JPH0124779B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel diolefinamides, methods for producing the same, and insecticides containing them. The novel diolefinamides according to the present invention are
It is represented by the following general formula []. (In the formula, R ¹ and R ² are the same or different and represent a hydrogen atom, a halogen atom, a tert-butyl group, or a trifluoromethyl group, and R ¹ and R ² are 3,
A 4-methylenedioxy group may also be formed. A represents a methylene group or an oxygen atom. R ³ represents a methyl group or a hydrogen atom, and R ⁴ has 4 to 4 carbon atoms.
5 represents a linear or branched lower alkyl group or cyclohexyl group. n represents an integer of 5 to 9. ) It is known that certain diolefinamides have insecticidal activity. That is, M. Jacobson (“Naturally
Occurring Insecticides”P137～176, Marcel
Dekker Inc. New York (1971)), a series of aliphatic N-isobutyl-2E,4E-
Diolefinamides In the formula, R represents a saturated or unsaturated linear hydrocarbon. ) has been reported to have a certain insecticidal effect. However, all of these compounds have insufficient insecticidal efficacy and are extremely unstable compounds, so they have not been put into practical use. On the other hand, the present inventors previously discovered that pepper fruit, a type of spice served as daily food, exhibits a certain insecticidal activity, and as a result of searching for its active ingredients, the following three compounds were discovered. was discovered as an insecticidal ingredient (Reference 1M. Miyakado, I.
Nakayama, H.Yoshioka, Agric.Biol.Chem.,
441701 (1980)). The unsaturated amides contained in these peppers (A), (B) and (C) are the aliphatic N-isobutyl-2E,
Compared to 4E-diolefinamides, its insecticidal efficacy against various insects is several to several tens of times superior to that of pyrethrins, the insecticidal components of pyrethrum, which have been frequently used as natural insecticides for many years. It is comparable. The present inventors used these insecticidal unsaturated amides (A), (B), and (C) as the basic core, and as a result of intensive study on structural modification using their insecticidal activity as an indicator, we found that they have excellent insecticidal activity. We have now found a group of compounds exhibiting the following, namely the compounds of the present invention represented by the general formula []. In the compound of the present invention represented by the general formula [], R ¹ and R ² represent substituents on the benzene ring,
Each is, for example, a 3-chloro group, a 4-chloro group,
3,4-dichloro group, 3-brome group, 4-brome group, 3-tert-butyl group, 4-tert-butyl group,
Examples include a 3,5-dichloro group, a 3-trifluoromethyl group, or a case where _R1 and _R2 form a 3,4-methylenedioxy group. A is a methylene group or an oxygen atom. R ³ is a hydrogen atom or a methyl group. R ⁴ represents a linear or branched lower alkyl group or cyclohexyl group having 4 to 5 carbon atoms, and a branched alkyl group is particularly preferred. Specific examples include isobutyl group, sec-butyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, and cyclohexyl group. Further, n represents an integer of 5 to 9, preferably 6 to 8. Regarding the geometric isomerism of the two olefins contained in the molecule, both are preferably trans isomers. To produce diolefinamides represented by the general formula [], the general formula [] (In the formula, R ¹ , R ² , R ³ , A and n have the same meanings as above.) An acid represented by the formula or its reactive derivative and the general formula [] R ⁴ -NH ₂ [] (in the formula, R ⁴ has the same meaning as above.) It is sufficient to react with an amine represented by The term "reactive derivative of an acid" as used herein refers to an acid halide. To describe in more detail the method for synthesizing diolefinamides represented by the general formula [], the reaction between an acid and an amine is carried out under appropriate dehydration conditions, for example, phosphorus nitride chloride trimer and an organic tertiary compound such as pyridine or triethylamine. This is achieved by reacting with a base in a suitable inert solvent at room temperature or with heating. When an acid halide is used as the reactive derivative, it is reacted with the amine to obtain the desired amide in good yield at room temperature. Although any acid halide may be used within the scope of the present invention, acid chloride is usually used. Furthermore, although the presence of a solvent is not essential during the reaction, its use is desirable in order for the reaction to proceed smoothly, and an inert solvent such as benzene, toluene or petroleum benzine is usually used. The method for producing the diolefinamides of the present invention will be explained in more detail with reference to Examples below. Example 1 Example of manufacturing N-isobutyl-2E,4E-12-(3,4-methylenedioxyphenoxy)-dodecadienoicamide (compound (1)) Add 2E,4E-12- to 20 ml of dry benzene 3.505 g (0.01 mol) of (3,4-methylenedioxyphenoxy)-dodecadienoic acid chloride was charged, and while cooling with ice water, isobutylamine was added.
