JPH1143494A - Phosphorus compound, its production and pest controlling agent for agriculture and horticulture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new phosphorus compound, comprising a hydrazone derivative of phosphinylmethyl-benzophenones and usable as a pest controlling agent, etc., for agriculture and horticulture useful as an insecticide, etc. SOLUTION: This new phosphorus compound is represented by formula I (R1 is an unsubstituted phenyl or a phenyl having a halogen atom as a substituent group; R2 and R3 are each H, a 2-5C alkoxycarbonyl, a 2-5C alkylcarbonyl, a 1-4C alkylaminosufonyl or a 3-6C cycloalkylaminosulfonyl; R4 and R5 are each a 1-4C alkoxy, a 1-4C alkyl or hydroxyl group) [e.g. 4- chloro-4'(dimethoxyphosphinylmethyl)benzophenone N'-ethoxycarbonylhydrazone] and is usable as a pest controlling agent, etc., for agriculture and horticulture useful as an insecticide, etc. The compound is obtained by a method for reacting a compound represented by formula II (Z is an eliminable group) with a compound represented by formula III (Y is H or an alkyl), etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel phosphorus compound which is a pest control agent for agricultural and horticultural use useful as an insecticide and the like.

[0002]

2. Description of the Related Art A compound closest to the structure of the phosphorus compound (1) of the present invention is described in JP-A-56-45452, which has the following formula:

[0003]

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Wherein R ^a is an optionally substituted alkyl group; X is an oxygen atom or a sulfur atom; R ₂ and R ₄ are the same or different and are hydrogen, Atom, an alkyl group, an acyl group, an optionally substituted alkylsulfonyl group, and an arylsulfonyl group.).

[0005] The phosphorus compound (1) of the present invention comprises a compound represented by "-P
(O) -X-Ph- "is structurally different at the" -X- "portion. Therefore, since the phosphorus compound (1) of the present invention is a novel compound, its biological activity was not known. The technology relating to the novel intermediate (4 ′) for producing the phosphorus compound (1) of the present invention includes Lie
bigs. Ann. Chem. 825 (1989)
As the Wittig-Honer reaction product, 4-benzoyl-2-nitrobenzylphosphonic acids are described; JP-A-1-151930 and Chem. L
ett. (4), 569 (1988) describe photodegradable surfactants and 4- (4-alkoxybenzoyl) benzylphosphonic acids as intermediates thereof; Japanese Patent Publication No. 6-62650 discloses a thyroxinase inhibitor. And 4-benzoylbenzylphosphonic acids as intermediates thereof. However, these are all compounds (4 ′) in which R _{1 ′} corresponds to an unsubstituted phenyl or alkoxyphenyl group, and the compound of the present invention in which R _{1 ′} is a halophenyl group is not known.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel phosphorus compound, a method for producing the same, and a pesticide for agricultural and horticultural use containing the same as an active ingredient, which is useful as an insecticide.

[0007]

Means for Solving the Problems As a result of investigations to solve the above problems, the present inventors have found that a novel phosphorus compound has a remarkable controlling activity as an agricultural and horticultural pesticide useful as an insecticide. And completed the present invention. That is, the present invention is as follows. According to a first aspect, the following formula (1):

[0008]

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(Wherein R ₁ represents an unsubstituted or phenyl group having a halogen atom as a substituent; R ₂ and R ₃
Is independently a hydrogen atom, an alkoxycarbonyl group having 2 to 5 carbon atoms, an alkylcarbonyl group having 2 to 5 carbon atoms, an alkylaminosulfonyl group having 1 to 4 carbon atoms or a carbon atom R ₄ and R ₅ each independently represent an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms or a hydroxyl group, each representing 3 to 6 cycloalkylaminosulfonyl groups; . )). The second invention is
The following equation (2):

[0010]

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(Wherein R ₁ , R ₂ and R ₃ have the same meaning as described above; Z represents a leaving group) and the following formula (3):

