JPH0635365B2 - How to control insects - Google Patents

Description

Detailed Description of the Prior Art Finding pesticides that are effective against a wide range of pests and are safe to use in agricultural and pasture areas has long been a challenge. One of these areas of concern is the control of ants and related insects, especially those that cause harm, such as the clams {eg Solenopsis Invicta (Sol
eonopsis invicta)}, which stings humans and livestock and feeds on germinated and growing seeds of cereals, thereby reducing yields and damaging their anthill impacting equipment. . The following points are characteristic of the necessary conditions for a pesticide composition effective for controlling the clams. (1) Do not repel ants, (2) be able to easily transfer from one ant to another, (3) show delayed toxicity. Repellents can reduce or counteract the toxic effects of ants in avoiding bait treated with the drug. Treated baits need to be able to be carried into nests or transferred by trophic transformation, and their toxicity must be delayed because soldier ants make up only a few percent of an ant population. And it must remain long enough to transmit its toxicity to the main population population, especially the queen ants. The pesticide composition is such that the active ingredient is diluted during trophic transformation [Banks et al. ARS-S169, 19
[October 1977] Therefore, it is preferable that the drug exhibits delayed-effect toxicity over a wide range of pesticide concentrations. Currently the only commercially available pesticide (Amdro, US Pat. No. 4,152,436
No.) is Solenopsis invict
a), halarids such as Solenopsis xyloni (S. xyloni), Solenopsis sichteri (S. richteri), and Pheidol megacephala (Pheidole megacepha)
la) and Iridomyrmex Fumilis (Iridomyrme
x humilis) are registered as baits for outdoor control of other ants, including Andro is also effective against lepidopteran larvae. However, it cannot be applied to food crops. Insecticide Mirex
(Millex) (U.S. Pat. No. 3,220,921) is also known to be effective against Hariari, but it is no longer registered as a practical product.

SUMMARY OF THE INVENTION We have found methods and compositions for controlling arthropod populations including ants, cockroaches, flies, mosquitoes and termites. The method is an effective amount of the toxic substance RfSO ₂ A of the following formula (wherein Rf is a fluorinated aliphatic group having up to 20 carbon atoms, and A represents a residue capable of being structured) or the toxic substance The pest is treated with the agriculturally acceptable salt of. The composition according to the invention comprises one or more bait ingredients of the abovementioned toxic substances.

The fluorinated aliphatic, Rf, is a fluorinated monovalent component, straight chain, branched chain and their combinations, such as cyclic or alkylcycloaliphatic groups, if sufficiently large. It may be a group. The backbone chain may contain heteroatoms such as chain oxygen and / or trivalent nitrogen bound only to carbon atoms, such heteroatoms providing a stable bond between the fluorocarbon groups, It does not interfere with the chemically inert character of the Rf group. Rf can have a large number of carbon atoms, but compounds with Rf of 20 or less carbon atoms are suitable and preferred, since larger groups are usually possible with smaller Rf groups. This is because it shows a lower efficacy. Generally, Rf can have up to 20 carbon atoms, with 5 to about 12 being preferred.
The end of the Rf group preferably has at least 3 all-fluorinated carbon atoms, eg CF ₃ CF ₂ CF ₂ —, where Rf is a perfluoroalkyl, C _n F _{2n + 1} Compounds in which all or substantially all Rf groups are fluorinated are preferred compounds.

In the above formula, A is a structurally consistent residual (ie,
A group capable of bonding to a SO ₂ group) and containing the groups: NR ₁ R ₂ and OR ₄ , wherein R ₁ and R ₂ are hydrogen, alkyl, alkenyl, alkynyl, aryl, aralkyl,
Aroyl, acyl, cycloalkyl, cycloalkenyl, cycloalkynyl; heterocycle containing an atom selected from the group consisting of carbon, nitrogen, sulfur or oxygen; hydroxyalkyl, haloalkyl, aminoalkyl, carboxyalkyl salt, ester, amide or structure Formula: − (C _x H _{2x
O) n (C y H 2y} O) m R 3 ( wherein, n + m = 1~20, x and y are 1
~ 4, R ₃ is selected from the same group as R ₁ and R ₂ ) and R ₄ is hydrogen, aryl, heterocycle or alkaline earth, alkali metal, organic amine or ammonium. It is a cation]. The formula: NR ₁ R ₂ also includes groups in which N, R ₁ , R ₂ are atoms selected from the group consisting of carbon, nitrogen, sulfur or oxygen taken together to form a ring.