0.876 g (0.012 mol) was added dropwise as a solution in 5 ml of dry benzene over about 10 minutes. After the dropwise addition, the reaction was completed by stirring at room temperature for 3 hours, and the reaction solution was soaked in ice water for 30 minutes.
g. After separating the benzene layer,
The aqueous layer was extracted once with 20 ml of benzene. The benzene layers were combined and washed sequentially with 10% hydrochloric acid, saturated sodium bicarbonate aqueous solution, and saturated brine. After drying the benzene layer with magnesium sulfate,
By distilling off benzene under reduced pressure and recrystallizing the obtained crude crystals from ethyl acetate, the melting point was 140.
2.88 g (74.4% of theoretical yield) of colorless needle crystals (compound (1)) at ~141°C were obtained. ν ^film _nax ; 3300, 1650, 1620, 1605, 1505 cm ^-1 δ (TMS-CDCl ₃ ); 7.0 to 7.4 (br.s, 1H), 6.3 to 6.7 (m, 3H), 5.4 to 6.3 (m, 4H) ), 5.8 (s, 2H), 3.85 (t, J=7Hz, 2H), 3.10 (t, J=7Hz, 2H), 1.1~2.3 (br, 13H), 0.88 (d, J=7Hz, 6H) Example 2 Preparation of N-isobutyl-2E,4E-12-(3-chlorophenoxy)-dodecadienoicamide (compound (12)) Dry 60 ml containing 0.73 g (0.01 mol) of isobutylamine Phosphorus chloride trimer nitrided to benzene 3.51
g (0.01 mol) and added 2E, 4E-12-(3
-chlorophenoxy)-dodecadienoic acid
3.23 g (0.01 mol) of benzene solution was added dropwise over 20 minutes. Next, 7.32 g (0.1 mol) of triethylamine was added, and the mixture was heated under reflux for 1 hour. After the reaction solution was cooled to room temperature, it was poured into 50 g of water. The benzene layer was separated, and the benzene layer was washed successively with 10% hydrochloric acid, saturated sodium bicarbonate aqueous solution, and saturated saline.
After drying the benzene layer with magnesium sulfate, the benzene was distilled off under reduced pressure, and the resulting crude amide was
2.98 g of colorless needle-like crystals (compound (12)) with a melting point of 74 to 77°C (theoretical yield) 78.9%). ν ^film _nax ; 3300, 1650, 1620, 1605, 1460, 990cm ^-1 δ (TMS-CDCl ₃ ); 6.5 to 7.3 (m, 5H), 5.5 to 6.1 (m, 4H), 3.90 (t, J=7Hz , 2H), 3.10 (t, J = 7Hz, 2H), 1.2-2.3 (m, 13H), 0.88 (d, J = 7Hz, 6H) The compounds shown in the table below were obtained in the same manner as Examples 1 and 2. . The symbols a and b in the ester method column in the table have the following meanings. a Amidation method using acid chloride b Amidation method using nitrided phosphorus chloride trimer Typical compounds of the present invention are described below. [Table] [Table] [Table] Next, a method for producing an intermediate of the compound of the present invention will be explained. Regarding the method for producing carboxylic acid represented by the general formula [], when A represents a methylene group, Cited Document 1 and Cited Document 2 (M. Miyakado,
H.Yoshioka Agric.Biol.Chem., 43 2413 (1979))
The method described in . Further, those in which A represents an oxygen atom and R ₃ represents a hydrogen atom are shown in Reference Example 1, and those in which A represents an oxygen atom and R ₃ represents a methyl group are shown in Reference Example 2. Reference example 1 Methyl-2E, 4E-12- in a 100ml eggplant flask
2.28 g (0.01 mol) of hydroxy-dodecadienoate (obtained according to the method described in Cited Document 1), 2.27 g of dicyclohexylcarbodiimide
(0.011 mol) and 0.01 g of cuprous chloride were added, and the mixture was kept at 60°C for 1 hour while stirring with a stirrer. Next, 1.41 g (0.011 mol) of m-chlorophenol was added to this reaction system, and the mixture was heated to 100° C. with stirring and maintained for an additional 1 hour. After cooling, the reaction solution was extracted with ether, and insoluble materials were separated with Celite. After drying the ether solution over magnesium sulfate, the ether was removed under reduced pressure. The obtained residue was purified by column chromatography using 40 g of silica gel (developing solvent: toluene-ethyl acetate 10:1) to obtain the desired ester, methyl-2E,4E-12-(m-chlorophenoxy )-dodecadienoate (2.59 g (77.0% of theoretical yield)) was obtained. ν ^film _nax 2920, 1705, 1635, 1240, 9995cm ^-1 δ (TMS-CDCl ₃ ) 6.7-7.4 (m, 5H), 5.6-6.25 (m, 3H), 3.90