[0012]

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(Wherein R ₄ and R ₅ have the same meanings as described above, and Y represents a hydrogen atom or an alkyl group).
a);

[0014]

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(Wherein R _{1 to} R ₅ have the same meanings as described above). A third invention provides the following equation (4):

[0016]

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(Wherein R ₁ , R ₄ and R ₅ are as defined above) and the following formula (5):

[0018]

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(Wherein R ₂ and R ₃ have the same meanings as described above), and a method for producing a phosphorus compound represented by the above formula (1), characterized by reacting the compound. . A fourth invention provides the following formula (1b):

[0020]

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(Wherein R ₁ , R ₂ , R ₄ and R ₅ are as defined above) and the following formula (6):

[0022]

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(Wherein Z ′ represents a leaving group; R ₃ represents
It is the same as the above. The present invention relates to a method for producing a phosphorus compound represented by the above formula (1), characterized by reacting a compound represented by the formula (1). The fifth invention provides the following formula (4 ′):

[0024]

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[In the formula, R _{1 ′} represents a phenyl group having a halogen atom as a substituent; R ₄ and R ₅ have the same meaning as described above. And a compound represented by the formula:
The sixth invention relates to a pesticide for agricultural and horticultural use containing the phosphorus compound represented by the formula (1) as an active ingredient.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. R _{1 to} R ₅ , R _{2 and} R ₃ in the novel phosphorus compounds [compounds (1) and (1a)] which are the target compounds,
R _{1 ′} , Y, Z and Z ′ are as follows.

[R ₁ ] R ₁ may be an unsubstituted or a phenyl group having a halogen atom as a substituent. Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; a chlorine atom is preferred.

[R ₂ and R ₃ ] As R ₂ and R ₃ ,
Each independently represents a hydrogen atom and an alkoxycarbonyl group having 2 to 5 carbon atoms, an alkylcarbonyl group having 2 to 5 carbon atoms, an alkylaminosulfonyl group having 1 to 4 carbon atoms, and a cycloalkyl having 3 to 6 carbon atoms. An alkylaminosulfonyl group can be mentioned. The alkoxycarbonyl group, there may be mentioned those having a straight-chain or branched alkoxy group having 1 to 4 carbon atoms; preferably -COOCH _3, a -COOC ₂ H _5. The alkyl group, there may be mentioned those having a straight-chain or branched alkyl group having 1 to 4 carbon atoms; preferably -COCH _3. Examples of the alkylaminosulfonyl group include those having a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the cycloalkylaminosulfonyl group include those having a cycloalkyl group having 3 to 6 carbon atoms.

[R ₄ and R ₅ ] As R ₄ and R ₅ ,
Each independently includes an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, and a hydroxyl group. As the alkoxy group, 1 to 1 carbon atoms
4, straight or branched;
Preferably -OCH _3, -OC ₂ H _5, a -C ₃ H ₇ -i. Examples of the alkyl group include those having a linear or branched alkyl group having 1 to 4 carbon atoms; preferably CH ₃ . [R _{1 ′} ] R _{1 ′} includes a phenyl group having a halogen atom as a substituent. Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; a chlorine atom is preferred.

[Y] Examples of Y include a hydrogen atom and an alkyl group. [Z] Z is a leaving group, and is not particularly limited, and is, for example, a halogen atom, an alkylsulfonyloxy group; preferably a halogen atom; more preferably a chlorine atom. [Z '] Z' is a leaving group, and is not particularly limited, and examples thereof include a halogen atom, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkoxy group, an aryloxy group, an imidazole group, and a hydroxyl group. Is preferably a halogen atom or an aryloxy group; and more preferably a chlorine atom or an o-hydroxyphenoxy group. The compound (1) of the present invention also includes geometric isomers and mixtures thereof.

