JPS6216921B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has the following structural formula (In the formula, R ₁ and R ₂ are hydrogen, halogen,
_CF3 represents a _C1 - _C4 alkyl group, a _C1 - _C4 alkoxy group or a _C1 - _C4 alkylthio group; _R3 is hydrogen or a methyl group, provided that when _R3 is a methyl group, _R1 and R ₂ is also a methyl group; R ₄
and R ₅ is hydrogen or a C ₁ -C ₄ alkyl group,
And when they jointly, R ₄ and R ₅ are
constitutes a C ₂ -C ₆ alkylene group, a C ₂ -C ₄ alkylene group substituted with 1 or 2 methyl or phenyl, or a 1,2-cyclohexylene group; and R ₆ is hydrogen or C ₁ - By contacting insects and/or applying to their habitat or food, an insecticidal effective amount of pentadienone hydrazone or its salt having a _C4 alkyl group is used to kill insects, specifically lepidopteran insects, directly This invention relates to a method for controlling insects of the order Ptera, insects of the order Diptera and insects of the order Hymenoptera. The present invention also provides a novel compound 1,5-bis(α・
α・α-trifluoro-p-tolyl)-1・4-
Relating to pentadien-3-one (1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinyl)hydrazone. The present invention also relates to a method for protecting agricultural crops, trees, shrubs, ornamental plants, etc. from insect attack by applying to the crops an insecticidal effective amount of a compound having the above structure. Pentadien-3-one-substituted amide hydrazones are used as antimalarial and antituberculous agents in mixed-breed animals.
Further, its manufacturing method is described in US Pat. No. 3,878,201 (1975). Compounds used in the insect control method of the present invention are described in the above specification. Preferred compounds for use as insecticides and protectants for crops are those in which R ₁ and R ₂ represent the same substituent, and the substituents are H, Cl, Br, CF ₃ , C ₁ -
C ₃ alkyl, methoxy or methylthio;
R ₃ is hydrogen; R ₄ and R ₅ are each hydrogen,
Representing a _C1 - _C3 alkyl group, a _C2 - _C6 alkylene group, or a methyl, dimethyl or phenyl _C2 - _C4 alkylene group; compounds having the above structural formula in which _R6 is hydrogen, and acid addition salts thereof , preferably hydrochloride, hydrobromide or hydroiodide. Even more preferred compounds are those in which R ₁ and R ₂ are each p-chloro or p-CF ₃ ; R ₃ and R ₆ are each hydrogen; and R ₄ and R ₅ are jointly
C ₂ -C ₆ alkylene group or methyl, dimethyl or phenyl C ₂ -C ₄ alkylene group; the above compounds in which R ₆ is hydrogen and acid addition salts thereof, preferably hydrochloride, hydrobromide or iodide; It is a hydrogen salt. Still more preferred compounds are those in which R ₁ and R ₂ are each p-chloro or p-CF ₃ ; R ₃ and R ₆ are each hydrogen; and R ₄ and R ₅ are jointly C ₂ -C ₆ alkylene group or methyl, dimethyl or phenyl C ₂ -C ₄ alkylene group, and acid addition salts thereof. According to the invention, the control of insects, in particular Lepidoptera, Orthoptera, Diptera and Hymenoptera, and the protection of agricultural crops, trees, shrubs and ornamental plants from attack by insects is achieved. It has been found that this can be achieved by applying insecticidal effective amounts of pentadienone hydrazone to crops or insect habitats or food sources. In practice, generally about 0.28 Kg/ha to 11.2 Kg/ha of pentadienone hydrazone, preferably 0.56 to 4.8 Kg/ha, are effective for insect control and/or crop protection. The hydrazone of the present invention can be applied in either liquid or solid form. They may be in solid form as powders or thick powders, or in liquid form as emulsifiable concentrates that are free-flowing liquids, or wettable powders that are dispersed in water or other inexpensive liquids for application as a fine spray. It can be used as A typical emulsifying concentrate is about 12-29% by weight pentadienone hydrazone, a blend of nonionic emulsifiers such as T-Mulz 339 (sold by Thompson Hayward of Kansas City, Kansas) or polyoxyethylene. Derivatives and blends with alkylaryl sulfonates from about 8 to 12
Weight%, and cyclohexanone or -1.1°~35
Mixed aniline point of °C (30~95〓), at 60゜/60〓
It can be prepared by mixing about 59-80% by weight of a highly aromatic solvent with a specific gravity of 0.880-1.5 and an aromatics content of 60-100%. These formulations provide 119.8-239.6 g/g of active hydrazone and are generally diluted with water for application as a dilute solution. However, the formulations can also be applied in the form of undiluted discrete droplets as a low-volume or ultra-low-volume spray.
