CA1139784A

CA1139784A - Phenylureas

Info

Publication number: CA1139784A
Application number: CA000344689A
Authority: CA
Inventors: Josef Ehrenfreund
Original assignee: Ciba Geigy Investments Ltd
Current assignee: Novartis AG
Priority date: 1979-02-01
Filing date: 1980-01-30
Publication date: 1983-01-18
Also published as: EP0014676A3; IL59282A; EP0014676A2; IL59282A0

Abstract

Case 5-12211/??

Absract Novel halogen-substituted N-phenyl-N'-benzoylureas of the formula wherein R1 is a C2-C3-alkenyl group, or a C2-C3-alkenyl group monosubstituted with chlorine, R2 and R3 are halogen, and R4 is hydrogen or halogen; processes for producing these compounds, as well as compositions containing them, for use in combating pests, especially in combating insects which infest plants and animals.
The novel compounds also have an action inhibiting insects damaging plants by eating, and some of the compounds are ovicidally and larvicidally effective.

Description

~ ~ 3 Case 5-12211/1+21+
PHENYLUREAS
The present invention relates to novel halogen-substituted N-phenyl-N'-benzoylureas, to processes for producing them, and to their use for combating pests.
The haLogen-substituted N-phenyl-N'-benzoylureas according to the invention have the following formula ~1~ ~E ~o-~ o-~

wherein Rl is a C2-C3-alkenyl group, or a C2-C3-alkenyl group monosubs~ituted with chlorine; R2 and R3 are halogen; and R4 is hydrogen or halogen.
Compounds of the formula I according to the inven~ion which are preferred on account of their action as pesticidal agents are those in which Rl is a C3-alkenyl group, or a C3-alkenyl group monosubstituted with chlorine; R2 is fluorine, chlorine or bromine; R3 is fluorine or chlorine;
and R4 is hydrogen, fluorine or chlorine.
Of particular interest are also compounds of the formula I wherein Rl is one of the radicals CH2=CH-CH2-or Cl-CH=CH-CH2-.

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, ~3~78 To be emphasised are also compounds of the formula I
wherein R2 is chlorine or bromine, and/or R3 and R4 are fluorine.
The compounds of the formula I occur, where this is possible, as cis/trans isomeric mixtures. Thus, the term 'compounds of the formula I' embraces both the cis or trans forms and the corresponding isomeric mixtures. An isomeric mixture can be separated, for example by means of known chromatographical methods of separation and subsequent elution, into the isomeric forms. For synthesis of stereochemically homogeneous compounds of the formula I, there are advantageously used stereochemically homogeneous starting compounds of the following formulae II and IV.
The compounds of the formula I can be produced by processes known per se (see, inter alia, the German Of~enlegungsschriften Nos. 2,123,236 and 2,601,780).
Thus, for example, a compound of the formula I can be obtained by reaction a) of a compound of the formula II

t=-~r with a compound of the formula III

CO-N=C=O (III);
_ --or b) of a compound of the formula IV

~L: L3~3'7~4 RlO ~ N=~=0 (IV), 3r optionally in the presence of a basic substance, with a compound of the formula V