(t, J=7Hz, 2H), 3.70 (s, 3H), 2.0~
2.4 (m, 2H), 1.2-2.0 (br.s, 10H) The obtained ester was kept at 80°C for 2 hours in a 30% aqueous sodium hydroxide solution to obtain the carboxylic acid. Reference Example 2 2.55 g (0.01 mol) of 8-(m-chlorophenoxy)-1-octanal and 2.50 g (0.01 mol) of 3-methoxycarbonyl-2-methyl-2-propenyl phosphonate are added to 60 ml of anhydrous DMF. Dissolve sodium methylate 0.594 under stirring at room temperature.
g (0.011 mol) in 5 ml of methanol was added dropwise over 30 minutes and then kept for 3 hours. The reaction solution was poured into 200 g of ice water and extracted twice with 200 ml of ether. The ether extract was washed with 10% aqueous hydrochloric acid, saturated aqueous sodium bicarbonate solution, and saturated brine, and then dried over anhydrous magnesium sulfate.
The ether was removed under reduced pressure to yield 3.08 g of crude ester as a pale yellow oil. By performing column chromatography using 60 g of silica gel (developing solvent: toluene-ethyl acetate 10:1),
2.40 g (68.2% of theoretical yield) of the desired ester, methyl-4E-12(m-chlorophenoxy)-3-methyl-2,4-dodecadienoate, was obtained. n ^20.5 _D 1.4882 ν ^film _nax 2910, 2840, 1710, 1630, 1230 cm ^-1 The obtained ester was kept at 80° C. for 2 hours in a 30% aqueous sodium oxide solution to obtain the carboxylic acid. The present insecticide, which contains the compound of the present invention represented by the general formula [] as an active ingredient, is suitable for sanitary pests such as houseflies, mosquitoes, and cockroaches, paddy field pests such as leafhoppers, leafhoppers, planthoppers, stink bugs, and weevils, fall armyworm, and mealybugs. It can be used to control field crop pests such as green leaf caterpillars and aphids, fruit tree pests such as Aphids, and grain storage pests such as grain weevils, staghorn weevils, and corn moths. In addition, as a result of intensive research into the properties of the compounds of the present invention, the compounds of the present invention have the same remarkable insecticidal activity against pyrethroid-resistant house flies, which have suddenly become a problem in recent years, as they do against pyrethroid-susceptible house flies. It has become clear that this shows that The emergence of insects resistant to existing insecticides is expected to become an increasingly serious problem in the future, and the compounds according to the present invention are considered to be an important step toward solving this resistance problem. . The details of the insecticidal effect of the compound of the present invention against pyrethroid-resistant house flies are explained in Example 7. Furthermore, as a result of intensive insect physiological research on the compounds of the present invention, the present inventors found that the compounds of the present invention have remarkable knockdown activity in addition to the remarkable insecticidal activity described in detail in Examples 3 to 5. It turned out that it was. The details of this knockdown effect will be explained in Example 8. When preparing the compound of the present invention represented by the general formula [] as an insecticide, it can be prepared as an oil solution, emulsion, powder, aerosol, or Hydrating powders, granules, mosquito coils, other heated or non-heated fumigants, and attractant powders containing attracting substances such as baits preferred by pests;
It can be made into any other dosage form, such as a solid agent, and can be put to practical use. Furthermore, by using two or more of these compounds in combination, it is possible to express superior insecticidal efficacy, and furthermore, it is possible to express superior insecticidal efficacy by combining two or more of these compounds.
