JPH06135933A - Substituted alkenyl ketone derivative and insecticide - Google Patents

Abstract

PURPOSE:To obtain a new substituted alkenyl ketone derivative useful as an insecticide capable of killing and controlling various kinds of noxious insects, especially rice insect pests such as Nilaparvata lugens and Nephotettix cincticeps, horticulture insect pests such as Plutella xylostella without exerting bad influence to crops. CONSTITUTION:A compound of formula I [R<1> is haloalkyl; R<2> is H; R<3> is alkyl which may be branched or phenyl which may be substituted with a substituent group (halogen, alkyl, alkoxy, etc.); R<4> is H or alkyl or haloalkyl which may be branched; Z is pyridyl, pyrimidinyl, thiazolyl or a compound of formula IV (R<5> and R<6> are R<4>; Q is phenyl or pyridyl which may be substituted)] which may each be substituted with halogen, alkyl, alkoxy, etc., e.g. 2-(4,6-dimethyl-2- pyridylamino)-1-propenyltrifluoro-methyl ketone. The compound of formula I is obtained by reacting a compound of formula II with a compound of formula III in a proper solvent at 0 deg.C to the boiling point of the solvent, preferably at 40-80 deg.C.

Description

Detailed Description of the Invention

[0002]

TECHNICAL FIELD The present invention relates to a substituted alkenyl ketone derivative and an insecticide containing the derivative as an active ingredient.

[0003]

2. Description of the Prior Art The following compounds have been known as 2-amino-1-alkenyl trihalomethyl ketone derivatives, but their insecticidal activity has not been known.
For example, the general formula

[0004]

[Chemical 3]

(Wherein X represents a chlorine atom or a fluorine atom, R ⁷ represents a methyl group or a phenyl group, R ⁸ represents an ethyl group or a phenyl group, and R ⁹ represents a hydrogen atom or an ethyl group. Compound) [synthesis (Synt
hesis) p. 1013 (1986)], general formula

[0006]

[Chemical 4]

(In the formula, R ¹⁰ represents a hydrogen atom, an ethyl group, a phenyl group, a benzyl group, a 2-pyridyl group or the like.) [Zh. Org. Khim. 26, No. 9, 187]
P. 7 (1990)], formula

[0008]

[Chemical 5]

(In the formula, R ¹¹ is 2-thiazolyl group, 3-chloro-5-trifluoromethyl-2-pyridyl group, 4-
A trifluoromethyl-2-pyrimidinyl group and the like are shown. )
Compound represented by [Gaodeng Xuexiao Huaxue Xuebao, 6
Vol. 9, No. 7, 799 (1985)], and 2-
(1,3-dimethyl-5-pyrazolylamino) -1,1,
1,5,5,5-hexafluoro-2-penten-4-one [Pol. J. Chem. Vol. 55, No. 10, p. 1995 (19
1981)] etc. In addition to this, JP-A-3-151363
No.

[0010]

[Chemical 6]

(In the formula, R ¹² independently represents a pyridyl group or a thiazolyl group having one or more substituents selected from a halogen atom, alkyl, etc., and R ¹³ represents a hydrogen atom, an alkyl group or an alkyl group. Represents a carbonyl group,
R ¹⁴ represents an alkyl group, R ¹⁵ represents a haloalkyl group, Y represents sulfur or a group of formula N—R ¹⁶ and n is 0 or 1. A butenone compound having a) is described as having insecticidal activity.

[0012]

DISCLOSURE OF THE INVENTION The present invention provides a novel substituted alkenyl ketone derivative having further improved insecticidal activity and an insecticide containing the same.

[0013]

The present inventors have synthesized various substituted alkenyl ketone derivatives in order to develop a useful insecticide, and have studied the insecticidal activity thereof. The present invention has been completed by finding that they have extremely excellent insecticidal activity against insects such as rice plant pests, rice leafhoppers and rice leaf pests and horticultural pests such as diamondback moth.

That is, the substituted alkenyl ketone derivative of the present invention has the general formula [I]

[0015]

[Chemical 7]

[In the formula, R ¹ represents a haloalkyl group, and R ²
Represents a hydrogen atom, and R ³ represents a branched alkyl group or a phenyl group (the phenyl group may be substituted with a halogen atom, a branched alkyl group, an alkoxy group or a haloalkyl group). , R ⁴ represents a hydrogen atom, an alkyl group which may be branched or a haloalkyl group, and Z is a pyridyl group, a pyrimidinyl group or a thiazolyl group (the pyridyl group, the pyrimidinyl group or the thiazolyl group is a halogen atom or an alkyl group which may be branched). A group, an alkoxy group or a haloalkyl group) or a formula

[0017]

[Chemical 8]

(In the formula, R ⁵ and R ⁶ represent a hydrogen atom, a branched alkyl group and a haloalkyl group, and R ⁵ and R ⁶ can form a ring having 3 to 7 carbon atoms. Is a halogen atom, an alkyl group which may be branched, a haloalkyl group,
A phenyl group optionally having a substituent selected from an alkoxy group, a haloalkoxy group and a phenoxy group or a pyridyl group optionally having a substituent is shown. ) Represents a group represented by. ] And the insecticide contains this compound as an active ingredient.