~CO--NH (V)-~=0 In the above formulae II, III, IV and V, the radicals Rl, R2, R3 and R4 have the meanings given under the formula I.
The processes a) and b) mentioned are preferably performed under normal pressure and in the presence of an organic solvent ar diluent. Suitable solvents or diluents are for example: ethers and ethereal compounds, such as diethyl ether, dipropyl ether, dibutyl ether, dioxane, dimethoxyethane and tetrahydrofuran; N,N-dialkylated carboxylic acid amides; aliphatic, aromatic as well as halogenated hydrocarbons, particularly benzene, toluene, xylene, chloroform, methylene chloride, carbon tetrachloride and chlorobenzene; nitriles such as acetonitrile or propionitrile; dimethylsulfoxide, and also ketones, for example methyl ethyl ketone, methylisopropyl ketone and methylisobutyl ketone. Process a) is in general performed at a temperature of -10 to 100C, preferably between 15 and 25C, optionally in the presence of an organic base, for example triethylamine. The process b) is performed at a temperature of 0 to 120C, preferably at the boiling .. ..... .
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point of the employed solvent, and optionally in the presence of an organic base, such as pyridine, and/or with the addition of an alkali metal salt or alkaline-earth metal salt, preferably sodium.
The starting materials of the formulae II, III, I~ and V are known, or can be produced by processes analogous to known processes.
It is already known that certain N-phenyl-N'-benzoyl-ureas have insecticidal properties (see German Offen-legungsschriften Nos. 2,123,236, 2,504,982, 2,537,413,

2,601,780 and 2,726,684, the Belgian Patent ~peci~ications Nos. 832,304, 843,906 and 844,066, and also the U.S.
Patent Specification No. 4,089,975).
It has now been found that surprisingly the compounds of the formula I according to the invention, whilst having good tolerance to plants and negligible toxicity to warm bloo~ed animals, have excellent activity as pesticidal agents. They are suitable in particular for comba-ting pests which infest plants and animals.
The compounds o~ the formula I are especially suitable for combating insects of the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Hymenoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isop~era and Psocoptera.
In addition to having very high activity against flies, such as Musca domestica, and against mosquito larvae, the compounds of the formula I are suitable also for combating insects which damage plants by eating, in crops of ornamental plants and useful plants, especially in cotton crops (for example against Spodoptera littoralis and Heliothis virescens~ and in crops of vegetables (for example against Leptinotarsa decemlineata and Myzus -:

~IL3 persicae). Some of the compounds of the formula I have a marked larvicidal and/or ovicidal action. When compounds of the formula I are taken with the ~eed by adult ;nsect stages, there can be observed in many cases, especially with Coleoptera, for example Anthonomus grandis, a reduced oviposition and/or a reduced hatching rate The compounds of the formula I are moreover suitable for combating ectoparasites in domestic animals and in productive animals, for example by trea~ment of animals, livestock housing and pasture land.
The action of the compounds of the invention or of compositions containing them can be considerably widened and adap~ed to suit prevailing conditions by the addition of other insecticides and/or acaricides. Suitable additives are for example the following active substances:
organic phosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates and chlorinated hydrocarbons.
The compounds of the formula I can be combined with particular advantage also with substances which have a pesticidally intensifying effect. Examples of such compounds are, inter alia: piperonylbutoxide, propynyl ethers, propynyl oximes, propynyl carbamates and propynyl 1~3~7~3 phosphonates, 2-(3,4-methyLenedioxyphenoxy)-3,6,9-trioxa-undecane or S,S,S-tributylphosphorotrithioates;
The compounds of the formula I can be used on their own or together with suitable carriers and/or additives.
Suitable carriers and ad~itives may be so~id or liquid and correspond to the substances common in formulation practice, such as natural or regenerated substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders and/or fertilisers. For application, the compounds of the formula I can be processed into the form of dusts, emulsion concentrates, granulates, dis-persions, sprays, solutions or suspensions, the formu-lation of these prepara~ions being effected in a manner commonly known in the art. Also to be mentioned are cattle dips and spray races, in which aqueous preparations are used. These forms of preparation are particularly suitable for combating zooparasitic pests.
The compositions according to the invention are produced in a manner known per sP by the intimate mixing and/or grinding of active substances of the formula I
with suitable carriers, optionally with the addition of dispersing a~ents or solvents which are inert to the active substances. The active substances can be obtained and used in the following forms:
solid_preparations: dusts, scattering agents or granulates (coated granules, impregnated granules and homogeneous granules);
liquid pre~a ations:
a~ water-dispersible concentrates of active substance:
wettable powders, pastes or emulsions;
b) solutions.
The content of active substance in the described compositions is between 0.1 and 95%.

