FI70211C - N-BENOSOYL-N'-PYRIDYLOXIFENYLUREADERIVAT ANVAENDBARA SOM INSEKTICIDER OCH FOERFARANDE FOER FRAMSTAELLNING AV DESSA - Google Patents

Description

¢ 355 ^ 71 roi / (M, ADVERTISEMENT

LB] ν ') UTLÄGGNINGSSKR1FT 7021 1 (45) p - -U -i. - 1 ^ -. j «7 - -Q pj r * (51) Kv.lk. * / lnt.CI.4 c 07 D 213/64 // A 01 N 47/34 FINLAND - FINLAND (21) Patent application - Patentansökning 781315 (22) Application date - Ansökningsdag 27 0L 78 (Fl) (23) Starting date - Giltlghetsdag 27.0 ^ .78 (41) Has become public - Blivit offentllg g η gg η ^

National Board of Patents and Registration of Finland Date of publication |

Patent- och registerstyrelsen ^ 'Ansökan utlagd oeh utl.skriften publieerad 28.02.86 (32) (33) (31) Privilege requested - Begärd priority gg q £ yg 17.03.78 Japan-Japan (JP) 12215/78, 29828/78 (71) Ishihara Sangyo Kaisha Ltd., no. 3 ~ 11, Edobori 1-chome, Nishi-ku,

Osaka, Japan-Japan (JP) (72) Ryuzo Nishiyama, Osaka-fu, Kanichi Fujikawa, Shiga-ken,

Rikuo Nasu, Shiga-ken, Tadaaki Toki, Shiga-ken, Japan-Japan (JP) (7 ^) Oy Koister Ab (5 ^) N-Benzoyl-N1-pyridyloxyphenylurea derivatives useful as insecticides and method for their preparation - N-benzoyl -N 1 - Pyridyloxyphenylureas are insecticides and insecticides and fractions

The invention relates to novel N-benzoyl-N'-pyridyloxyphenylurea derivatives useful as insecticides, to a process for their preparation and to insecticidal compositions containing them.

Almost all conventional insecticides are neurotoxins or contact poisons for all types of insects.

Attempts have been made to develop selective insecticides that are non-toxic to beneficial insects. Such insecticides include N-benzoyl-N'-phenylureas (U.S. Patent 3,748,356) and N-benzoyl-N'-phenoxyphenylureas (no pyridyloxy group) (U.S. Patent 4,005,223).

The N-benzoyl-N'-pyridyloxyphenylurea derivatives of the present invention have a much better effect than the above-mentioned known compounds.

2 70211

The compounds of the invention are selective insecticides which are remarkably effective against certain pests, but do not affect beneficial insects and are remarkably non-toxic to animals.

The N-benzoyl-N'-pyridyloxyphenylurea derivatives according to the invention have the formula X1 X3 X \ CONHCONH ------ ° - \ - * 6 (I) x2 ^ Χχ4 in which halogen or methyl, X2 is hydrogen or halogen, X 3 and X 6 are hydrogen or halogen, X 3 is hydrogen or halogen and X 6 is halogen or trifluoromethyl.

Suitable compounds of formula (I) are

N- (2-chlorobenzoyl) -N1- [3-chloro-4- (5-bromopyridyl-2-oxy) phenyl] urea, mp 196-199 ° C

