CA1230548A - Use of trifluoromethanesulfonanilides - Google Patents

Abstract

Abstract:
The invention provides an insecticidal composition which comprises as an active ingredient a compound of the formula:

Description

~23[)548 ( New Use Of_Trifluoromethanesulfonanilides The present invention relates to a new use for trifluoromethanesulfonanilides.
The trifluoromethanesulfonanilides can be represented by the formula:

CF3SO2N ~ SO N / Rl (I) wherein X is a hydrogen atom or an acyl group, Y is a hydrogen atom, a lower alkyl group or a halogen atom and Rl and R2, which may be the same or different, are each a hydrogen atom, a lower alkyl group, a cyclo (lower) alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxy group or an acyl group, provided that Rl and R2 are not simultaneously a hydrogen atom or an acyl group.
Particularly preferred are the compounds of the formula (I) wherein X is a hydrogen atom or an acyl group, Y is a fluorine atom or a chlorine atom and Rl is a hydrogen ~r~
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~230548 atom, a methyl group or an ethyl group and R2 is a methyl group, an ethyl group or a 2-propynyl group.
In the above definitions the term "lower" is intended to mean any group having not more than ~ carbon atoms.
Preferably, a lower alkyl group is an alkyl group having 1 to 5 carbon atoms, a lower alkenyl group is an alkenyl group having 2 to 5 carbon atoms and a lower al~ynyl group is an alkynyl group having 2 to 5 carbon atoms. A cyclo (lower) alkyl group preferably has 3 to 6 carbon atoms, and a lower alkoxy group preferably has 1 to 5 carbon atoms.
The term "acyl" preferably represents lower alkanoyl, lower alkenoyl, benzoyl, etc. Examples of the halogen atom include fluorine, chlorine, etc.
It is known that certain kinds of trifluoromethanesul-fonanilides are effective as herbicides. For instance, the herbicidal use of 2-methyl-4-(N-methylsulfamoyl) trifluor-omethanesulfonanilide and 3-(N,N-dimethylsulfamoyl) tri-fluoromethanesulfonanilide (U.S. patent 3,920,444) is known. However, their insecticidal activity has never been discovered.
It has now been found that the trifluoromethanesulfon-anilides (I) exert a remarkable insecticidal activity against a variety of insects belonging to the Hemiptera, Lepidoptera, Coleiptera, Diptera, Acarina, etc. orders of insects in agricultural fields (e.g. paddy fields, crop fields), orchards, forest lands, granaries, stored products, sanitary facilities, etc. SpeciEic examples of the insects are as follows:
1. Hemiptera:-brown planthopper (Nilaparvata lugens), smaller brown planthopper (Laodelphax striatellus , green rice leafhopper (Nephotettix cincticeps), green peach aphid (Myzus persicae), cotton aphid (Aphis gossvpii), etc.

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2. Lepidoptera:-rice stem borer (Chilo suppressalis), tobacco cutworm (Spodoptera litura), diamond back moth (Plutella xylostella), egger (Dendrolimus spectabilis), cotton lead worm (Spodoptera littoralis), etc.

3. Coleoptera:-varied carpet bee~le (Anthrenus verbasci), tobacco beetle (Lasioderma serricorne), powder-post beetle (Lyctus brunneus), etc.

4. Diptera:-yellow fever mosquito (Aedes aegypti), malaria mosquito (Anopheles stephansi), common mosquito (Culex ~piens pallens), housefly (Musca domestica), etc.