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The active substances of the formula I can be formulated for example as follows:
Dusts The following substances are used to produce a) a 5% dust and b) a 2% dust:
a) S parts of active substance, and parts of talcum;
b) 2 parts of active substance, 1 part of highly dispersed silicic acid, and 97 parts of talc~m.
The active substance is mixed and ground with the carriers Granulate The ~ollowing ingredients are used ~o produce a 5%
granulate:
parts of active substance, 0.25 part of epoxidised vegetable oil, 0.25 part of cetyl polyglycol ether,

3.50 parts of polyethylene glycol, and 91 parts o~ kaolin (particle size 0.3 - 0.8 mm).
The active substance is mixedwithepoxidised vegetabLe oil and dissolved in 6 parts of acetone, and the polyethylene glycol and cetyl polyglycol ether are then added. The solution obtained is sprayed onto kaolin and the acetone is subsequently evaporated off in vacuo.
Wettable powders The following constituents are used to produce a) a 40% wettable powder, b) and c) a 25% wettable powder, and d) a 10% wettable powder:

~ ~ ~ 3~ 4 a) 40 parts of active substance, parts of sodilm lignin sulfonate, 1 part of sodium dibutyl-naphthalene sulfonate, and 54 parts of silicic acid;
b) 25 parts of active substance,

4.5 parts of calcium lignin sulfonate, 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutyl-naphthalene sulonate, 19.5 parts of silicic acid, 19.5 parts of Champagne chalk, and 28.1 parts of kaolin;
c) 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyo~yethylene-ethanol, 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselgur, and 46 parts of kaolin;
d) 10 parts of active substance, 3 parts o a mixture of the sodium salts of saturated fatty alcohol sulfates, parts of naphthalenesulfonic acid/formaldehyde condensate, and 82 parts of kaolin.
The active substance is intimately mixed in suitable mixers with the additives, and the mixture is then ground in the appropriate mills and rollers to obtain wettable powders which can be diluted with water to give suspensions of the desired concentration.

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Emulsifiable concentrates The following substances are used to produce a) a 10%
emulsifiable concentra~e, b) a 25% emulsifiable concentrate and c) a 50% emulsifiable concentrate:
a) 10 parts of active substance, 3.4 par~s of epoxidised vegetable oil, 3.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkyl-aryl sulfonate calcium salt, parts of dimethylformamide, and 43.2 parts of xylene;
b) 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, parts of an alkylarylsulfonate/fatty alcohol polyglycol ether mixture, parts o dimethylformamide, and 57.5 parts of xylene;
c) 50 parts of active substance, 4.2 parts of tributylphenol-polyglycol ether,

5.8 parts of calcium-dodecy~benzenesulfonate, parts of cyclehexanone, and parts of xylene.
Emulsions of the concentration required can be prepared frcm these concentrates by dilution with water.
Spray The following constituents are used to produce a) a 5% spray and b) a 95% spray:
a) 5 parts of active substance, 1 part of epoxidised vegetable oil, 94 parts of ligroin ~boiling limits 160-190C);
b) 95 parts of active substance, and parts of epoxidised vegetable oil.

The invention is further illustrated by the following Examples~

Example 1 3.8 g of 2~6-difluorobenzoylisocyanate are added, at room temperature with the exclusion of moisture~ to a solution of 5.2 g of 3-chloro-4-allyloxy-5-bromoaniline in 25 ml of absolute ether. The precipitate which is formed is filtered off with suction after 1 hour, and is subsequently washed with ether. Recrystallisation from toluene yields N-(3-chloro-4-allyloxy-5-bromo)-phenyl-N'-difluorobenzoylurea having a melting point or 169-171C.