2. N- (2-chlorobenzoyl) -N'-β-chloro-4- (5-nitropyridyl-2-oxy) phenyl] urea, m.p. 209-2l2 ° C

3. N- (2-chlorobenzoyl) -N '- [4- (3,5-dibromopyridyl-2-oxy) -

phenyl7urea, m.p. 185-188 ° C

4. N- (2-chlorobenzoyl) -N '- / 3-chloro-4- (3,5-dibromopyridyl)

1H-2-oxy) phenyl / urea, m.p. 223-224 ° C

5. N- (2-chlorobenzoyl) -N '- / 4- (3,5-dichloropyridyl-2-oxy) -

phenyl / urea, m.p. 216-218 ° C

6. N- (2-chlorobenzoyl) -N '- / - 3-chloro-4- (3,5-dichloropyridyl)

1H-2-oxy) phenyl / urea, m.p. 225-228 ° C

7. N- (2-chlorobenzoyl) -N '- / 1,5-dichloro-4- (3,5-dichloropyrene)

II

3 7021 1

rysyl-2-oxy) phenyl / urea, m.p. 221-223 ° C

8. N- (2-chlorobenzoyl) -N '- [4- (5-bromopyridyl-2-oxy) phenyl] urea, m.p. 179-180 ° C

9. N- (2-chlorobenzoyl) -N '- [3-chloro-4- (5-chloropyridyl-2-oxy) phenyl] urea, m.p. 198-200 ° C

10. N- (2-chlorobenzoyl) -N1- [3,5-dichloro-4- (5-chloropyridyl-2-oxy) phenyl] urea, m.p. 147-148 ° C

11. N- (2-chlorobenzoyl) -N '- [4- (5-trifluoromethylpyridyl-2-oxy) phenyl] urea, m.p. l.49-151 ° C

12. N- (2-chlorobenzoyl) -N '- [3-chloro-4- (5-trifluoromethyl-pyridyl-2-oxy) phenyl] urea, m.p. 182-185 ° C

13. N- (2-chlorobenzoyl) -N '- [4- (3-chloro-5-trifluoromethyl-pyridyl-2-oxy) phenyl] urea, m.p. 186-187 ° C

14. N- (2-chlorobenzoyl) -N '- [3,5-dichloro-4- (5-trifluoromethylpyridyl-2-oxy) phenyl] urea, m.p. 206-208 ° C

15. N- (2-chlorobenzoyl) -N '- [3,5-dichloro-4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl] urea, m.p. 140-144 ° C

16. N- (2-chlorobenzoyl) -N '- [3-chloro-4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl] urea, m.p. 224-226 ° C

17. N- (2,6-dichlorobenzoyl) -N '- [4- (3,5-dichloropyridyl-2-oxy) phenyl] urea, m.p. 228-230 ° C

18. N- (2,6-dichlorobenzoyl) -N '- [3-chloro-4- (3,5-dichloropyridyl-2-oxy) phenyl] urea, m.p. 214-216 ° C

19. N- (2,6-dichlorobenzoyl) -N1- [3,5-dichloro-4- (3,5-dichloropyridyl-2-oxy) phenyl] urea, m.p. 273-275 ° C

20. N- (2,6-difluorobenzoyl) -N '- [4- (3,5-dichloropyridyl-2-oxy) phenyl] urea, m.p. 184-185 ° C

21 N- (2,6-difluorobenzoyl) -N '- [3-chloro-4- (3,5-dichloropyridyl-2-oxy) phenyl] urea, m.p. 230-231 ° C

22 N- (2,6-difluorobenzoyl) -N '- [3-chloro-4- (5-chloropyridyl-2-oxy) phenyl] urea, m.p. 210-212 ° C

23 N- (2,6-difluorobenzoyl) -N '- [4- (5-trifluoromethylpyridyl-2-oxy) phenyl] urea, m.p. 185-188 ° C

24. N- (2,6-difluorobenzoyl) -N '- [4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl] urea, m.p. 190-192 ° C

25. N- (2,6-difluorobenzoyl) -N '- [3-chloro-4- (5-trifluoromethylpyridyl-2-oxy) phenyl] urea, m.p. 195-198 ° C

4 7021 1

26. N- (2,6-difluorobenzoyl) -N '- / 3,5-dichloro-4- (5-trifluoromethylpyridyl-2-oxy) phenyl] urea, m.p. 209-212 ° C

27. N- (2,6-difluorobenzoyl) -N '- [3,5-dichloro-4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl] urea, m.p. 203-205 ° C

28. N- (2,6-difluorobenzoyl) -N '- [3-chloro-4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl] urea, m.p. 187-190 ° C

29. N- (2-methylbenzoyl) -N '- [4- (5-chloropyridyl-2-oxy) phenyl] urea, m.p. 198-200 ° C

30. N- (2-methylbenzoyl) -N '- [4- (5-bromopyridyl-2-oxy) phenyl] urea, m.p. 188-191 ° C

31. N- (2-methylbenzoyl) -N '- [4- (5-trifluoromethylpyridyl-2-oxy) phenyl] urea, m.p. 140-142 ° C

32. N- (2-methylbenzoyl) -N '- [3-chloro-4- (5-bromopyridyl-2-oxy) phenyl] urea, m.p. 207-209 ° C

33. N- (2-methylbenzoyl) -N '- [3-chloro-4- (5-trifluoromethyl-pyridyl-2-oxy) phenyl] urea, m.p. 188-191 ° C

34. N- (2-methylbenzoyl) -N '- [3-chloro-4- (3,5-dichloropyridyl-2-oxy) phenyl] urea, m.p. 213-215 ° C

35. N- (2-methylbenzoyl) -N '- [3,5-dichloro-4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl] urea, m.p. 214-217 ° C

36. N- (2-methylbenzoyl) -N '- [3-bromo-4- (3,5-dichloropyridyl-2-oxy) phenyl] urea, m.p. 222-224 ° C

37. N- (2-methylbenzoyl) -N '- [4- (3,5-dichloropyridyl-2-oxy) phenyl] urea, m.p. 216-219 ° C

38. N- (2-methylbenzoyl) -N '- [4- (3,5-dibromopyridyl-2-oxyphenyl] urea, mp 219-221 ° C

39. N- (2-methylbenzoyl) -N '- [4- (3-chloro-5-trifluoromethyl-pyridyl-2-oxy) phenyl] urea, m.p. 171-173 ° C

40. N- (2-methylbenzoyl) -N '- [3,5-dichloro-4- (5-trifluoromethylpyridyl-2-oxy) phenyl] urea, m.p. 219-221 ° C

41. N- (2-methylbenzoyl) -N '- [3-chloro-4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl] urea, m.p. 156-159 ° C.

