxygen atom, R is a substituted or unsubstituted phenoxy group, and n is 1. For example, there can be mentioned compounds 27 and 29 described in Tables 1 and 2 below. (9) The compound wherein X is an oxygen atom, and R is a compound in which a benzene ring and (R) _n form a condensed ring. For example, compounds 31, 33, and 35 described in Tables 1 and 2 described below can be exemplified. (10) The compound wherein X is an oxygen atom, R is CH ₂ PO (alkoxy group having 1 to 4 carbon atoms) ₂ and n is 1. For example, compounds 37 described in Tables 1 and 2 below can be mentioned. (11) The compound wherein X is an oxygen atom, R is an alkoxy group having 1 to 4 carbon atoms, and n is 2. For example, there can be mentioned Compound 49 described in Tables 1 and 2 described below.

The compound of the present invention can be produced, for example, by the following production method 1 or 2. (Production method 1) Compound (1a) [in compound (1),
When X is an oxygen atom], as shown below, can be synthesized by reacting compound (2) with compound (3) in a solvent in the presence of a base.

[0017]

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(Wherein, Y represents an alkoxy group having 1 to 4 carbon atoms and a halogen atom; R and n have the same meanings as described above.) The reaction temperature of the reaction is usually from 0 ° C. Up to the boiling point of the solvent used. The molar ratio of the raw materials is such that the compound (3) is 1 mol per 1 mol of the compound (2). The base is a theoretical amount of 1 mole, but can be arbitrarily changed depending on the reaction situation. Examples of the base include sodium hydride, triethylamine and the like. Examples of the solvent include tetrahydrofuran, 1,4-dioxane, toluene and the like. Starting compound (2) was obtained from Tetrahedron Lett. ,
34 (2), 293 (1993). In addition, the starting compound (3) can be obtained as a commercial product.

(Production Method 2) Compound (1b) (in the case where X is a sulfur atom in compound (1)) is reacted with compound (1a) in a solvent in the presence of a Lawesson reagent as shown below. Can be synthesized.

[0020]

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(Wherein R and n have the same meanings as described above.) The reaction temperature of the reaction is usually from 0 ° C. to the boiling point of the solvent. The theoretical molar ratio of the raw materials is a ratio of 1/4 mole of Lawesson's reagent to 1 mole of compound (2),
It can be arbitrarily changed depending on the reaction situation. Examples of the solvent include tetrahydrofuran and toluene. The compound (1) produced by the synthesis method 1 or the synthesis method 2 is subjected to ordinary post-treatments such as extraction, concentration, and filtration, and if necessary, is appropriately purified by a known method such as recrystallization or various types of chromatography. be able to.

[Control effect] The pests for agricultural and horticultural use which are effective in controlling the compound (1) of the present invention include agricultural and horticultural pathogens (for example, wheat rust, barley powdery mildew, cucumber downy mildew, rice) Agricultural and horticultural pests [eg, Hemiptera (hoppers, leafhoppers, aphids, whiteflies, etc.), lepidoptera (weevils, moths, leafy beetles, stalk beetles, sinkworms, and white butterfly) ), Coleoptera (Tenebrionidae, Weevil, Chrysomelidae, Scarabaeidae, etc.), Acarina (Rutaceae, Citrus spider mite, Nymphalid spider mite, etc., Necrotic nematode, Cyst nematode, Negusale) Nematodes, singare nematodes, pine wood nematodes, etc.); sanitary pests (eg, flies, mosquitoes, cockroaches) Li, etc.); stored grain pests (Kokusutomodoki acids, bean weevils, etc.) can be mentioned.

The pesticidal composition for agricultural and horticultural use of the present invention has a remarkable bactericidal, insecticidal, acaricidal and nematicidal effect, and contains at least one compound (1) as an active ingredient. is there. The compound (1) can be used alone, but usually, a carrier, a surfactant, a dispersant,
It is preferable to use a mixture of auxiliary agents and the like (for example, prepared as a composition such as powder, emulsion, fine granule, granule, wettable powder, oily suspension, and aerosol).

Examples of the carrier include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea, etc .; hydrocarbons (kerosene, mineral oil, etc.), aromatic hydrocarbons Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene, etc.) Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), water, etc .; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection) out and the like.

Surfactants and dispersants that can be used to improve the performance of the agent, such as adhesion to animals and plants, absorption, and dispersion, emulsification, and spreading of drugs include alcohol sulfates and alkyls. Sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like can be mentioned. In order to improve the properties of the preparation, for example, carboxymethylcellulose, polyethylene glycol, gum arabic and the like can be used as an auxiliary agent.

In the preparation of the present preparation, the above-mentioned carrier, surfactant, dispersant and auxiliary can be used alone or in appropriate combination according to the respective purposes.
When the compound (1) of the present invention is formulated, the concentration of the active ingredient is usually from 1 to 50% by weight in an emulsion, and usually 0.3% in a powder.
25 to 25% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, 0.5 to 5% by weight for oils and 0.1 to 5% by weight for aerosols. is there. These preparations can be diluted to an appropriate concentration and applied to various uses by spraying them on plant foliage, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.