5. Acarina:-carmine spider mite (Tetranychus cinnabarinus), two-spotted spider mite (TetranYchus urticae), citrus red mite (Panonvchus citri), cattle tick (Boophilus microplus), etc.
Accordingly, the trifluoromethanesulfonanilides (I) are useful as insecticides against a wide variety of harmful insects as above mentioned.
The trifluoromethanesulfonanilides (I) are known and may be prepared in conventional ways, such as those disclosed in U.S. patent 3,920,444 issued on November 18, 1975 to Tokasago Perfumery Co. Ltd. and Published European Patent Application No. 0072253A.
Thus, according to one aspect of the invention there is provided an insecticidal composition which comprises as an active ingredient an insecticidally effective amount of a compound of the formula:

C~3SO~1 ~ 2 ~ R2 l230~a wherein X is a hydrogen atom or an acyl group, Y is a hydrogen atom, a lower alkyl group or a halogen atom and Rl and R2, which may be the same or different, are each a hydrogen atom, a lower alkyl group, a cyclo (lower) alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxy group or an aeyl group, provided that Rl and R2 are not simultaneously a hydrogen atom or an acyl group, and an inert earrier or diluent.
Aeeording to another aspect of the invention there is provided a method for exterminating insects which eomprises applying an inseetieidally effeetive amount of a eompound of the formula:

CF3S02N~SO N~ 1 wherein X is a hydrogen atom or an aeyl group, Y is a hydrogen atom, a lower alkyl group or a halogen atom and Rl and R2, which may be the same or different, are eaeh a hydrogen atom, a lower alkyl group, a eyelo (lower) alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxy group or an acyl group, provided that Rl and R2 are not simultaneously a hydrogen atom or an acyl group, to the area where the insects live.
Speeific examples of the trifluoromethanesulfonanilides (I) are shown in Table 1.

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For practical application as insecticides, the tri-fluoromethanesulfonanilides (I) are used in the form of an appropriate composition e.g. oily preparatîons, emulsifi-able concentrates, wettable powders, granules, dusts and aerosols. The content of the trifluoromethanesulfonanilide (I) in such compositions may be from about 0.1 to 99.9 % by weight, preferab]y from about l to 80 % by weight.
The composition can be formulated in a per se conventional manner by mixing at least one of the triflu-oromethanesulfonanilides (I) with an appropriate solid, liquid or gaseous carrier(s) or diluent(s) with or without an appropriate auxiliary agent(s) e.g. surfactants, adherents, dispersants and stabilizers for improving the dispersibility and other properties of the active ingredient.
Examples of the solid carriers or diluents are clays (e.g. kaolin, diatomaceous earth, synthetic hydrated silica, fubasami clay, bentonite, terra abla), talcs and other inorganic materials (e.g. sericite, sulfur powder, active carbon, calcium carbonate, hydrated silica) in fine powders or powdery form. Chemical fertilizers (e.g.
ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride) may be also used as the solid carriers or diluents.
Examples of the liquid carriers or diluents are water, alcohols (e.g. methanol, ethanol), ketones (e.g. acetone, methyl ethyl ketone), aromatic hydrocarbons (e.g. benzene, toluene, xylene, ethylbenzene, methylnapthalene), aliphatic hydrocarbons (e.g. n-hexane, cyclohexanone, kerosene, petroleum), esters, nitriles, ethers, acid amides (e.g.
methylformamide, dimethylacetamide), halogenated hydro-carbons (e.g. dichloroethane, trichloroethylene, carbon tetrachloride), etc.

1230 :i48 Examples of the gaseous carriers or diluents are Freon (trademark) gas, butane gas, carbon dioxide gas, etc.
Examples of the surfactants are alkylsulfates, alkyl-sulfonates, alkylarylsulfonates, alkylaryl ethers and their condensates with polyoxyethylene, polyethylene glycol ethers, polyhydric alcohol esters, glycitol derivatives, etc. Examples of the adherents and dispersants may include casein, gelatin, polysaccharides (e.g. starch powder, gum arabic, cellulose derivative, alginic acid), lignin-sulfonater bentonite, monosaccharidesr synthetic water-soluble high polymer (e.g. polyvinyl alcoholr polyvinvy pyrrolidoner polyacrylic acid), etc. Examples of the stabilizers are PAP (isopropyl acid phosphates) r BHT
(2r6-di-t-butyl-4-methylphenol) r BHA (mixture of 2-t-butyl-4-methoxyphenol and 3-t-butyl-4-methoxyphenol) r natural vegetable oil r mineral oil r the above mentioned surfactantsr fatty acids (e.g. oleic acidr linolic acidr linolenic acid) and their esters r etc.
The trifluoromethanesulfonanilides (I) thus formulated into an appropriate composition may be applied as such or after being diluted with water in a conventional appli-cation mode e.g. sprayingr smokingr soil treatmentr soil surface treatment or in combination with animal feed. The compounds may also be used together with or in admixture with other insecticidesr acaricidesr namatocidesr fungi-cides, seed disinfectants, fertilizers, soil improvers.
Some practical embodiments of the insecticidal compositions according to the invention are illustratively shown in the following Examples wherein part(s) and percentages are by weight.
Example 1 Each of Compound Nos. 1 to 49 (50 parts) was separately mixed well with an emulsifier ("Sorpol 24~5 G" -trademark-a mixture of polyoxyethylene alkylaryl ether sulfate and alkylarylsulfonate) (5 parts), and the resultant mixtures ~230548 - 12 ~