The N-benzoyl-N'-pyridyloxyphenylurea derivatives of formula (I) are prepared according to the invention in such a way that the benzoyl isocyanate of formula

II

5 v 70211, xi

(x) —CO-NCO

V 1 and X 2 wherein X 1 and X 2 have the same meaning as above are reacted with pyridyloxyaniline of the formula X, X 5.

// \\ nh2 / 7 0 ^ N -x6 V :: \ N - 'X4 where X ^, X4, X, - and X ^ have the same meaning as above.

The reaction is preferably carried out in the presence of a solvent. Suitable solvents include e.g. benzene, toluene, xylene, pyridine, etc.

The reaction temperature is usually in the range of 0 to 120 ° C, and the reaction time is usually in the range of 0.1 to 24 hours. The reaction is preferably carried out at a temperature between room temperature and reflux for a reaction time of 1 to 5 hours.

The following examples illustrate the preparation of the compounds of the invention.

Example 1 Preparation of N- (2-chlorobenzoyl) -N 1 -Z -3-chloro-4- (3,5-dichloropyridyl-2-oxy) phenyl / urea

A solution prepared by dissolving 2.9 g of 3-chloro-4- (3,5-dichloropyridyl-2-oxy) aniline in 50 ml of toluene was heated at 80 ° C. A solution of 1.8 g of 2-chlorobenzoyl isocyanate in 20 ml of toluene was then added dropwise with stirring and the reaction was allowed to proceed for 1 hour. After the reaction mixture was cooled, the precipitate was collected by filtration, washed first with toluene and then with petroleum ether and dried to give 3.2 g of N- (2-chlorobenzoyl) -N '- / 3-chloro-4- (3,5-dichloropyridyl). 2-oxy) phenyl / urea (m.p. 225-228 ° C).

7021 1 6

Example 2 Preparation of N- (2,6-dichlorobenzoyl) -N1- [4- (3,5-dichloropyridyl-2-oxy) phenyl] urea

Following the procedure of Example 1, but using 2.5 g of 4- (3,5-dichloropyridyl-2-oxy) aniline instead of 3-chloro-4- (3,5-dichloropyridyl-2-oxy) aniline and 2.4 g 2,6-Dichlorobenzoyl isocyanate in place of 2-chlorobenzoyl isocyanate and an reaction time of 8 hours at 30 ° C instead of 1 hour at 80 ° C gave 3.8 g of N- (2,6-dichlorobenzoyl) -N N- [4- (3,5-dichloropyridyl-2-oxy) phenyl] urea (m.p. 228-230 ° C).

The compounds of this invention have excellent selective insecticidal activity, as will be seen from the experimental results presented below.

Example 3 Preparation of N- (2,6-difluorobenzoyl) -N '- / 4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl / urea

Following the procedure of Example 1, but using 1.0 g of 4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) aniline instead of 3-chloro-4- (3,5-dichloropyridyl-2-oxy) aniline and 0, 64 g of 2,6-difluorobenzoyl isocyanate in place of 2-chlorobenzoyl isocyanate and a reaction time of 3 hours at room temperature instead of 1 hour at 80 ° C gave 0.5 g of N- (2,6-difluorobenzoyl) -N'- [4- (3-Chloro-5-trifluoromethyl-pyridyl-2-oxy) -phenyl] -urea (m.p. 190-192 ° C).

Example 4 Preparation of N- (2-methylbenzoyl) -N '- [4- (5-trifluoromethylpyridyl-2-oxy) phenyl] urea 0.5 g of 4- (5-trifluoromethylpyridyl-2-oxy) aniline was dissolved in 20 ml: toluene. To this solution, a solution of 0.32 g of 2-methylbenzoyl isocyanate in 20 ml of toluene was added dropwise with stirring, and the reaction was allowed to proceed at room temperature for 1 hour. After the reaction mixture was cooled, the precipitate was collected by filtration, washed with hexane and then recrystallized from ethanol to give 0.3 g of N- (2-methylbenzoyl) -N 1 - [4- (5-trifluoromethylpyridyl-2-oxy) phenyl] urea ( mp 140-142 ° C).