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The following c~mpounds of the formula I are produced by procedures analogous to those described in the foregoing.
_ :. . _ __ Rl R2 R3 R4Melting point _ ~ __ _ _ _ _ H2C=CH-CH2- Cl F F 169-171 H2C=CH-C~2- Cl F Cl 199-201 H2C=CH-CH2- Cl Cl Cl 219-221 H2C=CH-CH2 Cl Cl H 172-173 H2C=CH-CH2- Cl F H 160-161 H2C=CH-CH2- Cl Cl F
H2C=CH-CH;~ 3r F F 179-180 C=CX-CH2- Br F Cl 206-207 H2C=CH-CH2- Br Cl Cl 227-229 H2C-CH CH2- Br Cl H 169-171 H2C=CH-CH2- Br F H 173-175 ClCX=CH-CX2- Cl F . ~171-172 ClCH=CH-CH2- Cl F Cl166-168 ClC~=CH-CH2- Cl Cl Cl ClCH=CH-C~2- Cl Cl H189-191 ClC~=CH-CH2- Cl F H179-180 ClCH=CH-CH2- Br F F182-183 ClCH=CH-CH2- Br F Cl161~163 ClCH=CH-CH2- Br Cl Cl192-194 ClCH=CH-CH2- Br Cl H179-182 ClCH=CH-CH2- lBr F H173-177 ClCH=CH-CH2- F F F138-143.
. .

CH2=CCl-CH2- Br F F187-188 *) stereoisomeric mixture :~ IL39 ~
,~
Example 2 Action a~ainst Musca domestica 50 g amounts of freshly prepared CSMAnutrientmedium for maggots was weighed off into each of a series of beakers.
A specific amount of a 1% (by weight) acetonic solution of the respective active substance was transferred by pipette to the nutrient medium in each beaker. Af~er a thorough mixlng of the nutrient medium, the acetone was allowed to evaporate off for at least 20 hours. There were then deposited per active substance and concentration in each case 25 on~-day-old Musca domestica maggots into each beaker containing the treated nutrient medium. After completion of pupation, the formed pupae were separated from the nutrient medium by flushing with water, and were placed into vessels closed with perforated lids. The pupae flushed out per batch were counted (toxic effect of the active substance on the development of the maggot), and then after 10 days the number of flies which had emerged from the pupae was determined.
Compounds according to the Example 1 exhibited a good action in the above test.
ample 3 Action a~ainst LUCi a sericata .

1 ml of an aqueous solution containing 0.5% of active substance was added to 9 ml of a culture medium at 50C.
About 30 freshly hatched Lucilia sericata maggots were then placed onto the culture medium, and a~ter 48 and 96 hours, respectively, the insecticidal action was determined by ascertaining the mortality rate.
Compounds according to the E~ample 1 exhibited in this test a good action against Lucilia sericata.

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Exam~le 4 Action a~ains_ Aedes aegypti:
Sufficient of a 001% acetonic solution of the respective active substance was transferred by pipette to the surface of 150 ml of water in a container to obtain concentrations of 10, 5 and 1 ppm in each case.
A~ter the acetone had evaporated off, 30-40 two-day-old Aedes larvae were placed into each container. The mortality rate was ascertained after 1, 2 and 5 days.
Compounds according to Example 1 exhibited~ -in this test a good action against Ae'des aegypti.
E mple 5~
Insecticidal ,stomach poison action Cotton plants were sprayed with a 0.05% aqueous emulsion of the active substance (obtained from a lQ%
emulsifiable concentrate).
After drying of the resulting coating, Spodoptera littoralis larvae and Heliothis virescens larvae in the third larval stage were placed onto the cotton plants.
The test was carried out at 24C with 60% relative humidity.
Compounds according to the Example 1 exhibited -in the above test a good insecticidal s~omach poison action against the larvae oi Spodoptera littoralis and Heliothis virescens.
Example 6 Ovicidal action on S~odoptera littoralis Eggs of Spodoptera littoralis, deposited on filter paper, were cut out of the paper and immersed in a 0.05 % ~by weight) solution of the active substance in an acetone ~:~l3917~