were admixed with diatomaceous earth (300 mesh) (45 parts~
in a pulverizer to make wettable powders.
Example 2 Each of Compound Nos. 1 to 49 (10 parts) was separately mixed well with an emulsifier ("Sorpol 5029 0" -trademark-sodium laurylsulfate) (5 parts), and the resultant mixtures were admixed with diatomaceous earth (300 mesh) (85 parts) in a pulverizer to make wettable powders.
Example 3 Each of Compound Nos. 1 to 49 (10 parts) was separately mixed well with an emulsifier ("Sorpol 3005 X" -trademark-a mixture of polyoxyethylenestyrylphenyl ether and alkylarylsulfate) (10 parts), dimethylformamide (40 parts) and xylene (40 parts), to make emulsifiable concentrates.
Example 4 Each of Compound Nos. 1 to 49 (0.1 part) was separately mixed with xylene (1 part) and were dissolved in kerosene (98.9 parts) to form oily preparations.
Example 5 Each of Compound Nos. 1 to 49 (1 part) was separately dissolved in an appropriate amount of acetone, and talc (300 mesh) (99 parts) was added thereto. The resultant mixtures were stirred and mixed well, followed by evaporation of acetone to form dusts.
The dosage rate of the trifluoromethanesulfonanilide (I) as the active ingredient may be from 1 to 1000 grams, preferably from 5 to 200 grams per are, and in the insecticidal composition the content thereof may be from 0.005 to 30 % by weight, although the contents may vary depending upon the season, the place to be applied, the mode of application, the kinds of insects, the degree of damage and so forth.

1230~4~3 The following Examples show some typieal test data indieating the exeellent inseeticidal activity of the trifluoromethanesulfonanilides (I) wherein the determinations were made with three replications unless otherwise ind;.cated. The compounds used for eomparison are as follows:

Compound No.Chemical structure ~emarks A S Commercially CH O \¦¦ r~~ available jP-O~ SCH3 insecticide CH O' ~ "phenthion"
~ `CX (trademark) s S ,CH3 Commercially C~ElrO \~ ~ available ' P-O~ `N insecticide C H 0/ N~=/ "diazinon"
2 5 ~ (trademark) C3H7(iso) C O Commercially ~ available < ~r~cNHcH3 insecticide "carbaryl"
(trademark) lZ30S48 ( Test Example 1 Each of Compound Nos. 1 to 49 formulated into an emulsifiable concentrate according to Example 3 was diluted with water to prepare four designated concentrations. Separately, an artificial diet (13 g) comprising powdered kidney beans and powdered soybean leaf for tobacco cutworm was supplied in plastic cups t250 ml volume) and coated with the above prepared concentrations.
Larvae of tobacco cutworm in the fourth instar (10 insects per cup) were released therein. Six days thereafter, the numbers of the surviving insects were counted, and LC50 (ppm) was calculated from the mortality of the insect in relation to the designated concentration. The results are shown in Table 2.

lZ30548 Table 2 Compound No . _ 50 4 ''252

6 7288 9 ',15 1~ ` 34 < 15 ~15 26 6.6 27 9.0 28 ~15 ~ 15 31 -~15 32 =15 34 5~ 1515 37 ~15 39 .15 . _ . .