[0027]

The present invention will be specifically described below with reference to examples. Note that these examples do not limit the scope of the present invention. Example 1 Synthesis of [Compound (1)] (1) Synthesis of 3 ', 4'-dichloro-2-fluoropropionic acid anilide [Compound 13] 4.32 g of ethyl 2-fluoropropionate and 3,4-
4.86 g of dichloroaniline and tetrahydrofuran 3
0 ml, 60% sodium hydride 1.3
2 g was slowly added at room temperature, followed by heating and stirring at 40 to 50 ° C. for 3 hours. After completion of the reaction, water was added to the reaction solution, and the mixture was extracted twice with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was washed with cold hexane to give the target compound as colorless crystals.
05 g were obtained.

(2) Synthesis of 3 ′, 4′-dichloro-2-fluoropropionate thioanilide [compound 14] 3.5 ′ g of 3 ′, 4′-dichloro-2-fluoropropionate anilide and 1.82 g of Lawesson's reagent Was added to a mixed solution of 10 ml of toluene and 5 ml of tetrahydrofuran, and the mixture was heated under reflux for 3 hours. The reaction solution was concentrated under reduced pressure to about 5 ml, and purified by column chromatography (toluene then toluene: ethyl acetate = 9: 1 elution) to obtain 1.10 g of the desired product as pale yellow crystals.

(3) Synthesis of 2'-n-butyl-2-fluoropropionic acid anilide [compound 47] 0.92 g of 2-fluoropropionic acid and 0.95 ml of thionyl chloride were added to 10 ml of toluene, and the mixture was added at 40 to 50 ° C. The mixture was heated and stirred for an hour, and then cooled to room temperature. 20 ml of toluene to which 0.90 g of 2-n-butylaniline and 3.03 g of triethylamine were added at room temperature.
And stirred at the same temperature for 1 hour. The resulting salt was filtered, the solvent was distilled off under reduced pressure, and the obtained residue was subjected to column chromatography (toluene: ethyl acetate = 9: 1 elution).
To give 0.75 g of the desired product as a pale orange oil.

(4) According to the method described in the above (1) to (3),
Other compounds (1) in Tables 1 and 2 were synthesized. The compounds (1) synthesized as described above and their physical properties are shown in Tables 1 to 3.

[0031]

[Table 1]

[0032]

[Table 2] Me represents a methyl group.

[0033]

[Table 3]

Example 2 [Preparation of Preparation] (1) Preparation of Granules Compound (1) 5 parts by weight, bentonite 35 parts by weight, talc 57 parts by weight, Neoperex powder (trade name; manufactured by Kao Corporation) 1 part by weight Part and sodium lignin sulfonate 2
The parts by weight were uniformly mixed, and then a small amount of water was added and kneaded, followed by granulation and drying to obtain granules.

(2) Preparation of wettable powder 10 parts by weight of compound (1), 70 parts by weight of kaolin, 18 parts by weight of white carbon, 1.5 parts by weight of Neoperex powder (trade name; manufactured by Kao Corporation) and Demol ( (Trade name; manufactured by Kao Corporation) 0.5 part by weight was uniformly mixed and then pulverized to obtain a wettable powder.

(3) Preparation of Emulsion To 20 parts by weight of the compound (1) and 70 parts by weight of xylene, 10 parts by weight of toxanone (trade name; manufactured by Sanyo Chemical Industries) was added, mixed uniformly, and dissolved to obtain an emulsion. Was.

(4) Preparation of Dust A powder was obtained by uniformly mixing 5 parts by weight of the compound (1), 50 parts by weight of talc, and 45 parts by weight of kaolin.

Example 3 [Efficacy Test] (1) Test for controlling efficacy against cucumber downy mildew One cucumber (cultivar: Sagami Hanjiro) was grown per plastic flowerpot having a diameter of 6 cm. To the 1.5-leaf seedlings, an acetone solution of the test compound was diluted to 200 ppm with water containing a surfactant (0.01%).
10 ml was sprayed per pot. After spraying, the plants were cultivated in a glass greenhouse for one day, and then a suspension of cucumber downy mildew zoospores (5 × 10 ⁴ cells / ml) was prepared and sprayed on the back of the leaves evenly. After inoculation, the plants were kept in a moist chamber at 20 ° C. for 1 day, cultivated in a glass greenhouse for 5 days, and the degree of onset of downy mildew appearing on the first leaves was examined. Judgment of the effect
Compared to the degree of onset in the untreated area, 5
The lesion area of 10% or less was indicated by 6 levels, with 4 indicating about 20%, 3 indicating about 40%, 1 indicating about 60%, and 0 indicating that the whole diseased area. In addition, the potency test was performed by the same test method as the compound (1) of the present invention, using Reference Compounds 1 to 3 and Comparative Compound 1 shown in Table 4.