The compound of the present invention can be generally prepared by the following synthetic methods, but is not limited thereto.

[0020]

[Chemical 9]

(In the formula, R ¹⁷ represents a lower alkyl group,
¹ , R ² , R ³ , R ⁴ , and Z have the same meanings as described above. )

That is, the compound of the general formula [I] can be obtained by reacting 1 equivalent of the compound of the general formula [II] with 1 equivalent of the compound of the general formula [III] in a suitable solvent. Here, the reaction temperature is from 0 ° C to the boiling point temperature range of the solvent, preferably from 40 to 80 ° C. Also 0.5-2
Let it run for 0 hours. Examples of the solvent used include alcohols such as methanol and ethanol, ethers such as diethyl ether, tetrahydrofuran, dioxane, and diglyme, aliphatic hydrocarbons such as pentane, hexane, and petroleum ether, dichloromethane, dichloroethane, chloroform, and four. Halogenated hydrocarbons such as carbon chloride, nitriles such as acetonitrile, dimethylformamide,
Aprotic polar solvents such as dimethylacetamide and dimethyl sulfoxide, and mixed solvents obtained by combining solvents selected from these can be used.

[0023]

EXAMPLES The compounds of the present invention represented by the general formula [I] are shown in Tables 1-8. In the table, Ph means a phenyl group.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

[Table 4]

[0028]

[Table 5]

[0029]

[Table 6]

[0030]

[Table 7]

[0031]

[Table 8]

Next, the production method of the compound of the present invention will be specifically described with reference to examples.

Example 1 2- (4,6-Dimethyl-2-pyrimidylamino) -1
-Synthesis of propenyltrifluoromethylketone (Compound 3) 2-Methoxy-5,5,5-trifluoro-2-penten-4-one (3 g) was dissolved in 60 ml of acetonitrile, and 4,6-dimethyl was added thereto. 2-Aminopyrimidine (2.2 g) was added and the mixture was heated under reflux for 10 hours. After completion of the reaction, the reaction solution is concentrated, and the concentrate is silica gel (Wakogel C-
200: manufactured by Wako Pure Chemical Industries, Ltd.) ・ Chromatography gave 1.8 g of the target product as pale yellow crystals (melting point: 69-70 ° C.) (yield 38.9%).

NMR data (60 MHz, CDCl ₃ solvent, δ value) 2.40 (s, 6H) 2.63 (s, 3H) 5.50 (s, 1H) 6.70 (s, 1H) 12.27 ~ 12.60 (bs, 1H)

Example 2 2- (4-chloro-α, α-dimethylbenzylamino)
Synthesis of -1-propenyl perfluoropropyl ketone (Compound 27) 2-Methoxy-5,5,6,6,7,7,7-heptafluoro-2-penten-4-one (3 g) was dissolved in 60 ml of acetonitrile. 4-chloro-α, α-dimethylbenzylamine (1.9 g) was added thereto, and the mixture was heated under reflux for 3 hours. After completion of the reaction, the reaction solution was concentrated and the concentrate was diluted with ethyl acetate-
Chromatography was performed on silica gel (Wakogel C-200) using an n-hexane mixed solution as a developing solvent to obtain 1.2 g of the target product as a yellow transparent liquid (refractive index 1.4983) (yield 26.4%). ).

NMR data (60 MHz, CDCl ₃ solvent, δ value) 1.67 (s, 3H) 1.73 (s, 6H) 5.30 (s, 1H) 7.27 (dd, 4H) 11.73 ~ 12.23 (bs, 1H)

Example 3 2- [N- (6-chloro-3-pyridylmethyl) -N-
Synthesis of Methylamino] -1-propenyltrifluoromethylketone (Compound 45) 2-Methoxy-5,5,5-trifluoro-2-penten-4-one (3 g) was dissolved in 60 ml of acetonitrile and added thereto. N- (6-chloro-3-pyridylmethyl)-
2-Methylamine (2.8g) was added and heated for 3 hours.
After completion of the reaction, the reaction solution was concentrated and the concentrate was diluted with ethyl acetate-n-
Chromatography was performed on silica gel (Wakogel C-200) using a hexane mixed solution as a developing solvent to obtain 3.2 g of the target product as a yellowish brown transparent viscous liquid (refractive index 1.5752) with a yield of 61.3%. It was