Il 7021 1

Most conventional insecticides are fast-acting neurotoxic or contact toxins. The compounds of this invention, on the other hand, have a delayed effect, meaning that the compound is taken orally by insects with feed or water, and then the compound has a lethal effect on the ecdysis or deformation of certain insects.

The compounds of this invention have significant insecticidal activity against the larvae of Lepidoptera, Coleoptera, Hymenoptera and Diptera, such as the larvae of the following insects: Plutella xylostella, Pieris rapae crucivora, Mamesta brassicae, Plusia nigrisigma, Prodenia litura contracta, Hyphatria cunea, Lymantria dispar, Chilo suppressalis, Heliothis Zea, Heliothis virescens, Anthonomus Gran-dis, Tribolium confusum, Leptinotarsa decenlineata, Neurotoma irdescens, Culex pipiens pallens, Culex pipiens molestus.

The compounds of this invention do not have a substantial insecticidal effect on adult insects and are ineffective against natural enemies such as predatory insects and have little toxicity to animals.

When these compounds are used as active ingredients in insecticidal compositions, it is possible to prepare various mixture forms, such as dusts, wettable powders, emulsifiable concentrates, invert emulsions, oil solutions, aerosol preparations, etc., each containing the necessary excipients specific to agricultural mixtures. The compositions may be used in appropriate concentrations undiluted or diluted.

Suitable excipients are e.g. powdered carriers such as talc, kaolin, bentonite, diatomaceous earth, silica, clay and starch, liquid diluents such as water, xylene, toluene, dimethyl sulfoxide, dimethylformamide, acetonitrile and alcohol, emulsifiers, dispersants, spreaders, etc.

The selective insecticide composition usually contains the active ingredient from 5 to 80% by weight of the oily concentrate, from 0.5 to 30% by weight of dust and from 5 to 60% by weight of the wettable powder.

Other agricultural ingredients such as other insecticides, acaricides and growth regulators may also be added to the composition.

The selective insecticides according to the invention are useful in controlling various pests and are usually used in concentrations such that the active ingredient is present in an amount of from 5 to 10,000 ppm, preferably from 20 to 2000 ppm.

When the active ingredient of the present invention is applied to harmful aquatic insects, a composition having the above-mentioned concentration may be used in the control, although the concentration of the active ingredient in water may be lower than said.

Test 1

The active ingredients were dispersed in water to the desired concentrations. The cabbage leaves were dipped in the dispersions for about 10 seconds, removed and dried in a stream of air.

A piece of moistened filter paper was placed in each Petri dish (diameter 9 cm), dried cabbage leaves were placed on filter paper, second or third larval Plutella xylostella larvae were placed on the leaves, Petri dishes were covered and kept at 28 ° C under illumination. 8 days after the dispersion treatment, the dead larvae were counted and the mortality value was calculated from the following equation:, .. dead larvae x 100 mortality value = --tt -: -; - ϊ-: ——- total number of larvae li 9 7021 1

Table 1 ! Well. Mortality value (%) Compound II no Mortality value (%)! I 1 (concentration) _____________ '(concentration \ 7yy.g) ___________j J f 2 (H) ppm 1 () 0 ppm _ 2 0 () ppm [100 ppm | j 1 100 100 20 100 j 100 2 100 100 21 100 100

3 j 100 100 22 100 100 I

4 I 100 100 23 100 100 i '! -1--4-f ------ 1 ---------- '! 5 I 1 0 0 1 0 0 2 4 1 0 0 1 0 0! -1 - [--------— -----— '! 6 100 100 25 100 100 j ___________ L ____- j; 7 100 80 2ft 100 100 Ϊ -------------—-------- 1-- 8 100 100 27 I 100 j 100; -i -------------- j - 1 --- 9 i 100 100 28! 100: 100 -— -—I ------- j- 10 100 ftO j 31 100 j 100 11 100 80 33 100 | 100 ---------- j --------------- 4—- 12 100 100 34 100 i 100 I: 1 3 1 0 0 1 0 0 3 5 1 0 0 1 0 0 j 14 1 0 0 10 0 3h 10 0 j 10 0:

---------------- J

1 5 1 0 0 100 38 1 0 0 1 0 0 j lft 100 100 30 100 j 100 17! 100 100 -10 1 00 ϊ 1 () 0 j I 18! 100 100 41 100 j ion!

j ---- r ^ -------- ---------- ---- · I

j 19 j 8 o ft 0 7021 1 10

Test 2

Adult Plutella xylostella insects were placed on young radish seedlings grown in unglazed pots and the eggs were blown away for 24 hours. After one day, the seedlings were sprayed with an aqueous dispersion of the active ingredient (500 ppm) until falling droplets began to form and then the seedlings were dried and kept in a greenhouse. Ten days after dispersion treatment, dead larvae were counted and mortality values were calculated from the following equation:, n. dead larvae.