For such applications emulsifying concentrates are usually 25 to 150
It is applied in equipment designed to disperse the liquid into fine discrete droplet shapes with a mass media diameter of microns. A typical wetting powder formulation contains about 34% by weight synthetic calcium silicate, 12% by weight a dispersing agent such as sodium lignosulfonate, 4% by weight a wetting agent such as an alkylaryl sulfonate, and 50% by weight pentadienone hydrazone. It can be produced by grinding together % by weight. Such formulations are generally dispersed in water for application as a liquid spray. The pentadienone hydrazones represented by the above formula are useful for controlling insects, particularly a variety of Lepidoptera, Orthoptera, Diptera, and Hymenoptera. The pentadienone hydrazone of the present invention is very effective in controlling insects of the order Orthoptera and Diptera, and
Southern armyworm [Spodoptera eridania (Cramer)], cabbage beetle [Trichoplusia ni (Hu¨bner)],
Tobacco budworm (Heliothis Virescens)
(Fabricus)], Gypsy moth (Porthetria dispar)
It is particularly active and highly selective against lepidopteran larvae such as (L.)]. They are not particularly toxic to many beneficial insects and are therefore useful in pest management and general control problems. Furthermore, the inventors have observed that the compound exhibits relatively low mammalian toxicity when ingested and is only slightly irritating when inserted directly into the eyes of rabbits. Moreover, these compounds show virtually no phytotoxicity to plants at application rates up to 11.2 Kg/ha. Advantageously, the pentadien-3-one hydrazone compounds of the present invention are active as gastrotoxic agents and are therefore effective against chewing mouth insects as well as sucking mouth insects. They are particularly effective in the control of ants, insects belonging to the family Formicidae, including the Southern Fire Ant, Solenopsis xyloni (xyloni), Leaf Cutting Ant, ACROMYRMEX versicolor
(Pergande), Argentine Ant
IRIDOMYREMEX humilis (Mayr), Black Carpenter Ant CAMPONOTUS pennsylvania
(De Geer), Cornfield Ant, LASIUS
alienus (Foerster)
TETRAMORIUM caespitum, Rajya Yellow Ant ACANTHOMYOPS interjectus
(Mayr), Thief Ant SOLENOPSIS molesta
(Say), and Red Imported Factory Ant Solenopsis invicta Bruen, and Black Imported Factory Ant Solenopsis
It can be used to control ferrets such as saevissima richteri. These ants are serious economic pests commonly found in hot areas such as subtropical and tropical regions. They feed on seeds and the soft stems of young seedlings and are responsible for causing significant damage to agricultural crops each year. They are known to attack humans, nesting birds, livestock, poultry, and indoor pets as well. It is therefore highly desirable to control these economic pests. Control of these pests can be accomplished with treated baits that are applied to crop areas, pastures, parks, or other areas where ant control is desired and made available to worker ants. Worker ants carry the treated bait to the colony, where it is consumed by the queen and young ants and thus exterminated. The bait can be prepared, for example, by mixing pentadienone hydrazone with peanut butter, citrus pulp, apple pomace, bran, cornmeal-sugar and a vegetable oil such as soybean oil, and can be sprayed as is. The compositions can be placed in soda straws on carriers such as coarse corn, clay, pumice, synthetic polymer compositions, etc. and distributed over populated areas. The use of these baits is particularly advantageous since this method of application often poses little or no risk to the animals that may frequent the crop area. The following examples illustrate the invention. Example 1 The insecticidal activity of the compounds of the invention is demonstrated by the following test. In this test, pentadienone hydrazone is evaluated against the test insect species at a rate of 10 to 1000 ppm. The test formulations and procedures used for evaluation are as follows. Test Formulation A Weigh 100 mg of the test substance, place it in a funnel on a 113 g narrow-mouth bottle, pour 1 tablespoon of acetone (35 mL), then 1 tablespoon of water, and then 1 tablespoon of acetone into the bottle.65
Produces 1000ppm in % acetone. If the substance is not soluble, grind it with a glass rod and use it as a suspension. B By pipetting 30 ml of this solution "A" into a bottle containing 70 ml of 50% acetone.