NMR data (60 MHz, CDCl ₃ solvent, δ value) 2.63 (s, 3H) 3.10 (s, 3H) 4.63 (s, 2H) 5.33 (s, 1H) 7.17 ~ 7.67 (m, 2H) 8.20 (d, 1H)

The insecticide of the present invention comprises a substituted alkenyl ketone derivative represented by the general formula [I] as an active ingredient. In order to use the compound of the present invention as an insecticide, the compound of the present invention may be used by itself, but a carrier generally used for formulation, a surfactant, a dispersant, an auxiliary agent or the like is added, and a powder, It can also be used by formulating it into a wettable powder, an emulsion, a fine granule or a granule. Carriers used for formulation include Sieglite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite,
Examples thereof include solid carriers such as slaked lime, silica sand, ammonium sulfate and urea, and liquid carriers such as isopropyl alcohol, xylene, cyclohexanone and methylnaphthalene. Surfactants and dispersants include alkylbenzene sulfonic acid metal salts, dinaphthylmethane disulfonic acid metal salts, alcohol sulfate ester salts, alkylaryl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers. , Polyoxyethylene sorbitan monoalkylate and the like. Examples of the auxiliary agent include carboxymethyl cellulose, polyethylene glycol, gum arabic and the like.

The compounding ratio of the active ingredient is appropriately selected according to need, but in the case of powder or granules, it is 0.05
~ 20% (weight), preferably 0.1% to 10% (weight) in range. When used as an emulsion or wettable powder, it is 0.5 to 80% (weight), preferably 1 to 60%.
It is preferable to appropriately select from the range of% (weight).

The insecticide of the present invention can be used by foliage application, soil application, nursery box application or water surface application.
Before use, dilute to an appropriate concentration and spray or apply directly. The application rate of the insecticide of the present invention varies depending on the type of compound used, target pest, development tendency, degree of damage, environmental conditions, dosage form used, etc., but when used as it is as in powder and granules As an active ingredient, it may be appropriately selected from the range of 0.05 g to 5 kg, preferably 0.1 g to 1 kg per 10 ares. When used in liquid form, such as when used as an emulsion or wettable powder, it is 0.1 to 5000 pp.
m, preferably from 1 to 1000 ppm.

The insecticide of the present invention includes other insecticides, fungicides,
A fertilizer and a plant growth regulator may be mixed and used.

Next, the formulation method will be specifically described with reference to typical formulation examples, but the types and compounding ratios of the compounds and additives are not limited to these and can be varied within a wide range. In the following description,% indicates weight percentage.

Formulation Example 1 Emulsion Compound (8) 30%, cyclohexanone 20%, polyoxyethylene alkylaryl ether 11%, calcium alkylbenzene sulfonate 4% and methylnaphthalene 35% were uniformly dissolved to obtain an emulsion. It is diluted with water and applied.

Formulation Example 2 Wettable powder Compound (9) 40%, diatomaceous earth 15%, clay 15%, white carbon 25%, sodium dinaphthylmethanedisulfonate 2% and sodium ligninsulfonate 3%
Was uniformly mixed and pulverized to obtain a wettable powder. It is diluted with water and applied.

Formulation Example 3 Dust Powder 2% of the compound (21), 5% of diatomaceous earth and 93% of clay were uniformly mixed and pulverized to obtain a powder. Apply this directly.

Formulation Example 4 Granules Compound (31) 5%, lauryl alcohol sulfate sodium salt 2%, sodium lignin sulfonate 5
%, Carboxymethylcellulose 2% and clay 86%
Are uniformly mixed and pulverized. 100 parts by weight of this mixture are mixed with 2 parts of water.
Add 0 parts by weight and knead.
It was processed into 32 mesh granules and then dried to obtain granules. Apply this directly.

[0048]

INDUSTRIAL APPLICABILITY The substituted alkenyl ketone derivative of the present invention does not adversely affect crops, and can be used in various insect pests, for example, planthoppers such as brown planthopper, sedgerow planthopper, and planthopper planthopper, leafhoppers such as leafhopper leafhopper and leafhopper leafhopper. It is effective for the control of aphids such as pests of the order Thysanoptera, cotton aphid, aphid peach, aphid aphid, and pests of the order Lepidoptera such as diamondback moth, Nikamei moth, Spodoptera litura, and Spodoptera litura, as well as spider mites such as spider mites, kanzawa mites and citrus spider mites. In particular, it can kill and control paddy rice pests such as brown planthoppers and leafhoppers and horticultural pests such as diamondback moth.