Mortality value = _ x 100 total number of larvae hatched from eggs

The results are shown in Table 2.

Table 2

Compound no Mortality value {%) 2 80 4 100 6 100

Experiment 3 3

About 20 cm germinated rice seeds were placed to grow in jars (diameter 9 cm, height 3 cm). After the rice had grown to 1-2 cm tall seedlings, 2 ml of an aqueous dispersion of known concentration was sprayed into each jar, dried, Chilo suppressalis larvae (freshly hatched from the egg) were placed and the jars were covered. Ten days after dispersion treatment, dead larvae were counted and mortality values were calculated from Equation 1 of the experiment. The results are shown in Table 3.

Il 7021 1

Il

Table 3 'I Mortality Value' (% ')' i Compound no. ! (concentration) _ _ j; _________ 200 ppm | ] _qq ppm | j 1 100 j 100 | i 2! loo i loo i j__________________j; 4 100! 100! k -------------------------- J ------------------! ; 6 loo i loo; i 11,100; 100 1 i ----—-- 1 ---: 12: loo | loo 23 100 I 100 | 24 100! 100 1Γ.

ν. 70211

Experiment 4 3

About 20 cm germinated rice seeds were grown in jars (diameter 9 cm, height 3 cm) to 1.5-2 cm tall seedlings, 2 ml of a mixture with the desired active ingredient concentration of 400 ppm was sprayed into the jars, dried and seedlings in the third larval stage were placed on the seedlings. Chilo suppressalis larvae and dishes were covered. Ten days after treatment, dead larvae were counted and mortality values were calculated from Experiment 1 equation. The results are shown in Table 4.

Table 4, Compound no. Mortality value! ___ CU_; I 31 100 ί »___j__f

33 100 I

—------------- 1 34 100 I ----------- 36 j 100 37 100

_ * I

_38______ i____100____ '39 i 100 _ _______] ______________________ Λ

II

13 ν, 70211

Experiment 5 N- (2-chlorobenzoyl) -N '- [4- (3,5-dibromopyridyl-2-oxy) -phenyl] urea (Compound No. 3) was prepared in aqueous dispersions of a certain concentration. The effect of dispersions was tested on different insects. Mortality values were calculated 10 days after treatment according to Experiment 1. The results are shown in Table 5.

Table 5 Insects Treatment Concentration (ppm) Mortality !___ oral value

Masesta brassicae ~ - 2-larval stage cabbage leaf (Lepidoptera) watering i ________________________ |

Tribolium contusum: ~! .....

2-larval grade Wheat flour 20Q j (Coleptera) mix! j: Neutotoma irdescens cherry tree, j j2-larval branch 250 1 100 (Hymenoptera) spraying j .... _ 1 14

Experiment 6 7 0 21 1

The azalea leaves were immersed for 10 seconds in an aqueous solution of the active ingredient (50 ppm), the leaves were air-dried, placed in a wide-mouthed glass bottle and Lymantria dispar larvae of second instar grade were placed on the leaves. The mouth of the flask was covered with gauze and the flask was kept under illumination at 28 degrees Celsius in a heat bath. After 6 days of treatment, dead larvae were counted and mortality values were calculated according to Experiment 1. The results are shown in Table 6.

Table 6

Compound no. Mortality value ------------------------------- Ul) ---------- ___3______100 _13__100 15_ 100 12 100 20_ 10 0 11 100 23 _ 10 0 24 100 25 100 I 27 100 I ----- J_ 28 100 35 100 i 41 100 j

II

15 7021 1

Test 7 t V £. \ \

The cabbage leaves were dipped for 10 seconds in an aqueous solution of the active ingredient (50 ppm) and air dried. Moistened filter paper was placed in each Petri dish (diameter 9 cm), a leaf was placed on the paper and Prodenia litura larvae in the second or third larval stage on the leaf, the Petri dishes were covered and kept under lighting at 28 ° C. After 7 days, dead larvae were counted and mortality values were calculated according to Experiment 1. The results are shown in Table 7.

Table 7 [j Compound no. Mortality value; ____ (%) __! __ 3_____100 j__4____i oo_ j__13_______100____ I 14 _j_ 100 __ '15! 100 i ---- 1 --- 12 _100_ 20 100 21 100 i 24 I 100 j 5 1 i i_25 _, _ 100____ '! 26; 100 i. - - - - —-I. «—— - 33 100 a ________ 35 100 i 39 100 16 7021 1

Test 8 (\ J £. \

Approximately 250 ml of an aqueous solution of the active substance (100 ppm) and third-instar Culex pipiens molestus larvae were placed in jars (diameter 9 cm), the jars were covered and kept under lighting at 28 ° C. Ten days after treatment, dead larvae were counted and mortality values were determined by the method of Experiment 1.