butoxyethoxy)ethoxy]-4,5-methylenedioxy-2-propyltoluene {referred to as piperonyl butoxide}, 1,2-methylenedioxy-4-[2-(octylsulfinyl)
propyl]benzene {referred to as sulfoxide},
4-(3,4-methylenedioxyphenyl)-5-
Methyl-1,3-dioxane {referred to as safroxane}, N-(2-ethylhexyl)-picyclo[2,2,1]hept-5-ene-2,3-dicarboximide {referred to as MGX-264}, Octachlorodipropyl ether {referred to as S-421},
Its insecticidal efficacy can also be enhanced by mixing it with other known synergists such as isobornylthiocyanoacetate {referred to as Garnite}. Also, other physiologically active substances, such as allethrin,
N-(chrysansemoxymethyl)-3,4,5,6
-tetrahydrophthalimide {hereinafter referred to as tetramethrin}, 5-benzyl-3-furylmethylchrysansemate {hereinafter referred to as resmethrin},
3-Phenoxybenzyl chrysanthemate and their d-trans primary chrysanthemum esters, d-cis, trans primary chrysanthemum esters or pyrethrum extract, d-trans primary chrysanthemum of d-arethrolone or d-cis , trans primary chrysanthemum acid ester, fenvalerate, and other known pyrethroid compounds, as well as O,O-dimethyl-O-(3-methyl-4-nitrophenyl)phosphorothioate {referred to as phenitrothion}, O,O-dimethyl -O-4-cyanophenyl phosphorothioate {referred to as cyanophos}, O,O-dimethyl-
Organophosphorus insecticides such as O-(2,2-dichlorovinyl)-phosphate {referred to as dichlorovos};
1-naphthyl N-methylcarbamate, 3,4
-dimethylphenyl N-methylcarbamate,
Carbamate insecticides such as O-sec-butylphenyl N-methylcarbamate, O-iso-propoxyphenyl N-methylcarbamate, other insecticides, or fungicides, nematicides, acaricides, and plant growth regulators. , BT agents, BM agents, and other microbial pesticides, insect hormones, herbicides, fertilizers, and other agricultural chemicals can be used to create multipurpose compositions with excellent efficacy. Synergistic effects can also be expected. Next, the present invention will be explained in further detail by giving formulation examples and examples of the present insecticide. Formulation Example 1 50 parts of each of the compounds (1) to (23) of the present invention are thoroughly mixed with 5 parts of an emulsifier {Sorbol 2495G (Toho Chemical registered trademark name, mixture of anionic surfactant and nonionic surfactant)}. Then, add 45 parts of 300 mesh diatomaceous earth and stir and mix thoroughly in a grinder to obtain each wettable powder. Formulation Example 2 10 parts each of the compounds (1) to (23) of the present invention and 5 parts of an emulsifier {Sorbol 5029-O (registered trademark name of Toho Chemical)} were thoroughly mixed, 85 parts of 300 mesh diatomaceous earth was added, and the mixture was crushed using a crusher. Each wettable powder is obtained by stirring and mixing thoroughly in the container. Formulation Example 3 To 10 parts each of the compounds (1) to (23) of the present invention, 10 parts of an emulsifier {Sorbol 3005X (registered trademark name of Toho Chemical)}, 40 parts of dimethylformamide, and 40 parts of xylene were added,
By stirring and mixing these thoroughly, each emulsion is obtained. Formulation Example 4 0.2 parts of each of the compounds (1) to (23) of the present invention and 1 part of xylene
1 part and dissolve it in white kerosene to make a total of 100 parts to obtain each oil agent. Formulation Example 5 Dissolve 1 part of each of the compounds of the present invention (1) to (23) in an appropriate amount of acetone, add 99 parts of 300 ml of acetone,
After thorough stirring and mixing, acetone is removed by evaporation to obtain each powder. Formulation Example 6 0.8 parts of piperonyl butoxide is added to 0.2 parts of each of the compounds (1) to (23) of the present invention and dissolved in white kerosene to make a total of 100 parts to obtain each oil solution. Example 3 A 10μ solution of the compounds (1) to (23) of the present invention in acetone was applied to the back of a male adult bean weevil using a micropipette.