A 300ppm solution or suspension can be made. Make further dilutions in 50% acetone if necessary. C Test requiring 10 ppm acetone solution: Pipetting 1 ml of "A" into 99 ml of acetone yields 10 ppm. Further dilute with 50% acetone if necessary. Initial Tests Tobacco Budworm - Heliothis virescens
(Fabricus) Immerse a cotton seedling with two true leaves in a 300ppm solution for 3 seconds while stirring. Also about 50-100
1.27 with budworm eggs (0-24 hours old)
Dip a ~1.91 cm square piece of cheesecloth into the test solution;
Place it on top of one leaf of the cotton seedling and put everything in a hood to dry. Remove the treated leaves with budworm eggs from the seedlings, along with a 5cm piece of wet dental gauze.
Place in a 226g cup and cover with a lid. The other leaves are placed in a similar cup with gauze and a piece of cheesecloth infected with 50-100 newly hatched larvae is added before the cup is covered. 26.7℃ (80〓),
Observe egg hatching after 3 days at 50% rh, as well as death of newly hatched larvae, any inhibition of feeding or any kind of disturbance of normal development. Southern armyworm - Spodoptera eridania
(Cramer) Sieva lima bean seedlings with primary leaves that have expanded to just 1.91 cm are soaked in 1000 ppm "A" solution for 3 seconds while stirring and placed in a hood to dry. One leaf is then placed in a 9 cm Petri dish with wet paper in the bottom and 10 third instar armyworm larvae approximately 1 cm long. cover the plate
Maintain at 26.7℃ (80〓) and 50% rh. After 2 days, the number of deaths was counted and the amount of food eaten was evaluated. Partial death and/or
Compounds that exhibit feeding inhibition are retained for an additional number of days for further observation. Substances that cause mortality of 75% or more or show only traces of feeding damage should be further tested. All the compounds exhibiting the activity identified above were extracted from the original treatment using the second leaves on legumes.
After a day of storage, retest to determine residual activity. Secondary test Tobacco budworm - Heliothis virescens
(Fabricus) 3rd instar Three cotton seedlings whose cotyledons have just expanded.
Soak in 1000ppm solution and place in hood to dry. When dry, cut each cotyledon in half and place 10 pieces into a 28 g plastic medical cup containing 1.25 cm of water-saturated dental gauze and one third instar budworm larva. Cover the cup and heat to 26.7℃ (80℃).
〓), the number of deaths was counted after keeping at 50% rh for 3 days. Compounds that kill more than 75% of larvae are further tested. Cabbage Trichoplusia ni (H
u¨bner) 3rd instar The true leaves of cotton seedlings are immersed in the test solution, stirred for 3 seconds, taken out and dried in an exhaust hood. When dry, place the leaves in a 9.0 cm Petri dish with wet paper on the bottom. Add 10 third instar larvae and cover the dish. Count the number of deaths after 3 days at 26.7℃ (80〓) and 50±10% rh. Compounds that kill more than 75% of the brown beetles will be further tested. The data obtained are shown in Table 1. R in Table 1 indicates a decrease in food intake. Food intake was evaluated not only in the initial test but also in the secondary test.

