JPH029868A - Pentadienone hydrazone - Google Patents

Abstract

NEW MATERIAL: A 1,5-bis(α,α,α-trifluoro-p-tolyl)-1,4-pentadien-3one(1,4,5,6- tetrahydro-2-pyrimidinyl)hydrazone compound of formula I.

USE: Useful as an insecticide. Effective to control insects, especially various lepidoptera, orthoptera, diptera and neuroptera. Sprayed in the form of a mixture with peanut butter, a residue left after juice is pressed out of an apple, wheat bran, corn or the like but is not hazardous to animals.

PREPARATION: As shown by the reaction formula, a diene is reacted with hydrazine in refluxing isopropanol to obtain a compound of formula I. After the reaction, the reaction mixture of stripped of the isopropanol and washed with an ether. The obtained yellow solid is agitated together with an ether and saturated sodium carbonate, and the ether layer is concentrated by drying.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 1,5-bis(α,α,α-trifluorop
-tolyl)-1,4-pentadien-3-one (1,4
.

5.6-Tetrahydro-2-pyrimidinyl)hydrazone. The present invention is based on our patent application filed in October 1982.
This invention relates to an invention that further develops the following invention described in the specification of No. 3513, and the above compound has an excellent insecticidal effect.

(Here, R+ and R2 are each hydrogen, halogen, CF
, , represents C0-C, alkyl, CI-C, alkoxy or C8-C4 alkylthio; R1 represents hydrogen or methyl, provided that when R1 is methyl, R1
and R2 shall also be methyl; R3 and R2 are hydrogen or O1-C, alkyl, and when both are bonded to each other, an alkylene group of 2 to 6 carbon atoms, an alkylene group of 2 to 4 carbon atoms, Dimethylalkylene group with 2 to 4 carbon atoms, whose carbon atoms are 11'i51
or two methyl or phenyl groups, or 1.
Optionally substituted with 2-cyclohexylene: and R
The present invention relates to a relatively broad class of pentagenon hydrazones represented by (6 is hydrogen or C, -C, alkoxy) and salts thereof, and a method for controlling insects using this compound as an active ingredient.

According to the invention, insects, in particular Lepidoptera, Orthoptera,
Control of Diptera and Orthoptera insects and protection of agricultural crops, trees, shrubs, and ornamental plants from attack by insects is achieved by applying an insecticidal effective amount of pentagenon hydrazone to crops or insect habitats or food sources. It was discovered that this can be achieved by In practice, generally about 0.28 kg/ha to 11.2 kg of pentagenon hydrazone
/ha, preferably 0.56-4.8 kg/ha
hectares 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 emulsifiable concentrate is about 12-29% by weight of pentagenonhydranone, T-Muαz
339 (sold by Thompson to Eward on Kansas City, Kansas) or a blend with a polyoxyethylene derivative and an alkylaryl sulfonate, about 8 to 12% by weight;
and cyclohexanone or = 1 river to 35°C (300 to 9
Mixed aniline point at 5°F), 0.8 at 60°/60°F
It can be prepared by mixing about 59-80% by weight of a highly aromatic solvent with a specific gravity of 80-1.5 and an aromatic content of 60-100%. These formulations provide 119.8-239.6 g/Q of active hydrazone and are generally diluted with water for application as dilute solutions. 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, emulsifiable concentrates are usually applied in equipment designed to disperse the liquid in the form of fine, discrete droplets having a mass media diameter of 25 to 150 microns.

A typical wettable powder formulation contains synthetic calcium silicate approximately 3
4% by weight, 12% by weight of a dispersing agent such as sodium lignosulfonate, 4% by weight of a wetting agent such as alkylaryl sulfonate and 50% by weight of pentagenone hydrazone.
It can be produced by grinding together. Such formulations are generally dispersed in water for application as a liquid spray.

The pentagenon hydrazones represented by the above formula are useful for controlling insects, particularly a variety of Lepidoptera, Orthoptera, Diptera, and Orthoptera.