Next, the effect of the compound of the present invention will be described with reference to test examples. In each test, the effect was evaluated based on the following criteria. Further, as a comparative drug, a known compound 4- (2-pyridylamino) -1,1,1-trifluoro-2-buten-3-one [Zh. Org. Khim. 26
Vol. 9, No. 9, page 1877 (1990) described compound] was used in the same manner as the test compound.

A is 90% to 100% mortality, B is 70% to less than 90% mortality, C is 50% to less than 70% mortality,
D means a mortality rate of less than 50%.

Test Example 1 Testimony of brown planthopper insecticidal The wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm. Dipping rice foliage in the drug solution, air-drying,
Placed in a test tube. Ten larvae of the brown planthopper were released therein and capped with absorbent cotton. After that, it was placed in a constant temperature room at 25 ° C., and after 6 days, the number of dead insects was investigated and the dead insect rate was calculated. The test was conducted in two consecutive cycles. The results are shown in Table 9.

[0052]

[Table 9]

Test Example 2 Black leafhopper insecticidal test A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm. Dipping rice foliage in the drug solution, air-drying,
Placed in a test tube. Five larvae of the leafhopper leafhoppers were released therein and capped with absorbent cotton. After that, it was placed in a constant temperature room at 25 ° C., and after 6 days, the number of dead insects was investigated and the dead insect rate was calculated. The test was conducted in two consecutive cycles. The results are shown in Table 10.

[0054]

[Table 10]

Test Example 3 Insecticidal test for Nikameiga A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm. Rice bud buds were soaked in the chemical solution and left still in a 60 cc vinyl chloride cup containing a filter paper. Ten larvae of the larvae of the larvae of the squid moth were released in it, placed in a lid and placed in a constant temperature room at 25 ° C., and after 6 days, the number of dead larvae was investigated and the mortality rate was calculated. The test was conducted in two consecutive cycles. The results are shown in Table 11.

[0056]

[Table 11]

Test Example 4 Diamondback moth insecticidal test A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm. Cabbage leaves were dipped in the chemical solution, air-dried, and then left still in a 60 cc vinyl chloride cup containing filter paper. Ten diamondback moth larvae were released therein, covered with a lid and placed in a thermostatic chamber at 25 ° C., and after 6 days, the number of dead larvae was investigated and the mortality rate was calculated.
The test was conducted in two consecutive cycles. The results are shown in Table 12.

[0058]

[Table 12]

Test Example 5 Cotton Aphid Insecticidal Test A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 100 ppm. Cucumber seedlings, which had been inoculated with cotton aphid nymphs in advance, were immersed in the drug solution and air-dried. The treated cucumber seedlings were placed in a constant temperature room at 25 ° C., and the number of dead insects was investigated 3 days later, and the dead insect rate was calculated. The test was conducted in two consecutive cycles.
The results are shown in Table 13.

[0060]

[Table 13]

[0061]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Kurihara 4-6-1, Aobadai, Kikugawa-cho, Ogasa-gun, Shizuoka Prefecture (72) Inventor Naokazu Minoguchi 1809 Kamo, Kikugawa-cho, Ogasa-gun, Shizuoka (72) Inventor Yuno Yano 1809 Kamo, Kikugawa-cho, Ogasa-gun, Shizuoka Prefecture (72) Inventor Tadami Hirano 2-9-3, Katsurugaoka, Kakegawa City, Shizuoka Prefecture

Claims (2)

[Claims] 1. A general formula: [In the formula, R ¹ represents a haloalkyl group, R ² represents a hydrogen atom, and R ³ represents a branched alkyl group or a phenyl group (the phenyl group is a halogen atom, a branched alkyl group, an alkoxy group). Or a haloalkyl group), R ⁴ represents a hydrogen atom, an optionally branched alkyl group or a haloalkyl group, Z represents a pyridyl group,
A pyrimidinyl group and a thiazolyl group (the pyridyl group, the pyrimidinyl group and the thiazolyl group may be substituted with a halogen atom, an alkyl group which may be branched, an alkoxy group or a haloalkyl group), or a compound represented by the formula: (In the formula, R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group and a haloalkyl group which may be branched, and R ⁵ and R ⁶ have 3 to 7 carbon atoms.
It is also possible to form a ring. Q has a halogen atom, an optionally branched alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group and a phenoxy group, which may have a substituent, and a similar substituent. Is a pyridyl group. ) Represents a group represented by. ] The substituted alkenyl ketone derivative represented by these. 2. An insecticide containing the substituted alkenyl ketone derivative according to claim 1 as an active ingredient. [0001]