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[Table] Red Imported Factory Ant
[Solenopsis invicta (Buren)] Red imported fiber obtained outdoors in natural state [Solenopsis invicta
(Buren)] was used for screening imported factories. Approximately 0.5 cubic feet of active anthills were placed in plastic tubes (13″ x 13″ x 8″) and placed in the laboratory for 3 days before use. The top 3 inches inside the tube was dusted with talc to prevent ants from escaping. Water was added to the mounds as needed both before and after treatment to keep them from becoming too dry.The compounds were dispersed in soybean oil and started at low concentrations of approximately 0.05%.Concentrations were increased in various increments. The compound increased to approximately 1.0% at low concentrations to determine whether the compound was palatable to ants. Approximately 7.5 g of soybean oil containing the toxin was poured onto a blob of absorbent cotton in a 3 oz. The sides of the jikucaps were located above the top of the mound. Three tubes were usually used per concentration. Mortality were counted and/or valued 6 weeks after treatment, or longer if approved. The temperature of the holding chamber is approximately 26℃ and the relative humidity is approximately 50%.
It was hot. The data obtained are shown in Tables 2 and 3.

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[Table] Example 2 The insecticidal activity of the compounds of the present invention was further demonstrated in the following test.
Rated as toxic to the tested insect species at a rate of 1000 ppm. The formulations tested and the evaluation procedure are as follows. Test Blattella germanica
(Linnaeus)] A 1,5-bis(α・α・α-trifluoro-
p-tolyl)-1,4-pentadien-3-one, 4,5,6,7-tetrahydro-1H-
1,3-Diazepin-2-ylhydrazone 11.0
mg was added to 11.0 g of creamed peanut butter and mixed thoroughly. This corresponds to a concentration of approximately 0.1% or 1000 ppm. B 1.0 g of A was added to 9.0 g of peanut butter and mixed thoroughly. This corresponds to 0.01% or 100ppm. C. 5.0 g of peanut butter was used as a control. Approximately 5.0 g of bait was placed in a plastic cup measuring 3 cm x 1 cm high. A plastic cup filled with bait and gauze moistened with water is 8 inches in diameter and 2.5 inches thick.
placed in an inch cage. The bottom of the cage was an 8 inch diameter glass plate overlying a half inch rim extending inward from the stainless steel sides. Twenty male adult Ziyaman cockroaches were placed in each cage. The cage was covered with a 16-mesh copper wire mesh lid. The cage was kept at approximately 27°C. The results are shown in the table.

TABLE Test Housefly (Musca domestica Linnaeus) 1 400 g sugar and 400 g powdered milk were thoroughly mixed in a 1 gallon ice cream carton. A 1,5-bis(α,α,α-trifluoro-p-tolyl)-1,4-pentadiene-3
-one, 4,5,6,7-tetrahydro-
222.2 mg of 1H-1.3-diazepin-2-yl-hydrazone with 90% purity was added to 200.0 g of #1 and thoroughly mixed. This is 0.1% or
Equivalent to a concentration of 1000ppm. 30.0 g of B A was added to 70 g of #1 and mixed well. Concentration = 0.03% or 300 ppm 10.0 g of C A was added to 90 g of #1 and mixed well. Concentration = 0.01% or 100 pmm 3.0 g of D A was added to 97 g of #1 and mixed well. Concentration = 0.003% or 30 ppm E Control was only #1. 50 g of dry food in the bottom of a 9.0 cm Petri dish was placed in each house fly cage. each cage,
The cages, 12" x 12" x 12", were made of 16 mesh copper wire mesh supported by a wooden frame. 100 housefly pupae and water gauze were placed in each cage. The cages were maintained at 28±2°C. Flies appeared within 2-3 days.The results are shown in the table below.

Table: Example 3 The insecticidal activity of the compounds of the invention is demonstrated in the following test. In this test, pentadienone hydrazone is evaluated against the test insect species at a rate of 10 to 1000 ppm. The test formulations and procedures used for evaluation are as follows. Test Formulation A Weigh 100 mg of the test substance, place it in a funnel over a 113 g narrow-mouth bottle, add 1 tablespoon of acetone, 35 mL, then add 1 tablespoon of water.
Pour into the bottle with 1 tablespoon of acetone and 1 tablespoon of acetone.