It was applied locally at a concentration of g/μ, transferred to a tray lined with paper, and the number of dead insects was observed after 48 hours to calculate the mortality rate. In addition, 40 males were tested for each dose. [Table] Example 4 Compounds of the present invention (1), (3), (4), (7), (8), (10) to (23)
xylene and an emulsifier (Sorbol SM-
200, Toho Chemical registered trademark name) in a ratio of 10:75:15, respectively, to make a 10% emulsion. Dissolve this in distilled water in a glass beaker to prepare 100ml of an aqueous solution containing 100ppm of the active ingredient. Twenty 4th instar larvae of Culex mosquito were released inside, and the number of dead insects was observed after 24 hours to calculate the mortality rate. [Table] Example 5 10% of the compound of the present invention formulated in the same manner as Example 4
15 ml of a chemical solution made by diluting the emulsion with water to a concentration of 0.1%
Soak in artificial food for Spodoptera g, diameter
It was placed in an 11 cm polyethylene cup. Twenty-five 3rd instar larvae of Spodoptera were released into the larvae, and 6 days later, their survival and death were examined (2 replicates). [Table] Example 6 A wettable powder obtained according to the formulation of Formulation Example 2 was diluted with water to a solution containing 500 ppm of the active ingredient of the compound of the present invention.
Five rice seedlings 10 days after sowing were immersed in the chemical solution for 1 minute and air-dried. Treated rice plants and 3rd instar larvae of N. japonica in a plastic cup with a diameter of 5.5 cm and a height of 3.5 cm.
I put in 10 heads. After 10 days, the number of dead insects was observed and the mortality rate was calculated. [Table] Example 7 Formulation Example 4 was prepared using a group of about 100 pyrethroid-resistant house fly adults (228e2b series) according to Camper's turn table method [Soap and Sanitary Chemicals Vol. 14 No. 6, page 119 (1938)].
The insects were sprayed with 5 ml of the oil obtained according to the above formulation, exposed to the descending spray for 10 minutes, and left to stand for 24 hours, after which the mortality rate was calculated. [Table] Example 8 A product obtained by the formulation of Formulation Example 6 using Camper's turn table method [Soap and Sanitary Chemicals Vol. 14 No. 6, p. 119 (1938)] using a group of about 100 adult houseflies. Oil agent 5
ml was sprayed, exposed to the falling spray for 10 minutes, and the rate of fallen insects after 30 minutes was calculated. [Table] [Table]

Claims (1)

[Claims] 1. General formula (In the formula, R ¹ and R ² are the same or different and represent a hydrogen atom, a halogen atom, a tert-butyl group, or a trifluoromethyl group, and R ¹ and R ² are 3,
A 4-methylenedioxy group may also be formed. A represents a methylene group or an oxygen atom. R ³ represents a methyl group or a hydrogen atom, and R ⁴ has 4 to 4 carbon atoms.
5 represents a linear or branched lower alkyl group or cyclohexyl group. n represents an integer of 5 to 9. ) Diolefinamides represented by 2 General formula (In the formula, R ¹ and R ² are the same or different and represent a hydrogen atom, a halogen atom, a tert-butyl group, or a trifluoromethyl group, and R ¹ and R ² are 3,
A 4-methylenedioxy group may also be formed. A represents a methylene group or an oxygen atom. R ³ represents a methyl group or a hydrogen atom, and n represents an integer of 5 to 9. ) or its reactive derivative and the general formula R ⁴ -NH ₂ (wherein R ⁴ represents a linear or branched lower alkyl group or cyclohexyl group having 4 to 5 carbon atoms). A general formula characterized by reacting with the amine represented by (In the formula, R ¹ , R ² , R ³ , R ⁴ , A and n have the same meanings as above.) A method for producing diolefinamides represented by the following. 3 General formula (In the formula, R ¹ and R ² are the same or different and represent a hydrogen atom, a halogen atom, a tert-butyl group, or a trifluoromethyl group, and R ¹ and R ² are 3,
A 4-methylenedioxy group may also be formed. A represents a methylene group or an oxygen atom. R ³ represents a methyl group or a hydrogen atom, and R ⁴ has 4 to 4 carbon atoms.
5 represents a linear or branched lower alkyl group or cyclohexyl group. n represents an integer of 5 to 9. ) An insecticide characterized by containing a diolefinamide represented by the following as an active ingredient.