As the compound (1), the above-mentioned various substituted
Examples of the combination of groups include;
Preferred from the viewpoint of R₁Is a halogen atom as a substituent
R is a phenyl group having_TwoAnd R_ThreeIs the same or
Hydrogen atom, al 2-6 carbon atoms which may be different
Coxycarbonyl group, alkyl group having 2 to 5 carbon atoms
Rubonyl group, cycloalkylamido having 3 to 6 carbon atoms
Nosulfonyl group, alkylamino having 1 to 4 carbon atoms
R is a group selected from a sulfonyl group;_FourAnd R _FiveAnd the same
Alkoxy with 1 to 4 carbon atoms which may be one or different
Groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms
Is a compound. As the compound (4 ′), each of the above
And combinations of different substituents.
But preferred is R₁Is a halogen atom as a substituent
A phenyl group having the formula:_FourAnd R_FiveIs the same or phase
Alkoxy groups having 1 to 4 carbon atoms which may be different, charcoal
Groups selected from alkyl groups and hydroxyl groups having 1 to 4 elementary atoms
Is a compound.

Compound (1) was prepared according to the following production methods 1 and 2.
Or 3 can be used. [Production Method 1] Compound (1a) (in compound (1),
The case where X is an oxygen atom) is carried out by reacting the compound (2) with the compound (3) without a solvent or in a solvent as shown below.

[0033]

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(In the formula, R _{1 to} R ₅ , Y and Z have the same meanings as described above.) The type of the solvent is not particularly limited as long as it does not directly participate in the reaction. Chlorinated or unchlorinated aromatics, aliphatics, fats such as toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloroethane, trichloroethylene, cyclohexane Cyclic hydrocarbons; diethyl ether, tetrahydrofuran,
Ethers such as dioxane; ketones such as acetone, methyl ethyl ketone; alcohols such as methanol, ethanol, ethylene glycol and the like or hydrates thereof; N, N-dimethylformamide, N,
Amides such as N-dimethylacetamide; nitriles such as acetonitrile, propionitrile; triethylamine, pyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] undec-7- Organic bases such as ene; 1,3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; mixtures of the above-mentioned solvents.

The amount of the solvent used is such that the concentration of the compound (2) is 5
It can be used in a concentration range of -100% by weight; however, 10-70% by weight is preferred. The reaction temperature is not particularly limited, but is usually in the range of from room temperature to the boiling point of the solvent to be used or lower; the temperature of the boiling point or lower is preferable. The reaction time varies depending on the above concentration and temperature; it is usually 0.3 to 24 hours. The amount of the starting compound used is 0.5 to 20 for the compound (3) relative to the compound (2).
It is a molar amount; preferably 0.8 to 10 times. Compound (2) can be synthesized by reacting compound (5) with compound (6) as shown below.

[0036]

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(In the formula, R _{1 to} R ₃ and Z have the same meanings as described above.) The compound (8) is a so-called benzyl halide when Z is a halogen atom, for example. Sy
nth. , V, 328 (1973). Compound (5) can be synthesized according to a known method such as the method described in JP-A-58-203980, when one of R ₂ and R ₃ is an alkoxycarbonyl group, Some can be used as commercial products. [Production Method 2] Compound (1) is carried out by reacting compound (4) with compound (5) in the absence or presence of a solvent, as shown below.

[0038]

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(In the formula, R _{1 to} R ₅ have the same meanings as described above.) The type of the solvent is not particularly limited as long as it does not directly participate in the reaction. For example, benzene, toluene, xylene, Chlorinated or unchlorinated aromatic, aliphatic and cycloaliphatic carbons such as methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloroethane, trichloroethylene, cyclohexane Hydrogens; ethers such as diethyl ether, tetrahydrofuran, dioxane and the like; alcohols such as methanol, ethanol, ethylene glycol and the like or hydrates thereof; N, N-dimethylformamide, N, N-dimethylacetamide and the like Amides; acetonitrile,
Nitriles such as propionitrile; triethylamine, pyridine, N, N-dimethylaniline, 1,8
Organic bases such as -diazabicyclo [5.4.0] undec-7-ene; 1,3-dimethyl-2-imidazolidinone; dimethylsulfoxide; acetic acid; and mixtures of the above solvents.