The results are shown in Table 8.

Table 8 i! i Compound no. Mortality value, I __________________________ I ________ (%) _______________ j! 3,100 j 8,100 11_______10 0_ 12__100__ 13__100____: ______ 15 [100! __________ 20 ___ | ___ 100; _21__j_100_ j 23 __100 24 100 ---------- 25 __ | __100 j 27 __'_ 100_ _: _ 28 100 | __39 _; _ 100 __ j 7021 1 17

Composition 1 (a) N- (2-chlorobenzoyl) -N '- [3-chloro-4- (3,5-dichloropyridyl-2-oxy) phenyl] urea 20 parts by weight (b) dimethyl sulfoxide 70 parts by weight part (c) 10 parts by weight of polyoxyethylene alkylphenyl ether

When the ingredients were mixed thoroughly to dissolve the active ingredient, an emulsifiable concentrate was obtained.

Composition 2 (a) N- (2-chlorobenzoyl) -N '- [4- (3,5-dichloropyridyl-2-oxy) phenyl] urea 5 parts by weight (b) talc 92 parts by weight (c) sodium naphthalene sulfonate formaldehyde condensate 3 parts by weight

A homogeneous dust was prepared from the composition.

Composition 3 (a) N- (2,6-dichlorobenzoyl) -N '- / 4- (3,5-dichloropyridyl-2-oxy) phenyl / urea 50 parts by weight (b) "Jeeklite" (fine clay ) 45 parts by weight (c) sodium lignin sulfonate 5 parts by weight

The ingredients were ground to a homogeneous wettable powder. Composition 4 (a) N- (2,6-difluorobenzoyl) -N '- [4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl] urea 20 parts by weight (b) N, N-dimethylformamide 70 parts by weight (c) polyoxyethylene alkylphenyl ether 10 parts by weight

When the ingredients were mixed thoroughly so that the active ingredient dissolved, an emulsifiable concentrate was obtained.

Composition 5 (a) N- (2-chlorobenzoyl) -N '- [3,5-dichloro-4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl] urea 5 parts by weight (b) talc 95 parts by weight

The composition was ground to a homogeneous dust.

7021 1 18

Composition 6 (a) N- (2-methylbenzoyl) -N '- [3-chloro-4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl] urea 5 parts by weight (b) talc 95 parts by weight -can

The composition was ground to a homogeneous dust.

The following table compares the insecticidal activity of the compounds of the invention with that of the closely related compounds described in U.S. Patent No. 4,005,223. The test method was the same as in Experiment 1.

Table 9 7021 1 19 i i Mortality rate (%)

Compound (concentration: 1 ppm) I

; A compound of the invention

I ci C1 I

'·' ^ / "Y, / λ \ 90;; 'y-CONHCONH -ύ y ~ 0- / V-CF 1 2 3 4

I 'c n ~ J 3 I

μ. . . _______ __________.... _______ ... ........ .............. I__________________________ ........ I

I US 4,005,223 j! ^ C1 Cl j | / - CONHCONH · / ''} O {\. CF3; 0,; The compound of the invention i j F Cl! '(' 'CONHCONH <W-0-f h CF,, 100 <| v <w V 3, i F! I ί:!]! US 4 005 223:!

• I

. F Cl! : / / ·. / - 7 0 1 '' -CONHCONH- / ^ -O · ^ CF3; V '! ; A compound of the invention

Cl ci I / ~ y / i i V 'CONHCONH <V O (\ - CF i 100; I x — χ N ^' j I Cl I! I!! US 4 005 223 j

\ j I

Cl Cl! 2 \ i 3! v ^ CONHCONH - ^ 'y O- ^ \ - CF3 30 4; 'ci 20

Table 9 (continued) 7021 1

Mortality rate (%)

Compound (concentration: 1 ppm)

The compound F “Cl ^ y ... according to the invention

'\ -CONHCONH, Λ-0 <N \ - C1 100 \ - / \ ri /' toll /

'F

Compound F according to the invention: ONHCONH - <QH? ' - Br 100 j

F

Compound according to the invention F Cl / 'τΚ "' λ 100 ό '> -CONHCONH -,' vO J '· ^ - Cl

'--- \' · x N

'F Cl

A compound of the invention

Cl / - \ ^ - \> - \ 100 <'> CONHCONH X) 0 - // - € 1 · ._ / N,' ci v Cl _ _ __ f ___ ______ _______

Compound of the invention j i

Br j

___ \ I

/. s \ f. / ^ n n | r 'VCONHCONH- <v' --Br u j \ ~ / \ '! - N-;

i ..... .....- ........- - - J

The compound of the invention j 'ci! ί ·. ·) (‘CONHCONH Λ v’ - CF3 100 j YU- / ‘N · j ^ CH3 ______________________ | US 4,005,223!