Produces 1000ppm in 65% acetone. If the substance is not soluble, grind it with a glass rod and use it as a suspension. B Using this stock solution "A", pipette 30 ml of "A" into a bottle containing 70 ml of 50% acetone.
Make a 300 ppm solution or suspension by producing 300 ppm. Additional 50% if required
Dilute in acetone. C Test "A" requiring a 10 ppm acetone solution 1 ml pipetted into 99 ml acetone yields 10 ppm. Further dilute with 50% acetone if necessary. Initial test Tobacco budworm (Heliothis virescens)
(Fabricus)] A cotton seedling with two expanded true leaves is immersed in the 300 ppm solution for 3 seconds while stirring. Also about 50
A 1.27-1.91 cm square of cheesecloth with ~100 budworm eggs (0-24 hours old) is soaked in the test solution, placed on one leaf of a cotton plant, and everything is placed in a hood to dry. Remove the treated leaves with budworm eggs from the plant and apply 5 cm of wet dental gauze.
Place the pieces in a 226g cup and cover with a lid. Place the other leaves in a similar cup with gauze and add a piece of cheesecloth infected with 50-100 newly hatched larvae before covering the cup.
Eggs hatch after 3 times at approximately 26.7℃ (80〓) and 50%RH,
Also observe the death of newly hatched larvae, any inhibition of feeding or any kind of disturbance of normal development. Secondary test Tobacco budworm [Heliothis virescens]
(Fabricus) 3rd instar Three cotton seedlings whose cotyledons have just expanded.
Soak in 1000ppm solution and place in hood to dry. Cut each cotyledon in half when dry and place 10 pieces of each in a 1.25 cm piece of water-saturated dental gauze.
Place one 3rd instar budworm larva in a plastic medical cup. Cover the cup and approx.
The number of deaths was counted after keeping at 26.7℃ (80〓) and 50% rh for 3 days. Compounds that kill more than 75% of larvae are further tested. Cabbage beetle [Trichoplusia ni (H
u¨bner)] 3rd instar Immerse the true leaves of cotton seedlings in the test solution, stir for 3 seconds, remove and dry in an exhaust hood. When dry, place the leaves in a 9.0 cm Petri dish with wet paper on the bottom. Add 10 third instar larvae and cover the dish. Count the number of deaths after 3 days at approximately 26.7℃ (80〓) and 50±10% rh. Compounds that kill more than 75% of the brown beetles will be further tested. The data obtained are shown in the table.

[Table] Production Example 1・5-bis(α・α・α-trifluoro-p
-Tolyl)-1,4-pentadien-3-one (1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinyl)-hydrazone production 5,5-dimethyl in 6 ml of absolute ethanol
1,4,5,6-tetrahydropyridinium-2
-ylhydrazine hydroiodide 2.1g and 1.5
- to a mixture of bis(α・α・α-trifluoro-p-tolyl)-1,4-pentadiene-3-one.
One drop of 47% hydroiodic acid was added. The mixture was heated at reflux for 2-3 hours and then cooled in ice. The precipitated yellow hydroiodide salt was collected by filtration and washed with ethanol. Hydroiodide to ethyl acetate 15
ml and 15 ml of saturated sodium carbonate solution. The ethyl acetate mixture was separated from the aqueous phase, dried over magnesium sulfate, and concentrated to give a red oil. The oil was mixed with a small amount of ether and the mixture was frozen. The resulting solid was collected and washed with ether, weighing 1.2 g. Melting point 163.5~
164.5℃. Analysis: Calculated value for C ₂₅ H ₂₄ F ₆ N ₄ , C, 60.72; H,
4.89; N, 11.33. Measured value C, 60.54; H, 4.73;
N, 10.43. The product exists in different crystalline forms and when recrystallized from isopropyl alcohol 189~
It has a melting point of 191°C.