1231[)5~3 (Continued) Compound No. LD50 (ppm) _ 49 50 - lG0 Test Example 2 Each of Compound Nos. 29, 33, 34, 35, 37, 38, 39, 41, 42, 43, 44 and 48 formulated into a wettable powder according to Example 1 was diluted with water to make a 50 ppm concentration in terms of the active ingredient. The thus prepared dilution was thoroughly sprayed onto cabbages planted in pots (diameter, 12 cm) and allowed to dry.
Larvae of tobacco cutworm in the fourth instar (5 insects) were released in each pot, which was then laid in a cylin-drical cage (diameter, 18 cm, height, 30 cm) and allowed to stand in a room. Six days thereafter, the numbers of surviving insects were counted, whereby the mortality was calculated. The results are shown in Table 3.

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Test Example 3 Each of Compound Nos. 35, 38 and 40 formulated into an emulsifiable concentrate according to Example 3 was diluted with water to make a 100 ppm concentration in terms of the active ingredient, and to this dilution there was added "New Gramine" (trademark - mixture of polyoxyethylenedo-decyl ether, polyoxyethylenealkylaryl ether and ligninsul-fonate) so as to make a 3000 fold dilution. Cabbage leaves at 2 months after sowing were dipped in the dilution and, after being allowed to dry, laid in plastic cups (diameter, 9 cm; height, 4 cm) together with the larvae of cotton leaf worm in the second instar ~10 worms per cut). The cups were then allowed to stand in a room for 3 days, and the numbers of surviving insects were counted, whereby the mortality was calculated. The results are shown in Table 4.

Table 4 , Com~ound ~o~~lortality (~) .. _ .. __ '1() 100 .. _ _ Non~tre.~tmen~ 7

Claims (13)

Claims:

1. An insecticidal composition which comprises as an active ingredient an insecticidally effective amount of a compound of the formula:

wherein X is a hydrogen atom or an acyl group, Y is a fluorine atom or a chlorine atom and Rl is a hydrogen atom, a methyl group or an ethyl group and R2 is a methyl group, an ethyl group or a 2-propynyl group.

2. A composition according to claim 1, wherein the azalea group is a lower alkanoyl, a lower alkenoyl or a benzoyl group.

3. A composition according to claim 1, wherein X is a hydrogen atom, Y is a chlorine atom and Rl and R2 are each a methyl group.

4. A composition according to claim 1, wherein X is a hydrogen atom, Y is a fluorine atom and Rl is a hydrogen atom and R2 is a 2-propynyl group.

5. An insecticidal composition according to claim 1, wherein X is a hydrogen atom, Y is a fluorine atom and Rl and R2 are each an ethyl group.

6. An insecticidal composition according to claim 1, wherein X is a hydrogen atom, Y is a fluorine atom, R1 is a methyl group and R2 is a 2-propenyl group.

7. A method for exterminating insects which com-prises applying an insecticidally effective amount of a compound of the formula:

wherein X is a hydrogen atom or an acyl group, Y is a fluorine atom or a chlorine atom and R1 is a hydrogen atom, a methyl group or an ethyl group and R2 is a methyl group, an ethyl group or a 2-propynyl group, to the area where the insects live.

8. A method according to claim 7, wherein the acyl group is a lower alkanoyl, a lower alkenoyl or a benzoyl group.

9. A method according to claim 7, wherein X is a hydrogen atom, Y is a chlorine atom and Rl and R2 are each a methyl group.

10. A method according to claim 7, wherein X is a hydrogen atom, Y is a fluorine atom, Rl is a hydrogen atom and R2 is a 2-propynyl group.

11. A method according to claim 7, wherein X is a hydrogen atom, Y is a fluorine atom, and Rl and R2 are each an ethyl group.

12. A method according to claim 7, wherein X is a hydrogen atom, Y is a fluorine atom, Rl is a methyl group and R2 is a 2-propenyl group.

13. A method according to claim 7, wherein the insects belong to Lepidoptera.