Cl I - - - \ 3 - ·. f Γ \ 55! / 'V-CONHCONH -. O · CF_. ; i Y: _2 V- / V-- ·

OF

ch3:

Claims (33)

7021 1 21 N-benzoyl-N1-pyridyloxyphenylurea derivative useful as an insecticide, characterized in that it has the formula X1 X3 \ CONHCONH_ ^ ~ ^ _0 - ^ Xg (χ) \ χ9 \ X4 in which halogen or methyl, X2 is hydrogen or halogen , X 3 and represent hydrogen or halogen, X 3 is hydrogen or halogen and X 8 is halogen or trifluoromethyl. 2 X 4 wherein X 1 is halogen or methyl, χ 2 is hydrogen or halogen, X 1 and χ 4 represent hydrogen or halogen, X 1 is hydrogen or halogen and ^ 2 is halogen or trifluoromethyl. N-benzoyl-N'-pyridyloxyphenylurea derivative according to Claim 1, characterized in that it has the formula χ X9 C1 / // \\ - CONHCONH U / ~ X10 v = y ΝΊΐ / X8 in which Xj and Xg represent hydrogen or halogen, Xg is hydrogen or halogen and X1q is halogen or trifluoromethyl. N-benzoyl-N'-pyridyloxyphenylurea derivative according to Claim 2, characterized in that it is N- (2-chlorobenzoyl) -N '- [3- (3,5-dibromopyridyl-2-oxy) -phenyl] urea. N-benzoyl-N'-pyridyloxyphenylurea derivative according to Claim 2, characterized in that it is N- (2-chlorobenzoyl) -N '- / 3-chloro-4- (3,5-dichloropyridyl-2 -oxy) phenyl / urea. 22 7 0 21 1 N-benzoyl-N'-pyridyloxyphenylurea derivative according to Claim 2, characterized in that it has the formula X x Cl / 7 9. r / (CONHCONH-^ y-O -N7) -CF3 X8 in which X7, Xg and Xg represent hydrogen or halogen. N-benzoyl-N'-pyridyloxyphenylurea derivative according to Claim 5, characterized in that it is N- (2-chlorobenzoyl) -N '- / 4- (3-chloro-5-trifluoromethyl-pyridyl-2-oxy ) phenyl / urea. N-benzoyl-N'-pyridyloxyphenylurea derivative according to Claim 1, characterized in that it has the formula / F * 7 XS Π 'i / λ H, Λ \ V-CONHCONH - //' / _0 "\ / -X10 \ '\ F X8 wherein Xy and Xg are hydrogen or halogen, Xg is hydrogen or halogen and X1q is halogen or trifluoromethyl. N-benzoyl-N'-pyridyloxyphenylurea derivative according to Claim 7, characterized in that it is N- (2,6-difluorobenzoyl) -N '- / T- (3,5-dichloropyridyl-2-oxy) phenyl / urea. N-benzoyl-N'-pyridyloxyphenylurea derivative according to Claim 7, characterized in that it is N- (2,6-difluorobenzoyl) -N '- / T: -chloro-4- (3,5-dichloro pyridyl-2-oxy) phenyl / urea. N-benzoyl-N'-pyridyloxyphenylurea derivative according to Claim 7, characterized in that it has the formula 7021 1 23 F * 7 fA Γ ~ \\ l · '\> - CONHCONH - // \} - 0 - Λ N V ---- CF0 W M. '»^ \ x F Xg where Xj, Xg and Xg represent hydrogen or halogen. N-benzoyl-N1-pyridyloxyphenylurea derivative according to Claim 10, characterized in that it is N- (2,6-difluorobenzoyl) -N '- / 4- (3-chloro-5-trifluoromethyl-pyridyl-2- oxy) phenyl / urea. N-benzoyl-N · -pyridyloxyphenylurea derivative according to Claim 10, characterized in that it is N- (2,6-difluorobenzoyl) -N '- / 3,5-dichloro-4- (5-trifluoromethylpyridyl) -2-oxy) phenyl / urea. N-benzoyl-N'-pyridyloxyphenylurea derivative according to Claim 10, characterized in that it is N- (2,6-difluorobenzoyl) -N '- / 3,5-dichloro-4- (3-chloro-5 -trifluorimetyylipyridyyli-2-oxy) phenyl / urea. N-benzoyl-N'-pyridyloxyphenylurea derivative according to Claim 10, characterized in that it is N- (2,6-difluorobenzoyl) -N '- / 3-chloro-4- (3-chloro-5-tri -fluorimetyylipyridyyli-2-oxy) phenyl / urea. N-benzoyl-N'-pyridyloxyphenylurea derivative according to Claim 1, characterized in that it has the formula OH .. X7 X9. y— CONHCONH o Λ 'CF3 X8 where Χη, Xg and Xg represent hydrogen or halogen. 7021 1 24 N-benzoyl-N1-pyridyloxyphenylurea derivative according to Claim 15, characterized in that it is N- (2-methylbenzoyl) -N '- / 3,5-dichloro-4- (3-chloro-5-trifluoromethylpyridyl- 2-oxy) phenyl! 