The amount of the solvent used is 5 to 10 for compound (4).
0% by weight can be used;
0-70% by weight is preferred. The reaction temperature is not particularly limited, but is in a temperature range from room temperature to 200 ° C; preferably 50 to 150 ° C. The reaction time varies depending on the concentration and temperature described above; it is usually 0.1 to 100 hours; preferably 0.3 to 24 hours. The amount of the starting compound used is such that the compound (5) is 0.5 to the compound (4).
５０50-fold molar; preferably 0.8- to 10-fold molar. If necessary, catalysts for the reaction include, for example, mineral acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as formic acid, acetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; Lewis acids such as boron fluoride-ether complex and titanium tetrachloride; pyridine hydrochloride. An acid addition salt of an amine such as triethylamine hydrochloride can be used in an amount of 0.001 to 1 mol based on Compound (4). Compound (4), for example, in the case of a phosphonic acid ester, can be synthesized according to the method described in JP-B-6-62650.

[Production Method 3] Compound (1) can be synthesized by reacting compound (1b) with compound (6) without solvent or in a solvent as shown below.

[0042]

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(In the formula, R _{1 to} R ₅ and Z ′ have the same meanings as described above.) As the type of the solvent, the same one as described in Production method 1 can be used. The amount of the solvent to be used may be such that the compound (1b) is 5 to 100% by weight; however, it is preferably 10 to 70% by weight. The reaction temperature is not particularly limited, but is in a temperature range of 0 to 200 ° C; preferably 0 to 150 ° C. The reaction time is
It varies depending on the concentration and temperature;
00 hours; preferably 0.3 to 24 hours. The amount of the starting compound to be used is 0.5 to 50 times mol of compound (6) relative to compound (1b); preferably 0.8 to 10 times mol.

A base is used if necessary. The type of base is not particularly limited, and includes, for example, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] undec-7-ene, and the like. Organic bases such as sodium methoxide, sodium ethoxide, etc .; sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate And the like.

The amount of the base used is the same as that of the compound (1
It is 0.001 to 5 times the molar amount of b). Compound (1
b) is a compound (1) in which at least one of R ₂ and R ₃ is a hydrogen atom (in the reaction formula, R ₃ is described as a hydrogen atom); Can be synthesized. Compound (6) can be synthesized according to a method known in the literature, and some are commercially available. For example, compounds in which R ₃ is an alkylsulfonyl group and Z ′ is a halogen atom are described in J. Am. Org.
Chem. , 41, 4028 (1976). After completion of the reaction, the target compound (1) produced as described above is subjected to ordinary post-treatments such as extraction, concentration and filtration, and if necessary, by known means such as recrystallization and various types of chromatography. It can be appropriately purified. Examples of the compound (1) include the compounds 1 to 30 shown in Tables 2 to 4 below (for example, the compound 1 is a compound represented by the formula (1) in which R ₁ is a 4-chlorophenyl group). , R ₂ and R ₃ are hydrogen atoms,
An ethoxycarbonyl group, and R ₄ and R ₅ are methoxy groups].

Pest control agent for agricultural and horticultural use [Control effect] The pests in agricultural and horticultural products having the controlling effect of the compound (1) of the present invention include agricultural and horticultural insect pests, for example, Hemiptera (Coleoptera, leafhopper) , Aphids,
Whiteflies, etc.), lepidopterans (armyworms, such as Spodoptera litura), moths, locust beetles, scabbards, sink beetles, cabbage beetles, etc., Coleoptera (e.g., beetles, weevil, chrysomelids, beetles, etc.),
Acarina (red spider mite of the spider mite family, spider mite, etc., citrus spider mite, etc.)], sanitary pests (eg, flies, mosquitoes, cockroaches, etc.), and grain storage pests (e.g., black beetles, etc.). Corn rootworm root-knot nematodes, pine wood nematodes, and mite in soil can be exemplified.