The pentagenon hydrazone of the present invention is very effective in controlling insects of the order Orthoptera and Diptera, and also has an
Southern army worm [S podop
tera eridania (Cramer)]
, cabbage beetle [Trichoplusi]
a ni (Hfibner) 1, tobacco budworm [He1ioLhis Virescens (F ab
ricus)] and is particularly active and highly selective against lepidopteran larvae such as . They are not particularly toxic to many beneficial insects and are therefore useful in pest management and general control problems. Furthermore, the inventors have discovered that the compounds exhibit relatively low mammalian toxicity when ingested;
He also noted that it caused only slight irritation when inserted directly into the rabbit's eye. Moreover, these compounds exhibit virtually no phytotoxicity to plants at application rates of 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 mouth-bearing insects as well as insects with sucking mouth parts. They are particularly effective in controlling ants, insects belonging to the Formicidae family, including the southern fire ant, 5olenopsis xy
loni (xyloni), leaf cutting ant, ACROMYRMEX versicolor (
Argentina Ant IRIDO
M Y RE M E X humilis (May
r), Black Carpenter Ant CAMPONOTU
S pennsy Ivania (De Gerr),
Cornfield Ant, L A S I U S a
lienus (F oerster), Tetramorium caespitum, Uja Yellow Ant ACANTHOMYOPSint
erjectus (Mayr), Seaphant 5OL
EN OP S IS molesta(Say),
and Red Imported Fire Ant S ole
nopsis 1nvictaBlue ruen, and Black Imported Fire Ant 5olenopsi
It can be used to control firehunds such as S. 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 processed bait to collective settlements where it is consumed by female workers and young ants, and thus exterminated.

The bait can be prepared, for example, by mixing pentagenon hydrazone with peanut butter, citrus pulp, apple pomace, bran, corn flour and vegetable oil, such as soybean oil, and sprayed directly, or by applying this composition. It can be placed in soda straws on carriers such as 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 German cockroach poison bait test [Blatella G
27.7 g (0,075 mol) of ermgenone and 18,0g (0,075 mol) of hydrazine were allowed to react with each other in refluxing isopropanol for 3 to 4 hours. When the inglobanol is dissipated, a pale yellow solid remains.

Wash this thoroughly with ether. This yellow solid is stirred with 200 ml of ether and 50 mQ of saturated sodium carbonate. After 15 minutes, the ether layer is dried and concentrated to leave 25 g (72% of theory) of a bright yellow solid. Recrystallization of a small sample from -CH3/hexane gives a bright yellow solid with a melting point of 196-197°C.

Analysis: Calculated for N4F6CZ3H20: C,59,
24; H, 4, 29; N, l 2.02; Measured value: C
, 58, 55;
This stainless steel supports the bottom of the m glass. The basket has a 16-mesh copper wire screen lid.

100 mg, 25 mg and 6.25 m of technical grade compounds in 5 g of creamed peanut butter in plastic cups (inner dimensions, height 8 mm, diameter 30 mm)
g to final concentrations of 2.0%, 0.5% and 0.0%, respectively.
Set it to 125%.

Stir the mixture for 2 minutes each. 1 cup of treated bait and 5 gN cup of untreated laboratory food (the above is the choice bait), wick for feeding 100+N12 water,
and 20 adult male German cockroaches were placed in each cage. The cage was heated to approximately 27℃35% to measure the number of deaths.
It was held at R,H. The data obtained are reported in the table below.

Table 1 Evaluation of Pentagenone Hydrazone as an Insecticide Mortality Percentage Structure German Cockroach 11-day Mortality Percentage 2.0% 0.5% 0.125% l 00 l 00 Example 3 Test Method The test was carried out on plastics that can be treated with 3Qn+Q capacity. The test was carried out using a manufactured medical cup (inner diameter of the upper part: 40 mm, tapered toward the bottom, inner diameter of the bottom part: 32 mm, height: 38 mm). A hole (6 mm diameter) was drilled through the bottom of each cup and a layer of calcined ceracola and builder cement (mixing ratio 9:1) was poured into the bottom. The Ceracola mixture covers the holes and acts as a wick to wick water when the cup is placed over a water-saturated 18" foam pad. Place the cup on a tray to prevent water from evaporating too quickly from the 7 ohm pad. Cover with another tray that is inverted to hold water.The water is necessary to keep the humidity high in the cup, thereby preventing dehydration of the ants.Cement is added to create a stiff mixture, and through this mixture the ants are Make it impossible to dig a tunnel or escape.

Approximately 20 worker ants were collected from a group collected in the field at the start of the test.
They were admitted to their respective testing rooms 4 hours in advance. This pretreatment retention time allows the ants time to adapt to the container and recover from handling. Candidate chemicals were dissolved directly in food materials such as soybean oil. Ants on cotton gauze saturated with the material were given the toxic solution and placed in the test chamber in the lid of a small vial. Preliminary test is 1.0%, 0.1
and at a concentration of 0.01%.