The salts of the present invention are generally metal, ammonium or organic amine and quaternary amine salts and can be prepared by treating the acid form of the compound with a suitable base under mild conditions. The metal salts of the present invention include salts of alkali metals (eg lithium, sodium and potassium), alkaline earth metals (eg barium, calcium and magnesium) and heavy metals (eg zinc and iron) and metal salts such as aluminum. Is included as well. Suitable bases for the production of metal salts are metal oxides, hydroxides, carbonates,
Bicarbonates and alkoxides. Some salts can also be prepared by cation exchange reactions (by reacting an organic or inorganic salt with a salt of the invention in a cation exchange reaction). Organic amine salts include salts of aliphatic (eg alkyl), aromatic and heterocyclic amines, as well as mixtures of these structures. The amines useful in preparing the salts of the present invention are primary, secondary or tertiary, with those having 20 or less carbon atoms being preferred. For example, such amines include morpholine, methyl cyclohexyl amine, glucosamine, amines derived from fatty acids, and others. Amine and ammonium salts can be prepared by reacting an acid compound with a suitable organic base or ammonium hydroxide. Any of the types of salts mentioned above are agriculturally satisfactory and are selected based on the particular application and economy. Of particular interest are alkali metal, alkaline earth, ammonium and amine salts.

The salts of the present invention are often formed by reacting the precursor in aqueous solution. The solution can be distilled off to obtain the salt of the compound, usually as a dry powder. In some cases,
It is more convenient to use alcohol, acetone or other non-aqueous solvent. The resulting solution is then used to formulate the composition by removing the solvent, for example by evaporation under reduced pressure.

These pesticides suitable for use in the present invention meet the above-mentioned requirements for controlling clams and, in addition, have very low toxicity to mammals. This is also valid for other arthropods.

DETAILED DESCRIPTION OF THE INVENTION The arthropod pests are treated according to the present invention in any method known in the art compatible with the use of the toxic compounds and mixtures described above. Suitable treatment methods include spraying solutions, suspensions and dispersions of the toxicants into sprays, and optionally collectors using pheromone attractants and the like, or for spreading near nests or on agricultural land. For example, it may be in the form of food.

The substances suitable according to the invention must be effective against at least one arthropod. However, there are factors that affect the efficacy of a particular substance depending on the particular insect and the particular treatment method. These elements include the following.

1. Odor repellency 2. Taste repellency 3. Solubility in solvents and carriers such as bait 4. Enzyme effects 5. Decomposing ants by atmospheric oxygen, UV irradiation and similar effects, especially abroad When the present invention is used for the control of Hariari coming in from, it is preferable to produce a bait into which a toxic substance can be introduced. It is understood by those skilled in the art that the term "bait" is a substance that attracts insects to ingest toxic substances. Suitable baits include edible oils, fats, plant seed meals, meat by-products such as blood, fish meal, sugar concentrates, honey, sucrose and other sugars, peanut butter, grains and the like. (See US Pat. No. 3,220,921). Suitable baits for clams are edible oils (as solvents for toxic compounds) and mixtures with corn cobs, granule carriers such as pregel defatted corn grits and the like. Is. These soaked baits easily fall to the ground when they are sprinkled with a ground coater to where the ants are feeding. When found by an ant, it is carried to a nest where the poison is ingested and distributed by the working and queen ants.

The compounds of the present invention are known. However, it was not known to be useful as a pesticide. Disclosures relating to their manufacture can be found in the following U.S. Patents: 2,003,615 2,346,612 2,732,378 2,759,019 2,803,656 2,915,554 3,398,182 3. , 787, 351 and 4,424, 178 The tests in the following examples show the effectiveness of the invention but are not intended to limit the scope of the invention as claimed. All percentages and parts are by weight unless otherwise stated.

Compounds that exhibit significantly greater mortality to the clams than the non-toxic diets are considered effective for the purposes of the present invention. Using the preferred toxicants, mortality of less than 15% at 24 hours, 50% or more at the end of the test, and 85% or more in the most preferred case. Also preferred compounds are those that exhibit a delayed toxicity of at least 1 between the maximum and minimum doses.
There should be 0 times the difference.

Example 1 Each compound for investigating toxicity to Hari is 20 worker ants [Solenopsis invicta]
Were tested in triplicate in a 30 ml cup for 14 days. A cotton swab soaked with soybean oil containing 1.0% of the test compound was given to the ants in the cup for 24 hours. The swab was removed and the ants were left without food for 24 hours. A cotton swab soaked with soybean oil only was placed in the cup and left there for the remainder of the test period. Mortality figures were recorded for the test compound and the standard ant pesticide. See Table 1.

Note that among the compounds listed in Table 1, compound No. 107
21, 10722, 10723, 10735, 1073
7,10738,10739,10740,1075
The compounds of 1,10752, 10753 and 10754 are not the compounds used in the composition of the present invention but the compounds for comparison.