[Pest Control Agent] The pest control agent of the present invention is a pesticide for agricultural and horticultural use which has particularly remarkable insecticidal activity and contains at least one compound (1) as an active ingredient. Compound (1) can be used alone,
Usually, a carrier, surfactant, dispersant, adjuvant, etc. are blended by a usual method (for example, prepared as a composition such as powder, emulsion, fine granule, granule, wettable powder, oily suspension, aerosol, etc.) Is preferably used.

Examples of the carrier include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea; hydrocarbons (kerosene, mineral oil, etc.), aromatic carbon Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene 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 which can be used to improve the performance of the agent, such as adhesion to animals and plants, improvement in absorption, dispersion, emulsification and spreading of drugs, include, for example, 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 production of the present agent, 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 1 to 50% by weight for emulsions, usually 0.3 to 25% by weight for powders, and usually 1 to 90% for wettable powders.
% By weight, 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. 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.

[0050]

EXAMPLES The present invention will be specifically described below with reference examples and examples. Note that these examples do not limit the scope of the present invention. Example 1 Synthesis of Compound (4) (1) Synthesis of 4-chloro-4 ′-(dimethoxyphosphinylmethyl) benzophenone [Compound (4) 1] 4-chloro-4′-bromomethylbenzophenone (3
g), and a mixture of trimethyl phosphite (1.2 g) was heated and stirred at 140 to 150 ° C. for 1.5 hours. After completion of the reaction, the obtained oil was subjected to column chromatography (Wakogel C200, chloroform-methanol = 100:
1 elution) to obtain the target compound as a pale yellow solid in 1.
08 g was obtained.

(2) 4-chloro-4 '-(diethoxyphosphinylmethyl) benzophenone [compound (4) 2]
Synthesis of 4-chloro-4′-bromomethylbenzophenone (10
g) and triethyl phosphite (5.4 g) were heated and stirred at 140 to 150 ° C. for 1.7 hours. After completion of the reaction, the obtained oil was subjected to column chromatography (Wakogel C200, chloroform-methanol = 100:
(1 elution) to give 8.5 g of the target compound as a yellow-green oil. Compound (4) synthesized as above
Among them, Table 1 shows the novel compound (4 ′) and its physical property values.

[0052]

[Table 1]

Example 2 [Synthesis of Compound (1)] (1) Synthesis of 4-chloro-4 ′-(dimethoxyphosphinylmethyl) benzophenone N′-ethoxycarbonylhydrazone [Compound 1] It was synthesized as follows. A mixture of 4-chloro-4'-bromomethylbenzophenone ethoxycarbonylhydrazone (1 g) and trimethylphosphite (3 ml) was heated under reflux for 6 hours. After completion of the reaction, excess trimethyl phosphite was distilled off under reduced pressure, and the obtained oil was subjected to column chromatography (Micro).
Sphere Gel D-150-60A, eluted with ethyl acetate) and crystallized from hexane-ethyl ether to give 0.8 g of the target compound as a white powder.
g was obtained.

(2) Synthesis of 4-chloro-4 '-(diethoxyphosphinylmethyl) benzophenone hydrazone [compound 4] The compound was synthesized according to Production Method 2 as follows. 4-chloro-4 '-(diethoxyphosphinylmethyl) benzophenone (1.4 g), hydrazine monohydrate (0.58
g) and a catalytic amount of concentrated hydrochloric acid were dissolved in ethanol and heated under reflux for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, water was added, extracted with ethyl acetate, washed with saturated sodium bicarbonate and brine, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography [Wakogel C200, eluted with toluene: ethyl acetate = (1: 4)-(1: 5)] to give 0.83 g of the target compound as a yellow oil. .