Ants were fed as desired on this poisoned bait for 24 hours. After this period, the poison was removed from the chamber and the ants were left without food for an additional 24 hours. At the end of this time, a new vial cap containing cotton gauze saturated with soybean oil was placed in the chamber and left in place for the remainder of the test. Falls and deaths were counted at 112.3.6.8, IO and at 14 day intervals from first contact. 3 each test
Repeated times. Room temperature was 23.9±1.1°C (75±2
°F). The data obtained are reported in the following table.

Table 2 Evaluation of pentagenon hydrazone as an insecticide - Wataru j
Fraction Structure 14-day Mortality Percentage 1.0% 0.1% Example 4 The insecticidal activity of the compound of the present invention is demonstrated by the following test. In this test, pentagenone hydrazone is evaluated at a rate of 10 to 1000 ppm on the test insect species. The test method used for evaluation is as follows.

Test (A) Weigh 100 mg of test material into a funnel on a 113 g narrow neck bottle, rinse into the bottle with 35 mQ of acetone, then rinse with 1 scoop of water and 1 scoop of acetone to 11000 pp in 65% acetone. If the material does not dissolve, crush it with a glass rod and use it as a suspension.

(B) 300 ppm using this raw material solution (A)
Make a solution or pipette (A) 30 mQ (200 ppp) into a bottle containing 70 mQ of 50% acetone.
Make a suspension of m. Further dilutions in 50% acetone are made as needed.

(C) Tests requiring lOppm acetone solution:
(A) Pipette 1 mQ into 99m4 of acetone to 10 ppm. Additional dilutions are made using 50% acetone as needed.

Observe for any inhibition of initial test feeding or any type of interference with normal development.

Second Test I Soak a cotton seedling with two leaves spread into the 300 ppm solution for 3 seconds with stirring. 1 or 2 Pando arm eggs with about 50 to 1 oota, 0-24 hours old after being laid.
A 7 cm - 1.91 cm square cane plant is also dipped in the test solution and placed on the leaves of a cotton seedling, and the whole thing is placed in a 7-door to dry. The treated leaves with eggs of Paradouarm are removed from the seedlings and placed in a 226g Dequin cup containing 5cm of moist dental gauze and covered with a lid.

Place the other leaf in a similar cup filled with gauze and remove the newly developed larvae 5O-100 before covering the cup with a lid.
Add a piece of dried fish. 26.7
After 3 days at 80°F (°C) and 50% relative humidity, egg formation and death of newly established larvae, three cotton seedlings with newly expanded cotyledons were soaked in a 1000 ppm solution. 7-
Place it in a box to dry. When dry, each cotyledon was cut in half and 10 pieces were placed in a 28 g plastic medical cup containing 1.25 cm of dental gauze saturated with water, and one third instar budworm larva was placed in the cup. Add.

The number of deaths is counted after the cups are covered and kept at 26.7°C (80°F) and 50% relative humidity for 3 days.

Compounds that cause greater than 75% larval mortality are further tested.

Cabbage inchworm - Trichoplnsia nl (H
iJbner) - Leaves of 3rd year cotton seedlings are immersed in the test solution, stirred for 3 seconds, removed and dried in an exhaust hood. When dry, place the leaves in a 9.0 cm Petri dish with moist filter paper in the bottom. 10
Add a third instar larva and cover the dish. 26.7°C
After 3 days at (80°F) and 50±10% relative humidity, mortalities are counted. Compounds that kill 75% or more of the inchworms are further tested.

Southern Army Arm - [S podoptera
eridania (Cramer)] Neuvuarima bean seedlings, pruned with two primary leaves spread to 7.62-10.16 cm (3 to 4 inches), were immersed in the treatment solution for 3 seconds with agitation and then placed in a hood. dry. After the leaves are dry, cut them out and place each cut leaf in a 4-piece container with a piece of wet filter paper.
Place in an inch Petri dish and add 10 third instar Southern Army Warm larvae each having a length of 9.5 mm. Place the lid on the Petri dish at a temperature of 26,7°C (80°F) and a relative humidity of 5.
Place in a room maintained at 0% for 2 days. The number of deaths will be counted after 20 years.

After 7 days of treating the bean seedlings described above, the leaves are cut again and the test procedure is repeated. The number of armyworm deaths occurring in this test demonstrates the residual effects of the compound remaining on the treated leaves.

The data obtained are reported in the following table.

Claims (1)

[Claims] 1,5-bis(α,α,α-trifluoro-p-tolyl)-1,4-pentadiene-3- represented by the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ on(
1,4,5,6-tetrahydro-2-pyrimidinyl)hydrazone compound.