Example 2 Some of the compounds tested in Example 1 were 0.01
Retested as in Example 1 at concentrations of 0.1%, 0.10% and 1.0%. See Table 2.

Example 3 Of the compounds listed in Table 1, compounds that are not readily soluble in soybean oil were used in a ratio of 1: 1 soybean oil honey and water.
Retested in the same manner as Example 1 except that the mixture was replaced with See Table 3.

Example 4 Some of the better compounds than in Example 2 were tested on the experimental population of Haryali (2 populations).

The population consists of queen ants, eggs, larvae, pupae and over 40,000 worker ants. The test compound was dissolved in soybean oil at a concentration of 1.0% and soaked in pregel-defatted ground corn so that the ground corn contained a 30% soybean oil mixture. Therefore, the test compound is 0.30% of the total diet weight.

Five grams of food were fed to each population for 4 days. The diet was then removed and fed a standard diet consisting of a 1: 1 honey-water mixture, boiled eggs and frozen fly pupae and cockroaches for the remainder of the study. The two populations were fed with toxin-free diets as controls. Observations on queen and worker ant status were recorded in Table 4. QD of the final state of the group
(Queen ant death) or CN (normal population). See Table 4.

Example 5 Fly diet (6 parts sugar, 6 parts powdered dry skim milk) containing 1% of the test compound after emergence to adult male and female house flies [Musca domestica] from insecticide-resistant laboratory lines. And 1 part egg yolk powder). The bait is a solution or suspension of the test compound in a volatile solvent in 10 g of fly feed in a small container.
It was prepared by adding 0 ml. The solvent was allowed to evaporate in 4-6 hours and the treated fly feed was pulverized again. A container of treated feed and a container of water were placed in a basket of 100 freshly emerged adult flies. Mortality in two replicates was determined after 3 days and compared to the results of the untreated fly diet. See Table 5.

Some of the above compounds may be more effective than indicated by the data. If the solubility is sufficient in the soybean oil or honey-water composition, the toxic concentration will not reach the required level. A large number of compounds that have shown poor efficacy may show high potency in other formulations.

Example 6 Compounds 29757, 29758 and 29759 (see Table 1 for structure) are each dissolved in soybean oil at a concentration of 1%. The bait was prepared by impregnating pregel defatted ground corn so that the ground corn mixture contained 30% soybean oil mixture and 0.3% test compound. Compound 29759 was also used at a 2.5% concentration, which would result in 0.75% of the total diet weight.

The treated bait was tracted by a tractor at a concentration of 1 pound per acre into an open-air compartment containing many vibrant Hariari mounds. The other compartment containing the haliari mound was treated in a similar manner with untreated pregel resin ground corn and ground corn insecticide treated ground corn as controls. The result is DP Harlan,
Southwestern Entomologist (S
outhwest Entomologist), vol. 6, pages 150-157, 1981. See Table 6,

Example 7 Compounds 29756, 29757, 29759 and 29
778 was used to treat an Orlando standard population of American cockroaches [Periplaneta americana]. Each group is GS Burden
By Pest Control, Vol. 48, pp. 22-24, 1980, containing 10 adult mixed sexes of the same sex. 2.0% of the above compounds or standard cockroach insecticide (Trichlorfone)
3: 1 with ground corn and powdered sugar
Composed of a mixture. An untreated 3: 1 mixture of ground corn and powdered sugar is used as a control. A container containing 2 grams of test or standard insecticidal bait and 2 grams of general feed [Purina Lab Chow 5
001] is placed in a round container containing cockroaches. The mortality rate is shown in Table 7.

Example 8 An Orlando standard population of German cockroaches (Blattella germanica) containing 25 adults is treated in the same manner as in Example 7. The results are shown in Table 8.

Example 9 Anopheles quadri
25 larvae of 3rd and 4th instars of maculatus) were dissolved in 100 ml of well water, a supplementary feed consisting of 0.05 g of crushed pork as food for larvae and a known amount of test compound in 1.0 ml or less of acetone. 500 with seaweed
Place in a ml glass bottle (9 x 8.5 cm diameter). Cover the bottle with a cloth net and keep it at 26.7-28.9 ° C in a constant temperature bath.
(80-84 ° F) and 65-75% RH (relative humidity)
To last. Low levels of lighting (approximately 0.5 foot candles in a constant temperature bath) were maintained during non-working hours. Seven days after the start,
The number of pupae that died, the number of adults that died or failed to fully emerge and the number of pupa husks were examined. Living adults observe gross abnormalities. The diet is replicated at at least one concentration and the standard larval insecticide, mesoprene, is used as a control in each test system.