(3) Synthesis of 4-chloro-4 '-(diethoxyphosphinylmethyl) benzophenone N'-methoxycarbonylhydrazone [compound 5] The compound was synthesized according to Production Method 2 as follows. 4-chloro-4 '-(diethoxyphosphinylmethyl) benzophenone (1.5 g), methylcarbazate (0.74
g) and a catalytic amount of the boron trifluoride-ether complex were dissolved in toluene (30 ml) and heated and stirred. After the reaction,
After cooling to room temperature, water was added, extracted with ethyl acetate, washed with saturated sodium bicarbonate and saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C2).
00, toluene: ethyl acetate = 1: 4) to give 1.57 of the target compound as a colorless oil.
g was obtained.

(4) Synthesis of 4-chloro-4 ′-(diethoxyphosphinylmethyl) benzophenone N′-acetylhydrazone [Compound 10] The compound was synthesized as follows according to Production Method 3. 4-Chloro-4 '-(diethoxyphosphinylmethyl) benzophenone hydrazone (0.65 g) and triethylamine (0.36 g) were dissolved in 15 ml of dichloromethane, and acetyl chloride (0.2 g) in dichloromethane (15 g) was dissolved.
ml) solution was added slowly. Then, the reaction was performed at room temperature for 2 hours. After completion of the reaction, water was added, extracted with ethyl acetate, washed with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wako gel C200, toluene: ethyl acetate = 1: 8 elution) to obtain 0.43 g of the target compound as a pale yellow solid.

(5) Synthesis of 4-chloro-4 '-(diethoxyphosphinylmethyl) benzophenone N'-(cyclopropylaminosulfonyl) hydrazone [compound 15] According to Production Method 3, it was synthesized as follows. . 4-chloro-4 ′-(diethoxyphosphinylmethyl) benzophenone hydrazone (0.43 g), 2- (cyclopropylaminosulfonyloxy) phenol (0.41 g)
g) and 0.4 ml of dimethylformamide were heated and stirred at about 85 ° C. for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, water was added, extracted with ethyl acetate, washed with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C200, toluene: ethyl acetate = 1: 2).
Purification by elution) gave 0.14 g of the target compound as a pale brown oil.

(6) Other compounds in Tables 2 to 4 (1)
Synthesis of Other Compounds (1) in Tables 2 to 4 were synthesized according to the methods described in the above (1) to (5). Tables 2 to 5 show the compounds synthesized as described above and the physical properties.

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

[Table 5]

Example 2 [Preparation of preparation] (1) Preparation of granule 5 parts by weight of compound 1, 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of Neoperex powder (trade name; manufactured by Kao Corporation) And 2 parts by weight of sodium ligninsulfonate were uniformly mixed, then kneaded by adding a small amount of water, and then granulated and dried 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) Name; manufactured by Kao Corporation)
Then, it was pulverized to obtain a wettable powder.

(3) Preparation of Emulsion To 20 parts by weight of 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. .

(4) Preparation of powder 5 parts by weight of compound 1, 50 parts by weight of talc and kaolin 4
5 parts by weight were uniformly mixed to obtain a powder.

Example 3 [Efficacy Test] (1) Efficacy Test against Conaga (Comparative) Compounds (1) shown in Tables 2 to 4 prepared according to Example 2
Was diluted to 300 ppm with water containing a surfactant (0.01%), and cabbage leaf pieces (5 cm × 5 cm) were immersed in each of these solutions for 30 seconds, and one piece was placed in each plastic cup. And air-dried. Next, 10 moths (3rd instar larvae) were released into each of these cups, covered, left in a constant temperature room at 25 ° C., and two days later, the number of live and dead insects in each cup was counted to determine the mortality. . The insecticidal effect is evaluated in four stages (A: 100%, B: less than 100 to 80%, C: less than 80 to 60%, D: less than 60%) according to the range of the mortality.
Indicated by Table 6 shows the results.