Claims (1)

[Claims] 1 formula (In the formula, R ₁ and R ₂ are hydrogen, halogen,
_CF3 , _C1 - _C4 alkyl, C1 _{- C3} alkoxy or
represents _C1 - _C4 alkylthio; _R3 is hydrogen or a methyl group, provided that when R3 is a methyl group, _{R1 and R2} are also methyl groups; _R4 and _R5
is hydrogen or a C ₁ -C ₄ alkyl group, or together they are substituted with a C ₂ -C ₆ alkylene group, one or two methyl or phenyl groups
is a _C2 - _C4 alkylene group or a 1,2-cyclohexylene group; and _R6 is hydrogen or _C1 - _C4
an insecticidal effective amount of a compound having (alkyl) or a salt thereof,
A method of controlling insects that involves contact with their habitat and/or their food. 2 R ₁ and R ₂ are the same substituent and each is H, Cl, Br, CF ₃ , C ₁ -C ₃ alkyl, methoxy or methylthio; R ₃ is hydrogen; R ₄
and R ₅ are each hydrogen or C ₁ -C ₃ alkyl,
or together they are C ₂ -C ₆ alkylene or methyl-, dimethyl- or phenyl-
_C2 - _C4 alkylene; _R6 is hydrogen; or an acid addition salt thereof Claim 1
Control methods listed in section. 3. The pest control method according to claim 2, wherein the acid addition hydrochloric acid is a salt of hydrobromic acid or hydroiodic acid. 4 R ₁ and R ₂ are each p-chloro or p-
CF ₃ ; R ₃ and R ₆ are each hydrogen; and R ₄ and R ₆ taken together are C ₂ -C ₆ alkylene. . 5 The compound is 1,5-bis(α・α・α-trifluoro-p-tolyl)-1,4pentadiene-3
-one, (1,4,5,6-tetrahydro-5,
5-dimethyl-2-pyrimidinyl)hydrazone.The method of controlling the pest according to claim 1. 6 The compound is 1,5-bis(α・α・αtrifluoro-p-tolyl)-1,4-pentadiene-3
-one, 4,5,6,7-tetrahydro-1H-
The pest control method according to claim 1, which is 1,3-diazepin-2-yl-hydrazone or an acid addition salt thereof. 7 Claim 1, wherein the compound is 1,5-bis(p-chlorophenyl)-1,4-pentadien-3-one, 4-phenyl-2-imidazolin-2-yl-hydrazone, or an acid addition salt thereof
Control methods listed in section. 8 The compound is 1,5-bis(p-chlorophenyl)-1,4-pentadien-3-one, 4.
The pest control method according to claim 1, which is 5,6,7-tetrahydro-1H-1,3-diazepin-2-yl-hydrazone or an acid addition salt thereof. 9 The compound is 1,5-bis(p-chlorophenyl)-1,4-pentadien-3-one, 3α.
4,5,6,7α-hexahydrobenzimidazol-2-yl-hydrazone or an acid addition salt thereof, the pest control method according to claim 1. 10 The compound is 1,5-bis(p-chlorophenyl)-1,4-pentadien-3-one, 1.
4,5,6-tetrahydro-5,5-dimethyl-
2-pyrimidinyl) hydrazone or an acid addition salt thereof. 11 The compound is 1,5-bis(p-chlorophenyl)-1,4-pentadien-3-one, 4,4
-Dimethyl-2-imidazolin-2-ylhydrazone or an acid addition salt thereof.The pest control method according to claim 1. 12 The compound is 1,4-pentadien-3-one, 1,5-bis(p-chlorophenyl)-, 5
-Methyl-2-imidazolin-2-ylhydrazone, hydrochloride, the pest control method according to claim 1. 13 The compound is 1,4-pentadien-3-one, 1,5-bis(p-chlorophenyl)-, (4
-phenyl-2-imidazolin-2-yl)hydrazone, or an acid addition salt thereof. 14 The compound is 1,4-pentadien-3-one, 1,5-bis(α・α・α-trifluoro-
The pest control method according to claim 1, which is p-tolyl)-, (1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinyl)hydrazone. 15. According to any one of claims 1 to 14, wherein the insect is a Lepidoptera, Orthoptera, Diptera, or Hymenoptera insect, and the compound is applied at a rate of 0.28 to 11.2 kg/ha. control method. 16 Compounds range from 0.50Kg/ha to 4.8Kg/ha
A pest control method according to claim 15 applied on a hectare basis.