water mixture (1:1). The deposited eggs treated in this manner were then taken out o~ the mixture, and placed at 21C with 60% relative humidity into plastic dishes. After 3 to ~ days, the hatching rate1 that is to say, the numb-er of larvae which had developed ~rom the treated eggs, was determined.
Compounds according to Exa~ple 1 exhibited a good action in the above test.
Example 7 Action against Laspeyresia pomonella (eg~s) Deposited Laspeyresia pomonella eggs, which were not older than 24 hours, were immersed on filter paper for 1 minute in an acetonic-aqueous solution containing 4~0 ppm of the active substance to be tested. A~ter drying off the solution, the eggs were transferred to Petri dishes and kept at a temperature o~ 28C. After

6 days, the percentage -hatching rate from the treated eggs was evaluated.
Compounds according to Example 1 exhibited a good action in the above test.
Example 8 Action a~ainst Spodoptera littoralis and ~eliothis virescens ~larvae and eggs) Three cotton plants about 15-20 cm in height and grown in pots were treated with a sprayable liquid preparation o the active substance to be tested. A~ter ~he drying o~ the coating which had been sprayed on, the potted plants were placed into a tin container o~ about 20 li~res capacity, which was covered with a glass plate: The humidity inside the covered container ,~

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iL397~4 was controlled in a manner ensuring that no condensation water formed. Direct light falling onto the plants was avoided. The three plants w~re then infested in all with:
a) 50 larvae of Spodoptera littoralis and Heliothis virescens, respectively, of the first larval stage;
b) 20 larvae of Spodoptera littoralis and Heliothis virescens, respectively~ of the third larval stage;
c) two coatings of eggs of Spodoptera littoralis and Heliothis virescens~ respectively: for this purpose, 2 leaves of a plant were in each case enclosed in a plexiglass cylinder- sealed at each end with gauze;
two coatings of eggs of Spodoptera, or a portion of a cotton-plant leaf on which were deposited eggs of Heliothis, were added to the enclosed leaves.
An evaluation, using untreated control plants as a comparison, was made after 4 to 5 days on the basis of the following criteria:
a) number of living larvae, b3 inhibition of larval development and shedding~
c) d~mage caused by eating (scraping and hole damage), d) hatching rate (number of larvae which have emerged from the eggs).
The compounds according to Example 1 exhibited a good overall effectiveness in the above test.

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of the formula I

(I) wherein R1 is a C2-C3-alkenyl group, or a C2-C3-alkenyl group monosubstituted with chlorine; R2 and R3 are halogen; and R4 is hydrogen or halogen.

2. A compound of the formula I according to Claim 1, wherein R1 is a C3-alkenyl group, or a C3-alkenyl group monosubstituted with chlorine; R2 is fluorine, chlorine or bromine; R3 is fluorine or chlorine; and R4 is hydrogen, fluorine or chlorine.

3. A compound of the formula I according to Claim 1 or 2, wherein R1 is one of the radicals CH2=CH-CH2- or Cl-CH=CH-CH2-.

4. A compound of the formula I according to Claim 1, wherein R2 is chlorine or bromine.

5. A compound of the formula I according to Claim 1, wherein R3 and R4 are each fluorine.

6. A compound according to Claim 5 of the formula

7. A compound according to Claim 5 of the formula

8. A process for producing a compound according to Claim 1, which process comprises reacting a) a compound of the formula II

(II) with a compound of the formula III

(III);

or a) a compound of the formula IV

(IV) with a compound of the formula V

(V), wherein the formulae II to V, the radicals R1, R2, R3 and R4 have the meanings given in Claim 1.

9. A method of combating pests, which comprises applying to a locus an effective amount of a compound of formula I defined in claim 1.

10. A method according to Claim 9, wherein the pests are insect pests.