7urea. N-benzoyl-N'-pyridyloxyphenylurea derivative according to Claim 15, characterized in that it is N- (2-methylbenzoyl) -N '- / - N- (3-chloro-5-trifluoromethyl-pyridyl-2- oxy) fenyyli7urea. N-benzoyl-N'-pyridyloxyphenylurea derivative according to Claim 15, characterized in that it is N- (2-methylbenzoyl) -N * - / 3-chloro-4- (3-chloro-5-trifluoromethylpyridyl -2-oxy) phenyl / urea. An insecticidal composition, characterized in that it contains an N-benzoyl-N1-pyridyloxyphenylurea derivative of the formula X1 X4 X5 ^ -CONHCONH - ^ ^ V_x6 (!) Y \ Insecticidal composition according to Claim 19, characterized in that it contains 0.5 to 80 parts by weight of an N-benzoyl-N1-pyridyloxyphenylurea derivative of the formula (I) and 20 to 99.5 parts by weight of an agricultural additive. Insecticidal composition according to Claim 19, characterized in that it contains N- (2-chlorobenzoyl) -N '- [4- (3,5-dibromopyridyl-2-oxy) phenyl] urea as active ingredient. Insecticidal composition according to Claim 19, characterized in that it contains N- (2-chlorobenzoyl) -N '- [3-chloro-4- (3,5-dichloropyridyl-2-oxy) phenyl] urea as active ingredient. 7021 1 25 Insecticidal composition according to Claim 19, characterized in that it contains N- (2-chlorobenzoyl) -N '- / 4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl / urea as active ingredient. Insecticidal composition according to Claim 19, characterized in that it contains N- (2,6-difluorobenzoyl) -N 1 - [4- (3,5-dichloropyridyl-2-oxy) phenyl] urea as active ingredient. Insecticidal composition according to Claim 19, characterized in that it contains N- (2,6-difluorobenzoyl) -N '- / T-chloro-4- (3,5-dichloropyridyl-2-oxy) phenyl / urea as active ingredient. Insecticidal composition according to Claim 19, characterized in that it contains N- (2,6-difluorobenzoyl) -N '- / 4- (3-chloro-5-trifluoromethyl-pyridyl-2-oxy) phenyl / urea as active ingredient. Insecticidal composition according to Claim 19, characterized in that it contains N- (2,6-difluorobenzoyl) -N 1 - [Z, 5-dichloro-4- (5-trifluoromethylpyridyl-2-oxy) phenyl] as active ingredient. urea. Insecticidal composition according to Claim 19, characterized in that it contains, as active ingredient, N- (2,6-difluorobenzoyl) -N * - / 3,5-dichloro-4- (3-chloro-5-trifluoromethylpyridyl-2- oxy) phenyl / urea. Insecticidal composition according to Claim 19, characterized in that it contains, as active ingredient, N- (2,6-difluorobenzoyl) -N '- / 3-chloro-4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl / urea. Insecticidal composition according to Claim 19, characterized in that it contains N- (2-methylbenzoyl) -N '- / 4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl / urea as active ingredient. Insecticidal composition according to Claim 19, characterized in that it contains N- (2-methylbenzoyl) -N '- [3-chloro-4- (3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl] as active ingredient. urea. 26 7021 1 A process for the preparation of N-benzoyl-N'-pyridyloxyphenylurea derivatives of the formula X1 ^ 3 \ ^ y_CONHCONH- ^ ^ \ -0- ^ -Xg (D X2 X4 wherein X1 is halogen or methyl, X2 is hydrogen or halogen, X 3 and X 1 represent hydrogen or halogen, X 1 is hydrogen or halogen, and X 8 is halogen or trifluoromethyl, characterized in that the benzoyl isocyanate of the formula and X 2 are as defined above, are reacted with pyridyloxyaniline of the formula X 3 Xr, ____ s * b \ NH 2 -? - X 6 \ X 4 wherein X 1, χ 2, χ 1 and X 8 are as defined above. Process according to Claim 32, characterized in that the reaction is carried out in a solvent at a temperature between room temperature and reflux temperature. ti 27 7021 1