[0039]

[Table 4]

Reference compound 1 is described in J. Am. Chem. Soc.
C, 4 , 319 (1967).
2-fluoropropionic anilide whose insecticidal activity is not known. Reference compound 2 is described in Appl. Radia
t. lost. No. 4, 45 (6), 715 (1994), which has no known fungicidal and insecticidal activity.
It is methyl-2-fluoropropionic anilide. Reference compound 3 is described in Org. Magn. Resonanc
e. , 5 (9), 413 (1973), 4'-methoxy-, whose bactericidal and insecticidal activity is not known.
2-fluoropropionic anilide. Comparative compound 1 was obtained from Appl. Microbiol. , 18 (3),
369 (1969) 3 ', 4'-dichloro-2-chloropropionic anilide. Table 5 shows the results.

[0041]

[Table 5]

(2) Efficacy test for Japanese moth The test compound was used as a wettable powder according to Example 2, and a cabbage leaf piece (5 cm) was added to a solution diluted to 500 ppm with water containing a surfactant (0.01%). × 5 cm) for 30 seconds and placed in a plastic cup. After air-drying, ten third-instar moths were released, covered, and left in a constant temperature room at 25 ° C. 2
After days, the number of live and dead insects was counted, and the mortality was determined. Judgment of the effect is A when the insecticidal rate is 100%, 80% or more and 100%
B less than 60% and less than 80% C, 6
Those with less than 0% were designated as D. Table 6 shows the results.

[0043]

[Table 6]

(3) Potato cabbage pot soil treatment efficacy test against Konaga (osmotic transferability)
20 ml of a chemical solution prepared by diluting the wettable powder of the compound (1) according to the above method to 500 ppm with water containing a surfactant (0.01%) was irrigated and allowed to stand in a glass greenhouse. Seven days later, the leaves were cut off and placed in plastic cups. Thereafter, 10 third instar larvae of the Japanese moth were released, covered, and left in a constant temperature room at 25 ° C. Two days later, the number of live and dead insects was counted, and the mortality was determined. The effect was determined in the same manner as in the efficacy test (2) described above. Table 7 shows the results.

[0045]

[Table 7]

(4) Efficacy test on adult female spider mite (Acari: Tetranychidae)
m), the wettable powder of the compound prepared according to Example 2 is washed with water containing a surfactant (0.01%) in 50%.
Infested leaf pieces were immersed in a chemical solution diluted to 0 ppm for 15 seconds. This was left in a constant temperature room at 25 ° C., and after 3 days, the number of live and dead insects was counted to determine the mortality. The effect was determined in the same manner as in the efficacy test (2). Table 8 shows the results.

[0047]

[Table 8]

(5) Efficacy test on spider mite eggs Five adult female spider mites were collected from kidney leaves (diameter: 20 mm).
, And allowed to lay eggs for 24 hours to remove female adults. On the other hand, the leaf pieces were immersed for 15 seconds in a chemical solution prepared by diluting a wettable powder of a compound prepared according to Example 2 with water containing a surfactant (0.01%) to 500 ppm. This was left in a constant temperature room at 25 ° C., and after 7 days, the number of hatching larvae was counted, and the ovicidal rate was determined. The effect was determined in the same manner as in the efficacy test (2). Table 9 shows the results.

[0049]

[Table 9]

(6) Efficacy test for sweet potato nematode Into each well of a 96-well plate, a chemical solution prepared by diluting a wettable powder of a compound prepared in accordance with Example 2 with water to 100 ppm was added. 500 larvae were released. Leave this in a constant temperature room at 25 ° C,
Two days later, observation was made under a microscope to determine the nematicidal rate. The effect was determined in the same manner as in the efficacy test (2). Table 10 shows the results.

[0051]

[Table 10]

[0052]

The fungicidal and insecticide containing the 2-fluoropropionic anilide derivative of the present invention as an active ingredient has excellent effects.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tomoya Noritake 5, 1978 Kogushi, Obe City, Ube City, Yamaguchi Prefecture Ube Industries, Ltd. Ube Research Laboratories F-term (reference) BC07 BC18 BC20 DA02 DA15 DA16

Claims (2)

[Claims] (1) The following formula (1): A 2-fluoropropionic anilide derivative represented by the formula:
However, 2-fluoropropionic anilide, 4'-methyl-2-fluoropropionic anilide and 4'-methoxy-2-fluoropropionic anilide are excluded. Here, X, R and n in the formula are as follows. X represents an oxygen atom or a sulfur atom. R represents a halogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a nitro group, a carbonyl group having an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or phenyl. Group, a condensed ring formed by a benzene ring and (R) _n , CH ₂ PO (R ¹ ) ₂ , and an alkoxy group having 1 to 4 carbon atoms. n represents an integer of 1 to 5. R
¹ represents an alkoxy group having 1 to 4 carbon atoms. 2. The following formula (1 '): A fungicidal and insecticide comprising a 2-fluoropropionic anilide derivative represented by the formula (1) as an active ingredient. Note that X and R in the formula have the same meanings as in claim 1. n ′ represents an integer of 0 to 5.