Several concentrations of each compound were tested to establish a dose-response relationship. The results obtained were corrected to control mortality (Abbott's formula) using statistical analysis methods supported by NERDC, and Probit analysis was performed using log-transformed mortality data. This analysis gave LC-50 and LC-90 ratings in ppm for the compounds.

Example 10 Anopheles quarim
Screening was performed as a pesticide for bowels (mixed growth regulator, IGR) by exposing 4th instar larvae of A. calulatus) to an aqueous solution or suspension of a test compound (double test). Test compounds were dissolved in acetone and added to water; water-soluble compounds remained in solution, water-insoluble compounds in finely divided suspension. Mortality was determined after 24 hours by placing the bow hula in such treated water.
The compounds were initially tested at concentrations of 10 and 1 ppm. If 50% mortality was obtained at 1 ppm, the test was conducted at a lower concentration. Standard larva insecticide,
Temehuos (Abate) was simultaneously tested as a control.

The results are shown in Table 10.

The following are criteria for compounds tested against mosquitoes.

The results are shown in Table 9.

Example 11 Cat cat chow is treated with 1% by weight of active compound to feed cockroaches with this treated food,
The feed was then removed. Cockroaches were observed once a day and the average mortality was recorded. The compounds used in the test are as follows.

HC-2 HC-5 HC-6 HC-7 HC-16 (In the above formula, each Rf is C ₈ F ₁₈ ) The obtained results are shown in Table 11.

Front Page Continuation (72) Inventor Lofgren, Cliff Aude Swanson 32604, Gains Zveil, Florida, United States, Northwest Thirty East Drive 1321

Claims (17)

[Claims] 1. A formula (1): CF ₃ (CF ₂ ) _x SO ₂ A [wherein, x is 4 to 19, A is (a) NR ₁ R ₂ , and R ₁ and R ₂ are Hydrogen, alkyl, alkenyl, alkynyl, aroyl, acyl, cycloalkyl, cycloalkenyl, cycloalkynyl; 3- to 6-membered ring containing carbon atom and one oxygen atom; hydroxyalkyl, haloalkyl, aminoalkyl, carboxyalkyl, carboxyalkyl ester, carboxyalkyl amide and structural _{formula: - (C x H 2x O} ) n - (C y H 2y O) m -R 3 ( wherein, n + m is 1 to 20, x and y are 1 Four
And R ₃ is a group selected from the group consisting of groups selected from the same group as R ₁ and R ₂ ) or (b) NR ₁ R ₂ and N, R ₁ and R ₂ together form a 5- or 6-membered ring containing a carbon atom and 1 or 2 nitrogen atoms] or a mixture of one or more toxic components which is an agriculturally acceptable salt thereof. And a (2) feed ingredient or an agriculturally acceptable carrier, for controlling a population of arthropods. 2. The composition according to claim 1, wherein x is 4 to 11. 3. The composition according to claim 1, wherein A is —NH ₂ . 4. In the formula, R ₁ is hydrogen or alkyl,
The composition of claim 1 wherein R ₂ is hydrogen, alkyl, alkenyl or alkynyl. 5. In the formula, R ₁ is hydrogen or alkyl,
R ₂ is And R ₃ is hydrogen or alkyl, n + m = 1 to
20. The composition of claim 1 wherein 20 and x and y = 1-4. 6. The formula: The composition according to claim 1, comprising a compound represented by: 7. A formula Or The composition according to claim 1, comprising a compound represented by: 8. The formula: The composition according to claim 1, comprising a compound represented by: 9. A compound containing a compound represented by the formula: CF ₃ SO ₂ NH ₂ , C ₆ F ₁₃ SO ₂ NH ₂ , C ₈ F ₁₇ SO ₂ NH ₂ , or C ₈ F ₁₇ SO ₂ NHNa. The composition according to item 1. 10. The formula: Or The composition according to claim 1, comprising a compound represented by: 11. The formula: Or The composition according to claim 1, comprising a compound represented by: 12. The composition according to claim 1, wherein the pest is Hariari. 13. A composition according to claim 1 wherein the compound is a composition with a suitable bait. 14. A composition according to claim 13 wherein the bait is selected from the group consisting of soybean oil, honey-water or other suitable food attractants. 15. The composition according to claim 14, wherein the bait is soaked in a carrier. 16. A bait carrier which is a corncob arbor, a pregel defatted ground corn, or another granular form which is compatible with food attractants and in which the harris easily falls onto the ground foraging food. A composition according to claim 15 selected from the group consisting of substances. 17. A composition according to claim 1, wherein the compound or mixture of compounds is a sprayable solution, emulsion or dispersion.