[0068]

[Table 6]

(2) Efficacy test on Spodoptera litura Compounds (1) shown in Tables 2 to 4 prepared according to Example 2
Each wettable powder was diluted to 500 ppm with water containing a surfactant (0.01%), soybean leaves were immersed in each of these solutions for 30 seconds, placed one by one into each plastic cup, and air-dried. did. Next, 10 cutworm cutworms (2nd instar larvae) were released into each of these cups, capped, left in a constant temperature room at 25 ° C., and two days later, the number of live and dead insects in each cup was counted to determine the mortality. . The results of the evaluation of the insecticidal effect are shown in Table 7 by the four-step evaluation method described in the above (1).

[0070]

[Table 7]

(3) Efficacy test on brown planthopper Compounds (1) shown in Tables 2 to 4 prepared according to Example 2
Was diluted to 300 ppm with water containing a surfactant (0.01%), and rice seedlings were immersed in each of these solutions for 30 seconds, air-dried, and inserted into a glass cylinder. Release 10 fourth instar larvae of the brown planthopper, stopper with a porous plug,
It was left in a 5 ° C constant temperature room. After 4 days, the number of live and dead insects was counted, and the mortality was determined. The results of the evaluation of the insecticidal effect are shown in Table 8 using the four-step evaluation method described in the above (1).

[0072]

[Table 8]

[0073]

The novel phosphorus compound of the present invention is an agricultural chemical useful as a pesticide.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07F 9/38 C07F 9/38 Z 9/40 9/40 C Z 9/53 9/53 (72) Inventor Akira Ooka Yamaguchi 5 Ube-shi Kobe, 1978 Ube Research & Development Co., Ltd. Ube Research Institute (72) Inventor Takaaki Kuwata Ube-shi Ube City Ube-shi Kobe Co., Ltd. Ube Research Lab.

Claims (6)

[Claims] (1) The following formula (1): (Wherein R ₁ represents an unsubstituted or a phenyl group having a halogen atom as a substituent; R ₂ and R ₃ each independently represent a hydrogen atom, an alkoxycarbonyl group having 2 to 5 carbon atoms, Represents an alkylcarbonyl group having 2 to 5 carbon atoms, an alkylaminosulfonyl group having 1 to 4 carbon atoms or a cycloalkylaminosulfonyl group having 3 to 6 carbon atoms; R ₄ and R ₅ are each independently do it,
C1-C4 alkoxy group, C1-C4 alkoxy group
Represents an alkyl group or a hydroxyl group. ). 2. The following formula (2): (Wherein R ₁ , R ₂ and R ₃ have the same meanings as in claim 1; Z represents a leaving group) and a compound represented by the following formula (3): (Wherein, R ₄ and R ₅ have the same meanings as in claim 1; Y represents a hydrogen atom or an alkyl group).
a); (Wherein, R _{1 to} R ₅ have the same meanings as described in claim 1). 3. The following formula (4): (Wherein R ₁ , R ₄ and R ₅ are as defined in claim 1) and a compound represented by the following formula (5): (Wherein, R ₂ and R ₃ have the same meanings as described in claim 1), wherein the compound represented by the formula (1) is reacted with the compound represented by the formula (1). Manufacturing method. 4. The following formula (1b): (Wherein R ₁ , R ₂ , R ₄ and R ₅ are as defined in claim 1) and a compound represented by the following formula (6): (Wherein, Z ′ represents a leaving group; R ₃ has the same meaning as described in claim 1), and is reacted with a compound represented by the formula (1). )). 5. The following formula (4 ′): [In the formula, R _{1 ′} represents a phenyl group having a halogen atom as a substituent; R ₄ and R ₅ have the same meaning as described in claim 1. ] The compound shown by these. 6. A pesticidal composition for agricultural and horticultural use, comprising the phosphorus compound represented by the formula (1) according to claim 1 as an active ingredient.